WO2011063628A1 - 可生物降解的烟用纤维材料及香烟过滤嘴棒 - Google Patents

可生物降解的烟用纤维材料及香烟过滤嘴棒 Download PDF

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Publication number
WO2011063628A1
WO2011063628A1 PCT/CN2010/073086 CN2010073086W WO2011063628A1 WO 2011063628 A1 WO2011063628 A1 WO 2011063628A1 CN 2010073086 W CN2010073086 W CN 2010073086W WO 2011063628 A1 WO2011063628 A1 WO 2011063628A1
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Prior art keywords
biodegradable
tow
cigarette
polylactic acid
temperature
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PCT/CN2010/073086
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English (en)
French (fr)
Inventor
季君晖
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北京中科高意引擎技术有限公司
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Publication of WO2011063628A1 publication Critical patent/WO2011063628A1/zh

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/067Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068Biodegradable or disintegrable
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/08Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08Lactones or lactides
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • the present invention relates to a tobacco fiber material and a cigarette filter rod made of the fiber material, wherein the tobacco fiber material and the cigarette filter rod are made of polylactic acid modified by copolymerization of a non-lactone monomer.
  • PHA poly(ethylene glycol) polymer
  • the cigarette filter has the function of filtering, blocking and adsorbing harmful components such as nicotine and tar in the flue gas.
  • the good filter material should also improve the taste of the flue gas and reduce the stimulation of the flue gas to the oral cavity. Human health damage.
  • the materials currently used in the manufacture of cigarette filters are generally made of cellulose acetate fibers and polypropylene fibers. From the viewpoint of processing properties and the comprehensive performance of the final production filter, cellulose acetate fibers are preferred. More cellulose acetate fiber filters are used in medium and high-grade cigarettes.
  • the remaining part of the filter after the cigarette is sucked is discarded, and the cellulose acetate fiber and the polypropylene fiber are difficult to be biodegraded in the natural environment.
  • the cigarette is on the basis of the crime of harmful human health, and it also causes Environmental pollution. Human beings cannot completely leave cigarettes. In addition to reducing the harm of cigarettes themselves to the human body, solving the environmental pollution problem caused by filter disposal has become a problem that the cigarette industry must face.
  • cellulose acetate fiber is a chemical product obtained from high-quality wood. From cellulose to cellulose to cellulose acetate, it requires a large amount of wood raw materials, and many pollution problems are involved in the production process.
  • the production process of the cigarette filter rod mainly includes the process of melt-spinning the raw material into a tobacco tow, and the process of plasticizing the shaped rod to be finally processed into a filter rod, and the spinnability of the raw material, that is, whether it is easy to be spun into a suitable one.
  • Cellulose acetate fiber is selected as the main processing material for cigarette filter rods because of its excellent properties. When looking for alternative materials, it is biodegradable and must meet the requirements of filter rod processing. It is the indispensable condition.
  • Lactic acid-based polymers such as polylactic acid (PLA) or related copolymers, are fully biodegradable under natural conditions or under human conditions and are well known as degradable materials.
  • a technique for producing a cigarette filter tow fiber and a filter rod for tobacco using a lactic acid-based polymer resin is disclosed in Chinese Patent Application No. 200610131699.0 and No. 200710055310.3.
  • lactic acid-based polymers can be used in the processing of cigarette filters, and compared to commercially available cellulose acetate filter rods and polypropylene filter rods, the polylactic acid cigarette filter rods not only have It has the advantages of complete biodegradation and low production cost, and the filter rods produced have good results in terms of filtration performance and physical and mechanical properties, but the main resin used in the technical solution can be seen from the description of the specification. Is a mixture of polylactic acid in one size or multiple specifications, or a copolymer of lactide and caprolactone, lactide, or lactide with caprolactone and glycolide. These resins are all from lactones.
  • the prepared polymer is a random polymer.
  • This material is brittle and easily hydrolyzed.
  • the water content of the material is required to be less than 10,000 parts per million, and the heat resistance of the material is poor.
  • the temperature is very low (less than 60 ° C). Since tobacco tows require a certain degree of flexibility and good deformation, and also require high heat resistance, there are still many unsatisfactory results for the pharmaceutical industry to produce the above-mentioned previously disclosed lactic acid polymer cigarette mouthstock materials. And where to improve. Summary of the invention
  • the technical problem to be solved by the present invention is to provide a biodegradable tobacco fiber material, and a cigarette filter rod processed by using the fiber tow, which is modified by a copolymerization of a non-lactone monomer. Lactic acid is used as a raw material, and the processing properties of the tobacco fiber material obtained by melt spinning, and the use properties such as toughness and heat resistance are remarkably improved, and the provided cigarette filter rod has the same performance as the current common cigarette filter, and the discarded filter can be used by the environment.
  • the decomposition of microorganisms is conducive to the protection of the environment.
  • the invention also provides a method for manufacturing the above biodegradable tobacco fiber material and a cigarette filter rod, and for the special properties of the selected non-lactone monomer copolymerized modified polylactic acid raw material, explores and proposes conditions for the manufacturing process. And the determination of the parameters to ensure that the manufactured cigarette filter rod products can meet the performance standards of the current common cigarette filter rods.
  • the invention provides a biodegradable tobacco fiber material, the raw material composition thereof comprises
  • the non-lactone monomer copolymerized modified polylactic acid is 1-30% of the total chain number in the molecular chain
  • the non-lactone type monomer chain link, the rest is a polymer of a polylactic acid chain link, and has a weight average molecular weight of 50,000-30,000, and a dispersion index of 1.2-3.0.
  • the tobacco fiber material is a molten material of the material. The spinning process is processed.
  • the copolymerized polylactic acid modified by the copolymerization of the non-lactone monomer has a significantly improved toughness compared with the homopolylactic acid, and has better processing performance and performance. Not only the requirements for environmental moisture are low, but also the heat resistance is improved to some extent.
  • the adsorption of the harmful substances in the flue gas by the nozzle rod prepared by using the polymer material is also remarkably improved.
  • the non-lactone monomer chain in the non-lactone monomer copolymerized modified polylactic acid molecular chain is a non-lactone type and can be copolymerized with lactic acid.
  • the monomer is obtained by polymerization, including ethylene glycol, propylene glycol, glycolic acid, ethylene glycol monomethyl ether, and the like or a mixture thereof.
  • ethylene glycol, glycolic acid, or the like or a mixture thereof can be selected.
  • the above-mentioned non-lactone monomer copolymer-modified polylactic acid polymer can be obtained by polymerizing a monomer raw material mixed in a certain ratio according to many published methods, and a copolymerization product having a desired chain ratio can be easily prepared, or
  • the basic theory of the open literature and related polymerization reactions is very convenient to prepare by chemical processes such as polymerization reaction and chain extension reaction.
  • the lactic acid and the selected non-inner The ester monomer is copolymerized in the desired ratio.
  • an appropriate stabilizer may be added, and the stabilizer refers to It can improve the stability of the non-lactone monomer copolymerized modified polylactic acid polymer raw material in the filter rod during processing, storage and use, and should be a food additive grade stabilizer, including but not limited to heat stabilizer, light Stabilizers and antacids, for example, may include trimethyl phosphate, diethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite, antioxidant 1010.
  • antioxidant 1076 ( ⁇ -(3,5-di-tert-butyl) -4-hydroxyphenyl) n-octadecyl propionate), antioxidant 1425 (calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid)), antioxidant 1222 (3,5-di-tert-butyl 4-hydroxyphenyl phosphate), magnesium hydroxide, aluminum hydroxide, titanium oxide, calcium oxide, etc. or Any mixture of. Preferred stabilizers are trimethyl phosphate, triphenyl phosphate, triphenyl phosphite, antioxidant 1010, antioxidant 1076, antioxidant 1222, antioxidant 1425, titanium oxide, magnesium hydroxide or Any mixture of.
  • the inventors' research results show that the non-lactone monomer copolymer-modified polylactic acid polymer material satisfying the above definition has good molding processability, and thus can meet the requirements of the cigarette filter rod standard according to the current spinning process for polypropylene fibers.
  • the tobacco is bundled with fiber.
  • the present invention further provides a biodegradable cigarette filter rod which is formed by using the tobacco fiber tow as a raw material, and the filter rod product has biodegradability and has Good toughness, heat resistance and other performance properties.
