EP2568833B1 - Filter additive - Google Patents
Filter additive Download PDFInfo
- Publication number
- EP2568833B1 EP2568833B1 EP11724440.0A EP11724440A EP2568833B1 EP 2568833 B1 EP2568833 B1 EP 2568833B1 EP 11724440 A EP11724440 A EP 11724440A EP 2568833 B1 EP2568833 B1 EP 2568833B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- filter
- additive
- sheet
- filter element
- materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000654 additive Substances 0.000 title claims description 79
- 230000000996 additive effect Effects 0.000 title claims description 65
- 239000000463 material Substances 0.000 claims description 143
- 238000000034 method Methods 0.000 claims description 54
- 239000007787 solid Substances 0.000 claims description 24
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- 230000000391 smoking effect Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 description 30
- 241000208125 Nicotiana Species 0.000 description 24
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 239000004014 plasticizer Substances 0.000 description 16
- 239000011236 particulate material Substances 0.000 description 12
- 239000000779 smoke Substances 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 229920000747 poly(lactic acid) Polymers 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 7
- 235000019504 cigarettes Nutrition 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004626 polylactic acid Substances 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000796 flavoring agent Substances 0.000 description 4
- 235000013773 glyceryl triacetate Nutrition 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 229960002622 triacetin Drugs 0.000 description 4
- 239000001069 triethyl citrate Substances 0.000 description 4
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 4
- 235000013769 triethyl citrate Nutrition 0.000 description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 238000006065 biodegradation reaction Methods 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001087 glyceryl triacetate Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- -1 poly(ε-caprolactone) Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 230000003313 weakening effect Effects 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 244000180278 Copernicia prunifera Species 0.000 description 1
- 235000010919 Copernicia prunifera Nutrition 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- 239000004150 EU approved colour Substances 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229920001800 Shellac Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical group [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000019506 cigar Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229940006093 opthalmologic coloring agent diagnostic Drugs 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940113147 shellac Drugs 0.000 description 1
- 235000013874 shellac Nutrition 0.000 description 1
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 description 1
- 239000004208 shellac Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
- A24D3/048—Tobacco smoke filters characterised by their shape or structure containing additives
-
- 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
- A24D3/02—Manufacture of tobacco smoke filters
- A24D3/0204—Preliminary operations before the filter rod forming process, e.g. crimping, blooming
- A24D3/0212—Applying additives to filter materials
-
- 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
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
Definitions
- the invention relates to methods for making filter elements and filters for smoking articles, the filter elements and filters comprising an additive material.
- the invention relates to methods of incorporating an additive which is solid at room temperature into filter material, the method comprising the step of melting the additive material.
- cellulose acetate tow A wide variety of materials have been used as filter materials for tobacco smoke.
- the most commonly used filter material is cellulose acetate tow.
- cellulose acetate has an excellent capacity to filter tobacco smoke, it has the drawback that it is slower to degrade than other materials and can therefore be disadvantageous environmentally.
- Efforts have been made to make cellulose acetate filters more biodegradable.
- EP 0766929 discloses a water-disintegrable tobacco smoke filter comprising cellulose ester fibres and an adsorbent resin, which are bound together into a rod-shaped fibre bundle using a water-soluble polymer.
- Filter materials made from non-woven sheet material and paper are known. Suitable sheet materials include polyvinyl alcohol, reconstituted tobacco, starch, and polylactic acid. These materials are much more readily degradable than cellulose acetate tow, however, they have drawbacks. In particular, in order to attain the desired structural rigidity when constructing a filter element from non-woven sheet materials and paper, the filter material is generally densely packed and this means that these filter elements have quite different properties to those made of cellulose acetate. They exhibit a greater resistance to the flow of smoke, resulting in a pressure drop which is higher than that of a conventional cellulose acetate (CA) filter, requiring the user to draw harder on the smoking article.
- CA cellulose acetate
- the smoke drawn through such filter material has been found to have different taste characteristics compared to the smoke drawn through conventional cellulose acetate filter material.
- filter elements comprising non-woven sheet materials or paper as the filter material have been shown to exhibit significantly less selective removal of semi-volatile compounds than conventional cellulose acetate tow filter materials.
- additives such as triacetin (glycerin triacetate), TEC (triethyl citrate) and PEG 400 (low molecular weight polyethylene glycol) in cellulose acetate filters.
- These additives function as plasticizers and they are generally used in cellulose acetate filters to give the filter rods sufficient hardness for cigarette manufacture and use.
- Some plasticizers have the additional advantage of providing cellulose acetate tow with an improved capacity to selectively remove semi-volatile compounds such as phenol, o-cresol, p-cresol and m-cresol from tobacco smoke.
- plasticizers are in liquid form at room temperature and they are sprayed on to cellulose acetate tow.
- the plasticizer coats the individual fibres within the tow and, with time, they bind or fuse adjacent fibres together at their points of contact, thereby increasing the hardness or rigidity of the filter material, to give the core of the filter the desired structural strength.
- the mode of action of the plasticizers does, however, mean that there is an upper limit to the amount that may be incorporated into cellulose acetate tow filter material. When above about 7% of plasticizer by weight of the filter is included, the plasticizer starts to have a detrimental effect on the cellulose acetate tow, forming holes which compromises its filtration properties.
- plasticizers such as triacetin, TEC or PEG 400 in CA filters are relatively common, their inclusion in non-woven sheet and paper filter materials is less attractive.
- the plasticizers are used in CA filters to bind fibres and the plasticizer would clearly not have this advantageous effect when added to non-woven sheet material or paper (in which the fibres are already bound within the sheet structure).
- these commonly used plasticizers are liquids and their application to non-woven sheet and paper filter materials will be limited as they will cause these materials to become soggy and to lose their structural integrity.
- Paper the most commonly used sheet filter material, may start to disintegrate when moist, and will therefore have a reduced acceptability to the user.
- many sheet materials, including polyvinyl alcohol and polylactic acid are soluble and therefore the addition of aqueous additives may result in the partial dissolution of the material.
- the method will also result in a filter element which exhibits an improved capacity to selectively remove semi-volatile compounds and which provides smoke having similar taste characteristics to that provided by conventional cellulose acetate filters.
- a method for making a smoking article filter element comprising sheet filter material and an additive. The method comprises the steps of:
- smoking article includes smokeable products such as cigarettes, cigars and cigarillos whether based on tobacco, tobacco derivatives, expanded tobacco, reconstituted tobacco or tobacco substitutes and also heat-not-burn products.
- the present invention relates to a method of producing a filter element for inclusion in a smoking article, the method comprising applying an additive to sheet filter material, the additive being solid at room temperature and the method involving heating the additive so that it melts.
- the additive is applied to the sheet filter material in solid form, for example in the form of a powder, prior to formation of the filter rod.
- the formed filter rod may then be heated to melt the additive whilst it remains in contact with the filter material.
- the additive material subsequently cools and re-solidifies, it provides the filter material and the filter element formed with one or more of: stability and rigidity; improved smoke taste characteristics; and improved selective removal of semi-volatile compounds.
- the methods according to the present invention may be used to add an additive to any type of sheet filter material, for example non-woven sheet materials or paper.
