CN106012290A - Non-woven fabric and carbon fiber non-woven fabric - Google Patents

Non-woven fabric and carbon fiber non-woven fabric Download PDF

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Publication number
CN106012290A
CN106012290A CN201610027778.0A CN201610027778A CN106012290A CN 106012290 A CN106012290 A CN 106012290A CN 201610027778 A CN201610027778 A CN 201610027778A CN 106012290 A CN106012290 A CN 106012290A
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CN
China
Prior art keywords
particle
woven fabrics
polymer
nanofiber
inorganic particulate
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Pending
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CN201610027778.0A
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Chinese (zh)
Inventor
吉冈祐树
山口贵义
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Publication of CN106012290A publication Critical patent/CN106012290A/en
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/413—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties containing granules other than absorbent substances
    • 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
    • D01D5/0007—Electro-spinning
    • 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
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/43—Acrylonitrile series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/14—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles

Abstract

A non-woven fabric includes nanofibers which contain a polymer and inorganic particles, the nanofibers being formed by an electrospinning method. The inorganic particles contain first particles and second particles, some parts of which are exposed from a surface of the polymer. A volume V1o of a portion of the first particles exposed from the surface of the polymer and a volume V1i of a portion buried in the polymer satisfy a relationship of V1o<V1i, a volume V2o of a portion of the second particles exposed from the surface of the polymer and a volume V2i of a portion buried in the polymer satisfy a relationship of V2o>=V2i and an average number N1 of the first particles and an average number N2 of the second particles per unit length of the nanofibers satisfy a relationship of N1>N2.

Description

Non-woven fabrics and carbon fiber nonwoven fabric
Technical field
The present invention relates to comprise the non-woven fabrics of nanofiber containing inorganic particulate and formed by method of electrostatic spinning and The carbon fiber nonwoven fabric that its carbonization is obtained.
Background technology
Having nanometer (nm) can be by using polymer to the non-woven fabrics of the nanofiber of the fibre diameter of sub-μm level The method of electrostatic spinning of solution etc. etc. manufacture.The non-woven fabrics of nanofiber is big due to surface area, thus except filter materials with Outward, it is also possible to expect utilization in a variety of applications where.If further function can be given to the non-woven fabrics of nanofiber, then may be used To be used in various uses.
In patent documentation 1, it is proposed that by comprising the catalyst particle and macromolecular material being coated to by not active material surface Spinning liquid manufactured the method for non-woven fabrics of nanofiber by method of electrostatic spinning.
Additionally, in patent documentation 2, it is proposed that make fabric filter component fiber surface on load pottery ultra micron. In patent documentation 2, by impregnating fabric filter component in comprising ceramic ultramicronized solution, remaining solution is removed also Carry out heat treatment, thus load pottery ultra micron.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2014-145140 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-040646 publication
Summary of the invention
Invent problem to be solved
When non-woven fabrics loads particle, it is believed that easily play the work of particle when particle is present in the surface of nanofiber With.But, if particle to expose change many, the most easily come off.Therefore, if using non-woven fabrics for a long time, then particle will not be obtained Effect.
It is an object of the invention to provide non-woven fabrics and the carbon fiber nonwoven fabric of the effect that can play inorganic particulate for a long time.
For solving the scheme of problem
An aspect of of the present present invention relates to a kind of non-woven fabrics, and it comprises and passes through electrostatic spinning containing polymer and inorganic particulate Method and the nanofiber that formed,
Above-mentioned inorganic particulate comprises the 1st particle and the 2nd particle exposing a part from the surface of above-mentioned polymer,
The volume V of the part that the surface from above-mentioned polymer of above-mentioned 1st particle is exposed1oBe embedded in above-mentioned polymer The volume V of part1iMeet V1o＜ V1i,
The volume V of the part that the surface from above-mentioned polymer of above-mentioned 2nd particle is exposed2oBe embedded in above-mentioned polymer The volume V of part2iMeet V2o≥V2i,
Mean number N of above-mentioned 1st particle of the per unit length of above-mentioned nanofiber1And above-mentioned 2nd particle is average Number N2Meet N1＞ N2。
Another aspect of the present invention relates to the carbon fiber nonwoven fabric obtained by carrying out burning till by above-mentioned non-woven fabrics.
Invention effect
Even if in accordance with the invention it is possible to providing the fiber generation deterioration constituting non-woven fabrics also to be able to play chronically catalyst The non-woven fabrics of the effect of the inorganic particulates such as particle and carbon fiber nonwoven fabric.
Accompanying drawing explanation
Fig. 1 is the upper surface schematically showing the nanofiber comprised in the non-woven fabrics described in one embodiment of the present invention Figure.
Fig. 2 is that the cross section of the structure representing the nanofiber comprised in the non-woven fabrics described in one embodiment of the present invention shows It is intended to.
