CN1720358A - Nanofiber aggregate, polymer-alloy fibre, blended fiber, fiber construct and their manufacture method - Google Patents
Nanofiber aggregate, polymer-alloy fibre, blended fiber, fiber construct and their manufacture method Download PDFInfo
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- CN1720358A CN1720358A CN 200380105030 CN200380105030A CN1720358A CN 1720358 A CN1720358 A CN 1720358A CN 200380105030 CN200380105030 CN 200380105030 CN 200380105030 A CN200380105030 A CN 200380105030A CN 1720358 A CN1720358 A CN 1720358A
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Images
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- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides and not restricted by shape and polymer, but extensive use, nanofiber aggregate that filament fiber number deviation is little and manufacture method thereof.Nanofiber aggregate of the present invention its to count the average single fiber fiber number be 1 * 10
-7～2 * 10
-4Dtex, fiber number ratio be 60% or its above filamentary filament fiber number be in 1 * 10
-7～2 * 10
-4The dtex scope, and constitute by thermoplastic polymer.
Description
Technical field
The present invention relates to nanofiber aggregate.The invention still further relates to the polymer-alloy fibre of the precursor that becomes nanofiber aggregate.The invention still further relates to the blended fiber and the fiber construct that contain nanofiber aggregate.In addition, the invention still further relates to these manufacture method.
Background technology
With polyethylene terephthalate (following abbreviation PET) and polybutylene terephthalate (PBT) (following abbreviation PBT) is the polyester of representative, be the polycondensation base polymers such as polyamide of representative perhaps with nylon 6 (following abbreviation N6) and nylon 66 (following abbreviation N66), owing to have the mechanical characteristic and the heat resistance of appropriateness, be suitable for before this using as dress material and industry raw material.On the other hand, be the addition polymerization base polymer of representative with polyethylene (following abbreviation PE) and polypropylene (following abbreviation PP), owing to having appropriate mechanical characteristic and resistance to chemical reagents, light weight, so mainly be suitable for using as the industry raw fiber.
Particularly therefore polyester fiber or polyamide fiber, not only will carry out upgrading to polymer sometimes also as dress material usefulness, and have also carried out positive discussion to the section configuration of fiber or by extra fine filament raising performance.One of inquire into as these, be born and utilized the island composite spinning and make the super extra fine filament of polyester, produce a new generation's weaving new product of the artificial leather of imitation buckskin liquor style.In addition, this super extra fine filament is suitable for doing general dress material, also can make and adopt the absolute unavailable dress material with good soft feel of common fiber.In addition, super extra fine filament not only can be used as dress material usefulness, and can be used as the means of livelihood such as cloth for wiping or dusting and the industry data is used, so present synthetic fiber have obtained firm status in the world.
Particularly nearest, the abrasive cloth and the application prospect in the special medical materials such as cell sorbing material of opening the record of 2002-172163 communique on hard disc of computer surface that the spy opens 2001-1252 communique record is vast.
Therefore, for artificial leather and the high texture dress material that obtains higher level, wish to develop thinner fiber.In addition,, must further make it level and smooth, reach average surface roughness 0.5nm or below it present average surface roughness 1nm or the harddisk surface more than it in order to make the hard disk high capacity, further to improve the packing density of hard disk.Therefore, as the fiber of the abrasive cloth that is used to grind harddisk surface, wish to reach more superfine nanofiber.
In addition, even medically using,, wish to have to reach the nanofiber that constitutes the same size of fiber with organism in order to improve the compatibility with cell.
Yet, adopting present island composite spinning technology, the filament fiber number is confined to 0.04 dtex (dtex) (being equivalent to diameter 2 μ m), does not reach and fully satisfies the required level of nanofiber.In addition, adopt the mixed with polymers fiber to make the method for super extra fine filament, opening flat 3-113082 communique and spy the spy, to open flat 6-272114 communique on the books, but the filament fiber number that obtains here is the thinnest is 0.001 dtex (being equivalent to diameter 0.4 μ m), does not reach yet and fully satisfies the required level of nanofiber.
In addition,, make the method for super extra fine filament,, done to disclose in 074 at USP 4,686 by the mixed with polymers fiber that adopts static mixing roll to obtain.Yet, even the super extra fine filament that adopts this technology to make does not reach yet and fully satisfies the required level of nanofiber.
Therefore, as the technology that makes super superfineization of fiber, what be subjected in recent years greatly paying close attention to has a so-called electronics textile technology (エ レ Network ト ロ ス ピ ニ Application グ).The electronics weaving is, polymer dissolution in electrolyte solution, when nozzle is extruded, polymer solution is applied the high voltage of thousands of～30,000 volt, make the polymer solution high velocity jet, then spray crooked (the bent Ga り of folding れ), expanding reaches the technology of superfineization by making.When this technology of employing, the filament fiber number reaches 10
-5Dtex magnitude (single fiber diameter is equivalent to tens nm) is compared with original mixed with polymers technology, sometimes fiber number 1/100 or below it, diameter is 1/10 or below it.As the polymer of object, majority is biopolymer and water-soluble polymers such as ossein, also has but thermoplastic polymer is dissolved in the example that carries out the electronics weaving in the organic solvent.Yet, as Polymer, vol.40, record is such in 4585 (1999), " cord " majority as super extra fine filament part links by polymer smooth " bead " (diameter 0.5 μ m), when observing, there is big filament fiber number deviation as super extra fine filament aggregate.Therefore, suppress the generation of " bead ", fibre diameter research is uniformly also being carried out, but this fiber number deviation also big (Polymervol.43,4403 (2002)).In addition, the fiber collection shape that adopts the electronics weaving to obtain only limits to nonwoven fabric, and simultaneously, resulting fiber assembly majority can not crystallographic orientation, compares with common fibre, only obtains the very poor goods of intensity, so application prospect is subjected to severely restricts.In addition, the thickness of the fibre that obtains by electronics weaving reaches 100cm
2About, in addition, the great talent of production efficiency reaches several Grams Per Hours, compares with common melt spinning, and production efficiency is very low.In addition, when adopting high voltage, there are problems such as organic solvent and super extra fine filament suspend in air.
Therefore,, disclose load aggregation catalyst on mesoporous silica, carried out the PE polymerization, made diameter and reach 30～50nm and (be equivalent to 5 * 10 by it at Science vol.2113 (1999) as the specific process that makes nanofiber
-6～2 * 10
-5The method of PE nanofiber part dtex).Yet, adopt this method only to obtain the cotton shape piece of nanofiber, can not be by its stretched fiber.In addition, used polymer also only limits to the PE of addition polymerization class, polycondensation base polymers such as polyester and polyamide, owing in polymerization process, must dewater, so from the principle operating difficulties.Therefore, adopt the application prospect of the nanofiber that this method obtains also to be subjected to severely restricts.
Summary of the invention
The invention provides that a kind of shape and polymer do not restricted, but extensive use, nanofiber condensate and manufacture method thereof that filamentary fiber number deviation is little.
Of the present invention being constructed as follows.
(1) a kind of aggregate of nanofiber, number average single fiber fiber number is 1 * 10
-7～2 * 10
-4Dtex, fiber number ratio be 60% or its above filamentary filament fiber number 1 * 10
-7～2 * 10
-4The scope of dtex, and constitute by thermoplastic polymer.
(2) nanofiber aggregate described in above-mentioned (1) is long fiber shape and/or weaving filament shape.
(3) nanofiber aggregate described in above-mentioned (1) or (2), number average single fiber fiber number is 1 * 10
-7～1 * 10
-4Dtex, fiber number ratio be 60% or its above filamentary filament fiber number 1 * 10
-7～1 * 10
-4The scope of dtex.
(4) any one described nanofiber aggregate in above-mentioned (1)～(3), wherein, constitute the polymeric filament medium titre of nanofiber ratio and be 50% or its above filamentary single fiber diameter deviation be that 30nm is wide.
(5) any one described nanofiber aggregate in above-mentioned (1)～(4), wherein, thermoplastic polymer is the polycondensation base polymer.
(6) any one described nanofiber aggregate in above-mentioned (1)～(5), wherein, the fusing point of thermoplastic polymer is more than 160 ℃ or 160 ℃.
(7) any one described nanofiber aggregate in above-mentioned (1)～(6), wherein, thermoplastic polymer is selected from polyester, polyamide and polyolefin.
(8) any one described nanofiber aggregate in above-mentioned (1)～(7), wherein, intensity is at 1cN/dtex or more than the 1cN/dtex.
(9) any one described nanofiber aggregate in above-mentioned (1)～(8), wherein, hydroscopicity is more than 4% or 4%.
(10) any one described nanofiber aggregate in above-mentioned (1)～(9), wherein, the moisture expantion rate of filament length degree direction is more than 5% or 5%.
(11) any one described nanofiber aggregate in above-mentioned (1)～(10), it contains functional medicine.
(12) a kind of fiber construct wherein, contains any one described nanofiber aggregate in above-mentioned (1)～(11).
(13) fiber construct described in above-mentioned (12), wherein, it is 20～2000g/m that the order of fiber is paid
2
(14) fiber construct described in above-mentioned (12) or (13), wherein, the hollow part of the air silk of nanofiber aggregate is by encapsulated.
(15) fiber construct described in above-mentioned (14), wherein, air silk exists many diameter 100nm or the pore below it at length direction.
(16) any one described fiber construct in above-mentioned (12)～(15) wherein, contains functional medicine.
(17) any one described fiber construct in above-mentioned (12)～(16), wherein, fiber construct is selected from silk, cotton, packing material, fabric, felt, nonwoven fabric, artificial leather and sheet material.
(18) fiber construct described in above-mentioned (17), wherein, fiber construct is nonwoven fabric and the stacked lamination nonwoven fabric of nonwoven fabric beyond it that contains nanofiber aggregate.
(19) any one described fiber construct in above-mentioned (12)～(18), wherein, fiber construct is the fibre that is selected from dress material, dress material material, interior decoration goods, vehicle interior decorated articles, life material, environment industry material product, IT parts and medical articles.
(20) liquid dispersion of any one described nanofiber aggregate in a kind of above-mentioned (1)～(11).
(21) a kind of polymer-alloy fibre, wherein, have by the different island structure that organic polymer constitutes more than 2 kinds of dissolubility, island component is made of easy dissolubility polymer difficult dissolubility polymer, sea component, several average diameters in zone, island are 1～150nm, area than 60% or several average diameters in its above zone, island be 1～150nm, and island component is dispersed into striated.
(22) polymer-alloy fibre described in above-mentioned (21), wherein, several average diameters in zone, island are 1～100nm, area than be 60% or several average diameters in its above zone, island be 1～100nm.
(23) polymer-alloy fibre described in above-mentioned (21) or (22), wherein, in the polymer-alloy fibre in the contained zone, island area than be 60% or the diameter difference in its above zone, island in the 30nm scope.
(24) any one described polymer-alloy fibre in above-mentioned (21)～(23), wherein, the containing ratio of island component relatively all fiber reaches 10～30 weight %.
(25) any one described polymer-alloy fibre in above-mentioned (21)～(24), wherein, sea component is to be made of diffluent polymer in aqueous alkali or hot water.
(26) any one described polymer-alloy fibre in above-mentioned (21)～(25), wherein, the fusing point of island component is more than 160 ℃ or 160 ℃.
(27) a kind of polymer-alloy fibre, any one described polymer alloy and other the polymer-bonded composite fibre that forms in its (21)～(26) that are above-mentioned.
(28) any one described polymer-alloy fibre in above-mentioned (21)～(27), wherein, 20% or more than it, perhaps crispation number is 5/25mm or more than it as the CR value of curl characteristics index.
(29) any one described polymer-alloy fibre in above-mentioned (21)～(28), wherein, the Wu Site spot is 5% or below it.
(30) any one described polymer-alloy fibre in above-mentioned (21)～(29), wherein, intensity is 1.0cN/dtex.
(31) a kind of fiber construct wherein, contains any one described polymer-alloy fibre in above-mentioned (21)～(30).
(32) fiber construct described in above-mentioned (31), wherein, fiber construct is selected from silk, cotton, packing material, textiles, knitted fabric, felt, nonwoven fabric, artificial leather and sheet material.
(33) fiber construct described in above-mentioned (31) or (32) wherein, contains polymer-alloy fibre and fiber in addition thereof.
(34) any one described fiber construct in above-mentioned (31)～(33), wherein, fiber construct is selected from the fibre of dress material, dress material material, interior decoration goods, vehicle interior decorated articles, life material, environment industry material product, IT parts and medical articles.
(35) a kind of manufacture method of polymer-alloy fibre, this method is difficult dissolubility polymer and easy dissolubility polymer melting mixing in addition, the polymer alloy that obtains is carried out the manufacture method of the polymer-alloy fibre of melt spinning, and it satisfies the condition of following (1)～(3):
(1) difficult dissolubility polymer with after easily the dissolubility polymer independently measures respectively, supplies with kneading device independently and carry out melting mixing;
(2) containing ratio of the difficult dissolubility polymer in the polymer alloy is in 10～50 weight % scopes;
(3) easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, and perhaps easily the fusing point of dissolubility polymer is in the model figure of difficult dissolubility melting point polymer-20～+ 20 ℃.
(36) manufacture method of the polymer-alloy fibre described in above-mentioned (35) wherein, is extruded mixing roll with twin shaft and is carried out melting mixing, and the kneading part length that twin shaft is extruded mixing roll is 20～40% of screw rod effective length.
(37) manufacture method of the polymer-alloy fibre described in above-mentioned (35) wherein, is carried out melting mixing with static mixing roll, and cutting apart of static mixing roll counted more than 1,000,000 or 1,000,000.
(38) manufacture method of any one described polymer-alloy fibre in above-mentioned (35)～(37), wherein, the stress of cutting off between the nozzle hole wall of melt spinning and the polymer is 0.2MPa or below the 0.2MPa.
(39) a kind of polymer alloy particle, wherein, have by 2 kinds of different island structures that organic polymer constitutes of dissolubility, island component is made of easy dissolubility polymer difficult dissolubility polymer, sea component, and, easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, and perhaps easily the fusing point of dissolubility polymer is in the Fan Tunei of difficult dissolubility melting point polymer-20～+ 20 ℃.
(40) a kind of organic/inorganic mixture of fibers wherein, contain any one described nanofiber aggregate 5～95 weight % in above-mentioned (1)～(11), and this inorganic matter at least a portion is present in nanofiber aggregate inside.
(41) a kind of fiber construct wherein, contains the organic/inorganic mixture of fibers described in above-mentioned (40).
(42) the organic/inorganic mixture of fibers manufacture method described in above-mentioned (40) wherein, is immersed in inorganic monomer in the nanofiber aggregate, makes the inorganic monomer polymerization then.
(43) manufacture method of the fiber construct described in above-mentioned (41) wherein, is immersed in inorganic monomer in the fiber construct that contains nanofiber aggregate, makes the inorganic monomer polymerization then.
(44) a kind of manufacture method of blended fiber wherein, is immersed in organic monomer and makes this organic monomer polymerization in above-mentioned (1)～(11) behind any one described nanofiber aggregate.
(45) a kind of manufacture method of fiber construct wherein, is immersed in organic monomer and makes this organic monomer polymerization in above-mentioned (12)～(19) behind any one described fiber construct.
(46) a kind of porous fibre, wherein, 90 weight % of composition or be made of inorganic matter more than it have many pores at length direction, and the several average pore diameter in the section of short-axis direction are 1～100nm.
(47) a kind of fiber construct wherein, contains the porous fibre described in above-mentioned (46).
(48) a kind of manufacture method of porous fibre wherein, is immersed in inorganic monomer in the nanofiber aggregate, makes the inorganic monomer polymerization then, removes nanofiber from the organic/inorganic blended fiber that obtains, and obtains the porous fibre described in above-mentioned (46).
(49) a kind of manufacture method of fiber construct, wherein, be immersed in the fiber construct that contains nanofiber aggregate from containing the handlebar inorganic monomer, remove nanofiber in the structure of the organic/inorganic blended fiber that makes the inorganic monomer polymerization then and obtain, obtain the fiber construct described in above-mentioned (47).
(50) a kind of manufacture method of nonwoven fabric, wherein, after any one described polymer-alloy fibre was cut into the long 10mm of fiber in above-mentioned (21)～(30), the easy dissolubility polymer of stripping was copied paper without temporary transient drying then.
(51) a kind of manufacture method of nonwoven fabric, wherein, in formation contains above-mentioned (21)～(30) behind the nonwoven fabric or felt of any one described polymer-alloy fibre, behind the substrate bonding that constitutes this nonwoven fabric or felt with by difficult dissolubility polymer, make the stripping of easy dissolubility polymer.
Description of drawings
Fig. 1 is the TEM photo of aggregate fiber cross sections of the nylon nano fiber of expression embodiment 1.
Fig. 2 is the TEM photo in cross section of the polymer-alloy fibre of expression embodiment 1.
Fig. 3 is the SEM photo of aggregate fiber cross sections state of the nylon nano fiber of expression embodiment 1.
Fig. 4 is the optical microscope photograph of fiber side surface state of aggregate of the nylon nano fiber of expression embodiment 1.
Fig. 5 is the figure of filament fiber number deviation of the nanofiber of expression embodiment 1.
Fig. 6 is the figure of filament fiber number deviation of the nanofiber of expression embodiment 1.
Fig. 7 is the figure of filament fiber number deviation of the nanofiber of expression comparative example 4.
Fig. 8 is the figure of filament fiber number deviation of the super extra fine filament of expression comparative example 4.
Fig. 9 is the figure of filament fiber number deviation of the super extra fine filament of expression comparative example 5.
Figure 10 is the figure of filament fiber number deviation of the super extra fine filament of expression comparative example 5.
Figure 11 is the reversible water-swollen figure of expression embodiment 1.
Figure 12 is the figure of expression spinning machine.
Figure 13 is the figure of expression nozzle.
Figure 14 is the figure of expression stretching-machine.
Figure 15 is the figure of expression spinning machine.
Figure 16 is the figure of expression spinning machine.
Figure 17 is the figure of expression spinning machine.
Figure 18 is the figure of expression swivel head device for spinning
Figure 19 is the figure that ammonia is eliminated in expression.
Figure 20 is the figure that the formaldehyde stink is eliminated in expression.
Figure 21 is the figure that the toluene stink is eliminated in expression.
Figure 22 is the figure of expression removal of hydrogen sulfide stink.
The specific embodiment
The preferred thermoplastic of using in the nanofiber aggregate of the present invention can be enumerated polyester, polyamide, polyolefin, polyphenylene sulfide etc.Wherein, be the polycondensation base polymer of representative with polyester and polyamide, most preferred fusing points are high.When melting point polymer more than 160 ℃ or 160 ℃ the time, the heat resistance of nanofiber is good, is preferred.For example, PLA (following abbreviation PLA) is that 170 ℃, PET are that 255 ℃, N6 are 220 ℃.In addition, in polymer, can also contain additives such as particle, fire retardant, antistatic additive.In addition, in the scope of not damaging polymer property, also can with other composition copolymerization.
So-called nanofiber among the present invention is meant that single fiber diameter is the fiber of 1～250nm, and its material that gathers together is referred to as nanofiber aggregate.
And in the present invention, the mean value and the deviation of the filament fiber number in this nanofiber aggregate are important.With the cross section of infiltration type electron microscope (TEM) observation nanofiber aggregate, in same cross section, extract out arbitrarily and measure single fiber diameter more than 300 or 300.One of fiber cross sections of nanofiber of the present invention is illustrated in Fig. 1.This mensuration carry out at least 5 places or its above, add up to and measure 1500 or its above single fiber diameter, obtain the mean value and the deviation of the filament fiber number in the nanofiber aggregate whereby.These locate, and the inhomogeneity viewpoint of the fibre that obtains in the collateral security nanofiber aggregate considers, as nanofiber aggregate length 10m disconnected from each other or its with on be preferred.
Here, filament fiber number mean value is obtained by laxative remedy.That is, from the single fiber diameter measured and constitute filamentary density polymer and calculate fiber number, obtain their simple mean value.In the present invention it is called " fiber number of number average single fiber ".Also have, the density value that uses in the calculating adopts the general value that adopts of various polymer respectively.In the present invention, the fiber number of counting average single fiber reaches 1 * 10
-7～2 * 10
-4(it is important being equivalent to single fiber diameter 1～150nm) to dtex.This is owing to compare with the super extra fine filament that original island composite spinning obtains, carefully to 1/100～1/100, and 000, can access the fabric for clothing that has with the original complete different texture of super extra fine filament.In addition, when using as the hard disk abrasive cloth, with original comparing, the flatness of hard disk is improved far away.The filament fiber number preferred 1 * 10 that number is average
-7～1 * 10
-4Dtex (is equivalent to single fiber diameter 1～100nm), more preferably 0.8 * 10
-5～6 * 10
-5(single fiber diameter is equivalent to 30～80nm) to dtex.
In addition, the filament fiber number deviation of nanofiber is estimated by laxative remedy.That is each filamentary filament fiber number dt,
iExpression, its summation is as total fiber number (dt
1+ dt
2+ dt
3+ ... dt
n).In addition, nanofiber fiber number and frequency (number) with identical filament fiber number are long-pending, divided by the resulting value of total fiber number, as the fiber number ratio of this filament fiber number.The fiber number ratio is equivalent to the weight rate (volume fraction) of each filament fiber number composition to all (nanofiber aggregate), and the filament fiber number composition that its value is big is big to the property effect of nanofiber aggregate.In the present invention, fiber number ratio 60% or its above filament are in 1 * 10
-7～2 * 10
-4(it is important that single fiber diameter is equivalent to 1～150nm) scope to dtex.That is, meaning ought be greater than 2 * 10
-4Dtex is when (single fiber diameter is equivalent to 150nm), and the existence of nanofiber approaches zero.
Also have, in above-mentioned USP 4,686,074, disclose mixed with polymers fiber, make the method for super extra fine filament by utilizing static mixing roll to obtain.Recording when counting the theoretical filament fiber number that calculates from cutting apart of static mixing roll is 1 * 10
-4Dtex can obtain nanofiber when (diameter is equivalent to about 100nm), but the filament fiber number results measured of the super extra fine filament that will obtain is 1 * 10
-4Dtex～1 * 10
-2During dtex (about diameter 1 μ m), can not get the uniform nanofiber of single fiber diameter.Think that this is owing to island polymer in the mixed with polymers fiber merges, thereby the island polymer can not be with due to the even dispersion of nano-scale.Therefore, the super extra fine filament that adopts this technology to obtain can only be that the deviation of filament fiber number is big.When the deviation of filament fiber number is big, because the performance of goods is subjected to thick filamentary influence strongly, so the advantage of super extra fine filament can not be given full play to.In addition, because the deviation of filament fiber number, so quality stability etc. also have problem.In addition, when as above-mentioned hard disk when use abrasive cloth, owing to the fiber number deviation is big, abrasive material can not evenly load on abrasive cloth, the problem that the result exists the flatness of harddisk surface to descend on the contrary.
With respect to this, nanofiber aggregate of the present invention because filament fiber number deviation is little, can give full play to the function of nanofiber, and Products Quality stability is also good.In addition, as above-mentioned hard disk during with surface grinding cloth, because the fiber number deviation is little, even but also uniform load abrasive particle of nanofiber, the result is that the flatness of harddisk surface obtains leap and rises.Preferably, fiber number ratio 60% or its above filament are in 1 * 10
-7～1 * 10
-4Dtex (single fiber diameter is equivalent to 1～100nm), and more preferably 1 * 10
-7～6 * 10
-5(single fiber diameter is equivalent to 1～80nm) scope to dtex.More preferably fiber number ratio 75% or its above filament are in 1 * 10
-7～6 * 10
-5(single fiber diameter is equivalent to 1～80nm) scope to dtex.
In addition, another index of fiber number deviation is that the single fiber diameter difference enters the wide filamentary fiber number ratio of 30nm.As mentioned above, to various single fiber diameters counting frequency, cut 30nm when wide with the single fiber diameter difference, the filamentary fiber number ratio aggregate value that the 30nm that frequency is the highest is wide enters the wide filamentary fiber number ratio of 30nm as the single fiber diameter difference.This means deviation and concentrates near the fiber number of center, and this fiber number ratio is higher, and deviation is littler.In the present invention, the single fiber diameter difference enters the wide filamentary fiber number ratio of 30nm and reaches 50% or be preferred more than it.More preferably 70% or more than it.
