CN101824708B - Fully-degradable polylactic acid fiber melt-blowing nonwoven fabric and preparation method thereof - Google Patents
Fully-degradable polylactic acid fiber melt-blowing nonwoven fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses fully-degradable polylactic acid fiber melt-blowing nonwoven and a preparation method thereof. The nonwoven is characterized in that polylactic acid slices are spinned at a melting temperature; and fiber filaments stretched by hot air is formed by self-adhesion and hot rolling, wherein, the even fineness of the nonwoven fiber filaments is 0.52-5mu m, the surface density is 5-50g/m2, the thickness is 0.1-0.9mm, the ratio of longitudinal strength to transverse strength is 0.9-1.2, and the filtering efficiency to bacteria is above 95%. The filtering efficiency of the melt-blowing nonwoven product of the invention to bacteria reaches up to 95% which is far higher than that of the existing similar products. The invention solves the problem of low and uneven longitudinal strength and transverse strength of the existing melt-blowing nonwoven. The invention lowers the melt-blowing die head temperature to 180-185 DEG C and brings optimal spinning effect. The technology of the invention is easy to operate and control, has favorable technical stability and can carry out industrial production.
Description
Technical field
The invention belongs to textile material non-weaving cloth field, be specifically related to a kind of full degradation-type acid fiber by polylactic melt-blowing nonwoven product with and preparation technology.
Background technology
Owing to receiving from exhausted day by day dual-pressures of non-renewable resources such as continuous enhancing of environmental consciousness and oil, the exploitation of Biodegradable material has become one of focus of people's concern with application.PLA (PLA) is that renewable resources such as employing corn, wheat and potato are that raw material is processed, and its product environmental protection can be degraded into CO after the use fully
2And H
2O has the ability of compost simultaneously, so PLA is a kind of desirable degradable raw material.
To the research and development and the application of PLA, the U.S., Japan and some developed countries of Europe are walked in other national prostatitis.PLA manufacturer U.S. Nature Works company the biggest in the world successfully develops trade name Ingeo
TMThe polylactic acid slice of series fibre-grade; Have the characteristic of general synthetic fiber through the acid fiber by polylactic of melt spinning production, like higher intensity and percentage elongation, good resilience and conformality; Have simultaneously hydrophily and wicking property preferably again; It is close that advantages such as low flammability, flue dust are little, processing characteristics and good spinning property in addition, made poly-lactic acid products have a product of processing with synthetic fiber.
These excellent properties of PLA have promoted its application in textile industry; The good one after another PLA market of some large enterprises of developed countries such as America and Japan Europe; As except Nature Works company; Toray (TORAY), clock spin the PLA product that (Konebo) and You Jinika companies such as (Unitika) develop One's name is legion in succession; But this mostly be adopt the fusion spun-bond process produce the PLA fiber again through spinning, weave and operation such as post processing is produced the PLA product; The method that is adopted is the methods such as spunbond, acupuncture, water thorn and heat bonding in traditional textile, the nonwovens process, and the company that does not up to the present also have to adopt melt-blowing nonwoven explained hereafter PLA product, Dieter H.
people of etc.ing once cut into slices PLA and was used for melt-blown process; Think that through research PLA can be applicable to melt-blown process; But because the problem of aspects such as raw material and technology, experimental result is undesirable, and the fibre web of formation does not have purposes basically.
China just just begins the development that melts and sprays polylactic acid non-weaving cloth and exploitation, does not also have enterprise to commercially produce at present, but relevant scholar, researcher and enterprise test, and has obtained certain achievement.Introduced a kind of ultra-fine acid fiber by polylactic non-weaving cloth among the Chinese patent ZL200410017776.0, it is the non-weaving cloth that utilizes melt-blown process to process, and it is said that fibre fineness can reach 2.7～9.07 μ m, quantitatively is 44～123.7g/m
2, thickness is 0.645～1.339mm, and its product is used for the medical filter field, and its fibre web average pore size is at 11.3865～24.9693 μ m, and the blood middle leukocytes clearance can reach 99.934% in the given instance.But because the leucocyte diameter is usually more than 10 μ m, and the bacterium diameter is merely 0.3～5 μ m, so the non-weaving cloth that method is produced is relatively poor for the filter effect of bacterium, does not almost have filter effect, has had a strong impact on the application of this series products; And this melt-blowing nonwoven is little and irregular to brute force in length and breadth, and is powerful in length and breadth than more than 1.5, has among the embodiment to reach 2.27; Its meltblown beam temperature is more wide in range aborning for it; Properties of product change greatly; Meltblown beam need remain on higher temperature in this method practical application, causes the MFI value of PLA section lower, and the viscosity after the fusion is bigger; When spinning, cause certain difficulty, and the not even fibre web of more fracture of wire, long filament occurs clouding is arranged.The PLA non-weaving cloth that people such as the Liu Ya of Tianjin University of Technology utilize melt-blown process to make in the laboratory to be used for filtering material; But the non-weaving cloth of being made possibly be owing to section or equipment reason cause melt-blown non-woven irregular and have fracture of wire to occur; And its fiber extrusion temperature is about 220 ℃, and this high temperature very easily causes PLA to decompose influences its drawing effect.
