CN109563660A - The nano-fiber structure and non-woven fabrics being made of poly (hydroxyalkanoate) - Google Patents

The nano-fiber structure and non-woven fabrics being made of poly (hydroxyalkanoate) Download PDF

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Publication number
CN109563660A
CN109563660A CN201680088059.8A CN201680088059A CN109563660A CN 109563660 A CN109563660 A CN 109563660A CN 201680088059 A CN201680088059 A CN 201680088059A CN 109563660 A CN109563660 A CN 109563660A
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China
Prior art keywords
nano
fiber structure
structure according
poly
hydroxyalkanoate
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K·苏德希·库马尔
井上浩三
新田和也
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Fuence Co Ltd
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Fuence Co Ltd
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43838Ultrafine fibres, e.g. microfibres
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/02Moisture-responsive characteristics
    • D10B2401/021Moisture-responsive characteristics hydrophobic
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/02Moisture-responsive characteristics
    • D10B2401/022Moisture-responsive characteristics hydrophylic
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/12Physical properties biodegradable

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

Nano fibrous membrane obtained in embodiment 1 (nano-fiber structure) is placed in soil, the biological degradability based on microorganism etc. is had studied.Fig. 4 (a) is that nano fibrous membrane has just been put into the photo after soil.Fig. 4 (b) is the photo after being placed 12 days with the state of Fig. 4 (a).By comparing these photos it is found that poly (hydroxyalkanoate) nano fibrous membrane can be rapidly decomposed in the soil.PHA can be produced by the plant resources of nature as a result, and the shortcomings that being returned in nature by the microbial degradation in soil, be able to solve existing PP non-woven fabrics (generates CO when burning2), it can be used as the resource material manufacture non-woven fabric that can permanently use.

Description

The nano-fiber structure and non-woven fabrics being made of poly (hydroxyalkanoate)
Technical field
The present invention relates to the nano-fiber structures being made of poly (hydroxyalkanoate) (Polyhydroxyalkanoic acid) And non-woven fabrics, in particular to oil, organic solvent absorbability and have in a natural environment can be fast by microorganism etc. The characteristic that speed is decomposed, the nano-fiber structure and non-woven fabrics that are made of poly (hydroxyalkanoate).
Background technique
In recent years, its purposes of the non-woven fabrics manufactured by various organic polymers constantly expands, from fiber industry (lining cloth neck Domain) arrive hygienic material, medical material, automotive interior material, industry material (filtering wiping etc.), civil engineering material, agricultural The multi industries such as material, geotextile (soil fixation fiberboard), environment, are widely used in various uses.It is expected that nonwoven from now on Cloth continuous enlargement will produce year by year.Wherein, the growth rate of polypropylene (PP) non-woven fabrics is high, it can be expected that nearly 10% growth.
However, while this organic polymer non-woven fabrics industry development, there is also more serious problems.Make Organic polymer for non-woven fabrics principal component is that synthesis is purified from petroleum resources, can cause Future exhaustion and produce after The problem of product processing.As resource recycling, burning after using the processing of rear product (waste) granulate etc. processing Processing, landfill disposal etc..The waste that can be used as resource and recycle is extremely a small amount of on the whole for waste therefore existing Shape is to take burning disposal or landfill disposal mostly.Burning disposal can give off a large amount of CO2, thus global warming is influenced, It is very important project.In addition, for landfill disposal, be decomposed from the resin of petroleum is extremely difficult, almost lasting residue in In soil, earth environment will be polluted for a long time.
The solution of these problems first is that in the raw material of non-woven fabrics use Biodegradable polymer.Currently, making Exploitation with the biological degradabilities organic macromolecule naval stores such as polylactic acid, poly (hydroxyalkanoate) is underway.State for many years Inside and outside enterprise has been devoted to the exploitation of poly (hydroxyalkanoate), but is produced using microorganism, purifies with high costs, functionization It makes slow progress.
In recent years, report has KANEKA company is honest to push the dynamic commercialized development by poly (hydroxyalkanoate) manufacture naval stores. But the said firm is only intended to develop so-called naval stores, does not carry out the exploitation in above-mentioned non-woven fabrics field.