Fig. 3 is for obtaining nothing in the manufacture method schematically showing the non-woven fabrics described in one embodiment of the present invention Spin the figure of the composition of the system of cloth.
Fig. 4 is the front elevation of releasing portion 42A schematically showing Fig. 3.
Fig. 5 is the side view of releasing portion 42A schematically showing Fig. 3.
Fig. 6 is the amplification sectional view schematically showing Ore Flows.
Detailed description of the invention
[non-woven fabrics]
Non-woven fabrics described in embodiments of the present invention comprises and passes through method of electrostatic spinning containing polymer and inorganic particulate And the nanofiber formed.Inorganic particulate comprises the surface from polymer and exposes the 1st particle and the 2nd particle of a part.Wherein, The volume V of the part that the surface from polymer of the 1st particle is exposed1oVolume V with the part being embedded in polymer1iMeet V1o＜ V1i, the volume V of the part that the surface from polymer of the 2nd particle is exposed2oVolume with the part being embedded in polymer V2iMeet V2o≥V2i.Mean number N of the 1st particle of the per unit length of nanofiber1And the 2nd mean number N of particle2Full Foot N1＞ N2。
So, in present embodiment, expose from the surface of the polymer of the matrix constituting nanofiber less than 50 volume % Mean number N of the 1st particle1Mean number N of 2nd particle more exposed above for volume % than 502Many.Making by non-woven fabrics With, even if nanofiber deteriorates, it is also difficult to come off, owing to comprising many 1st particles, it is possible to play inorganic chronically The effect of particle.Additionally, due to comprise the 2nd particle that degree of exposing is high, even if simultaneously degree of exposing is low but the 1st particle is to nanofiber Outside first expose, even if so the effect of inorganic particulate also can be obtained fully at the use initial stage.Such non-woven fabrics by In being formed easily by method of electrostatic spinning, it is possible to obtain non-woven fabrics with high productivity ratio.
Fig. 1 is the upper surface figure schematically showing the nanofiber in the non-woven fabrics described in present embodiment, and Fig. 2 is to represent Schematic cross-section (the length direction with nanofiber of the structure of the nanofiber comprised in the non-woven fabrics described in present embodiment Vertical sectional view).Polymer (polymeric matrix) that nanofiber 5 comprises the shape giving fiber 6 and be scattered in polymer 6 In inorganic particulate 4.In illustrated example, inorganic particulate 4 comprises from different the 1st particle the 1, the 2nd particle 2 of the degree of exposing of polymer 6 And the 3rd particle 3, but it is not necessarily required to comprise the 3rd particle 3.1st particle 1 exposing less than 50 bodies from the surface of polymer 6 Long-pending %, the 2nd particle 2 is 50 more than volume % from exposing of the surface of polymer 6, and the 3rd particle 3 is fully embedded in polymer 6. Further, when observing the region with specific length of nanofiber 5, the number of the 1st particle 1 becomes the number than the 2nd particle 2 Many, thus, it is possible to suppress coming off of inorganic particulate (the particularly the 2nd particle 2).
The number of the 1st particle and the 2nd particle is respectively with mean number N of the per unit length of nanofiber1And N2Compare Relatively.Specifically, first, to optional many (such as 5 in scanning electron microscope (SEM) photo of non-woven fabrics Root) the region with specific length L (μm) of nanofiber, count the 1st particle and the number of the 2nd particle respectively.Length L is only To be such as 3～5 μm.The number making each particle is 2 times, is converted into per unit length (1 μm), and averages, can To obtain mean number N1And N2.It addition, the region that what is called has specific length L (μm) refers to, in SEM image, receive at 1 Rice fiber on draw 1st straight line vertical with the length direction of nanofiber and and the 1st straight line between the distance is L (μm) the 2nd Straight line (wherein, the 1st straight line and the 2nd straight line parallel), the region between the 1st straight line and the 2nd straight line.
It addition, the 1st particle and the 2nd particle can also be by visually distinguishing in SEM photograph.By being visually difficult to district In the case of other, it is also possible in the SEM photograph of nanofiber, measure the particle diameter of the part exposed from the surface of polymer ( Big particle diameter), if more than the mean diameter of the inorganic particulate used in the manufacture of this particle diameter non-woven fabrics being then judged as the 2nd particle, If less than mean diameter, being judged as the 1st particle.
As shown as example, inorganic particulate can also comprise the 3rd particle being fully embedded in polymer further.The 3 particles are owing to being enclosed in polymer, even if so the deterioration carrying out nanofiber is also difficult to come off.Thus, it is possible to further Play the effect of inorganic particulate chronically.
Mean number N of the 1st particle1And mean number N of the 3rd particle of the per unit length of nanofiber3Can also be N1≥N3, but meet N1＜ N3Time, it is possible to guarantee the effect of inorganic particulate in non-woven fabrics the most chronically.Putting down of 3rd particle All numbers N3Such as can transmission electron microscope (TEM) photo based on non-woven fabrics, according to N1Situation calculate.