  • the invention also provides a cigarette product provided with the biodegradable filter material prepared by using the non-lactone monomer copolymerized modified polylactic acid polymer material as a raw material, and the filter discarded by the smoker can be decomposed in a short time in a natural environment. While satisfying the production of cigarettes, it also solves the environmental pollution impact of current cigarettes.
  • the method of making the biodegradable tobacco fiber tow of the present invention comprises the steps of:
  • the raw material is melt-spun, and the screw temperature of the spinning machine is set to 180 ° C - 240 ° C to make the extruded material.
  • the wire is spun through the spinneret.
  • the temperature of the filter is controlled from 170 °C to 250 °C
  • the temperature of the tank is 170 °C-250 °C
  • the straight pipe temperature is 170 ° C -250 ° C
  • the sprayed wire is cooled with dry air, the cooling temperature is 0 ° C -50 ° C;
  • the cooled tow is coated with oil to carry out slow traction machine winding, steam box traction, fast traction machine winding and belt conveyor winding traction.
  • the oil agent is treated with fiber surface concentration of 0.8%-1%.
  • Aqueous solution for example: polyethylene glycol, ethanolamine methyl ester, nonylphenol surfactant, etc.
  • roller winding speed of slow tractor is 200-1500m/min
  • roller speed of fast tractor is 400-2500r/min
  • frequency 25-50HZ
  • the tow drawn from the belt conveyor is drawn in a water bath in a water bath having a water temperature of 40 ° C - 90 ° C, and then crimped and dried, and the obtained tow is used for the biodegradable tobacco. Fiber material.
  • an appropriate amount of stabilizer may be included in the raw material composition of the tow.
  • the non-lactone monomer copolymerized modified polylactic acid content is ⁇ 90 wt% / S ⁇ 100 wt%, and the stabilizer content is >0. ⁇ 10 ⁇ %
  • the manufacturing method further includes:
  • the non-lactone monomer copolymerized modified polylactic acid and the stabilizer are dried, uniformly mixed, and subjected to extrusion granulation, and the temperature of the extruder barrel is 160-240 °C.
  • the moisture content of the raw material is required to be less than 1% by weight. It is usually possible to dry in an environment of 40-60 ° C, more preferably 50-55 ° C for 4-8 hours; and the extruder barrel temperature is preferably 190-220 ° C. It is generally possible to use a twin-screw extruder to set a suitable barrel temperature in the above temperature range according to the melting characteristics of the material to effect granulation to provide a special material for manufacturing a cigarette filter rod.
  • the present invention has a targeted method for manufacturing a tobacco tow material, and the specific scheme thereof may be:
  • the extruder screw temperature is 190-230 ° C;
  • the setting of each parameter can be adjusted within the above range according to the specific properties of the material and the operation of the equipment, for example, the winding speed of the slow tractor is 400-900 m/min; The speed of the fast tractor is 1000-2000 r/min, the frequency is 35-40HZ; the feeding speed of the belt conveyor is 500-1000 r/min, and the frequency is 38-42HZ.
  • the present invention further provides a method of making a biodegradable cigarette filter rod using the above modified copolymerized lactic acid polymer tobacco tow, the method comprising:
  • the adhesive plasticizer is sprayed with 0.5 to 15% by weight of the tow to uniformly coat the tow;
  • the glued tow is rolled into a strip shape in a cigarette stick shaper, wrapped and wrapped with a filter stick paper to form a dough stick strip, and the fibers in the tow are hung together and are torn by hand. It can be clearly seen that the fibers of the tow have formed a connected three-dimensional network nozzle strip;
  • the above-mentioned nozzle bar is cut into a predetermined length to obtain the biodegradable cigarette nozzle;
  • the above-mentioned adhesive plasticizer refers to a fiber capable of copolymerizing the non-lactone monomer to modify the polylactic acid nozzle bar.
  • Effective cross-linking, bonding, swelling or fluffy substances including but not limited to dioctyl terephthalate, dibutyl terephthalate, trioctyl trimellitate, tridecyl trimellitate, partial Triglyceride, glyceryl phosphate, glyceryl lactate, butyl citrate, diethylene glycol diacetate, propylene carbonate, ethylene glycol monoethyl ether, water-based starch gel, carboxymethyl starch gel, acrylic acid Ester glue, polyethylene glycol glue, polyvinyl alcohol glue, protein glue, collagen glue, etc. or any mixture thereof.
  • the adhesive plasticizer comprises trimellitic acid triglyceride, diethylene glycol diacetate, lactic acid glyceride, carboxymethyl starch gel, acrylate glue, polyethylene glycol glue, collagen glue or they Any mixture of.
  • the binder plasticizer used is dissolved in a suitable solvent which is selected from the group which is effective for dissolving the binder plasticizer, preferably with ethanol or an aqueous ethanol solution.
  • the modified polylactic acid material cigarette mouthpiece provided by the invention has good biodegradability, and can ensure that the performance in mechanics, appearance and taste is basically unchanged within 2 years under normal storage and transportation conditions after receiving the cigarette. , fully meet the requirements of cigarettes, and discard the filter after the cigarette is used When the garbage is rich in microbial environment, the degradation rate can exceed 75% within three months, and it can be completely degraded within six months.
  • the invention obtains the physical property of the cigarette mouth stick in terms of safety performance, suction resistance, weight, hardness, circumference and the like, and fully meets the requirements of the cigarette mouth stick.
  • the filter rod for smoke of the present invention is superior to the currently used polypropylene fiber nozzle and cellulose acetate fiber nozzle in the smoking process of cigarettes (see the table below for the test results). Comparison of Flue Gas Indexes of Non-lactone Monomer Copolymer Modified Polylactic Acid and Cellulose Acetate Mouth Rods
  • the "vinegar mouth stick” in the table is the market brand cigarette mouth stick; the "non-lactone monomer copolymer modified polylactic acid mouth stick” smoke index is derived from the mouth stick product prepared by the embodiment of the present invention. statistical results.
  • the detection method of the above indicators is carried out in accordance with the GB5606-2004 "cigarette" standard.
  • the polylactic acid polymer modified by the copolymerization of the non-lactone monomer of the present invention not only provides the degradability of the nozzle, the material Both processability and performance (reflection of heat resistance) are significantly improved.
  • the relevant indicator comparisons are provided in the table below:
  • the filter rod for tobacco manufactured by using the non-lactone monomer copolymerized modified polylactic acid as a raw material can reach the industry standard of the cigarette mouth stick in quality and properties, and is processed into a cigarette, after use.
  • the waste filter can achieve complete biodegradation, which has incomparable advantages from the environmental protection point compared with the current acetate fiber nozzle; on the other hand, the non-lactone monomer copolymerization modification of the biodegradable nozzle provided by the present invention
  • Polylactic acid raw materials can be synthesized by chemical methods. The raw materials are abundant, and it is no longer necessary to import high-quality wood, which is more conducive to industrial production. Therefore, the implementation of the present invention can completely replace the currently used cellulose acetate nozzle stick and polypropylene fiber nozzle stick, and has very broad economic and social benefits. Specific implementation
  • Lactic acid is the base resin, according to the modified polylactic acid: triphenyl phosphate: antioxidant 1222 (3,5-di-tert-butyl-4-hydroxyphenyl phosphate) in a weight ratio of 97:2.5: Weigh the raw material at a ratio of 0.5, dry it in an oven at 55 ° C for 5 hours, stir well in a high-speed mixer, and then extrude and granulate on a ⁇ 57 twin-screw extruder with a length to diameter ratio of 32.
  • the first section is 190 ° C
  • the second section is 195
  • the third section is 200 ° C
  • the fourth section is 200 ° C
  • the fifth section is 190 ° C
  • the extruded strip is pelletized by a pelletizer.
  • the hot air is dried and packaged to obtain the special material for the cigarette holder of the present invention.
  • the above-mentioned cigarette holder is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature of the spinning machine is set to be: 200 ° C in the first stage and 205 ° C in the second stage.
  • the three sections are 205 ° C; the filter temperature is 205 ° C, the cabinet temperature is 200 ° C, and the straight tube temperature is 200 ° C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is a fiber surface treatment agent having the following composition: polyethylene glycol 1700, concentration of 0.2%, triethanolamine dimethyl sulfate, concentration is 0.15%, nonylphenol polyepoxy, with a concentration of 0.1%.
  • the tow is wound by a slow tractor, and the winding speed of the roller is 800 m/min.