Summary of the invention
For solve melt-blowing nonwoven powerful low with in length and breadth to the bigger shortcoming of brute force; Further improve its filter efficiency simultaneously; Reduce the extrusion temperature at PLA meltblown beam place; Reduce that fiber is irregular, fracture of wire and tangle rate, and reach the purpose that industrialization is produced, the invention provides a kind of full degradation-type acid fiber by polylactic melt-blowing nonwoven.The present invention adopts and melts and sprays special-purpose polylactic acid slice, optimizes melt-blown process parameter particularly die head temperature control and hot-air parameter, and melt spray fibre web is carried out hot rolling handle; The present invention has found out 180～185 ℃ of best meltblown beam temperature, under this temperature, carries out spinning, and made melt-blowing nonwoven fibre fineness is at 0.4～1.5dtex; Can reach below the 5 μ m; The product of being produced can filter bacterium, and filter efficiency can reach more than 95%, and its fibre web is powerful, aspect ratio is powerful, uniformity improves a lot; And product has good biodegradability after using, and has the ability of biological compost simultaneously.
Another object of the present invention is to provide the manufacturing approach of the above-mentioned novel high-fall PLA of separating melt-blowing nonwoven.This production technology has easy operation and control, has good stability, and can carry out suitability for industrialized production, and the even and steady quality of the melt-blowing nonwoven of being made can be used to make the medical and hygiene article with promptly abandoning.
The object of the invention can reach through following measure:
A kind of fully-degradable polylactic acid fiber melt-blowing nonwoven, this non-weaving cloth are by polylactic acid slice spinning under melt temperature, and the fiber filament after hot-air stretches forms through self-adhesion and hot rolling; The fiber filament average fineness of this non-weaving cloth is 0.52～5 μ m, and surface density is 5～50g/m
2, thickness is 0.1～0.9mm, and is vertically powerful and horizontal powerful than being 0.9～1.2, to the filter efficiency of bacterium more than 95%.
The longitudinal stretching brute force of this non-weaving cloth is 30～80N/5cm, and the longitudinal fracture percentage elongation is 8～26%, the powerful 25～70N/5cm of cross directional stretch, and transverse breakage percentage elongation 10～35%, Air permenbility is at 258.62～843.60l/m
2S, bending rigidity is 0.32～2.84cNcm, hydrostatic pressing is 8～30cm H
2O.
The weight average molecular weight of the polylactic acid slice that non-weaving cloth of the present invention adopted is 80,000～150,000, and melt index is 75～85g/10min.The melt temperature that this non-weaving cloth prepares in the process is 180～185 ℃.Requirement to melt temperature in the existing method is very extensive; There is document to point out at 150～300 ℃; The present invention finds in 180～185 ℃ of scopes, can reach the effect of very suitable product of the present invention, is higher or lower than this temperature and all can brings totally unfavorable influence to product.
The preparation method of fully-degradable polylactic acid fiber melt-blowing nonwoven of the present invention comprises the steps:
A, chip drying: earlier polylactic acid slice is dried to moisture＜50ppm;
The weight average molecular weight of the polylactic acid slice that adopts is 80,000～150,000, and melt index is 75～85g/10min, and melt temperature is 150～190 ℃, and the thermal cracking temperature is 280～350 ℃; The dry temperature of polylactic acid slice is 50～120 ℃, and be 3～12h drying time;
B, melt extrude: dried polylactic acid slice is sent into fusion in the screw extruder, and melt spray under 180～185 ℃ meltblown beam temperature thread;
The screw extruder draw ratio is 25～40, and the screw extruder internal temperature is 120～300 ℃, and spin manifold temperature is 160～220 ℃; Feed zone is 130～160 ℃, and the compression section is at 160～185 ℃, and metering section is 180～200 ℃; Screw speed is 10～60rpm; The measuring pump rotating speed is 10～40rpm, and the melt extrusion capacity of meltblown beam is 0.065～0.780g/ (hole min), and the meltblown beam aperture is 0.1～0.4mm;
C, spin-drawing become net: temperature is that 190～205 ℃, flow velocity are the high-temperature hot air air drawing of 200～1000m/s to the melt of meltblown beam ejection through both sides, and cooling and crystallization under 10～35 ℃ cooling air again is paved into fibre web; Wherein the pressure of high-temperature hot air is 0.15～0.6Mpa, and the wind speed of said cooling air is 0.2～0.6m/s;
D, hot rolling: fibre web through after the precompressed, is sent hot-rolling mill to and is carried out hot rolling earlier; Hot calendering bonding dot density scope during hot rolling is 2.5 * 10
4～15 * 10
4Point/m
2, the bond area ratio accounts for 8～20% of the fibre web gross area.
