CN1961765A - A cigarette filter filament and preparation method thereof - Google Patents
A cigarette filter filament and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a tobacco filter tip and relative preparation, wherein it is formed by spinning the lactic acid polymer resin, drawing, coiling and shaping, while the line density is 2-6dtex, the beam density is 3-6ktex, the coil number is 15-30n/25mm. And it uses the adhesive method similar acetate fabric. Therefore, its polymer structure and large specific area can support the adsorption on organic, and filter the solid particle.
Description
Technical field
The present invention relates to a kind of cigarette filter filament and preparation method thereof, be specifically related to biodegradable lactide acid polymer cigarette filter filament and preparation method thereof
Background technology
Cigarette filter is the indispensable part of cigarette, and it has filtration, stops and suction-operated the oxious component in breathing one's last such as nicotine, tar, can improve the mouthfeel of flue gas, reduces flue gas to the stimulation in oral cavity with to the injury of health.For a long time, main two kinds of filter-tip materials, the one, cellulose acetate fibre, the 2nd, the polypropylene fibre of using on the market.Cellulose acetate is spun into fine count fiber easily, and the adhesion process ratio from the fiber to the filter stick is easier to, and made filter stick and filter tip have superior combination property, are adapted at using in the medium-to-high grade cigarette.But it is a raw material with the timber of high-quality, and the process to cellulose acetate is accompanied by many pollution problems again from timber to the wood pulp, adopts dry spinning, must use solvent, has both increased cost, pollutes unavoidably again.China's Forest Resources is limited, and cellulose acetate can not be self-supporting, the import of the main dependence of China at present, and price is higher, can not use in low and middle-grade cigarette.Cellulose itself is can be biodegradable, but biological degradability descends greatly after the esterification, no longer belongs to proper biodegradation material.Pp material is cheap, can use the melt spinning process spinning, thereby has lower price.But its spinnability is poor, be difficult to obtain fine denier filament, nonpolar and the high-crystallinity of polypropylene fibre itself, it is bonding that it is difficult to, thereby the filter stick of making by polypropylene fibre and the filterability of filter tip, and mechanical performances such as outward appearance, hardness, empty resistance are very difficultly compared with cellulose acetate, can only use in low and middle-grade cigarette, tow, filter stick manufacturer's profit margin is very little.The pp material price that causes owing to petroleum price rise soaring more makes tow, filter stick production cost rise significantly.Polypropylene is a long chain hydrocarbon, can not biodegradation, and a large amount of the use accumulated over a long period, and be very unfavorable to environment.
So, two kinds of cigarette filter tip materials of Shi Yonging in the market, polypropylene fibre especially, combination property is not ideal enough, can not satisfy the minimizing tar content, safeguards the needs of health of smokers.Can not biodegradation, in mankind today more and more higher, also be significant disadvantages to environmental quality requirement.Must there be better filter-tip material to replace.
On the other hand, in recent years, Biodegradable high molecular has had significant progress, lactide acid polymer especially, and as PLA, the copolymer of lactic acid and 6-caprolactone or glycolic etc.Biodegradation or under people's concrete conditions in the establishment of a specific crime, can take place under field conditions (factors), finally becomes carbon dioxide and water, does not stay any pollutant, so be genuine " green material ".Because lactic acid makes with amylaceous fermented method, its raw material is annual plants such as corn, potato, sweet potato, is out-and-out " renewable resource ", originates and enriches, and is cheap, is not subjected to the impact of petroleum price rise etc.Another advantage of lactide acid polymer is that their processing characteristics is better, can adopt the various processing methods of general thermoplastic to process, and comprises melt spinning.Both can be spun into long filament, also can be spun into short silk.In fact, the clock of the NatureWorks company of the U.S. and Japan spins, company such as Dong Li cooperate, successfully developing weaving usefulness acid fiber by polylactic and goods thereof, and selling on market.Concerning textile fabric, must satisfy the requirement of the requirement of fibre spinning, braiding and fabric printing, washing, flatiron, higher degree of crystallinity, the degree of orientation and mechanical strength must be arranged, must be very little in dissolving in washing agent and the organic solvent and swelling, to the absorption of gaseous matter in the surrounding environment also seldom.And as the cigarette filter fiber, at first will satisfy physicochemical property requirements such as the stopping of harmful substance in the flue gas, filtration and absorption, reduce the harm of flue gas to human body, secondly be to satisfy the technology requirement that bunch fiber is bonded into rod.Facts have proved, commercially available PLA textile fabric although can satisfy the requirement that tow is produced on line density and curl characteristics, can not satisfy the technological requirement that is bonded into rod at present, because use the triacetyl glycerine of generally acknowledging at present, they can not be bonded into filter stick at normal temperatures.So to PLA cigarette filter filament fiber, is not simple imitation and peculation from the PLA textile fabric, and special fluoropolymer resin and corresponding spinning and post-processing technology must be arranged.Application number is 200610016643.0 Chinese invention patent application documents, discloses to can be used to make the raw-material lactide acid polymer of cigarette filter.They are copolymers of PLA or lactide and 6-caprolactone and/or glycolide, wherein in PLA, the percentage by weight of L-lactic acid unit is 1～12%, total percentage by weight of 6-caprolactone and glycolic is 1～10% in the copolymer, the weight average molecular weight molecular weight of polymer is in 5～200,000 scopes, 140～175 ℃ of melting ranges, the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～30g/10min scope with the bonding intensity of triacetyl glycerine room temperature.Such polymer has suitable degree of crystallinity, dissolubility, adsorption capacity and mechanical strength, can satisfy spinning, post processing, be bonded into the technological requirement of rod and the filtration and the mechanical and physical performance requirement of filter tip.But this patent application document does not relate to the method for cigarette filter filament and preparation thereof.