- Paper filter material usually comprises gathered, pleated, crimped, crepe or even shredded paper. Paper filter materials tend to have a low air permeability, exhibit a basic pH, and can be gathered or formed easily to form the filter element.
- a preferred filter material for filter elements of the present invention is a gathered or pleated paper. Examples of suitable papers are PuracelTM and MyriaTM papers (Filtrona plc, United Kingdom).
- Non-woven sheet materials may be used as filter materials.
- Non-woven materials are broadly defined as sheet or web structures bonded together by entangling fibres or filaments mechanically, thermally or chemically, or by a combination of two or more of these. They tend to be flat, porous sheets that are made directly from separate fibers. They are not made by weaving or knitting and do not require converting the fibers to yarn.
- the non-woven sheet materials used in the present invention are preferably ones which are readily biodegradable.
- materials include polyvinyl alcohol (PVOH), polylactic acid or polylactide (PLA), poly( ⁇ -caprolactone) (PCL), poly(1-4 butanediol succunate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT).
- PVOH polyvinyl alcohol
- PLA polylactic acid or polylactide
- PCL poly( ⁇ -caprolactone)
- PBS poly(1-4 butanediol succunate)
- PBAT poly(butylene adipate-co-terephthalate)
- Other suitable filter materials include starch fibres and calcium alginate.
- Non-woven sheet materials and paper are more readily biodegradable than cellulose acetate tow.
- the filter material In order to attain the desired structural rigidity when constructing a filter element from non-woven sheet materials and paper, the filter material must be very densely packed and this means that these filter elements have quite different properties to those made of cellulose acetate. They exhibit a greater resistance to the flow of smoke, resulting in a pressure drop which is higher than that of a conventional cellulose acetate filter, requiring the user to draw harder on the smoking article.
- the sheet material used in the method of the invention may comprise paper, polyvinyl alcohol, reconstituted tobacco, starch, or polylactic acid.
- the sheet filter material is paper.
- Preferred non-woven sheet materials have a thickness greater than about 0.05 mm, preferably from about 0.06 mm to about 0.08 mm.
- the paper filter materials may comprise paper having a basis weight of about 15g/m 2 to about 40g/m 2 , preferably about 20g/m 2 to about 35g/m 2 .
- the sheet material used in the method of the invention may additionally or alternatively comprise polyvinyl alcohol (PVOH).
- PVOH polyvinyl alcohol
- PVOH is unique in being the only biodegradable, carbon-carbon backbone polymer that can completely biodegrade to small molecules, e.g., carbon dioxide and water.
- the method may comprise the use of the sheet material polylactic acid.
- the lactate from which PLA is produced can be derived from the fermentation of agricultural by-products.
- an additive which is solid at room temperature may provide firmness and rigidity to the filter without damaging the filter material by making it soggy.
- the method of the present invention uses a solid additive which has been melted, but which re-solidifies at room temperature and bonds parts of the filter material together. Therefore, the additive has the benefit that it can actually increase the structural integrity and rigidity of the filter material.
- addition of a solid additive by a method according to the present invention may make it possible to use less of the filter material in the filter element. This provides further flexibility when forming the filter element with regard to the amount of filter material required to achieve the desired hardness and rigidity. This in turn would allow the manufacturer to adjust the pressure drop of the filter element. This would allow a filter element according to the present invention to be designed having properties which closely resemble those of conventional CA filter elements.
- the addition of a solid additive to the filter material by the methods according to the present invention can eliminate the shortcomings that are currently associated with the use of sheet filter materials, by improving the rigidity of the filter, improving the taste of the smoke, and increasing the selective removal of semi-volatile compounds. Furthermore, the combination of filter material and solid additive may provide vastly improved disintegration, dispersion and/or biodegradability of the filter element.
- the methods of the invention allow the properties of non-woven sheet and paper filter materials to be fine-tuned, so that the performance of the filter element can more closely resemble that of a cellulose acetate filter element.
- These additives also give the use of sheet filter material much greater flexibility, widening the range of its applicability whilst retaining the beneficial biodegradable properties.
- the additive comprises a high molecular weight polyethylene glycol which is solid at room temperature.
- Suitable PEGs include PEG 600 and higher, and preferably PEG 1000 and higher.
- High molecular weight polyethylene glycol has the additional advantage of providing selective removal of semi-volatile compounds.
- This selective removal of semi-volatile compounds provided by the addition of the PEG to the filter element is proportional to the amount of PEG included.
- the methods of the present invention which involve the use a PEG which is solid at room temperature (in contrast to the PEG previously used in filters) provide flexibility which allows the addition of greater amounts of PEG than would be possible if using a liquid PEG.
- PEG may be included in the filter material of the filter element in an amount of up to about 30%, preferably up to about 20%, and more preferably about 5-10% by weight of the filter element.
- PEG poly(ethylene glycol)
- its inclusion in the filter elements should not adversely affect the biodegradation of the product. Indeed, it has been surprisingly found that the addition of PEG to a filter element comprising a non-woven sheet material or paper as the filter material actually enhances biodegradation.
- MPEGs high molecular weight methoxypolyethylene glycols
- MPEG 750 1000, 2000, 3000 and 5000
- waxes which are solid at room temperature, including beeswax, carnauba, shellac, castor wax, paraffin and various synthetic waxes.
- the method can further comprise the incorporation into the sheet filter material of further additives such as tobacco extracts, glycerine, menthol, carbon fibres, carbon particles, and the like.
- further additives such as tobacco extracts, glycerine, menthol, carbon fibres, carbon particles, and the like.
- a further advantage of the method of the invention is that filter elements to which additive has been applied using the claimed method are more stable to the subsequent addition of additives, including liquid additives.
- additives including liquid additives, which would otherwise have been difficult to apply to sheet material without making it soggy, can be added to the filter rod to adjust the properties of the filter as required, or provide further qualities to the filter element, such as flavourants for enhanced flavour.
- Methods according to the present invention encompass different ways of applying the additive to the filter material.
- the method involves applying the additive to the sheet filter material in solid form, for example in the form of a powder, before the filter material is formed into the filter rod or core of the filter element. Once formed, the filter rod is heated to melt the additive. The additive melts and subsequently re-solidifies, bonding the filter material without making it soggy.
- This method allows the additive to be applied to the filter material in a controlled and uniform manner, and with minimal wastage of additive material. It also avoids any potential disadvantages associated with applying a liquid to the filter material. For example, this embodiment avoids the potential weakening of the sheet structure by applying a liquid.
- steps will need to be taken to ensure that the solid additive remains in contact with the sheet filter material whilst the sheet is being fashioned into a filter rod. This may require the application of some adhesive or special orientation of the sheet material.
- Filter elements comprising sheet materials are generally manufactured using a process which comprises the steps of crimping the sheet material and then gathering the sheet material to form a cylindrical filter rod.
- the additive may be added prior to or during the crimping process, or may be added to the sheet material after it has been crimped. The additive may even be added to the crimped material as it is gathered to form the filter rod, with the effect that it is immediately contained within the rod and does not need to be adhered.
- the additive may be adhered to the filter material using any suitable adhesive, for example, using liquid starch adhesives, or EVA and PVA adhesives.
