Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/06—Use of materials for tobacco smoke filters
  • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
  • A24D3/068—Biodegradable or disintegrable
• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/02—Manufacture of tobacco smoke filters
• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/06—Use of materials for tobacco smoke filters
• • A—HUMAN NECESSITIES
  • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
  • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
  • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
  • A24D3/06—Use of materials for tobacco smoke filters
  • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
  • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/05—Filamentary, e.g. strands
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
  • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
  • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
  • D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]

Definitions

• the present invention concerns biodegradable composite materials, especially for use in cigarette filter tows.
• the first cigarette filters were developed in the 1920s and were composed of crepe paper, sometimes together with cellulose wadding. Subsequent concerns over the adverse link between smoking and health led to a surge in demand for filters yielding lower tar levels.
• a dual filter comprising cellulose acetate fibres within a paper sheath was developed, allowing for the addition of other functional components such as activated carbon.
• cigarette filters typically comprise a "filter tow", generally crimped fibres of cellulose acetate, encased in a tipping paper.
• This invention is concerned with the filter tow component.
• One of the most pressing issues for manufacturers of cigarettes and cigarette filters is the rate at which the filters biodegrade.
• Cellulose acetate filters can take between one month and three years to biodegrade, dependant on environmental conditions, which is not sufficiently fast to avoid the issue of litter.
• Discarded cigarette filters top the list of almost all coastal clean-up surveys. The issue of litter is not just a visual one, the toxins adsorbed by used cigarette filters have been found to leach into the environment, and present a potential biohazard.
• a range of approaches to the preparation of biodegradable filter tow have been suggested and include the use of composites of cellulose acetate with other biodegradable polymers, additives for increasing the rate of degradation of cellulose acetate, cellulose acetate with a low degree of substitution (DS) for increased biodegradability, and biodegradable polymers such as PHB/PVB and starches as the filter tow raw material.
• biodegradable polymers such as PHB/PVB and starches as the filter tow raw material.
• Cellulose and cellulose acetate are typically cast in the form of fibres or films. Either form of casting is suitable for preparing the biodegradable cigarette filter tows of the invention. When cast in the form of films it is necessary then to shred the resulting film to produce material suitable for cigarette filter tows.
• Preferred filter tows in accordance with the invention comprise fibres spun from a coagulated solution of cellulose and cellulose acetate.
• composite filaments of cellulose/cellulose acetate shall be understood to mean either fibres spun from a dope comprising cellulose and cellulose acetate, or shredded films cast from similarly constituted dope.
• composite filaments of cellulose/cellulose acetate have significantly greater biodegradability than equivalent filaments comprising only cellulose or cellulose acetate. Without wishing to be bound by any such theory, we believe that the presence of acetate in the composite may disrupt the crystallinity of the cellulose, causing it to biodegrade more rapidly than cellulose itself.
• cellulose is cast or spun from viscose, and it is difficult or impossible to cast or spin cellulose acetate from the same blend because of the likelihood of hydrolysis of the cellulose acetate under such conditions.
• cellulose acetate is conventionally cast or spun from acetone and P T/GB2010/051562 it is difficult or impossible to cast or spin cellulose from the same blend because of the limited solubility of cellulose in acetone.
• the cigarette filter tow of the invention is preferably formed from fibres or films of cellulose and cellulose acetate spun or cast as a blend from an ionic liquid (IL) or from A/-methylmorphilone-/V-oxide (NMMO).
• IL ionic liquid
• NMMO A/-methylmorphilone-/V-oxide
• Suitable IL include those based on imidazole, pyrrole, thiazole or pyrazole cations in combination with halogen, phosphate, carboxylate or metal chloride anions.
• Particularly preferred ILs include 1-butyl-3-methylimidazolium chloride (BMIM-CI) 1-butyl- 3-methylimidazolium acetate (BMIM-Ac) and 1 -ethyl-3-methylimidazolium acetate (EMIM-Ac).
• the solution of cellulose and cellulose acetate from which fibres are spun or films are cast is referred to herein as a dope.
• the dope may also comprise an aprotic solvent such as DMSO, DMF, THF or dioxane to aid dissolution of the cellulose and/or cellulose acetate.
• aprotic solvent such as DMSO, DMF, THF or dioxane
• One particularly preferred aprotic solvent is DMSO.
• the blend of cellulose acetate and cellulose in the dope may also comprise one or more further thermoplastic materials, such as polyhydroxyalkanoates such as PHB and/or PHVB which may add further functionality, such as water barrier functionality, to the cigarette filter tows of the invention.
• Other functional additives may include triacetin, polyacrylonitrile (PAN), poly-2- hydroxyethylmethylacrylate (PHEMA), polyvinylalcohol (PVA), polyaniline and polyethylene glycol for functional purposes such as modification of absorption and/or taste profile, degradation enhancement (by, for example, water-soluble materials), and processability improvement, in connection for example with wet strength.
• PAN polyacrylonitrile
• PHEMA poly-2- hydroxyethylmethylacrylate
• PVA polyvinylalcohol
• polyaniline polyethylene glycol