Up to the present, still find no lactide acid polymer and comprise the filter filament of the copolymer of PLA, lactide and 6-caprolactone and/or glycolide, the preparation method of this cigarette filter filament is not provided yet as raw material preparing.
Summary of the invention
One of purpose of the present invention provides a kind of cigarette filter filament, it by spinning component through melt spinning and follow-up drawing-off, curl and the fiber obvolvent undaform fibre bundle sheet together that curls that thermal finalization forms, monofilament linear density 2～6dtex, tow line density 3～6ktex, 15～30/25mm of crispation number.
Described spinning component, it is formed through melt blending, granulation by one or more lactide acid polymers and processing aid or modifier.Use the double-screw extruding pelletizing machine that composite preferably effect is arranged.
The material formation and the proportioning of spinning component of the present invention are as follows:
(1) lactide acid polymer (hereinafter to be referred as matrix resin) is a specification of PLA or the mixture of a plurality of specifications, or lactide and 6-caprolactone, lactide and glycolide, or the copolymer of lactide and 6-caprolactone and glycolide;
Described matrix resin is a PLA, and the percentage by weight of its L-lactic acid unit is 3～7%;
Described matrix resin is the bipolymer of lactide and 6-caprolactone, lactide and glycolide, and its weight percent proportioning is: lactide is 92～95%, and 6-caprolactone or lactide are 92～95%;
Described matrix resin is the terpolymer of lactide and 6-caprolactone and glycolide, its weight percent proportioning is: lactide is 92～95%, the weight percent proportioning of 6-caprolactone and glycolide sum is 5-8%, and the ratio between 6-caprolactone and the glycolide units is not limit;
The weight average molecular weight of PLA or copolymer is in 5～200,000 scopes, 150～170 ℃ of melting ranges, and the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～20g/10min scope with the bonding intensity of triacetyl glycerine room temperature.
(2) heat stabilizer is: calcium stearate, lithium stearate, aluminum stearate, calcium laurate, calcium lactate or zinc lactate; With respect to 100 parts of matrix resins, the mass fraction of heat stabilizer is 0.1～0.5;
(3) antioxidant is nontoxic or the phosphorous acid esters stabilizing agent and the phenolic antioxidant of low toxicity, and it is: triphenyl phosphite, trisnonyl phenyl phosphite, antioxidant 1010, antioxidant 1076, antioxidant 2246 or antioxidant 264; With respect to 100 parts of matrix resins, the mass fraction of antioxidant is 0.1～0.5;
(4) the lactic acid trapping agent is: nano silicon, nano titanium oxide, nanometer hydroxyapatite or 1, two (beta-amino butenoic acid) esters of 4-butanediol; With respect to 100 parts of matrix resins, the mass fraction of lactic acid absorbent is 0.1～1.0;
(5) mobile and caking property improver is: glyceride lactate, triacetyl glycerine, ATBC or tributyl 2-acetylcitrate; With respect to 100 parts of matrix resins, the mass fraction of improver is 0～5;
(6) delustring and brightening agent are: titanium dioxide, with respect to 100 parts of matrix resins, the mass fraction of titanium dioxide is 0.2～0.6.
Two of purpose of the present invention provides a kind of preparation method of cigarette filter filament, and its step and condition are as follows:
(1) before spinning, spinning component is carried out drying handle, water content wherein is reduced to below the 1000ppm;
(2) spinning component that drying is crossed carries out melt spinning, 190～210 ℃ of spinning temperatures, spinneret hole count 6000～20000, spinneret orifice is a trilobal, effective aperture 0.25～0.5mm, draw ratio 2: 1～4: 1,20～25 ℃ of dry air coolings, drum process coated finish, tow gathering speed 30～100m/min;
(3) with 5 rollers or 7 roller drafting machines to fibrillation Shu Jinhang drawing-off, the drawing-off medium is a water, 60～80 ℃ of temperature, 2～5 times of drawing-off multiplying powers;
(4) will carry out nervous thermal finalization and cooling through the fibre bundle of drawing-off, heat medium is a water, 55～70 ℃ of setting temperatures, and fibre length conservation rate 100～90%, cooling medium are running water;
(5) will curl through the fibre bundle of drawing-off with crimping machine, heat medium is air or steam, 50～70 ℃ of preheat temperatures, 15～30/25mm of crispation number;
(6) fibre bundle after curling is carried out drying and relaxation heat setting, heat medium is an air, 50～60 ℃ of setting temperatures, and shaping time 10～15min obtains a kind of cigarette filter filament.