  • the speed of the fast traction roller is 1500 r/min, the frequency is 38HZ, and then passes.
  • Conveyor belt conveyor, belt conveyor feed wheel speed 800r/min, frequency is 40HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 75 °C.
  • the drawn tow was crimped in a crimper, the number of crimps was 24 / 25 mm, and the crimped tow was dried by a steam dryer.
  • the tow After drying, the tow is placed in the silk container by a pendulum machine, and the package is obtained to obtain the present invention.
  • the tow is pulled out from the bin, passed through the roller conveyor, and sent to the Y11 tow opener for opening the tow. After the opening, the tow enters the casing, and the weight of the tow is 6% by the wind rubber disc and the nozzle.
  • the solvent for bonding the plasticizer is a mixed solvent of water: ethanol mass ratio of 50:50, and the adhesive plasticizer composition is: diethylene glycol diacetate, 20%, acrylate glue, and a concentration of 4%.
  • the glued tow is rolled into a round bar shape in the Y21 type mouthpiece shaper, wrapped with a filter rod, and shaped to form a nozzle bar, and the cutting bar will be used to remove the bar from the former.
  • the strip is cut into a predetermined length, and the biodegradable nozzle for tobacco of the present invention is obtained by loading the package through a tray loading machine using a packaging processing device.
  • the non-lactone monomer copolymer-modified polylactic acid base resin used in the embodiment can be mixed with the ethylene glycol monomer in a molar ratio of 85:15 according to the polymerization method disclosed in the invention patent application CN200610016643.0. It is obtained by copolymerization.
  • the above-mentioned nozzles have good biodegradability and fully meet the degradation standard requirements according to ISO 14855, and the degradation rate reaches 95% in 90 days.
  • Material biosafety meets the requirements for cigarette sticks.
  • the circumference is 24.1mm
  • the roundness is 0.2mm
  • the suction resistance is 3089Pa
  • the hardness is 91%
  • the physical properties meet the requirements of the nozzle.
  • the smoke index is: nicotine 1.08mg / support, wet tar 15.9mg / support, C015.7mg / support, tar 12.5mg / support.
  • a copolymerization of 99.6 kg of copolymerized non-lactone monomer with a weight average molecular weight of (10 ⁇ 1) million, a dispersion index of 1.2, and a 1% (number of links) randomly distributed ethylene glycol monomethyl ether chain links was selected.
  • the modified polylactic acid is a base resin, and 0.4 kg of triphenyl phosphite is dried in an oven at 45 ° C for 8 hours, and then uniformly stirred in a high-speed mixer. In the environment with a drying device, the aspect ratio is adopted. Extrusion granulation on a 32 ⁇ 75 twin-screw extruder.
  • the temperature of the barrel is set to 160 °C for the first stage, 185 °C for the second stage, 195 °C for the third stage, and 200 °C for the fourth stage.
  • the fifth paragraph is 195 °C.
  • the cigarette holder is spun on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature of the spinning machine is set to: 195 ° C in the first stage and 200 ° C in the second stage.
  • the three sections are 205 °C, the filter temperature is 200 °C, the tank temperature is 200 °C, and the straight pipe temperature is 200 °C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1700, concentration 0.2%, triethanolamine dimethyl sulfate, concentration 0.15 %, nonylphenol polyepoxy, with a concentration of 0.1%.
  • the tow after passing through the oil sump is wound by a slow tractor, and the winding speed of the roller is 1000 m/min. Then, by pulling the steam box, it enters the fast traction machine winding, the speed of the fast traction roller is 1800 r/min, the frequency is 40HZ, then It is transported by a belt conveyor.
  • the belt conveyor feeds at a speed of 1000 r/min and has a frequency of 40 Hz.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 60 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 25 / 25 mm, and the crimped tow was dried by a steam dryer.
  • the tow After drying, the tow is placed in a silk container by a pendulum machine, and the biodegradable tobacco tow of the present invention is obtained by packaging.
  • the tow is pulled out from the bin, passed through the roller conveyor, and sent to the Y11 tow opener for opening the tow. After the opening, the tow enters the casing, and the weight of the tow is sprayed by the wind rubber disc and the nozzle by 2%.
  • the adhesive plasticizer uses ethanol as a solvent, and the adhesive plasticizer composition is: trioctyl trimellitate concentration is 30%, and polyethylene glycol gum concentration is 4%.
  • the glued tow is rolled into a round bar shape in the Y21 type mouthpiece shaper, wrapped with a filter rod, and shaped to form a nozzle bar, and the cutting bar will be used to remove the bar from the former.
  • the strip is cut into a predetermined length, and the biodegradable nozzle for tobacco of the present invention is obtained by loading the package through a tray loading machine using a packaging processing device.
  • the non-lactone monomer copolymer-modified polylactic acid base resin used in the embodiment can refer to the polymerization method disclosed in the invention patent application CN200610016643.0, and the lactic acid and the ethylene glycol monomethyl ether monomer.
  • the copolymerization reaction was carried out in accordance with a molar ratio of 99:1.
  • the above-mentioned nozzle has good biodegradability and completely meets the degradation standard according to ISO 14855, and the degradation rate reaches 96% in 90 days.
  • Material biosafety meets the requirements for cigarette sticks.
  • the circumference is 24.1mm
  • the roundness is 0.2mm
  • the suction resistance is 3210Pa
  • the hardness is 92%
  • the physical properties meet the requirements of the nozzle.
  • the smoke index is: nicotine 1.07mg / support, wet tar 15.9mg / support, C015.8mg / support, tar 12.4mg / support.
  • a copolyesteride monomer with a weight average molecular weight of 300,000, a dispersion index of 3.0, and a 30% (number of links) randomly distributed glycolic acid chain copolymers was used to modify the polylactic acid as a base resin.
  • spinning was carried out on a ⁇ 65 melt spinning machine with a screw length to diameter ratio of 28, the first stage of the screw temperature of the spinning machine was set to 190 ° C, and the second stage was set to 205. °C, the third section is set to 220 ° C, the filter temperature is 200 ° C, the cabinet temperature is 205 ° C, and the straight pipe temperature is 205 ° C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is a fiber surface treatment agent aqueous solution of the following composition: polyethylene glycol 1700, concentration 0.6%, triethanolamine dimethyl sulfate, concentration 0.2 , nonylphenol polyepoxyhydrazine, the concentration is 0.2%.
  • the tow after passing through the oil sump is wound by a slow tractor, and the winding speed of the roller is 1500 m/min. Then, by pulling the steam box, it enters the fast traction machine winding, the speed of the fast traction roller is 2500 r/min, the frequency is 50HZ, then It is transported by a belt conveyor.
  • the belt conveyor feeds at a speed of 1500r/min and has a frequency of 60HZ.
  • the tow is pulled out from the belt conveyor and drafted by a multi-roll drafter.
  • the drafting medium is water, and the temperature of 7j is 90 °C.
  • the tow was crimped in a crimper, the number of crimps was 22 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco of the present invention is obtained by packaging.
  • the tow is pulled out from the bin, passed through the roller conveyor, and sent to the Y11 tow opener for opening the tow. After the opening, the tow enters the casing, and the weight of the tow is 0.5% by the wind rubber disc and the nozzle. Plasticizer, and silk The bundle is evenly coated with glue.
  • the glued tow is rolled into a round bar shape in a Y21 type cigarette mouthpiece shaper, wrapped with a filter bar paper to form a nozzle bar, and the cutting bar will be used to remove the nozzle bar from the former.
  • the nozzle bar of the present invention is cut into a predetermined length, and the biodegradable nozzle for tobacco of the present invention is obtained by loading the package through a packaging machine.
  • the non-lactone monomer copolymer-modified polylactic acid base resin used in the embodiment can be mixed with the glycolic acid monomer in a molar ratio of 70:30 according to the polymerization method disclosed in the invention patent application CN200610016643.0. It is obtained by copolymerization.
  • the above-mentioned nozzle has good biodegradability and fully meets the degradation standard according to ISO 14855, and the degradation rate reaches 89% in 90 days.
  • Material biosafety meets the requirements for cigarette sticks.
  • the circumference is 24.1mm
  • the roundness is 0.2mm
  • the suction resistance is 3354Pa
  • the hardness is 91%
  • the physical properties meet the requirements of the nozzle.
  • the smoke index is: nicotine 1.08mg / support, wet tar 15.9mg / support, C015.4mg / support, tar 12.4mg / support.