Fiber diameter D of nanofiberfFor example, more than 100nm, preferably more than 150nm or more than 200nm, enter One step is preferably more than 300nm.DfSuch as less than 1000nm, preferably below 800nm or below 600nm.These lower limits with Higher limit can at random combine.DfCan also be such as 100nm less than 1000nm, 150nm less than 1000nm, 200nm are less than 1000nm.
Fiber diameter D of nanofiberfSuch as can be by the SEM image of non-woven fabrics, to the most The diameter at 1 measured respectively by the fiber of (such as 10), and averages and obtain.The diameter of so-called fiber is relative to receiving The diameter in the vertical cross section of length direction of rice fiber.In the case of such cross section is not circle, it is also possible to by maximum diameter It is considered as diameter.
Mean diameter D of inorganic particulatepFor such as more than 5nm, preferably more than 10nm, it is also possible to for more than 15nm or More than 20nm.DpCan be below 200nm or below 150nm, it is also possible to for below 100nm or below 80nm.These lower limits Can at random combine with higher limit.DpCan also be such as 5～200nm or 20～200nm.
Mean diameter D of inorganic particulatepFor the volume reference obtained of inorganic particulate that uses in the making to non-woven fabrics Median particle diameter (D in particle size distribution50)。
Fiber diameter DfRelative to mean diameter DpRatio Df/DpFor example, more than 0.5, preferably more than 3, Can also be more than 5 or more than 7.Ratio Df/DpCan also be less than 30 or less than 25, but preferably less than 10 or less than 9.This A little lower limits can at random combine with higher limit.Ratio Df/DpCan also be such as 0.5～30,0.5～25, more than 0.5 and Less than 10 or 3～9.It is difficult to be formed the nanofiber of the state that inorganic particulate exposes by method of electrostatic spinning.But, if regulation Ratio Df/Dp, then easily dimmable 1st particle and the degree of exposing of the 2nd particle are become.From such a viewpoint, preferably by ratio Df/DpIt is set below 10.
The amount of inorganic particulate is relative to polymer 100 mass parts for example, 5～50 mass parts, preferably 5～30 mass parts (such as 10～30 mass parts), more preferably 5～20 mass parts.
DfAnd Dp, ratio Df/DpAnd/or the amount of inorganic particulate is when being scope as described above, easily inorganic particulate is imbedded In nanofiber, regulation the 1st particle and the number of the 3rd particle the most significantly.
Hereinafter, the composition of non-woven fabrics is more specifically illustrated.
(polymer)
Polymer constitutes the matrix of nanofiber.That is, the matrix that nanofiber comprises polymer and being scattered in this matrix Inorganic particulate (the 1st～the 3rd particle).
As long as polymer can then be not particularly limited by electrostatic spinning, include, for example out polyolefin, vinylite (vinegar Vinyl acetate resin or its saponified, polystyrene, polyacrylonitrile (PAN) etc.), acrylic resin, fluororesin, polyether sulfone (PES), polysulfones, polyester (aromatic polyester etc.), polyamide, polyimides (PI), cellulose derivative, Biodegradable polymerization Thing etc..These polymer can be used alone one or are used in combination of two or more.In them, preferably PES, polysulfones, fragrance Adoption ester (the poly terephthalic acid diol ester etc. such as polyethylene terephthalate), polyamide, PI (are obtained by polyamic acid The Thermocurable polyimides such as condensed type polyimides, bimaleimide resin；TPI etc.), PAN etc..Poly- Compound can be homopolymer, it is also possible to be copolymer.From easily prepare polymer solution (or the 1st dispersion liquid described later) and From the viewpoint of easily carrying out electrostatic spinning (and stringiness is excellent), preferably PAN and/or PI etc..
Weight average molecular weight M of polymerwAlso different because of the kind of polymer, for example, 30000～120000, it is preferably 50000～100000 or 50000～80000.Weight average molecular weight M of polymerwRelative to number-average molecular weight MnRatio (=Mw/ Mn) for example, 1.1～3.0.
It addition, in this specification, the weight average molecular weight of polymer and number-average molecular weight are by passing through gel permeation chromatography The value that the molecular weight distribution measured is obtained.
Constitute the nanofiber of non-woven fabrics as required in addition to polymer and inorganic particulate, it is also possible to comprise known Additive.The content of additive can also for constitute 5 mass % of the nanofiber of non-woven fabrics overall (or non-woven fabrics is overall) with Under.