More than carry out continuously on a production line from melt spinning to each step that obtains cigarette filter filament, be called for short " single step spining ", its feature is continuous, efficient, but concerning the resin of some specification of crystallizing power difference, the stretching multiple proportions and the oriented crystalline degree of resulting fiber are limited, curling unfavorable to the back.To this class spinning component, preferably adopt " two-step method spinning ", be about to as-spun fibre and handle a period of time at 25～55 ℃, then in drawing-off, curling and typing, correspondingly, the technological parameter of spinning, drawing-off and typing is done suitably to adjust.Concrete step and condition are as follows:
(1) before spinning, spinning component is carried out drying handle, water content wherein is reduced to below the 1000ppm;
(2) spinning component that drying is crossed carries out melt spinning, 190～210 ℃ of spinning temperatures, spinneret hole count 6000～20000, spinneret orifice is a trilobal, effective aperture 0.25～0.5mm, draw ratio 2: 1～4: 1,20～25 ℃ of dry air coolings, drum process coated finish, tow gathering speed 50～150m/min;
(3) primery vascular bundle of collecting is handled 48～2h at 25～55 ℃;
(4) treated fibre bundle carries out drawing-off on 5 rollers or 7 roller drafting machines, and the drawing-off medium is a water, 70～90 ℃ of drawing temperatures, 1～3 times of drawing-off multiplying power;
(5) will carry out nervous thermal finalization and cooling through the fibre bundle of drawing-off, heat medium is a water, 55～70 ℃ of setting temperatures, and fibre length conservation rate 100～90%, cooling medium are running water;
(6) will curl through the fibre bundle of drawing-off with crimping machine, heat medium is air or steam, 50～70 ℃ of preheat temperatures, 15～30/25mm of crispation number;
(7) fibre bundle after curling is carried out drying and relaxation heat setting, heat medium is an air, 50～60 ℃ of setting temperatures, and shaping time 10～15min obtains cigarette filter filament.
In above-mentioned melt spinning process, must be at as-spun fibre surface coated finish, the general drum process coated that adopts, finish in the i.e. cylinder bottom of the horizontal direction of the rotation contact finish groove, the even coated of finish is at cylinder surface, the as-spun fibre that moves down nuzzles up from the side of cylinder, and finish is transferred to fiber surface, plays cooling, lubricated, obvolvent, antistatic.
The finish that described coated as-spun fibre uses is the aqueous solution of water-soluble polymer, and is added with quaternary ammonium salt, nonionic and/or anionic surfactant and/or antistatic additive.
Described water-soluble polymer is selected from polyvinyl alcohol, polyethylene glycol or polyoxyethylene; Its weight concentration is 0.05～0.5%;
Described quaternary ammonium salt surface active agent and/or antistatic additive are selected from antistatic agent TM (trihydroxyethyl ammonium methyl Methylsulfate salt), antistatic additive SP (hard amido propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate), antistatic additive P (alkyl phosphate diethanolamine salt); Weight concentration is 0.02～0.2%;
Described nonionic surface active agent is selected from polysorbas20,40,60 or 80, C
8-10APES, polyoxyethylene lauryl ether, polyoxyethylene glycerol ether, polyethylene glycol monolaurate, polyoxyethylene glycol monostearate, polyethylene glycol monooleate, or the mixture of 2～3 kinds of above-mentioned substances; Weight concentration is 0.02～0.2%;
Described anionic surfactant is selected from neopelex, lauryl sodium sulfate or their mixture; Weight concentration is 0.02～0.2%.
Above spinning, drawing-off, curl and the selection of the technology of thermal finalization, taken into full account the characteristic of PLA itself, especially three of PLA and lactide acid polymer characteristic temperatures: 140～175 ℃ of crystalline melt points, near 60 ℃ of the glass transition temperatures, 90～110 ℃ of crystallization temperatures (to the sample of no thermal history and internal stress free, crystallization temperature is 70～90 ℃ under fiber and state of orientation).In the melt rheology characteristic of 170～250 ℃ of temperature ranges and the possibility of thermal decomposition, selecting 190～210 ℃ is spinning temperature according to polymer, and concrete spinning temperature is determined according to the melt viscosity size of polymer with to the requirement of monofilament linear density.Because the vitrification point of lactide acid polymer is near 60 ℃, crystallization temperature is 70～90 ℃ under fiber and state of orientation, carry out drawing-off and nervous thermal finalization at 60～90 ℃, after 50～70 ℃ of preheatings, curl, carry out drying and relaxation heat setting at 50～60 ℃, might reach best drawing-off, curling and typing effect.
Compare with polypropylene rayon bunch for filter of cigarette with present existing cellulose acetate cigarette filter filament, the cigarette filter silk that the present invention obtains has following advantage: they are biodegradable for (1), tow itself and their catabolite are nontoxic to human body, and environment is not polluted; (2) the primary raw material lactic acid of production lactide acid polymer tow be the tunning of starch, and starch is renewable resource, can produce low price in a large number; (3) adopt the melt spinning technology to be spun into fine count fiber, lower than solution spinning cost, pollute few; (4) they have certain solubility and dissolution velocity in edible nontoxic organic solvent, thereby can adopt simple technology that the fiber that curls is bonded into filter stick, and filter stick has filterability and physical and mechanical properties preferably.