Hot rolling is after can obtain the fully-degradable polylactic acid fiber melt-blowing nonwoven of moulding behind the continuous later adjusting and the coiling of cutting edge.
The production procedure of fully-degradable polylactic acid fiber melt-blowing nonwoven of the present invention is PLA chip drying-screw extruder fusion-filtration-metering-meltblown beam-melt thread stretching-cooling-reception-coiling.Its concrete manufacturing technique is following:
(1) select the polylactic acid slice that is fit to melt-blown process for use: the used polylactic acid slice of the present invention is that chemical structure of general formula is following:
Wherein X is 400～2500, and its weight average molecular weight is 30,000～180; 000, PLLA (PLLA) content＞98% during the used PLA of the present invention cuts into slices, its weight average molecular weight is preferably 80; 000～150,000, melt index is at 75～85g/10min; Melt temperature is 150～190 ℃, and the thermal cracking temperature is 280～350 ℃.
The polylactic acid slice that the present invention adopted is through infrared spectrum (FTIR) test, in the spectrogram that obtains, at 3505.5cm
-1, 1045.6cm
-1There is an absworption peak at the place, and this is respectively-stretching vibration and the flexural vibrations of OH; At 2997.5cm
-1, 2945.9cm
-1, 1384.7cm
-1, 1365.4cm
-1Absworption peak appears in the place, and this is-CH-symmetry and asymmetric flexible with due to the flexural vibrations; At 1756.4cm
-1, 1266.8cm
-1It is because contain-C=O-that crest appears in the place; At 1455.5cm
-1The crest explanation at place contains-CH
3Crest explanation at 1184.7,1132.7,1092.5 places contains-C-O-.
(2) chip drying operation: on chip dryer, carry out drying to melting and spraying with PLA section, its baking temperature is set to 50～120 ℃, and criteria thus the drying time is at 3～12h, its PLA section moisture＜50ppm behind the drying.
(3) the PLA section melt extrudes operation: dried PLA section is sent in the screw extruder, and the screw extruder draw ratio that the present invention adopts is 25～40, and its process conditions: the screw extruder internal temperature is 120～300 ℃; Spin manifold temperature is 160～220 ℃, and feed zone is 130～160 ℃, and the compression section is at 160～185 ℃; Metering section is 180～200 ℃; Screw speed is at 10～60rpm, and the measuring pump rotating speed is 10～40rpm, and the meltblown beam optimum temperature is at 180～185 ℃; The melt extrusion capacity of meltblown beam is at 0.065～0.780g/ (hole min), and the aperture of meltblown beam is at 0.1～0.4mm.
(4) PLA fibre spinning and stretching process: the both sides after the ejection of spray silk die head of the melt after the fusion are high-temperature hot air air drawings; And the certain position below die head of cooling air subsequently mend from both sides into; And the superfine fibre after the stretching is cooled off and crystallization fast; Under the effect of spraying air-flow, be layered on on the lace curtaining equably; Become the below of lace curtaining to be provided with vacuum aspirator, mixed and disorderly superfine fibre silk is owing to self also have higher temperature, and it can be through self bonding melt-blowing nonwoven that becomes.The related hot air temperature of this patent is 190～205 ℃; The hot-air flow velocity is 200～1000m/s; Its pressure is at 0.15～0.6Mpa, 10～35 ℃ of cold air temperature, and wind speed is at 0.2～0.6m/s; Workshop humidity is limited in 25～60%, and meltblown beam is 5～30cm with becoming the distance between net drum.
(5) become the net operation: this patent adopts into lace curtaining and receives the fiber web after stretching, and below becoming lace curtaining, is provided with vacuum suction apparatus.Differ greatly and irregular shortcoming to brute force in length and breadth for improving conventional melt-blowing nonwoven, parameters such as the nozzle parameter of the present invention through changing sprayer unit, wind speed increase melt-blowing nonwoven in length and breadth to powerful and reduce irregularity.Its main technologic parameters is: the sprayer unit nozzle diameter suitably increases 1～6mm, and wind speed is at 50～200m/s, and becoming the lace curtaining transfer rate is 20～200cm/min.