  • the modified polylactic acid is a base resin
  • the weight of 1010 is 0.1 kg
  • the weight of 1076 is 0.2 kg
  • the weight of titanium oxide is 0.7 kg.
  • the mixture After drying in an oven at 55 ° C for 7 hours, the mixture is uniformly stirred in a high-speed mixer, and the aspect ratio is Extrusion on a ⁇ 60 twin-screw extruder of 36, the first stage of the barrel temperature setting is 190 ° C, the second stage is 195 ° C, the third section is 205 ° C, the fourth section is 215 ° C, the fifth The segment is 200 °C.
  • the extruded strand is granulated by a pelletizer, dried by hot air on the line, and packaged to obtain a special material for the cigarette holder of the present invention.
  • the above-mentioned cigarette holder is spun on a ⁇ 60 melt spinning machine with a screw length to diameter ratio of 28, and the screw temperature of the spinning machine is set to be: 200 ° C in the first stage and 215 ° C in the second stage.
  • the third section is 215 ° C
  • the filter temperature is 205 ° C
  • the cabinet temperature is 205 ° C
  • the straight pipe temperature is 205 ° C.
  • the cooled tow is coated with an oil agent in the oil sump, and the oil agent in the oil sump is an aqueous solution of the fiber surface treatment agent of the following composition: polyethylene glycol 1700, concentration 0.8%, triethanolamine dimethyl sulfate, concentration 0.1 %, nonylphenol polyepoxide, at a concentration of 0.1%.
  • the tow after passing through the oil sump is wound by a slow tractor, and the winding speed of the roller is 200 m/min. Then, by pulling the steam box, the fast traction machine is wound, the speed of the fast traction roller is 400 r/min, the frequency is 25HZ, and then conveyed by the belt conveyor.
  • the belt conveyor feeds the wheel speed 200r/min, and the frequency is 30HZ.
  • the tow drawn from the belt conveyor was drawn by a multi-roll drafter, and the drafting medium was water at a water temperature of 65 °C. After drawing, the tow was crimped in a crimper, the number of crimps was 22 / 25 mm, and the crimped tow was dried by a steam dryer. After drying, the tow is placed in a silk container by a pendulum machine, and the tow of the biodegradable tobacco of the present invention is obtained by packaging.
  • the tow is pulled out from the bin, passed through the roller conveyor, and sent to the Y11 tow opener for opening the tow. After the opening, the tow enters the casing, and the weight of the tow is 15% by the wind rubber disc and the nozzle. Combine the plasticizer and evenly apply the tow.
  • the solvent for bonding the plasticizer is water: ethanol is a mixed solvent of 50:50, and the adhesive plasticizer composition is: diethylene glycol diacetate, the concentration is 20%, and the collagen gel has a concentration of 4%.
  • the glued tow is rolled into a round bar shape in the Y21 type mouthpiece shaper, wrapped with a filter rod, and shaped to form a nozzle bar, and the cutting bar will be used to remove the bar from the former.
  • the strip is cut into a predetermined length, and the biodegradable nozzle for tobacco of the present invention is obtained by loading the package through a packaging machine through a packaging machine.
  • the non-lactone monomer copolymer-modified polylactic acid base resin used in the embodiment can refer to the polymerization method disclosed in the invention patent application CN200610016643.0, and the lactic acid and the propylene glycol and the ethylene glycol monomer are in accordance with 80:10:10. The molar ratio of the mixture is obtained by copolymerization.