Be not difficult to find out, the preparation method of a kind of cigarette filter silk of the present invention, no matter be one-step method or two-step method, all belong to melt spinning, be the short fiber production process of not cutting off operation, thereby it has the advantage of melt-spun staple process, the production efficiency height, production cost is low, does not use solvent, chemical assistant is few, thereby low in the pollution of the environment.Produce the equipment of fibre beam for polypropylene cigarette at present,, can produce high-quality breast and pour a libation the base polymer tow, thereby the capital construction investment meeting of producing is lower through suitable transformation.In above-mentioned two kinds of technologies, the advantage of one-step method is that equipment investment is less relatively, and it is suitable for the higher lactide acid polymer of crystallinity.The advantage of two-step method is spinning and drawing-off, curls and carry out in two steps, do not pin down mutually, thereby the quality of tow controls easily, and the spinning section allows higher production, and it is applicable to the resin that crystallinity is relatively poor.
The specific embodiment
Further specify the present invention below by embodiment.
Below among each embodiment, (1) each spinning component all passes through the drying of step 1 and handles, water content all below 1000ppm, repeated description no longer below; (2) except that writing exactly especially, the finish of use is the aqueous solution of 0.2% polyoxyethylene (molecular weight 600,000), and is added with 0.1% antistatic agent TM and 0.1% neopelex.
Embodiment 1:
Select a kind of PLA (PLA) for use, wherein contain 97% D-lactic acid unit and 3% L-lactic acid unit.The weight average molecular weight 7.8 ten thousand of polymer, melt flow index 15.4g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 7.0MPa.The fusing point that records with the DSC method is 161 ℃.
Calculate by weight ratio, take by weighing 100 parts PLA, add 0.2 part Wytox 312,0.2 part of antioxidant 1010,0.2 part calcium stearate, 1.0 parts tributyl 2-acetylcitrate, 0.4 part of rutile type titanium white (Du Pont 902) and 1.0 parts nanometer titanium dioxide silicon powder, make spinning component.
Take " single step spining " technology, promptly go up spinning at the melt spinning machine (two spinning seats in the plane) of a φ 65 * 28, the metering section temperature is controlled at 220 ± 2 ℃, the temperature of filament spinning component is controlled at 205 ± 1 ℃, two melt-stoichiometry pump sizes are all 10ml/r, speed all is 30r/min, two each 6000 holes of spinneret, rectanglar arrangement, spinneret orifice is trilobal, diameter 0.5mm of equal value, with the cooling of 25 ℃ dry air cross air blastings, with drum process coated finish (0.2% polyethylene glycol 1700 aqueous solution are added with 0.1% antistatic agent TM and 0.1% Nonyl pheno (15)), speed 50m/min is collected in two bundle birth fiber plying backs with seven roller drafting machines.Carry out drawing-off with seven roller drafting machines, the drawing-off medium is a water, 75 ℃ of drawing temperatures, gathering speed 150m/min.In 60 ℃ of tanks, carry out nervous thermal finalization, cool off gathering speed 150m/min after the water outlet of tow sheet with running water.Crimping machine with effective width 30mm curls, and heat medium is a steam, 60 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 55 ℃ of setting temperatures, and typing dewatering time 10min obtains the cigarette filter filament sheet.Its total linear density 5.0 ± 0.4ktex, single fiber line density are 4.1 ± 0.4dtex, 22 ± 3/25mm of crispation number, room temperature filament strength 1.6 ± 0.4cN/dtex, percentage elongation 5.2 ± 1.0%.
Embodiment 2:
Calculate by weight ratio, select same spinning component of embodiment 1 and spinning-drawing machine, measuring pump, spinneret for use, adopt " two-step method spinning " technology to carry out the light engine position spinning, spinning speed 30r/min, nascent tow is directly drawing-off not, but after the speed collection with 100m/min, place 4h at 50 ℃.Drawing-off is carried out with seven roller drafting machines in two bursts of nascent tow plying backs, and wire feed rate 60m/min, drawing-off medium are water, 80 ℃ of drawing temperatures, and with the running water cooling, gathering speed 150m/min obtains cigarette filter filament after the water outlet of tow sheet.Its total linear density 3.0 ± 0.3ktex, single fiber line density are 2.5 ± 0.3dtex, 22 ± 3/25mm of crispation number, room temperature filament strength 2.0 ± 0.5cN/dtex, percentage elongation 4.3 ± 0.9%.
Embodiment 3:
Select the random copolymer resin (PLGA) of a kind of levorotatory lactide and glycolide for use, wherein the lactic acid weight content 94%, glycolide weight content 6%.The weight average molecular weight 12.8 ten thousand of polymer, melt flow index 10.4g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 7.5MPa.The fusing point that records with the DSC method is 156 ℃.
Calculate by weight ratio, take by weighing 100 parts PLGA, add 0.2 part Wytox 312,0.2 part of antioxidant 1010,0.2 part lithium stearate, 1.0 parts tributyl 2-acetylcitrate, 0.5 part of rutile type titanium white (Du Pont 902) and 1.0 parts nanometer titanium dioxide silicon powder, make spinning component.
Adopt " single step spining " technology, spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 220 ± 2 ℃, and the temperature of filament spinning component is controlled at 200 ± 1 ℃.Two melt-stoichiometry pump sizes are all 10ml/r, each 30r/min of speed, two each 8000 holes of spinneret, rectanglar arrangement, spinneret orifice is trilobal, and diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish (0.2% polyethylene glycol 1700 aqueous solution are added with 0.1% antistatic additive SP and 0.1% polysorbate60).Two bundle birth fiber plying are collected and drawing-off with seven roller drafting machines, and gathering speed 50m/min, drawing-off medium are water, and 72 ℃ of drawing temperatures cool off 3.0 times of drawing-off multiplying powers with running water after the water outlet of tow sheet.Crimping machine with effective width 30mm curls, and heat medium is a steam, 55 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 55 ℃ of setting temperatures, and typing dewatering time 15min obtains cigarette filter filament.Its single fiber line density is 3.1 ± 0.4dtex, total linear density 5.0 ± 0.4ktex, 21 ± 3/25mm of crispation number, room temperature filament strength 1.3 ± 0.3cN/dtex, percentage elongation 5.8 ± 1.0%.