- the solid additive may be applied to sheet filter material as a powder or in larger pieces, such as in the form of flakes or pellets.
- the additive may be applied to the sheet filter material by any suitable method that is known to the skilled person.
- powdered additive may be sprayed on to the filter material, or it may be applied by an applicator which may or may not be in direct physical contact with the filter material.
- the additive may be loosely applied to the filter material, for example by being sprayed or sprinkled, or may be applied using a degree of force, such as by being pressed or smeared on to the filter material.
- the sheet filter material is formed with the solid additive embedded in or on it. Applying the additive which is solid at room temperature to the filter material in this way can simplify the methods of the present invention. Once the filter material has been formed into the filter rod, the rod may be heated to melt the additive, and then allowed to re-solidify.
- the additive may be applied to the sheet material during its manufacture or as part of a post-manufacture processing step. In this way, the additive may be incorporated within the sheet, or as a coating on one or both sides of the sheet material.
- the additive may be uniformly present within or on the surface of the sheet, or may be present in discreet areas, such as in patches or strips on the sheet material.
- the additive is to be melted after the filter material has been formed into a rod or core, sufficient heat needs to be applied to ensure that all of the additive, which is dispersed throughout the rod, is melted.
- the application of heat to the formed filter rod must be carried out with care, as it may have a detrimental effect on other components of the filter rod, including the filter material and any wrapper (which is likely to be paper and could be singed or scorched by exposure to high temperatures).
- the temperature that the filter rod must be heated to, and the duration of heating, is dependent upon the melting point of the additive.
- a preferred additive, PEG 1000 has a melting point of around 37°C, and therefore in this case, the filter rod is heated to a temperature exceeding 37°C.
- the filter rod may be heated to a temperature exceeding 40°C, preferably exceeding 45°C, and most preferably exceeding 50°C.
- the heat needs to be applied for a period sufficient to ensure that the whole rod is heated and not just the outer areas.
- Heat may be applied using any suitable means.
- the filter rod or filter element may be brought into close proximity with a heating element.
- the filter rod or filter element may be heated by means of a current of hot gas, such as hot air or steam, or via the application of radiation, such as microwave radiation.
- Heat may be applied to the filter rod as soon as it is formed.
- heating of the filter rod may occur at some stage between formation of the filter rod at the garniture and the cut-off, where the filter rod is separated into sections. Heating of the rod will generally be for a very brief period, such as less than 1 second, due to the linear motion of the rod through the machine.
- concomitant forming and heating of the filter rod may require expensive modification of the current apparatus.
- the filter rod is preferably heated at a later stage, and this may be achieved using a heater which is essentially separate from the apparatus involved in forming the filter rod.
- the heating is preferably carried out in a separate conditioning step, where lengths of filter rod are kept at an elevated temperature for an extended period of time to ensure that all of the additive is melted and bonds to the filter material.
- the method of the invention may further comprise wrapping the filter rod in a suitable wrapper such as a plugwrap.
- a suitable wrapper such as a plugwrap.
- the heat may be applied before the filter rod is wrapped.
- the filter rod may be wrapped and then heated.
- the assembled filter is heated to melt the additive, although this approach can be complicated by the insulating properties of the filter material.
- the speed of filter manufacture means that the time available for heating the filter is limited. Having said that, heating of the assembled filter may be achieved in various ways.
- the filter rod may be exposed to heat by conductance, such as on a heated drum in the presence of hot air.
- trays of filter rods (such as 4,000 filters per tray) may be passed through a heated tunnel or similar arrangement, in the presence of hot air.
- the filter trays may alternatively be heated by the application of radiation such as microwave radiation.
- the methods of the present invention may further comprise a step of incorporating particulate material into the filter element.
- Suitable particulate material includes sorbents (e.g. selected from activated carbon, charcoal, silica gel, sepiolite, alumina, ion exchange material etc.), pH modifiers (e.g. alkaline materials such as Na 2 CO 3 , acidic materials), flavourants, other solid additives and mixtures thereof.
- the particulate material may be selected from a group of relatively high surface area materials capable of adsorbing smoke constituents without a high degree of specificity.
- Suitable general adsorbents can be selected from the group consisting of carbon, activated carbon, activated charcoal, activated coconut carbon, activated coal-based carbon or charcoal, zeolite, silica gel, meerschaum, aluminium oxide (activated or not), carbonaceous resin or combinations thereof.
- particulate material which may be used in the method of the invention is carbon, for instance activated carbon, or charcoal or other carbonaceous absorbent material.
- activated carbon is activated coconut carbon.
- the particulate material may be incorporated into the filter element in such a way that it is interspersed throughout the filter element, or it may be interspersed in some parts (but not all) of the filter element.
- the particulate material may be interspersed over the full longitudinal length of the core.
- the particulate material may be interspersed from one end of the core to a section that is short of the other end.
- the particulate material may be present in discrete areas that need not extend from - or be present at - any end of the core. Different areas may have different loadings of particulate material and/or different types of particulate material.
- the methods of the present invention may further comprise wrapping the filter element in a suitable wrapper.
- the wrapper of the filter element is preferably a paper wrapper, and most preferably comprises conventional plugwrap, such as plugwrap having a basis weight of between about 20g/m 2 and about 35g/m 2 , preferably about 27g/m 2 .
- the plugwrap may be porous or non-porous.
- the method may comprise the use of a wrapper which includes a particulate material adhered to one or more portions of its surface.
- the particulate material is adhered to two or more portions of the wrapper, the portions being circumferentially spaced from one another, with at least one of the portions extending over the full longitudinal length of the wrapper.
- the smoking article filter element produced according to the method of the present invention may be incorporated into a smoking article filter.
- the smoking article filter may comprise a single filter element of the method of the invention.
- the smoking article filter may include two or more filter elements produced according to the method of the invention.
- the filter element may be part of a composite (or multi-component) filter.
- the filter elements of the composite filter are arranged longitudinally of one another with the end of each filter element abutting the next.
- the composite filter may have 2, 3, 4 or more distinct or discrete sections.
- the filter is a triple-filter with three sections.
- the filter is a dual-filter with two sections.
- the filter sections of the composite filter may be identical, or alternatively, one or more of the sections may have a composition which is different to that of the other section or sections.
- one or more of the sections may optionally comprise: (i) cellulose acetate filter material; (ii) a biodegradable filter material, such as crepe, crimped or gathered paper material; (iii) one or more additives, such as adsorbent or flavouring materials, which may be encapsulated; and/or, (iv) a cavity, which may comprise granular material such as adsorbent material.
- the smoking article filter element produced according to the method of the present invention may be incorporated into a smoking article.
- the filter element may be in the form of a smoking article filter as described above.
- the filter element and/or filter comprising the filter element may be attached to a wrapped smokeable filler material rod (i.e. a wrapped tobacco rod, for instance) by conventional tipping overwrap to form the smoking article, which may be a cigarette.
- a wrapped smokeable filler material rod i.e. a wrapped tobacco rod, for instance
- the smokeable filler material may be tobacco material or a tobacco substitute material.
- the smokeable material is a tobacco material.
