CN1059719C - Preparation of composite porous hollow stereo crimped fiber with side-by-side bicomponent - Google Patents
Preparation of composite porous hollow stereo crimped fiber with side-by-side bicomponent Download PDFInfo
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- CN1059719C CN1059719C CN98111067A CN98111067A CN1059719C CN 1059719 C CN1059719 C CN 1059719C CN 98111067 A CN98111067 A CN 98111067A CN 98111067 A CN98111067 A CN 98111067A CN 1059719 C CN1059719 C CN 1059719C
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Abstract
The present invention relates to the preparation of a parallel bi-component porous hollow tridimensional crimped fiber, which belongs to a fiber making class. The fiber is a tridimensional crimped fiber with 3 to 17 pores, and is prepared by adopting bi-component polymers (such as PE/PP, PET/PBT and high viscosity PET/low viscosity PET) through composite spinning. Because of the difference of the shrinkage stress of bi-component melting bodies when the melting bodies are extruded from the spinning pores and are cooled by circular blowing, the obtained fiber is naturally tridimensional and crimped, and the crimped durability is fully improved. The fiber can be produced by utilizing composite spinning devices and slightly rebuilding a spinning subassembly.
Description
The invention relates to the preparation of the compound porous type hollow of side-by-side bicomponent stereo crimped fiber.It is to adopt two component condensates: different polymer (PE/PP, PET/PBT); The polymer of different molecular weight (High Viscosity PET/low viscosity PET).Enter the spinnerets guide hole side by side through fusion, extrude, cool off and stretching makes the compound many hollow stereo crimped fiber of side-by-side bicomponent (Fig. 1) by the porous spinnerets.Because the introducing of two components makes the final products crimp property be able to basic improvement, gives nature lasting curling feature, the fastness of curling and elastic recovery also are improved.
For resilience and the warmth retention property that improves fiber, du pont company has been released four holes and seven apertures in the human head fiber the nineties.EP 352,389, and US 5,540,993 and US 5,540, the 994th, be raw material with polyester (PET), through fusion, by the porous spinnerets extrude, encircle blast-cold but, closed loop is shaped and post processing has made four holes and seven apertures in the human head fiber, the gained fiber can bear high-tenacity and good springiness.Du Pont's spinneret orifice is to be similar worker's shape slit composition at center around the spinneret orifice center of circle, because slit arrangement is subjected to the plane figure restriction, can't make it continue to increase the hole count of fiber.
In order to make finished fiber have the three-dimensional crimp performance, the U.S., Japan have adopted the asymmetric cooling method of a kind of off-centre as (JP1981-29007) 80～nineties: this technology is that the one-component melt is adopted special strong cooling when being shaped single hollow or many hollow, when closed loop is shaped, because the existence of middle cavity, hindered the transmission of heat, made fiber Temperature Distribution on the cross section gradient occur; This thermograde has caused the macromolecule crystallization and the degree of orientation difference to occur, has given the curling potential performance of as-spun fibre thus.Yet the restriction that quench air velocity degree and temperature are subjected to all conditions and same condensate be difference and the shrinkage stress that causes is subjected to this condensate inherent characteristic limitation (to become fine condensate hotline expansion coefficient to be generally 10 thus
-5k
-1Level), this is to cause the curling naturally unsettled basic reason of three-dimensional conformation of fiber; As-spun fibre is carried out stretch processing, though can be by means of its potential shrinkage stress, after height stretching external force disappeared, the big molecule that high elastic deformation stretches promptly relaxed, and fiber forms helical corrugation around axially being distorted on the macroscopic view.But this depends on the size of potential precursor shrinkage stress, though adopt by moment cool off fast (the cooling wind speed up to 5.5～6.0m/s) stress differences still difficulty to keep fiber crimp lasting; Although people adopt heat setting method again, attempt to reach the purpose of fixing its coil conformation, this after all big molecular order structure is to be in metastable state, under external force or after the long period uses, this crimp property will fade away.The essential defective of the asymmetric cooling forming method of this off-centre is the polymer that is to adopt same molecular weight.The energy that strong cooling consumed that adopts in producing simultaneously is very big, has improved production cost thus significantly.
JP96-22608 has adopted two kinds of different viscosities similar polymers, and by being that the circular arc slit at center is extruded around the spinneret orifice center of circle, the cooling closed loop is shaped, and makes single doughnut through post processing.Because single mesopore cavity is narrow and small and easily sunken, so fiber obviously exists the warmth retention property difference and resilience is difficult to lasting defective.