In addition, in the present invention, nanofiber aggregate forms the long fiber shape and/or the weaving filament shape is preferred.So-called long fiber shape here and/or weaving filament shape refer to following state.That is, as compound silk and weaving silk, the aggregate of 1 yuan of orientation of many nanofibers is with limited length continuum of states.One of side photo of nanofiber aggregate of the present invention is illustrated in Fig. 3.With respect to this, with the nonwoven fabric that the electronics weaving obtains, nanofiber all is unoriented 2 meta structure aggregates, sees it is diverse form from this point.What the present invention relates to is the nanofiber aggregate of 1 yuan of orientation, and this point is very novel.Nanofiber aggregate length of the present invention reaches several m equally with common multifilament or is preferred more than it.Therefore, much less textiles, knitted fabric can make various fiber constructs such as staple fibre and nonwoven fabric, hot compression formed body.
In addition, nanofiber aggregate of the present invention is characterized in that, single fiber diameter be original super extra fine filament 1/10～1/100 or below it, so the specific area leap strengthens.Therefore, demonstrate the ins and outs that adopt the nanofiber that common super extra fine filament do not see.
For example, can enumerate the significantly raising of characterization of adsorption.In fact, the absorption of water vapour, i.e. hygroscopicity, polyamide nanofiber aggregate of the present invention is compared with the common super extra fine filament of polyamide, the hydroscopicity of the common super extra fine filament of polyamide is about 2%, and polyamide nanofiber aggregate of the present invention reaches 6%.Hygroscopicity is to consider it is very important characteristic as the dress material time spent from the comfortableness viewpoint, and in the present invention, hydroscopicity reaches 4% or be preferred more than it.Also have, introduce below about the assay method of hydroscopicity (Δ MR).
In addition, the adsorptivity excellence of odorants such as Dichlorodiphenyl Acetate and ammonia, hydrogen sulfide is compared with common polyamide fiber, and the smelly rate that disappears and the smelly speed that disappears are all good.In addition, except that single odorant, harmful substances such as formaldehyde of one of house decoration disease reason material and Environmental Hormone, heavy metal compound also can be adsorbed.
In addition, adopt nanofiber aggregate of the present invention, because in the gap that generates between the filament of nanofiber about a plurality of several nm～hundreds of nm, so present the such special character of super porous material sometimes.
For example, can enumerate the significantly raising of liquid-absorbent.In fact, the water imbibition of polyamide nanofiber monomer of the present invention is compared with the water imbibition of common polyamide fiber, and the water absorption rate of common polyamide fiber is about 26%, and polyamide nanofiber water absorption rate of the present invention reaches 83%, is that they are more than 3 times.In addition, adopt the common super extra fine filament of polyamide, the expansion rate of filament length degree direction by suction reaches about 3%, and the expansion rate of polyamide nanofiber aggregate of the present invention reaches 7%.Yet this imbibition returns to the original length when drying, so present reversible change in size.The dilatancy of the filament length degree direction by this reversible suction/drying considers it is important characteristic from the soil release characteristics of cloth and silk, reaches 5% or be preferred more than it in the present invention.The so-called soil release characteristics here means by washing, the character that pollutant comes off easily.Therefore, owing to pass through the suction nanofiber aggregate in the imbibition of filament length degree direction, space between the fiber in textiles and the knitted fabric (weaving hole, knitting hole) enlarges, so remove easily attached to interfibrous pollutant.
Also have, when nanofiber aggregate of the present invention is used as dress material, can obtain the fibre of the excellent quality style of the same soft feeling of thin,tough silk and artificial silky dry sensation.In addition,, open the fine nanofiber that is, also can obtain to imagine the super feel and the moist like that feel fiber with excellent goods of people's skin that obtain in the past from nanofiber aggregate by adopting polishing etc.
In addition, nanofiber aggregate of the present invention, the crystallographic orientation person is preferred.The degree of directional crystallization can be estimated with wide-angle X-ray diffraction (WAXD).Here, when the crystallization degree that adopts the Rouland method reaches 25% or 25% above person, the percent thermal shrinkage of fiber reduces, and the DIMENSIONAL STABILITY raising is preferred.In addition, when the crystal orientation degree reaches 0.8 or 0.8 when above, molecular orientation improves, and the intensity of silk improves, and is preferred.
If nanofiber aggregate intensity of the present invention is at 1cN/dtex or more than the 1cN/dtex, then the mechanical property of fibre improves, so be preferred.Nanofiber aggregate intensity is 2cN/dtex or more than the 2cN/dtex more preferably.In addition, the percent thermal shrinkage of nanofiber aggregate of the present invention can be adjusted according to purposes, but as dress material the time, 140 ℃ of xeothermic being contracted in below 10% or 10% are preferred.
Adopt nanofiber aggregate of the present invention, can form various fiber constructs.The so-called fiber construct here generally is called 1 yuan, 2 yuan, 3 yuan fiber constructs.Example as 1 yuan of fiber construct has long fiber, staple fibre, weaving silk, rhabodoid (rod) etc., example as 2 yuan of fiber constructs has cloth and silks such as textiles, knitted fabric and nonwoven fabric, sheet material etc., as the example of 3 yuan of fiber constructs dress material, WEB, thermally molded article each, cotton etc. is arranged.Also mean by these and other materials are made up assembly that obtains and end article etc.
In addition, the weight fraction of the nanofiber aggregate in the structure of the present invention is when 10% or 10% when above, and the good performance of nanofibers such as characterization of adsorption can be given full play to, and is preferred.The weight fraction of nanofiber aggregate is more preferably more than 50% or 50%.
When particularly requiring goods that washing is had morphological stability and durability, the fiber order is paid and is reached 20～2000g/m
2The person is preferred.Here, to pay be that fibre weight is divided by the resulting value of the area of pars fibrosa to so-called fiber order.Order is paid little the healing gently of healing, and is loosely organized, DIMENSIONAL STABILITY and poor durability.Order is paid bigger heavier, rugged construction, and DIMENSIONAL STABILITY and durability improve.Particularly in the present invention, owing to adopt nanofiber, DIMENSIONAL STABILITY and durability often worsen, and fix on 20g/m so preferred order is paid
2Or more than it, to guarantee DIMENSIONAL STABILITY and durability.In addition, by being paid, order reaches 2000g/m
2Or below it, can guarantee lightweight to a certain degree.The optimum value that order is paid is different because of the kind of goods, as wrapping nonwoven fabric, gently to 25～40g/m
2About, as dress material with about 50～200g/m
2About, as about 100～250g/m such as curtain
2About, as about 100～350g/m such as car pads
2About, as heavy product such as woollen blankets with about 1000～1500g/m
2About be preferred.For the goods of washing, the washing distortion takes place, 50g/m in order to prevent to wash particularly
2Or be preferred more than it.
The fiber construct that contains nanofiber aggregate of the present invention can be made intermediates such as silk, cotton (cotton), packing material, textiles, knitted fabric, felt, nonwoven fabric, artificial leather, sheet material.In addition, as dress material, dress material raw material, interior decoration goods, vehicle interior decorated articles, life material daily necessitiess such as (cloth for wiping or dusting, cosmetic product, health treatment, toys etc.) and, fibre such as environment industry raw material goods (building materials, abrasive cloth, filter cloth, remove harmful substance goods etc.) and IT parts (sensor element, battery component, robot components etc.), medical articles (blood filter, extracorporeal circulation column, support, wound with dressing, artificial blood vessel, medicament slowly-releasing body etc.) is well-adapted.
The major part of such use, the nano fiber non-woven fabric that the weaving of employing electronics obtains is because intensity and morphological stability deficiency, size (width) deficiencies etc. can not be used in extensive fields, but begun to make it to become possibility by nanofiber aggregate of the present invention.For example, because dress material and interior decoration goods, vehicle interior decorated articles, abrasive cloth, filter cloth, various IT parts etc. require product strength, so, can reach by the nanofiber aggregate with good silk intensity of the present invention.
In addition, the such use major part, nanofiber adsorptivity originally and liquid-absorbent deficiency, because of the problem of absolute size causes abrasiveness and wiping deficiency etc., the performance of some purposes can not satisfy.
Therefore, nanofiber aggregate of the present invention reaches the various goods from its derivation, can solve the problem of original fine fibre and electronics weaving nonwoven fabric.
In addition, nanofiber aggregate of the present invention, when the hollow part of its air silk was made encapsulated structure, the color emissivity of fiber form stability and product dyed thereby improved, so be preferred.The excessive cohesion of nanofiber is prevented, and can suppress the decline of the good characteristic that nanofiber had originally.In addition, this encapsulated structure, even fiber bending reaches and exerts pressure from the fiber side, the nanofiber of hollow part can play cushion pad, the liquor style that presents the such softness of cotton candy, very useful to dress material purposes and interior decoration purposes, vehicle interior decorative use, dress material material applications, life material applications etc.
In addition, as the air silk polymer that uses in the capsule, concrete is to work as the density of air silk at 1.25g/cm
3Or it is when following, and the nanofiber adsorptivity and the liquid water imbibition of hollow part can be given full play to, and are preferred.This is that promptly strand is wide at interval because the density of air silk is low, sees through due to the various molecules easily.As preferred examples of polymers, can enumerate PLA (1.25g/cm
3), N6 (1.14g/cm
3), N66 (1.14g/cm
3), PP (0.94g/cm
3), PE (0.95g/cm
3), polymethylpentene (PMP, 0.84g/cm
3) etc.In the bracket is density polymer.The density of air silk is preferably 1.20g/cm
3Here, the density of air silk can be estimated by the density of measuring separately the sample made from air silk.
In addition, when the polymer possess hydrophilic property of air silk, hydrophilic molecules such as hydrone and alcohol see through easily, are preferred.Here the polymer possess hydrophilic property of so-called air silk, the moisture containing ratio that means the air silk of measuring under 20 ℃, the standard state of relative humidity 65% is 2% or more than it.The polymer of air silk is polyamide such as N6 and N66 more preferably.
In addition, when air silk when length direction has many diameter 100nm or the pore below the 100nm, various molecules are more prone to see through, the nanofiber characterization of adsorption and the liquid water imbibition of hollow part can be given full play to, and are preferred.The pore diameter here can adopt the fiber section of electron microscope observe and polymer under the freezing point of water degradation estimate.Pore diameter is 50nm or below the 50nm more preferably, the following or 10nm of especially preferred 10nm.Thus, color emissivity descends in the time of can suppressing stock-dye.Particularly air silk is made of hydrophilic polymers such as polyamide, and when further having more above-mentioned pore, hygroscopicity improves, and is very preferred.
Manufacture method to nanofiber aggregate of the present invention is not particularly limited, and for example, can adopt the following polymers alloy fiber to make the method for precursor.
That is,, make the polymer alloy molten mass, with cooling curing and fibration after its spinning the polymer alloyization more than 2 kinds different to the dissolubility of solvent.Then, implement as required to stretch and heat treatment, obtain having the polymer-alloy fibre of island structure.Then, remove easy dissolubility polymer, obtain nanofiber aggregate of the present invention by solvent.As the preferred polymers alloy fiber of nanofiber aggregate precursor, enumerate as follows here.
Promptly, have by the different island structure that organic polymer constitutes more than 2 kinds of dissolubility, island component is embarrassed the dissolubility polymer, marine origin is divided into easy dissolubility polymer and constitutes, several average diameters in zone, island are 1～150nm, area than 60% or the diameter in its above zone, island be 1～150nm, and island component is dispersed into the polymer-alloy fibre of striated.
In the present invention, it is important forming island structure by 2 kinds of different organic polymers of dissolubility, and the so-called dissolubility here means the different dissolubilities to solvent.So-called solvent can adopt aqueous slkali or acid solution, organic solvent, also have supercritical fluid etc.
In addition, in the present invention, in order simply to remove sea component with solvent, adopt easy dissolubility polymer as sea component, adopting difficult dissolubility polymer is important as island component.In addition, when selecting the diffluent polymer of aqueous alkali, during as easy deliquescent polymer, dissolution equipment need not antiknock device, sees it is preferred from cost, versatility viewpoint.As the easy dissolubility polymer of alkali, can enumerate polyester, Merlon (following abbreviation PC) etc., combined polymerization PET or PLA are particularly preferred.Also have, when selecting hot water solubility's polymer and Biodegradable polymer as easy dissolubility polymer, the liquid waste processing load alleviates, and is preferred.As hot water solubility's polymer, can enumerate that poly alkylene glycol, polyvinyl glycol and derivative thereof, 5-sodium sulphur isophthalic ester polyester copolymerization (5-Na ト リ ウ system ス Le ホ イ ソ Off Le acid high rate overlaps Port リ エ ス テ Le altogether) etc., particularly poly alkylene glycol carry out the high polymer of the heat resistance of chain lengthening, generation by ehter bond and the PET of 10 moles of % of 5-sodium sulphur isophathalic acid or its above combined polymerization is preferred.As the Biodegradable polymer, can enumerate PLA etc.
In addition, when consider the silk processability after polymer-alloy fibre is made, the knitting property of weaving, repeatedly during processability, it is preferred that the fusing point of the polymer of formation sea component reaches more than 160 ℃ or 160 ℃.But about not observing the amorphism polymer of fusing point, glass transition temperature (Tg) or Vickers softening temperature or heat distortion temperature reach that the person is preferred more than 160 ℃ or 160 ℃.
On the other hand, the polymer as constituting island component can adopt the polymer that is suitable for above-mentioned nanofiber.
In addition, island component forms striated structure person, from seeing it is important as the viewpoint of nanofiber precursor.In addition, be dispersed into the island component of striated,, also can make the refining effect of spinning stable owing to as the iron bar line, support the refinement of polymer alloy.The so-called striated structure here means the fiber axis direction length-to-diameter on island more than 4 or 4.Usually, axial length of fiber and diameter ratio are more than 10 or 10, and be most beyond the visual field of tem observation.
The containing ratio of island component can adopt arbitrary value in polymer-alloy fibre, when considering the sea component stripping during nanofiber, reaches 10 weight % or is preferred more than the 10 weight % at whole fibers.The containing ratio of island component is 20 weight % or more than the 20 weight % more preferably.But, when the containing ratio of island component is too high, by being inverted and not forming the island in the island, so 50 weight % or be preferred below the 50 weight %.In addition, for example, when copying paper and produce nonwoven fabric, because the low person of the containing ratio of island component disperses easily, so more preferably 30 weight % or below the 30 weight % of the containing ratio of island component by wet method.
In the present invention, in order to obtain the little nanofiber of filament fiber number deviation, several average diameters in zone, island and deviation are important in the polymer-alloy fibre.Its evaluation method is carried out according to the evaluation of the filament fiber number deviation of above-mentioned nanofiber.The cross section tem observation of polymer-alloy fibre, the diameter in 300 of arbitrary extractings of mensuration or the zone, island more than it in same cross section.One of cross section photo of polymer-alloy fibre of the present invention is illustrated in Fig. 2.This mensuration is carried out more than 5 places at least, obtains behind the diameter in 1500 of mensuration totals or its above zone, island.In addition, it is preferred being separated by mutually in filament length degree direction that 10m or the position more than it measure.
, count average diameter here, obtain the simple mean value of the island regional diameter that records.It is important that several average diameters in zone, island reach 1～150nm.Whereby, when removing extra large polymer, can obtain having the nanofiber that is not original fineness.Preferred 1～the 100nm of several average diameters in zone, island, more preferably 20～80nm.
In addition, the deviation of island regional diameter is by the laxative remedy evaluation.That is, the zone of measuring, island is counted the frequency (number) of each diameter.The area in each zone, island is S
1, then its summation is the gross area (S
1+ S
2+ ... S
n).In addition, the long-pending value divided by the gross area of the area of the frequency of equal area S (number) and frequency is as the area ratio in this zone, island.For example, the number in the zone, island of diameter 60nm is 350, the gross area 3.64 * 10
6Nm
2Time, its area ratio are (3.14 * 30nm * 30nm * 350)/(3.64 * 10
6Nm
2) * 100%=27.2%.Area ratio is equivalent to the volume fraction of the zone, island of each size to the block polymer alloy fiber, zone, the island composition that volume fraction is big, and the influence to bulk property when making nanofiber is big.Zone, island in the polymer-alloy fibre of the present invention, the scope that area ratio 60% or its above zone, island are in diameter 1～150nm is important.This means, and almost whole filaments all reach diameter 150nm or the nanofiber that did not in the past have below it when making nanofiber.In addition, the part that the area ratio in zone, island is high, it is preferred concentrating on the littler composition of island regional diameter, area ratio 60% or its above zone, island, it is preferred that diameter is in 1～100nm scope.Diameter be in 1～100nm scope the zone, island area ratio preferred 75% or 75% above, more preferably more than 90%, especially preferred 95% or 95%, most preferably more than 98% or 98%.Equally, area ratio 60% or 60% above zone, island, it is preferred that diameter is in 1～80nm scope.More preferably area ratio 75% or 75% above zone, island, diameter is in 1～80nm scope.
In addition, the index of one of island regional diameter deviation is the area ratio that island regional diameter difference reaches the wide zone, island of 30nm.As mentioned above,, the diameter difference is slit into 30nm when wide, the area ratio aggregate value in the wide zone, island of the highest frequency 30nm is reached the area ratio in the wide zone, island of 30nm as island regional diameter difference the frequency of island each diameter of zone counting.This is that the half value that distributes with the number of degrees is wide or near the deviation concentration degree corresponding parameter of central straight warp, it is higher to mean this area ratio, and deviation is littler.In the present invention, to reach the area ratio in the wide zone, island of 30nm be preferred more than 60% or 60% to the diameter difference.More preferably more than 70% or 70%, more than especially preferred 75% or 75%.
As mentioned above, in the polymer-alloy fibre cross section, the size in zone, island and deviation thereof are important, but this point of the quality stability of the fibre after the nanofiberization considers that the also little person of slubbing of filament length degree direction is preferred.For example, when the abrasive cloth, the slubbing of filament length degree direction is big to the influence of the size of scratch (scar on grinding charge surface) and number at nanofiber.Therefore, below the Wu Site spot preferred 15% or 15% of polymer-alloy fibre of the present invention, more preferably below 5% or 5%, below especially preferred 3% or 3%.
In addition, when the intensity of polymer-alloy fibre of the present invention reach 1.0cN/dtex or more than the 1.0cN/dtex, elongation reaches 25% or 25% when above, curl, twist yarn, operation such as knitting, accidents such as fluffing and broken yarn are few, are preferred.Intensity is 2.5cN/dtex or more than the 2.5cN/dtex more preferably, especially preferred 3cN/dtex or more than the 3cN/dtex.In addition, when the boiling water shrinkage (Boiliingwater shrinkage) of polymer-alloy fibre 25% or 25% when following, the change in size of cloth and silk was little when the sea component stripping was handled, and was preferred.Boiling water shrinkage is more preferably below 15% or 15%.
Polymer-alloy fibre of the present invention also can be polymer alloy and the polymer-bonded composite fibre that forms beyond it that becomes the nanofiber precursor.For example, the polymer alloy that becomes the nanofiber precursor is configured in core, and the polymer beyond it is configured in after shell portion forms core shell composite yarn, when the sea component stripping of polymer alloy, can obtain hollow part nanofiber at above-mentioned hollow yarn by encapsulated specialty fibers.In addition, when this core shell exchanges, can obtain around common fiber, disposing the blended fiber silk of nanofiber easily.In addition, being used as sea component as the polymer alloy of nanofiber precursor, and other polymer as the bird composition, when forming the island composite yarn, can obtain the blended fiber silk of nanofibrils and slight fiber easily.Like this, can obtain the blended fiber silk of this nanofibrils and slight fiber or common fiber easily.Therefore, the morphological stability as fiber construct significantly improves.In addition, polymer that uses in the nanofibrils and the charging property of other polymer such as remarkable different because of resulting from the Coulomb repulsion of fiber surface potential difference, also may improve the dispersiveness of nanofiber.
Polymer-alloy fibre of the present invention can improve the lint degree by the processing of curling.False twist yarn in this way, it is preferred reaching more than 20% or 20% as the curling values of stiffness (CR value) of crimpiness index.In addition, machine crimp silk and air flow jetting processing silk etc. reach 5/25mm or 5/be preferred more than the 25mm as the crispation number of crimpiness index.In addition, by making arranged side by side or eccentric core shell compound silk, also can give curling.At this moment, crispation number reaches 10/25mm or 10/be preferred more than the 25mm.The CR value generally can be adjusted by false twisting processing conditions such as coiling method, crimping device, twisting machine revolution, heter temperatures.For the CR value is reached more than 20% or 20%, can by heter temperature is transferred to (melting point polymer-70) ℃ or (melting point polymer-70) ℃ with on reach.In order further to improve the CR value, it is effective improving heter temperature.
In addition, reach 5/25mm or 5/more than the 25mm, can reach for the crispation number that makes machine crimp silk and air flow jetting processing silk etc. by the conditions such as selected or rate of feed of suitable change crimping device.
When being arranged side by side or eccentric core shell compound silk, the melt viscosity difference of polymer that can be by making applying reaches more than 2 times, or the thermal contraction rate variance during spinning can reach 10/25mm of crispation number or 10/more than the 25mm thus more than 5% or 5% separately.
In order to be contained above-mentioned thick island component hardly, and island component is with the homodisperse polymer-alloy fibre of nano-scale, as described below, consider polymer each other the compatibility or the combination of viscosity balance and to reach highly mixing compounding process and the selected of polymer supply method be important.
Polymer-alloy fibre of the present invention both can be made long fiber by melt spinning, stretching, also can make staple fibre behind machine crimp.In addition, even this staple fibre is weaved, both can copy paper and make nonwoven fabric by needle point method or wet method.In addition, also can adopt spunbond or molten stream to make nonwoven fabric of long fibers.
Above-mentioned polymer-alloy fibre is knitted by mixing with other fibers, mixed cotton, blending, to interweave, hand over volume, lamination, bonding etc., makes complex easily.Morphological stability in the time of can significantly improving nanofiber whereby.In addition, also can obtain the goods of higher function by compoundization of function.
Remove sea component from the polymer-alloy fibre that the island component containing ratio is low, when carrying out nanometer, goods become more significant open structure by nanometer separately, and morphological stability, mechanical characteristic can not satisfy actual use sometimes.Yet, during other fibers of the solvent-stable that in using with, uses as supporter, can address these problems sea component stripping operation.Be not particularly limited as this other fibers, but, preferably use aqueous slkali to handle stable nylon or polyolefin the polymer-alloy fibre of nylon/polyester.
For example, the polymer-alloy fibre of nylon/polyester and general nylon fiber mix and knit, make fabric or knitted fabric, through associating their stripping operation, make the nylon nano fiber goods, compare with independent nylon nano fiber goods, the mechanical characteristic of morphological stability, cloth and silk can significantly improve, and the operability of nanofiber cloth and silk also significantly improves.
In addition, the stacked nonwoven fabric that constitutes by other fibers on the nonwoven fabric that constitutes by polymer-alloy fibre, after making the lamination nonwoven fabric,, can obtain nonwoven fabric that constitutes by nanofiber aggregate and the made lamination nonwoven fabric of nonwoven fabric that constitutes by other fibers by through the stripping operation.For example when on the nonwoven fabric that constitutes at polymer-alloy fibre during bonding PP nonwoven fabric by nylon/polyester, the very fast raising of nylon sodium rice fiber form stability during with alkali stripping polyester.Particularly when the containing ratio of the nylon in the polymer-alloy fibre (island component) hangs down, goods form significantly loose structure by nanofiberization separately, sometimes morphological stability, mechanical characteristic can not satisfy actual use, but bonding by carrying out as supporter with the insoluble PP of alkali, can address these problems a little.In addition, the nylon nano fiber that obtains thus/PP lamination nonwoven fabric, the hydrophily of its nylon one side, cohesiveness height, but PP one side is that hydrophobicity, cohesiveness are low, be the high-performance nonwoven fabric that satisfies both opposite characteristic, not only can be used as the industry material and use, and also useful as dress material.In addition, laminating method also can adopt adhesives such as thermal bonding fiber.Also have, as only improving morphological stability, mechanical characteristic, the way of then so-called mixed cotton nonwoven fabric also can be used, but is pursuing functional occasion, and the lamination nonwoven fabric is preferred.