- the tobacco material comprises one or more of stem, lamina, and tobacco dust. It is preferred that the tobacco material comprises one or more of the following types: Virginia or flue-cured tobacco, Burley tobacco, Oriental tobacco, reconstituted tobacco. It is much by preference that the smokeable material comprises a blend of tobacco material.
- the smokeable filler material may also comprise one or more of the following: burn additive, ash improver, inorganic filler material, organic filler, aerosol generating means, binder, flavouring and/or colouring agents.
- the tipping overwrap may be ventilating or non-ventilating overwrap.
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- Chemical & Material Sciences (AREA)
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- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Filtering Materials (AREA)
Description
- The invention relates to methods for making filter elements and filters for smoking articles, the filter elements and filters comprising an additive material. In particular, the invention relates to methods of incorporating an additive which is solid at room temperature into filter material, the method comprising the step of melting the additive material.
- A wide variety of materials have been used as filter materials for tobacco smoke. The most commonly used filter material is cellulose acetate tow. However, whilst cellulose acetate has an excellent capacity to filter tobacco smoke, it has the drawback that it is slower to degrade than other materials and can therefore be disadvantageous environmentally. Efforts have been made to make cellulose acetate filters more biodegradable. For example,
EP 0766929 discloses a water-disintegrable tobacco smoke filter comprising cellulose ester fibres and an adsorbent resin, which are bound together into a rod-shaped fibre bundle using a water-soluble polymer. - Filter materials made from non-woven sheet material and paper are known. Suitable sheet materials include polyvinyl alcohol, reconstituted tobacco, starch, and polylactic acid. These materials are much more readily degradable than cellulose acetate tow, however, they have drawbacks. In particular, in order to attain the desired structural rigidity when constructing a filter element from non-woven sheet materials and paper, the filter material is generally densely packed and this means that these filter elements have quite different properties to those made of cellulose acetate. They exhibit a greater resistance to the flow of smoke, resulting in a pressure drop which is higher than that of a conventional cellulose acetate (CA) filter, requiring the user to draw harder on the smoking article. Perhaps more significantly, the smoke drawn through such filter material has been found to have different taste characteristics compared to the smoke drawn through conventional cellulose acetate filter material. What is more, filter elements comprising non-woven sheet materials or paper as the filter material have been shown to exhibit significantly less selective removal of semi-volatile compounds than conventional cellulose acetate tow filter materials.
- It is known to use additives such as triacetin (glycerin triacetate), TEC (triethyl citrate) and PEG 400 (low molecular weight polyethylene glycol) in cellulose acetate filters. These additives function as plasticizers and they are generally used in cellulose acetate filters to give the filter rods sufficient hardness for cigarette manufacture and use. Some plasticizers have the additional advantage of providing cellulose acetate tow with an improved capacity to selectively remove semi-volatile compounds such as phenol, o-cresol, p-cresol and m-cresol from tobacco smoke.
- These plasticizers are in liquid form at room temperature and they are sprayed on to cellulose acetate tow. The plasticizer coats the individual fibres within the tow and, with time, they bind or fuse adjacent fibres together at their points of contact, thereby increasing the hardness or rigidity of the filter material, to give the core of the filter the desired structural strength. The mode of action of the plasticizers does, however, mean that there is an upper limit to the amount that may be incorporated into cellulose acetate tow filter material. When above about 7% of plasticizer by weight of the filter is included, the plasticizer starts to have a detrimental effect on the cellulose acetate tow, forming holes which compromises its filtration properties.
- Whilst inclusion of plasticizers such as triacetin, TEC or PEG 400 in CA filters is relatively common, their inclusion in non-woven sheet and paper filter materials is less attractive. Firstly, the plasticizers are used in CA filters to bind fibres and the plasticizer would clearly not have this advantageous effect when added to non-woven sheet material or paper (in which the fibres are already bound within the sheet structure). Secondly, these commonly used plasticizers are liquids and their application to non-woven sheet and paper filter materials will be limited as they will cause these materials to become soggy and to lose their structural integrity. Paper, the most commonly used sheet filter material, may start to disintegrate when moist, and will therefore have a reduced acceptability to the user. Furthermore, many sheet materials, including polyvinyl alcohol and polylactic acid, are soluble and therefore the addition of aqueous additives may result in the partial dissolution of the material.
- It is therefore an object of the invention to provide a method of constructing a filter element which is more readily degradable than filter elements comprising a conventional cellulose acetate tow as the filter material. Preferably, the method will also result in a filter element which exhibits an improved capacity to selectively remove semi-volatile compounds and which provides smoke having similar taste characteristics to that provided by conventional cellulose acetate filters.
- According to a first aspect of the present invention, a method for making a smoking article filter element comprising sheet filter material and an additive is provided. The method comprises the steps of:
- i) applying an additive which is solid at room temperature to the sheet filter material in solid form;
- ii) heating the additive so as to melt it; and
- iii) forming the sheet filter material and additive into a filter element, wherein steps ii) and iii) of the method may be carried out in any order.
- As used herein, the term "smoking article" includes smokeable products such as cigarettes, cigars and cigarillos whether based on tobacco, tobacco derivatives, expanded tobacco, reconstituted tobacco or tobacco substitutes and also heat-not-burn products.
- The present invention relates to a method of producing a filter element for inclusion in a smoking article, the method comprising applying an additive to sheet filter material, the additive being solid at room temperature and the method involving heating the additive so that it melts.
- In one embodiment of the invention, the additive is applied to the sheet filter material in solid form, for example in the form of a powder, prior to formation of the filter rod. The formed filter rod may then be heated to melt the additive whilst it remains in contact with the filter material. When the additive material subsequently cools and re-solidifies, it provides the filter material and the filter element formed with one or more of: stability and rigidity; improved smoke taste characteristics; and improved selective removal of semi-volatile compounds.
- The methods according to the present invention may be used to add an additive to any type of sheet filter material, for example non-woven sheet materials or paper.
- Paper filter material usually comprises gathered, pleated, crimped, crepe or even shredded paper. Paper filter materials tend to have a low air permeability, exhibit a basic pH, and can be gathered or formed easily to form the filter element. A preferred filter material for filter elements of the present invention is a gathered or pleated paper. Examples of suitable papers are Puracel™ and Myria™ papers (Filtrona plc, United Kingdom).
- Other, non-woven sheet materials may be used as filter materials. Non-woven materials are broadly defined as sheet or web structures bonded together by entangling fibres or filaments mechanically, thermally or chemically, or by a combination of two or more of these. They tend to be flat, porous sheets that are made directly from separate fibers. They are not made by weaving or knitting and do not require converting the fibers to yarn. The non-woven sheet materials used in the present invention are preferably ones which are readily biodegradable. Examples of materials include polyvinyl alcohol (PVOH), polylactic acid or polylactide (PLA), poly(ε-caprolactone) (PCL), poly(1-4 butanediol succunate) (PBS) and poly(butylene adipate-co-terephthalate) (PBAT). Other suitable filter materials include starch fibres and calcium alginate.