(6) hot rolling is reinforced: PLA melt-blown non-woven fibre web that will be fluffy is sent hot-rolling mill to after applying certain pressure through a pair of pony press earlier again, utilizes a pair of heating steel rider that fibre web is heated, and in addition certain pressure makes fibre web obtain the thermal point bond reinforcing simultaneously.The top roll that need to prove the heating steel rider is the bonding texturing line of point, and lower roll is a smooth roll, that is to say that thermal point bond is the one side to the melt-blown non-woven fibre web.Technological parameter involved in the present invention is following: pressure roller pressure is 0.5～4kpa; 40～120 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 20～50N/mm; Linear velocity 30～150cm/min, hot calendering bonding dot density scope is 2.5 * 10
4～15 * 10
4Point/m
2, the bond area ratio accounts for 8～20% of the fibre web gross area.
Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Preparation method of the present invention is the production of spinning technique technology and melt-blowing nonwoven to the effect that, it compared with prior art, advantage of the present invention is:
1. the raw material for preparing this melt-blown non-woven is that polylactic acid PLA has favorable biological degradability; (PLA can promote plant growing at the intermediate product of degradation process to have the ability of biological compost simultaneously; Therefore can be used for compost); And its physical and mechanical properties is superior to PET near traditional PET on performances such as hygroscopicity, wicking capacity, flexibility.
2. melt-blowing nonwoven product involved in the present invention reaches more than 95% the filter efficiency of bacterium (diameter is usually at 0.3～5 μ m), far above existing like product.
3. solved existing melt-blowing nonwoven in length and breadth to the very low and irregular problem of brute force.This patent is through changing the jet size of sprayer unit, and make the fiber after the stretching carry out lapping more mussily, and melt spray fibre web is carried out hot rolling handle, and under the cooperation of other necessary conditions, thereby solved powerful problem well.
4. PLA section melt temperature involved in the present invention is lower; Overcome PLA melt facile hydrolysis when high temperature preferably; The meltblown beam place temperature that particularly melt-blown process is had very important effect; This patent is guaranteeing that meltblown beam place temperature can be reduced to below 200 ℃ under the normal spinning of melt ability, and finds that spinning effect is best in the time of 180～185 ℃.
5. utilize the made melt-blowing nonwoven of this patent technology, the surface evenly, steady quality, thickness, fabric width and quantitatively adjustable, its physical and mechanical properties near or partial properties be superior to traditional P P melt-blowing nonwoven.
6. the present invention's operation and control easily, technology stability is good, and can carry out suitability for industrialized production.
Description of drawings
Fig. 1 is the structure Electronic Speculum picture of the PLA melt-blowing nonwoven of embodiment 1 preparation.
Fig. 2 is a PLA melt-blowing nonwoven explained hereafter flow chart.
Wherein, 1-motor, 2-feeding hopper, 3-screw rod, 4-screw extruder; The 5-screen pack, 6-measuring pump, 7-hot-air, 8-cold air, 9-long filament; The 10-sprayer unit, 11-receives curtain, 12-vacuum suction apparatus, 13-fibre web, 14-top roller; The 15-bottom roll, 16-hot rolling engraved roll, 17-hot rolling smooth roll, 18-take up roll.
The specific embodiment
Below in conjunction with instance practical implementation process of the present invention is further specified.Preparation method of the present invention adopts the novel high-fall PLA of separating section to be raw material, and prepares non-weaving cloth with melt-blown process.The PLA melt-blowing nonwoven technology of the present invention's preparation mainly comprises following four steps: (1) PLA section is selected for use and is dry.(2) melt extrude operation.(3) spinning and stretching process.(4) net-forming process.(5) hot rolling reinforcement process.According to prior art, the technical issues that need to address mainly are selecting for use and drying, melt-spinning technology, net-forming process and hot-rolled process parameter of PLA section.
Consider PLA melt rheological property and the melt viscosity of section after the fusion, section has following requirement to melt-blown process to PLA: the section molecular weight should concentrate on than in the zonule; Melt index (MFI) is greater than 70g/10min; Melt temperature is about 200 ℃.This patent proves through experimental study, is used for the PLA section of melt-blown process, PLLA (PLLA) content＞98%; Its average molecular weight is 80000～150000; Melt index is at 75～85g/10min, and melt temperature is 150～190 ℃, and the thermal cracking temperature is 280～350 ℃.