Polymer-alloy fibre of the present invention, not only as the nanofiber precursor because the polymer of different in kind all evenly disperses with nano-scale, pretend into polymer-alloy fibre also useful.For example, when in PLA, evenly disperseing nylon or polyester, can improve as the heat resistance of PLA shortcoming bad with nano-scale.In addition, when evenly disperseing polyester with nano-scale in nylon, the DIMENSIONAL STABILITY in the time of can improving the suction as the nylon shortcoming is bad.In addition, when in polystyrene (below claim PS) when evenly disperseing nylon or polyester, can improve fragility as the PS shortcoming with nano-scale.When in PP, evenly disperseing nylon or polyester, can improve dyeability as the PP shortcoming with nano-scale.
Polymer-alloy fibre of the present invention and above-mentioned nanofiber aggregate are same, can form various fiber constructs.The fiber construct that contains polymer-alloy fibre of the present invention can be used as intermediates such as silk, cotton (cotton), packing material, fabric, knitted fabric, felt, nonwoven fabric, artificial leather and sheet material.In addition, the fibre as dress material, dress material material, interior decoration goods, vehicle interior decorated articles, life material, environment industry data goods, IT parts and medical articles also is suitable for.
Here, in the polymer-alloy fibre as the nanofiber aggregate precursor, control island component size is important.Here, the island component size adopts infiltration type electron microscope (TEM) to observe the cross section of polymer-alloy fibre, converts by diameter and is estimated.Owing to can be similar to the diameter of decision nanofiber by the size on the island in precursor, the Size Distribution of Gu Dao can distribute according to nanofiber diameter of the present invention and design.Therefore, the polymer of alloying mixing extremely important, it is preferred adopting mixing extruder or static mixing roll etc. to carry out the degree of depth mixing in the present invention.Also have, open flat 6-272114 communique etc. the spy and adopted in the example simple section to mix (do and mix) to carry out mixing insufficiently, be difficult to such tens of nm size dispersion island in the past with the present invention.
Therefore, adopt twin shaft to extrude mixing roll or cut apart static mixing roll more than several 1,000,000 or 1,000,000 to carry out highly mixing be preferred.In addition, for fear of mixed stain or the change of mixed proportion in time, various polymer independently measure respectively, independently polymer supplied with kneading device is preferred.At this moment, polymer both can be made into particle and had supplied with respectively, or supplied with respectively with molten condition.In addition, both can supply with polymer more than 2 kinds and extrude the mixing roll main body, or a composition from extruding supplying with as the side charging of mixing roll midway.
When adopting twin shaft to extrude mixing roll as kneading device, not only can be highly mixing but also the holdup time that can suppress polymer, be preferred.Screw rod is made of transport unit and kneading part, but kneading part length reaches more than 20% or 20% of screw rod effective length, can carry out highly mixingly, is preferred.In addition, reach below 40% or 40% of screw rod effective length, can avoid the excessive stress of cutting off, and shorten the holdup time, can suppress the heat ageing of polymer or the gelation that polyamide becomes to grade by making kneading part length.In addition,, can shorten the holdup time after mixing, suppress the cohesion again of island polymer by kneading part is located at the exit side that twin shaft is extruded mixing roll as far as possible.In addition, when reinforcement is mixing, the reverse flow screw rod that polymer is transmitted also can be set in the other direction in extruding mixing roll.
In addition, adopt ventilation cellular type extruder to carry out when mixing, by the suction decomposition gas or reduce moisture in the polymer, suppress the hydrolysis of polymer, amine end groups in the polyamide and the carboxylic end group amount in the polyester also are suppressed.
In addition, by making the b that chromogenic indicator as the polymer alloy particle
*Value is below 10 or 10, and the tone in the time of can adjusting fibration is preferred.As easy dissolubility composition, preferred hot water solubility's polymer, from its molecular structure, general poor heat resistance, painted easily, but can suppress painted by the operation of shortening the above-mentioned holdup time.
These kneading devices can be independent of the spinning machine setting, in case both can after the polymer alloy particle is made it be supplied with spinning machine, also can be connected on the spinning machine mixing molten polymer is directly carried out spinning.In addition, when adopting static mixing roll, also can insert in the spinning machine pipe arrangement or in the filament spinning component.
Also have, in order to reduce the cost of spinning process, carry out also can adopting following method when mixing in mixings of cutting into slices (doing mixing).
That is,, temporarily in mixing channel, preserve, in this mixing of cutting into slices independently measuring and supply with through the polymer beads that mixes.At this moment, reach 5～20kg, can suppress mixed stain as far as possible and improve mixing efficiency by the capacity that makes mixing channel.And, extruding mixing roll, make molten polymer from this mixing channel through the pellet supply that mixes.Both can adopt twin shaft to extrude mixing roll here, or also can undertaken the polymer of fusion mixing by the static mixing roll that inserts in pipe arrangement or the groove.In addition, also can adopt the many precursor granules of combined amount of easy dissolubility polymer this moment.
In addition, the cohesion again of island polymer from suppress spinning suppresses the viewpoint that thick cohesion polymer particle generates and sees, from polymer alloy form, melt to from the holdup time that spinning nozzle sprays also be important.From the front end of polymer alloy fusing department to time from the spinning nozzle ejection reach 30 fens with interior be preferred.
In addition, evenly disperse with nano-scale in order to make the island polymer, the combination of composition also is important, by improving the affinity of difficult dissolubility polymer and easy dissolubility polymer, becomes easily with nano-scale as the easy dissolubility polymer of island component and to disperse.Approaching circular for the section that makes the zone, island, the non-person of mixing of island component and sea component is preferred.Yet,, be difficult to make island component to disperse with nano-scale by the combination of simple non-phase insoluble polymer may.Therefore, the intermiscibility optimization person who makes combination of polymers is preferred, and one of its index is solubility parameter (a SP value).So-called SP value is defined as (evaporation energy/molal volume)
1/2, be the parameter of reflection material cohesiveness, the material that the SP value is close each other can obtain the good polymer alloy of intermiscibility.The SP value of many polymer is known, and for example, " the plastics handbook, ア ミ ダ ス Co., Ltd. of Asahi Chemical Industry/plastics editorial office edits jointly, 189 pages of records to some extent.When the difference of the SP of 2 kinds of polymer value is 1～9 (MJ/m
3)
1/2The time, zone, the island formation circle owing to non-dissolving mutually, and evenly disperse with nano-scale easily, so be preferred.For example, the difference that can enumerate the SP value of N6 and PET is 6 (MJ/m
3)
1/2About be preferred example, and the difference of the SP value of N6 and PE is 11 (MJ/m
3)
1/2About be preferred example not.Certainly, by the also usefulness of various combined polymerizations and phase solvation, polymer compatibility each other can be controlled to a certain degree.
When the melting point polymer difference that constitutes island component and sea component below 20 ℃ or 20 ℃ the time, particularly adopt and extrude mixing roll and carry out when mixing, it is poor to be difficult to produce the fusion situation in extruding mixing roll, so it is mixing easily to carry out high efficiency, is preferred.In addition,, must reduce mixing and spinning temperature when the polymer that adopts easy thermal decomposition or heat ageing during as a kind of composition, also favourable to it.
In addition, melt viscosity also is important, when the melt viscosity of the difficult dissolubility polymer that forms island component is set in low value, causes the island component distortion easily under the shear strength effect, and island component is finely divided easily, sees it is preferred from the viewpoint of nanometer.But, cross when low when the island component melt viscosity, become the sea easily, mixing ratio to whole fibers can not be high, so the polymer melt viscosity that constitutes island component is preferred more than 0.1 or 0.1 for the polymer melt viscosity that constitutes sea component, more preferably 0.5～1.5.
On the other hand, the absolute value of the melt viscosity of the easy dissolubility polymer of formation sea component also is important, and it is preferred reaching the following low viscous polymer of 100Pas or 100Pas.Therefore, make the dispersion of island polymer become quite easy, or the distortion of polymer alloy becomes smoothly in spinning process, with the polymer phase ratio that adopts common viscosity, spinnability can be significantly improved.At this moment, the melt viscosity of polymer, the speed of cutting off is 1216 seconds under the nozzle surface temperature
-1Value.
In polymer alloy because island component and sea component are non-mixing, so island component cohesion person each other sees it is stable on the thermodynamics.Yet, because the island polymer disperses with nano-scale arbitrarily, so the polymeric blends that this polymerization billon and common dispersion diameter are big is compared, and forms much very unsettled polymer interface.Therefore, when polymer alloy carries out simple spinning, because unsettled polymer interface is many, so behind nozzle ejection polymer, big polymer flow expands (expanded phenomenon), or owing to the instabilityization on polymerization billon surface to produce reeling off raw silk from cocoons property bad, the joint spot of silk is excessive, spinning itself can not be carried out sometimes.For fear of this problem, when nozzle sprays, cutting off that stress reaches 0.2MPa or be preferred below the 0.2MPa between nozzle hole wall and the polymer.Cut off that stress can (Ha one ゲ Application Port ワ ズ ュ: Hagen-Poiseuille) formula (be cut off stress (dyne/cm from the Ha Jinbo show between nozzle hole wall and the polymer here,
2)=R * P/2L) calculate.Also has R: be the radius (cm) of nozzle squit hole, P: be the pressure loss (MPa) of nozzle squit hole, L: be nozzle squit hole long (cm).In addition, P=(8L η Q/ π R
4), η is polymer viscosity (pool), Q is spray volume (cm
3/ second), π is a pi.In addition, 1 dyne of cgs unit system/cm
2With SI unit is 0.1Pa.
When the single composition melt spinning of common polyester, even cut off that stress reaches 1MPa or more than the 1MPa, also can guarantee metering property and reeling off raw silk from cocoons property between nozzle hole wall and the polymer.Yet polymer alloy of the present invention is different with common polyester, and when cutting off stress when big between nozzle hole wall and the polymer, the viscoplasticity balance of polymer alloy is destroyed easily, compares with common polyester melt spinning, must reduce and cut off stress.Reach 0.2MPa or 0.2MPa when following when cutting off stress, nozzle hole wall side flow and the polymer flow velocity of nozzle orifice center portion reaches evenly deviation diminishes so the mitigation of expanded phenomenon can obtain good reeling off raw silk from cocoons property owing to cut off, and is preferred.Cut off more preferably 0.1MPa or below the 0.1MPa of stress.Generally cut off stress in order to reduce more, strengthen the ejection aperture of nozzle, shorten the ejection length of nozzle, but when excessively carrying out, metering reduction at the polymer of the squit hole of nozzle has the tendency that produces the fiber number spot between the hole, so, on the top of nozzle squit hole, it is preferred adopting the nozzle that is provided with the polymer metering portion littler than nozzle squit hole aperture.When the stress of cutting off between nozzle hole wall and the polymer reaches 0.01MPa or 0.01MPa when above, polymer-alloy fibre can be stable carries out melt spinning, below 15% or 15%, is preferred as the Wu Site spot (U%) of the joint spot index of silk.
As mentioned above, use in the present invention carry out melt spinning with the homodisperse polymer alloy of nano-scale the time, the stress of cutting off when suppressing the nozzle ejection is important, but the cooling condition of adjusting silk also is preferred.When common polyester carried out melt spinning, owing to suppressed elastic vibration, cooling generally was slow cooling.Yet, in the present invention, owing to being very unsettled melt flow stream, so rapid cooling curing is preferred after the nozzle ejection with the homodisperse polymer alloy of nano-scale.As the distance that below nozzle, begins, preferred 1～15cm to cooling.When below nozzle to the distance of cooling beginning be 1cm or 1cm when above, can suppress the temperature spots of nozzle face, thereby can obtain the little silk of silk joint spot, be preferred.In addition, when reaching 15cm or 15cm when following, by making rapid curing, can suppress the refinement of the unstable fixed thread of drizzle shape in May, the raising of reeling off raw silk from cocoons property can obtain the little silk of silk joint spot simultaneously, so be preferred.Here, so-called cooling starting position means the position that the positive cooling of silk begins, but when adopting actual melt spinning device, refers to the upper end of air flue.
In addition, from the reeling off raw silk from cocoons property of fully guaranteeing melt spinning and the viewpoint of stability of spinning process, nozzle surface temperature (surface temperature of nozzle ejection face central portion) is for the fusing point (Tm)+20 of volume composition polymer ℃ or be preferred more than it.In addition, when the nozzle surface temperature reaches the fusing point (Tm)+80 ℃ of volume composition polymer or its when following, can suppress the pyrolysis of polymer, be preferred.
The viewpoint that several average diameters in the zone, island from polymer-alloy fibre reduce, the ventilation in spinning process is healed height better, and it is preferred reaching 100 or 100 above persons.Therefore, carrying out high speed spinning is excellent washing.
In addition, to implementing to stretch through the polymer-alloy fibre of spinning and heat treatment is preferred, but the preheat temperature when stretching can suppress a spot when reaching the glass transition temperature (Tg) of polymer of formation island component or the temperature more than it, is preferred.In addition, also can implement curling processing to polymer-alloy fibre and wait silk processing.The heat treatment temperature add man-hour when curling is set in when surpassing ((constituting the melting point polymer of sea component)-30 ℃), can suppress molten sticking, fracture of wire and fluffing, is preferred.
As mentioned above, the melt spinning method of preferred polymer-alloy fibre of the present invention gathers as follows.
A kind of polymer-alloy fibre manufacture method, it is difficult dissolubility polymer and easy dissolubility polymer melting mixing and the polymer alloy that obtains carries out the polymer-alloy fibre manufacture method of melt spinning in addition, it is characterized in that, satisfy the condition of following (1)～(3).
(1) behind independent respectively difficult dissolubility polymer of metering and the easy dissolubility polymer, the independent kneading device of supplying with carries out melting mixing;
(2) containing ratio of the difficult dissolubility polymer in the polymer alloy is in the scope of 10～50 weight %;
(3) easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, perhaps easily the fusing point of dissolubility polymer is in-20～+ 20 ℃ the scope of difficult dissolubility melting point polymer.
In addition, when adopting twin shaft to extrude mixing roll to carry out melting mixing, the kneading part length that twin shaft is extruded mixing roll is 20～40% of screw rod effective length, and is preferred.
In addition, when adopting the silent oscillation mixing roll to carry out melting mixing, the silent oscillation mixing roll to cut apart that number reaches more than 1,000,000 or 1,000,000 be preferred.
In addition, the melt spinning method of the polymer-alloy fibre that the present invention relates to, it is characterized in that, when adopting section to mix, mixing channel is set, after the particle of interim storage therein more than 2 kinds done and mixed, dry mixed pellet supply fusing department before particle fusion, when difficult dissolubility polymer and easy dissolubility polymer carry out the mixed melting spinning, satisfy the condition of following (4)～(6) and carry out spinning.
(4) mixing ratio of the difficult dissolubility polymer in the fiber=10～50 weight %;
(5) easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, and perhaps easily the fusing point of dissolubility polymer is in the scope of difficult dissolubility melting point polymer-20～+ 20 ℃;
(6) mixing channel capacity=particle 5～20kg of particle.
Method of the present invention by above-mentioned polymer is made up, is carried out optimization to spinning and stretching condition, and island component is evenly disperseed with the tens of nm sizes of diameter, can obtain the little polymer-alloy fibre of a spot.Therefore, by at the length direction of silk the little polymer-alloy fibre of silk spot as precursor, not only any section of certain section but also length direction can obtain the little nanofiber aggregate of filament fiber number deviation.In addition, adopt the manufacture method of nanofiber aggregate of the present invention, different fully with the nanofiber that adopts the electronics weaving, by stretching as the polymer-alloy fibre of precursor and heat treatment, the stretching of nanofiber and heat treatment also begin to become possibility, so TENSILE STRENGTH and shrinkage factor can freely be controlled.Therefore, can obtain having the above-mentioned good mechanical characteristic and the nanofiber of shrinkage.
From the polymer-alloy fibre that obtains like this,, can obtain nanofiber aggregate with the easy dissolubility polymer of solvent stripping as sea component.At this moment,, can adopt aqueous solution kind solvent, consider it is preferred from the viewpoint that reduces carrying capacity of environment as solvent.Concrete is that employing aqueous alkali or hot water are preferred.Therefore, as easy dissolubility polymer, polyester etc. can be preferred by the polymer of basic hydrolysis or polyalkylene glycols and polyvinyl alcohol and these hot water solubility's polymer such as derivative.
In addition, the easily stripping of dissolubility polymer both can be carried out at silk or cotton stage, also can carry out in the cloth and silk stages such as fabric, knitted fabric, nonwoven fabric, or carry out in the stage of thermally molded article each.And, polymer-alloy fibre with weight be the dissolution rate of benchmark reach 20 weight %/hour or its, can obtain the good nanofiber aggregate of production efficiency whereby.
Therefore, for nanofiber aggregate further is dispersed into one one nanofiber from long fiber shape and/or weaving filament shape, can reach from the nonwoven fabric that adopts following wet type to copy the paper method.That is, be polymer-alloy fibre of the present invention be cut into the long 10mm of fiber or 10mm following after, the easy dissolubility polymer of stripping then, does not carry out primary drying to the nanofiber that obtains and the nonwoven fabric manufacture method of copying paper.When adopting this method, the diameter of nanofiber aggregate can fully be dispersed to 1 μ m or below the 1 μ m.In addition, when adopting, also can be dispersed to 300nm to the diameter of nanofiber aggregate or below the 300nm with the high dispersion liquid of the polymer compatibility that constitutes nanofiber.
Nanofiber aggregate of the present invention is owing to showing good adsorption/absorption characteristic, so but the various functional medicines of load.The called function medicament here means the material that can improve the fiber function, for example, can adopt hygroscopic agent, humectant, fire retardant, hydrophober, cold-retaining agent, heat preserving agent and smooth agent etc.The proterties of functional medicine is not limited to microgranularly, and poly-phenol or amino acid, protein, capsicim, vitamins etc. are used to the medicament that keeps healthy or improve looks and also can be used as object as skin disease medicaments such as pimple etc. use.In addition, also can be used as uses such as pharmaceuticals such as disinfectant, antiphlogistic, analgestic.Perhaps, also can be used as the medicament of absorption and harmful substances such as decomposition polyamine and photochemical catalyst nano particle.
In addition, the carrying method of functional medicine is not particularly limited yet,,, or is contained in the polymer-alloy fibre of nanofiber precursor and can yet by back processing load on nanofiber by handling in bathing or coating is handled.In addition, also can directly load on functional medicine on the nanofiber aggregate, or after loading on the nanofiber this precursor substance is transformed into desirable functional medicine to the precursor substance of functional medicine.
As the object lesson of latter's method, can enumerate organic monomer is immersed in the nanofiber aggregate, make the method for its polymerization then; And, easy dissolved matter is handled by in bathing, carry out redox reaction or carry out dentate replacing after being immersed in the nanofiber aggregate, by making it reach difficult deliquescent method etc. to ion-exchange reactions etc.As organic monomer, can enumerate various organic monomers and replace a part of metal alkoxide compound etc. with hydrocarbon.In addition, when the precursor of loading functional medicament in spinning process, in spinning process, form the high molecular structure of heat resistance, be back to the method that presents functional molecular structure by back processing and also can adopt.
For example, give hygroscopicity, even molecular weight 1000 or its above polyethylene glycol (following show with pet sheet sometimes) are that hygroscopic agent also almost can not exhaust in order to give the cloth and silk that constitutes by common polyester fiber.Yet, when the cloth and silk of constituting for nanofiber of the present invention is given same hygroscopic agent, can exhaust in a large number.
Recently, as the material that has the skin care function by preserving moisture, the natural oil composition squalene that extracts from shark liver comes into the picture.Even give the cloth and silk that constitutes squalene to common polyester fiber, almost can not exhaust, the cloth and silk that is made of nanofiber of the present invention then can exhaust in a large number, and washing resistance also significantly improves.This is for being very surprising with the affine material of common polyester fiber.
In addition, by making its polymerization behind the metal alkoxide compound that the dipping alkyl replaces in nanofiber aggregate, also can be in nanofiber aggregate load silicone polymer or silicone oil, washing resistance is also good.In original processing, extremely difficulty loads on the silicone durability in the fiber goodly, but adopts nanofiber aggregate of the present invention, begins it is become possibility.Equally, with polyurethane etc. other organic the mixing also become possibility.
In addition, nanofiber aggregate of the present invention not only can add various functional medicines, and slow release is also good.By adopting above-mentioned various functional medicine, can be applicable to good slow release base material or delivery system.
In addition, have inorganic polymer and form and to make its polymerization after the monomer of ability or oligomer are exhausted by nanofiber aggregate of the present invention, then inorganic matter is present in nanofiber aggregate inside.That is, can obtain the organic/inorganic blended fiber that inorganic matter disperses in nanofiber aggregate.At this moment,, adjust the exhaustion amount of inorganic monomer, can adjust the nanofiber containing ratio in the blended fiber in order to present desirable performance.As monomer or oligomer, can enumerate metal alkoxide and these oligomer or metal salt solution etc. with inorganic polymer formation ability.In addition, the type that these monomers and oligomer carry out polymerization by heating considers it is preferred from this point of production efficiency, but adopts redox reaction in solution, to ion-exchange or dentate exchange its insoluble type also can be used.Example as the former can be enumerated silicate etc., and can enumerate platinum chloride or silver nitrate etc. as the latter's example.
Therefore, when the containing ratio of nanofiber aggregate reaches 5～95 weight %, can obtain the organic/inorganic blended fiber, wherein have at least a part of inorganic matter to be dispersed in the nanofiber aggregate.Here, when illustrating in greater detail the admixture of organic/inorganic, inorganic matter immerses the nanofiber gap, and wherein inorganic matter is in nanofiber and forms bonding form mutually, or nanofiber is dispersed in the form in the inorganic matter matrix.Therefore, inorganic matter to internal communication, can be given full play to the characteristic of inorganic matter from the surface of organic/inorganic blended fiber whereby.For example, the blended fiber that adopts nanofiber and hygroscopicity silica to constitute, the good hydroscopicity and the rate of moisture absorption of the hygroscopicity silica of can directly applying in a flexible way.
In addition, to reach 5～95 weight % be preferred to the nanofiber containing ratio in the organic/inorganic blended fiber of the present invention.Whereby, can make the flexibility of inorganic matter characteristic and organic fiber all excellent.Preferred 20～90 weight % of nanofiber containing ratio, more preferably 25～80 weight %.
Organic/inorganic blended fiber of the present invention not only can be made into the fiber of monobasic, and can be made into bi-component fibres structure and sheet-like structures such as knitted fabric or nonwoven fabric.Certainly, adopt them also can make ternary structural bodies such as assembly or member, thermally molded article each, cotton.
In addition, as method, for example, can enumerate the preparation monomer solution to nanofiber aggregate dipping inorganic monomer, the method of dipping or immersion nanofiber aggregate in this solution, high order processing unit (plant)s such as the dyeing of common fibre or coating also can adopt.As solution, for example can adopt the aqueous solution, organic solvent solution, supercritical fluid solution etc.
When being immersed in the monomer polymerization in the nanofiber aggregate, adopt low temperature such as sol-gel method to carry out polymerization, because of the fusing point that do not reach nanofiber or more than it, from suppressing because of the nanofiber fusion or mobilely causing the viewpoint of cohesion sees it is preferred.In addition, when reducing metal chloride etc., can or reduce below it at the fusing point of nanofiber, in addition, do one's utmost to avoid using strong acid, the highly basic of nanofiber modification, the condition of selecting to relax is preferred.Also have,, in " ソ Le-ゲ Le forensic science " (make flower Ji husband work, ア グ ネ holds wind society) etc., be documented about sol-gel method.
Organic/inorganic blended fiber of the present invention also can directly be used, and also can remove nano components from it, makes the porous fibre of inorganic matter.
Inorganic porous fibrous 90 weight % or be inorganic matters such as metal, metal oxide, metal halide, metal complex more than it see it is important from improving stable on heating viewpoint.In addition, several average diameters of pore, when when minor axis section direction reaches 1～5000nm, specific area strengthens, and characterization of adsorption improves, and sees it is preferred from the viewpoint of lighting.Several average diameters of pore are 1～100nm more preferably.The so-called minor axis section direction here means the radial direction of the nanofiber that uses in mold.