Embodiment 4:
Calculate by weight ratio, use the spinning component of embodiment 3, adopt " two-step method spinning " technology, on the melt spinning machine of the two-shipper position of a φ 65 * 28, carry out the light engine position spinning, the metering section temperature is controlled at 225 ± 2 ℃, it is 10ml/r that the temperature of filament spinning component is controlled at 205 ± 1 ℃ of melt-stoichiometry pump sizes, speed 30r/min, spinneret 8000 holes, rectanglar arrangement, spinneret orifice is trilobal, diameter 0.5mm of equal value, with 25 ℃ dry air cross air blasting cooling, with drum process coated finish, gathering speed 100m/min.The nascent tow of collecting is placed 48h in room temperature (25 ℃).Two strands of nascent tow are pieced together a burst back and are carried out drawing-off with seven roller drafting machines, and wire feed rate 80m/min, drawing-off medium are water, 80 ℃ of drawing temperatures, and 2.0 times of drawing-off multiplying powers are cooled off gathering speed 160m/min with running water after the water outlet of tow sheet.Crimping machine with effective width 30mm curls, and heat medium is a steam, 65 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 60 ℃ of setting temperatures, typing dewatering time 12min.The single fiber line density of gained tow is 2.3 ± 0.3dtex, total linear density 3.7 ± 0.3ktex, 23 ± 3/25mm of crispation number, room temperature filament strength 1.6 ± 0.3cN/dtex, percentage elongation 4.2 ± 1.0%.
Embodiment 5:
Select the random copolymer resin (PCLA) of a kind of levorotatory lactide and 6-caprolactone for use, wherein lactic acid content 95%, 6-caprolactone 5%.The weight average molecular weight 10.8 ten thousand of polymer, melt flow index 15.4g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 8.0MPa.The fusing point that records with the DSC method is 164 ℃.
Calculate by weight ratio, take by weighing 100 parts PCLA, add 0.2 part Wytox 312,0.2 part of antioxidant 1010,0.2 part calcium stearate, 1.0 parts tributyl 2-acetylcitrate, 0.5 part of rutile type titanium white (Du Pont 902) and 1.0 parts nanometer titanium dioxide silicon powder, make spinning component.
Adopt " single step spining " technology, spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 225 ± 2 ℃, and the temperature of filament spinning component is controlled at 200 ± 1 ℃.Two melt-stoichiometry pump sizes are 10ml/r, speed is respectively 32r/min and 24r/min, corresponding spinneret is 8000 and 6000 holes, rectanglar arrangement, spinneret orifice is trilobal, and diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish (0.1% polyoxyethylene (the weight average molecular weight 600,000) aqueous solution is added with 0.1% antistatic agent TM and 0.1% neopelex).Two strands of nascent tow merge the back to be collected and drawing-off with seven roller drafting machines, and gathering speed 50m/min, drawing-off medium are water, and 70 ℃ of drawing temperatures cool off 3.0 times of drawing-off multiplying powers with running water after the water outlet of tow sheet.Crimping machine with effective width 30mm curls, and heat medium is a steam, 55 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 55 ℃ of setting temperatures, and typing dewatering time 15min obtains cigarette filter filament.Its single fiber line density is 3.5 ± 0.4dtex, total linear density 5.0 ± 0.4ktex, 21 ± 3/25mm of crispation number, room temperature filament strength 1.4 ± 0.3cN/dtex, percentage elongation 5.2 ± 1.0%.
Embodiment 6:
Calculate by weight ratio, use the spinning component of embodiment 5, adopt " two-step method spinning " technology, on the melt spinning machine of the two-shipper position of a φ 65 * 28, carry out the light engine position spinning, the metering section temperature is controlled at 225 ± 2 ℃, it is 10ml/r that the temperature of filament spinning component is controlled at 205 ± 1 ℃ of melt-stoichiometry pump sizes, speed 35r/min, spinneret 6000 holes, rectanglar arrangement, spinneret orifice is trilobal, diameter 0.5mm of equal value, with 25 ℃ dry air cross air blasting cooling, with drum process coated finish, gathering speed 80m/min.The tow of collecting is placed 24h in room temperature (25 ℃).Two strands of nascent tow merge the back and carry out drawing-off with seven roller drafting machines, and the drawing-off medium is a water, 85 ℃ of drawing temperatures, 2.5 times of drawing-off multiplying powers, gathering speed 160m/min.In 60 ℃ of tanks, carry out nervous thermal finalization, cool off gathering speed 150m/min after the water outlet of tow sheet with running water.Crimping machine with effective width 30mm curls, and heat medium is a steam, 60 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 55 ℃ of setting temperatures, and typing dewatering time 12min obtains cigarette filter filament.Its total linear density 4.6 ± 0.4ktex, single fiber line density are 3.8 ± 0.3dtex, 22 ± 3/25mm of crispation number, room temperature filament strength 1.8 ± 0.3cN/dtex, percentage elongation 4.2 ± 1.0%.