The PLA section drying process that preparation method of the present invention relates to, this mainly is that the moisture in its section is more than 250ppm owing to contain terminal hydroxy group and a large amount of ester groups in the PLA molecule; PLA after the fusion at high temperature is prone to degraded; Thereby cause the PLA molecular weight to reduce, molecular weight distribution broadens, and influences viscosity and shearing force after the fusion; And bubble not of uniform size can appear when spinning, and unfavorable to drawing of fiber.The present invention adopt melt and spray drying equipment to PLA section carry out drying, concrete technological parameter is: baking temperature is at 50～120 ℃, and criteria thus the drying time is at 3～12h, and PLA cuts into slices behind drying, and its moisture is less than 50ppm.
The described melt-spinning technology of preparation method of the present invention mainly is meant dried PLA section is put in the storage bin(hopper), and is transported in the screw extruder, makes the PLA progressively fusion of cutting into slices through adding hot extrusion.The present invention draws optimal processing parameter through experimental study repeatedly: screw pitch adopts 2～5mm; Its draw ratio (L/D) is 25～40, and screw speed is at 10～60rpm, and the screw extruder internal temperature is at 120～300 ℃; Spin manifold temperature is at 160～220 ℃; Feed zone is at 130～160 ℃, and the compression section is at 160～185 ℃, and metering section is at 180～200 ℃.
PLA melt after the fusion is again through the meter accurate measurement and guarantee that the PLA melt evenly and continuously is transported to filter course, and in course of conveying, in spinneret assembly, produces certain pressure and make it to spray from spinneret hole through filter course and with accurate flow.Through filter mainly is with the impurity among the PLA after the filtering molten, in case it stops up spinneret orifice.Its main technologic parameters that relates to is 10～40rpm for the measuring pump rotating speed.
Melt through filter can be extruded the PLA long filament through meltblown beam again; Its expressing technique parameter: the meltblown beam width is at 200～500mm; Spray silk die head temperature is at 180～185 ℃, and the aperture is at 0.1～0.4mm, and the melt extrusion capacity is at 0.065～0.780g/ (hole min).
It is an important step of the excellent melt-blowing nonwoven of processability that the PLA long filament stretches.The PLA long filament of extruding attenuates elongated under the stretching action of both sides high velocity, hot air air-flow rapidly, and cold air on every side mend from both sides into, and the superfine fibre silk after the stretching is cooled off and crystallization fast, obtain certain degree of orientation and degree of crystallinity.Main technologic parameters is following: hot air temperature is 190～205 ℃, and the hot-air flow velocity is 200～1000m/s, and its pressure is at 0.15～0.6Mpa; The hot air injection angle is at 30～90 °; 10～35 ℃ of cold air temperature, wind speed are at 0.2～0.6m/s, and workshop humidity is limited in 25～60%.
PLA long filament after the stretching arrives under the traction of hot-air and receives cylinder, and spinning head can make the vertical transverse strength of cloth, bending stiffness reduce to cylinder apart from increase, and fibre diameter slightly increases, the fluffy softness of feel, and filter efficiency and filtration resistance descend.Through repeatedly the experiment show, its receiving range when 5～30cm, the non-weaving cloth better performances of preparation.In order to make long filament more disorderly and more unsystematic when the lapping; This patent is through increasing the diameter of the nozzle in the sprayer unit; The back long filament that stretches is layered on under the promotion of more disorderly air-flow on the lace curtaining mussily, has played the effect that improves melt-blowing nonwoven brute force and skewness thereof largely.
Autoadhesion between the PLA fiber filament is reinforced fibre web and is improved its brute force, and this patent also utilizes the hot rolling effect that fibre web is reinforced.Technological parameter involved in the present invention is following: pressure roller pressure is 0.5～4kpa; 40～120 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 20～50N/mm; Linear velocity 30～150cm/min, hot calendering bonding dot density scope is 2.5 * 10
4～15 * 10
4Point/m
2, the bond area ratio accounts for 8～20% of the fibre web gross area.
Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Preparation method of the present invention does not address part and is applicable to prior art.
The PLA melt-blowing nonwoven that utilizes the inventive method to make carries out performance test, and its result sees table 1.
The high-fall performance indications of separating the PIA melt-blowing nonwoven of table 1
Annotate: the filter efficiency index is a test gained under 0.3 μ m rank dust;
Can find out from above-mentioned data; The made melt-blowing nonwoven of this patent has higher bacterium filter capacity, has overcome routine and has melted and sprayed the powerful relatively poor weakness of product, and had feel and gas permeability preferably; The good water effect of refusing is arranged; Because adopt the high-fall raw material polylactic acid slice of separating, prepared product has good biodegradability, has the ability of biological compost simultaneously.
Specify preparation method involved in the present invention through embodiment below.