  • the above-mentioned nozzle has good biodegradability and completely meets the degradation standard according to ISO 14855, and the degradation rate reaches 93% in 90 days.
  • Material biosafety meets the requirements for cigarette sticks.
  • the circumference is 24.1mm
  • the roundness is 0.2mm
  • the suction resistance is 3167Pa
  • the hardness is 91%
  • the physical properties meet the requirements of the nozzle.
  • the smoke index is 1.04 mg/piece of nicotine, 15.9 mg/piece of wet tar, C015.8 mg/piece, and tar 12.5 mg/piece.

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Description

可生物降解的烟用纤维材料及香烟过滤嘴棒 技术领域
本发明涉及一种烟用纤维材料及利用该纤维材料所制成的香烟过滤嘴 棒, 所述烟用纤维材料和香烟过滤嘴棒采用经非内酯单体共聚改性的聚乳酸
(PLA)聚合物为基材树脂, 具有优良的生物降解性, 可用于香烟的生产。 背景技术
香烟过滤嘴具有过滤、 阻挡和吸附烟气中烟碱、 焦油等有害成分的作用, 好的过滤嘴材料除具有上述作用外, 还应该能改善烟气的口感, 减少烟气对 口腔的剌激及对人体健康的伤害。 作为一个比较成熟的技术, 目前用于制造 香烟过滤嘴的材料一般是以醋酸纤维素纤维和聚丙烯纤维为原料, 从加工性 能和最终生产过滤嘴的综合使用性能考虑, 以醋酸纤维素纤维为首选, 在中 高档卷烟中多使用醋酸纤维素纤维滤嘴。
香烟吸完后剩下的过滤嘴部分是要丢弃的, 而醋酸纤维素纤维和聚丙烯 纤维在自然环境中很难被生物降解, 香烟在背负有害人体健康的罪名的基础 上, 同时还造成了对环境的污染。 人类不能完全离开香烟, 除了减少香烟本 身对人体的危害以外, 解决滤嘴丢弃带来的环境污染问题就成为香烟行业必 须面对的课题。
另一方面, 醋酸纤维素纤维是以优质木材为原料得到的化工产品, 从木 材到纤维素再到酯化的醋酸纤维素需要消耗大量的木材原料, 而生产环节中 也伴随着很多污染问题。
所以, 无论是从木材资源匮乏, 还是从改善环境污染角度出发, 寻找替 代现有的醋酸纤维素和聚丙烯纤维原料的可生物降解材料, 制造出可生物降 解的香烟过滤嘴棒, 至少在环境保护方面降低香烟生产所带来的危害, 是香 烟生产行业急需解决的问题。 香烟过滤嘴棒的生产工艺主要包括对原料实施熔融纺丝制成烟用丝束, 以及增塑定型制棒最终加工成过滤嘴棒的工艺过程, 原料的可纺性能, 即, 是否容易纺成适合于烟用的细旦纤维, 以及纤维丝束的牵伸性能和粘合效果, 最终都将影响滤棒和滤嘴的综合性能, 包括滤过性能, 以及外观、 硬度和空 阻等机械性能。 醋酸纤维素纤维就是由于这些性质的优异, 才被选择成为香 烟过滤嘴棒的主要加工原料。 在寻找其替代材料时, 既具有生物降解性, 还 必须满足过滤嘴棒加工要求, 是缺一不可的二个条件。
乳酸类聚合物, 例如聚乳酸 (PLA) 或相关共聚物在自然条件下或人体 条件下可完全生物降解, 早已是公知的可降解材料。 中国专利申请 200610131699.0和 200710055310.3中公开了一种利用乳酸类聚合物树脂制造 香烟过滤嘴丝束纤维以及烟用滤棒的技术。 虽然该在先公开的专利申请教导 了乳酸类聚合物可以用于香烟过滤嘴的加工, 且与已经商业化的醋酸纤维素 滤棒和聚丙烯滤棒相比, 所述聚乳酸香烟滤棒不仅具有可完全生物降解和生 产成本低廉的优势, 而且制成的滤棒在滤过性能和物理机械性能方面都显示 良好的结果, 但是从其说明书记载内容可以看到, 该技术方案中采用的主体 树脂是聚乳酸的一个规格或多个规格的混合物, 或是丙交酯与己内酯、 丙交 酯, 或丙交酯与己内酯和乙交酯的共聚物, 这些树脂都是由内酯聚合而成, 制备的聚合物是无规聚合物, 这种材料脆性大, 易水解, 加工时要求材料的 含水量低于万分之零点五, 而且这种材料耐热性能差, 热变型温度很低 (不 到 60°C )。 由于烟用丝束需要一定的柔性和较好的形变, 同时也要求具有较高 的耐热性, 对于香烟企业工业生产上述在先公开的乳酸类聚合物香烟嘴棒原 料仍有很多不尽人意和有待改进的地方。 发明内容
本发明主要解决的技术问题在于提供一种可生物降解的烟用纤维材料, 以及利用该纤维丝束加工而成的香烟过滤嘴棒, 利用非内酯单体共聚改性聚 乳酸为原料, 经熔融纺丝得到的烟用纤维材料的加工和韧性、 耐热性能等使 用性能显著提高,所提供的香烟过滤嘴棒与目前通用的香烟过滤嘴性能相当, 而丢弃的过滤嘴可被环境中微生物分解, 利于对环境的保护。
本发明还提供了制造上述可生物降解的烟用纤维材料及香烟过滤嘴棒的 方法, 针对所选择的非内酯单体共聚改性聚乳酸原料的特殊性质, 摸索和提 出了对制造工艺的条件和参数的确定, 确保所制造的香烟过滤嘴棒产品能达 到目前通用的香烟过滤嘴棒的性能标准。
本发明提供了一种可生物降解的烟用纤维材料, 其原料组成包括
90-100wt%的非内酯单体共聚改性聚乳酸和 0-10wt%的稳定剂,所述非内酯单 体共聚改性聚乳酸为分子链中含有总链节数的 1-30%的非内酯型单体链节, 其余为聚乳酸链节的高分子聚合物, 且其重均分子量为 5-35万, 分散指数 1.2-3.0, 该烟用纤维材料是所述原料经熔融纺丝工艺加工而成。
在前述公开技术的基础上, 本案发明人的进一步研究发现, 非内酯单体 共聚改性的共聚聚乳酸较均聚聚乳酸的韧性有显著的提高, 具有更好的加工 性能和使用性能, 不仅对环境水气要求较低, 而且耐热性能也有一定程度的 提高。 另一方面, 由于非内酯型共聚链节的引入, 利用这种聚合物材料制备 得到的嘴棒对烟气中有害物质的吸附性也有显著提高。
在上述研究结果的基础上, 本发明的实施方案中, 所述非内酯单体共聚 改性聚乳酸分子链中的非内酯单体链节是由非内酯型且能与乳酸实现共聚的 单体聚合得到的, 包括乙二醇、 丙二醇、 乙醇酸、 乙二醇单甲醚等或其混合 物。 例如可以选择乙二醇、 乙醇酸等或其混合物。
上述非内酯单体共聚改性聚乳酸聚合物可以按照很多已经公开的方法使 按一定比例混合的单体原料聚合得到, 很容易地制备具有所要求的链节比例 的共聚产物, 也可以在公开文献及相关聚合反应的基础理论教导下通过聚合 反应、 扩链反应等化学过程实现非常方便地制备得到。 例如按照发明专利申 请 CN 200610016643.0中公开的聚合反应方法, 将乳酸与所选择确定的非内 酯单体按照要求的比例实现共聚。
本发明提供的烟用纤维材料 (丝束) 所利用的原料中, 除上述非内酯 单体共聚改性聚乳酸聚合物材料外, 还可以添加适当的稳定剂, 所述的稳 定剂是指能提高过滤嘴棒中非内酯单体共聚改性聚乳酸聚合物原料在加 工、 储存和使用过程中稳定性的物质, 且应为食品添加剂级的稳定剂, 包 括但不限于热稳定剂、 光稳定剂和抑酸剂, 例如可以包括磷酸三甲酯、 磷 酸二乙酯、 磷酸三苯酯、 磷酸二苯酯、 亚磷酸三苯酯、 亚磷酸二苯酯、 亚 磷酸铵、抗氧剂 1010(四 [亚甲基 3-(3',5'-二叔丁基 -4-羟苯基) 丙酸酯]甲垸)、 抗氧剂 1076 ( β- (3,5-二叔丁基 -4-羟基苯基) 丙酸正十八碳醇酯)、 抗氧剂 1425 (双 (3,5-二叔丁基 -4-羟基苄基磷酸单乙酯)钙)、 抗氧剂 1222(3,5-二叔 丁基 _4-羟苯基磷酸二乙酯)、 氢氧化镁、 氢氧化铝、 氧化钛、 氧化钙等或它 们的任意混合物。 优选采用的稳定剂为磷酸三甲酯、 磷酸三苯酯、 亚磷酸 三苯酯、抗氧剂 1010 、抗氧剂 1076、抗氧剂 1222、抗氧剂 1425、氧化钛、 氢氧化镁或它们的任意混合物。
发明人的研究结果显示, 满足以上定义的非内酯单体共聚改性聚乳酸聚 合物材料具有良好的成型加工性能, 因而按照目前对聚丙烯纤维的类似纺丝 工艺可以制造满足香烟过滤嘴棒标准的烟用纤维丝束。
在此基础上, 本发明进一步提供了一种利用该烟用纤维丝束为原料, 经 定型加工制成的可生物降解的香烟过滤嘴棒, 该过滤嘴棒产品在具有可生物 降解性外, 还具有较好的韧性、 耐热性能等使用性能。