- Non-woven sheet materials and paper are more readily biodegradable than cellulose acetate tow. However, they currently have drawbacks when used as filter materials. In order to attain the desired structural rigidity when constructing a filter element from non-woven sheet materials and paper, the filter material must be very densely packed and this means that these filter elements have quite different properties to those made of cellulose acetate. They exhibit a greater resistance to the flow of smoke, resulting in a pressure drop which is higher than that of a conventional cellulose acetate filter, requiring the user to draw harder on the smoking article.
- The sheet material used in the method of the invention may comprise paper, polyvinyl alcohol, reconstituted tobacco, starch, or polylactic acid. Preferably the sheet filter material is paper.
- Preferred non-woven sheet materials have a thickness greater than about 0.05 mm, preferably from about 0.06 mm to about 0.08 mm. The paper filter materials may comprise paper having a basis weight of about 15g/m2 to about 40g/m2, preferably about 20g/m2 to about 35g/m2.
- The sheet material used in the method of the invention may additionally or alternatively comprise polyvinyl alcohol (PVOH). PVOH is unique in being the only biodegradable, carbon-carbon backbone polymer that can completely biodegrade to small molecules, e.g., carbon dioxide and water.
- The method may comprise the use of the sheet material polylactic acid. The lactate from which PLA is produced can be derived from the fermentation of agricultural by-products.
- However, because of the hygroscopicity of PVOH and PLA, prior art attempts to process such materials have resulted in filter rods which are too soft to be efficiently handled in high speed cigarette manufacturing machines. Furthermore, cigarette filter elements formed from PVOH and PLA have failed to provide a sufficiently stable porous matrix to permit proper draw characteristics and avoid collapse in use. Using the method of the present invention to apply additive, the qualities of these sheet materials may be modified to make them suitable for use in filter elements.
- In contrast to the use of additives which are liquid at room temperature (such as the plasticisers frequently used in conventional cellulose acetate filters, including low molecular weight PEG, triacetin and TEC), an additive which is solid at room temperature may provide firmness and rigidity to the filter without damaging the filter material by making it soggy.
- Indeed, rather than weakening a non-woven sheet or paper filter material, the method of the present invention uses a solid additive which has been melted, but which re-solidifies at room temperature and bonds parts of the filter material together. Therefore, the additive has the benefit that it can actually increase the structural integrity and rigidity of the filter material. In the case of sheet filter materials, addition of a solid additive by a method according to the present invention may make it possible to use less of the filter material in the filter element. This provides further flexibility when forming the filter element with regard to the amount of filter material required to achieve the desired hardness and rigidity. This in turn would allow the manufacturer to adjust the pressure drop of the filter element. This would allow a filter element according to the present invention to be designed having properties which closely resemble those of conventional CA filter elements.
- Thus, the addition of a solid additive to the filter material by the methods according to the present invention can eliminate the shortcomings that are currently associated with the use of sheet filter materials, by improving the rigidity of the filter, improving the taste of the smoke, and increasing the selective removal of semi-volatile compounds. Furthermore, the combination of filter material and solid additive may provide vastly improved disintegration, dispersion and/or biodegradability of the filter element.
- The methods of the invention allow the properties of non-woven sheet and paper filter materials to be fine-tuned, so that the performance of the filter element can more closely resemble that of a cellulose acetate filter element. These additives also give the use of sheet filter material much greater flexibility, widening the range of its applicability whilst retaining the beneficial biodegradable properties.
- In one embodiment of the invention, the additive comprises a high molecular weight polyethylene glycol which is solid at room temperature. Suitable PEGs include PEG 600 and higher, and preferably PEG 1000 and higher.
- High molecular weight polyethylene glycol has the additional advantage of providing selective removal of semi-volatile compounds. This selective removal of semi-volatile compounds provided by the addition of the PEG to the filter element is proportional to the amount of PEG included. The methods of the present invention, which involve the use a PEG which is solid at room temperature (in contrast to the PEG previously used in filters) provide flexibility which allows the addition of greater amounts of PEG than would be possible if using a liquid PEG.
- This means that the ability of the filter element to selectively remove semi-volatile compounds may easily be adjusted to a desirable level. This is in contrast to the situation where low molecular weight PEG is added to cellulose acetate filters as a plasticizer. Cellulose acetate filters are generally disclosed as including less than 10% plasticizer because including higher levels of plasticizer than this has a detrimental effect on the cellulose acetate tow, causing holes to be formed. Consequently, the amount of plasticizer available to provide selective removal of semi-volatile compounds in cellulose acetate filters is limited.
- According to the method of the invention, PEG may be included in the filter material of the filter element in an amount of up to about 30%, preferably up to about 20%, and more preferably about 5-10% by weight of the filter element.
- As PEG is water-soluble, its inclusion in the filter elements should not adversely affect the biodegradation of the product. Indeed, it has been surprisingly found that the addition of PEG to a filter element comprising a non-woven sheet material or paper as the filter material actually enhances biodegradation.
- A study was conducted to assess the effect of the use of a paper filter material and additives on biodegradability. Degradation of cigarette butts under environmental conditions was assessed. The samples used included a filter with Puracel™ (7mg) with no additive and a filter with Puracel™ with 7% PEG 400. The results show that the inclusion of the PEG as an additive significantly increased the rate of biodegradation of the butts on a grass surface. It is speculated that this may have been due to the presence of microorganisms, insects and the like, which fed on the butts and the presence of the PEG additive made some butts more attractive. It is anticipated that a similar effect will be observed upon use of a high molecular weight PEG as an additive.
- Other additives which may be used in the methods of the present invention include high molecular weight methoxypolyethylene glycols (MPEGs), such as MPEG 750, 1000, 2000, 3000 and 5000; and waxes which are solid at room temperature, including beeswax, carnauba, shellac, castor wax, paraffin and various synthetic waxes.
- If desired, the method can further comprise the incorporation into the sheet filter material of further additives such as tobacco extracts, glycerine, menthol, carbon fibres, carbon particles, and the like.
- A further advantage of the method of the invention is that filter elements to which additive has been applied using the claimed method are more stable to the subsequent addition of additives, including liquid additives. Other additives, including liquid additives, which would otherwise have been difficult to apply to sheet material without making it soggy, can be added to the filter rod to adjust the properties of the filter as required, or provide further qualities to the filter element, such as flavourants for enhanced flavour.
- Methods according to the present invention encompass different ways of applying the additive to the filter material.
- In an alternative embodiment, the method involves applying the additive to the sheet filter material in solid form, for example in the form of a powder, before the filter material is formed into the filter rod or core of the filter element. Once formed, the filter rod is heated to melt the additive. The additive melts and subsequently re-solidifies, bonding the filter material without making it soggy.
- This method allows the additive to be applied to the filter material in a controlled and uniform manner, and with minimal wastage of additive material. It also avoids any potential disadvantages associated with applying a liquid to the filter material. For example, this embodiment avoids the potential weakening of the sheet structure by applying a liquid.
- Where the solid additive is being applied to a sheet material, such as the non-woven sheet materials and papers discussed herein, steps will need to be taken to ensure that the solid additive remains in contact with the sheet filter material whilst the sheet is being fashioned into a filter rod. This may require the application of some adhesive or special orientation of the sheet material.