Embodiment 7:
Calculate by weight ratio, select a kind of polylactic resin (PLA1) for use, it contains 99% D-lactic acid unit and 1% L-lactic acid unit, viscosity average molecular weigh 6.2 ten thousand, melt flow index 23g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 4.2MPa.The fusing point that records with the DSC method is 171 ℃.
Select another kind of polylactic resin (PLA2) for use, it contains 91.5% D-lactic acid unit and 8.5% L-lactic acid unit, weight average molecular weight 12.8 ten thousand, melt flow index 5.7g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 9.8MPa.The fusing point that records with the DSC method is 138 ℃.
More than two kinds of polylactic resin press PLA1: PLA2=2: 1 part by weight mixes.Take by weighing the hybrid resin of 100 weight portions, add 0.2 part Wytox 312,0.2 part of antioxidant 1076,0.3 part of nanometer hydroxyapatite, 0.4 part calcium stearate, 2.0 parts tributyl 2-acetylcitrate, 0.5 part of rutile type titanium white, make spinning component.
Adopt " single step spining " technology, spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 220 ± 2 ℃, and the temperature of filament spinning component is controlled at 205 ± 1 ℃.Two melt-stoichiometry pump sizes are 10ml/r, each 30r/min of speed, and two each 6000 holes of spinneret, rectanglar arrangement, spinneret orifice is trilobal, and diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish.Two bundle as-spun fibres merge, and collect and drawing-off with seven roller drafting machines, and gathering speed 60m/min, drawing-off medium are water, and 70 ℃ of drawing temperatures cool off 2.5 times of drawing-off multiplying powers with running water after the water outlet of tow sheet.Crimping machine with effective width 30mm curls, and heat medium is a steam, 55 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 55 ℃ of setting temperatures, and typing dewatering time 15min obtains cigarette filter filament.Its total linear density 4.8 ± 0.4ktex, single fiber line density are 4.0 ± 0.5dtex, 20 ± 3/25mm of crispation number, room temperature filament strength 1.3 ± 0.3cN/dtex, percentage elongation 5.6 ± 1.1%.
Embodiment 8:
Calculate by weight ratio, use the spinning component of embodiment 7.
Adopt " two-step method spinning " technology, carry out the light engine position spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 225 ± 2 ℃, and the temperature of filament spinning component is controlled at 205 ± 1 ℃.The melt-stoichiometry pump size is 10ml/r, speed 32r/min, and spinneret 8000 holes, rectanglar arrangement, spinneret orifice is trilobal, and diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish, gathering speed 100m/min.The tow of collecting is placed 48h in room temperature (25 ℃).Two strands of tow merge the back and carry out drawing-off with seven roller drafting machines, and the drawing-off medium is a water, 80 ℃ of drawing temperatures, 2.0 times of drawing-off multiplying powers, gathering speed 160m/min.In 65 ℃ of tanks, carry out nervous thermal finalization, cool off gathering speed 150m/min after the water outlet of tow sheet with running water.Crimping machine with effective width 30mm curls, and heat medium is a steam, 65 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 65 ℃ of setting temperatures, and typing dewatering time 10min obtains cigarette filter filament.Its total linear density 4.2 ± 0.3ktex, single fiber line density are 2.6 ± 0.4dtex, 22 ± 3/25mm of crispation number, room temperature filament strength 1.8 ± 0.4cN/dtex, percentage elongation 4.5 ± 1.0%.
Embodiment 9:
Calculate by weight ratio, select a kind of PLA (PLA) for use, wherein contain 97% D-lactic acid unit and 3% L-lactic acid unit.The weight average molecular weight 7.8 ten thousand of polymer, melt flow index 15.4g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 7.0MPa.The fusing point that records with the DSC method is 161 ℃.
Calculate by weight ratio, take by weighing 100 parts PLA, add 1 of 0.2 part Wytox 312,0.2 part of antioxidant 1010,0.2 part aluminum stearate, 2.0 parts three triacetin fat, 0.4 part of rutile type titanium white (Du Pont 902) and 1.0 parts, two (beta-amino butenoic acid) esters of 4-butanediol are made spinning component.
Adopt " single step spining " technology, spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 225 ± 2 ℃, and the temperature of filament spinning component is controlled at 200 ± 1 ℃, two melt-stoichiometry pump sizes are 10ml/r, speed is 25r/min, two each 6000 holes of spinneret, rectanglar arrangement, spinneret orifice is trilobal, diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish.Two strands of nascent tow merge the back to be collected and drawing-off with seven roller drafting machines, and gathering speed 60m/min, drawing-off medium are water, and 75 ℃ of drawing temperatures cool off 2.5 times of drawing-off multiplying powers with running water after the water outlet of tow sheet.Crimping machine with effective width 30mm curls, and heat medium is a steam, 70 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 70 ℃ of setting temperatures, and typing dewatering time 10min obtains cigarette filter filament.Its total linear density 4.0 ± 0.3ktex, single fiber line density are 3.4 ± 0.3dtex, 23 ± 3/25mm of crispation number, room temperature filament strength 1.5 ± 0.4cN/dtex, percentage elongation 4.6 ± 1.0%.