本发明同时还提供了设置有上述以非内酯单体共聚改性聚乳酸聚合物材 料为原料的可生物降解过滤嘴的香烟产品, 吸烟者丢弃的过滤嘴在自然环境 中能短时间内被分解, 在满足香烟生产的同时也解决了目前香烟遗弃物对环 境的污染影响。
制造本发明可生物降解的烟用纤维丝束的方法包括如下步骤:
将原料进行熔融纺丝, 设定纺丝机的螺杆温度 180°C-240°C, 使挤出物料 流经过滤器、 箱体、 计量泵和直管后, 通过喷丝板喷丝, 该过程中控制过滤 器温度 170°C-250°C, 箱体温度 170°C-250°C, 直管温度 170°C-250°C, 然后对 喷出的丝以干燥空气冷却, 冷却温度为 0°C-50°C ;
冷却后的丝束经涂覆油剂, 进行慢牵引机绕卷、 蒸汽箱牵引、 快牵引机 绕卷以及皮带输送机的卷绕牵引, 油剂是浓度为 0.8%-1%的纤维表面处理剂 (例如: 聚乙二醇、 乙醇胺甲酯、 壬基酚类表面活性剂等) 的水溶液, 慢牵 引机的辊卷绕速度 200-1500m/min, 快牵引机的辊转速 400-2500r/min, 频率 25-50HZ, 皮带输送机喂入轮速度 200-1500 r/min, 频率为 30-60HZ;
将从皮带输送机牵弓 I出来的丝束在水温为 40°C-90°C的水槽中水浴牵伸, 然后经卷曲和干燥定型, 得到的丝束即为所述可生物降解的烟用纤维材料。
如前面所述, 为了提高过滤嘴棒中非内酯单体共聚改性聚乳酸在加工、 储存和使用过程中的稳定性, 在制造丝束的原料组成中还可以包括适量的稳 定剂, 利用该混合原料纺丝前, 还需要先实施混料制粒, 即, 原料组成中, 所述非内酯单体共聚改性聚乳酸含量为≥90wt°/ S<100wt%, 稳定剂含量 >0 但≤10^%时, 所述制造方法还包括:
将非内酯单体共聚改性聚乳酸和稳定剂干燥后混合均匀,进行挤出制粒, 挤出机螺筒温度为 160-240 °C。 实际操作中要求原料的含水率低于 lwt%。, 通 常可以在 40-60 °C、 更优选在 50-55°C的环境中干燥 4-8小时即可满足要求; 而挤出机螺筒温度优选为 190— 220°C。 一般可使用双螺杆挤出机, 根据物料 的熔融特性在上述温度范围内分段设定合适的螺筒温度, 实现制粒, 以提供 制造香烟过滤嘴棒的专用料。
根据所采用的改性共聚乳酸聚合物原料的性质, 本发明有针对性地确定 了的制造烟用丝束材料的方法, 其具体方案可以为:
熔融纺丝工序中, 挤出机螺杆温度 190-230°C ;
卷绕牵引工艺中, 各参数的设定可以在以上范围内根据物料的具体性质 以及设备运转情况进行调整, 例如, 慢牵引机的辊卷绕速度 400-900 m/min; 快牵引机的辊转速为 1000-2000 r/min, 频率为 35-40HZ; 皮带输送机喂入轮 速度为 500-1000 r/min, 频率为 38-42HZ。
上述混料制粒、 纺丝及卷绕牵伸的具体操作和设备以及没有特别说明的 处理剂均为烟用丝束生产中的公知和常规技术。
本发明进一步提供了采用上述改性共聚乳酸聚合物烟用丝束制造可生物 降解的香烟过滤嘴棒的方法, 该方法包括:
对所述丝束开松后喷施该丝束重量 0.5~15%的粘合增塑剂使丝束被均匀 上胶;
在烟用嘴棒成形器内将所述上了胶的丝束揉卷成条形, 用滤棒盘纸包裹 定型, 成为嘴棒料条, 丝束中的纤维抱合在一起, 用手撕开可以明显看到丝 束的纤维已经形成连通的三维网络嘴棒料条;
将上述嘴棒料条切割成规定长度, 即得到所述可生物降解香烟嘴棒; 上述粘合增塑剂是指能使所述非内酯单体共聚改性聚乳酸嘴棒中的纤维 实现有效交联、 粘接、 膨胀或蓬松的物质, 包括但不限于对苯二甲酸二辛酯、 对苯二甲酸二丁酯、 偏苯三酸三辛酯、 偏苯三酸三癸酯、 偏苯三酸三甘油酯、 磷酸甘油酯、、 乳酸甘油酯、 柠檬酸丁酯、 二甘醇二醋酸酯、 碳酸丙烯酯、 乙 二醇单乙醚、 水基淀粉胶、 羧甲基淀粉胶、 丙烯酸酯胶、 聚乙二醇胶、 聚乙 烯醇胶、 蛋白胶、 胶原胶等或它们的任意混合物。
优选地, 所述粘合增塑剂包括偏苯三酸三甘油酯、 二甘醇二醋酸酯、 乳 酸甘油酯、 羧甲基淀粉胶、 丙烯酸酯胶、 聚乙二醇胶、 胶原胶或它们的任意 混合物。
本发明的具体方案中, 所用粘合增塑剂以适当的溶剂溶解, 该溶剂以能 有效溶解粘合增塑剂为选择标准, 优选以乙醇或乙醇水溶液为溶剂。
本发明所提供的改性聚乳酸材料烟用嘴棒具有良好的生物降解性能, 接 到烟上后在正常等储存和运输条件下可以保证在 2年内力学、 外观、 口感等 方面性能基本没有变化, 完全符合香烟要求, 而在香烟吸用后废弃过滤嘴进 入垃圾等富含微生物环境时三个月内降解率可超过 75%, 六个月内可完全降 解。 本发明得到烟用嘴棒在安全性能, 吸阻、 重量、 硬度、 圆周等理化指标 完全符合烟用嘴棒要求。
经吸收试验, 本发明的烟用过滤嘴棒在香烟抽吸过程中对于对人体有害 物质的吸附性能优于目前使用的聚丙烯纤维嘴棒和醋酸纤维素纤维嘴棒 (检 测结果见下表)。 非内酯单体共聚改性聚乳酸及醋酸纤维素嘴棒的烟气指标对比
Figure imgf000008_0001
注: 1、 表中的 "醋纤嘴棒"为市场品牌香烟用嘴棒; "非内酯单体共聚改性聚乳酸嘴 棒"的烟气指标来自本发明实施例制备的嘴棒产品的统计结果。
2、 以上指标的检测方法按照 GB5606— 2004 《卷烟》标准进行。 与现有技术记载的聚乳酸类聚合物制造烟用嘴棒的技术效果相比, 本 发明采用非内酯单体共聚改性的聚乳酸聚合物不仅提供了嘴棒的可降解 性, 材料的加工性能和使用性能 (耐热性能的体现) 都有明显提高。 例如, 下表中提供相关的指标对比:
Figure imgf000008_0002
注: 1、实验序号 1-3中的" PLA (对) "为 CN 200610131699.0中使用的乳酸聚合物 材料, 由于该专利申请没有提供材料力学性能, 相关性能由文献获得; 2、 实验序号 4-7的实施例是本发明实施例的结果。 以上指标中的使用性能实际上就是耐热性能的体现, 耐热性能越高, 可以 使用的温度范围越大; 加工性能指高温耐环境湿度的性能。 可以看出, 本发明 使用特殊改性后的聚乳酸材料在使用性能和加工性能上都明显得到提高。 本发明的嘴棒较现有技术制备的嘴棒具有显著优点:
1、 具有生物降解性能, 更加环保;
2、 对烟气具有更好的吸附性能, 减少了吸烟危害;
3、 原料来源广泛, 既可采用传统的化石基资源, 又可采用生物质通过生 物技术得到, 既避免了醋酸纤维素嘴棒依赖木浆的资源问题, 又可真正实现 源自自然 (生物质) 又回归自然 (降解) 的绿色生产。 综上所述, 本发明采用非内酯单体共聚改性聚乳酸为原料制造的烟用过 滤嘴棒在质量和性质上均能达到烟用嘴棒的行业标准, 并且加工成香烟, 使 用后的废弃过滤嘴能实现完全生物降解, 与目前的醋酸纤维嘴棒相比, 从环 保角度具有不可比拟的优势; 另一方面, 本发明提供的可生物降解嘴棒利用 的非内酯单体共聚改性聚乳酸原料可以通过化学方法合成制备, 原料来源丰 富, 不再需要进口优质木材, 更利于工业化生产。 所以, 本发明的实施完全 可以取代目前使用的醋酸纤维嘴棒和聚丙烯纤维嘴棒, 同时具有非常广阔的 经济效益和社会效益。 具体实施方案
以下通过具体实施例进一步详细说明本发明的实施过程以及所产生的 有益效果, 以帮助阅读者更好地理解本发明, 但不能对本发明的可实施范 围构成任何限定。
除特别说明外, 本发明权利要求书和说明书中出现的比例或浓度均理 解为重量比或以重量为基准的百分浓度, 以下实施例中所用稳定剂均为食 品添加剂级。 实施例 1
称取 100公斤重均分子量为(15±1 )万, 分散指数为 1.5, 且分子链上含 有 15% (链节数) 随机分布的乙二醇链节的非内酯单体共聚改性聚乳酸为基 材树脂, 按改性聚乳酸: 磷酸三苯酯 : 抗氧剂 1222(3,5_二叔丁基— 4—羟 苯基磷酸二乙酯)的重量份比例为 97 : 2.5 : 0.5的比例称取原料, 在 55°C烘 箱中烘干 5小时后, 在高速搅拌机中搅拌均匀, 随后在长径比为 32的 Φ57 双螺杆挤出机上挤出制粒, 螺筒温度设定: 第一段为 190°C, 第二段为 195, 第三段为 200°C,第四段为 200°C,第五段为 190°C,挤出的条用切粒机切粒, 在线热风干燥, 包装, 得到本发明烟嘴棒用专用料。