As the prior art non-patent literature of above-mentioned Biodegradable polymer, for example, having " public with German biotechnology Is department's signature about KANEKA Biopolymer AONILEX? commodity development comprehensive agreement (http: // Www.kaneka.co.jp/service/news/150217) " (non-patent literature 1), " Science and Technology Agency identification plant Success (the http://www.kaneka.co.jp/service/news/ of source organism degradability resin manufacturing techniques exploitation 140710-2) " (non-patent literature 2), " using microorganism manufacture biodegradable plastic (Microbiol.Cult.Coll.29 (1): 25-29,2013) " (non-patent literature 3), " world is for the first time.100% plant origin and the life with soft property, heat resistance Formally (http://www.kaneka.co.jp/service/news/n090206.html) is unfolded in object polymer " (non-patent text 4) etc. it offers.
Existing technical literature
Non-patent literature
Non-patent literature 1: " sign with German biotech company about KANEKA Biopolymer AONILEX? commodity Comprehensive agreement of exploitation " network address:http://www.kaneka.co.jp/service/news/150217)
Non-patent literature 1: " sign with German biotech company about KANEKA BiopolymerAONILEX? commodity Comprehensive agreement of exploitation " network address:http://www.kaneka.co.jp/service/news/150217)
Non-patent literature 2: " Science and Technology Agency assert the exploitation of plant origin Biodegradable resin manufacturing technology Success " network address:http://www.kaneka.co.jp/service/news/140710-2
Non-patent literature 3: rattan wood wise man, which also writes, " manufactures biodegradable plastic using microorganism (Microbiol.Cult.Coll.29 (1): 25-29,2013) "
Non-patent literature 4: " world is for the first time.100% plant origin and with soft property, heat resistance biopolymer just Formula expansion " network address: http://www.kaneka.co.jp/service/news/n090206.html
Summary of the invention
Problems to be solved by the invention
According to certain market report, predict that the market scale of non-woven fabrics, particularly polypropylene (PP) non-woven fabrics increases every year from now on It is about 8%, can reach about 30,000,000,000 dollars in the year two thousand twenty.Its main application has the health of diaper (child, Elderly patients) etc. to use Product, geotextile, environmental pollutants processing, automobile industry, furniture etc. depend on population and increase the faster Asian-Pacific area Development.
In addition, non-woven fabrics yield in 2013 is 5,940,000 tons, it is predicted that the year two thousand twenty will rise to 9,970,000 tons.As long as using stone The PP of oily source resource, that is, violating prevents the world of global warming from knowing together, and leads to CO2Discharge amount increases, thus needs Imitate countermeasure.Present inventor etc. establishes to carry out the biological degradability poly (hydroxyalkanoate) (PHA) based on microorganism at a low price The technical method of production and purifying process, and application study has been carried out towards various uses.
Also, present inventor etc. studied and thought repeatedly in order to solve the above problems, as a result, it has been found that will Biological degradability poly (hydroxyalkanoate) realizes nanofiber, as the nano-fiber structure (non-woven fabrics etc.) with various characteristics Technical method.
The object of the present invention is to provide a kind of nano-fiber structures being made of poly (hydroxyalkanoate).Another mesh of the invention Be to develop nano-fiber structure for non-woven fabrics, to solve the problems of existing synthetic resin non-woven fabrics.
Solve the technological means of project
To solve above-mentioned each project, nano-fiber structure involved in the 1st invention is by (a kind or more of poly (hydroxyalkanoate) Kind) constitute nano-fiber structure.
In addition, nano-fiber structure involved in the 2nd invention is characterized in that above-mentioned poly (hydroxyalkanoate) is with poly- hydroxyl fourth Acid esters is as principal component.
It should be noted that structural body preferably based on poly butyric ester and be combined with other poly (hydroxyalkanoate)s (such as with it is poly- The copolymer of hydroxycaproic acid).
In addition, nano-fiber structure involved in the 3rd invention is characterized in that, the fiber of above-mentioned nano-fiber structure Diameter is 1 μm or less.
In addition, nano-fiber structure involved in the 4th invention is characterized in that, have in soil in a natural environment The characteristic being degraded by microorganisms.