(inorganic particulate)
Inorganic particulate suitably can select according to purposes, when forming nanofiber by electrostatic spinning, preferably poly- Polymer solution (the specifically solvent of solution) will not dissolve or occur the inorganic particulate of deterioration.As inorganic particulate, can List the particle of such as metallic, metallic compound (oxide, hydroxide, nitride, carbide, halogenide etc.) Deng.In inorganic particulate, preferably metallic, the particle etc. of metal-oxide (also comprising pottery).As constituting metallic Metal, can list the transition metal such as such as titanium, manganese, cobalt, nickel, palladium, platinum, copper, silver, gold.As metal-oxide, can list The oxide (such as titanium oxide, copper oxide, silver oxide etc.) of above-mentioned metal.Inorganic particulate can be used alone one or by two kinds Combination of the above uses.
Every 1 piece of the thickness of non-woven fabrics can the scope from about 1～1000 μm select, and for example, 10～700 μm are preferably 10～600 μm or 20～500 μm.
In non-woven fabrics described in present embodiment, compared with the number exposing the 2nd big particle in nanofiber surface The number exposing the 1st little particle is more.Therefore, even if nanofiber deteriorates, it is also possible to play inorganic particulate chronically Effect.
(manufacture method of non-woven fabrics)
Above-mentioned non-woven fabrics can disperse inorganic grain by example as used in the solution comprising polymer (or its precursor) Son and the method for electrostatic spinning of dispersion liquid that obtains and obtain.Specifically, can by via preparation comprise polymer or its before 1st operation of the dispersion liquid (the 1st dispersion liquid) of body and inorganic particulate and in fiber forms space by electrostatic attraction by the 1st Dispersion liquid generates nanofiber and makes the nanofiber of generation pile up and form the 2nd operation of non-woven fabrics, manufactures non-woven fabrics.? In 2nd operation, when generating nanofiber, the respective part of some or all of inorganic particulate expose from nanofiber and Become the 1st particle and the 2nd particle.Additionally, the inorganic particulate of a part becomes the 3rd of the state being embedded in nanofiber sometimes Particle.
It addition, in the case of polymer is polyimides etc., it is also possible to comprise polyimide precursor (polyamides by use Amino acid etc.) and the dispersion liquid of inorganic particulate as the 1st dispersion liquid, the manufacture process of non-woven fabrics suitably carries out heating etc., by Polyimide precursor generates polyimides (polymer).
(the 1st operation)
In the 1st operation, the preparation method of the 1st dispersion liquid is not particularly limited, such as can also by polymer (or Its precursor) it is dissolved in the polymer solution obtained in solvent and disperses inorganic particulate to prepare.Inorganic particulate can be with powder Form use, it is also possible to use with the form of dispersion liquid (the 2nd dispersion liquid).For example, it is also possible to by inorganic particulate is being divided It is scattered in the solvent of dissolving polymer (or its precursor) the 2nd dispersion liquid obtained add polymer and makes it be dissolved in solvent In, prepare the 1st dispersion liquid.If additionally, mixed with the 2nd dispersion liquid comprising inorganic particulate by polymer solution, preparing bag Containing polymer and the 1st dispersion liquid of inorganic particulate, the most easily improve the dispersibility of inorganic particulate.
As solvent, as long as the solvent that polymer (or its precursor) can be dissolved and be removed by volatilization etc., then It is not particularly limited.As such solvent, the polar organic solvent of aprotic can be listed.Also because of polymer or its precursor Kind and different, but as solvent, the polarity parameters P ' that Rohrschneider is preferably used is more than 5 (such as 5～7.5) The polar organic solvent of aprotic.As such solvent, such as DMF (DMF), N, N-can be listed The amide (chain or cyclic amide etc.) such as dimethyl acetylamide (DMAc), METHYLPYRROLIDONE (NMP)；Dimethyl sulfoxide Deng sulfoxide etc..These solvents can be used alone one, it is also possible to is used in combination of two or more.
Further preferably use the solvent comprising amide.Such as, in the case of polymer comprises PES and/or PAN, it is also possible to Use the solvent comprising DMF and/or DMAc.In the case of polymer comprises PI or its precursor, it is possible to use comprise NMP's Solvent.
In nanofiber, from suppression inorganic particulate assemble from the viewpoint of, preferably by by polymer solution with comprise nothing The 1st dispersion liquid is prepared in 2nd dispersion liquid mixing of machine particle.In this case, particularly preferably will polymer solution comprise Solvent disperses the disperse medium of inorganic particulate to use as in the 2nd dispersion liquid.For example, it is preferable to make the disperse medium of the 2nd dispersion liquid 50 mass % more than (more than preferably 70 mass % or more than 80 mass %) be with in the solvent that comprises in polymer solution The identical solvent of main solvent (accounting for the solvent of more than 50 mass % in the solvent comprised in polymer solution).
Polymer concentration in 1st dispersion liquid is such as 3～60 mass %, preferably 5～50 mass %.
1st dispersion liquid can also comprise the known additive used in electrostatic spinning as required.
(the 2nd operation)
In 2nd operation, by the 1st dispersion liquid that obtains in the 1st operation by electrostatic spinning fibrosis, form non-woven fabrics.