- Filter elements comprising sheet materials are generally manufactured using a process which comprises the steps of crimping the sheet material and then gathering the sheet material to form a cylindrical filter rod. The additive may be added prior to or during the crimping process, or may be added to the sheet material after it has been crimped. The additive may even be added to the crimped material as it is gathered to form the filter rod, with the effect that it is immediately contained within the rod and does not need to be adhered.
- The additive may be adhered to the filter material using any suitable adhesive, for example, using liquid starch adhesives, or EVA and PVA adhesives.
- The solid additive may be applied to sheet filter material as a powder or in larger pieces, such as in the form of flakes or pellets.
- The additive may be applied to the sheet filter material by any suitable method that is known to the skilled person. For example, powdered additive may be sprayed on to the filter material, or it may be applied by an applicator which may or may not be in direct physical contact with the filter material. The additive may be loosely applied to the filter material, for example by being sprayed or sprinkled, or may be applied using a degree of force, such as by being pressed or smeared on to the filter material.
- In a particular embodiment, the sheet filter material is formed with the solid additive embedded in or on it. Applying the additive which is solid at room temperature to the filter material in this way can simplify the methods of the present invention. Once the filter material has been formed into the filter rod, the rod may be heated to melt the additive, and then allowed to re-solidify.
- It is known to add various materials in or on sheet materials such as non-woven sheet materials and paper. For example, the additive may be applied to the sheet material during its manufacture or as part of a post-manufacture processing step. In this way, the additive may be incorporated within the sheet, or as a coating on one or both sides of the sheet material. The additive may be uniformly present within or on the surface of the sheet, or may be present in discreet areas, such as in patches or strips on the sheet material.
- Where the additive is to be melted after the filter material has been formed into a rod or core, sufficient heat needs to be applied to ensure that all of the additive, which is dispersed throughout the rod, is melted.
- The application of heat to the formed filter rod must be carried out with care, as it may have a detrimental effect on other components of the filter rod, including the filter material and any wrapper (which is likely to be paper and could be singed or scorched by exposure to high temperatures).
- Obviously, the temperature that the filter rod must be heated to, and the duration of heating, is dependent upon the melting point of the additive. A preferred additive, PEG 1000, has a melting point of around 37°C, and therefore in this case, the filter rod is heated to a temperature exceeding 37°C. The filter rod may be heated to a temperature exceeding 40°C, preferably exceeding 45°C, and most preferably exceeding 50°C. In addition, the heat needs to be applied for a period sufficient to ensure that the whole rod is heated and not just the outer areas.
- Heat may be applied using any suitable means. For example, the filter rod or filter element may be brought into close proximity with a heating element. Alternatively or additionally, the filter rod or filter element may be heated by means of a current of hot gas, such as hot air or steam, or via the application of radiation, such as microwave radiation.
- Heat may be applied to the filter rod as soon as it is formed. In other words, heating of the filter rod may occur at some stage between formation of the filter rod at the garniture and the cut-off, where the filter rod is separated into sections. Heating of the rod will generally be for a very brief period, such as less than 1 second, due to the linear motion of the rod through the machine. Clearly, since filter rods are currently formed without a heating process, then concomitant forming and heating of the filter rod may require expensive modification of the current apparatus.
- For this reason, the filter rod is preferably heated at a later stage, and this may be achieved using a heater which is essentially separate from the apparatus involved in forming the filter rod. The heating is preferably carried out in a separate conditioning step, where lengths of filter rod are kept at an elevated temperature for an extended period of time to ensure that all of the additive is melted and bonds to the filter material.
- The method of the invention may further comprise wrapping the filter rod in a suitable wrapper such as a plugwrap. In this case the heat may be applied before the filter rod is wrapped. Alternatively, the filter rod may be wrapped and then heated.
- According to some embodiments, the assembled filter is heated to melt the additive, although this approach can be complicated by the insulating properties of the filter material. In addition the speed of filter manufacture means that the time available for heating the filter is limited. Having said that, heating of the assembled filter may be achieved in various ways. For example, the filter rod may be exposed to heat by conductance, such as on a heated drum in the presence of hot air. Alternatively, trays of filter rods (such as 4,000 filters per tray) may be passed through a heated tunnel or similar arrangement, in the presence of hot air. The filter trays may alternatively be heated by the application of radiation such as microwave radiation.
- The methods of the present invention may further comprise a step of incorporating particulate material into the filter element. Suitable particulate material includes sorbents (e.g. selected from activated carbon, charcoal, silica gel, sepiolite, alumina, ion exchange material etc.), pH modifiers (e.g. alkaline materials such as Na2CO3, acidic materials), flavourants, other solid additives and mixtures thereof.
- Advantageously, the particulate material may be selected from a group of relatively high surface area materials capable of adsorbing smoke constituents without a high degree of specificity. Suitable general adsorbents can be selected from the group consisting of carbon, activated carbon, activated charcoal, activated coconut carbon, activated coal-based carbon or charcoal, zeolite, silica gel, meerschaum, aluminium oxide (activated or not), carbonaceous resin or combinations thereof.
- One type of particulate material which may be used in the method of the invention is carbon, for instance activated carbon, or charcoal or other carbonaceous absorbent material. The preferred type of activated carbon is activated coconut carbon.
- The particulate material may be incorporated into the filter element in such a way that it is interspersed throughout the filter element, or it may be interspersed in some parts (but not all) of the filter element. The particulate material may be interspersed over the full longitudinal length of the core. Alternatively, the particulate material may be interspersed from one end of the core to a section that is short of the other end. Alternatively, the particulate material may be present in discrete areas that need not extend from - or be present at - any end of the core. Different areas may have different loadings of particulate material and/or different types of particulate material.
- The methods of the present invention may further comprise wrapping the filter element in a suitable wrapper.
- The wrapper of the filter element is preferably a paper wrapper, and most preferably comprises conventional plugwrap, such as plugwrap having a basis weight of between about 20g/m2 and about 35g/m2, preferably about 27g/m2. The plugwrap may be porous or non-porous.
- The method may comprise the use of a wrapper which includes a particulate material adhered to one or more portions of its surface. Preferably, the particulate material is adhered to two or more portions of the wrapper, the portions being circumferentially spaced from one another, with at least one of the portions extending over the full longitudinal length of the wrapper.
- The smoking article filter element produced according to the method of the present invention may be incorporated into a smoking article filter.
- The smoking article filter may comprise a single filter element of the method of the invention. Alternatively, the smoking article filter may include two or more filter elements produced according to the method of the invention. In other words, the filter element may be part of a composite (or multi-component) filter. Suitably the filter elements of the composite filter are arranged longitudinally of one another with the end of each filter element abutting the next. The composite filter may have 2, 3, 4 or more distinct or discrete sections. In one embodiment the filter is a triple-filter with three sections. In another embodiment the filter is a dual-filter with two sections.
- The filter sections of the composite filter may be identical, or alternatively, one or more of the sections may have a composition which is different to that of the other section or sections. For example, in some embodiments, one or more of the sections may optionally comprise: (i) cellulose acetate filter material; (ii) a biodegradable filter material, such as crepe, crimped or gathered paper material; (iii) one or more additives, such as adsorbent or flavouring materials, which may be encapsulated; and/or, (iv) a cavity, which may comprise granular material such as adsorbent material.