In addition, nano-fiber structure involved in the 5th invention is characterized in that, the hole of above-mentioned nano-fiber structure Rate is 50% or more.Due to porosity height, so the gas permeability of structural body is high, weight.
In addition, nano-fiber structure involved in the 6th invention is characterized in that, there is water-repellancy, pure water is relative to upper The contact angle for stating the surface of nano-fiber structure is 100 degree or more.
In addition, nano-fiber structure involved in the 7th invention is characterized in that, have oil absorbing.
In addition, nano-fiber structure involved in the 8th invention is characterized in that, there is organic solvent absorbability.
In addition, nano-fiber structure involved in the 9th invention is characterized in that, the surface of above-mentioned nano-fiber structure By plasma treatment, corona discharge, electron beam irradiation or laser irradiation surface modification and have hydrophily.Pass through table Face is modified after assigning hydrophily, can be used for health product etc..
In addition, nano-fiber structure involved in the 10th invention is characterized in that, contain adsorbent material.Adsorbent is for example For active carbon or zeolite etc., it is included in nanofiber and surface.
In addition, nano-fiber structure involved in the 10th invention is characterized in that, one of the nano-fiber structure Point clinkering and in membranaceous.
Solution of the invention is illustrated with nano-fiber structure as described above, but the present invention can also be by substantial It is realized with the manufacturing method of this comparable nano-fiber structure, these are all contained in the scope of the present invention.
Invention effect
According to the present invention, it is possible to provide a kind of nano-fiber structure (film), it is soft, there is the absorption of oil, organic solvent Property, and can be degraded rapidly by microorganism etc. in a natural environment, having not will lead to CO2The increased characteristic of gas flow.Nanowire Dimension structural body can be utilized in various industries as non-woven fabrics.
Detailed description of the invention
Fig. 1 is the concept map constituted substantially for indicating electrospray deposition device.
Fig. 2 is the SEM photograph of manufactured nano-fiber structure in the embodiment 1 as material.
Fig. 3 is the electron micrograph (SEM photograph) of PHA nano-fiber structure shown in Fig. 2.
Fig. 4 is the figure for indicating the biological degradability of nano fibrous membrane of embodiment 1.
Fig. 5 is the figure for indicating the water-repellancy of nano fibrous membrane of embodiment 1.
Fig. 6 is the oil-water separativeness and oil absorbing figure for indicating the nano fibrous membrane of embodiment 1.
Fig. 7 is the figure for indicating the organic solvent absorbability of the nano fibrous membrane of embodiment 1.
Fig. 8 be a part of clinkering of nano fibrous membrane and be in membranaceous nano fibrous membrane (nano-fiber structure) electronics Microscope photo (SEM photograph).
Fig. 9 is the electron micrograph (SEM photograph) of the nano fibrous membrane containing adsorbent material particle.
Specific embodiment
Hereinafter, referring to each attached drawing embodiment that the present invention will be described in detail.
Poly (hydroxyalkanoate) used in the embodiment of the present invention is using the reason of Malaysia belonging to one of present inventor University, section obtained patent culture of microorganism and method of purification made from sample.It can be used by said sample manufacture nanofiber The method of electrospray deposition (ESD) method, meltblown or other manufacture nanofibers, but preferably ESD method or meltblown.
<electrospray deposition method>
Before illustrating embodiment of the present invention, first to electrospray deposition method (ESD used in embodiment of the present invention Method) principle and the electrospray deposition device (ESD: electrostatic atomizer) of implementable electrospray deposition method be illustrated.
<electrospray deposition device>
Fig. 1 is the concept map constituted substantially for indicating electrospray deposition device.As shown, container CNT is for accommodating examination Sample solution S L.Sample solution SL is, for example, organic polymer solution or polymer solution etc..In the present embodiment, sample solution For poly (hydroxyalkanoate), the i.e. poly (hydroxyalkanoate) solution for being dissolved in solvent.