In method of electrostatic spinning, generate nanofiber by electrostatic stretch phenomenon.More specifically, if disperseing the 1st Liquid uses as the material liquid of electrostatic spinning, then by the material liquid flowed out in charged space, solvent is the most in-flight It is slowly evaporated.Thus, the volume of aloft material liquid reduces at leisure, but the electric charge giving material liquid rests on raw material In liquid.As a result of which it is, the charge density of the most aloft material liquid rises at leisure.Further, the electric charge of material liquid is close Degree improves, and the Coulomb force repelling direction produced in material liquid surpasses the capillary moment of material liquid, produces material liquid The phenomenon being stretched with wire explosion type.This phenomenon is electrostatic stretch phenomenon.Utilize electrostatic stretch phenomenon, it is possible to make efficiently Make nanofiber.
The nanofiber generated in space by making fiber be formed is stacked into the surface of base material, can obtain present embodiment Described non-woven fabrics.The non-woven fabrics formed can also be from the sur-face peeling of base material.In this case, the manufacture method of non-woven fabrics The operation peeled off by non-woven fabrics from the surface of base material can be comprised further.Wherein, as base material, it is possible to use the base of fissility Material sheet material or for transport fiber conveyance conveyer belt band etc..In addition it is also possible to there is non-woven fibrous structure by use Base material (commercially available non-woven fabrics etc.) is as base material so that it is pile up nanofiber on surface, forms non-woven fabrics with to have nonwoven fine The non-woven fabrics that the base material of dimension structure is integrated and obtains.
In the operation forming non-woven fabrics, as required, it is possible to use multiple electrostatic spinning unit, generate with each unit Respectively different nanofiber also makes it pile up.For example, it is also possible to by generating fibre diameter and/or polymer group with each unit Become different nanofibers and make it pile up to form non-woven fabrics.It addition, nanofiber diameter can by the state of material liquid, The composition of Ore Flows, the size etc. of the electric field formed by charged elements are adjusted.
Fig. 3 is the system schematically showing the manufacture method for implementing the non-woven fabrics described in one embodiment of the present invention The figure of the composition of manufacturing system.Fig. 3 is the example of the situation utilizing the base material E with non-woven fibrous structure.
The manufacturing system construction of Fig. 3 is for manufacturing the manufacture line of non-woven fabrics.Manufacture system possess non-woven fabrics formed device 40, With the retracting device 70 for reclaiming the non-woven fabrics formed.In the manufacture system of Fig. 3, base material E removes from the upstream manufacturing line Deliver to downstream.On base material E in conveyance way, carry out the formation of the non-woven fabrics of nanofiber at any time.
In the most upstream of the system of manufacture, it is provided with the base material feedway having received the base material E with web-like winding in inside 20.Base material feedway 20 is by the base material E uncoiling of web-like, to other unit feeding base material E adjacent with the downstream of self.Tool For body, base material feedway 20 makes supply spool 22 rotate by electromotor 24, the base material E that will be wound on supply spool 22 Supply is to the 1st carrying roller 21.
The base material E of uncoiling is transferred to non-woven fabrics by the 1st carrying roller 21 and is formed in device 40.
Non-woven fabrics forms device 40 and possesses electrostatic spinning mechanism.More specifically, electrostatic spinning mechanism possesses and comprises setting Top in device for release material liquid nozzle (Ore Flows) releasing portion 42A, make released material liquid the (the 1st Dispersion liquid) non-woven fabrics E transports to downstream from upstream side by charged charged elements with according to the mode relative with releasing portion 42A The conveyance conveyer belt 41 of side.Conveyance conveyer belt 41 and base material E, together as the collection portion function of collection fiber, make base material E Surface (first type surface) upper pile up the nanofiber released from releasing portion 42A.
Charged elements is by Ore Flows being executed alive voltage bringing device 43 and arranging abreast with conveyance conveyer belt 41 And electrical connection electrode 44 is constituted.To electrode 44 ground connection.Thus, Ore Flows and to electrode 44 between, can arrange with logical The corresponding potential difference of voltage (such as 20～200kV) that overvoltage bringing device 43 applies.It addition, being constructed without of charged elements It is particularly limited to, such as, to electrode 44 the most not necessarily ground connection, it is also possible to apply high voltage.Additionally, replace arranging electrode 44, also The band portion etc. of conveyance conveyer belt 41 can be made up of conductor.
Fig. 4 is the front elevation of releasing portion 42A schematically showing Fig. 3, and Fig. 5 is the releasing portion schematically showing Fig. 3 The side view of 42A.Fig. 6 is to carry out cutting and by a part by the plane of discharge port 42a by the Ore Flows 42 of Fig. 4 and Fig. 5 The Longitudinal cross section schematic amplified and obtain.
