CN1097101C - Microporous fibers - Google Patents

Microporous fibers Download PDF

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Publication number
CN1097101C
CN1097101C CN97196669A CN97196669A CN1097101C CN 1097101 C CN1097101 C CN 1097101C CN 97196669 A CN97196669 A CN 97196669A CN 97196669 A CN97196669 A CN 97196669A CN 1097101 C CN1097101 C CN 1097101C
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CN
China
Prior art keywords
fiber
micropore
less
hole
fibre
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CN97196669A
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Chinese (zh)
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CN1226292A (en
Inventor
F·－J·蔡
V·A·托波尔卡雷夫
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Kimberly Clark Worldwide Inc
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Priority claimed from US08/697,993 external-priority patent/US5766760A/en
Application filed by Kimberly Clark Worldwide Inc filed Critical Kimberly Clark Worldwide Inc
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure

Abstract

A porous fiber (54) includes a distinctive configuration of voids (52) therein to achieve advantageous levels of wettability, liquid penetration and mechanical properties. The fiber has a denier of not more than about 50, and a percent elongation at break of not less than about 30 %. The fiber can also have a tensile strength at break of not less than about 200 MPa.

Description

Microporous fibre
Invention field
The present invention relates to fiber, or rather, what the present invention relates to is synthesizing porous fiber, and this fiber is wettable and it has the mechanical property of improvement.
Background of invention
Porous fibre has the structure by using some traditional phase disengagement methods to make.These methods generally include mixes fluoropolymer resin with diluent or plasticizer, polymer solution cooled off to cause to be separated in a kind of liquid medium, stays a kind of crosslinked loose structure thereby rinse out diluent then.Produced the porous fibre of other type by some technology of using blowing agent or swelling agent to produce microcellular structure.Produced the other porous material by using a kind of environmental cracking technology (environmental crazing technique).
Traditional porous fibre, for example above-mentioned porous fibre can not provide the combination property of the accessibility of required mechanical property and water.In addition, above-mentioned prior art can not satisfy produce have minor diameter, low dawn number, high wettable, to the fiber of the combination property of the high osmosis of liquid and high-tensile strength.Therefore, all need to have the fiber of the loose structure that has improved always.
Summary of the invention
In general, the invention provides a kind of distinguished porous fibre, this fiber comprises some holes, thereby obtains the wettable and the permeability for liquids of desired degree, and still has good mechanical property.Fiber can have the dawn number that is not more than about 50 dawn and be not less than about 30% elongation at break.This fiber also can have the fracture tensile strength that is not less than about 200Mpa.
In its different situations, porous fibre of the present invention can be effectively and have the ability to produce have small size, the fiber of the required combination property of high wettable, high water accessibility, high-tensile strength and high elongation rate.Therefore, this fiber can have further processing with the improvement that forms supatex fabric and other fabricated product ability.
The accompanying drawing summary
Consult the following the detailed description and the accompanying drawings of the present invention, will understand the present invention more fully, and some other advantage also will become more clear, wherein:
Fig. 1 is the one scan electron micrograph with the 850x magnifying power, and it has represented a schematic sectional view of porous fibre of the present invention;
Fig. 2 is the one scan electron micrograph with the 1700x magnifying power, and its expression is shown in the enlarged drawing of the part of Fig. 1 middle section;
Fig. 3 is the one scan electron micrograph with the 250x magnifying power, and it has represented to include a schematic sectional view of the prior art fiber in a chamber;
Fig. 4 is the one scan electron micrograph with the 8000x magnifying power, its expression be cross section shown in Figure 3 at enlarged drawing adjacent to a position of fiber outer surface;
Fig. 5 is the one scan electron micrograph with the 250x magnifying power, and it has represented to include a schematic sectional view of another prior art fiber in a chamber, and this fiber is produced by incrementally stretched technology gradually;
Fig. 6 is the one scan electron micrograph with the 5000x magnifying power, and its expression is shown in the enlarged drawing of the part of Fig. 5 middle section;
Fig. 7 is a light micrograph that obtains with the magnifying power of 1500x according to the oil immersion light microscope, the schematic diagram of the hole in its expression porous fibre of the present invention surface and the volume;
Fig. 8 is a light micrograph that obtains with the 1500x magnifying power according to the oil immersion light microscope, and it has been represented along the surface of porous fibre of the present invention and another view of the hole in its volume;
Fig. 9 represented with 3, the magnifying power of 000x and the hole schematic diagram along another porous fibre outer surface of the present invention that obtains;
Fig. 9 A has represented to be shown in the schematic diagram in special hole among Fig. 9 typically;
Figure 10 is with 15, the magnifying power of 000x and the one scan electron micrograph that obtains, and it provides the schematic diagram on the surface of fiber shown in Figure 3;
Figure 11 is with 15, the magnifying power of 000x and the one scan electron micrograph that obtains, and it provides the schematic diagram on the surface of fiber shown in Figure 5;
Figure 12 is with 5, the magnifying power of 000x and the back scattered electron microphoto that obtains, and it has represented the schematic cross-section of fiber of the present invention;
Figure 13 has represented a kind of exemplary variations of Figure 12, is the usefulness of graphical analysis, and it is digitized;
Figure 14 has represented according to gain in weight curve map with time relationship of the suction of a porous fibre sample.
Detailed Description Of The Invention
Consult Fig. 1,2,7,8,9,9A and 12, porous fibre 20 comprise a longitudinal direction size 44 and an overall cross direction dimension 38. Porous fibre has hole or the hole 22 of special shape, thereby obtains wettable, permeability for liquids and other liquid accessibility of required degree. This fiber can have and is not more than every fiber Denier (d) of about 50 and is not less than about 30% desirable elongation at break. This fiber also can have the fracture tensile strength that is not less than about 200MPa. In special circumstances more of the present invention, porous fibre 54 also can comprise the other characteristic, and can comprise hole and the hole with special shape, size, distribution and structure.
In its different situations, the inside that microporous fibre of the present invention can be incorporated into water or other liquid fibre quickly to be improving wicking, and can the accelerate dissolution motion for will being confirmed as flushable fibre. In addition, microporous fibre can help to guarantee to improve the absorbability of liquid, improves the distribution of liquid, improves the gas permeability of goods such as surgery long gown and diaper, improves feel and aesthetic property, and/or improves biodegradability. This fiber is with traditional formation technique, and example as is known spunbond process can be formed directly in and is non-woven webs. On the other hand, fiber can be cut into short fiber, and can mix with other fiber, uses subsequently traditional air lay technology to form non-woven webs. Above-mentioned non-woven webs especially can be used for producing flushable personal care product, diaper for example, tampon, the liner that the women uses, trousers linings (pantiliners), tampon band and similar products.
In deformed configuration more of the present invention, porous fibre 54 can be a kind of synthetic fiber of being produced by original material, and its original material comprises that a kind of thermoplasticity can be orientated material, for example thermoplasticity and orientable polymer, copolymer, admixture, mixture, other composition of compound and its.Be preferably, thermoplastic does not comprise high reactive group.
In concrete schemes more of the present invention, original material can be a kind of polyolefine material.For example, original material can comprise polyethylene or polyacrylic homopolymers, maybe can comprise ethene and polyacrylic copolymer.In the other scheme, original material can comprise other polymeric material, polyethers for example, copolyether, polyamide, copolyamide, polyester, copolyesters, and copolymer, admixture, mixture and other composition.
Thermoplastic can be melted processing, and in concrete condition of the present invention, and material can have and is not less than/10 minutes melt flow rate (MFR) value (based on ASTM D1238-L) of about 1 gram.Perhaps, the MFR value can be not less than about 10 grams/10 minutes, and alternatively, the MFR value can be not less than 20 grams/10 minutes.In others of the present invention, the MFR value can be not more than 200 grams/10 minutes.Perhaps, the MFR value can be not more than about 100 grams/10 minutes, and alternatively it is not more than about 40 grams/10 minutes, so that the processability of required degree to be provided.