When the fibre length of inorganic porous fiber reaches 1mm or 1mm when above, can keep the form of fibre, be preferred.The preferred 10cm of fibre length or more than the 10cm.
Here, as the method for removing the nanofiber composition, can use by calcination the nanofiber gasification is removed, or adopt solvent to extract the method for being removed.Calcination temperature also depends on the organic polymer composition, can adopt about 500～1000 ℃.In addition, owing to generally shrink, so the pore size of removing behind the nanofiber by calcination temperature also can be controlled by calcination.As firing device, can adopt metal oxides such as silica or titanium dioxide with or the charcoal fiber original known firing device such as use.In addition, when extracting, preferably use the good solvent of organic polymer, when for example organic polymer is nylon, with acid such as formic acid; When for polyester, adopt halogenated organic solvents such as aqueous alkali or o-chlorphenol; When for PP, adopt organic solvents such as toluene.As extraction equipment, can adopt the high order processing device of original known woven product.
Organic/inorganic blended fiber of the present invention or inorganic porous fiber, same with above-mentioned nanofiber aggregate, owing to can adopt cloth such as knitted fabric or nonwoven fabric or adopt various fiber constructs such as thermally molded article each, so, can be widely used as cloth, assembly, with the other materials applying etc.And, effectively utilize its characterization of adsorption and hygroscopicity, in order to improve residential environment, in upholsterys such as curtain, wallpaper, carpet, cushion, furniture, use, also can in organic filter of removing organic pollution that Clean room is used, use.In addition, also can be used as the lavatory and indoorly disappear smelly, and the upholstery material that is used to improve environment inside car, more particularly as cover for seat or ceiling with clad material etc.In addition, also can in comfortable dress material or dress material materials such as cap, liner, use with certain smelly performance that disappears.In addition, utilize its metallic conductivity to can be used as electromagnetic shielding material.In addition, can also use aspect medical at industry raw material such as filter, sensor, cell sorbing material etc.
Explain the present invention below by embodiment.Also have, the assay method among the embodiment adopts following method.
A. the melt viscosity of polymer
Adopt Japan smart machine キ ヤ PVC ロ グ ラ Off 1B to measure the melt viscosity of polymer.Also having, is 10 minutes from putting into sample to the polymer time of staying of measuring beginning.
B. fusing point
Adopt Perkin Elmaer DSC-7, showing that top temperature that polymer fuses the 2nd rotation is as melting point polymer.The programming rate of this moment is 16 ℃/minute, sample size 10mg.
C. the nozzle squit hole cuts off stress
Cut off stress between nozzle hole wall and the polymer, available Ha Jinbo show formula (is cut off stress (dyne/cm
2)=R * P/2L) calculate.Also has R: be the radius (cm) of nozzle squit hole, P: be the pressure loss (dyne/cm of nozzle squit hole
2), L: be nozzle squit hole long (cm).In addition, P=(8L η Q/ π R
4), η is polymer viscosity (pool), Q is spray volume (cm
3/ second), π is a pi.Here, polymer viscosity adopt the nozzle squit hole temperature (℃), cut off speed (second
-1) time value.
1 dyne of cgs unit system/cm
20.1Pa for SI unit.Also have, the polymer alloy melt viscosity of (embodiment 8～16, comparative example 2～4 etc.) when mixing and spinning is directly carried out, be spinning ejection silk do not batch, the cutting silk of 10cm place snap cure is as sample under nozzle, 1B measures with キ ヤ PVC ロ グ ラ Off.
D. the Wu Site spot (U%) of polymer-alloy fibre
The USTER TESTER 4 that adopts Star エ Le ベ ガ one ウ ス one Co., Ltd. to make gives silk speed 200m/ branch, measures with normal mode.
E. carrying out the fiber section with TEM observes
Cross-sectional direction at fiber cuts ultra-thin section, observes the cross section of fiber with infiltration type electron microscope (TEM).In addition, carry out metallochromy as required.
The TEM device: society of Hitachi makes, the H-7100FA type
F. the several average single fiber fiber numbers and the single fiber diameter of nanofiber
The mean value of filament fiber number is obtained by laxative remedy.That is,, calculate single fiber diameter and filament fiber number, obtain its simple mean value with image processing software (WINROOF) the fiber cross sections photo that arrives with tem observation.Should be worth as " number average single fiber fiber number and single fiber diameter ".At this moment, being used for average nanofiber number, is that arbitrary extracting is measured single fiber diameter more than 300 or 300 in same cross section.This mensuration is to carry out as long 10cm disconnected from each other of nanofiber aggregate or 5 places more than it, calculating with the single fiber diameter that amounts to more than 1500 or 1500.
G. the filament fiber number deviation of nanofiber
The filament fiber number deviation of nanofiber is estimated by laxative remedy.That is, use above-mentioned data when obtaining several average single fiber fiber number, each filamentary filament fiber number dt
iExpression, its summation is as total fiber number (dt
1+ dt
2+ dt
3+ ... dt
n).In addition, counting has the frequency (number) of nanofiber fiber number of identical filament fiber number, filament fiber number and frequency long-pending divided by the resulting value of total fiber number, as the fiber number ratio of this filament fiber number.
H. the diameter deviation width of nanofiber
The diameter deviation width of nanofiber is estimated by laxative remedy.That is, being used near the central value of single fiber diameter of nanofiber the single fiber diameter difference is in the wide filamentary fiber number ratio of 30nm and estimates.This means near the deviation concentration degree the fiber number of center.This fiber number ratio is high more, deviation is more little, this also can adopt the numerical value that uses when obtaining above-mentioned several average single fiber fiber number, as mentioned above, count the frequency of every kind of filament fiber number, when cutting apart, the aggregate value of the wide filament fiber number of the extra high 30nm of frequency is in the fiber number ratio of the wide filament fiber number of 30nm as the single fiber diameter difference with diameter difference 30nm.
I. several average diameters in zone, island
Several average diameters in zone, island are obtained by laxative remedy.That is, the fiber cross sections photo that arrives with tem observation, (WINROOF) handled with image processing software, converts by circle and obtain diameter in the zone, island.Obtain its simple mean value.At this moment, being used for average island number of regions is to have measured 300 or its above zone, island of extracting out arbitrarily in the same cross section.These length direction 10m disconnected from each other or its 5 above places that are determined at polymer-alloy fibre carry out, adopt 1500 of totals or its above island regional diameter to calculate.
J. the diameter deviation in zone, island
The diameter deviation in zone, island is by the laxative remedy evaluation.That is, adopt the numerical value that uses when obtaining above-mentioned several average diameter, the cross sectional area of each island component is S
i, its summation is as the gross area (S
1+ S
2+ ... S
n).In addition, the product with the island zone frequency (number) of same diameter (area) and area is divided by total fiber number, and resulting value is as the area ratio in this zone, island.
K. the diameter deviation width in zone, island
The diameter deviation width in zone, island is by the laxative remedy evaluation.That is, be used near the central value of several average diameters in zone, island or area ratio that the island regional diameter difference of the part that area ratio is high is in the wide zone, island of 30nm is estimated.This also can adopt the data of using when asking above-mentioned several average diameter.As mentioned above, the frequency to every kind of diameter of zone, island counting when cutting apart with diameter difference 30nm, is in the wide island region area ratio of 30nm to the aggregate value of the wide island region area ratio of the extra high 30nm of frequency as island regional diameter difference.For example, so-called 55～84nm, the scope of the island regional diameter difference 30nm that the above 84nm of expression 55nm is following.In addition, area ratio is represented the area ratio in the zone, island of this diameter range.
L.SEM observes
Evaporation platinum-palldium alloy on fiber is observed the fiber side with scanning electron microscope.
The SEM device: society of Hitachi makes, the S-4000 type
M. mechanical characteristic
Measure weight n=5 time of nanofiber aggregate 10m, obtain the fiber number (dtex, dtex) of nanofiber aggregate from its mean value.Polymer-alloy fibre is cut 100m silk partly as sample, measure its weight n=5 time, obtain the fiber number (dtex) of fiber from its mean value.Then, in room temperature (25 ℃), initial stage sample length=200mm, draw speed=200mm/ branch, obtain loading-extension curve by the condition shown in the JIS L 1013.Then, the loading value during fracture is divided by initial titre, and as intensity, the elongation during fracture as elongation, is obtained intensity elongation curve divided by initial specimen length with it.
N. wide-angle X-ray diffraction figure
The 4036A2 type X-ray diffraction device that adopts motor of science society to make is taken WAXD sheet photo by following condition.
X line source: Cu-K α line (Ni filter)
Output: 40kV * 20mA
Crack: 1mm φ, pinhole collimator
Camera radius: 40mm
Time for exposure: 8 minutes
Film: Kodak DEF-5
O. crystal size
The 4036A2 type X-ray diffraction device that adopts motor of science society to make is measured the diffracted intensity of equatorial line direction by following condition.
X line source: Cu-K α line (Ni filter)
Output: 40kV * 20mA
Crack: one 1 ° one 1 ° of 1mm φ
Detector: scintillation counter
Count recording device: the RAD-C type that motor of science society makes
Progressively scanning: 0.05 ° of per step
Accumulated time: 2 seconds
(200) face direction crystallite size L calculates with following Scherrer formula:
L＝Kλ/(β
0cosθ
B)
L: crystallite size (nm)
K: constant=1.0
λ: the wavelength=0.15418nm of X line
θ
B: black angle
β
o＝(β
E 2-β
I 2)
1/2
β
E: apparent half value wide (measured value)
β
I: device constant=1.046 * 10
-2Rad
P. crystalline orientation degree
(200) the crystalline orientation degree of face direction is obtained by laxative remedy.
Adopt the same device of mensuration with above-mentioned crystal size, the half value of the intensity distributions that obtains from the peak that along the circumferential direction scans corresponding to (200) face is wide, calculates according to following formula.
Crystalline orientation degree (π)=(180-H)/180
H: half value wide (degree)
Measurement range: 0～180 °
Progressively scanning: 0.5 ° of per step
Accumulated time: 2 seconds
Q.Rouland method degree of crystallinity (χ)
＜sample adjustment 〉
After the cut-out of razor handle sample, powder is made in freezing pulverizing.It is filled to (20mm * 18mm * 1.5mm), be made for mensuration in the anchor clamps of aluminum.
＜determinator 〉
X-ray device: the RU-200 that motor of science society makes (Ni changes the target type)
X line source: Cu-K α line (using the graphite bent crystal monochromator)
Output: 50kV 200mA
Angular instrument: the 2155D type that motor of science society makes
Crack: 1 °-0.15mm-1 °-0.45mm
Detector: scintillation counter
Count recording device: the RAD-B type that motor of science society makes
2q/q: continuous sweep
Measurement range: 2q=5～145 °
Impulse modulation: 0.02 °
Sweep speed: 2 °/minute
＜resolve
Degree of crystallinity is resolved by the Ruland method.Degree of crystallinity (χ) is calculated according to following formula:
D＝exp(-ks
2)
S: wave number (=2sin θ/λ)
λ: the wavelength of X line (Cu:1.5418 )
I (s): from the interference capability X line scattering strength of sample
Ic (s): from the interference capability X line scattering strength of crystallization
f
2: the quadratic average atomic scattering factor
When resolving, determination data adopts the data through the polarisation factor, absorption factor, air scattering correction.Then, remove Compton scattering, carry out unformed curve and separate, carry out the degree of crystallinity evaluation from the strength ratio of crystal diffraction peak and amorphous scattering.
R. boiling water shrinkage
With the dipping machine of girth 1m sample is carried out reeling for 10 times and make reeled yarn.Then, on reeled yarn, hang 1/10 loading of total fiber number, measure former length (L0).Then, reeled yarn is in lose the state of loading, carries out handling in 15 minutes with 98 ℃ boiling water baths, treat that reeled yarn is air-dry after, same with former length, measure length (L1) after handling down in 1/10 loading of total fiber number.Then, calculate by following formula.
Boiling water shrinkage (%)=((L0-L1)/L0) * 100 (%)
S.140 ℃ dry-hot shrinkage
Sample is marked at the wide place of 10cm, in 140 ℃ of baking ovens, carrying out handling the length (L2) between the mensuration mark in 15 minutes under the state of no loading.Then, calculate according to following formula:
140 ℃ of dry-hot shrinkages (%)=((L0-L2)/L0) * 100 (%)
T. hydroscopicity (Δ MR)
In measuring cup, take by weighing about sample 1～2g, keep measuring in 2 hours dry weight (W0) in 110 ℃, then, object material gravimetry (W65) after 20 ℃, relative humidity 65% keep 24 hours.Then, object material gravimetry (W90) after 30 ℃, relative humidity 90% keep 24 hours.Then, calculate hydroscopicity Δ MR according to following formula:
MR65＝[(W65-W0)/W0]×100％ (1)
MR90＝[(W90-W0)/W0]×100％ (2)
ΔMR＝MR90-MR65 (3)
The expansion rate of U. reversible hydroexpansivity and filament length degree direction
Sample fiber is measured former length (L3) in 60 ℃ of dryings after 4 hours.Then, this fiber flooded 10 minutes in 25 ℃ of water after, from water, take out and handle back measured length (L4) rapidly.Again this fiber is measured fibre length (L5) in 60 ℃ of dryings after 4 hours.And drying/water retting repeats 3 times, and the expansion rate of the filament length degree direction that the expansion rate of the 3rd time filament length degree direction is relative the 1st time then has reversible hydroexpansivity as 50% or more than it.The expansion rate of filament length degree direction is calculated by laxative remedy.Also have, the length of fiber is tied the silk of being with look at fiber two places, measures distance therebetween.Make this distance reach about 100mm.
The expansion rate (%) of filament length degree direction=((L4-L3)/L3) * 100 (%)
V. crispation number
Get fiber sample 50mm, count its curling joint number, obtain the joint number of every 25mm, this last 1/2 back on duty is as crispation number.
W. tone (b
*Value)
Adopt tintometer MINOLTA SPECTROPHOTOMETER CM-3700d, the b of working sample
*Value.At this moment, adopt D
65(color temperature 6504K) measures with 10 ° of visuals field as light source.
With melt viscosity is 53Pas (262 ℃ were cut off speed 121.6 seconds
-1), fusing point is that 220 ℃ the terminal end group amount with acetic acid end-blocking, amine of amine reaches 5.0 * 10
-5The N6 of molar equivalent/g (20 weight %); With melt viscosity be 310Pas (262 ℃ were cut off speed 121.6 seconds
-1), fusing point is the copolymerization PET (80 weight %) of 225 ℃ of 8 moles of % of isophathalic acid of 225 ℃, fusing point that 4 moles of % copolymerization of bisphenol-A form, extrudes mixing roll with twin shaft, carries out mixingly in 260 ℃, obtains b
*The polymer alloy section of value=4.In addition, the PET of this combined polymerization was at 262 ℃, 1216 seconds
-1Melt viscosity be 180Pas.The mixing condition of this moment is as follows:
The equidirectional complete occlusal pattern of screw rod model, 2 screws
Screw diameter 37mm, effective length 1670mm, L/D=45.1
Kneading part length is 28% of screw rod effective length
Kneading part more is positioned at the ejection side than screw rod effective length 1/3
3 places backflow portion is arranged midway
N6 and combined polymerization PET are measured in the supply of polymer respectively, supply with mixing roll respectively.
Temperature: 260 ℃
Outlet: 2 places
Secondly, this polymer alloy section is carried out spinning with spinning machine shown in Figure 12, obtain polymer-alloy fibre.The polymer alloy section enters from hopper 1, carries out fusion at 275 ℃ fusing departments 2, imports the spill spin block 3 of the filament spinning component 4 that contains 280 ℃ of spinning temperatures.And, filter the polymer alloy molten mass with the metal nonwoven fabric of ultrafiltration diameter 15 μ m after, the nozzle 5 that reaches 262 ℃ from the nozzle surface temperature carries out melt spinning.At this moment, nozzle 5 has the metering portion 12 of diameter 0.3mm as shown in figure 13 on squit hole top, and squit hole is that 0.7mm, squit hole long 13 are 1.75mm through 14.And the single hole spray volume of this moment is the 1.0g/ branch.The stress of cutting off between the nozzle hole wall of this moment and the polymer fully is low to moderate 0.058MPa (polymer alloy viscosity is that 140Pas, 262 ℃, the speed of cutting off are 416 seconds
-1).In addition, below nozzle to the distance of cooling off starting point (upper end of air flue 6) be 9cm.20 ℃ of cold wind cooling curings of strand 7 usefulness 1m of ejection, with being arranged on after oil supply guide rail 8 oil supply of nozzle 51.8m below, by the 1st draw roll 9 and the 2nd draw roll 10 of non-heating, the winding speed that divides with 900m/ batches, and obtains the undrawn yarn packing material 11 that 6kg reels.The spinnability of this moment is good, and fracture of wire is 1 time during spinning 1t.And the polymer-alloy fibre undrawn yarn adopts stretching device shown in Figure 14, and heat treatment stretches.Undrawn yarn 15 usefulness feed rollers 16 are supplied with, and by the heat treatment that stretches of the 1st warm-up mill the 17, the 2nd warm-up mill the 18, the 3rd roller 19, obtain drawn yarn 20.At this moment, the temperature of the 1st warm-up mill 17 is that 90 ℃, the temperature of the 2nd warm-up mill 18 are 130 ℃.Stretching ratio between the 1st warm-up mill 17 and the 2nd warm-up mill 18 is 3.2 times.Resulting polymer-alloy fibre has the good characteristic of 120 dtexs, 36 threads, intensity 4.0cN/dtex, elongation 35%, U%=1.7%, boiling water shrinkage 11%.In addition, the cross section of resulting polymer-alloy fibre shows that with the result of tem observation obtaining copolymerization PET (thin part) is that 53nm, N6 are with the homodisperse polymer-alloy fibre of nano-scale for sea, N6 (dense part) for several average diameters in the island structure on island (Fig. 2), zone, N6 island.
Adopt the polymer-alloy fibre that obtains to make circular knit here, it at 3% sodium hydrate aqueous solution (90 ℃, bath raio 1: 100), was flooded 2 hours, whereby 99% or its above hydrolysis of the PET of copolymerization in the polymer-alloy fibre are removed.The result obtain by the independent circular knit that constitutes of silk of N6, not only removed copolymerization PET, and continuous as long fiber, the shape of maintenance circular knit from macroscopic view as sea component.In addition, this circular knit is different fully with the circular knit that common N6 fiber constitutes, and nylon distinctive " smooth feeling " loses, obtains thin,tough silk such " harsh feeling " or such " dry sensation " of artificial silk on the contrary.
Extract silk out from a circular knit that constitutes by the independent silk of this N6, at first the observed result of carrying out the fiber side with light microscope shows that compare with the fiber before the alkali treatment, fibre diameter becomes about 2/3 approximately, by removing extra large polymer, cause contraction (Fig. 4) in the fiber radius direction.Secondly, this fiber side shows that with the observed result of SEM this is not 1 rhizoid but does not have several nanofibers and condensed the nanofiber aggregate (Fig. 3) that is wound in the weaving filament shape.In addition, there is minimum space in the nanofiber of this N6 nanofiber aggregate being spaced apart about several nm～hundreds of nm each other between nanofiber.In addition, this fiber side is shown in Fig. 1 with the observed result of TEM, and the single fiber diameter that shows this N6 nanofiber is about tens of nm.In addition, several average single fiber diameters of nanofiber reach 56nm (3 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number reaches 1 * 10
-7Dtex～1 * 10
-4(it is 99% that single fiber diameter is equivalent to 1～105nm) filament fiber number ratio to dtex.Particularly to reach the filament fiber number ratio between 55～84nm be 71% to the filament fiber number, and filament fiber number deviation is very little.The single fiber diameter and the filament fiber number histogram of the nanofiber of resolving from the photo of TEM are shown in Fig. 5,6.At this moment, on single fiber diameter, engrave the rag of 10nm, counting radical (frequency) and fiber number ratio.When engraving the rag of 10nm at single fiber diameter, for example, the rag that means single fiber diameter 55～64nm is single fiber diameter 60nm, and the rag of single fiber diameter 75～84nm is single fiber diameter 80nm.
In addition, the result that measures of the hydroscopicity (Δ MR) of the circular knit that is made of separately this N6 represents to have and surpasses 6% and cotton extremely good hygroscopicity.In addition, extract the silk that constitutes by the N6 nanofiber aggregate, measure various rerum naturas from circular knit.Its expansile investigation result to the filament length degree direction of water is to carry out reversible imbibition/drying repeatedly and shrink (Figure 11).The expansion rate of water absorption of filament length degree direction is 7%, compares with 3% of common N6 fiber, and be the value that obviously raises.In addition, the mechanical characteristic measurement result of the silk of N6 nanofiber aggregate formation is that intensity is 2.0cN/dtex, elongation 50%.In addition, 140 ℃ dry-hot shrinkage is 3%.In addition, from its wide-angle X-ray diffraction photo as can be known, reached oriented crystallineization.In addition, the demonstration of crystalline orientation degree is sufficiently high to 0.85 value.But from the nanofiber aggregate that circular knit extracts, all silk takes place to curl, and thinks that therefore orientation is terriblely chaotic, and actual crystalline orientation degree is than the crystalline orientation degree height that records.Rouland method degree of crystallinity is 55%, shows the value slightly higher than common N6 fiber.
In addition, the result who this circular knit is implemented polishing shows that super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Except N6 adopts melt viscosity 212Pas (262 ℃ were cut off speed 121.6 seconds
-1), the amine of 220 ℃ of fusing points is terminal uses the acetic acid end-blocking, the end group amount of amine reaches 5.0 * 10
-5The N6 of molar equivalent/g (20 weight %) operates in addition similarly to Example 1, extrudes mixing roll with twin shaft and obtains b
*The polymer alloy section of value=4.In addition, be that the stress of cutting off between 1.0g/ branch, nozzle hole wall and the polymer is that (viscosity of polymer alloy is that 170Pas, 262 ℃, the speed of cutting off are 416 seconds to 0.071MPa except the spray volume of each single hole
-1) in addition, carry out melt spinning similarly to Example 1, obtain the polymer alloy undrawn yarn.The spinnability of this moment is good, and fracture of wire is 1 time during spinning 1t.And, except the stretching ratio of polymer-alloy fibre undrawn yarn is 3.0 times, stretch similarly to Example 1, resulting polymer-alloy fibre has the good characteristic of 128 dtexs, 36 threads, intensity 4.1cN/dtex, elongation 37%, U%=1.2%, boiling water shrinkage 11%.In addition, the cross section of resulting polymer-alloy fibre shows with the result of tem observation, similarly to Example 1, obtaining copolymerization PET is that the island structure on island, several average diameters in zone, N6 island are that 40nm, N6 are with the homodisperse polymer-alloy fibre of nano-scale for sea, N6.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 43nm (2 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is very little.
In addition, the result that the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is measured is 6%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this nanofiber aggregate constitutes, intensity is 2.2cN/dtex, elongation 50%.In addition, be 3% in 140 ℃ dry-hot shrinkage.
In addition, the result who this circular knit is implemented polishing shows that super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Except N6 adopts melt viscosity 500Pas (262 ℃ were cut off speed 121.6 seconds
-1), the N6 (20 weight %) of 220 ℃ of fusing points in addition, carry out melt spinning similarly to Example 2.Then, be that (polymer alloy viscosity is 200Pas, 262 ℃, 416 seconds to 0.083MPa except the stress of cutting off between nozzle hole wall and the polymer
-1) in addition, carry out melt spinning similarly to Example 1, obtain the polymer alloy undrawn yarn.The spinnability of this moment is good, and fracture of wire is 1 time during spinning 1t.And, stretching similarly to Example 2 and heat treatment, resulting polymer-alloy fibre has the good characteristic of 128 dtexs, 36 threads, intensity 4.5cN/dtex, elongation 37%, U%=1.9%, boiling water shrinkage 12%.The cross section of resulting polymer-alloy fibre shows with the result of tem observation, similarly to Example 1, obtaining copolymerization PET is that the island structure on island, several average diameters in zone, N6 island are that 60nm, N6 are with the homodisperse polymer-alloy fibre of nano-scale for sea, N6.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 65nm (4 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is very little.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 6%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this nanofiber aggregate constitutes, intensity is 2.4cN/dtex, elongation 50%.In addition, be 3% in 140 ℃ dry-hot shrinkage.