- The smoking article filter element produced according to the method of the present invention may be incorporated into a smoking article. The filter element may be in the form of a smoking article filter as described above.
- The filter element and/or filter comprising the filter element may be attached to a wrapped smokeable filler material rod (i.e. a wrapped tobacco rod, for instance) by conventional tipping overwrap to form the smoking article, which may be a cigarette.
- Suitably, the smokeable filler material may be tobacco material or a tobacco substitute material. Preferably the smokeable material is a tobacco material. Suitably the tobacco material comprises one or more of stem, lamina, and tobacco dust. It is preferred that the tobacco material comprises one or more of the following types: Virginia or flue-cured tobacco, Burley tobacco, Oriental tobacco, reconstituted tobacco. It is much by preference that the smokeable material comprises a blend of tobacco material.
- The smokeable filler material may also comprise one or more of the following: burn additive, ash improver, inorganic filler material, organic filler, aerosol generating means, binder, flavouring and/or colouring agents.
- The tipping overwrap may be ventilating or non-ventilating overwrap.
- Various modifications and variations of the described methods and system of the present invention will be apparent to those skilled in the art without departing from the scope of the present invention. Although the present invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims.
Claims (8)
- A method for making a smoking article filter element comprising sheet filter material and an additive, wherein the method comprises the steps of:i) applying an additive which is solid at room temperature to the sheet filter material in solid form;ii) heating the additive so as to melt it; andiii) forming the sheet filter material and additive into a filter element, wherein steps ii) and iii) of the method may be carried out in any order.
- A method as claimed in claim 1, wherein the additive material is applied to the sheet filter material in solid form before formation of the filter element and subsequent heating of the additive.
- A method as claimed in claim 1, wherein the additive is heated before the formation of the filter element.
- A method according to any one of the preceding claims, wherein the additive comprises a high molecular weight polyethylene glycol which is solid at room temperature.
- A method according to claim 4, wherein the polyethylene glycol is PEG 1000.
- A method according to any one of the preceding claims, wherein the additive is included in the filter element in an amount of up to about 50% by weight of the filter element.
- A method according to any one of the preceding claims, wherein the sheet filter material is a non-woven sheet material or paper.
- A method according to any one of the preceding claims, wherein the filter element further comprises at least one adsorbent material.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GBGB1007946.5A GB201007946D0 (en) | 2010-05-12 | 2010-05-12 | Filter additive |
PCT/GB2011/050899 WO2011141735A1 (en) | 2010-05-12 | 2011-05-11 | Filter additive |
Publications (2)
Publication Number | Publication Date |
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EP2568833A1 EP2568833A1 (en) | 2013-03-20 |
EP2568833B1 true EP2568833B1 (en) | 2017-01-18 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP11724440.0A Active EP2568833B1 (en) | 2010-05-12 | 2011-05-11 | Filter additive |
Country Status (18)
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US (1) | US20130137561A1 (en) |
EP (1) | EP2568833B1 (en) |
JP (1) | JP5872547B2 (en) |
KR (2) | KR20150144820A (en) |
CN (1) | CN102883629B (en) |
AR (1) | AR084386A1 (en) |
AU (1) | AU2011251791B2 (en) |
BR (1) | BR112012028950B1 (en) |
CA (1) | CA2798042C (en) |
CL (1) | CL2012003121A1 (en) |
GB (1) | GB201007946D0 (en) |
HK (1) | HK1176525A1 (en) |
MX (1) | MX2012012474A (en) |
NZ (1) | NZ603222A (en) |
RU (1) | RU2565566C2 (en) |
UA (1) | UA106913C2 (en) |
WO (1) | WO2011141735A1 (en) |
ZA (1) | ZA201208308B (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110353311A (en) | 2011-12-30 | 2019-10-22 | 菲利普莫里斯生产公司 | Smoking article and method with front plug |
AR089602A1 (en) | 2011-12-30 | 2014-09-03 | Philip Morris Products Sa | AEROSOL GENERATOR ARTICLE FOR USE WITH AN AEROSOL GENERATOR DEVICE |
US11039642B2 (en) | 2011-12-30 | 2021-06-22 | Philip Morris Products S.A. | Smoking article with front-plug and aerosol-forming substrate and method |
EP2625975A1 (en) * | 2012-02-13 | 2013-08-14 | Philip Morris Products S.A. | Aerosol-generating article having an aerosol-cooling element |
PL2854570T3 (en) | 2012-05-31 | 2017-08-31 | Philip Morris Products S.A. | Flavoured rods for use in aerosol-generating articles |
AR091509A1 (en) | 2012-06-21 | 2015-02-11 | Philip Morris Products Sa | ARTICLE TO SMOKE TO BE USED WITH AN INTERNAL HEATING ELEMENT |
TWI629008B (en) * | 2012-10-22 | 2018-07-11 | 菲利浦莫里斯製品股份有限公司 | Filter segment comprising an acetate salt and glycerine |
WO2014207704A2 (en) * | 2013-06-26 | 2014-12-31 | Pan Jiayi | Filter media |
EP3086938B1 (en) * | 2013-12-23 | 2020-02-19 | Philip Morris Products S.a.s. | Method and apparatus for treating continuous sheet material |
GB201400990D0 (en) * | 2014-01-21 | 2014-03-05 | British American Tobacco Co | Filter materials and filters made therefrom |
CN107224007A (en) * | 2017-07-24 | 2017-10-03 | 云南中烟工业有限责任公司 | A kind of cigarette filter |
CN107927904A (en) * | 2017-10-09 | 2018-04-20 | 广西中烟工业有限责任公司 | Cigarette filter rod curing agent and its preparation and application |
CN108095191A (en) * | 2017-11-10 | 2018-06-01 | 河南中烟工业有限责任公司 | A kind of tobacco plug plasticizer and its application |
CN108185518A (en) * | 2017-12-22 | 2018-06-22 | 云南养瑞科技集团有限公司 | A kind of filter core with degradable function |
CN109288123B (en) * | 2018-08-24 | 2021-08-20 | 湖南中烟工业有限责任公司 | Cooling filter tip and cigarette |
US11432581B2 (en) | 2018-09-07 | 2022-09-06 | Altria Client Services Llc | Capsule containing a matrix, device with the matrix, and method of forming the matrix |
GB201817563D0 (en) * | 2018-10-29 | 2018-12-12 | Nerudia Ltd | Heat-not-burn consumable |