The thermoplastic of this melt-processable for example can be provided by a kind of homopolymer polypropylene.Commercially available polyolefin, for example Himont PF301, PF304 and PF305, Exxon PP3445, Shell Polymer E5D47 also are some suitable examples of material.The material that other is suitable can comprise for example random copolymer, as a kind of random copolymer that contains propylene and ethene (for example, containing the Exxon 9355 of 3.5% ethene), and homopolymers, as homopolymer polyethylene, it has similar above-mentioned MFR value.Fluoropolymer resin can contain treatment additive (0.05 to 5 part of additive was than 100 fens resins according to appointment) in a small amount, and its additive for example is calcium stearate or other acid clarifier.Other additive can comprise, silicon diol copolymer for example, organo-silicon compound, olefin type elastomer and molecular weight alkanes or other lubricating additive.Also can add various additives of pigments.Condensed pigment for example, as the TiO 2 pigment concentrate with low-molecular-weight polyethylene plasticizer can be used as a kind of treatment additive.Various additives can have a kind of plasticization effect, can improve the brute force and the pliability of fiber, and can help extruding, fibre spinning and/or scratching process.
The original material that is used for fiber 54 also can comprise other auxiliary material, and auxiliary material can comprise a kind of packing material, and/or surfactant or other surface active material.Packing material can be a kind of microparticle material, and it can help to provide triggering porous (porosity-initiating), the node of loosening, thereby the ideal that strengthens the hole during putting on the various stretched operations of fiber is shaped.Packing material helps to provide a kind of fiber of desirable surface modification, and can help to strengthen a kind of desirable " sliding effect " that produces during stretched operation subsequently.In addition, packing material helps to remain on the hole that produces during the various stretched operations.
Auxiliary material described here comprise a kind of surface active material, as surfactant, or having other material (as silicone oil) of low-surface-energy, surface active material can help to reduce the surface energy of fiber, and provides lubricated in the polymer segment that forms fiber.The surface energy that reduces helps to produce " sliding effect " with lubricating in stretched operation subsequently.
Auxiliary packing material can be organic or inorganic, and packing material is preferably with form independent, discrete particles.Filler can carry out surface treatment with various coating and surfactant, thereby give to the fluoropolymer resin in the original material with affinity, to reduce agglomeration, improve filler and disperse, and provide and fluid, as the controllable interaction of body fluid, blood or water.Some examples of inorganic filler can comprise metal oxide, and the hydroxide of metal, carbide and sulfate.Other suitable inorganic filler material can comprise for example calcium carbonate, various clays, silica, alumina, barium sulfate, sodium carbonate, talcum, magnesium carbonate, magnesium sulfate, brium carbonate, potter's clay, mica, carbon, calcium oxide, magnesia, aluminium hydroxide, titanium dioxide, granulated metal, glass microsphere, or contain the particulate of hole hole.The other inorganic filler can comprise the particulate with high aspect ratio, potter's clay for example, and mica and wollastonite, but such filler may have less effect.Exemplary organic filler can comprise for example pulp powder, wooden powder, cellulose derivative, chitin, the particle of chitosan power, high crystalline powder, high molten polymer, high cross-linked polymer, organosilicon powder or the like, and their composition and derivative.
Of the present invention concrete aspect, filler can have average particle size, it is not more than 10 microns (μ m).Perhaps, average particle size is not more than 5 μ m, and alternatively, it is not more than 1 μ m, improves machinability to reach.In others of the present invention, the particle size of top cut (top cut) is for being not more than 25 μ m, in addition, the particle size of its top cut can be and is not more than 10 μ m, and alternatively, it is not more than 4 μ m, so that provide its machinability during the fiber with desired size and loose structure forms.Filler also can improve the surface as stearic acid Huo behenic acid by adding surfactant and/or other material, and it can be used to improve the machinability of original material.
Some examples that are suitable for the filler material comprise following one or more.
(1) Dupont R-101 TiO 2, it can obtain from de Nemous E.1.Dupont
Get, and provide with the form of concentrate by Standrich Color company,
It is at Social Circle, and Georgia30279 maintains an office.This material
Good machinability can be provided.
(2) pigment orchid (Pigment Blue) 15: 1 (10% bronze medal), it passes through
Standridge Color company dispensing.With the fiber of this manufacture of materials usually
Can fracture.
(3) OMYACARB UF CaCO 3, it can be from OMYA, Inc. obtains, it
Proctor, Vermont 05765 maintains an office.This material can have approximately
The top cut particle size of 4 μ m and the average particle size of about 0.7 μ m, and
And can provide good machinability.With original material 56 combination or chemical combination it
Before, this filler can be with a kind of surfactant such as Dow Corning 193
Surfactant-coated.Also available other the suitable surface-activity of this filler
Agent, other locates described surfactant-coated as the present invention.
(4) be coated with stearic OMYACARB UFT CaCO 3, it can be from OMYA, Inc
Obtain.This material can have the top cut particle size peace treaty of about 4 μ m
0.7 the average particle size of μ m, and can provide good machinability.
(5) SUPERCOAT TMCaCO 3, it can obtain from international ECC, it
Atlanta, Georgia 30342,5775 Peachtree-Dunwoody Road are provided with
Office.This material can have the top cut particle size of about 8 μ m and about 1 μ m's
Average particle size.Fiber with this manufacture of materials usually can rupture.
(6) Powdered poly dimethyl silsesquioxane (polydimethyl
Silsesquioxane) (#22 or #23 Dow Corning additive), it can
Obtain from Dow Corning, it is at Midland, and Michigan 48628-0997 establishes
Office is arranged.This material can provide good machinability, but can be observed some knot
Piece.
Auxiliary material selectively comprise a kind of surface active material, have the material (as silicone oil) of low-surface-energy as a kind of surfactant or other.Of the present invention concrete aspect in, surfactant or other surface active material can have a hydrophilic-lipophilic balance (HLB) numerical value, this numerical value is not more than about 18.Perhaps, it is about 16 that HLB numerical value is not more than, and alternatively it is not more than about 15.In another aspect of this invention, HLB numerical value is not less than about 6.Perhaps, it is about 7 that HLB numerical value is not less than, and alternatively HLB numerical value is not less than about 12.When HLB numerical value was too low, it had not enough wettable, and HLB numerical value is when too high, and surfactant can not be enough to be attached on the polymeric matrix of original material, and is very easy to during use wash off.The HLB numerical value of commercially available surfactant can for example known among nineteen ninety-five McCUTCHEON ' s the 2nd volume " functional material " (Functional Materials).
Suitable surfactant can comprise the silicon glycol copolymer, carbonylation fat alcohol ethoxyl compound, various ethoxylation ethanol, ethoxylated alkylphenol, ethoxylated fat ester etc., and their composition.Other suitable surfactant for example can comprise following one or more:
(1) surfactant that constitutes by ethoxylated alkylphenol.As IGEPAL RC-
620，RC-630，CA-620，630，720，C0-530，610，630，
660,710 and 730, these can obtain from Rhone-Poulenc, it
Cranbury, New Jersey maintains an office.
(2) surfactant that is made of the silicon glycol copolymer is as Dow Corning
D190, D193, FF400, and D1315, they can obtain from Dow Corning,
It is at Midland, and Michigan maintains an office.
(3) surfactant that constitutes by single glyceride of ethoxylation and double glyceride, as
Mazel 80, MGK, and Masil SF 19 and Mazel 165c, they can be from PPG
Industry obtains, and it maintains an office at Gurnee 1L 60031.
(4) surfactant that is made of ethoxylation ethanol is as Genapol 26-L-
98N, Genapol 26-L-60N and Genapol 26-L-5, they can from
Hoechst Celanese company obtains, and it is at Charoltte, and NC28217 establishes
Office is arranged.
(5) surfactant that constitutes by the hydroxylating fat alcohol ethoxyl compound, as
Marlowet 4700 and Marlowet 4703, they can be from Huls Americal
Lnc. obtain, it is at Piscataway, and NJ 08854 maintains an office.