In addition, the result who this circular knit is implemented polishing shows that super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Except the mixing ratio of N6 reaches the 50 weight % whole polymer alloies, carry out melt spinning similarly to Example 3.Then, the stress of cutting off between nozzle hole wall and polymer is the 0.042MPa, carries out melt spinning similarly to Example 3, obtains the polymer alloy undrawn yarn.The spinnability of this moment is good, and fracture of wire is 1 time during spinning 1t.And, stretching similarly to Example 3 and heat treatment, resulting polymer-alloy fibre has the good characteristic of 128 dtexs, 36 threads, intensity 4.53cN/dtex, elongation 37%, U%=2.5%, boiling water shrinkage 13%.The cross section of resulting polymer-alloy fibre shows with the result of tem observation, similarly to Example 1, obtaining copolymerization PET is that the island structure on island, several average diameters in zone, N6 island are that 80nm, N6 are with the homodisperse polymer-alloy fibre of nano-scale for sea, N6.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 84nm (6 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is very little.
In addition by this N6 nanofiber aggregate constitute the silk, intensity is that 2.6cN/dtex, elongation are 50%.
Comparative example 1
Adopt melt viscosity 180Pas (290 ℃ were cut off speed 121.6 seconds
-1), the PET of 255 ℃ of fusing points is as island component, melt viscosity 100Pas (290 ℃ were cut off speed 121.6 seconds
-1), the polyethylene (PS) of 107 ℃ of Vickers softening temperatures is as sea component, the embodiment 1 described method of opening clear 53-106872 communique according to the spy obtains the island compound silk.And, it is handled with trichloro-ethylene with the special described method of embodiment of opening clear 53-106872 communique, remove 99% or its above PS, obtain super extra fine filament.The cross section of resulting this fiber shows that with the result of tem observation the single fiber diameter of this super extra fine filament is greatly to 2.0 μ m (0.04 dtex).
Comparative example 2
Except adopt melt viscosity 50Pas (280 ℃, 121.6 seconds
-1), the N6 of 220 ℃ of fusing points and melt viscosity 210Pas (280 ℃, 121.6 seconds
-1), after the PET of 255 ℃ of the fusing points mode that reaches 20 weight % with the mixing ratio of N6 cuts into slices and mixes, in 290 ℃ of fusions, in 296 ℃ of spinning temperatures, 280 ℃ of nozzle surface temperatures, adopt beyond the short tube nozzle of nozzle hole count 36, ejection aperture 0.30mm, the long 0.50mm of squit hole, carry out melt spinning similarly to Example 1, divide with spinning speed 1000m/ and batch undrawn yarn.Owing to be that simple section mixes, polymer fusing point difference each other is also big, so the mixed stain of N6 and PET is big, not only produce big limit slag under the nozzle, and stringiness is also poor, can not stably batch silk, obtain a spot of undrawn yarn, the temperature of the 1st hot-rolling 17 is 85 ℃, 3 times of stretching ratios, stretch similarly to Example 1, obtain the drawn yarn of 100 dtexs, 36 threads.
Adopt this silk, make circular knit similarly to Example 1, use alkali treatment equally, remove 99% or its above PET composition.Extract the independent silk of N6 out from making circular knit, with result's demonstration of tem observation fiber cross sections, the generation single fiber diameter is 400nm～4 μ m (filament fiber numbers 1 * 10
-3～1 * 10
-1Dtex) super extra fine filament.Yet it counts the average single fiber fiber number greatly to 9 * 10
-3Dtex (single fiber diameter 1.0 μ m).In addition, the filament fiber number deviation of the super extra fine filament of this N6 is big.
Comparative example 3
Except adopt melt viscosity 395Pas (262 ℃, 121.6 seconds
-1), the N6 of 220 ℃ of fusing points and melt viscosity 56Pas (262 ℃, 121.6 seconds
-1), the PE of 105 ℃ of fusing points, after the mode that reaches 65 weight % with the mixing ratio of N6 is cut into slices and is mixed, adopt device shown in Figure 15, extrude mixing roll 21 after 260 ℃ of fusions with single shaft, beyond the short tube nozzle with nozzle hole count 12, ejection aperture 0.30mm, the long 0.50mm of squit hole, carry out melt spinning similarly to Example 1.The mixed stain of N6 and PE is big, not only produces big limit slag under the nozzle, and stringiness is also poor, can not stably batch silk, obtains a spot of undrawn yarn, stretches similarly to Example 1 and heat treatment, obtains the drawn yarn of 82 dtexs, 12 threads.The stretching ratio of this moment is 2.0 times.
Adopt this silk, make circular knit similarly to Example 1, the PE stripping was handled 1 hour or more than it, remove 99% or its above PE composition with 85 ℃ of toluene.Extract the N6 monofilament out from the circular knit that obtains, carry out result's demonstration that fiber cross sections is observed with TEM, the generation single fiber diameter is 500nm～3 μ m (filament fiber numbers 2 * 10
-3～8 * 10
-2Dtex) super extra fine filament.It counts average filament fiber number greatly to 9 * 10
-3Dtex (single fiber diameter 1.0 μ m).In addition, the filament fiber number deviation of the super extra fine filament of this N6 is big.
Comparative example 4
Except adopt melt viscosity 150Pas (262 ℃, 121.6 seconds
-1), the N6 of 220 ℃ of fusing points and melt viscosity 145Pas (262 ℃, 121.6 seconds
-1), the PE of 105 ℃ of fusing points, after the mode that reaches 20 weight % with the mixing ratio of N6 was cut into slices and mixed, polymer was measured on the limit respectively, the limit imports twin shaft and extrudes mixing roll, adopts device shown in Figure 17, carries out melt spinning equally with comparative example 3.But the mixed stain of N6 and PE is big, not only produces big limit slag under the nozzle, and stringiness is also poor, can not stably batch silk, obtains a spot of undrawn yarn, stretches similarly to Example 1 and heat treatment, obtains the drawn yarn of 82 dtexs, 12 threads.The stretching ratio of this moment is 2.0 times.
Adopt this silk, make circular knit similarly to Example 1,, remove 99% or its above PE composition with PE that 85 ℃ of toluene strippings were handled 1 hour or it is above.Extract the N6 monofilament out from the circular knit that obtains, carry out result's demonstration that fiber cross sections is observed with TEM, the generation single fiber diameter is 100nm～1 μ m (filament fiber number 9 * 10
-5～9 * 10
-3Dtex) super extra fine filament.Yet it counts the average single fiber fiber number greatly to 1 * 10
-3Dtex (single fiber diameter 384nm).In addition, the filament fiber number deviation of the super extra fine filament of this N6 big (Fig. 7, Fig. 8).
Comparative example 5
Adopt the filament spinning component and the nozzle of special public clear 60-28922 communique Figure 11 record, adopt the PS and the PET of record in this communique comparative example 1, make the island compound silk according to the method for putting down in writing in this communique comparative example 1.At this moment, the island component of island compound silk is the mixed polymer of PS and PET 2: 1 (weight ratio), makes sea component with PS.The compound ratio in island is 1: 1 by weight.Concrete is, the A composition among this communique Figure 11 is PET, and B and C composition are PS.And, its also with this communique comparative example 1 in the handling with trichloro-ethylene equally of record, remove 99% or its above PS, obtain super extremely oil silk.Observing this result who surpasses the fiber cross sections of extremely oily silk is, the filament about minimum single fiber diameter 100nm is trace existence especially also, but owing to the dispersion deterioration of PET in PS, so it counts the average single fiber diameter greatly to 9 * 10
-4Dtex (single fiber diameter 326nm), the filament fiber number deviation of super extra fine filament big (Fig. 9, Figure 10).
Table 1
| The island polymer | The sea polymer | Squit hole is cut off ying power (MPa) | |||||
| Polymer | Dissolve viscosity (Pas) | Than (wt%) | Polymer | Dissolve viscosity (Pas) | Than (wt%) | ||
| | N6 N6 N6 N6 | 53 212 500 500 | 20 20 20 50 | Copolymerization PET copolymerization PET copolymerization PET copolymerization PET | 310 310 310 310 | 80 80 80 50 | 0.058 0.071 0.083 0.042 |
| Bi More example 1 Bi More example 2 Bi More example 3 Bi More example 4 Bi More example 5 | PET N6 N6 N6 PS/PET | 180 50 395 150 - | 96 20 65 20 50 | PS PET | 100 210 56 145 - | 4 80 35 80 50 | - 0.41 0.64 0.40 - |
Table 2
| Island number of regions average diameter (nm) | The deviation in zone, island | Intensity (cN/dtex) | U％ (％) | ||
| Mian Plot ratio (%) | Scope diameter range: | ||||
| Embodiment | |||||
| 1 | 53 40 60 80 | 100 100 99 85 | 45～74nm：72％ 35～64nm：75％ 55～84nm：70％ 65～94nm：66％ | 4.0 4.1 4.5 4.3 | 1.7 1.2 1.9 2.5 |
| Bi More example 1 Bi More example 2 Bi More example 3 Bi More example 4 Bi More example 5 | 2000 1000 1000 374 316 | 0 0 0 0 0 | - 974～1005nm：10％ 974～1005nm：10％ 395～424nm：10％ 395～424nm：10％ | - - - - - | - 23.5 22.7 20.3 17.3 |
Area ratio: the island regional diameter is in the area ratio of 1～100nm scope
Scope: be in the area ratio between the diameter difference 30nm.
Table 3
| The nanofiber number is average | The nanofiber deviation | Nanofiber intensity (cN/dtex) | |||
| Diameter (nm) | Fiber number (dtex) | Fiber number ratio (%) | Scope diameter range: fiber | ||
| Embodiment | |||||
| 1 | 56 43 65 84 | 3×10 -5 2×10 -5 4×10 -5 6×10 -5 | 99 100 98 78 | 55～84nm：71％ 45～74nm：75％ 65～94nm：70％ 75～104nm：64％ | 2.0 2.2 2.4 2.6 |
| Bi More example 1 Bi More example 2 Bi More example 3 Bi More example 4 Bi More example 5 | 2000 1000 1000 384 326 | 4×10 -2 9×10 -3 9×10 -3 1×10 -3 9×10 -4 | 0 0 0 0 0 | - 974～1005nm：10％ 974～1005nm：10％ 395～424nm：10％ 395～424nm：10％ | - - - - - |
The fiber number ratio: filament number is in 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex scope
Scope: be in the fiber number ratio between the diameter difference 30nm.
N6 and copolymerization PET using among the embodiment 1 adopt device shown in Figure 16, after 270 ℃ of fusions, polymer melts are imported in the spill spin block 3 of 280 ℃ of spinning temperatures.Then, with being installed in static mixing roll 22 in the filament spinning component 4 (the Ha イ ミ キ サ one that eastern レ エ Application ジ ニ ア リ Application グ society makes), 2 kinds of polymer segments 1,040,000 and after fully mixing, melt spinning is carried out in operation similarly to Example 1.The mixed with polymers of this moment is that 20 weight %, copolymerization PET are 80 weight % than N6, and the stress of cutting off of nozzle is 0.060MPa.Spinnability is good, and fracture of wire is 1 time during spinning 1t.This undrawn yarn also stretches and heat treatment similarly to Example 1.Resulting polymer-alloy fibre has the good characteristic of 120 dtexs, 36 threads, intensity 3.9cN/dtex, elongation 38%, U%=1.7%, boiling water shrinkage 11%.The cross section of this polymer-alloy fibre shows with the result of tem observation, similarly to Example 1, show that obtaining copolymerization PET is that the island structure on island, several average diameters in zone, N6 island are that 52nm, N6 are with the homodisperse polymer-alloy fibre of nano-scale for sea, N6.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 54nm (3 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is very little.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 6%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this nanofiber aggregate constitutes, intensity is 2.0cN/dtex, elongation 50%.In addition, be 3% in 140 ℃ dry-hot shrinkage.
In addition, the result who this circular knit is implemented polishing shows to have, and super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Except adopting N6 and the copolymerization PET that uses among the embodiment 4, the mixing ratio of N6 and copolymerization PET adopts beyond 80 weight %/20 weight %, and melt spinning is carried out in operation similarly to Example 1, makes precursor granules.Adopt device shown in Figure 17,,, supply with mixing channel 25 (capacity 7kg) with the independent respectively metering of metering portion 24 respectively the new particle of the N6 that uses in this precursor granules and the melting mixing hopper 1 of packing into.At this moment, the mixing ratio of precursor granules and the new particle of N6 is 1: 1 by weight, is used to prevent that the antistatic agent (Sanyo changes into industry (strain) society and makes, エ マ Le ミ Application (registration mark) 40) that particle adheres on the mixing channel wall from containing 20ppm.And, after in this mixing channel, particle being stirred each other, supply with twin shaft and extrude mixing roll 23, make the polymer alloy of the N6 containing ratio 40 weight % that melting mixing crosses.At this moment, kneading part length is 33% of screw rod effective length, 270 ℃ of melting temperatures.Then, polymer melts is imported in the spill spin block 3 of 280 ℃ of spinning temperatures.Melt spinning is carried out in operation similarly to Example 4.This undrawn yarn also stretches and heat treatment similarly to Example 4.Resulting polymer-alloy fibre has the good characteristic of 120 dtexs, 36 threads, intensity 3.0cN/dtex, elongation 30%, U%=3.7%.The cross section of this polymer-alloy fibre shows with the result of tem observation, similarly to Example 1, shows that copolymerization PET is the sea, and N6 is the island structure on island, and several average diameters in zone, N6 island are 110nm, and the filament fiber number of ratio nano fiber is big slightly, and deviation is big.
Adopt the polymer-alloy fibre obtain here, similarly to Example 4, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 120nm (1.3 * 10
-4Dtex), compare with embodiment 4, the filament fiber number is big, and filament fiber number deviation is also big.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 5%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this N6 nanofiber aggregate constitutes, intensity is 1.2cN/dtex, elongation 50%.In addition, be 3% in 140 ℃ dry-hot shrinkage.
Table 4
| The island polymer | The sea polymer | Mix in proper order | Squit hole is cut off ying power (MPa) | |||||
| Polymer | Dissolve viscosity (Pas) | Than (wt%) | Polymer | Dissolve viscosity (Pas) | Than (wt%) | |||
| | N6 N6 | 53 500 | 20 40 | Copolymerization PET copolymerization PET | 310 310 | 80 60 | Before the interior filament spinning component of filament spinning component | 0.060 0.20 |
Table 5
| Island number of regions average diameter (nm) | The deviation in zone, island | Intensity (cN/dtex) | U％ (％) | ||
| Area ratio (%) | Scope diameter range: | ||||
| Embodiment | |||||
| 5 | 52 110 | 100 60 * | 45～74nm：72％ 95～124nm：50％ | 3.9 3.0 | 1.7 3.7 |
Area ratio: the island regional diameter is in the area ratio of 1～100nm scope
*: the island regional diameter is in the area ratio of 1～150nm scope
Scope: be in the area ratio between the diameter difference 30nm.
Table 6
| The nanofiber number is average | The nanofiber deviation | Nanofiber intensity (cN/dtex) | |||
| Diameter (nm) | Fiber number (dtex) | Fiber number ratio (%) | Scope diameter range: fiber | ||
| Embodiment | |||||
| 5 | 54 120 | 3×10 -5 1.3×10 -4 | 99 95 * | 55～84nm：72％ 105～134nm：50％ | 2.0 1.2 |
The fiber number ratio: filament number is in 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex scope
*: filament number is in 1 * 10
-7～2 * 10
-4The fiber number ratio of dtex scope
Scope: be in the fiber number ratio between the diameter difference 30nm.
Except hot water solubility's polymer " パ オ グ Application (registration mark) PP-15 " (melt viscosity 350Pas, 262 ℃, 121.6 seconds made from Di-ichi Kogyo Seiyaku Co., Ltd.
-1, 55 ℃ of fusing points) replace copolymerization PET, beyond spinning speed 5000m/ divides, adopt static mixing roll similarly to Example 5, in filament spinning component, carry out mixing and melt spinning.In addition, this " パ オ ゲ Application (registration mark) PP-15 " 262 ℃, 1216 seconds
-1Melt viscosity be 180Pas.Resulting polymer-alloy fibre has the good characteristic of 70 dtexs, 12 threads, intensity 3.8cN/dtex, elongation 30%, U%=1.7%.The cross section of this polymer-alloy fibre shows that with the result of tem observation obtaining copolymerization PET is that sea, N6 are that the island structure on island, several average diameters in zone, N6 island are 53nm, the homodisperse polymer-alloy fibre of N6 nanofiber.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 56nm (3 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 6%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this N6 nanofiber aggregate constitutes, intensity is 2.0cN/dtex, elongation 60%.
In addition, the result that this circular knit is implemented to polish shows to have super feel and the such wet good liquor style of tender and lovely sense of human skin that original superfine fiber can't obtain.
Except with melt viscosity 100Pas (280 ℃, 121.6 seconds
-1), the N66 of 250 ℃ of fusing points replaces N6, beyond the hot water solubility's polymer replacement copolymerization PET that uses among the embodiment 7, adopt device shown in Figure 16, to N66 with 270 ℃, to hot water solubility's polymer with 80 ℃ of fusions after, polymer melts is imported the spill spin block 3 of 280 ℃ of spinning temperatures.Carry out melt spinning similarly to Example 5.At this moment, the mixing ratio N66 of polymer is that 20 weight %, hot water solubility's polymer are 80 weight %, and each single hole spray volume is the 1.0g/ branch.The spinning speed of this moment is the 5000m/ branch.Obtain having 70 dtexs, the polymer-alloy fibre of 12 threads, intensity 4.5cN/dtex, elongation 45%.The cross section of this polymer-alloy fibre obtains with result's demonstration of tem observation, and hot water solubility's polymer is that the island structure on island, several average diameters in zone, N66 island are 58nm, the homodisperse polymer-alloy fibre of N66 nanofiber for sea, N66.
Adopt the polymer-alloy fibre obtain here, similarly to Example 1, use alkali treatment, the nanofiber aggregate of the filament shape that obtains weaving.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 62nm (3 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 6%, and the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this N66 nanofiber aggregate constitutes, intensity is 2.5cN/dtex, elongation 60%.
In addition, the result who this circular knit is implemented polishing shows to have, and super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Except with melt viscosity 300Pas (262 ℃, 121.6 seconds
-1), the copolymerization PET (PEG1000 is 8 weight %, 7 moles of % copolymerization of isophathalic acid) of 235 ℃ of fusing points replaces beyond the N66, and is mixing copolymerization PET and hot water solubility's polymer similarly to Example 8, carries out melt spinning.At this moment, the mixing ratio of polymer is that copolymerization PET is that 20 weight %, hot water solubility's polymer are 80 weight %, and each single hole spray volume is the 1.0g/ branch.The spinning speed of this moment is the 6000m/ branch.The nozzle hole wall of this moment and the stress of cutting off between the polymer fully are low to moderate 0.11MPa.Obtain having 60 dtexs, the polymer-alloy fibre of 36 threads, intensity 3.0cN/dtex, elongation 55%.The cross section of the polymer-alloy fibre that this obtains shows with the result of tem observation, obtaining hot water solubility's polymer is the island structure on island for sea, copolymerization PET, several average diameters in zone, copolymerization PET island are 52nm, the homodisperse polymer-alloy fibre of copolymerization PET nanofiber.
Adopt the polymer-alloy fibre that obtains here, make circular knit similarly to Example 1, with 100 ℃ of hot water stripping hot water solubility polymer, obtain the circular knit that the nanofiber aggregate by such " harsh feeling " of silk fabrics or artificial silk such " dry sensation " constitutes.In addition, the result that the filament fiber number deviation of these nanofibers is resolved similarly to Example 1 is that several average single fiber diameters of nanofiber are 54nm (3 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
In addition, the hydroscopicity (Δ MR) of the circular knit that is made of this nanofiber aggregate is 2%.In addition, by the silk that this copolymerization PET nanofiber aggregate constitutes, intensity is 2.0cN/dtex, elongation 70%.
Except with melt viscosity 190Pas (280 ℃, 121.6 seconds
-1), the PET of 255 ℃ of fusing points replaces carrying out mixing and melt spinning similarly to Example 9 beyond the copolymerization PET.At this moment, the mixing ratio of polymer is that PET is that 20 weight %, hot water solubility's polymer are 80 weight %, and the melt temperature of PET is that 285 ℃, the melt temperature of hot water solubility's polymer are 80 ℃, and the single hole spray volume is the 1.0g/ branch.The nozzle hole wall of this moment and the stress of cutting off between the polymer fully are low to moderate 0.12MPa.Obtain having 60 dtexs, the polymer-alloy fibre of 36 threads, intensity 3.0cN/dtex, elongation 45%.The cross section of this polymer-alloy fibre shows that with the result of tem observation obtaining hot water solubility's polymer is that the island structure on island, several average diameters in zone, PET island are 62nm, the homodisperse polymer-alloy fibre of PET nanofiber for sea, PET.
Adopt the polymer-alloy fibre that obtains here, nanofiber aggregate is made in operation similarly to Example 9.Several average single fiber diameters of this nanofiber are 65nm (3 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Except with melt viscosity 120Pas (262 ℃, 121.6 seconds
-1), the PBT of 225 ℃ of fusing points replaces carrying out mixing and melt spinning similarly to Example 9 beyond the copolymerization PET.At this moment, the mixing ratio of polymer is that PBT is that 20 weight %, hot water solubility's polymer are 80 weight %, and the melt temperature of PBT is that 255 ℃, the melt temperature of hot water solubility's polymer are 80 ℃, and 265 ℃ of spinning temperatures, single hole spray volume are the 1.0g/ branch.The nozzle hole wall of this moment and the stress of cutting off between the polymer fully are low to moderate 0.12MPa.Obtain having 60 dtexs, the polymer-alloy fibre of 36 threads, intensity 3.0cN/dtex, elongation 45%.The cross section of this polymer-alloy fibre obtains with result's demonstration of tem observation, and hot water solubility's polymer is the sea, and PBT is the island structure on island, and several average diameters in zone, PBT island are 62nm, the homodisperse polymer-alloy fibre of PBT nanofiber.
Adopt the polymer-alloy fibre that obtains here, nanofiber aggregate is made in operation similarly to Example 9.Several average single fiber diameters of this nanofiber are 65nm (4 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Except with melt viscosity 220Pas (262 ℃, 121.6 seconds
-1), the PTT of 225 ℃ of fusing points replaces carrying out mixing and melt spinning similarly to Example 9 beyond the copolymerization PET.At this moment, the stress of cutting off between nozzle hole wall and the polymer fully is low to moderate 0.13MPa.Obtain having 60 dtexs, the polymer-alloy fibre of 36 threads, intensity 3.0cN/dtex, elongation 45%.The cross section of this polymer-alloy fibre shows that with the result of tem observation obtaining hot water solubility's polymer is the island structure on island for sea, PTT, and several average diameters in zone, PTT island are 62nm, the homodisperse polymer-alloy fibre of PTT nanofiber.
Adopt the polymer-alloy fibre that obtains here, nanofiber aggregate is made in operation similarly to Example 9.Several average single fiber diameters of this nanofiber are 65nm (4 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Except with melt viscosity 350Pas (220 ℃, 121.6 seconds
-1), the PLA of 170 ℃ of fusing points replaces carrying out mixing and melt spinning similarly to Example 9 beyond the combined polymerization PET.At this moment, the mixing ratio PLA of polymer is that 20 weight %, hot water solubility's polymer are 80 weight %, 235 ℃ of spinning temperatures, and 220 ℃ of nozzle surface temperatures, single hole spray volume are the 1.0g/ branch.Obtain having 60 dtexs, the polymer-alloy fibre of 36 threads, intensity 2.5cN/dtex, elongation 35%.The cross section of this polymer-alloy fibre obtains with result's demonstration of tem observation, and hot water solubility's polymer is the sea, and PLA is the island structure on island, and several average diameters in zone, PL4 island are 48nm, the homodisperse polymer-alloy fibre of PLA nanofiber.