The present invention seeks to prepare many doughnuts of crimp property excellence, the method for seeking out a kind of suitability for industrialized production easy to implement prepares the three-dimensional curling fiber of side-by-side bicomponent porous type hollow.
Principle of the present invention is the memory effect according to " bimetal leaf ", is subjected to thermal deformation to cause that the bending of bimetal leaf depends on the thermal coefficient of expansion of two kinds of sheet metals and the thickness of sheet metal.Infer thus, the increase of hollowness of fibre, it will reduce the fibre pipe wall thickness widely, help fiber crimp and elastic raising; Because fiber cross sections loose structure cavity increases, the heat-blocking action of air has caused fiber that good warmth retention property is arranged simultaneously; And two component asymmetric polymer structures make fiber can keep its three-dimensional rolled state enduringly.
Enforcement approach of the present invention is: with two-component polymer fusion respectively, through special spinning pack (Fig. 2), it comprises that presorting matching board, first distribution plate, second distribution plate, composite regulating board enters the spinnerets guide hole side by side, extrude by many mesopores spinneret orifice, obtain the compound porous type hollow of side-by-side bicomponent stereo crimped fiber through the cooling post processing.Only, can realize the production of this kind fiber as long as the filament spinning component of compined spinning apparatus is adjusted.
Technology of the present invention basis is the match selection of two-component polymer.With the difference of the shape composite fibre arranged side by side of routine be that this fiber is many doughnuts.Be subjected to the limitation of bi-component polymeric rheological property and spinneret orifice slit extrusion capacity, keep the porous cross section complete again, satisfy the stable requirement of spinning properties, so be extremely important the selection of two-component polymer for forming the crimp property excellence.The condition restriction that following several respects are arranged for this selection to two-component polymer: (i) shrinkage of two-component polymer---select the thermal contraction performance difference of two-component polymer big more, the contraction internal stress of as-spun fibre is then big more under same cooling condition.On two component couplings, can select the big two components of condensate thermal expansion coefficient difference.With PE/PP and PET/PBT is that the hotline expansion coefficient of example: PE and PP is 20.0～22.0 * 10
-5K
-1With 6.0～8.0 * 10
-5K
-1, the hotline expansion coefficient of PET/PBT is 7～8 * 10
-5K
-1With 13 * 10
-5K
-1, further optimize and select different PE and PP specification, can reach above-mentioned requirements; The greatly different difference of this thermal contraction is curled for solid provides inherent assurance, the more important thing is because the fibrous elasticity response rate that the polymer difference of bi-component arranged side by side forms is a lasting stability, and because the existence of many hollow structures makes this performance particularly evident.(ii) the compatibility of two-component polymer---selecting two good condensates of ingredient compatibility is to guarantee the integrality of as-spun fibre pore-forming and the essential condition of the crimpiness of the back finished fiber that stretches.Because many slits are extruded quantitative limitation, the contact of two component interfaces is very limited on the fibre section, the integrality of unshaped fibre section depends on the compatibility of two-component polymer contact interface to a great extent, more specifically the say so mutual cementability of two polymer interfaces, select improper very easy the fibre section mesopore is broken or two components occur through after-drawing separate.In the selection of two components, but the solubility parameters of selective polymer component close to each other, or adopt the compatible principle of structural similarity to screen.The solubility parameters that with PE/PP is example: PE and PP is respectively 6.2 * 10
-3(J/m
2)
1/2With 6.6 * 10
-3(J/m
2)
1/2, determine the compatible feasible of its pair component.Again on this basis further the model of preferred material to reach the optimum Match purpose.Experimental result shows: the selection of following pair of component is feasible, and they are: polyethylene (PE)/polypropylene (PP); Polyester (PET)/polybutylene terephthalate (PBT); High Viscosity PET/low viscosity PET; The rheological characteristic of (iii) two components---the rheological characteristic of selecting each component in the two-component polymer under spinning condition as far as possible near being an essential condition stablizing spinning.Because bicomponent structural difference is big more, generally speaking it shrinks the variation of great disparity of meeting appearance, yet this also causes the polymeric rheology performance difference to occur.After two components enter the spinnerets guide hole, residing external environment condition is an identical conditions, be that temperature, pressure etc. are unanimity, two component rheological properties comparatively near the time, curling to the stability of spinning, to the closed loop pore-forming of as-spun fibre, to the solid of the symmetry of two components and finished fiber all has remarkable influence.Therefore, after the two-component polymer kind was determined, the spinning temperature of two-component polymer and the selection of melt pressure coupling for the uniformity of the empty rate of the one-tenth that forms two component porous hollow fibers, degree of hollowness and compound interface arranged side by side, were extremely important.