(6) ethoxylated fat ester, as Pationic 138c, Pationic 122A,
With Pationic SSL, they can obtain from R.I.T.A company, it
Woodstock.1L60098 maintains an office.
The original material that is used for porous fibre 54 can comprise that percentage by weight is no less than the auxiliary material of about 0.35wt% (percentage by weight), and its percentage by weight is according to the gross weight of the original material that is combined and definite.Of the present invention concrete aspect in, the amount of auxiliary material is not less than about 0.5wt%, preferably is at least about 1wt%.Perhaps, the amount of auxiliary material is no less than about 5wt%, and alternatively is no less than about 10wt%.In others of the present invention, the amount of auxiliary material can reach about 50wt% or more.The amount of auxiliary material preferably is not more than about 30wt%.Perhaps, the amount of auxiliary material is for being not more than about 20wt%, and alternatively is not more than about 15wt%, so that desirable machinability characteristic is provided.
Of the present invention concrete aspect in, original material can comprise much filler materials of about 0.35wt% of percentage by weight.Of the present invention concrete aspect in, the amount of filler material is no less than 0.5wt% (percentage by weight).Perhaps, the amount of filler material is no less than about 1wt%, and alternatively it is no less than about 5wt%.In others of the present invention, the amount of filler material can reach about 50wt% or more.The preferably no more than about 30wt% of the amount of packing material.Perhaps, the amount of filler material is no more than 20wt%, and its no more than about 10wt% alternatively.
In others of the present invention, auxiliary material comprise a kind of surface active material, and the amount of surface active material such as surfactant can be at least about 0.1wt%.Perhaps, the quantity of surface active material is at least about 1wt%, and alternatively is at least about 3wt%.In others of the present invention, the no more than about 20wt% of the amount of surface active material.Perhaps, the no more than about 15wt% of the amount of surface active material, and its no more than about 10wt% alternatively.
The suitable technique that is used to form porous fibre 54 is disclosed in the u.s. patent application serial number No.08/697 that is proposed on September 4th, 1996 by people such as F.J.Tsai, in 996, its exercise question is " being used to make the method and apparatus with the porous fibre that improves characteristic " (" METHODAND APPARATUS FOR MAKING MICROPOROUS FIBERS WITH IMPROVEDPROPERTIES "), (agent No, 12,242), its whole contents is introduced into as a reference in corresponding to it (not having contradiction) mode at this.
Traditional porous fibre wherein usually includes some cavitys.Each cavity generally has the hole of a perforating fiber material tubular body, as illustrating in Fig. 3 and 5.Therefore, cavity generally provides a kind of hollow fibre, and wherein the diameter ratio in the external diameter of tubular body and hole can be in 50: 1 to 50: 48 scope.Fiber with cavity is normally fulsome for manufacturing industry, and when fiber at full speed and it is easy to produce undesirable flat contracting when processed.In addition, such fiber has had unsuitable mechanical strength property, makes further processing fiber form particularly difficulty of supatex fabric like this.
But, in fact porous fibre 54 of the present invention does not have cavity.Therefore, during fiber formed, fiber can show the increase of melt strength.Bigger melt strength can improve the online spinnability and the draftability of fiber.For example, can adopt simple wire drawing die structure, to form as-spun fibre.Porous fibre can also have the mechanical strength of raising, thereby the DIMENSIONAL STABILITY that is enhanced is provided, and can also have the mechanical property that other is enhanced, so that the processing subsequently of fiber.For example, the mechanical property that is enhanced can be improved the ability that further processing fiber comes the production nonwoven fabric web.In its various situations, porous fibre 54 also can show the following combination property that is enhanced, i.e. minor diameter, low dawn number, TENSILE STRENGTH, (the toughness here is the ability of absorption energy, as is described in " fiber and textile technology dictionary " (Dictionary of Fiber ﹠amp for percentage elongation and toughness; Textile Technology), HoechstCelanese, 1990).
The porous fibre 54 of different shape can have relatively little diameter and relative little dawn number.In aspect concrete, porous fibre can have and is not more than about 50 fiber Denier.Perhaps, porous fibre dawn number is about 20 for being not more than, and selectively is to be not more than about 10.In others, porous fibre can have about 0.5 dawn or littler dawn number, and alternatively can have about 0.1 dawn or littler dawn number, so that the performance that is enhanced is provided.
In others, the fracture tensile strength of porous fibre 54 is for being not less than about 200 megapascal (MPa)s (Mpa).Perhaps, TENSILE STRENGTH is for being not less than about 250MPa, and alternatively it is not less than about 300MPa.In others, method and apparatus of the present invention can provide the tensile strength of fiber that is not more than about 1000 megapascal (MPa)s (MPa).Perhaps, tensile strength of fiber is to be not more than about 750MPa, and alternatively it is not more than about 450MPa, so that the characteristic and the machinability of improvement are provided in process operation subsequently.
In others, porous fibre 54 can present and is not less than about 30% elongation at break, determines as following formula: (L f-L i)/L iL in the formula fFinal lengths when being fibrous fracture, L iIt is the initial length of fiber before the elongation.Perhaps, it is about 50% that elongation at break is not less than, and alternatively be not less than about 90%.In others, the elongation at break that the porous fibre 54 that method and apparatus of the present invention provides can present reaches about 500% or bigger.Perhaps, elongation at break is about 200% for being not more than, and alternatively be not more than about 160% so that desirable operation characteristic and working ability are provided.
In others of the present invention, the toughness index that porous fibre 54 can have for be not less than about 0.1 gram-centimeter/dawn-centimetre (g-cm/d-cm).Perhaps, tenacity of fibre is for being not less than about 1.5g-cm/d-cm, and alternatively it is not less than about 2g-cm/d-cm.On the other hand, the present invention's porous fibre 54 that can provide has the toughness index that is not more than about 20g-cm/d-cm.Perhaps, the tenacity of fibre index is not more than about 10g-cm/d-cm, and alternatively it is not more than about 5g-cm/d-cm, so that the characteristic of improvement is provided.Toughness index represent fiber to absorb can ability, and determine by following manner, that is: toughness of fibre multiply by the fibrous fracture percentage elongation, then divided by 2.For example, general calculating formula be (load during fracture restrains number * elongation at break)/(dawn number * 2), and unit is (gram-centimeter)/(dawn-centimetre).
Further describe in the chapters and sections of following test procedure for the experimental technique that obtains to adopt in order to each mechanical property desired data of determining porous fibre.
Porous fibre 54 can advantageously provide the water accessibility of improvement.Of the present invention concrete aspect in, the water absorption rate of porous fibre 54 can be not less than about 0.1mg/sec (milli Grams Per Second).Perhaps, water absorption rate can be not less than about 0.15mg/sec, and alternatively its water absorption rate is not less than about 0.2mg/sec.In others, water absorption rate can be not more than about 15mg/sec.Perhaps, water absorption rate can be not more than about 5mg/sec, and selectively is that its water absorption rate can be not more than about 1.5mg/sec, so that the effect of improvement is provided.Comparatively speaking, nonporous fiber will have the water absorption rate less than 0.1mg/sec, as being illustrated by following embodiment 8,9 and 10.
In addition, the water absorption of porous fibre 54 is to be no less than 0.1mg in 60 seconds.Perhaps, water absorption is to be no less than about 0.2mg in 60 seconds, and alternatively is no less than about 0.3mg in its 60 seconds.In others, water absorption is no more than about 25mg in 60 seconds.Perhaps, water absorption is no more than about 5mg in 60 seconds, and no more than about 2.5mg in its 60 seconds alternatively is so that provide the effect of improvement.Comparatively speaking, nonporous fiber will have the water absorption that is less than 0.1mg in 60 seconds.As illustrating by following embodiment 8,9 and 10.
To further describe in following test procedure chapters and sections for the experimental technique that adopts in order to the various water accessibility characteristic desired datas of determining porous fibre.