Adopt the polymer-alloy fibre that obtains here, nanofiber aggregate is made in operation similarly to Example 9.Several average single fiber diameters of this nanofiber are 50nm (2 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Table 7
| The island polymer | The sea polymer | Mix in proper order | |||||
| Polymer | Dissolve viscosity (Pas) | Than (wt%) | Polymer | Dissolve viscosity (Pas) | Than (wt%) | ||
| | N6 N66 combined polymerization PET PET PBT PTT PLA | 53 100 300 190 120 220 350 | 20 20 20 20 20 20 20 | Hot water dissolvable polymer Hot water dissolvable polymer Hot water dissolvable polymer Hot water dissolvable polymer Hot water dissolvable polymer Hot water dissolvable polymer Hot | 350 220 350 220 350 350 600 | 80 80 80 80 80 80 80 | In the interior filament spinning component of the interior filament spinning component of the interior filament spinning component of the interior filament spinning component of the interior filament spinning component of the interior filament spinning component of filament spinning component |
Table 8
| Island number of regions average diameter (nm) | The island region difference | Intensity (cN/dtex) | U％ (％) | ||
| Area ratio (%) | Fan Wall diameter range: | ||||
| Embodiment | |||||
| 7 | 53 58 52 62 62 62 48 | 100 100 100 97 98 98 100 | 45～74nm：72％ 55～84nm：70％ 45～74nm：72％ 55～84nm：65％ 55～84nm：68％ 55～84nm：65％ 45～74nm：75％ | 3.8 4.5 3.0 3.0 3.0 3.0 2.5 | 1.7 1.7 1.6 2.3 2.0 2.0 1.2 |
Area ratio: the island regional diameter is in the area ratio of 1～100nm scope
Scope: be in the area ratio between the diameter difference 30nm.
Table 9
| The nanofiber number is average | The nanofiber deviation | Nanofiber intensity (cN/dtex) | |||
| Diameter (nm) | Fiber number (dtex) | Fiber number ratio (%) | Scope diameter range: fiber | ||
| Embodiment | |||||
| 7 | 56 62 54 65 65 65 50 | 3×10 -5 3×10 -5 3×10 -5 5×10 -5 4×10 -5 4×10 -5 2×10 -4 | 99 98 99 98 98 98 100 | 55～84nm：72％ 55～84nm：68％ 55～84nm：71％ 55～84nm：65％ 55～84nm：65％ 55～84nm：65％ 45～74nm：72％ | 2.0 2.5 2.0 2.0 2.0 2.0 1.9 |
The fiber number ratio: filament number is in 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex scope
Scope: be in the fiber number ratio between the diameter difference 30nm.
Except with melt viscosity 300Pas (262 ℃, 121.6 seconds
-1), the Merlon (PC) of 140 ℃ of heat distortion temperatures replaces carrying out mixing and melt spinning similarly to Example 8 beyond the N66.At this moment, the mixing ratio PC of polymer is that 20 weight %, hot water solubility's polymer are 80 weight %, and the single hole spray volume is the 1.0g/ branch.Obtain having 70 dtexs, the polymer-alloy fibre of 36 threads, intensity 2.2cN/dtex, elongation 35%.The cross section of this polymer-alloy fibre obtains with result's demonstration of tem observation, and hot water solubility's polymer is the island structure on island for sea, PC, and several average diameters in zone, PC island are 85nm, the homodisperse polymer-alloy fibre of PC nanofiber.
Adopt the polymer-alloy fibre obtain here, operation similarly to Example 1, make circular knit after, it in 40 ℃ of hot water treatment 10 hours, hot water solubility's polymer stripping 99% or more than it, is obtained nanofiber aggregate.Several average single fiber diameters of this nanofiber are 88nm (8 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Except with melt viscosity 300Pas (262 ℃, 121.6 seconds
-1), the polymethylpentene (PMP) of 220 ℃ of fusing points and melt viscosity 300Pas (262 ℃, 121.6 seconds
-1), the replacement N6 and the PET of 105 ℃ of Vickers softening temperatures, spinning speed 1500m/ carries out mixing and melt spinning beyond dividing similarly to Example 8.Then, with 1.5 times of stretching ratios, stretch similarly to Example 1, heat treatment.At this moment, the mixing ratio of polymer is that PMP is that 20 weight %, PS are 80 weight %, and the single hole spray volume is the 1.0g/ branch.Obtain having 77 dtexs, the polymer-alloy fibre of 36 threads, intensity 3.0cN/dtex, elongation 40%.The cross section of this polymer-alloy fibre obtains with result's demonstration of tem observation, and PS is the sea, and PMP is the island structure on island, and several average diameters in zone, PMP island are 70nm, the homodisperse polymer-alloy fibre of PMP nanofiber.
Adopt the polymer-alloy fibre that obtains here, circular knit is made in operation similarly to Example 1.After making the PS embrittlement with 40 ℃ of concentrated hydrochloric acids, remove PS, obtain the circular knit that constitutes by the PMP nanofiber aggregate with MEK.Several average single fiber diameters of this nanofiber are 73nm (5 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Embodiment 16
Except with melt viscosity 300Pas (220 ℃, 121.6 seconds
-1), the PP of 162 ℃ of fusing points and hot water solubility's polymer that embodiment 7 uses replace beyond PMP and the PS, carries out mixing, melt spinning, stretching, heat treatment similarly to Example 15.At this moment, the mixing ratio PP of polymer is that 20 weight %, hot water solubility's polymer are 80 weight %, and 235 ℃ of spinning temperatures, nozzle surface temperature are 220 ℃, and the single hole spray volume is the 1.0g/ branch.Obtain having 77 dtexs, the polymer-alloy fibre of 36 threads, intensity 2.5cN/dtex, elongation 50%.The cross section of resulting polymer-alloy fibre obtains with result's demonstration of tem observation, and hot water solubility's polymer is the sea, and PP is the island structure on island, and several average diameters in zone, PP island are 48nm, the homodisperse polymer-alloy fibre of PP nanofiber.
Adopt the polymer-alloy fibre that obtains here, nanofiber aggregate is made in operation similarly to Example 9.Several average single fiber diameters of this nanofiber are 50nm (2 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Embodiment 17
Except with melt viscosity 200Pas (300 ℃, 121.6 seconds
-1), the polyphenylene sulfide (PPS) of 280 ℃ of fusing points and melt viscosity 200Pas (300 ℃, 121.6 seconds
-1) N6 replace beyond PMP and the PS, carry out mixing, melt spinning, stretching and heat treatment similarly to Example 15.At this moment, the mixing ratio of polymer is that PPS is that 20 weight %, N6 are 80 weight %, and the PPS melt temperature is that 320 ℃, N6 melt temperature are that 270 ℃, spinning temperature are that 320 ℃, 300 ℃ of nozzle surface temperatures, single hole spray volume are the 1.0g/ branch.Obtain having 77 dtexs, the polymer-alloy fibre of 36 threads, intensity 5.2cN/dtex, elongation 50%.The cross section of resulting polymer-alloy fibre obtains with result's demonstration of tem observation, and N6 is the sea, and PPS is the island structure on island, and several average diameters in zone, PPS island are 65nm, the homodisperse polymer-alloy fibre of PPS nanofiber.
Adopt the polymer-alloy fibre obtain here, operation similarly to Example 1, make circular knit after, with formic acid stripping N6, obtain the circular knit that constitutes by the PPS nanofiber aggregate.Several average single fiber diameters of this nanofiber are 68nm (5 * 10
-5Dtex), reach the fineness that did not have originally, filament fiber number deviation is also very little.
Table 10
| The island polymer | The sea polymer | Mix in proper order | |||||
| Polymer | Dissolve viscosity (Pas) | Than (wt%) | Polymer | Dissolve viscosity (Pas) | Than (wt%) | ||
| | PC | 300 300 300 200 | 20 20 20 20 | Hot water dissolvable polymer P S Hot water | 350 300 600 200 | 80 80 80 80 | In the interior filament spinning component of the interior filament spinning component of the interior filament spinning component of filament spinning component |
Table 11
| Island number of regions average diameter (nm) | The island region difference | Intensity (cN/dtex) | U％ (％) | ||
| Area ratio (%) | Scope diameter range: | ||||
| Embodiment | |||||
| 14 | 85 70 48 65 | 73 95 100 98 | 75～104nm：70％ 65～94nm：73％ 45～74nm：75％ 55～84nm：70％ | 2.2 3.0 2.5 5.2 | 5.1 2.0 2.0 2.0 |
Area ratio: the island regional diameter is in the area ratio of 1～100nm scope
Scope: be in the area ratio between the diameter difference 30nm.
Table 12
| The nanofiber number is average | The nanofiber deviation | Intensity (cN/dtex) | |||
| Diameter (nm) | Fiber number (dtex) | Fiber number ratio (%) | Scope diameter range: fiber | ||
| Embodiment | |||||
| 14 | 88 73 50 68 | 8×10 -5 5×10 -5 2×10 -5 5×10 -5 | 70 94 100 92 | 85～114nm：70％ 65～94nm：72％ 45～74nm：72％ 65～94nm：68％ | 1.5 1.7 1.5 3.0 |
The fiber number ratio: filament number is in 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex scope
Scope: be in the fiber number ratio between the diameter difference 30nm.
Embodiment 18
The polymer-alloy fibre that adopts embodiment 1～6 to make is made flat fabric.The flat fabric that obtains (bath raio 1: 100) in 100 ℃ of hot water of surfactant (Sanyo changes into " グ ラ Application ア Star プ " (registered trade mark)) that contains concentration 2g/ liter respectively and sodium carbonate is carried out refining.Refining time 40 minutes.Carry out centre adjustment in 140 ℃.Then, carried out alkali treatment 90 minutes, remove 99% or its above copolymerization PET as sea component with 10% sodium hydrate aqueous solution (90 ℃, bath raio 1: 100).Finally adjust in 140 ℃ again.Obtain the fabric that constitutes by nanofiber aggregate thus.
The cloth and silk that obtains is implemented dyeing by well-established law, and any cloth and silk all obtains the dyeing of the beauty of dye-free spot.The fabric that is made of the nanofiber aggregate that here obtains is by the fabric of the excellent quality style of silk fabrics such " harsh feeling " or artificial silk such " dry sensation ".In addition because Δ MR=6% and hygroscopicity are good, pretend for comfortable dress material be preferred.In addition, the result who this fabric is implemented the polishing processing shows to have, and super feel that superfine fiber originally can't obtain and human skin be the wet good liquor style of tender and lovely sense like that.
Comparative example 6
The N6 blended fiber that adopts comparative example 2～4 to make is made flat fabric similarly to Example 18.Yet, because the spinning instability, produce many joint spots and fluffing at the length direction of silk, therefore, the fabric of many surface quality differences that only obtains fluffing carries out refining to them, carries out centre adjustment then.Then, with the silk of comparative example 2, carry out alkali treatment similarly to Example 18 after, finally adjust.Also dye with well-established law.On the other hand, adopt the silk of comparative example 3 and comparative example 4, dipping is 60 minutes in 85 ℃ of toluene, removes 99% or the PE more than it.Then, it is finally adjusted.Dye with well-established law again.Such cloth and silk is the many poor qualities' of stain or fluffing a fabric.In addition, its liquor style belongs to original superfine fibre category, do not have " harsh feeling " or " dry sensation ", hygroscopicity also with common N6 fiber quite (Δ MR=2%).
Embodiment 19
Adopt the polymer-alloy fibre of making among the embodiment 4 to make high-density fabric (5 blocks of back of the body satin).And, similarly to Example 18, obtain paying 150g/m by the order that nanofiber aggregate constitutes
2Fabric.Then, the filament fiber number deviation analysis result similarly to Example 1 of this nanofiber is that the single fiber diameter of nanofiber is 86nm (6 * 10
-5Dtex), thinner than original.In addition, the filament fiber number is 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex is 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is little.When its textile impregnation is in water, show special cohesiveness.In addition, this fabric is implemented polishing handle, can obtain cloth for wiping or dusting.This cloth for wiping or dusting is compared with adopting original extra fine filament cloth for wiping or dusting, and the wiping property handled is good, is preferred as cloth for wiping or dusting.In addition, this cloth for wiping or dusting is with washing in the family expenses rinsing maching input Washing net and dewatering, and its form does not change, and shows good DIMENSIONAL STABILITY.
In addition plying of the polymer-alloy fibre that embodiment 1 is made as implementing machine crimp behind the 4 special very much tow, obtains the crimped filament of 8/25mm of crispation number.Be cut into the long 51mm of fiber, separate fibre with carding machine after, make web with intersecting web machine (Network ロ ス ラ Star プ ウ エ one バ one).Then, make this web implement acupuncture and reach 3000/cm
2, make order and pay 750g/m
2Fiber complexing nonwoven fabric.Then, be bonded on this nonwoven fabric as supporter with the PP nonwoven fabric.After polyvinyl alcohol being given to this lamination nonwoven fabric, implement alkali treatment in 2 hours with 3% sodium hydrate aqueous solution (60 ℃, bath raio 1: 100), remove 99% or its above copolymerization PET.Again this lamination nonwoven fabric being immersed in polyethers is that polyurethane is as the 13 weight % urethane compositions (being called for short PU) of main body and the N of 87 weight %, in the liquid that N '-dimethyl formamide (being called for short DMF) constitutes, washed after in the aqueous solution of the 40 weight % of DMF, PU being solidified, obtained the fiber construct of thick about 1mm of constituting by N6 nanofiber aggregate and PU.Also have, extract nanofiber aggregate out from this fiber construct, to the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 is that several average single fiber diameters of nanofiber reach 60nm (3 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 97%, and particularly to be in the filament fiber number ratio between 55～84nm be 70% to single fiber diameter, and the deviation of filament fiber number is especially little.Then, downcut the PP nonwoven fabric, obtain the N6 nano fiber non-woven fabric from above-mentioned lamination nonwoven fabric.Single face to this N6 nano fiber non-woven fabric polishes processing with sand paper, after making thickness reach 0.8mm, another side is handled with emery buff, formed nanofiber aggregate piloerection face, process after dyeing again, obtain the artificial leather that the imitation buckskin leather is transferred.Resulting products appearance is fabulous, the dye-free spot, and mechanical property is no problem also.In addition, compare, have soft and fine and smooth more feel with adopting original super superfine artificial leather.In addition, because hygroscopicity is good, so have the such tender and lovely excellent quality style of similar people's skin that original artificial leather does not have.
Comparative example 7
The N6/PE blended fiber that comparative example 3 is made in addition behind the machine crimp, is cut into the long 51mm of fiber, separate fibre with carding machine after, make web with intersecting the web machine.Then, make this web implement acupuncture, make order and pay 500g/m
2Fiber complexing nonwoven fabric.Then, it is that polyurethane is as 13 weight % urethane compositions (PU) of main body and the N of 87 weight % that this fiber complexing nonwoven fabric is immersed in polyethers, in the liquid that N '-dimethyl formamide (DMF) constitutes, washed after in the aqueous solution of the 40 weight % of DMF, PU being solidified, obtained containing the fiber construct of N6/PE blended fiber and PU.Also have, this fiber construct is polished processing, obtain the fiber construct of thick about 1mm of N6 ultrafine wire and PU formation, single face to this fiber construct polishes processing with sand paper, after making thickness reach 0.8mm, another side is handled with emery buff, formed nanofiber aggregate piloerection face, process after dyeing again, obtain the artificial leather that suede is transferred.Resulting liquor style, the liquor style of the artificial leather of original superfine fiber above employing.
Embodiment 21
The polymer-alloy fibre that embodiment 1 makes, operation similarly to Example 20 obtains the N6 nanofiber aggregate of PU containing ratio 40 weight % and the fiber construct that PU constitutes.Also have, extract nanofiber aggregate out from this fiber construct, to the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 is that several average single fiber diameters of nanofiber reach 60nm (3 * 10
-5Dtex), get in the past do not have thin.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 97%, and particularly to be in the filament fiber number ratio between 55～84nm be 70% to single fiber diameter, and the deviation of filament fiber number is especially little.This fiber construct be divided into two cut off after, polish with JIS#240, #350, #500 sand paper on the surface.With being spaced apart 1mm, surface temperature is that 2 warm-up mills through fluorine processing up and down of 150 ℃ are clamped, and uses 0.7kg/cm with it
2Pressure compacting after, the chill roll chilling with 15 ℃ of surface temperatures obtains ganoid abrasive cloth.Then, estimate this abrasive cloth with following method, the results are shown in table 13, compare with the cloth that has adopted original super extra fine filament, the flatness of grinding charge raises, and it is also few to become the indentation number of shortcoming, shows good ABRASION RESISTANCE.
＜grind and estimate: the distortion of hard disk (テ キ ス チ ヤ リ Application グ) 〉
Grinding charge: at the substrate of implementing to carry out after Ni-P electroplates overground light processing on the aluminium sheet of market sale (average surface roughness=0.28nm)
Grinding condition: under following condition, this substrate is installed on the experimental rig, grinds.
Abrasive particle material: the adamantine free abrasive material slurry of average grain diameter 0.1 μ m
Rate of addition: 4.5ml/ branch
Rotation number: 1000rpm
Belt speed: 6cm/ branch
Grinding condition: amplitude 1mm-oscillation crosswise 300 times/minute
Estimate the sheet number: 30/level of this substrate
The average surface roughness Ra of＜grinding charge 〉
Employing is arranged on force microscope (AFM) between the precursor that the Veeco society of the anti-acoustic device of band in 20 ℃, the clean room of relative humidity 50% makes, and measures the surface roughness of 30/level of substrate, asks its average surface roughness Ra.Measurement range is a benchmark with the disc centre of each substrate, and symmetry is selected 2 places, radius central point, measures at the 5 μ m * 5 μ m width of each point.
＜indentation number 〉
Adopt the interfere type microscope of ZYGO society manufacturing, measure the indentation number (X) of each sample surfaces.Counting indentation size is 0.1 μ m * 100 μ m or its above number.It is measured as 30/level of substrate, be defined as indentation from the y that counts of injured number and count β.
X≤4 o'clock y=*
X 〉=5 o'clock y=5
β＝∑y
i (i＝1～30)
Here, ∑ y
iIt is the indentation sum of 30 in sample.
Comparative example 8
Operate equally with comparative example 7, obtain the fiber construct that constitutes by super extra fine filament of N6 and PU.Adopt it, operation makes abrasive cloth similarly to Example 21.This abrasive cloth is estimated, Ra=1.60nm, β=32 are compared with adopting nanofiber aggregate, and the flatness of grinding charge is low, and many as the indentation number of shortcoming, abrasiveness is poor.
Table 13
| Precursor | Ra(nm) | β (individual/30 slice) | |
| Embodiment 21 comparative examples 8 | | 0.09 1.60 | 2 32 |
Embodiment 22
The polymer-alloy fibre that uses embodiment 1 to make, operation obtains order and pays 350g/m similarly to Example 20
2Fiber complexing nonwoven fabric.This nonwoven fabric is implemented alkali treatment in 2 hours with 10% sodium hydrate aqueous solution (90 ℃, bath raio 1: 100), remove 99% or its above copolymerization PET, obtain the N6 nano non-woven fabric.Also have, extract nanofiber aggregate out from this nonwoven fabric, to the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 is that several average single fiber diameters of nanofiber reach 60nm (3 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 97%, and particularly to be in the filament fiber number ratio between 55～84nm be 70% to single fiber diameter, and the deviation of filament fiber number is especially little.Then, be cut into the circle of diameter 4.7cm from the N6 nano non-woven fabric that obtains, with its overlapping 5, be arranged in the post of circular filter, the ox blood that contains white blood cell (5700/microlitre), the flow velocity that divides with 2ml/ feeds liquid, the time that makes the pressure loss reach 100mmHg is 100 minutes, the particle ball clearance of this moment is more than 99%, and quinoline crust ball clearance is 60%, can select the leukocytic particle ball of inflammation.It is believed that this is because the effect in the gap between the nanofiber.
Nano fiber non-woven fabric 0.5g embodiment 22 makes with the autoclave sterilization, makes to contain the endotoxic cow's serum feeding carrying out of 15ml absorption affinity evaluation (37 ℃, 2 hours).Endotoxin concns LPS is reduced to 1.5ng/ml from 10.0ng/ml, shows good adsorption capacity.This is because the active surface of nylon nano fiber is bigger than common nylon fiber, due to amino terminal is Duoed than common nylon fiber.
Polymer is similarly to Example 13 made up, adopted device shown in Figure 180, made spun-bonded nonwoven fabric.At this moment, be 225 ℃ with the melt temperature in the biaxial extruder 23, spinning temperature is 230 ℃, the nozzle surface temperature is 217 ℃.In addition, nozzle adopts spot similarly to Example 1, and the single hole spray volume is the 0.8g/ branch, and the distance to the cooling beginning below nozzle is 12cm.
This polymer alloy nonwoven fabric that obtains is implemented to handle in 2 hours with 60 ℃ of hot water, and dissolving removes 99% or its above hot water solubility's polymer, obtains the nonwoven fabric that the PLA nanofiber constitutes.The number of the single fiber diameter of its nanofiber on average reaches 50nm (2 * 10
-5Dtex).In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 98% or more than it, the filament fiber number ratio that single fiber diameter is between 45～74nm is 70%.
The circular knit that the nanofiber aggregate made among the embodiment 1～6 is constituted, dipping is 30 minutes in the 15 weight % aqueous solution of the hexa-methylene Merlon (molecular weight 3000～4000) of hexamethylene diisocyanate and molecular weight 1000.Then, take out circular knit, made polyurethane prepolymer crosslinked 20 minutes in 120 ℃.By this operation, the polyurethane prepolymer that immerses space between the nanofiber generates the complex that is made of crosslinked polyurethane and N6 nanofiber by crosslinked and insoluble.The complex of resulting circular knit shape has big extensibility, has the satisfied surperficial feel of cohesiveness simultaneously.
The circular knit that the nanofiber aggregate that embodiment 1～6 is made constitutes is immersed in the ion exchange water, then, add 1, two (trimethoxysilyl) ethane of 2-, stirred 3 hours, after room temperature leaves standstill 14 hours, stirred again 13 hours, and after room temperature leaves standstill 14 hours, stirred again 7 hours again, make silica polymerization.Then, circular knit is done with ion-exchange water washing after wind.By this operation, the N6 nanofiber as casting mold, is obtained the N6/ silica composite of cloth and silk shape.This is the material with sufficient rigidity and flexible excellence.In addition, also be composite material with excellent fire retardant.
The N6/ silica complex that obtains among the embodiment 26 in 600 ℃ of calcinations, is removed the used N6 of casting mold thus, obtain having the silica sheet material of the minute aperture of the tens of nm of many diameters.It shows good absorption, smelly performance disappears.
The knitted fabric that the polyester nano fiber assembly that embodiment 9～12 is made constitutes exhausts " SR1000 " (aqueous dispersion product of 10%) of making as the high terebinth (strain) of hygroscopic agent.The processing conditions of this moment is that the solid constituent of hygroscopic agent is 20%owf, bath raio 1: 20,130 ℃ of treatment temperatures, 1 hour processing time.Common polyester fiber is almost 0% to the exhaustion rate of this hygroscopic agent, but the polyester nano fiber to the exhaustion rate of this hygroscopic agent 10% or more than it, Δ MR=4% or more than it can obtain and cotton equal above good hygroscopic polyester knitted.
Embodiment 29: mixture (nanofiber/organic silicone)
MTMS oligomer (n=3～4) is dissolved in the mixed solution of isopropyl alcohol/ethylene glycol=1/1, and adding relative silane low polymer is the dibutyltin diacetate as polymerization catalyst of 4 weight %, adjusts the silicone polymer coating fluid.The fabric that in this coating fluid the N6 nanofiber aggregate of making among the embodiment 19 is constituted flooded abundant dip coated liquid 20 minutes in 30 ℃.Then, this fabric is taken out from coating fluid, carry out drying respectively at 60 ℃, 2 minutes, 80 ℃, 2 minutes, 100 ℃, 2 minutes, carry out silicone polymer simultaneously, obtain the fabric that the N6 nanofiber is coated with by silicone polymer.It is the fabric with good hydrophobicity and anti-flammability.