Embodiment 1:
(1) PLA chip drying.Continuous drying equipment is put in the PLA section carried out intensive drying, its section molecular weight is 100000, and melt index is 80～85, and the thermal cracking temperature is 305 ℃.Baking temperature is 100 ℃, and criteria thus the drying time is at 5h, and PLA cuts into slices behind drying, and its moisture is 22ppm.
(2) the PLA section melt extrudes operation.Screw pitch adopts 3mm, and its draw ratio (L/D) is 30, and screw speed is at 25rpm, and the screw extruder internal temperature is at 208 ℃, and spin manifold temperature is at 190 ℃, and feed zone is at 150 ℃, and the compression section is at 180 ℃, and metering section is at 215 ℃.The meltblown beam temperature is at 195 ℃, and the aperture is 0.2mm, and the melt extrusion capacity is at 0.344g/ (hole min).
(3) PLA long filament stretching process.Hot air temperature is 205 ℃, and the hot-air flow velocity is 600m/s, and its pressure is at 0.3Mpa, and the hot air injection angle is 60 °, and the cold air temperature is at 25 ℃, and wind speed is at 0.4m/s, and workshop humidity is limited in 45%.
(4) become the net operation.The involved process conditions of this patent are that meltblown beam is 18cm with becoming the distance between net drum, and the sprayer unit nozzle diameter suitably increases 2mm, and wind speed is at 70m/s, and becoming the lace curtaining transfer rate is 60cm/min.
(5) hot rolling is reinforced.Technological parameter: pressure roller pressure is 2kpa, and 80 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 35N/mm, linear velocity 120cm/min, and hot calendering bonding dot density scope is 5 * 10
4Point/m
2, the bond area ratio accounts for 11% of the fibre web gross area.
(6) coiling operation.Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Made PLA melt-blowing nonwoven performance test results is:
Surface density is 35g/m
2, the fiber average fineness is 2.4 μ m, and thickness is 0.2646mm, and the longitudinal stretching brute force is 48N/5cm, and elongation at break is 15%, and the cross directional stretch brute force is 42N/5cm, and elongation at break is 16%, and Air permenbility is 404.04l/m
2S, bending rigidity 1.28cNcm, filter efficiency is 97% (0.3 μ m rank, down together), hydrostatic pressing has reached the 18cm water column.
In the testing time in 12 weeks of PLA sample of being developed, CO
2Resolution ratio is 95%; In 12 testing times in week and under the screen aperture of 2mm, measured decomposed sample residual component is 7%, has reached desirable degradation effect.
Embodiment 2:
(1) PLA chip drying.Continuous drying equipment is put in the PLA section carried out intensive drying, its section molecular weight is 100000, and melt index is 80～85, and the thermal cracking temperature is 340 ℃.Baking temperature is 80 ℃, and criteria thus the drying time is at 8h, and PLA cuts into slices behind drying, and its moisture is 18ppm.
(2) the PLA section melt extrudes operation.Screw pitch adopts 3mm, and its draw ratio (L/D) is 35, and screw speed is at 45rpm, and the screw extruder internal temperature is at 198 ℃, and spin manifold temperature is at 190 ℃, and feed zone is at 155 ℃, and the compression section is at 185 ℃, and metering section is at 210 ℃.The meltblown beam temperature is at 185 ℃, and the aperture is 0.2mm, and the melt extrusion capacity is at 0.144g/ (hole min).
(3) PLA long filament stretching process.Hot air temperature is 195 ℃, and the hot-air flow velocity is 800m/s, and its pressure is at 0.28Mpa, and the hot air injection angle is 60 °, and the cold air temperature is at 25 ℃, and workshop humidity is limited in 45%.
(4) become the net operation.The involved process conditions of this patent are that meltblown beam is 25cm with becoming the distance between net drum, and the sprayer unit nozzle diameter suitably increases 2mm, and wind speed is at 70m/s, and becoming the lace curtaining transfer rate is 90cm/min.
(5) hot rolling is reinforced.Technological parameter: pressure roller pressure is 4kpa, and 85 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 35N/mm, linear velocity 120cm/min, and hot calendering bonding dot density scope is 8 * 10
4Point/m
2, the bond area ratio accounts for 13% of the fibre web gross area.
(6) coiling operation.Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Made PLA melt-blowing nonwoven performance test results is:
Surface density is 26g/m
2, the fiber average fineness is 1.4 μ m, and thickness is 0.1425mm, and the longitudinal stretching brute force is 35N/5cm, and elongation at break is 21%, and the cross directional stretch brute force is 33N/5cm, and elongation at break is 19%, and Air permenbility is 584.06l/m
2S, bending rigidity 0.98cNcm, filter efficiency is 99%, hydrostatic pressing is the 21cm water column.