Some holes or hole 52 that desirable porosity is imparted on the fiber 54 can distribute on the outer surface of fiber.And also can be distributed in fibrous inside.In aspect concrete, the loose structure of fiber 54 comprises the elongated porosity of overall elliptoid elongated porosity and/or bipyramid shape, as Fig. 7,8,9 and 9A in illustrate.Be preferably, slot crack 52 has its major axis 46 along the longitudinal size 44 on the fibre length direction.Of the present invention concrete aspect in, the slot crack can have a major axis 46, wherein the length 42 of major axis is not less than about 0.1 μ m.Perhaps, long axis length is not less than about 0.2 μ m, and alternatively it is not less than about 0.25 μ m.In others, the length of major axis is not more than about 30 μ m.Perhaps, long axis length 42 is not more than about 10 μ m, and alternatively is not more than about 7 μ m, so that the performance of improvement is provided.
For helping to provide the combination property of desirable mechanical strength and water accessibility, aspect porous fibre of the present invention concrete in, the hole of desired aperture size will be formed with about 30% of total hole number at least on its fiber outer surface or fiber cross section.Perhaps, total hole number that the hole of desirable aperture size forms on its fiber outer surface or fiber cross section at least about 50%, and alternatively form about 60% at least.
In the others of porous fibre of the present invention, the hole of long axis length in the 0.25-10 mu m range is formed with about 30% of total hole number at least on its fiber outer surface or fiber cross section.Perhaps, the hole of 0.25-10 μ m aperture size is formed with the about 50% of total hole number at least on fiber outer surface or fiber cross section, and alternatively forms at least and have an appointment 60%, so that the mechanical property and the water accessibility of improvement are provided.
Slot or hole also have ratio in length and breadth, it is determined by following relationship, that is: the ratio of the length 42 of the major axis 48 in hole and the length 40 of minor axis 46, its minor axis perpendicular alignmnet major axis is as can be observed in the microphoto that is used for measuring aspect ratio or other imaging or measuring mechanism.In others of the present invention, it is about 1.5 that aspect ratio is not less than, and alternatively be not less than about 2.In others, aspect ratio is not more than about 50.Perhaps, it is about 20 that aspect ratio is not more than, and alternatively be not more than about 15 so that the porosity characteristics and the fibre property of improvement are provided.The major axis of each elongated hole or hole is normally roughly along the axis of the alignment of fiber longitudinal size, and generally can measure and represented by the longest dimension in each hole.
As at Fig. 7,8,9 and 9A in illustrate, the loose structure of fiber 54 can have the hole that distributes along the fiber outer surface.Surface holes has a distribution, and promptly the hole count of per unit exterior surface area is no less than 0.01/ μ m 2Perhaps, the hole count of per unit exterior surface area is no less than about 0.015/ μ m 2, and alternatively it is no less than 0.05/ μ m 2In others, the hole count of per unit exterior surface area is no more than about 10/ μ m 2Perhaps, the hole count of per unit exterior surface area is no more than about 8/ μ m 2, and its no more than about 5/ μ m alternatively 2, so that the wettable and the permeability for liquids of improvement are provided.
As at Fig. 1, shown in 2,12 and 13, with respect to the cross-sectional area of fiber 54, loose structure of the present invention can present average hole area (every hole) and be no less than 0.001 μ m 2Hole.Perhaps, average hole area (every hole) is no less than about 0.002 μ m 2, and alternatively be no less than about 0.03 μ m 2In others, average hole area (every hole) is no more than about 20 μ m 2Perhaps, the average no more than about 10 μ m of hole area (every hole) 2, and its no more than about 3 μ m alternatively 2, so that the wettable and the permeability for liquids of improvement can be provided.
The loose structure of fiber 54 also can have the hole that distributes along its cross-sectional area, is no less than about 0.01/ μ m so that provide 2The per unit area hole count.Perhaps, the per unit area hole count is no less than about 0.015/ μ m 2, and alternatively it is no less than 0.1/ μ m 2In others, the no more than about 10/ μ m of per unit area hole count 2Perhaps, the no more than about 8/ μ m of per unit area hole count 2, and its no more than about 5/ μ m alternatively 2, so that the wettable and the permeability for liquids of improvement are provided.
In others, the loose structure of fiber 54 has the hole that distributes along fiber cross section, the summation of the area in hole wherein independent, that be broken away provides a total hole area, and this total hole area is no less than about 0.1% (hole area percentage is no less than about 0.1%) by the gross area that fiber surrounded that is broken away.Perhaps, it is about 1% that hole area percentage is no less than, and alternatively it is no less than about 2%.In others, hole area percentage is no more than about 70%.Perhaps hole area percentage is no more than about 50%, and alternatively it is no more than about 20%, so that the wettable and the permeability for liquids of improvement are provided.
With reference to figure 1,2,9,9A and 12, the concrete aspect of porous fibre can comprise some mainly due to the structural scrambling of fibrous material or other physics anisotropism and the hole or the hole that cause, these holes or hole are stretched thus and are expanded.The structural anisotropism of this initator can be provided by in the following mechanism one or more: particulate filler/fluoropolymer resin interface, the modulus fluctuation of density and/or fibrous material, ultra-fine hole and/or air bubble, field trash with modulus different and/or density and any kind, and the combination of these mechanism with fibrous material.Especially, fiber can be desirable comprises the hole that some are stretched or otherwise are expanded, and wherein each hole is relevant with the particulate initator 50 that is provided by a kind of material, and this material is made of as particles filled thing material many independent particulates.
Hole or hole basically can be around initators or can be directly adjacent to initator.The hole also can be arranged in the zone between each independent initator.Therefore, each hole that is expanded can have a length, and this length is greater than the length of the initator that is associated with it, can see when the hole observed on the fibre length profile direction.With regard to regard to the direction of fibre length, hole can have an elongated basically elliptical shape, and/or can have a kind of profile of bipyramid basically, and this bipyramid appearance has the taperer of two bases facing to the base.With regard to the cross section perpendicular to fibre length, hole can have substantially spherical or an ellipse or an egg type slightly.Aspect microporous fibre of the present invention concrete, on the surface view of fiber or other vertical figure, do not see the special floral designs in hole or regularly arranged basically.On the other hand, in the schematic cross section of fiber, do not see the special floral designs of hole or regularly arranged basically.Therefore, the arrangement of apertures in the fibrous material can be irregular, and can be have some random troop basically at random.For example, can so be clustered in bunch collection zone of any filler material that is added into.The viewed structure of porous fibre of the present invention can have wide pore size distribution on the certain cross section of fiber, this be because the distribution in the hole that disperses and along the variation in hole on the fibre length, gradually thin cross section character causes.The elongated shape of hole (as ellipse or bipyramid shape) and do not have the special distribution of pores pattern can be microporous fibre structure of the present invention with the porous fibre that obtains distinguishes significantly by its drawing process drawing process of increase gradually of CELGARD microporous fibre (as be used to produce) by phase disengagement method or its.
With 15, in the exterior view of the CELGARD fiber of 000x magnifying power, as illustrating among Figure 11, oval substantially or similar OBL many micropores are arranged in roughly rectangular along the substantitally planar micropore zone of aliging on the direction perpendicular to fibre length.Rectangular some ranks that further are arranged in these micropore zones, wherein rectangular with approximate periodic, clocklike form occurs.
Referring to Fig. 3,4 and 10, the porous fibre that is obtained by traditional phase disengagement method includes the hole of being separated by relative thin-walled or the similar sponge system of hole.This system combinations becomes lacelike interconnection structure, and it defines the hole that has similar membrane wall.Shown in configuration in, this system has formed some adjacent to the macroporous layer of the finger-like in doughnut chamber.Especially providing a kind of along the arrangement of apertures of fiber cross section is well-regulated arrangement basically.Referring to Figure 10,15, under the magnifying power of 000x, what fiber surface manifested basically is atresia.