The selection of the compound ratio of two-component polymer of the present invention relates to the key of fiber crimp performance and finished fiber cost height.From the angle that reduces production costs, selecting cheap component is that main ratio is reasonably, however the too high crimp property that can influence fiber of proportion, and general A component should be at 20: 80～80: 20 with the ratio of B component; Crimp property angle from fiber, it is suitable selecting comparatively approaching two component ratios, because this ratio can increase the contraction internal stress of as-spun fibre, thus the crimp property of raising fiber, and general A component should be at 40: 60～60: 40 with the ratio of B component.
The enforcement of the of the present invention pair of compound ratio of component is to depend on a kind of special filament spinning component, and it comprises: presort matching board, first distribution plate, second distribution plate, composite regulating board and porous spinnerets (see for details people such as Shanghai Tak-chuen Chemical Fiber Plant Wang Yong is bright submit to about " the compound porous type doughnut of side-by-side bicomponent filament spinning component " patent application).Two-component polymer arrives the both sides (two components are spaced apart by composite regulating board) of spinnerets guide hole evenly, evenly by presorting matching board, first distribution plate, second distribution plate and composite regulating board, enters the spinnerets guide hole by required compound ratio side by side.The adjustment of the compound ratio of two components can be implemented (also can be controlled by two component output measuring pump rotating speeds) by means of the ratio that composite regulating board is cut apart spinnerets guide hole mouth.The ratio of being cut apart the pinning hole cross section should be between 40: 60～60: 40, and the ratio of more desirable area is 50: 50.
The present invention is that change with two-component polymer changes to the selection of assembly temperature.After two components are determined, the determining of assembly temperature reaches with the two-component polymer rheological property that to coincide be terminal point, be embodied in the stability of spinning and the uniformity of as-spun fibre, be that the unshaped fiber maintenance of spinneret orifice exit is straight and upright and smooth more intuitively, decide spinning body temperature with this.Selection to following pair of component spinning body temperature is: PE/PP should be at 258～282 ℃; PET/PBT should be at 270～284 ℃; High Viscosity PET/low viscosity PET should be at 265～298 ℃.
The porous spinnerets that the present invention adopts is made up of the arcuate slots that different rays one side that around the spinneret orifice center of circle is the center distributes, and each arcuate slots can be: similar C font; Similar E font.The cavity number that is made of arcuate slots is 3～17, generally with 3～15 be advisable (Fig. 3).Adopt different cavity numbers can obtain different porous fibres, determining of hole count is the requirement that relies on finished fiber.
The present invention is owing to the inherent characteristic of having utilized the cooling shrinkage factor difference of two-component polymer great disparity, and is no longer very overcritical to the requirement of chilling temperature and air quantity thus, can reach technological requirement.The quench air velocity degree that the present invention adopts only is 0.4～0.8m/s, and wind-warm syndrome is 14～28 ℃, and this requires energy consumption to reduction equipment, and stable spinning technique is very favourable.
The present invention implements stretch processing to as-spun fibre, and its jet stretch ratio should be at 50～100 times, and the after-drawing ratio should be at 2.8～4.8 times; More desirable jet stretch ratio is 40～80 times, and the after-drawing ratio is 3.0～4.0.
The present invention has been owing to selected two kinds of great condensates of percent thermal shrinkage difference, caused the natural crispation number of gained fiber be increased to 7.4/2.5cm above (one-component only be 5.6/2.5cm).Moreover, the more single hollow side-by-side bicomponent of the elastic recovery rate fiber of Composite Double component porous hollow fiber increases again and (sees example 2 side by side, reference examples 2), the initial elasticity response rate of fiber is through 100,000 load compressions, single hollow bicomponent fibers (reference examples 2), its elastic recovery conservation rate 30%, and porous type hollow bicomponent fibers (embodiment 2), can reach 58%, improve nearly one times.