ESD method is extremely complex physical phenomenon, and process not yet all illustrates, it is generally understood that being following phenomenon.Examination Sample solution is accommodated in very thin capillary nozzle NZL, thousands of extremely to target substrate TS (to the electrode) application opposed with its The voltage of tens of thousands of volts.Strong electrical field is generated because of electric field concentration effect in capillary tip, the fine droplet with charge is gathered in Liquid surface forms cone (referred to as " taylor cone (Taylor Cone) ").Sample solution breaks surface tension from the top and forms spray Jet stream.Injection stream is charged by force, is repelled by electrostatic force and is formed spraying (COULOMB EXPLOSION).It is very small by the drop formed by spraying, Short time internal solvent, that is, evaporation drying becomes small nanoparticle or nanofiber.It can certainly be without evaporating, doing Make its accumulation under dry moisture state.The tiny nanofiber of small nanoparticle, the diameter of the band point is made by electrostatic force Target substrate TS to function to electrode attracts.The pattern of accumulation can pass through insulator mask (not shown) or auxiliary electrode To control.Sample is liquid, is not particularly limited, is also possible to dispersion liquid.
Additionally, it is preferred that molten to the sample in container CNT using air pressure syringe pump or plunger etc. (spraying means, not shown) Liquid applies extrusion pressure to the side nozzle NZL.Extrusion pressure is for example assigned by stepper motor and screw feed mechanism are (not shown).It receives Internal pressure of the sample solution SL in container CNT to extrusion pressure increases and is discharged from the top nozzle NZL.As described above, can lead to Setting adjustment is crossed to spray the adjustment mechanism (stepper motor and screw feed mechanism) of sample solution speed and be adjusted to spray appropriate Speed out.
Nozzle NZL is made of metal, is supplied to positive voltage by conductor lines WL by high voltage power supply HPS.High voltage power supply HPS's is negative Pole side is connected with target substrate TS (as the substrate to electrode).By applying voltage from high voltage power supply HPS, thus via nozzle NZL applies positive voltage to sample solution SL, and solution is positively charged.It should be noted that the polarity of voltage for being applied to sample solution SL can also To be negative.
In addition, preferably placing non-woven fabrics, and the heap on non-woven fabrics on target substrate TS when production nano-fiber structure Product nano-fiber structure.In addition, the adjustment height of voltage, the concentration of sample solution, the type of poly (hydroxyalkanoate) in sample, molten The various conditions such as agent type make nano-fiber structure.
The material for being atomized becomes fiber or drop, repels because of electrification, to divide repeatedly in flight course, shape At nanofiber or nanoparticle.The material for being atomized is nano-scale, so surface area is big, is almost become when reaching substrate Drying regime.It can change shapes and sizes by adjusting spray condition, for example, using Polymer Solution, if Increase molecular weight, improve concentration, then form thick nanofiber, if reduce molecular weight, reduce concentration, formed thin nanofiber or Nanoparticle.In addition, the various conditions such as voltage and distance, ambient temperature, humidity between nozzle and substrate have an impact.In this reality It applies in mode, uses the poly (hydroxyalkanoate) of various solvent solubles as sample, make nanofiber under various conditions, and press The method that embodiment is recorded carries out the confirmation of water-repellancy, gas permeability, hydrophily etc..As electrospray deposition device, in addition to above-mentioned Outside device, other kinds of ESD device also can be used.Especially when for volume production purpose, the preferably exploitations such as applicant The method of air-flow is used documented by patent 5491189.
In addition, in volume production, in addition to above-mentioned ESD device, it is possible to use using the non-woven cloth manufacturing device of meltblown.
The nanofiber of<embodiment 1>based on ESD method
Fig. 2 is the poly (hydroxyalkanoate) nano fibrous membrane (PHA nano-fiber structure) made using the ESD device of Fig. 1 Photo.Sample solution has used poly (hydroxyalkanoate) (PHA) to account for the chloroformic solution of 10 weight %.ESD device (ES- is used when manufacture 4000, FUENCE corporation), it is sprayed under conditions of voltage 50KV, 10 μ of flow l/ minutes.The nano fibrous membrane of diagram Film thickness be 20 μm.The nano fibrous membrane is very thin, and fibre diameter is small, but is self-supported membrane, can also be laminated in other non-woven fabrics Or film etc. or group enter other components, in utensil, it is highly useful.