On the contrary, the concrete aspect of porous fibre of the present invention can comprise some by the hole that elongated region defined that tensile stress causes, wherein said zone is provided by the plastic deformation in the fibrous material.Stress area can be observed along the interface edge that fiber exposes the surface pore of the prolongation on the outmost surface at least.In porous fibre of the present invention, to become sharp angles to limit basically non-fibrous and non-basically spongy presenting in the zone of extending the elongation hole for the edge interface of fibrous material and perimeter.Therefore, hole is defined effectively by the fibrous material with this interface edge, and these interface edge can be along any or all surface view, cross-sectional view or the overall diagram of fiber and observe.Fibrous material between hole in the viewed zone has the form of the straight portion that is disconnected by hole usually.
Be further described in the chapters and sections of following test procedure for the appropriate technology that adopts in order to the desired data of determining various hole dimension characteristics of porous fibre and pore size distribution situation. Test procedure Mechanical property:
The technology that adapts that is used for the mechanical property of definite porous fibre 54 can be used Sintech tension test instrument (SINTECH 1/D) and Testworks 3.03 softwares.The tension test instrument is a kind of device that can obtain from MTS System company, and it is at Cary, and Nc 27513 maintains an office.Software can obtain from the Sintech Divison of MTS System company, and it is at Cary, and NC27513 maintains an office.Also can use equipment and software with basic identical function.
Mechanical property can utilize the tension test instrument to measure by the test fiber shape.Test is implemented with 10 pounds of (44.5N) load transducers with by air operated, the anchor clamps that are coated with 3 inches (7.6cm) rubber.Fiber test is implemented with 2 inches (5.08cm) gauge lengths and 500.00mm/ branch crosshead speed.The single sample fiber to be being loaded perpendicular to anchor clamps and in the position at anchor clamps center, and is secured in place when air pressure closes anchor clamps to abut against its fiber of a time-out.Before tension test begins, import fibre diameter by the user.For the hollow fibre sample, as be shown in fiber in example 11 and 12, use the ring section area to come tensile strength calculated, promptly annulus area is π ((external diameter) 2-(internal diameter) 2).In each experiment, fiber is stretched up to producing fracture, and device software or miscellaneous equipment program form the stress and strain curve and calculate the desired mechanical property of sample.For example, mechanical property can comprise Young's modulus, fracture strength, strain rate (%) or elongation at break.The accessibility of water
The appropriate technology of accessibility that is used to measure the comparison water of fiber can use CAHN DCA322 microbalance, and it is can (the said firm is at Madison for Analytical Technology, Inc) a kind of device of Huo Deing, and WI maintains an office from ATI.This balance can be to only being that the variation of the power of 0.1 microgram produces reaction, and two weighing locations (" A " and " B " encircles) and bare weight position (" C " ring ") are housed." A " encircles the maximum loads that can bear 1.5 grams and the loads that " B " ring can bear 3.5 grams.Therefore, A ring has preferably sensitiveness and the B ring can support than heavy duty.Should will appreciate that operating personnel will select better measurement sensitiveness can be provided but also maintenance can be measured the ring of desired maximum load at duration of test.The string proof test that is used for said example carries out according to balance " A " ring.Each fiber sample has enough length (15mm according to appointment), thus make fiber can be practically along and pasting the suspension line or the similar supporter that are used to provide test specimen and fastening or fix with other method with band.In test specimen, the fiber sample that is fixed that the Support Level of a 5mm length is adjacent with it extends under band and keeps exposing and can reaching with water contacting at test period.
The CAHN system comprises a movably platform, and this platform can be with speed translation up and down stably.Specimen hangs over or is installed in the balance on the selected ring with other method, and the switch of water is arranged on movably on the platform.This platform be raised so that the lower limb of sample just in time on the surface of water, and test beginning.The software that the CAHN system is housed is controlled test according to the parameter of user's input.For fiber test, specimen is contained on the balance, and balance is by taring, so as when sample to contact with water the energy measurement water absorption.Software is instructed to the reading of the power of collecting at interval with 1 second.The long exposed parts of the 2mm of specimen is immersed in the water, and platform is braked.When software was collected the reading of power at interval with 1 second, specimen was placed in the water 1 minute.Then specimen is pulled out outside the water.
The data of collecting from test are organized subsequently.Particularly, data can be output in the corresponding expansion sheet software, as Microsoft Excel version 5.0, and processed form to immerse the weight in 1 minute and the curve of time in the water.This curve shows the suction trend of specimen, and the basis of providing convenience for the relative water absorbing properties of more different fiber samples and relative water accessibility.Comparing in order to have preferably between the sample of different size fiber, for different samples, is standard and by nominalization as the drawn data of the weight gain of the function of time with the fiber with 0.0416mg weight.The nominal factor is the dry weight of tested fiber and the ratio of 0.0416mg.Water absorption rate be with in the time in 1 minute immersion cycle by draw through the weight gain of nominalization and past tense curve that the area of a room is formed two second time mark measure.Be illustrated in water absorption rate in the example and be to be recorded in the 1st second of DATA REASONING and measure, as in Figure 14, schematically showing at the slope of data point place curve plotting by calculating.The water absorption of listing in example is to measure total weight weightening finish of 1 minute (60 seconds) record in data and curves.Should will notice that the weight gain that is measured to and is recorded can comprise owing to the weight gain that is absorbed into the water in the initial apertures structure, and because the weight gain that other interaction causes between fiber and the water.For example, the coating of water can be formed on the fiber.In addition, have the hole that increases pore space for providing, fibre structure can be heaved, and perhaps for acquisition being provided and holding the increase capacity that is absorbed water, fiber can change shape with other method. Scanning electronic microscope and graphical analysis
Electron micrograph can be made by the known conventional art in image technology field.In addition, be used for required imaging by using known traditional preparation process technology can prepare some samples.
Even extend, therefore when for the fiber cross section imaging being cut off and when preparing fiber sample, importantly will being avoided making undue the bluring of fibrous material because porous fibre of the present invention also can be very easy to distortion at low temperatures.In a kind of suitable technology of preparing, for example sample can be immersed in the ethanol 1 hour and be immersed in the liquid nitrogen subsequently.For fiber cross section, the surface can prepare by the low temperature microtomy, for example uses to have FCS low temperature cut-out system (Leica, Deerfield, IL) Reichert Ultracut S microscopy cutter wherein adopts a new-type glass cutter of 6mm under-180 ℃ of temperature.Resulting fiber is fixed on the approximate stub then and is coated with gold or Au/Pd (gold/palladium).Microstructure fiber is by scanning electronic microscope, for example use JSM6400 with auxiliary and back scattered electron detector (JEOL, Peabody, MA) scanning electronic microscope and can imaging.
The automation graphical analysis of hole and fiber holes can be implemented by known conventional art.Some examples of these technology are described among " for the microscopical application of the autoelectrinic of single particulate analysis " (" APPLICATION OF AUTOMATED ELECRON MICROSCOPYTO INDIVIDUAL PARTICLE ANALYSIS "), the author is the breadboard Marks.Germani of the U.S., and it is published by international scientific communication company (International CommunicationsInc.); With in " particulate analysis introduction automatically " (" INTRODUCTI ON TO AUTOMATEDPARTICLE ANALYSIS "), the author is a T.B.Vander Wood (copyright 1994, MVA.Inc., 550 Oakbrook Parkawy #200, Norcross, GA 30093), 52 annual meetings of U.S. microscope association, G.W.Bailey and A.J.Garratt-Reed edit, and are published by San Francisco Press..
Provide the graphical analysis of pore size distribution data to be undertaken by material analysis mechanism (Material Analytical Services) for example 1, it is the laboratory that maintains an office at Norcross.GA.For example 4 provides the graphical analysis of pore size distribution data is by MVA, and Inc. carries out, and it is at Norcross, the laboratory that GA maintains an office.