In the testing time in 12 weeks of PLA sample of being developed, CO
2Resolution ratio is 96%; In 12 testing times in week and under the screen aperture of 2mm, measured decomposed sample residual component is 6.5%, has reached desirable degradation effect.
Embodiment 3:
(1) PLA chip drying.Continuous drying equipment is put in the PLA section carried out intensive drying, its section molecular weight is 120000, and melt index is 80～85, and the thermal cracking temperature is 350 ℃.Baking temperature is 110 ℃, and criteria thus the drying time is at 4.5h, and PLA cuts into slices behind drying, and its moisture is 20ppm.
(2) the PLA section melt extrudes operation.Screw pitch adopts 3mm, and its draw ratio (L/D) is 33, and screw speed is at 25rpm, and the screw extruder internal temperature is at 205 ℃, and spin manifold temperature is at 200 ℃, and feed zone is at 155 ℃, and the compression section is at 175 ℃, and metering section is at 185 ℃.The meltblown beam temperature is at 180 ℃, and the aperture is 0.4mm, and the melt extrusion capacity is at 0.684g/ (hole min).
(3) PLA long filament stretching process.Hot air temperature is 193 ℃, and the hot-air flow velocity is 400m/s, and its pressure is at 0.25Mpa, and the hot air injection angle is 60 °, and the cold air temperature is at 25 ℃, and workshop humidity is limited in 45%.
(4) become the net operation.The involved process conditions of this patent are that meltblown beam is 15cm with becoming the distance between net drum, and the sprayer unit nozzle diameter suitably increases 3mm, and wind speed is at 150m/s, and becoming the lace curtaining transfer rate is 80cm/min.
(5) hot rolling is reinforced.Technological parameter: pressure roller pressure is 3.8kpa, and 82 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 33N/mm, linear velocity 120cm/min, and hot calendering bonding dot density scope is 12 * 10
4Point/m
2, the bond area ratio accounts for 16% of the fibre web gross area.
(6) coiling operation.Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Made PLA melt-blowing nonwoven performance test results is:
Surface density is 35g/m
2, the fiber average fineness is 4.5 μ m, and thickness is 0.3646mm, and the longitudinal stretching brute force is 58N/5cm, and elongation at break is 12%, and the cross directional stretch brute force is 52N/5cm, and elongation at break is 14%, and Air permenbility is 364.04l/m
2S, bending rigidity 2.28cNcm, filter efficiency is 96%, hydrostatic pressing has reached the 27cm water column.
In the testing time in 12 weeks of PLA sample of being developed, CO
2Resolution ratio is 95%; In 12 testing times in week and under the screen aperture of 2mm, measured decomposed sample residual component is 7%, has reached desirable degradation effect.
Embodiment 4:
(1) PLA chip drying.Continuous drying equipment is put in the PLA section carried out intensive drying, its section molecular weight is 100000, and melt index is 75～80, and the thermal cracking temperature is 315 ℃.Baking temperature is 90 ℃, and criteria thus the drying time is at 6h, and PLA cuts into slices behind drying, and its moisture is 25ppm.
(2) the PLA section melt extrudes operation.Screw pitch adopts 3mm, and its draw ratio (L/D) is 25, and screw speed is at 58rpm, and the screw extruder internal temperature is at 208 ℃, and spin manifold temperature is at 185 ℃, and feed zone is at 138 ℃, and the compression section is at 165 ℃, and metering section is at 198 ℃.The meltblown beam temperature is at 180 ℃, and the aperture is 0.1mm, and the melt extrusion capacity is at 0.082g/ (hole min).
(3) PLA long filament stretching process.Hot air temperature is 195 ℃, and the hot-air flow velocity is 600m/s, and its pressure is at 0.35Mpa, and the hot air injection angle is 60 °, and the cold air temperature is at 25 ℃, and workshop humidity is limited in 45%.
(4) become the net operation.The involved process conditions of this patent are that meltblown beam is 26cm with becoming the distance between net drum, and the sprayer unit nozzle diameter suitably increases 3mm, and wind speed is at 120m/s, and becoming the lace curtaining transfer rate is 100cm/min.
(5) hot rolling is reinforced.Technological parameter: pressure roller pressure is 1kpa, and 83 ℃ of hot-rolled temperatures heat the steel rider temperature up and down and differ and be no more than 1 ℃, and roll nipper pressure adjustable range is 65N/mm, linear velocity 120cm/min, and hot calendering bonding dot density scope is 7.5 * 10
4Point/m
2, the bond area ratio accounts for 12% of the fibre web gross area.