Description of drawings
The compound porous type hollow of Fig. 1 side-by-side bicomponent stereo crimped fiber produces schematic diagram a-screw rod b-spinning manifold and compound porous assembly c-arranged side by side reels
The compound porous type hollow of Fig. 2 side-by-side bicomponent stereo crimped fiber filament spinning component schematic diagram 1 cap 2 outer collar 3 division boards 4 filters 5 are presorted matching board 6 first distribution plates 7 second distribution plates 8 composite regulating boards 9 spinneretss 10 spinneret orifice 11A compositions and are accumulated place's 12B composition and accumulate place 13 and presort matching board A composition and accumulate place 14 and presort matching board B composition and accumulate place's 15 first distribution plate A composition cannelures, 16 first distribution plate B composition cannelures, 17 aluminium packing rings
Many hollow spray of Fig. 3 filament plate slit pass schematic diagram a-five hole pattern b-nine hole pattern c-13 hole patterns
Three-dimensional many doughnuts of the figure b-sectional view b1-five doughnut sectional view b2-nine doughnut sectional view b3-13 doughnut sectional views that curl of the many doughnuts of many doughnuts of Fig. 4 and porous fibre sectional view a-
The compound many hollow stereo crimped fiber of the many doughnuts of Fig. 5 bi-component (PE/PP) DSC figure (5 ℃/min intensification) a-PE section b-PP section c-PE/PP bi-component
The present invention is illustrated with the following example, but Patent right requirement of the present invention is not limited by the embodiment condition.Embodiment 1
Use A, two screw rods of B (φ 80mm) are respectively to low sticking PET[η]=0.58 (with phenol-tetrachloroethanes is solvent, under 25 ℃ of temperature, test) and high sticking PET[η]=0.70 (method of testing is the same) carry out fusion, input to spinning manifold and compound filament spinning component arranged side by side (spinnerets φ=160mm by measuring pump 10cc/rpm, spinnerets hole count 200 holes) extrude, blow (wind speed=0.6m/s through ring, 24 ℃ of wind-warm syndrome) cooling, spinning body temperature 265-298 ℃, spinning speed 620m/min, 60 times of jet stretch multiples are to the coiling tow employing two-stage stretching at 650,000 dawn of boundling total denier, 3.2 times (72 ℃ of oil bath temperatures) of one-level stretching; 1.12 times of secondary drawing (125 ℃ of superheated steams), heat setting temperature (125 ℃ in a district; 135 ℃ in two districts; 120 ℃ in three districts), heat-setting time 16 minutes, make the compound many hollow stereo crimped fiber of bi-component arranged side by side (Fig. 4) thus, it becomes empty rate to reach 97%, ∑ degree of hollowness 31.8%, and number 7.5/2.5cm naturally curls, elongation 38%, intensity 3.9CN/dtex, shearing length 65mm, elastic recovery rate 88.8%.Embodiment 2
Adopt A, B screw rod and spinning manifold and the compound porous assembly of embodiment 1, A screw rod fusion PET[η]=0.65, B screw rod fusion PBT[η]=0.72,270～284 ℃ of spinning body temperatures, ring blowing wind speed 0.6m/s, 60 times of 24 ℃ of wind-warm syndrome, spinning speed 580m/min, jet stretch multiple, 650,000 dawn of boundling total denier, (70 ℃ of the oil baths of after-drawing temperature, 120 ℃ of superheated steams), draw ratio (3.0 times of one-levels, 1.11 times of secondarys), heat setting temperature (120 ℃ in a district; 135 ℃ in two districts; 120 ℃ in three districts) and heat-setting time 16 minutes.The gained fiber becomes empty rate 95.7%, ∑ degree of hollowness 26.5%, the 7.4/2.5cm of number that curls naturally, elongation 48%, intensity 3.4CN/dtex, shearing length 65mm, elastic recovery rate 91.8%.Embodiment 3
Adopt A, B screw rod and spinning manifold and the compound porous assembly of embodiment 1, A screw rod fusion PP, B screw rod fusion PE, compound one-tenth PP/PE porous hollow fiber arranged side by side.270 ℃ of spinning body temperatures, quench air velocity 0.4m/s, 16 ℃ of ring blowing temperature, spinning speed 650m/min, 60 times of jet stretch multiples, 3.2 times of after-drawing I levels (50 ℃ of oil bath temperatures), 1.16 times of II levels (105 ℃ of superheated steams), heat setting temperature (105 ℃ in a district; 115 ℃ in two districts; 110 ℃ in three districts).The gained fiber becomes empty rate 95%, ∑ degree of hollowness 27%, the 7.2/2.5cm of number that curls naturally, elongation 54%, intensity 3.2CN/dtex, shearing length 65mm, elastic recovery rate 86.6%.