For example, various graphical analysiss can be with 5, and the Noran Voyager ias of 000x magnifying power is finished.Data adopt the average of 12 scanning total amounts to obtain.Said system can be from NORAN Instrument, and Inc. obtains, and it is at Middleton, and WI maintains an office, and also can use the basic system that equates performance that provides.During the graphical analysis process, the image of loose structure can use conventional art to be digitized.The example of a digitized picture is shown among Figure 13. Light microscope
In order to observe along the microstructure of porous fibre outer surface, light microscope is a kind of appropriate technology.Especially can use traditional immersion oil light microscope.Utilize this technology, prepare in 23 ℃ of following refractive indexes (Nd) are 1.516 immersion oil by sample being placed on a kind of on the glass slides part, and this sample is capped slip.Immersion oil is a kind of oil that can obtain from OLYMPUSOPTICAL CO.LTD, and it is at Lake Success, and NY. maintains an office also can use and has basic other light microscope and the equipment that equates performance.
Following example is for reaching the purpose of understood in detail more to the present invention.These examples are exemplary and are not to be used for limiting specially scope of the present invention. Example 1
A kind of by polypropylene (Himont PF301) (90wt%) and TiO 2The resin that filler particulate (by the SCC4837 of Standridge Color Corporation) (10wt%) constitutes mixes with Dow Corning D193 surfactant (based on the 6wt% of filler and total resin weight) by twice extruded laboratory Haake twin (double) screw extruder excessively.TiO 2The size range of particulate is about 0.1 to 0.5 μ m, as measuring by scanning electronic microscope (SEM).The density of filler is measured by the ashes analysis.Surfactant D ow CorningD193 has HLB several 12.2.Fiber spinning process comprises being fed in the feed hopper and material being pressed through to have the single-screw extrusion machine that draw ratio is 24 (L/D=24/1) to mixed material.This extruder has 3 thermals treatment zone, a measuring pump, and an online static mixer and have the filament spinning component in 4 holes, wherein the diameter in each hole is 0.3mm.During the fibre spinning extruding, the draw ratio that fiber will stand is 40.Between the fiber cold snap, as-spun fibre utilizes the first surface active liquid by pre-humidifying, and this surface-activity liquid applies mould through metering and carries.The first surface active liquid is a kind of solution that is made of with the mixed of 9 fens isopropyl alcohols and 1 part of water (by volume) isopropyl alcohol and water.Fiber stretches with the 2x extensibility in air subsequently, is that 1.7x stretches with the draw ratio in the bath that is provided by second kind of surface-activity liquid then.Second kind of surface-activity liquid is a kind of solution of being made up of isopropyl alcohol and water, and this solution is that the volume ratio with 9 parts of isopropyl alcohols and 1 part of water mixes.Then fiber before being accumulated to spooler by with 80 ℃ of HEAT SETTING.The mechanical property of final porous fibre is measured by Sintech tension test instrument subsequently, and is summarised in following table 1 and 2.Every μ m in the fiber cross section 2Hole count be about 0.74, and the every μ m of outer surface 2Hole count be about 0.08. Example 2
A kind of by polypropylene 95.3% (Himont PF301), 1.4%TiO 2The resin that the organic filler of siliceous half oxidation of Powdered poly dimethyl (Dow Corning #23Additive) of concentrated inorganic filler (by the SCC4837 of Standridge Color Corporation) and 3.3wt% is formed mixes through twice silicon ethylene glycol surfactant with 6wt% (based on resin and filler gross weight) of laboratory Haake twin (double) screw extruder extruding.The particle size scope of organic filler is 1 to 5 μ m, as being recorded by SEM.Composite material is extruded by a single-screw extrusion machine (L/D=24/1), and this extruder comprises 3 thermals treatment zone, an online static mixer, and a measuring pump and a filament spinning component with 4 holes, the diameter in this each hole is 0.3mm.During the fibre spinning extruding, the draw ratio that fiber stands is 33.Between the fiber cold snap, as-spun fibre utilizes first kind of surface activity liquid and by pre-humidifying, and this surface activity liquid applies mould through a metering and carries.First kind of surface-activity liquid is a kind of solution that is made of the surfactant that accounts for 2wt% in the isopropanol solvent (IGEPAL RC-630).Described solvent is to be mixed by the volume ratio with 9 parts of isopropyl alcohols and 1 part of water.Fiber draw ratio with 1.17x in air stretches then, and stretches with the 2X draw ratio in the bath of second kind of surface-activity liquid subsequently.Second kind of surface-activity liquid is a kind ofly to be formed by isopropyl alcohol and the water mixed with 9 parts of isopropyl alcohols and 1 part of water (by volume).Then fiber before gathering spooler in an online baking oven under 85 ℃ by HEAT SETTING.The mechanical property of porous fibre is recorded by the Sintech tester for elongation, and is summarised in down in the tabulation 1. Example 3
A kind of by 93.2wt% polypropylene (Himont PF301), 1.4wt%TiO 2Concentrate (by the SCC4837 of Standridge Color Corporation) and 5.4w%CaCO 3The resin that (by the Omyacarb UF of Omya Inc.) constitutes, its silicon ethylene glycol D193 surfactant that utilizes 6wt% (based on the weight of filler) are by surface modification, and this resin is mixed mutually through twice of laboratory Haake twin (double) screw extruder extruding.CaCO 3The particle size scope of filler is 1 to 3 μ m, as recording by SEM.Composite material is extruded by a single-screw extrusion machine (L/D=24/1) then, and this screw extruder comprises an online static mixer, a measuring pump and a filament spinning component with 8 holes, and wherein the diameter in each hole is 0.3mm.During the spinning extruding, the draw ratio that fiber stands is 33.Between the fiber cold snap, as-spun fibre utilizes first kind of surface-activity liquid by preliminary wetting, and this first surface active liquid applies mould by a metering and carries.First kind of surface-activity liquid is a kind of solution that is mixed with the volume ratio of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber extensibility with 1.17x in air stretches then, and then the extensibility with 2x stretches in the bath of second kind of quantitative surface-activity liquid.Second kind of surface-activity liquid is the solution that is made of the IGEPAL RC-630 that accounts for 1wt% in the isopropanol solvent.Its solvent is to be mixed by isopropyl alcohol and the water volume ratio with 9 parts of isopropyl alcohols and 1 part of water.Then fiber before gathering spooler under 80 ℃ by HEAT SETTING.The mechanical property of porous fibre records by Sintech tension test instrument subsequently, and is summarised in the following table 1. Example 4
A kind of by 88.8wt% polypropylene (Himont PF301), 1.3wt%TiO 2Concentrate (by the SCC 4837 of Standridge Color Corporation) and 9.9wt%CaCO 3(by Omya, Inc. the resin of Zu Chenging Omyacarb UF), its utilize 6wt% (based on the weight of filler) silicon ethylene glycol D193 surfactant and by surface modification, and this resin twice of chamber Haake twin (double) screw extruder extruding and being mixed mutually by experiment.CaCO 3The scope of particle size be 1 to 3 μ m, as recording by SEM.Mixed material is extruded then by this extruder of a single-screw extrusion machine (L/D=24/1) and comprises 3 thermals treatment zone, an online static mixer, and a measuring pump and a filament spinning component with 15 holes, wherein every bore dia is 0.5mm.In extrusion spinning operating period, the draw ratio that fiber will experience is 40.Between cold snap, as-spun fibre utilizes first kind of surface-activity liquid by pre-humidifying, and its surface-activity liquid applies mould by a metering and carries.First kind of surface-activity liquid is the mixture of isopropyl alcohol and water, and their volume ratio is 9.8 parts isopropyl alcohol and 0.2 part water.Fiber draw ratio with 1.5x in air is stretched then, and then the draw ratio with 1.4x stretches in the bath of second kind of quantitative surface-activity liquid.Second kind of surface-activity liquid is to be mixed with 9 parts the isopropyl alcohol and the volume ratio of 1 part of water by isopropyl alcohol and water.Fiber, then forms case by a fiber web and collects 90 ℃ of following HEAT SETTING with an online baking oven subsequently.The mechanical property of porous fibre is measured by the Sintech tester for elongation then, and is summarised in following table 1 and 2, the every μ m of fiber cross section 2Hole count be about 0.19. Example 5