Fig. 3 is the electron micrograph (SEM photograph) of PHA nano-fiber structure shown in Fig. 2.The multiplying power of photo is 1000 times.In addition, the average diameter of nanofiber is about 1 μm.As shown, can be observed what fiber was entwined in mesh-shape Perforated membrane is formed with the structural body of porosity height, lightweight.PHA nano-fiber structure can be used as filtering due to its porosity Device.Its nanofiber diameter, porosity, density etc. can change according to the various solution compositions of purpose change, spray condition, from And it can be controlled.
<embodiment 2>biological degradability
Fig. 4 is the figure for indicating the biological degradability of nano fibrous membrane of embodiment 1.By Nanowire obtained in embodiment 1 Dimension film (nano-fiber structure) is placed in soil, studies the biological degradability based on microorganism etc..Fig. 4 (a) is just will Nano fibrous membrane is put into the photo after soil.Fig. 4 (b) is that the nano fibrous membrane of Fig. 4 (a) is kept to the photo after placing 12 days. By the comparison of these photos it is found that poly (hydroxyalkanoate) nano fibrous membrane is rapidly decomposed in the soil.PHA can be by nature as a result, The plant material on boundary is produced by microbial fermentation, then returns to nature by the microorganism decomposition in soil, therefore It not will increase greenhouse gases, can be used as permanent available utilization of resources nano fibrous membrane.
<embodiment 3>water-repellancy
Fig. 5 is the figure for indicating the water-repellancy of nano fibrous membrane of embodiment 1.Fig. 5 is the Nanowire obtained in embodiment 1 It ties up and the photo after pure water has just been added dropwise on film dropwise with pipettor.The pure water WD of dropwise addition is stopped in droplets as shown in the photo On film.Visually to measure its contact angle, the variable for obtaining 10 drops is 87.5-130.5 °, 113.7 ° of average out to.Nanofiber Film shows water-repellancy.
<embodiment 4>oil-water separativeness and oil absorbing
Fig. 6 is the oil-water separativeness and oil absorbing figure for indicating the nano fibrous membrane of embodiment 1.It will be obtained in embodiment 1 To nano fibrous membrane be put into a manner of covering from above in the container equipped with aqueous solution of methylene blue and salad oil.Fig. 6 (a) is Photo before nano fibrous membrane to be put into container.Aqueous solution of methylene blue is mixed with salad oil with isolated state.Fig. 6 (b) It is the photo after nano fibrous membrane is added container 1 minute.As shown in figure (b), nano fibrous membrane can be observed and float on methylenum careuleum On aqueous solution, salad oil OL is only remained on nano fibrous membrane.Fig. 6 (c) be after being put into nano fibrous membrane by 10 minutes when Photo.As shown in the photo of Fig. 6 (c), nano fibrous membrane within 10 points can be observed and only absorb salad oil, finally by salad oil All it is absorbed into film.In addition, nano fibrous membrane does not absorb aqueous solution of methylene blue completely.I.e., it is known that poly (hydroxyalkanoate) Nanowire Dimension film has the function of separating water and oil, and has the function of only selectively absorbing oily.
<embodiment 5>organic solvent absorbability
Fig. 7 is the figure for indicating the organic solvent absorbability of the nano fibrous membrane of embodiment 1.Fig. 7 (a) is will be in embodiment 1 Obtained nano fibrous membrane be put into the container equipped with aqueous solution of methylene blue MB and hexane HX before photo.At this point, methylenum careuleum Aqueous solution MB and hexane HX are separated into 2 layers.Fig. 7 (b) be after nano fibrous membrane to be put into container by 10 minutes when photo.Such as In figure shown in photo, hexane HX within 10 minutes can be observed and fully absorbed by nano fibrous membrane.The amount of aqueous solution of methylene blue MB Do not change, it may thus be appreciated that nano fibrous membrane only selective absorbing as organic solvent hexane without absorb water.I.e., it is known that Nano fibrous membrane shows excellent organic solvent absorbability.