The component of this fiber can be measured (Fig. 5 c) by DSC.Reference examples 1
Adopt A, B screw rod and composite spinning casing, A screw rod fusion High Viscosity PET [η]=0.70, B screw rod fusion low viscosity PET[η]=0.58, becoming single empty composite fibre side by side, the gained fiber becomes empty rate 95%, degree of hollowness 18%, naturally curling 6.8/2.5cm of number, elongation 42%, intensity 3.6CN/dtex, shearing length 65mm, elastic recovery rate 87%.Reference examples 2
Adopt A, B screw rod and composite spinning casing, A screw rod fusion PET[η]=0.65, B screw rod fusion PBT[η]=0.72, the empty composite fibre of gained list becomes empty rate 96%, degree of hollowness 19.5%, and number 6.5/2.5cm naturally curls, elongation 52%, intensity 3.3CN/dtex, shearing length 65mm, elastic recovery rate 89.8%.
Claims (13)
1, a kind of pair component compound porous type hollow stereo crimped fibers arranged side by side that comprise, it is characterized in that: described pair of component is two kinds of compatible polymers components, and they can be: polyethylene (A) and polypropylene (B); Polyester (A) and polybutylene terephthalate (B); Perhaps high-viscosity polyester (A) and low-viscosity polyester (B), described two-component polymer is entered side by side the guide hole of spinnerets by certain compound ratio, extrude by the porous spinnerets, melt is closed into ring under ring blowing cooling effect, form the two compound porous type hollow of component shape arranged side by side precursor, it is after jet stretch, after-drawing make the compound porous type hollow of side-by-side bicomponent stereo crimped fiber.
2, fiber according to claim 1, the wherein said pair of compound ratio of component can be: component A accounts for 20～80% of total component, and component B accounts for 80～20% of total component.
3, fiber according to claim 2, the compound ratio of wherein said pair of component can be: the A component accounts for 40～60% of total component, and the B component accounts for 60～40% of total component.
4, fiber according to claim 1, wherein two-component polymer arrives the spinnerets guide hole by presorting matching board, first distribution plate, second distribution plate and composite regulating board respectively, two-component polymer in guide hole aperture symmetry separately, the ratio of area that is separated guide hole is between 40: 60～60: 40.
5, fiber according to claim 4, the wherein said ratio that is separated the area of guide hole is 50: 50.
6, according to any one described fiber in the claim 1 to 5, wherein different two components are selected different spinning body temperatures, and they are respectively: (1) polyethylene and polyacrylic spinning body temperature are 258～282 ℃; (2) spinning body temperature of polyester and polybutylene terephthalate is 270～284 ℃; Perhaps the spin manifold temperature of (3) high-viscosity polyester and low-viscosity polyester is 265～298 ℃.
7, fiber according to claim 6, wherein said porous spinnerets is made up of the arcuate slots that with the spinneret orifice center of circle is the different ray one sides distributions in center.
8, fiber according to claim 7, wherein said arcuate slots are that the center is distributed in the similar C font on the spinneret orifice or the arcuate slots of similar E font symmetrically.
9, fiber according to claim 1, wherein the gained porous fibre is the two component shape composite fibres arranged side by side in 3～17 holes.
10, fiber according to claim 9, wherein the gained porous fibre is the two component shape composite fibres arranged side by side in 3～15 holes.
11, fiber according to claim 1, the wherein said quench air velocity degree that is closed into ring under ring blowing cooling effect is 0.4～0.8 meter per second, wind-warm syndrome is 14～28 ℃.
12, fiber according to claim 1, the draw ratio of wherein said jet stretch are 50～80 times, and the draw ratio of described after-drawing is 2.8～4.8 times.
13, fiber according to claim 12, the draw ratio of wherein said after-drawing are 3.0～4.0 times.
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| CN98111067A CN1059719C (en) | 1998-09-07 | 1998-09-07 | Preparation of composite porous hollow stereo crimped fiber with side-by-side bicomponent |
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| CN98111067A CN1059719C (en) | 1998-09-07 | 1998-09-07 | Preparation of composite porous hollow stereo crimped fiber with side-by-side bicomponent |
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| CN1059719C true CN1059719C (en) | 2000-12-20 |
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