A kind of by polypropylene (Himont PF301) (90wt%) and TiO 2Resin that filling particulate (by the SCC 4837 of Standridge Color Corporation) (10wt%) is formed and Dow Corning D193 surfactant (6wt% is based on the gross weight of filler and resin) chamber Haake twin (double) screw extruder by experiment push twice and are mixed mutually.TiO 2The particle size scope is 0.1 to 0.5 μ m, as recording by scanning electronic microscope (SEM).The density of filler is measured by the ashes analysis.Surfactant D ow Corning D193 has 12.2 HLB number.Fiber spinning process comprises mixed material is fed in the hopper and by a single-screw extrusion machine and pushes this material that the draw ratio that this extruder has is 24 (L/D=24/1).This extruder has 3 thermals treatment zone, a measuring pump, and an online static mixer and a filament spinning component with 4 holes, wherein the diameter in each hole is 0.3mm.During the fibre spinning extruding, the draw ratio that fiber will experience is 11.Between the fiber cold snap, as-spun fibre utilizes first kind of surface-activity liquid by pre-humidifying, and its surface-activity liquid applies mould by a metering and carries.First kind of surface-activity liquid is a kind of solution that is mixed with the ratio (by volume) of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber extensibility with 1.58x in air is stretched then, and then the extensibility with 2.2x stretches in the bath of second kind of surface-activity liquid.Second kind of surface-activity liquid is a kind of solution that is mixed with the volume ratio of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber then before accumulating in spooler 80 ℃ of following HEAT SETTING.The mechanical property of comprehensive porous fibre is measured by the Sintech tester for elongation subsequently, and is summarized in down in the tabulation 1. Example 6
A kind of by polypropylene (Himont PF301) (90wt%) and TiO 2Twice extruding of chamber Haake twin (double) screw extruder and mutually mixing by experiment of resin that filler particulate (by the SCC 4837 of Standridge Color Corporation) (10wt%) is formed and Dow Corning D193 surfactant (6wt% is based on the gross weight of filler and resin).TiO 2The particulate scope is 0.1 to 0.5 μ m, as measuring by scanning electronic microscope (SEM).Filler density is measured by the ashes analysis.Surfactant D ow Corning D193 has 12.2 HLB numerical value.Fiber spinning process comprises and mixed material being fed in the feed hopper and by a single-screw extrusion machine extrded material, the draw ratio that this extruder has is 24 (L/D=24/1).Extruder has 3 thermals treatment zone, a measuring pump, and an online static mixer and a filament spinning component with 4 holes, the diameter in its each hole is 0.3mm.During the spinning extruding of fiber, the draw ratio that fiber will stand is 11.Between the fiber cold snap, as-spun fibre utilizes first kind of surface-activity liquid and by pre-humidifying, and its surface-activity liquid applies mould by a metering and carries.First kind of surface-activity liquid is a kind of solution that is mixed with the ratio (by volume) of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber extensibility with 1.17x in air is stretched then, and then the extensibility with 1.5x is stretched in the bath of second kind of surface-activity liquid.Second kind of surface-activity liquid is a kind of solution that is mixed with the volume ratio of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber then before gathering spooler under 80 ℃ by HEAT SETTING.The mechanical property of final porous fibre is subsequently by the Sintech tester for elongation and measured, and is summarised in down and tabulates in 1. Example 7
A kind of by polypropylene (Himont PF301) (90wt%) and TiO 2Resin that filler particulate (by the SCC 4837 of Standridge Color Corparation) (10wt%) is formed and Dow Corning D193 surfactant (6wt% is based on the gross weight of filler and resin) chamber Haake twin (double) screw extruder by experiment push twice and are mixed mutually.TiO 2The particle size scope is 0.1 to 0.5 μ m, as measuring by scanning electronic microscope (SEM).The density of filler is measured by the ashes analysis.The HLB numerical value of surfactant D ow Corning D193 tool 12.2.Fiber spinning process comprises being fed in the feed hopper and material being pressed through to have the single-screw extrusion machine that draw ratio is 24 (L/D=24/1) to mixed material.Extruder has 3 thermals treatment zone, a measuring pump, and an online static mixer and have the filament spinning component in 4 holes, wherein the diameter in each hole is 0.3mm.During the fibre spinning extruding, fiber will be subjected to 33 draw ratio.Between the fiber cold snap, as-spun fibre utilizes first kind of surface activity liquid by pre-humidifying, and this surface-activity liquid applies mould by a metering and carries.First kind of surface-activity liquid is a kind of solution that is mixed in the ratio (specific volume) of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber extensibility with 1.17x in air is stretched then, and then the extensibility with 1.5x stretches in the bath of second kind of surface activity liquid.Second kind of surface activity liquid is a kind of solution that is mixed with the volume ratio of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.Fiber subsequently before gathering spooler under 80 ℃ by HEAT SETTING.The mechanical property of final porous fibre is measured by a kind of Sintech tester for elongation, and is summarised in down in the tabulation 1. Example 8
A kind of by polypropylene (Himont PF301) (90wt%) and TiO 2Resin that the little material of filler (by the SCC 4837 of Standrige Color Corporation) (10wt%) is formed and Dow Corning D193 surfactant (6wt% is based on the gross weight of filler and resin) chamber twin (double) screw extruder by experiment push twice and mix mutually.TiO 2The particle size scope is 0.1 to 0.5 μ m, measures as state electron microscope (SEM) by scanning.The density of filler is measured by the ashes analysis.Surfactant D ow Corning D193 has 12.2 HLB numerical value.Fiber spinning process comprises mixed material is fed in the feed hopper and this material is pressed through one to have the single-screw extrusion machine that draw ratio is 24 (L/D=24/1).Extruder has 3 thermals treatment zone, a measuring pump, and an online static mixer and a filament spinning component with 4 holes, wherein the diameter in each hole is 0.3mm.During the fibre spinning extruding, fiber is able to freely fall.Between the fiber cold snap, as-spun fibre utilizes surface activity liquid by pre-humidifying, and this surface activity liquid applies mould by a metering and carries.Surface-activity liquid is a kind of solution that is mixed with the volume ratio of 9 parts of isopropyl alcohols and 1 part of water by isopropyl alcohol and water.The mechanical property of final porous fibre is measured by the Sintech tester for elongation, and is summarised in the following table 1. Example 9
This sample is made of commercially available polypropene staple, and it can obtain from U.S. Barmag, and it is at Charlotte, and North Carolina maintains an office.Staple fibre has the fibre length of 38mm, and before test in the following manner by surface modification, it was immersed in the solution that accounts for 10wt% hydrophily silicon ethylene glycol in the acetone 1 hour, and before test 50 ℃ dry 6 hours down.The characteristic of fiber determined and be summarised in down the tabulation 1 in. Example 10
This sample is made of commercially available polypropene staple, and its fibre length is 38mm, and can obtain from U.S. Barmag, and it is at Charlotte, and North Carolina maintains an office.The characteristic of fiber is tested to be made and is summarised in down in the tabulation 1. Example 11
This sample is a kind of traditional porous fibre that obtains from Asahi Medical Co.Ltd, and it is at Tokyo, and Japan has office.As be shown schematically in Fig. 3, in 4 and 10, fiber have one along fibre length by the fibrous inside tubular wall extending therebetween.What can be sure of is that loose structure in the illustrational fiber produces by the solvent spinning technology, and its cavity shape can contact the introducing of coagulating liq along the inside and outside surface of fibrous material with as-spun fibre.Its structure has the hole of some big finger-like in the fiber inwall, and has the lacelike hole of similar sponge profile near outer wall.In addition, general fiber has a thin top layer at its outer surface, and it can stop water to be penetrated in the fiber.The characteristic of fiber measured and be summarized in down the tabulation 1 in. Example 12
This sample is another kind of traditional porous fibre, and its trade name is the CELGARD of HoechstCelanese company, and the said firm is at Charlotte, and North Carolina maintains an office.As be shown schematically in Fig. 5, in 6 and 11, fiber has vertical cavity, and what can be sure of is that the loose structure of fiber is to produce by the technology of using some increment stretching step.As directed cross-sectional view, this structure comprises the structure of a similar stratiform, it produces inner stratiform volume and generates in pre-crystalline texture.In this structure, the hole includes some microfibers, and it is orientated on the longitudinal direction of fiber, and the coupling part is made up of stacked thin layer.The characteristic of fiber measured and be summarized in down the tabulation 1 in. Example 13
This sample is a kind of microporous polypropylene fibers, and it is illustrated in the U.S.P.4 that is had by AlbanyInternationt, and in 550,123 the example 1, the said firm is at Msfield, and MA maintains an office.According to the description of example 1 in this patent, fiber has the dawn number at 8.8 dawn.Other property column of fiber under tabulate in 1.