As shown in Fig. 4 and Fig. 5, releasing portion 42A has the Ore Flows 42 for releasing material liquid, at Ore Flows The top of 42, connects and has for the conduit 50 to Ore Flows 42 base feed liquid 45.Additionally, above Ore Flows 42, arrange There is not shown wind pushing mechanism.By utilizing wind pushing mechanism to blow from the top of Ore Flows 42, it is possible to efficiently to obstruction Solvent vapour or ion wind that nanofiber generates are taken a breath.
Ore Flows 42 has the shape of strip, in the inside of Ore Flows 42, is formed with the receipts of the hollow cylindrical of diameter D1 Receive portion 52.In the side that the band (base material) with conveyance conveyer belt 41 of Ore Flows 42 is relative, at certain intervals, with regular row Row are provided with multiple discharge port 42a.
The top of Ore Flows 42 is formed with cross section with the width of square formation and cross sectional shape towards discharge port 42a slowly Tapered portion 42b that ground diminishes.So, by formation tapered portion 42b around the discharge port 42a of Ore Flows 42, it is possible to suppression Generation because of the ion wind that charge concentration causes in corner etc..
Additionally, the width of the cross sectional shape by reducing Ore Flows 42 at leisure towards discharge port 42a, it is possible to make electric charge fit Degree is concentrated, it is possible to the material liquid released from discharge port 42a is effectively supplying electric charge.Incorporating section 52 is connected with discharge port 42a The diameter for example, 0.25～0.4mm of through hole, the length of through hole for example, 0.1～5mm.The cross sectional shape of through hole can With selection, polygon, the star etc. such as circular, triangle or tetragon have the arbitrary shapes such as the shape of the prominent part in inside side Shape.
Material liquid 45 utilizes the pressure of the pump 46 connected with the hollow bulb of Ore Flows 42, from raw material flow container 45a through conduit 50 supply to the incorporating section 52 of Ore Flows 42.Further, material liquid 45 utilizes the pressure of pump 46 from multiple discharge port 42a towards nothing The first type surface spinning cloth E is released.The material liquid released when charged in Ore Flows 42 and conveyance conveyer belt 41 (or nonwoven Cloth E) between space move, movement causes electrostatic explosion, generates the nanofiber with sheath and core structures.Generated receives Rice fiber is attracted to the first type surface of base material by electrostatic attraction, and piles up at this.Thus, non-woven fabrics F is formed.
The band portion of conveyance conveyer belt 41 can also be dielectric substance.In the case of band portion is made up of conductor, exists and receive The tendency that rice fiber somewhat concentrates on the collection portion of the discharge port close to Ore Flows 42 and piles up.From making nanofiber more uniformly From the viewpoint of being scattered in collection portion, more preferably formed the band portion of conveyance conveyer belt 41 by dielectric substance.
In the case of forming band portion by dielectric substance, it is possible to to the inner peripheral surface of electrode 44 and band portion (with The face of the opposition side in the face of non-woven fabrics E contact) contact.By such contact, cause dielectric polarization in the inside of band portion, With produce on the contact surface of base material E electric charge.Thus, in the part of the surface Ea that nanofiber concentrates on base material E The probability piled up reduces further.
In Fig. 3, the band at non-woven fabrics F with conveyance conveyer belt 41 separates the position of (stripping), during in order to suppress them to peel off The generation of the spark that may cause, it is also possible to arrange and non-woven fabrics F is carried out except the neutralizer of electricity.Additionally, formed at non-woven fabrics Near window portion between device 40 and each device being adjacent, it is also possible to arrange charged molten by produce in spinning space Agent steam, charged air carry out taking a breath and improving the attraction pipeline of spinning properties.
Form the non-woven fabrics F completed that takes out of of device 40 via carrying roller 71 from non-woven fabrics, be recycled in retracting device 70. Retracting device 70 is built-in with the recovery spool 72 batching the non-woven fabrics F that conveyance comes.Reclaim spool 72 to be turned by electromotor 74 Dynamic driving.
In manufacture system as shown in Figure 3, the electromotor 74 that the retracting device 70 making recovery non-woven fabrics rotates is controlled The conveyance speed (speed of conveyance conveyer belt 41) being made as non-woven fabrics F becomes constant such velocity of rotation.Thus, non-woven fabrics F Limit maintains the tension force limit of regulation to transport.Such control is entered by the control device (not shown) possessed in manufacture system OK.Control device according to can be blanket control, manage the mode of each device of composition manufacture system and constitute.
Formed between device 40 and non-woven fabrics retracting device 70 at non-woven fabrics, it is also possible to configure pre-recoverer.Pre-recoverer Become easy way according to the recovery utilizing retracting device 70 of the non-woven fabrics F completed to arrange.Specifically, reclaim pre- In portion, the device 40 non-woven fabrics F completed that comes of transfer will be formed not batch and lax state is recycled to one from non-woven fabrics Fixed length.During this, the recovery spool 72 of retracting device 70 does not rotate and stops.Further, to be reclaimed by pre-recoverer When the length of the non-woven fabrics F of lax state reaches certain length, the recovery spool 72 of retracting device 70 is made only to rotate regulation Time, recovery spool 72 is utilized to be batched by non-woven fabrics F.