<embodiment 6>a part is membranaceous nano fibrous membrane (nano-fiber structure)
Fig. 8 be a part of clinkering of nano fibrous membrane and be in membranaceous nano fibrous membrane (nano-fiber structure) electronics Microscope photo (SEM photograph).As shown, can be observed nearby to be membranaceous, there is nano fibrous membrane in distal side.The membranaceous portion makes The intensity of film itself improves, thus useful.
The nano fibrous membrane of<embodiment 7>containing adsorbent material
Fig. 9 is the electron micrograph (SEM photograph) of the nano fibrous membrane containing adsorbent material particle.As shown, It can be observed to be wound as micro activated carbon particle AC1, AC2 of adsorbent material and be held in nanofiber FBR1, FBR2.In addition, living Property carbon particle is located in nanofiber or on surface.Adsorbent material can effectively be absorbed by the organic solvent between nano fibrous membrane The ingredient (impurity or the ingredient of pre-separation etc.) of dissolution.Adsorbent can for example select active carbon or zeolite etc. depending on the application.
Finally, it is indicated that the advantages of nano fibrous membrane involved in various embodiments of the present invention (nano-fiber structure etc.). Biological degradability poly (hydroxyalkanoate) (PHA) as nanofiber film raw material can be carried out the plant component of nature as raw material Production.Then nano-fiber structure is made using biological degradability poly (hydroxyalkanoate), and is widely used in non-woven fabrics purposes, thus It is able to suppress the increase of carbon dioxide gas.
Polypropylene non-woven fabric as conventional products is soft and has intensity, also excellent with the adaptation of other materials, because This is used in various uses.Especially polypropylene non-woven fabric can absorb oil, so also serving as oily adsorbent material.Pass through experiment It is found that raw material, that is, poly (hydroxyalkanoate) of nano-fiber structure involved in the embodiment of the present invention or polyhydroxybutyrate etc. are no Only absorb oil, also absorption organic solvent and the toxic organics for dissolving in solvent.
For example, using the property, if making by organic solvent and the ocean, the river that are dissolved in orgnic compound pollution therein Stream, lakes and marhshes, underground water etc. through the embodiment of the present invention involved in nano-fiber structure, then may filter that, absorb polluter, Obtain clean water.
As described above, it can be expected that nano-fiber structure according to the present invention (nano fibrous membrane) is mainly as non-woven fabrics Applied to various uses.
Description of symbols
CNT container
HPS high voltage power supply
NZL nozzle
SL sample solution
TS target substrate
ESD electrospray deposition device
WL line

Claims (11)

1. a kind of nano-fiber structure, which is characterized in that be made of poly (hydroxyalkanoate).
2. nano-fiber structure according to claim 1, which is characterized in that the poly (hydroxyalkanoate) is with polyhydroxybutyrate Ester is as principal component.
3. nano-fiber structure according to claim 1, which is characterized in that the fiber of the nano-fiber structure is straight Diameter is 1 μm or less.
4. nano-fiber structure according to claim 1, which is characterized in that have quilt in soil in a natural environment The characteristic of microbial degradation.
5. nano-fiber structure according to claim 1, which is characterized in that the porosity of the nano-fiber structure It is 50% or more;By improving porosity, the gas permeability of structural body is got higher, weight saving.
6. nano-fiber structure according to claim 1, which is characterized in that there is water-repellancy, pure water is relative to described The contact angle on nano-fiber structure surface is 100 degree or more.
7. nano-fiber structure according to claim 1, which is characterized in that have oil absorbing.
8. nano-fiber structure according to claim 1, which is characterized in that have organic solvent absorbability.
9. nano-fiber structure according to claim 1, which is characterized in that the surface of the nano-fiber structure passes through It crosses surface modification of plasma treatment, corona discharge, electron beam irradiation or laser irradiation etc. and there is hydrophily.
10. nano-fiber structure according to claim 1, which is characterized in that contain adsorbent material.
11. nano-fiber structure according to claim 1, which is characterized in that one of the nano-fiber structure Point clinkering and film-like.
CN201680088059.8A 2016-06-07 2016-06-07 The nano-fiber structure and non-woven fabrics being made of poly (hydroxyalkanoate) Pending CN109563660A (en)

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