Table 1
Instance number No. Water absorption rate (milli Grams Per Second) Water absorption rate (milli Grams Per Minute) Fracture tensile strength (MPa) Elongation at break (%) Fiber size Toughness index (gram-centimeter/dawn-centimetre)
1 0.79 1.2 427 157 4.7d 4.2
2 0.58 1.1 391 111 5.7d 2.7
3 0.84 1.5 310 95 5.8d 1.8
4 0.89 1.3 358 150 1.8d 3.3
5 1.01 1.8 295 119 16d 2.2
6 0.67 1.4 231 168 18d 2.4
7 0.21 0.3 251 183 5.6d 2.9
8 0.014 0.015 47 966 68d 2.8
9 0.02 0.25 220 55 2.8d 0.75
10 0.002 0.005 362 60 2.8d 1.30
11 -- -- 8.4 10.1 300 μm 0.003
12 -- -- 51 207 300 μm 0.65
13 -- -- 217 23 8.8d 0.30
The present invention has carried out quite detailed description, and is apparent, can make various changes and modifications and do not break away from spirit of the present invention.All these changes and improvements all fall within the scope of the invention, in the defined scope of claims.

Claims (20)

1. porous fibre, this fiber comprises the fibrous material with some elongated micropores, described micropore be formed on the packing material expansion from be included in described fibrous material and the fibrous material that trails in, described fiber has:
Be not more than the dawn number at 50 dawn;
Be not less than 30% elongation at break;
Be not less than the fracture tensile strength of 200MPa;
Being distributed with on the outer surface of described fiber and being evenly distributed density is the individual micropore of every square micron 0.01-10.
2. according to the fiber of claim 1, it is characterized in that its dawn number of described fiber was not more than for 20 dawn.
3. according to the fiber of claim 1, its special sheet is that its dawn number of described fiber was not less than for 10 dawn.
4. according to the fiber of claim 1, it is characterized in that described fiber has and is not less than 50% elongation at break.
5. according to the fiber of claim 1, it is characterized in that described fiber has and is not less than 90% elongation at break.
6. according to the fiber of claim 1, it is characterized in that described micropore comprises surface micropore, it is distributed on the outer surface of described fiber brokenly.
7. according to the fiber of claim 1, it is characterized in that described micropore comprises the random micropore that is distributed on the fibre section.
8. according to the fiber of claim 1, it is characterized in that described fiber comprises the micropore of some elongated shapes.
9. fiber according to Claim 8 is characterized in that, described fiber comprises that some totally are the micropore of elliptical shape.
10. fiber according to Claim 8 is characterized in that, described elongated micropore has along the major axis of the longitudinal direction substantial alignment of described fiber.
11. fiber according to Claim 8 is characterized in that, described elongated micropore has the major axis that its length is not less than 0.1 μ m.
12. fiber according to Claim 8 is characterized in that, described elongated micropore has the major axis that its length is not more than 30 μ m.
13. the fiber according to claim 6 is characterized in that, described micropore has and is not less than 0.01 micropore/μ m 2Outer surface be evenly distributed density.
14. the fiber according to claim 6 is characterized in that, described micropore has and is not more than 10 micropores/μ m 2Outer surface be evenly distributed density.
15. the fiber according to claim 7 is characterized in that, described micropore has and is not less than 0.01 micropore/μ m 2Cross section be evenly distributed density.
16. the fiber according to claim 7 is characterized in that, described micropore has and is not more than 10 micropores/μ m 2Cross section be evenly distributed density.
17. the fiber according to claim 1 is characterized in that, described porous fibre is no cavity basically.
18. the fiber according to claim 1 is characterized in that, described fiber is to be made of fibrous material, and described fiber comprises some micropores, and these micropores are that the structure interruptions at described fibrous material is initiated.
19. the fiber according to claim 1 is characterized in that, described fiber comprises the micropore of some extensions, and each micropore has a particulate initator that is associated; And the length that micropore had of each described extension is greater than the length of associated particulate initator.
20. the fiber according to claim 1 is characterized in that, described micropore is to define by the fibrous material with angle boundary edge.
CN97196669A 1996-07-23 1997-06-19 Microporous fibers Expired - Fee Related CN1097101C (en)

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US2229996P 1996-07-23 1996-07-23
US60/022,299 1996-07-23
US08/697,993 1996-09-04
US08/697,993 US5766760A (en) 1996-09-04 1996-09-04 Microporous fibers with improved properties

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CN1097101C true CN1097101C (en) 2002-12-25

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US20100035045A1 (en) * 2008-01-21 2010-02-11 Imerys Pigments, Inc. Fibers comprising at least one filler and processes for their production
US9394630B2 (en) * 2009-09-03 2016-07-19 Toray Industries, Inc. Pilling-resistant artificial leather
AU2013365874A1 (en) * 2012-12-19 2015-07-09 Kimberly-Clark Worldwide, Inc. Low density fibers and methods for forming same
RU2617356C1 (en) * 2013-06-12 2017-04-24 Кимберли-Кларк Ворлдвайд, Инк. Multifunctional fabric
BR112015030619B1 (en) * 2013-06-12 2022-02-22 Kimberly-Clark Worldwide, Inc absorbent article
JP2015158022A (en) * 2014-02-24 2015-09-03 株式会社ジェイエスピー Polyolefin foamed fiber
JP6996868B2 (en) * 2017-05-19 2022-01-17 花王株式会社 Non-woven fabric
CN113062033A (en) * 2020-12-29 2021-07-02 张屹 Preparation process of antibacterial wear-resistant cloth

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US5439626A (en) * 1994-03-14 1995-08-08 E. I. Du Pont De Nemours And Company Process for making hollow nylon filaments

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HUP9903824A3 (en) 2002-04-29
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CO4850632A1 (en) 1999-10-26
AU719272B2 (en) 2000-05-04
PL331150A1 (en) 1999-06-21
HUP9903824A2 (en) 2000-03-28
DE69716603T2 (en) 2003-06-12
EP0914502B1 (en) 2002-10-23
KR20000067995A (en) 2000-11-25
WO1998003706A1 (en) 1998-01-29
KR100488383B1 (en) 2005-05-11
ID19284A (en) 1998-06-28
EG21213A (en) 2001-02-28
CN1226292A (en) 1999-08-18
BR9710757A (en) 1999-08-17
PE100398A1 (en) 1998-12-25
IL127472A0 (en) 1999-10-28
AR008779A1 (en) 2000-02-23
NZ333655A (en) 1999-10-28
TR199900112T2 (en) 1999-04-21
IL127472A (en) 2001-09-13
CA2257862A1 (en) 1998-01-29
SK5299A3 (en) 2000-02-14
AU3405497A (en) 1998-02-10
PL182692B1 (en) 2002-02-28
DE69716603D1 (en) 2002-11-28

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