Embodiment 10:
Select a kind of polylactic resin (PLA) for use, it contains 99% D-lactic acid unit and 1% L-lactic acid unit, viscosity average molecular weigh 6.2 ten thousand, and melt flow index 23g/10min is with the bonding intensity of triacetyl glycerine room temperature (overlap joint area 10 * 3mm
2) be 4.2MPa.The fusing point that records with the DSC method is 171 ℃.
Calculate by weight ratio, take by weighing 100 parts PLA, add 0.2 part triphenyl phosphite, 0.2 part of antioxidant 2246,0.2 part calcium laurate, 1.0 parts lactyl-lactic acid glyceride, 2.0 parts three triacetin fat, 0.4 part of rutile type titanium white (Du Pont 902) and 1.0 parts nanometer hydroxyapatite, make spinning component.
Adopt " single step spining " technology, spinning on the melt spinning machine of the two-shipper position of a φ 65 * 28, the metering section temperature is controlled at 225 ± 2 ℃, and the temperature of filament spinning component is controlled at 200 ± 1 ℃, two melt-stoichiometry pump sizes are 10ml/r, speed is 30r/min, two each 6000 holes of spinneret, rectanglar arrangement, spinneret orifice is trilobal, diameter 0.5mm of equal value is with 25 ℃ dry air cross air blasting cooling, with drum process coated finish.Two strands of nascent tow merge the back to be collected and drawing-off with seven roller drafting machines, and gathering speed 80m/min, drawing-off medium are water, 80 ℃ of drawing temperatures, 2.0 times of drawing-off multiplying powers.In 64 ℃ of tanks, carry out nervous thermal finalization, cool off gathering speed 150m/min after the water outlet of tow sheet with running water.Crimping machine with effective width 30mm curls, and heat medium is a steam, 60 ℃ of preheat temperatures; Fibre bundle after curling is carried out relaxation heat setting and dehydration, and heat medium is an air, 60 ℃ of setting temperatures, and typing dewatering time 10min obtains cigarette filter filament.Its total linear density 4.9 ± 0.2ktex, single fiber line density are 4.0 ± 0.4dtex, 23 ± 3/25mm of crispation number, room temperature filament strength 2.1 ± 0.4cN/dtex, percentage elongation 4.0 ± 1.0%.
In above embodiment, only used a spinning-drawing machine, carried out the spinning of light engine position or two-shipper position, spinneret has only the two kinds of specifications in 8000 holes and 6000 holes, all is the rectangle spinneret.Be familiar with the technical staff of melt staple fiber spinning process, according to principle provided by the present invention and method, be not difficult to design bigger spinning-drawing machine production capacity, more spinning seat in the plane, spinning speed faster, different spinneret shapes (as annular) and hole count or the like.
Claims (9)
1, a kind of cigarette filter filament, it is characterized in that, it by spinning component through melt spinning and follow-up drawing-off, curl and the fiber obvolvent undaform fibre bundle sheet together that curls that thermal finalization forms, monofilament linear density 2～6dtex, tow line density 3～6ktex, 15～30/25mm of crispation number.
2, a kind of cigarette filter filament according to claim 1 is characterized in that, described spinning component is to be made of following ingredients and proportioning:
(1) lactide acid polymer (hereinafter to be referred as matrix resin) is a specification of PLA or the mixture of a plurality of specifications, or lactide and 6-caprolactone, lactide and glycolide, or the copolymer of lactide and 6-caprolactone and glycolide;
(2) heat stabilizer is: calcium stearate, lithium stearate, aluminum stearate, calcium laurate, calcium lactate or zinc lactate; With respect to 100 parts of matrix resins, the mass fraction of heat stabilizer is 0.1～0.5;
(3) antioxidant is nontoxic or the phosphorous acid esters stabilizing agent and the phenolic antioxidant of low toxicity, and it is: triphenyl phosphite, trisnonyl phenyl phosphite, antioxidant 1010, antioxidant 1076, antioxidant 2246 or antioxidant 264; With respect to 100 parts of matrix resins, the mass fraction of antioxidant is 0.1～0.5;
(4) the lactic acid trapping agent is: nano silicon, nano titanium oxide, nanometer hydroxyapatite or 1, two (beta-amino butenoic acid) esters of 4-butanediol; With respect to 100 parts of matrix resins, the mass fraction of lactic acid absorbent is 0.1～1.0;
(5) mobile and caking property improver is: glyceride lactate, three triacetin ketone, ATBC are clashed tributyl 2-acetylcitrate; With respect to 100 parts of matrix resins, the mass fraction of improver is 0～5;
(6) delustring and brightening agent are: titanium dioxide, with respect to 100 parts of matrix resins, the mass fraction of titanium dioxide is 0.2～0.6.
3, a kind of cigarette filter filament as claimed in claim 2, it is characterized in that, described matrix resin is a PLA, the percentage by weight of its L-lactic acid unit is 3～7%, weight average molecular weight is in 5～200,000 scopes, 150～170 ℃ of melting ranges, the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～20g/10min scope with the bonding intensity of triacetyl glycerine room temperature.