将上述烟嘴棒用专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定为: 第一段为 200°C, 第二段为 205°C, 第三段为 205 °C ; 过滤器温度为 205°C, 箱体温度为 200°C, 直管温度为 200°C。从规格 为 1050x3的喷丝板喷出后用温度范围为 (15±5) °C的干燥空气侧吹风冷却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的纤 维表面处理剂水溶液为:聚乙二醇 1700,浓度为 0.2%,三乙醇胺硫酸二甲酯, 浓度为 0.15%, 壬基酚聚环氧乙院, 浓度为 0.1%。 经过上油槽后丝束通过慢 牵引机绕卷, 辊卷绕速度为 800 m/min; 然后通过牵引蒸汽箱, 进入快牵引机 绕卷, 快牵引辊转速 1500 r/min, 频率 38HZ, 然后通过皮带输送机输送, 皮 带输送机喂入轮速度 800r/min, 频率为 40HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水温 为 75°C。牵伸后的丝束在卷曲器中进行卷曲, 卷曲数为 24个 /25mm, 卷曲后 的丝束通过蒸气干燥器干燥。
干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本发明的可 生物降解烟用丝束。
从料箱拉出丝束, 经过辊道, 送达 Y11丝束开松机进行丝束开松, 开松 后丝束进入箱体, 用風胶盘和喷嘴喷施该丝束重量 6%的粘合增塑剂, 并使丝 束均匀地沾上胶。 粘合增塑剂的溶剂采用水 : 乙醇质量比为 50 : 50的混合 溶剂, 粘合增塑剂组成为: 二甘醇二醋酸酯, 浓度为 20%, 丙烯酸酯胶, 浓 度为 4%。
将上了胶的丝束在 Y21型烟用嘴棒成形器内揉卷成圆条形, 用滤棒盘纸 包裹, 定型形成嘴棒料条, 用切割刀将从成型器中出来嘴棒料条切割成规定 长度, 利用包装处理装置, 经由装盘机装入包装盒即得到本发明的烟用可生 物降解嘴棒。
本实施例所采用的非内酯单体共聚改性聚乳酸基材树脂可参照发明专利 申请 CN200610016643.0 中公开的聚合反应方法, 将乳酸与乙二醇单体按照 85 : 15的摩尔比混合发生共聚反应而得到。
上述嘴棒具有良好的生物降解性能, 按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 95%。 材料生物安全性符合烟用嘴棒要求。 圆周 24.1mm, 不圆度 0.2mm, 吸阻 3089Pa, 硬度 91%, 物理性能符合嘴棒要求。 经卷烟测试, 烟气指标为: 烟碱 1.08mg/支, 湿焦油 15.9mg/支, C015.7mg/ 支, 焦油 12.5mg/支。 实施例 2
选取 99.6公斤重均分子量为(10±1 )万, 分散指数为 1.2, 且分子链上含 有 1% (链节数)随机分布的乙二醇单甲醚链节的共聚非内酯单体共聚改性聚 乳酸为基材树脂, 和 0.4公斤亚磷酸三苯酯, 分别在 45°C烘箱中烘干 8小时 后, 在高速搅拌机中搅拌均匀, 在有干燥装置的环境中, 采用长径比为 32的 Φ75 双螺杆挤出机上挤出制粒, 螺筒温度设定第一段为 160°C, 第二段为 185°C, 第三段为 195°C, 第四段为 200°C, 第五段为 195°C。挤出料条用切粒 机切粒, 在线热风干燥, 包装, 得到本发明烟嘴棒用专用料。
将上述烟嘴棒用专用料在螺杆长径比为 28的 Φ65熔融纺丝机上进行纺 丝, 纺丝机螺杆温度设定为: 第一段为 195°C, 第二段为 200°C, 第三段为 205 °C , 过滤器温度为 200 °C, 箱体温度 200°C , 直管温度 200 °C。 从规格为 1050x3的喷丝板喷出后用温度范围为 0〜15°C的干燥空气侧吹风冷却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的纤 维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.2%, 三乙醇胺硫酸二甲酯, 浓度为 0.15%, 壬基酚聚环氧乙院, 浓度为 0.1%。 经过上油槽后的丝束通过 慢牵引机绕卷, 辊卷绕速度为 1000 m/min; 然后通过牵引蒸汽箱, 进入快牵 引机绕卷, 快牵引辊转速 1800 r/min, 频率 40HZ, 然后通过皮带输送机输送, 皮带输送机喂入轮速度 1000r/min, 频率为 40HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水温 为 60°C。牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 25个 /25mm, 卷曲后的 丝束通过蒸气干燥器干燥。
干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本发明的可 生物降解烟用丝束。
从料箱拉出丝束, 经过辊道, 送达 Y11丝束开松机进行丝束开松, 开松 后丝束进入箱体, 用風胶盘和喷嘴喷施该丝束重量 2%的粘合增塑剂, 并使丝 束均匀地沾上胶。 粘合增塑剂采用乙醇为溶剂, 粘合增塑剂组成为: 偏苯三 酸三辛酯浓度为 30%, 聚乙二醇胶浓度为 4%。
将上了胶的丝束在 Y21型烟用嘴棒成形器内揉卷成圆条形, 用滤棒盘纸 包裹, 定型形成嘴棒料条, 用切割刀将从成型器中出来嘴棒料条切割成规定 长度, 利用包装处理装置, 经由装盘机装入包装盒即得到本发明的烟用可生 物降解嘴棒。
本实施例所采用的非内酯单体共聚改性聚乳酸基材树脂可参照发明专利 申请 CN200610016643.0中公开的聚合反应方法,将乳酸与乙二醇单甲醚单体 按照 99 : 1的摩尔比混合发生共聚反应而得到。
上述嘴棒具有良好的生物降解性能, 按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 96%。 材料生物安全性符合烟用嘴棒要求。 圆周 24.1mm, 不圆度 0.2mm, 吸阻 3210Pa, 硬度 92%, 物理性能符合嘴棒要求。 经卷烟测试, 烟气指标为: 烟碱 1.07mg/支, 湿焦油 15.9mg/支, C015.8mg/ 支, 焦油 12.4mg/支。 实施例 3
选取重均分子量为 30万, 分散指数为 3.0, 且分子链上含有 30% (链节 数) 随机分布的乙醇酸链节的共聚非内酯单体共聚改性聚乳酸为基材树脂, 在 50°C烘箱中烘干 8小时后, 在螺杆长径比为 28的 Φ65熔融纺丝机上进行 纺丝, 纺丝机螺杆温度第一段设定为 190 °C, 第二段设定为 205°C, 第三段设 定为 220°C, 过滤器温度 200°C, 箱体温度 205°C, 直管温度 205°C。 从规格 为 1250x1的喷丝板喷出后用温度范围为 20〜40°C的干燥空气侧吹风冷却。
上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的纤 维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.6%, 三乙醇胺硫酸二甲酯, 浓度为 0.2, 壬基酚聚环氧乙垸,浓度为 0.2%。经过上油槽后的丝束通过慢牵 引机绕卷, 辊卷绕速度为 1500 m/min; 然后通过牵引蒸汽箱, 进入快牵引机 绕卷, 快牵引辊转速 2500 r/min, 频率 50HZ, 然后通过皮带输送机输送, 皮 带输送机喂入轮速度 1500r/min, 频率为 60HZ。
从皮带输送机牵引出来等丝束用多辊牵伸机牵伸, 牵伸介质为水, 7j温 为 90°C。牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 22个 /25mm, 卷曲后的 丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本发明的可生物降解烟用丝束。
从料箱拉出丝束, 经过辊道, 送达 Y11丝束开松机进行丝束开松, 开松 后丝束进入箱体, 用風胶盘和喷嘴喷施丝束重量 0.5%的粘合增塑剂, 并使丝 束均匀地沾上胶。 粘合增塑剂溶剂水 : 乙醇为 50 : 50的混合溶剂, 羧甲基 淀粉胶浓度为 5%。 将上了胶的丝束在 Y21型烟用嘴棒成形器内揉卷成圆条 形, 用滤棒盘纸包裹, 形成嘴棒料条, 用切割刀将从成型器中出来嘴棒料条 中切割成规定长度的嘴棒, 经包装处理装置, 经由装盘机装入包装盒即得到 本发明的烟用可生物降解嘴棒。
本实施例所采用的非内酯单体共聚改性聚乳酸基材树脂可按照发明专利 申请 CN200610016643.0 中公开的聚合反应方法, 将乳酸与乙醇酸单体按照 70 : 30的摩尔比混合发生共聚反应而得到。