By arranging such pre-recoverer, become to there is no need to make the conveyance speed of conveyance conveyer belt 41 and non-woven fabrics to return The velocity of rotation of the electromotor 74 that receiving apparatus 70 is possessed strictly interlocks and is controlled, it is possible to by the control dress of the system of manufacture Put simplification.
It addition, the manufacture system of above-mentioned non-woven fabrics only can be used for manufacturing the nothing described in embodiments of the present invention Spin an example of the manufacture system of cloth.As long as the manufacture method of non-woven fabrics have preparation the 1st dispersion liquid the 1st operation and Nanofiber is formed and is generated nanofiber by the 1st dispersion liquid in space and make it pile up and form the 2nd operation of non-woven fabrics, then do not have It is particularly limited to.
Additionally, about the 2nd operation, as long as also the nanofiber in regulation is formed in space, by the 1st dispersion liquid by quiet Electric attraction and generate nanofiber, and make the operation that generated nanofiber piles up, then can use arbitrary electrostatic spinning Mechanism.Such as, the shape of Ore Flows is not particularly limited.In the shape such as Fig. 5 in the cross section vertical with the length direction of Ore Flows As Suo Shi, however it is not limited to the shape (V-type nozzle) tapered into towards lower section from top, it is also possible to carry out structure by rotor Become Ore Flows.
In nanofiber forms device, by piling up fiber continuously on the first type surface of the band of conveyance conveyer belt, can To form the non-woven fabrics of strip.Additionally, by the accumulation carrying out nanofiber off and on, it is also possible to form the nonwoven of rectangle Cloth.
[carbon fiber nonwoven fabric]
In embodiments of the present invention, also comprise the carbon-fibre nonwoven obtained by carrying out burning till by above-mentioned non-woven fabrics Cloth.By being burnt till by above-mentioned non-woven fabrics, the polymer of the matrix constituting nanofiber is carbonized, the Nanowire of polymer Dimension is transformed into carbon fiber.In such carbon fiber nonwoven fabric, owing to inorganic particulate becomes to be easily fixed in further Nanowire In dimension, it is possible to suppress coming off of inorganic particulate further.Therefore, it is possible to play the effect of inorganic particulate chronically.
Formed in the case of carbon fiber nonwoven fabric, in above-mentioned polymer, be preferably used easily carry out carbonization polymer, Such as PAN and/or PI.
Firing temperature can also be such as 300～1300 DEG C or 500～1000 DEG C.Burning till can be at inactive gas (nitrogen Gas, argon etc.) atmosphere under carry out, it is also possible to carry out (such as in the presence of hydrogen etc.) under reducing atmosphere.Firing time example As 0.5～5 hour can also be set to.
Additionally, carbon fiber nonwoven fabric can also be the non-woven fabrics implementing known activation processing as required.
The fiber diameter of the carbon fiber in carbon fiber nonwoven fabric for example, 50～500nm, preferably 80～400nm. The fiber diameter of carbon fiber can be based on fiber diameter D of above-mentioned nanofiberfSituation and obtain.
The inorganic particulate comprised in non-woven fabrics can also reduce by burning till.For example, it is also possible to by oxidation will be comprised The non-woven fabrics of the particle of the metal-oxide such as copper or silver oxide burns till under reducing atmosphere, by metal oxide particle also The metallics such as former one-tenth copper or silver.The carbon fiber nonwoven fabric comprising the inorganic particulate reduced by such burning till is also contained in In the present invention.
In carbon fiber nonwoven fabric, the mean diameter of inorganic particulate for example, 5～80nm, it is also possible to be 8～50nm.Carbon is fine Dimension non-woven fabrics in inorganic particulate mean diameter such as can TEM image based on carbon fiber nonwoven fabric and calculate.Concrete and Multiple positions (such as, 10 positions) of the carbon fiber of TEM image can be obtained the maximum gauge of inorganic particulate, go forward side by side by speech Row equalization, thus obtain mean diameter.
Embodiment
Hereinafter, based on embodiment and comparative example, the present invention is specifically described, but the present invention is not limited to following Embodiment.
Embodiment 1
The preparation of (1) the 1st dispersion liquid
PAN is dissolved in DMAc and prepares polymer solution (concentration is 5～10 mass %).
By by polymer solution with comprise copper oxide particle (mean diameter Dp: 20nm) slurry (the 2nd dispersion liquid, oxygen The concentration changing copper particle is 15 mass %) reach the mode of 1.3: 0.15 according to the mass ratio of PAN Yu copper oxide particle and mix Closing, preparation comprises the 1st dispersion liquid of PAN and copper oxide particle.