(6) coiling operation.Melt-blowing nonwoven after the hot rolling again through tension-adjusting gear, forms the non-weaving cloth coiled material on the side cut up-coiler after a pair of chill roll cooling.This package non-weaving cloth also can be cut on cutting machine as required, reaches the width of customer requirements.
Made PLA melt-blowing nonwoven performance test results is:
Surface density is 35g/m
2, the fiber average fineness is 1.02 μ m, and thickness is about 0.1mm, and the longitudinal stretching brute force is 31N/5cm, and elongation at break is 15%, and the cross directional stretch brute force is 29N/5cm, and elongation at break is 16%, and Air permenbility is 663.08l/m
2S, bending rigidity 0.54cNcm, filter efficiency is 98%, hydrostatic pressing has reached the 14cm water column.
In the testing time in 12 weeks of PLA sample of being developed, CO
2Resolution ratio is 99.6%; In 12 testing times in week and under the screen aperture of 2mm, measured decomposed sample residual component is 8%, has reached desirable degradation effect.
Claims (6)
1. a fully-degradable polylactic acid fiber melt-blowing nonwoven is characterized in that this non-weaving cloth by polylactic acid slice spinning under 180～185 ℃ melt temperature, and the fiber filament after hot-air stretches forms through self-adhesion and hot rolling; The fiber filament average fineness of this non-weaving cloth is 0.52～5 μ m, and surface density is 5～50g/m
2, thickness is 0.1～0.9mm, and is vertically powerful and horizontal powerful than being 0.9～1.2, to the filter efficiency of bacterium more than 95%; The weight average molecular weight of wherein said polylactic acid slice is 80,000～150,000, and melt index is 75～85g/10min; Hot calendering bonding dot density scope during hot rolling is 2.5 * 10
4～15 * 10
4Point/m
2, the bond area ratio accounts for 8～20% of the fibre web gross area.
2. fully-degradable polylactic acid fiber melt-blowing nonwoven according to claim 1; The longitudinal stretching brute force that it is characterized in that this non-weaving cloth is 30～80N/5cm; The longitudinal fracture percentage elongation is 8～26%; Powerful 25～the 70N/5cm of cross directional stretch, transverse breakage percentage elongation 10～35%, Air permenbility is at 258.62～843.60l/m
2S, bending rigidity is 0.32～2.84cNcm, hydrostatic pressing is 8～30cm H
2O.
3. the preparation method of the described fully-degradable polylactic acid fiber melt-blowing nonwoven of claim 1 is characterized in that comprising the steps:
A, chip drying: earlier polylactic acid slice is dried to moisture＜50ppm, the weight average molecular weight of said polylactic acid slice is 80,000～150; 000; Melt index is 75～85g/10min, and melt temperature is 150～190 ℃, and the thermal cracking temperature is 280～350 ℃;
B, melt extrude: dried polylactic acid slice is sent into fusion in the screw extruder, and melt spray under 180～185 ℃ meltblown beam temperature thread;
C, spin-drawing become net: temperature is that 190～205 ℃, flow velocity are the high-temperature hot air air drawing of 200～1000m/s to the melt of meltblown beam ejection through both sides, and cooling and crystallization under 10～35 ℃ cooling air again is paved into fibre web;
D, hot rolling: fibre web through after the precompressed, is sent hot-rolling mill to and is carried out hot rolling earlier; Hot calendering bonding dot density scope during hot rolling is 2.5 * 10
4～15 * 10
4Point/m
2, the bond area ratio accounts for 8～20% of the fibre web gross area.
4. the preparation method of fully-degradable polylactic acid fiber melt-blowing nonwoven according to claim 3 is characterized in that the dry temperature of polylactic acid slice is 50～120 ℃, and be 3～12h drying time.
5. the preparation method of fully-degradable polylactic acid fiber melt-blowing nonwoven according to claim 3 is characterized in that melt extruding in the step, and the screw extruder draw ratio is 25～40; The screw extruder internal temperature is 120～300 ℃, and spin manifold temperature is 160～220 ℃, and feed zone is 130～160 ℃; The compression section is at 160～185 ℃; Metering section is 180～200 ℃, and screw speed is 10～60rpm, and the measuring pump rotating speed is 10～40rpm; The melt extrusion capacity of meltblown beam is 0.065～0.780g/ (hole min), and the meltblown beam aperture is 0.1～0.4mm.
6. the preparation method of fully-degradable polylactic acid fiber melt-blowing nonwoven according to claim 3 is characterized in that spin-drawing becomes in the net step, and the pressure of said high-temperature hot air is 0.15～0.6MPa, and the wind speed of said cooling air is 0.2～0.6m/s.
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