The moisture content and the water retention rate of the knitted fabric that the N6 nanofiber aggregate that mensuration is made by embodiment 1～4 constitutes.This knitted fabric shows deadweight 160% or its above moisture content, deadweight 80% or its above water retention rate, and suction and water-retaining property are good.Here, moisture content and water retention rate are sample is fully flooded 60 minutes in tank after, with its taking-up, mensuration is removed the fabric weight (Ag) behind the surface attachment water, then it is used centrifugal dehydrator (3000rpm, 7 minutes) dehydration back mensuration fabric weight (Bg), measure warp again in 2 hours fabric weight of 105 ℃ of dryings (Cg), calculate according to following formula:
Moisture content (%)=(A-C)/C * 100 (%)
Water retention rate (%)=(B-C)/C * 100 (%)
In addition, the knitted fabric that this N6 nanofiber aggregate constitutes, particularly, contain 15% or the state of its above water under present special cohesiveness.
Embodiment 31
Adopt the N6 nano fiber non-woven fabric of making among the embodiment 22, make the base cloth of patch material, coating medicament on it, the exhaustion of this medicament is good, and shows good cohesiveness, can be used as good paste.
Embodiment 32
Adopt the knitted fabric of the N6 nanofiber aggregate formation of making among the embodiment 1, make bag, in bag, put into cold-retaining agent, make hot cold compress apparatus (the cold ま of Hot apparatus) through pouch-packaged.This hot cold compress apparatus absorbs the water of dewfall in the bag, shows good cohesiveness, so hot cold compress apparatus is difficult to break away from affected part, operability is good.
Embodiment 33
The circular knit that the N6 nanofiber aggregate of making among the employing embodiment 1 is constituted, the ability of removing of its organic pollution materials is by the laxative remedy evaluation.1g puts into 0.005m sample strip
3In the four-hole groove of (5 liters), feed the air contain organic pollution matter and make and reach desirable concentration.This contaminated air is taken a sample at any time, with the organic pollution materials concentration in the gas chromatograph monitoring four-hole groove.
Show good removal ability (Figure 19～Figure 22) as the removal evaluation result of ammonia, formaldehyde, toluene and the hydrogen sulfide of organic pollution materials.
Comparative example 9
Adopt the N6 plain of market sale,, almost do not have the removal ability with the embodiment 33 same removal abilities of estimating organic pollution materials.
Embodiment 34
The circular knit that the N6 nanofiber aggregate of making among the employing embodiment 1 is constituted is made leather shoes, and it is flooded the back in " new Port リ カ イ Application (registration mark) liquid " that roc medicine society makes dry.Whereby, can obtain leather shoes by sweat stripping beriberi medicine.These leather shoes by athlete's foot patient 10 people dress, are more renewed footwear every day.Continuous 1 month, symptom was seen 7 of the subjects of improvement.This is because due to the slow release of beriberi medicine.
Therefore, nanofiber of the present invention is owing to have the slow releasability of effective component, pretend for medical product be suitable.
Embodiment 35
The circular knit of making among the embodiment 4 is immersed in the 10 weight % aqueous solution of silicone PP (special modified silicone/this grease of pine (strain) is made), gives the circular knit base material treatment fluid, make the impregnation rate of the aqueous solution reach 150%.Behind the imparting treatment solution, in 110 ℃ of baking ovens dry 3 minutes in relaxed state.Carry out breaking after the drying and handle, present very thin feel different and the lubricated sense as the human skin with polishing.In addition, also has contact coldness.In addition, this circular knit base material washs with family expenses rinsing maching input Washing net and dewaters, and form does not change, and shows good DIMENSIONAL STABILITY.
The order that adopts this silicone-treated to cross is paid 150g/cm
2The circular knit base material that constitutes of N6 nanofiber, make T-shirt, have the such feel of human skin as snug as a bug in a rug, and also have anti-pilling effects.In addition, this circular knit base material washs with family expenses rinsing maching input Washing net and dewaters, and form does not change, and shows good DIMENSIONAL STABILITY.
Embodiment 36
The polymer-alloy fibre of making among the embodiment 4, adopt friction disc false twisting processing unit (plant) to implement false twisting processing.At this moment, 180 ℃ of heat treatment temperatures, 1.01 times of stretching ratios.Adopt the false twist yarn that obtains here, similarly to Example 1, use alkali treatment, obtain paying 100g/m by the order that nanofiber aggregate constitutes
2The circular knit base material.The filament fiber number deviation analysis result similarly to Example 1 of these nanofibers is that several average single fiber diameters of nanofiber are 84nm (6 * 10
-5Dtex), be the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filamentary fiber number ratio of scope is 78%, and particularly to be in the filament fiber number ratio of 75～104nm scope be 64% to single fiber diameter, and the deviation of filament fiber number is little.In addition, this N6 nanofiber false twist yarn intensity is 2.0cN/dtex, and elongation is 45%.
This circular knit base material and embodiment 35 are carried out silicone-treated equally, show the tender and lovely liquor style of the moistening profit that very thin feel and human skin are such.Also has contact coldness.In addition, with this round pin fabric, use the family expenses rinsing maching, the input Washing net washs and dewaters, and form does not change, and shows good DIMENSIONAL STABILITY.
Embodiment 37
Adopt the order of making among the embodiment 36 of crossing through silicone-treated to pay 100g/m
2The round pin fabric that constitutes of N6 nanofiber, make women's pants and since have as the human skin feel as snug as a bug in a rug, and also have the effect of anti-balling-up.In addition, with this round pin fabric, with washing in the family expenses rinsing maching input Washing net and dewatering, form does not change, and shows good DIMENSIONAL STABILITY.
Embodiment 38
As shell silk (sheath yarn), the elastic polyurethane silk " ラ イ Network ラ " (registration mark) of using the manufacturing of オ ペ ロ Application テ Star Network ス society is as cladded yarn the N6/ copolymerization PET alloy false twist yarn of making among the embodiment 36.With this cladded yarn make Lingerie with knitwear after, use alkali treatment equally with embodiment 36, make the Lingerie knitwear that constitute by nanofiber.This Lingerie is paid with the order of knitwear and is 100g/m
2, the weight rate of N6 nanofiber and polyurethane fiber silk is respectively 90% and 10%.Be immersed in the 10 weight % aqueous solution of silicone (シ Le コ one ト) PP (special modified silicone/this grease of pine (strain) is made), give knitwear treatment fluid, make the impregnation rate of the aqueous solution reach 150%.Behind the imparting treatment solution, in 110 ℃ of baking ovens dry 3 minutes in relaxed state.Carrying out breaking after the drying handles.Then, this Lingerie is made with knitwear, made Lingerie.This Lingerie presents very thin feel and the such lubricated sense of human skin.Dress as snug as a bug in a rug.
Embodiment 39
The speed of the 1st draw roll 9 (spinning speed) is decided to be the 3500m/ branch, carry out melt spinning similarly to Example 4, obtain the N6/ copolymerization pet polymer alloy fiber of 400 dtexs, 96 threads, the intensity 2.5cN/dtex of this polymer-alloy fibre, elongation 35%, U%=1.9%.Then, this polymer-alloy fibre is implemented draw false twisting, obtain the false twist yarn of 333 dtexs, 96 threads.This moment, heat treatment temperature was 1.2 times of 180 ℃, stretching ratio.Resulting false twist yarn intensity 3.0cN/dtex, elongation 32%.
To the weak twist of this false twist yarn enforcement 300 commentaries on classics/m, adopt S sth. made by twisting/Z to twist with the fingers mariages as warp and parallel, make 2/2 Dou pattern fabric.Then, the Dou pattern fabric that obtains, embodiment 1 carries out alkali treatment equally, obtains paying 150g/m by the order that the N6 nanofiber constitutes
2The curtain gray fabric.Also have, to the filament fiber number deviation of nanofiber, the result of Xie Xiing is similarly to Example 1, and several average single fiber diameters of nanofiber reach 86nm (6 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.In addition, the intensity of this N6 nanofiber false twist yarn is that 2.0cN/dtex, elongation are 40%.
In addition, this curtain is implemented the silicone-treated same with embodiment 35 with gray fabric, the result shows very thin feel and the such lubricated ridge lattice of human skin.In addition, also has contact coldness.Its hydroscopicity (Δ MR) is 6%, shows sufficient hygroscopicity, carries out the disappear result of olfactory test of acetic acid to be, reduces to 1ppm with 10 minutes its concentration from 100ppm, shows the good smelly property that disappears.In addition, adopt this gray fabric to make curtain, the result that 6 straw mattress rooms are hung forms lucid and lively indoor environment, can also suppress dewfall.This curtain is with washing in the family expenses rinsing maching input Washing net and dewatering, and form does not change, and shows good DIMENSIONAL STABILITY.
Respectively melt viscosity 500Pas (262 ℃ were cut off speed 121.6 seconds of using among N6/ copolymerization pet polymer alloy that uses among the embodiment 4 and the embodiment 4
-1), in addition fusion of the N6 of 220 ℃ of fusing points, adopt the nozzle of Y type squit hole, make core shell compound silk similarly to Example 4.At this moment, the core composition is a N6/ copolymerization pet polymer alloy, and shell component is N6, and the compound ratio of core composition is 50 weight %.Spin silk and divide to stretch, then, carry out 2 sections stretchings, give with nozzle again and batching after curling, obtain the bulk processing thread of 500 dtexs, 90 threads in the condition of 3.5 times of the 1st stretching ratios 1.3, total stretching ratio with 800m/.Processing that this is bulk silk intensity is that 5.2cN/dtex, elongation are 25%.
2 of bulk processing silks that obtain and in addition plying together, carry out first twist (200T/m), adopt its 2, carry out twisted with retwist (200T/m), in xeothermic 170 ℃ implement to twist with the fingers end handle after, the employing known method is made the pattern wool yarn as velvet carpet.At this moment, adopt common horizontal resection, regulate needle tracking, make reach 1/1 line-spacing, order is paid 1500g/m
2, make the pattern wool yarn.Then, implement packing.When making the pattern wool yarn, the base cloth that adopts the blended ratio by acrylic fibers peacekeeping polyester fiber to be made into as base cloth.In addition, only alkali treatment is partly carried out in clipping, the N6 nanofiber presents the structure of wrapping up N6 in the clipping part.In addition, several average single fiber diameters of resulting N6 nanofiber reach 86nm (6 * 10
-5Dtex).In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.Therefore, the order of clipping part is paid and is become 1200g/m
2, the weight fraction of N6 nanofiber is 33 weight % of clipping part, is 15 weight % of carpet integral body.This carpet, the clipping part is because by shell component N6 maintenance N6 nanofiber, so a falling property of hair (the hair property of falling れ) problem does not take place.In addition, because N6 nanofiber content is 15 weight %,, can reach salubrious indoor environment to whole carpets so show the sufficient adjustable wet and the smelly property that disappears.And, can also suppress dewfall.
Embodiment 41
The N6/ copolymerization PET alloy false twist yarn that obtains among 4 embodiment 36 of plying as warp and parallel, is made 2/2 Dou pattern fabric.Then, carry out alkali treatment equally, obtain paying 200g/m by the order that N6 nanofiber false twist yarn constitutes with embodiment 36
2Indoor decoration sheet material epidermis.Also have, to the filament fiber number deviation of nanofiber, the result of Xie Xiing is similarly to Example 1, and several average single fiber diameters of nanofiber reach 86nm (6 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.When it is used as the chair surface, not only soft and very comfortable, and show sufficient adjustable wet and the smelly property that disappears, form lucid and lively indoor environment.
Embodiment 42
Respectively melt viscosity 500Pas (262 ℃ were cut off speed 121.6 seconds of using among N6/ copolymerization pet polymer alloy that uses among the embodiment 4 and the embodiment 4
-1), in addition fusion of the N6 of 220 ℃ of fusing points, adopt the circular apertures nozzle, make core shell compound silk similarly to Example 4.At this moment, the core composition is a N6/ copolymerization pet polymer alloy, and shell component is N6, and the compound ratio of core composition is 30 weight %.Spinning that silk divide to stretch with 1600m/ in case after batching, is that 90 ℃, the temperature of the 2nd warm-up mill 18 are 130 ℃ with the temperature of the 1st warm-up mill 17, stretches for 2.7 times with stretching ratio.Resulting polymer-alloy fibre is 220 dtexs, 144 threads, intensity 4.8cN/dtex, elongation 35%, U%=1.9%.Then,, adopt warp and parallel, make plain cloth with the weak twist of 300 commentaries on classics/m.Then, carry out alkali treatment similarly to Example 4, obtain being paid 220g/m by the order that fiber constituted that shell component N6 coats by the N6 nanofiber
2Fabric.Also have, several average single fiber diameters of resulting nanofiber reach 86nm (6 * 10
-4Dtex).In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.In addition, itself and embodiment 36 are implemented silicone-treated equally, the result presents very thin feel and and the similar lubricious liquor style of human skin.Make quilt cover and sheet with it, its liquor style is good, hygroscopicity as snug as a bug in a rug.In addition, because its good smelly property that disappears, even gatism also can suppress stink.In addition, these bedding are put into Washing net with the family expenses rinsing maching and are washed and dewater, and form does not change, and shows good DIMENSIONAL STABILITY.
Embodiment 43
The speed of the 1st work beam 9 is the 3500m/ branch, with the embodiment 40 same core shell compound silks of making, obtains the N6/ copolymerization pet polymer alloy fiber of 264 dtexs, 144 threads.The intensity of this polymer-alloy fibre is 3.5cN/dtex, elongation 110%, U%=1.9%.Then, it is implemented draw false twisting, obtain the false twist yarn of 220 dtexs, 144 threads.At this moment, in 180 ℃ of heat treatments, 1.2 times of stretching ratios.Resulting false twist yarn intensity is 4.1cN/dtex, elongation 32%.
This false twist yarn is carried out weak twist with 300 commentaries on classics/m, it with being warp and parallel, is made plain cloth.Then, carry out alkali treatment similarly to Example 1, obtain paying 100g/m by the order that the N6 nanofiber is constituted
2The fabric that constitutes of the fiber that coated by the N6 shell component of N6 nanofiber.Also have, the filament fiber number deviation of resulting nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 86nm (6 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.This fabric is the N6 nanofiber encapsulated structure in addition in the N6 air silk, presents the liquor style of feel and excellent spring like the cotton candy.The false twist yarn intensity that contains the N6 nanofiber is 2.9cN/dtex, elongation 41%.
In addition, to this fabric and the embodiment 35 same silicone-treated of implementing, the result shows very thin feel and the such lubricated texture of human skin.In addition, also has contact coldness.Its hydroscopicity (Δ MR) is 6%, shows sufficient hygroscopicity.Make women's shirt with this fabric, as snug as a bug in a rug, also have anti-pilling effects.In addition, these women's shirts are put into Washing net with the family expenses rinsing maching and are washed and dewater, and form does not change, and the N6 fiber is by showing good DIMENSIONAL STABILITY with the N6 air silk is encapsulated in addition.
Embodiment 44
Adopt the N6/ copolymerization PET alloy false twist yarn of making among the embodiment 39 as matrix, the polybutylene terephthalate (PBT) (PBT) of 100 dtexs, 36 threads silk as section's braided fabric in the spy of piloerection suede portion, with 28 needle knitting machines, weave with the count of 64 lines.Then, its in 10% sodium hydrate aqueous solution (90 ℃, bath raio 1: 100) were flooded 1 hour, the copolymerization PET in hydrolysis removal 99% or its above polymer-alloy fibre obtains the automobile interior trim cloth and silk.The result is that resulting automobile interior trim is paid with the order of cloth and silk and is 130g/m
2, N6 nanofiber containing ratio 40 weight %.In addition, the order of N6 nanofiber is paid and is 120g/m
2In addition, several average single fiber diameters of N6 nanofiber reach 84nm (6 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.And, with its in the 30% diethylenetriamines aqueous solution in 50 ℃ the dipping 1 minute, thus, load diethylenetriamines on the N6 nanofiber.Result to the removal merit rating of its acetyl acetaldehyde is that with 10 minutes, concentration was reduced to 1ppm from 30ppm, showed good removal ability.
Embodiment 45
Respectively N6/ copolymerization pet polymer alloy and melt viscosity 240Pas (262 ℃ were cut off speed 121.6 seconds of using among the embodiment 4
-1), in addition fusion of the PBT of 220 ℃ of fusing points, adopt the nozzle of hole count 24, ejection aperture 1.0mm, the long 1.0mm of squit hole, carry out the island composite spinning similarly to Example 4.At this moment, marine origin is divided into N6/ copolymerization pet polymer alloy, and island component is PBT, and the compound ratio of island component is 35 weight %, and the island number in every hole is 36 islands.Spinning after silk divide to stretch with 900m/, is that 80 ℃, the temperature of the 2nd warm-up mill 18 are 130 ℃ with the temperature of the 1st warm-up mill 17, stretches and heat treatment for 3.0 times with stretching ratio.The polymer alloy of gained 240 dtexs, 24 threads, intensity 3.0cN/dtex, elongation 40%, U%=2.0% is the sea, and PBT is the island compound silk on island.Then, behind 300 commentaries on classics/m enforcement weak twist, adopt it, make 2/2 Dou pattern fabric as warp and parallel.Then, with this textile impregnation (90 ℃, bath raio 1: 100) in 10% sodium hydrate aqueous solution, the combined polymerization PET in hydrolysis removal 99% or its above polymer-alloy fibre.Obtaining N6 nanofiber and PBT weight ratio thus is 48 weight %: the mixed order of knitting the silk formation of the N6 nanofiber of 52 weight % and the super extra fine filament of PBT (0.08 dtex) is paid and is 200g/m
2Fabric.In addition, several average single fiber diameters of N6 nanofiber reach 84nm (6 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 78%, and particularly to be in the filament fiber number ratio between 75～104nm be 64% to single fiber diameter, and the deviation of filament fiber number is especially little.
This fabric is by resulting from the different Coulomb repulsion of charging property of N6 nanofiber and PBT, the N6 nanofiber is opened fibre, do not handle and silicone-treated even do not polish, can obtain super soft super feel yet, show to have the such tender and lovely excellent quality style of human skin.In addition, because PBT supports fabrics skeleton, not only can improve DIMENSIONAL STABILITY but also tool is good resilience sense.Adopt this fabric, make windproof sportswear, but open fibre by making the N6 nanofiber, not only can present good windproof property, and, by making the sportswear of super soft liquor style, even vigorous exercise does not have the sound of " sand rustles " yet, in addition, owing to the good hygroscopicity of N6 nanofiber has dress character as snug as a bug in a rug.In addition, it is put into Washing net with the family expenses rinsing maching wash and dewater, form does not change, and shows good DIMENSIONAL STABILITY.
Embodiment 46
The nanofiber aggregate of making among the embodiment 1 is blended in water, add the nonionic dispersant 0.1 weight % of polyoxyethylene styrene sulfonation ether, obtain N6 nanofiber aqueous dispersion as principal component.N6 nanofiber concentration in the water counts 1% with weight ratio.This aqueous dispersion curtain coating on the compound that contains the charcoal nanofiber is made dry, on the composite surface of charcoal fiber, coat the N6 nanofiber thinly.Improve the hydrophily of the composite surface of charcoal fiber whereby.
Embodiment 47
After the polymer-alloy fibre that obtains among the embodiment 1 being made the tow of 10 dtexs, fritter into the long 2mm of fiber.Then, it is carried out alkali treatment similarly to Example 1, obtain nanofiber aggregate.Be dispersed with the aqueous alkali of this nanofiber aggregate with watery hydrochloric acid neutralization, add the nonionic dispersant 0.1 weight % of polyoxyethylene styrene sulfonation ether as principal component after, copy paper, obtain nonwoven fabric.Here the nonwoven fabric that obtains, to reach nonwoven fabric made in diameter 10 μ m or the acupuncture more than it different with nanofiber aggregate cohesion, and the nanofiber aggregate diameter disperses to reach 300nm or below it.Also have, extract nanofiber aggregate from this nonwoven fabric, the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 60nm (3 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 99%, and particularly to be in the filament fiber number ratio between 55～84nm be 70% to single fiber diameter, and the deviation of filament fiber number is especially little.
Embodiment 48
Except adopt weight average molecular weight 120,000, melt viscosity 30Pas (240 ℃, 2432 seconds
-1), the poly-L-lactic acid (optical purity is more than 99.5%) of 170 ℃ of fusing points replaces copolymerization PET, beyond 220 ℃ of the melting temperatures, carries out melting mixing similarly to Example 1, obtains b
*The polymer alloy sheet of value=3.Also have, the weight average molecular weight of PLA is obtained by laxative remedy.In the chloroformic solution of sample, mix oxolane (being called for short THF) as measuring solution.Gel permeation chromatograph (GPC) Waters2690 that this solution is made with Waters society measures in 25 ℃, obtains the weight average molecular weight that is converted into polystyrene.The N6 that uses among the embodiment 1 was at 240 ℃, 2432 seconds
-1Melt viscosity be 57Pas.This poly-L-lactic acid was at 215 ℃, 1216 seconds
-1Melt viscosity be 86Pas.
Except this polymer alloy sheet 230 ℃ of melt temperatures, spinning temperature 230 ℃ of (215 ℃ of nozzle surface temperatures), spinning speed 3500m/ divide, carry out melt spinning similarly to Example 1.At this moment, as nozzle, use the common spinning nozzle of nozzle diameter 0.3mm, the long 0.55mm in hole, but limit slag phenomenon do not observe almost, compare with embodiment 1, spinnability is significantly improve also, and fracture of wire is 0 time during 1 ton of spinning.The single hole spray volume of this moment is the 0.94g/ branch.Therefore, can obtain the high orientation undrawn yarn of 92 dtexs, 36 threads, its intensity is 2.4cN/dtex, elongation 90%, boiling water shrinkage 43%, U%=0.7%, is extremely excellent as high orientation undrawn yarn.Particularly be accompanied by declining to a great extent of limit slag, the silk spot also significantly improves.
Should high the orientation undrawn yarn, except that 130 ℃ of 90 ℃ of draft temperatures, 1.39 times of stretching ratios, heat fixation temperature, heat treatment similarly to Example 1 stretches.It is the advantageous property of 3.6cN/dtex, elongation 40%, boiling water shrinkage 9%, U%=0.7% that resulting drawn yarn has 67 dtexs, 36 threads, intensity.
The cross section of resulting polymer-alloy fibre shows that with the result of tem observation PLA (thin part) is the sea, and N6 (dense part) is the island structure on island.The several average diameters that obtain zone, N6 island are 55nm, and N6 is with the homodisperse polymer-alloy fibre of nano-scale.
Here the polymer-alloy fibre that obtains is carried out using alkali treatment after the circular knit similarly to Example 1, hydrolysis removes in the polymer-alloy fibre 99% or its above PLA.Obtain nanofiber aggregate thus.The filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 60nm (3 * 10
-5Dtex), reach the fineness that did not have originally.Filament fiber number deviation is very little.
The hydroscopicity (Δ MR) of the circular knit that this nanofiber aggregate constitutes reaches 6%, the expansion rate of water absorption of filament length degree direction is 7%.In addition, by the silk that this N6 nanofiber aggregate constitutes, intensity is 2.0cN/dtex, elongation 45%.In addition, be 3% at 140 ℃ dry-hot shrinkage.In addition, the result who this circular knit is implemented the polishing processing is to show to have unavailable super feel of original superfine fiber and the such lubricious liquor style of human skin.
Table 14
| Island number of regions average diameter (nm) | The island region difference | Intensity (cN/dtex) | U％ (％) | ||
| Area ratio (%) | Scope diameter range: area ratio | ||||
| Embodiment 48 embodiment 49 | 55 50 45 50 40 | 100 100 100 100 100 | 45～74nm：73％ 45～74nm：70％ 35～64nm：70％ 45～74nm：70％ 35～64nm：70％ | 3.6 1.2 1.4 1.3 1.3 | 0.7 2.0 2.0 2.0 2.0 |
Area ratio: the island regional diameter is in the area ratio of 1～100nm scope
Scope: be in the area ratio between the diameter difference 30nm.