上述嘴棒具有良好的生物降解性能, 按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 89%。 材料生物安全性符合烟用嘴棒要求。 圆周 24.1mm, 不圆度 0.2mm, 吸阻 3354Pa, 硬度 91%, 物理性能符合嘴棒要求。 经卷烟测试, 烟气指标为: 烟碱 1.08mg/支, 湿焦油 15.9mg/支, C015.4mg/ 支, 焦油 12.4mg/支。 实施例 4
选取 99公斤重均分子量为 5万, 分散指数为 1.3, 且分子链上随机分布 有 10% (链节数) 的丙二醇和 10% (链节数) 乙二醇的共聚非内酯单体共聚 改性聚乳酸为基材树脂, 1010重量为 0.1公斤, 1076重量为 0.2公斤, 氧化 钛 0.7公斤, 在 55°C烘箱中烘干 7小时后, 在高速搅拌机中搅拌均匀, 在长 径比为 36的 Φ60双螺杆挤出机上挤出, 螺筒温度设定第一段为 190°C, 第二 段为 195°C, 第三段为 205°C, 第四段为 215°C, 第五段为 200°C。 挤出料条 用切粒机切粒, 在线热风干燥, 包装, 得到本发明烟嘴棒用专用料。
将上述烟嘴棒用专用料在螺杆长径比为 28的 Φ60熔融纺丝机上进行纺 丝, 纺丝机的螺杆温度设定为: 第一段为 200°C, 第二段为 215°C, 第三段为 215°C ,过滤器温度 205 °C,箱体温度 205 °C,直管温度 205 °C。从规格为 1250x1 的喷丝板喷出后用温度范围为 30〜50°C的干燥空气侧吹风冷却。 上述冷却后的丝束在上油槽中涂覆油剂, 上油槽中油剂为以下组成的纤 维表面处理剂水溶液: 聚乙二醇 1700, 浓度为 0.8%, 三乙醇胺硫酸二甲酯, 浓度为 0.1%, 壬基酚聚环氧乙垸, 浓度为 0.1%。经过上油槽后的丝束通过慢 牵引机绕卷, 辊卷绕速度为 200 m/min。然后通过牵引蒸汽箱, 进入快牵引机 绕卷, 快牵引辊转速 400 r/min, 频率 25HZ, 然后通过皮带输送机输送, 皮带 输送机喂入轮速度 200r/min, 频率为 30HZ。
从皮带输送机牵引出来的丝束用多辊牵伸机牵伸, 牵伸介质为水, 水温 为 65°C。牵伸后丝束在卷曲器中进行卷曲, 卷曲数为 22个 /25mm, 卷曲后的 丝束通过蒸气干燥器干燥。 干燥后通过摆丝机将丝束在盛丝容器中摆放好, 打包即得到本发明的可生物降解烟用丝束。
从料箱拉出丝束, 经过辊道, 送达 Y11丝束开松机进行丝束开松, 开松 后丝束进入箱体, 用風胶盘和喷嘴喷施丝束重量 15%的粘合增塑剂, 并使丝 束均匀地沾上胶。 粘合增塑剂的溶剂采用水 : 乙醇为 50 : 50的混合溶剂, 粘合增塑剂组成为: 二甘醇二醋酸酯, 浓度为 20%, 胶原胶, 浓度为 4%。
将上了胶的丝束在 Y21型烟用嘴棒成形器内揉卷成圆条形, 用滤棒盘纸 包裹, 定型形成嘴棒料条, 用切割刀将从成型器中出来嘴棒料条切割成规定 长度, 通过包装处理装置, 经由装盘机装入包装盒即得到本发明的烟用可生 物降解嘴棒。
本实施例所采用的非内酯单体共聚改性聚乳酸基材树脂可参照发明专利 申请 CN200610016643.0中公开的聚合反应方法,将乳酸与丙二醇和乙二醇单 体按照 80 : 10 : 10的摩尔比混合发生共聚反应而得到。
上述嘴棒具有良好的生物降解性能, 按照 ISO 14855要求完全达到降解 标准要求, 90天降解率达到 93%。 材料生物安全性符合烟用嘴棒要求。 圆周 24.1mm, 不圆度 0.2mm, 吸阻 3167Pa, 硬度 91%, 物理性能符合嘴棒要求。 经卷烟测试, 烟气指标为烟碱 1.04mg/支, 湿焦油 15.9mg/支, C015.8mg/支, 焦油 12.5mg/支。

Claims

权利要求书
1、 一种可生物降解的烟用纤维材料, 其原料组成包括 90-100^%的非 内酯单体共聚改性聚乳酸和 0-10wt%的稳定剂, 所述非内酯单体共聚改性 聚乳酸为分子链中含有总链节数的 1-30%的非内酯型单体链节, 其余为乳 酸链节的高分子聚合物, 且其重均分子量为 5-35万, 分散指数 1.2-3.0, 该 烟用纤维材料是所述原料经熔融纺丝工艺加工而成。
2、 如权利要求 1所述的可生物降解的烟用纤维材料, 其中, 所述非内 酯单体共聚改性聚乳酸分子链中的非内酯单体链节是由非内酯型且能与乳 酸实现共聚的单体聚合得到的, 所述能与乳酸实现共聚的单体包括但不限 于乙二醇、 丙二醇、 乙醇酸、 乙二醇单甲醚或其混合物。
3、 如权利要求 1所述的可生物降解的烟用纤维材料, 其中, 所述稳定 剂包括磷酸三甲酯、 磷酸二乙酯、 磷酸三苯酯、 磷酸二苯酯、 亚磷酸三苯 酯、 亚磷酸二苯酯、 亚磷酸铵、 抗氧剂 1010 、 抗氧剂 1076、 抗氧剂 1425、 抗氧剂 1222、 氢氧化镁、 氢氧化铝、 氧化钛、 氧化钙或它们的任意混合物。
4、 如权利要求 3所述的可生物降解的烟用纤维材料, 其中, 所述稳定 剂包括磷酸三甲酯、 磷酸三苯酯、 亚磷酸三苯酯、 抗氧剂 1010 、 抗氧剂 1076、抗氧剂 1222、抗氧剂 1425、氧化钛、氢氧化镁或它们的任意混合物。
5、 一种可生物降解的香烟过滤嘴棒, 该香烟过滤嘴棒是利用权利要求 1_4任一项所述的可生物降解的烟用纤维材料加工而成。
6、 一种设置有过滤嘴的香烟, 所述过滤嘴为权利要求 5所述的可生物 降解的香烟过滤嘴棒加工而成。
7、权利要求 1-4任一项所述的可生物降解的烟用纤维材料的制造方法, 该方法包括如下步骤: 将原料进行熔融纺丝: 设定纺丝机的螺杆温度 180°C-240°C, 使挤出物 料流经过滤器、 箱体、 计量泵和直管后, 通过喷丝板喷丝, 该过程中控制 过滤器温度 170°C-250°C, 箱体温度 170°C-250°C, 直管温度 170°C-250°C, 然后对喷出的丝以干燥空气冷却, 冷却温度为 0°C-50°C ;
冷却后的丝束经涂覆油剂, 进行慢牵引机绕卷、 蒸汽箱牵引、 快牵引 机绕卷以及皮带输送机的卷绕牵引, 油剂是浓度为 0.8%-1%纤维表面处理 剂的水溶液, 慢牵引机的辊卷绕速度 200-1500m/min, 快牵引机的辊转速 400-2500r/min, 频率 25-50HZ, 皮带输送机喂入轮速度 200-1500 r/min, 频 率为 30-60HZ;
将从皮带输送机牵引出来的丝束在水温为 40°C-90°C的水槽中水浴牵 伸, 然后经卷曲和干燥定型, 得到的丝束即为所述可生物降解的烟用纤维 材料。
8、如权利要求 7所述的可生物降解的烟用纤维材料的制造方法,其中, 原料组成中, 所述非内酯单体共聚改性聚乳酸含量为≥90wt°/c^S< 100wt%, 稳定剂含量 >(Hg≤10wt%, 所述制造方法还包括:
将非内酯单体共聚改性聚乳酸和稳定剂干燥后混合均匀, 进行挤出制 粒, 挤出机螺筒温度为 160-240°C。
9、 如权利要求 7或 8所述的可生物降解的烟用纤维材料的制造方法, 其中, 熔融纺丝工序中, 挤出机螺杆温度 190-230 °C。
10、 权利要求 5所述的可生物降解的香烟过滤嘴棒的制造方法, 该方 法包括:
按照权利要求 7-9 中任一项所述的方法制造可生物降解的烟用纤维材 料丝束;
对所述丝束开松后喷施该丝束重量 0.5~15%的粘合增塑剂使丝束被均 匀上胶; 在烟用嘴棒成形器内将所述上了胶的丝束揉卷成条形, 用滤棒盘纸包 裹定型, 成为嘴棒料条;
将上述嘴棒料条切割成规定长度, 即得到所述可生物降解香烟嘴棒; 上述粘合增塑剂包括对苯二甲酸二辛酯、 对苯二甲酸二丁酯、 偏苯三 酸三辛酯、 偏苯三酸三癸酯、 偏苯三酸三甘油酯、 磷酸甘油酯、 乳酸甘油 酯、 柠檬酸丁酯、 二甘醇二醋酸酯、 碳酸丙烯酯、 乙二醇单乙醚、 水基淀 粉胶、 羧甲基淀粉胶、 丙烯酸酯胶、 聚乙二醇胶、 聚乙烯醇胶、 蛋白胶、 胶原胶或它们的任意混合物。
11、 如权利要求 10所述的可生物降解的香烟过滤嘴棒的制造方法, 其 中, 所述粘合增塑剂包括偏苯三酸三甘油酯、 二甘醇二醋酸酯、 乳酸甘油 酯、 羧甲基淀粉胶、 丙烯酸酯胶、 聚乙二醇胶、 胶原胶或它们的任意混合 物。
12、 如权利要求 10或 11所述的可生物降解的香烟过滤嘴棒的制造方 法, 其中, 所用粘合增塑剂以乙醇或乙醇水溶液为溶剂。
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