4, a kind of cigarette filter filament as claimed in claim 2 is characterized in that, described matrix resin is a specification of PLA or the mixture of a plurality of specifications, and the percentage by weight of its L-lactic acid unit is 3～7%; The weight average molecular weight of PLA is in 5～200,000 scopes, 150～170 ℃ of melting ranges, and the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～20g/10min scope with the bonding intensity of triacetyl glycerine room temperature.
5, a kind of cigarette filter filament as claimed in claim 2, it is characterized in that, described matrix resin is the bipolymer of lactide and 6-caprolactone or lactide, its weight percent proportioning is: lactide is 92～95%, 6-caprolactone or lactide are respectively 5-8%, the weight average molecular weight of copolymer is in 5～200,000 scopes, 150～170 ℃ of melting ranges, the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～20g/10min scope with the bonding intensity of triacetyl glycerine room temperature.
6, a kind of cigarette filter filament as claimed in claim 2, it is characterized in that, described matrix resin is a terpolymer, its weight percent proportioning is: lactide is 92～95%, 6-caprolactone and glycolide sum are 5-8%, ratio between 6-caprolactone and the glycolide units is not limit, the weight average molecular weight of copolymer is in 5～200,000 scopes, 150～170 ℃ of melting ranges, the melt flow index of measuring under 190 ℃ and 2.16kg load is 4～12MPa in 5～20g/10min scope with the bonding intensity of triacetyl glycerine room temperature.
7, the preparation method of the described a kind of cigarette filter filament of claim 1, its step and condition are as follows:
(1) before spinning, spinning component is carried out drying handle, water content wherein is reduced to below the 1000ppm;
(2) spinning component that drying is crossed carries out melt spinning, 190～210 ℃ of spinning temperatures, spinneret hole count 6000～20000, spinneret orifice is a trilobal, effective aperture 0.25～0.5mm, draw ratio 2: 1～4: 1,20～25 ℃ of dry air coolings, drum process coated finish, tow gathering speed 30～100m/min;
(3) with 5 rollers or 7 roller drafting machines to fibrillation Shu Jinhang drawing-off, the drawing-off medium is a water, 60～80 ℃ of temperature, 2～5 times of drawing-off multiplying powers;
(4) will carry out nervous thermal finalization and cooling through the fibre bundle of drawing-off, heat medium is a water, 55～70 ℃ of setting temperatures, and fibre length conservation rate 100～90%, cooling medium are running water;
(5) will curl through the fibre bundle of drawing-off with crimping machine, heat medium is air or steam, 50～70 ℃ of preheat temperatures, 15～30/25mm of crispation number;
(6) fibre bundle after curling is carried out drying and relaxation heat setting, heat medium is an air, 50～60 ℃ of setting temperatures, and shaping time 10～15min obtains cigarette filter filament.
8, the preparation method of a kind of cigarette filter filament as claimed in claim 1, its step and condition are as follows:
(1) before spinning, spinning component is carried out drying handle, water content wherein is reduced to below the 1000ppm,
(2) spinning component that drying is crossed carries out melt spinning, 190～210 ℃ of spinning temperatures, spinneret hole count 6000～20000, spinneret orifice is a trilobal, effective aperture 0.25～40.5mm, draw ratio 2: 1～4: 1,20～25 ℃ of dry air coolings, drum process coated finish, tow gathering speed 50～150m/min;
(3) primery vascular bundle of collecting is handled 48～2h 25～55 ℃ of healths;
(4) treated fibre bundle carries out drawing-off on 5 rollers or 7 roller drafting machines, and the drawing-off medium is a water, 70～90 ℃ of drawing temperatures, 1～3 times of drawing-off multiplying power;
(5) will carry out nervous thermal finalization and cooling through the fibre bundle of drawing-off, heat medium is a water, 55～70 ℃ of setting temperatures, and fibre length conservation rate 100～90%, cooling medium are running water;
(6) will curl through the fibre bundle of drawing-off with crimping machine, heat medium is air or steam, 50～70 ℃ of preheat temperatures, 15～30/25mm of crispation number;
(7) fibre bundle after curling is carried out drying and relaxation heat setting, heat medium is an air, 50～60 ℃ of setting temperatures, and shaping time 10～15min obtains cigarette filter filament.
9. as the preparation method of lactide acid polymer cigarette filter filament as described in claim 7 or 8, it is characterized in that, finish at step (2) drum process coated, be the aqueous solution of water-soluble polymer, and be added with quaternary ammonium salt, nonionic and/or anionic surfactant and/or antistatic additive;
Described water-soluble polymer is selected from polyvinyl alcohol, polyethylene glycol or polyoxyethylene; Its weight concentration is 0.05～0.5%;
Described quaternary ammonium salt surface active agent and/or antistatic additive, be selected from antistatic additive trihydroxyethyl ammonium methyl Methylsulfate salt, antistatic additive hard amido propyl dimethyl-beta-hydroxyethyl ammonium dihydrogen orthophosphate, antistatic additive alkyl phosphate diethanolamine salt, weight concentration 0.02～0.2%;
Described nonionic surface active agent is selected from polysorbas20,40,60 or 80, C
8-10One or more of APES, polyoxyethylene lauryl ether, polyoxyethylene glycerol ether, polyethylene glycol monolaurate, polyoxyethylene glycol monostearate and polyethylene glycol monooleate, weight concentration 0.02～0.2%;
Described anionic surfactant is selected from neopelex, lauryl sodium sulfate or their mixture, weight concentration 0.02～0.2%.
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