Table 15
| The nanofiber number is average | The nanofiber deviation | Nanofiber intensity (cN/dtex) | |||
| Diameter (nm) | Fiber number (dtex) | Fiber number ratio (%) | Scope diameter range: fiber number ratio | ||
| Embodiment 48 embodiment 49 | 60 55 50 55 40 | 3×10 -5 3×10 -5 2×10 -5 3×10 -5 1×10 -5 | 99 100 100 100 100 | 55～84nm：70％ 45～74nm：70％ 45～74nm：70％ 45～74nm：70％ 35～64nm：70％ | 2.0 2.0 2.0 2.0 2.0 |
The fiber number ratio: filament number is in 1 * 10
-7～1 * 10
-4The fiber number ratio of dtex scope
Scope: be in the fiber number ratio between the diameter difference 30nm.
Embodiment 49
(copolymerization-PS), copolymerization PET containing ratio is that 20 weight %, melting temperature are beyond 235 ℃, carries out melting mixing similarly to Example 1, obtains b except adopting the copolymerization PET that uses among the embodiment 9 and the polystyrene of 2-ethylhexyl acrylate copolymerization 22%
*The polymer alloy of value=2.At this moment, copolymerization-PC was at 262 ℃, 121.6 seconds
-1Melt viscosity be 140Pas, at 245 ℃, 1216 seconds
-1Melt viscosity be 60Pas.
Except 260 ℃ of melt temperatures, spinning temperature 260 ℃ of (245 ℃ of nozzle surface temperatures), spinning speed 1200m/ divide, similarly to Example 1 this polymer alloy is carried out melt spinning.At this moment, as nozzle, use spinning nozzle similarly to Example 1, spinnability is good, and fracture of wire is 1 time during 1 ton of spinning.The single hole spray volume of this moment is the 1.15g/ branch.Therefore, resulting undrawn yarn adopts the hot plate of effective length 15cm to replace hot-rolling as thermal-curable system at 100 ℃ of draft temperatures, 2.49 times of stretching ratios, is 115 ℃ with heat curing temperature, and heat treatment similarly to Example 1 stretches.It is the character of 1.2cN/dtex, elongation 27%, U%=2.0% that resulting drawn yarn has 166 dtexs, 36 threads, intensity.
The cross section of resulting polymer-alloy fibre shows that with the result of tem observation copolymerization-PS is sea (a thin part), and copolymerization PET is the island structure of island (dense part).The several average diameters that obtain zone, copolymerization PET island are 50nm, and copolymerization PET is with the homodisperse polymer-alloy fibre of nano-scale.
The polymer-alloy fibre that obtains is carried out flooding with oxolane (THF) after the circular knit similarly to Example 1 stripping 99% or its above copolymerization-PS here as sea component.Obtain nanofiber aggregate by it.The filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 55nm (3 * 10
-5Dtex), reach the fineness that did not have originally.Filament fiber number deviation is very little.
In addition, this polymer-alloy fibre is carried out plying, make 10 special very much tow after, chop up into the long 2mm of fiber.Then, it is handled with THF, copolymerization-PS reaches nanofiberization by stripping.Paper is pulled an oar, copied to the THF solution ethanol that this nanofiber disperses after then water carries out solvent exchange,, obtains nonwoven fabric.Here the nonwoven fabric that obtains is the fabric that nanofiber is dispersed to the filament level.
Except adopting the copolymerization adopted among the PBT that uses among the embodiment 11 and the embodiment 49-PS), beyond 240 ℃ of the PBT containing ratio 20 weight %, melting temperature, carry out melting mixing similarly to Example 1, obtain b
*The polymer alloy sheet of value=2.
Except 260 ℃ of melt temperatures, spinning temperature 260 ℃ of (245 ℃ of nozzle surface temperatures), spinning speed 1200m/ divide, similarly to Example 1 this polymer alloy sheet is carried out melt spinning.At this moment, as nozzle, use spinning nozzle similarly to Example 1, spinnability is good, and fracture of wire is 1 time during 1 ton of spinning.The single hole spray volume of this moment is the 1.0g/ branch.Resulting undrawn yarn and embodiment 49 heat treatment that stretches equally.Resulting drawn yarn is that 161 dtexs, 36 threads, intensity are 1.4cN/dtex, elongation 33%, U%=2.0%.
The cross section of resulting polymer-alloy fibre shows that with the result of tem observation copolymerization-PS is sea (a thin part), and copolymerization PET is the island structure of island (dense part).The several average diameters that obtain zone, copolymerization PET island are 45nm, and copolymerization PET is with the homodisperse polymer-alloy fibre of nano-scale.
The polymer-alloy fibre that obtains is carried out flooding with trichloro-ethylene after the circular knit similarly to Example 1 stripping 99% or its above copolymerization-PS here as sea component.Obtain nanofiber aggregate by it.The filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 50nm (2 * 10
-5Dtex), reach the fineness that did not have originally.Filament fiber number deviation is very little.
Embodiment 51
(methyl methacrylate copolymer, melt viscosity are 110Pas to the copolymerization PS that makes except the chemical society of PTT and Nippon Steel that adopts use among the embodiment 12,262 ℃, 121.6 seconds for " エ ス チ レ Application (registration mark) ", KS-18
-1), the PTT containing ratio is that 20 weight %, melting temperature are beyond 240 ℃, carries out melting mixing similarly to Example 1, obtains b
*The polymer alloy sheet of value=2.In addition, this copolymerization PS was at 245 ℃, 1216 seconds
-1Melt viscosity be 76Pas.
Except 260 ℃ of melt temperatures, spinning temperature 260 ℃ of (245 ℃ of nozzle surface temperatures), spinning speed 1200m/ divide, carry out similarly to Example 1 it is carried out melt spinning.At this moment, as nozzle, use spinning nozzle shown in Figure 13 similarly to Example 1, promptly have the metering portion 12 of diameter 0.23mm on top, nozzle hole, ejection aperture 14 is that 2mm, squit hole long 13 are the spinning nozzle of 3mm.Spinnability is good, and fracture of wire is 1 time during 1 ton of spinning.The single hole spray volume of this moment is the 1.0g/ branch.The in addition plying of resulting undrawn yarn, make tow, it is stretched 2.6 times in 90 ℃ of hot baths, give machine crimp after, be cut into the long 51mm of fiber, separate fibre with carding machine after, make web with intersecting the web machine.Then, implement acupuncture, to make 300g/m
2Fiber complexing nonwoven fabric.Then, again nonwoven fabric being immersed in polyethers is that polyurethane is as the 13 weight % urethane compositions (being called for short PU) of main body and the N of 87 weight %, in the liquid that N '-dimethyl formamide (be called for short DMF) constitutes, washed after in the aqueous solution of the 40 weight % of DMF, PU being solidified.Then, this nonwoven fabric is carried out trichloro-ethylene handle,, obtain the nano-fiber structure of the about 1mm of thickness that constitutes by PTT nanofiber and PU by stripping copolymerization PS.Its one side is polished processing with sand paper, make thickness reach 0.8mm after, another side is handled with emery buff, forms nanofiber aggregate piloerection face, processes after dyeing again, obtains the artificial leather that imitation buckskin is transferred.Resulting artificial leather is compared with original artificial leather, has soft and fine and smooth more whippy excellent quality style.
Result with tem observation shows the cut staple cross section that obtains, and copolymerization-PS is sea (a thin part), and copolymerization PET is the island structure of island (dense part).The several average diameters that obtain zone, copolymerization PET island are 50nm, and copolymerization PET is with the homodisperse polymer-alloy fibre of nano-scale.In addition, these are that the filament fiber number is that 3.9 dtexs, intensity are 1.3cN/dtex, elongation 25%.
In addition, take a sample, this polymer-alloy fibre is carried out flooding with trichloro-ethylene after the circular knit similarly to Example 1, stripping 99% or its above copolymerization-PS as sea component from the silk that fiber is cut before cutting.Obtain nanofiber aggregate thus.The filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 55nm (3 * 10
-5Dtex), reach the fineness that did not have originally.Filament fiber number deviation is also very little.
Embodiment 52
Copolymerization-the PS, the PLA containing ratio that use among PLA that uses in adopting embodiment 48 and the embodiment 49 are 20 weight %, melting temperature are 215 ℃, to carry out melting mixing equally with embodiment 49, obtain b
*The polymer alloy sheet of value=2.
Except 230 ℃ of melt temperatures, spinning temperature 230 ℃ of (215 ℃ of nozzle surface temperatures), spinning speed 1200m/ divide, similarly to Example 1 it is carried out melt spinning.At this moment,, use ejection aperture 2mm, have the spinning nozzle of the metering portion of diameter 0.23mm on top, nozzle hole as nozzle.Spinnability is good, and fracture of wire is 1 time during 1 ton of spinning.The single hole spray volume of this moment is the 0.7g/ branch.Resulting undrawn yarn and embodiment 49 heat treatment that stretches equally.The drawn yarn that must obtain is that 111 dtexs, 36 monofilament, intensity are that 1.3cN/dtex, elongation are 35%, U%=2.0%.
Resulting polymer-alloy fibre cross section shows that with the result of tem observation copolymerization-PS is sea (a thin part), and PLA is the island structure of island (dense part).The several average diameters that obtain zone, PLA island are 40nm, and PLA is with the homodisperse polymer-alloy fibre of nano-scale.
After the polymer-alloy fibre that obtains like this and embodiment 49 carried out circular knit equally, with the trichloro-ethylene dipping, stripping as the copolymerization-PS of sea component 99% or more than it.Obtain nanofiber aggregate by it, the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 40nm (1 * 10
-5Dtex), reach sufficient fineness.Filament fiber number deviation is also very little.
Embodiment 53
The circular knit 5g that nanofiber aggregate constituted that makes among the embodiment 48, in 110 ℃ of dryings 1 hour, dipping is 2 hours in the treatment fluid of following composition, make nanofiber aggregate fully flood dimethoxydiphenylsilane, after handling cloth and silk and fully washing with pure water, in 140 ℃ of curing 3 minutes, make in nanofiber aggregate inside and make the dimethoxydiphenylsilane polymerization.It is carried out home washings 10 times, and in 110 ℃ of dryings 1 hour, the result of gravimetry was, compared with untreated, and weight increases by 38%.Therefore, the composite material of diphenyl silicone that can obtain on nanofiber aggregate load, the washing resistance of diphenyl silicone might as well.
The composition of treatment fluid:
Dimethoxydiphenylsilane: 100ml
Pure water: 100ml
Ethanol: 300ml
10% hydrochloric acid: 50
Embodiment 54
The knitted fabric that the PBT nanofiber aggregate that embodiment 50 is made constitutes, the natural oil composition that absorption is extracted from shark liver, i.e. absorption has the squalene of skin effect because of preserving moisture.The treatment conditions of this moment are mixtures of squalene 60% and emulsifying dispersant 40%, and the concentration that rises with 7.5g/ is dispersed in the water, and bath raio is 1: 40, and temperature is 130 ℃, and the processing time is 60 minutes.Handle the back in 80 ℃ of washings 2 hours, the squalene of this moment reaches 21 weight % to the adhesion amount of cloth and silk.Then, the squalene adhesion amount of implementing after the home washings 20 times is 12 weight %, shows sufficient washing resistance.
The circular knitted fabric that the PBT nanofiber aggregate that adopts this process squalene to process is made is made socks, and dry serious subject 10 people carry out 1 all wearing tests with heel, and the result is that dry skin mitigator has 8 people.Can think that the squalene that nanofiber aggregate captures slowly extracts out by subject's sweat, due to skin contacts.
Embodiment 55
Except the N6 containing ratio is set at 35%, carry out melt spinning equally with embodiment 48, obtain the high orientation of the N6/PLA polymer alloy undrawn yarn of 400 dtexs, 144 threads.This high orientation undrawn yarn and embodiment 48 heat treatment that stretches equally.Resulting drawn yarn shows the good characteristic of 288 dtexs, 96 threads, intensity 3.6cN/dtex, elongation 40%, boiling water shrinkage 9%, U%=0.7%.
The cross section of resulting polymer-alloy fibre shows with the result of tem observation, PLA is sea (a thin part), N6 is the island structure of island (dense part), and the several average diameters that obtain zone, N6 island are 63nm, and N6 is with the homodisperse polymer-alloy fibre of nano-scale.With its overfeeding 15%, and carry out air with the N6 false twist yarn of 165 dtexs of other preparation, 96 threads and mix and knit.In addition, mix the weak twist of knitting enforcement 300 commentaries on classics/m in the silk, adopt S sth. made by twisting/Z to twist with the fingers mariages, make 2/2 TWILL CLOTH as organizine and tram at this.Resulting TWILL CLOTH is carried out alkali treatment equally with embodiment 48, obtains paying 150g/m by the order that the N6 nanofiber constitutes
2The curtain grey cloth.This curtain with grey cloth in the N6 nanofiber be in the position that coats the false low bank between fields processing of common N6 silk, nanofiber mainly exposes on fabric face.In addition, the filament fiber number deviation of nanofiber, the result who resolves similarly to Example 1 are that several average single fiber diameters of nanofiber reach 67nm (4 * 10
-5Dtex), reach the fineness that did not have originally.In addition, the filament fiber number is in 1 * 10
-7～1 * 10
-4The filament fiber number ratio of dtex scope reaches 82%, and particularly to be in the filament fiber number ratio between 55～84nm be 60% to single fiber diameter, and the deviation of filament fiber number is especially little.In addition, the intensity of N6 nanofiber is that 2.0cN/dtex, elongation are 40%.
In addition, this curtain grey cloth and the embodiment 35 same results that implement silicone-treated are shown very thin feel and the such mixed quality style of profit of human skin.In addition, also has contact coldness.In addition, its hydroscopicity (Δ MR) is 4%, shows sufficient hygroscopicity, and the result who carries out the olfactory test that disappears of acetic acid reduces to 1ppm with 10 minutes concentration from 100ppm, shows to have the good smelly property that disappears.In addition, adopt this blank to make curtain, hang 6 straw mattress results within doors and can obtain salubrious indoor environment, in addition, can also prevent dewfall.The Washing net that this curtain is put into the home washings machine washs and dewaters and also do not deform, and shows good DIMENSIONAL STABILITY.
The possibility of utilizing on the industry
Adopt nanofiber aggregate of the present invention, can obtain cloth and silk that common super extra fine filament be can not see, before this unexistent liquor style and high-performance abrasive cloth.
The fiber construct that contains nanofiber aggregate of the present invention can be as the intermediate of silk, cotton (cotton), packing material, fabric, knitted fabric, felt, nonwoven, artificial leather, sheet material etc. In addition, as dress material, the dress material material, the interior decoration goods, the in-built goods of vehicle, life material (cloth for wiping or dusting, cosmetic product, health products, toy etc.) etc. life purposes, or, Environmental Industry material product (building materials, abrasive cloth, filter cloth, harmful substance is removed goods etc.), or IT parts (sensor element, battery component, automatic device part etc.), and medical articles (blood filter, extracorporeal circulation column, scaffold (scaffold), hinder with dressing (wound dressing)), artificial blood vessel, the fibres such as medicament sustained release are preferred.
Claims (51)
1. nanofiber aggregate, it counts the average single fiber fiber number is 1 * 10
-7～2 * 10
-4Dtex, fiber number ratio are that filamentary filament fiber number more than 60% or 60% is 1 * 10
-7～2 * 10
-4The dtex scope, and constitute by thermoplastic polymer.
2. nanofiber aggregate as claimed in claim 1, it is long fiber shape and/or weaving filament shape.
3. nanofiber aggregate as claimed in claim 1, wherein, number average single fiber fiber number is 1 * 10
-7～1 * 10
-4Dtex, fiber number ratio are that filamentary filament fiber number more than 60% or 60% is 1 * 10
-7～1 * 10
-4The dtex scope.
4. nanofiber aggregate as claimed in claim 1 wherein, constitutes in the filament of nanofiber aggregate, and the fiber number ratio is the filament more than 50% or 50%, and it is wide that its fibre diameter difference is in 30nm.
5. nanofiber aggregate as claimed in claim 1, wherein, thermoplastic polymer is the polycondensation base polymer.
6. nanofiber aggregate as claimed in claim 1, wherein, the fusing point of thermoplastic polymer is 160 ℃ or more than it.
7. nanofiber aggregate as claimed in claim 1, wherein, thermoplastic polymer is selected from polyester, polyamide and polyolefin.
8. nanofiber aggregate as claimed in claim 1, its intensity are 1cN/dtex or more than it.
9. nanofiber aggregate as claimed in claim 1, its water absorption rate is more than 4% or 4%.
10. nanofiber aggregate as claimed in claim 1, wherein, the expansion rate of water absorption of filament length degree direction is more than 5% or 5%.
11. nanofiber aggregate as claimed in claim 1 wherein, contains functional medicine.
12. a fiber construct wherein, contains the described nanofiber aggregate of claim 1.
13. fiber construct as claimed in claim 12, wherein, it is 20～2000g/m that the order of fiber is paid
2
14. fiber construct as claimed in claim 12, wherein, the hollow part of the air silk of nanofiber aggregate is by encapsulated.
15. fiber construct as claimed in claim 14, wherein, air silk exists a plurality of diameter 100nm or the pore below it at length direction.
16. fiber construct as claimed in claim 12 wherein, contains functional medicine.
17. fiber construct as claimed in claim 12, wherein, fiber construct is selected from silk, cotton, packing material, fabric, knitted fabric, felt, nonwoven fabric, artificial leather, sheet material.
18. fiber construct as claimed in claim 17, wherein, fiber construct is to contain the nonwoven fabric of nanofiber aggregate and the lamination nonwoven fabric of other nonwoven fabric laminate.
19. fiber construct as claimed in claim 12, wherein, fiber construct is the fibre that is selected from dress goods, life material, environment industry material product, IT parts and medical articles in dress material, dress material material, interior decoration goods, the vehicle.
20. the liquid dispersion of the described nanofiber aggregate of claim 1.
21. polymer-alloy fibre, wherein, have by the different island structure that organic polymer constitutes more than 2 kinds or 2 kinds of dissolubility, island component is made of easy dissolubility polymer difficult dissolubility polymer, sea component, several average diameters in zone, island are 1～150nm, area than be 60% or the diameter in its above zone, island be 1～150nm size, and island component is dispersed into strip.
22. polymer-alloy fibre as claimed in claim 21, wherein, several average diameters in zone, island are 1～100nm, area than be 60% or the diameter in its above zone, island be 1～100nm size.
23. polymer-alloy fibre as claimed in claim 21, wherein, in the contained zone, island of polymer-alloy fibre, area than be 60% or the diameter difference in its above zone, island be in the 30nm scope.
24. polymer-alloy fibre as claimed in claim 21, wherein, the island component containing ratio is 10～30 weight % of whole fibers.
25. polymer-alloy fibre as claimed in claim 21, wherein, sea component is made of diffluent polymer in aqueous alkali or hot water.
26. polymer-alloy fibre as claimed in claim 21, wherein, the fusing point of island component is 160 ℃ or more than it.
27. a polymer-alloy fibre, it is described polymer alloy of claim 21 and the polymer-bonded composite fibre that forms beyond it.
28. polymer-alloy fibre as claimed in claim 21 wherein, is 20% or more than it as the CR value of the index of curl characteristics, or crispation number is 5/25mm or 5/more than the 25mm.
29. polymer-alloy fibre as claimed in claim 21, wherein, the Wu Site spot is below 5% or 5%.
30. polymer-alloy fibre as claimed in claim 21, wherein, intensity is 1.0cN/dtex or more than it.
31. a fiber construct wherein, contains the described polymer-alloy fibre of claim 21.
32. fiber construct as claimed in claim 31, wherein, fiber construct is selected from silk, cotton, packing material, fabric, knitted fabric, felt, nonwoven fabric, artificial leather, sheet material.
33. fiber construct as claimed in claim 31 wherein, contains polymer-alloy fibre and fiber in addition thereof.
34. fiber construct as claimed in claim 31, wherein, fiber construct is the fibre that is selected from dress goods, life material, environment industry material product, IT parts and medical articles in dress material, dress material material, interior decoration goods, the vehicle.
35. the manufacture method of a polymer-alloy fibre, the polymer alloy that obtains difficult dissolubility polymer and easy dissolubility polymer melt are mixed carries out melt spinning, it is characterized in that, satisfies the condition of following (1)～(3):
(1) difficult dissolubility polymer with after easily the dissolubility polymer independently measures respectively, supplies with kneading device independently and carry out melting mixing;
(2) containing ratio of the difficult dissolubility polymer in the polymer alloy is in 10～50 weight % scopes;
(3) easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, and perhaps easily the fusing point of dissolubility polymer is in the scope of difficult dissolubility melting point polymer-20～+ 20 ℃.
36. the manufacture method of polymer-alloy fibre as claimed in claim 35 wherein, is extruded mixing roll with twin shaft and is carried out melting mixing, and the kneading part length that twin shaft is extruded mixing roll is 20～40% of screw rod effective length.
37. the manufacture method of polymer-alloy fibre as claimed in claim 35 wherein, is carried out melting mixing with static mixing roll, and cutting apart of static mixing roll counted more than 1,000,000 or 1,000,000.
38. the manufacture method of polymer-alloy fibre as claimed in claim 35, wherein, the stress of cutting off between the nozzle hole wall of melt spinning and the polymer is 0.2MPa or below the 0.2MPa.
39. polymer alloy particle, wherein, have by 2 kinds of different island structures that organic polymer constitutes of dissolubility, island component is made of easy dissolubility polymer difficult dissolubility polymer, sea component, and, easily the melt viscosity of dissolubility polymer is 100Pas or below the 100Pas, and perhaps easily the fusing point of dissolubility polymer is in the scope of difficult dissolubility melting point polymer-20～+ 20 ℃.
40. an organic/inorganic blended fiber wherein, contain described nanofiber aggregate 5～95 weight % of claim 1, and at least a portion of this inorganic matter is present in the inside of nanofiber aggregate.
41. a fiber construct wherein, contains the described organic/inorganic blended fiber of claim 40.
42. the manufacture method of the described organic/inorganic blended fiber of claim 40 wherein, is immersed in inorganic monomer in the nanofiber aggregate, makes the inorganic monomer polymerization then.
43. the manufacture method of fiber construct as claimed in claim 41 wherein, is immersed in inorganic monomer in the fiber construct that contains nanofiber aggregate, makes the inorganic monomer polymerization then.
44. the manufacture method of a blended fiber, wherein, organic monomer is immersed in the described nanofiber aggregate of claim 1 after, make this organic monomer polymerization.
45. the manufacture method of a fiber construct, wherein, organic monomer is immersed in the described fiber construct of claim 12 after, make this organic monomer polymerization.
46. a porous fibre, wherein, 90 weight % of composition or be to be made of inorganic matter more than it have a plurality of pores at length direction, and the several average pore diameter in the section of short-axis direction are 1～100nm.
47. a fiber construct wherein, contains the described porous fibre of claim 46.
48. the manufacture method of a porous fibre wherein, from inorganic monomer is immersed in the nanofiber aggregate, makes the inorganic monomer polymerization then and removes nanofiber in the organic/inorganic blended fiber that obtains, obtains the described porous fibre of claim 46.
49. the manufacture method of a fiber construct, wherein, from the structure that contains the organic/inorganic blended fiber, remove nanofiber, obtain the described fiber construct of claim 47, the described structure that contains the organic/inorganic blended fiber makes the inorganic monomer polymerization obtain by inorganic monomer being immersed in the fiber construct that contains nanofiber aggregate then.
50. the manufacture method of a nonwoven fabric, wherein, the described polymer-alloy fibre of claim 21 is cut into the long 10mm of fiber or below it after, the easy dissolubility polymer of stripping is copied paper without temporary transient drying then.
51. the manufacture method of a nonwoven fabric, wherein, form contain the nonwoven fabric or felt of the described polymer-alloy fibre of claim 21 after, behind the substrate bonding that constitutes this nonwoven fabric or felt with by difficult dissolubility polymer, make the stripping of easy dissolubility polymer.
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|---|---|---|---|---|
| WO1984003470A1 (en) * | 1983-03-03 | 1984-09-13 | Toray Industries | Crossed polymer laminate, and process and apparatus for its production |
| JPH01282390A (en) * | 1988-05-06 | 1989-11-14 | Toray Ind Inc | Ultra-fine ion-exchange fiber and production thereof |
| JP2002173308A (en) * | 2000-12-04 | 2002-06-21 | Mitsubishi Chemicals Corp | Carbon nano-tube |
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