• Triacetin may improve taste profile, as well as acting as a plasticiser.
• the weight ratio of cellulose to cellulose acetate in the dope, and consequently in the cigarette filter tow of the invention is from 10:90 to 90:10, for example from 20:80 to 80:20, or from 30:70 to 70:30.
• the dope comprises a solids content of up to about 50% w/w, preferably up to about 40% w/w, more preferably up to about 30% w/w and most preferably up to about 20% w/w.
• the filter tows of the invention may additionally comprise one or more plasticisers, such as triacetin, which may aid crimping of the composite filaments.
• the composite filaments of cellulose/cellulose acetate are preferably crimped to provide smoke barrier contact points.
• the plasticiser may be included in the dope, or may added subsequent to spinning or casting, for example by spraying onto the surface of the filter tow before or during crimping.
• the tows may also comprise one or more lubricants to reduce electrostatic charge.
• Preferred lubricants include mineral oils.
• 1 % w/w of mineral oil with an emulsifier may be applied to the composite filaments during spinning of the fibres or casting of the films.
• the filter tows of the invention comprise composite filaments of cellulose/cellulose acetate manufactured at 1 , 5 or 9 denier per filament (filament thickness (denier per filament) being defined as the mass (grams) of 9000 m of a single uncrimped filament).
• total tow mass (total denier) (defined as the total mass of 9000 m of uncrimped filter tow, typically comprising many thousands, for example 1 1 ,000, individual fibres) will vary considerably depending on the methods employed in fibre spinning and the number of individual fibres in the tow. One typical tow mass would 35,000g.
• the filter tows of the invention comprise fibres having a trilobal filament cross-section (optionally formed using triangular spinneret holes) to optimise surface area.
• the filter tows of the invention preferably comprise crimped fibres, the crimp structure defined by the crimp index, which is the ratio between stretched (25 kg load) and unstretched (0.25 kg load) filter tow.
• the crimp index will vary considerably depending on the precise method of manufacture.
• the moisture content of the cigarette filter tows according to the invention is preferably at least about 2% w/w, more preferably at least about 5% w/w, even more preferably at least about 10% w/w.
• Moisture content has been found to be important for preventing electrical charges, but should preferably not be too high (e.g. not higher than 50% w/w) because with a very high moisture content it may be difficult for the tow to retain a crimp.
• a cigarette filter comprising the cigarette filter tow as hereinbefore described encased in a tipping wrapper.
• the tipping wrapper is itself a biodegradable substance and may for example comprise paper or an alternative biodegradable substrate such as cellulose, PLA, hydroxyalkanoates, a starch based polymer, or other form of biopolymer.
• the tipping wrapper comprises a biopolymer, it preferably comprises a softener in an amount of not more than about 25% by weight to achieve suitable properties particularly in connection with elongation and tube curl.
• the softener may in the biopolymeric tipping wrapper may be selected from any suitable material, but is preferably selected from glycerol, propane-1 ,2- diol, and any other suitable softener selected from the German Tobacco Ordnance (TVO) list.
• TVO German Tobacco Ordnance
• Figure 1 shows three slides showing fibres of i) cellulose acetate; ii) cellulose; and iii) a blend of cellulose and cellulose acetate in accordance with the invention.
• Figure 2 shows the slides of Figure 1 after 2 weeks biodegradation under anaerobic conditions.
• Figure 3 shows the slides of Figure 1 weeks biodegradation under anaerobic conditions.
• Figure 4 shows the slides of Figure 1 after 6 weeks biodegradation under anaerobic conditions.
• fibres were spun from solutions of i) cellulose (DP -800) and ii) 1 :1 cellulose: cellulose acetate (Eastman, CA-398- 30), at 10 % solids in EMIM-Ac: DMSO (20:80).
• EMIM-Ac DMSO (20:80).
• a 40-orifice spinneret with an orifice diameter of 70 pm was used, which was submerged in a room temperature coagulation bath containing clean water.
• the fibres were reeled- up wet, extensively washed on the reel then dried at 50 °C.
• Filter tow according to the invention is manufactured using a dry-spinning process.
• a dope is first prepared by dissolving cellulose diacetate and cellulose (1 :1 blend) at 10 % solids in EMIM-Ac: DMSO (20:80). Ti0 2 is added to give a whitened appearance.
• the dope is then filtered and spun into chambers, causing the filaments to solidify and become thinner. More than 10,000 filaments are spun from a series of spinning cabinets, which are combined to form a single band.
• a stuffer box is used to emboss the filter tow with a crimp structure, and the resulting filter tow is encased in a tipping paper to form a cigarette filter.
• the resulting cigarette filter is found to retain to advantageous biodegradability properties as shown in Example 1 and to have an acceptable taste signature.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biodiversity & Conservation Biology (AREA)
• Mechanical Engineering (AREA)
• Artificial Filaments (AREA)
• Cigarettes, Filters, And Manufacturing Of Filters (AREA)
• Multicomponent Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Woven Fabrics (AREA)
• Materials For Medical Uses (AREA)

Priority Applications (11)

Applications Claiming Priority (2)

Publications (1)

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Cited By (9)

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Citations (10)

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• 2009
  • 2009-10-23 GB GB0918633A patent/GB2474694B/en not_active Expired - Fee Related
• 2010
  • 2010-09-17 EP EP10760393.8A patent/EP2490557B1/en not_active Not-in-force
  • 2010-09-17 CN CN2010800467767A patent/CN102595942A/zh active Pending
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• 2013
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• 2016
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