(2) electrostatic spinning
By manufacture system as shown in Figure 3, use the 1st dispersion liquid obtained in above-mentioned (1) as material liquid, pass through Under conditions of following, carry out electrostatic spinning make to pile up on the first type surface of base material nanofiber, make non-woven fabrics.
Electrospinning conditions:
Apply voltage: 60kV
Solution ejection pressure: 25kPa
Temperature: 26 DEG C
Humidity: 37%RH
In obtained non-woven fabrics, fiber diameter D of nanofiberfFor 320nm, ratio Df/DpIt is 16.Additionally, The thickness of non-woven fabrics is 100 μm, and the quality of per unit area is 13g/m2。
SEM photograph based on non-woven fabrics, by above-mentioned method, obtains the 1st particle and the 2nd respective mean number of particle N1And N2, result is N1＞ N2。
Embodiment 2
Except replacing PAN to use PI, the mass ratio of PI Yu copper oxide particle is changed to beyond 2:0.15, with reality simultaneously Execute example 1 and similarly make the non-woven fabrics of nanofiber, be evaluated.
The thickness of obtained non-woven fabrics is 20 μm, and the quality of per unit area is 5g/m2, the average fiber of nanofiber Diameter DfFor 440nm, ratio Df/DpIt is 22, N1＞ N2。
Embodiment 3
By by the non-woven fabrics obtained in embodiment 1 under an argon atmosphere, carry out 0.5 hour burning till at 800 DEG C, making carbon Fabric nonwoven cloth.
Be analyzed to identify the state of particle by energy dispersion-type X-ray, result copper oxide particle is transformed to copper particle.
Industrial applicability
Non-woven fabrics described in embodiments of the present invention and carbon fiber nonwoven fabric are according to the kind of inorganic particulate, except filtering Beyond material etc., it is also possible to be used in the various uses such as medical application, sanitary use, electric energy storage device, catalyst sheet material.
Symbol description
1: the 1 particle, 2: the 2 particles, 3: the 3 particles, 4: inorganic particulate, 5: nanofiber, 6: polymer (polymer base Body), 20: base material feedway, 21: the 1 carrying rollers, 22: supply spool, 24: electromotor, 40: non-woven fabrics formed device, 41: Conveyance conveyer belt, 42A: releasing portion, 42: Ore Flows, 42a: discharge port, 42b: tapered portion, 43: voltage bringing device, 44: to electricity Pole, 45: material liquid (the 1st dispersion liquid), 45a: raw material flow container, 46: pump, 48: the 1 supporters, 49: the 2 supporters, 50: conduit, 52: incorporating section, 70: retracting device, 71: carrying roller, 72: reclaim spool, 74: electromotor, E: there is the base of non-woven fibrous structure The first type surface of material, Ea: base material, F: non-woven fabrics.

Claims (7)

1. a non-woven fabrics, it comprises the nanofiber formed by method of electrostatic spinning containing polymer and inorganic particulate,
Described inorganic particulate comprises the 1st particle and the 2nd particle exposing a part from the surface of described polymer,
The volume V of the part that the surface from described polymer of described 1st particle is exposed1oWith the portion being embedded in described polymer The volume V divided1iMeet V1o＜ V1i,
The volume V of the part that the surface from described polymer of described 2nd particle is exposed2oWith the portion being embedded in described polymer The volume V divided2iMeet V2o≥V2i,
Mean number N of described 1st particle of the per unit length of described nanofiber1And mean number N of described 2nd particle2 Meet N1＞ N2。
Non-woven fabrics the most according to claim 1, wherein,
Fiber diameter D of described nanofiberfMean diameter D relative to described inorganic particulatepRatio Df/DpFor More than 0.5 and less than 30.
Non-woven fabrics the most according to claim 1, wherein,
Fiber diameter D of described nanofiberfFor 150nm less than 1000nm,
Mean diameter D of described inorganic particulatepIt is 20～200nm.
Non-woven fabrics the most according to claim 1, wherein,
Described inorganic particulate also comprises the 3rd particle being fully embedded in described polymer,
Mean number N of described 1st particle1And mean number N of described 3rd particle of the per unit length of described nanofiber3 Meet N1＜ N3。
Non-woven fabrics the most according to claim 1, wherein,
The amount of described inorganic particulate is 5～50 mass parts relative to 100 mass parts of described polymer.
6. a carbon fiber nonwoven fabric, it is to obtain by carrying out burning till by the non-woven fabrics described in claim 1.
Carbon fiber nonwoven fabric the most according to claim 6, wherein,
Described polymer is at least one in the group selecting free polyacrylonitrile and polyimides composition,
Described carbon fiber nonwoven fabric is carbonized by described polymer and is formed.
CN201610027778.0A 2015-03-25 2016-01-15 Non-woven fabric and carbon fiber non-woven fabric Pending CN106012290A (en)

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