WO2020115897A1 (en) * | 2018-12-07 | 2020-06-11 | 日本たばこ産業株式会社 | Non-combustible heating-type smoking article, electric heating-type smoking system, and method for producing non-combustible heating-type smoking article |
JP7150977B2 (en) * | 2019-03-29 | 2022-10-11 | 日本たばこ産業株式会社 | Cooling segment, non-combustion heating flavor inhalation article, method of using non-combustion heating flavor inhalation article, and non-combustion heating flavor inhalation system |
KR102445558B1 (en) * | 2020-07-06 | 2022-09-20 | 주식회사 케이티앤지 | Filter for smoking articles containing solid flavoring agents and manufacturing method thereof |
Family Cites Families (101)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH319210A (en) * | 1952-12-05 | 1957-02-15 | Eastman Kodak Co | Filtering element intended in particular to filter tobacco smoke |
US2904050A (en) * | 1955-01-05 | 1959-09-15 | Eastman Kodak Co | Tobacco smoke filtering elements |
US3079929A (en) * | 1958-08-09 | 1963-03-05 | Mueller Paul Adolf | Filter plugs for cigarettes |
US2992648A (en) * | 1959-06-10 | 1961-07-18 | Maxwell E Sparrow | Cigarette filters |
US3347247A (en) * | 1964-05-14 | 1967-10-17 | Philip Morris Inc | Tobacco smoke filter |
GB1113070A (en) * | 1964-08-27 | 1968-05-08 | Courtaulds Ltd | Filter elements |
FR1446578A (en) * | 1964-08-27 | 1966-07-22 | Courtaulds Ltd | Method of manufacturing filter elements for cigarettes |
US3310060A (en) * | 1964-08-31 | 1967-03-21 | Olin Mathieson | Cellulosic filter for tobacco smoke |
FR1456985A (en) * | 1964-10-09 | 1966-07-08 | Eastman Kodak Co | Process and apparatus for the manufacture of filament filters for tobacco smoke |
US3390039A (en) * | 1964-10-09 | 1968-06-25 | Eastman Kodak Co | Method and apparatus for making additive filters |
US3501361A (en) * | 1965-09-22 | 1970-03-17 | Eastman Kodak Co | Method for producing cigarette filters |
US3407822A (en) * | 1966-02-07 | 1968-10-29 | Eastman Kodak Co | Tobacco smoke filters containing polyethylene encapsulated cellulose particles |
US3704192A (en) * | 1966-09-21 | 1972-11-28 | Celanese Corp | Process of making tobacco smoke filters from extruded polymer and binder |
US3640742A (en) * | 1967-07-03 | 1972-02-08 | Eastman Kodak Co | Plasticizer blend for cellulose esters |
US3476120A (en) * | 1968-12-11 | 1969-11-04 | Eastman Kodak Co | Cigarette filter tow |
US3599646A (en) * | 1969-04-30 | 1971-08-17 | American Filtrona Corp | Cigarette filter |
US3635226A (en) * | 1969-06-16 | 1972-01-18 | British American Tobacco Co | Tobacco-smoke filters |
US3605759A (en) * | 1969-12-22 | 1971-09-20 | Olin Corp | Filter for tobacco smoke |
US3900037A (en) * | 1969-12-24 | 1975-08-19 | Brown & Williamson Tobacco | Tobacco-smoke filters |
US3800676A (en) * | 1970-05-13 | 1974-04-02 | Celanese Corp | Filters |
US4156431A (en) * | 1971-07-08 | 1979-05-29 | Epstein Samuel S | Smoke processing |
US4059121A (en) * | 1973-04-20 | 1977-11-22 | Rothmans Of Pall Mall Canada Limited | Filter for tobacco smoke |
US3847064A (en) * | 1972-09-11 | 1974-11-12 | American Filtrona Corp | Tobacco smoke filter |
US4283186A (en) * | 1976-10-06 | 1981-08-11 | Celanese Corporation | Method of forming cigarette filter material |
GB1592549A (en) * | 1976-10-06 | 1981-07-08 | British American Tobacco Co | Tobacco-smoke filters |
CH625403A5 (en) * | 1977-08-11 | 1981-09-30 | Celfil Co | |
GB2020158B (en) * | 1978-04-21 | 1982-11-24 | Cigarette Components Ltd | Production of tobacco smoke filters |
US4274914A (en) * | 1978-08-28 | 1981-06-23 | Celanese Corporation | Filter material |
US4221226A (en) * | 1979-02-15 | 1980-09-09 | Eastman Kodak Company | Hot melt adhesive for bonding filter tow, and filter elements bonded thereby |
US4357188A (en) * | 1979-10-22 | 1982-11-02 | Mitsubishi Rayon Co., Ltd. | Method for manufacturing cigarette filters |
CH647935A5 (en) * | 1980-08-04 | 1985-02-28 | Molins Ltd | PROCESS FOR THE PRODUCTION OF A FILLING MATERIAL, MACHINE FOR IMPLEMENTING SAME, APPLICATION OF THE PROCESS AND PLANT FOR THE PRODUCTION OF A SEAL OF CIGARETTE FILTERS. |
US4528050A (en) * | 1981-07-30 | 1985-07-09 | Molins Plc | Producing filler material, particularly for cigarette filters |
US4481958A (en) * | 1981-08-25 | 1984-11-13 | Philip Morris Incorporated | Combustible carbon filter and smoking product |
JPS6048156B2 (en) * | 1982-07-07 | 1985-10-25 | 三菱アセテート株式会社 | tobacco smoke filter |
US4476807A (en) * | 1983-02-18 | 1984-10-16 | R. J. Reynolds Tobacco Company | Apparatus for application of additives to cigarette filter tow |
US4549875A (en) * | 1983-06-02 | 1985-10-29 | R. J. Reynolds Tobacco Co. | Manufacture of tobacco smoke filters |
US4655230A (en) * | 1985-03-29 | 1987-04-07 | Celanese Corporation | Localized liquid additive applicator system for continuous cylindrical product |
US4756316A (en) * | 1985-08-12 | 1988-07-12 | Philip Morris Incorporated | Method for producing a cigarette filter rod |
US4715390A (en) * | 1985-11-19 | 1987-12-29 | Philip Morris Incorporated | Matrix entrapment of flavorings for smoking articles |
US4807809A (en) * | 1988-02-12 | 1989-02-28 | R. J. Reynolds Tobacco Company | Rod making apparatus for smoking article manufacture |
GB8823388D0 (en) * | 1988-10-05 | 1988-11-09 | Cigarette Components Ltd | Tobacco smoke filter containing particulate additive |
US5074320A (en) * | 1989-10-26 | 1991-12-24 | R. J. Reynolds Tobacco Company | Cigarette and cigarette filter |
US5105834A (en) * | 1989-12-18 | 1992-04-21 | R.J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
US5141006A (en) * | 1990-02-28 | 1992-08-25 | Eastman Kodak Company | Tobacco smoke filter material and process for production thereof |
US5053066A (en) * | 1990-05-04 | 1991-10-01 | Hassenboehler Charles B | Nonwoven filter and method of manufacture |
US5246017A (en) * | 1990-11-06 | 1993-09-21 | R. J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
AU658372B2 (en) * | 1990-11-19 | 1995-04-13 | Cigarette Components Limited | Smoke filter containing particulate smoke modifying additive |
GB9121782D0 (en) * | 1991-10-14 | 1991-11-27 | Cigarette Components Ltd | Cigarette filter containing particulate smoke modifying additive |
US5465739A (en) * | 1992-04-15 | 1995-11-14 | R. J. Reynolds Tobacco Company | Cigarette and cigarette filter element therefor |
US5531235A (en) * | 1992-09-28 | 1996-07-02 | Hassenboehler, Jr.; Charles B. | Cigarette filter micropleated web and method of manufacture |
JP3316309B2 (en) * | 1993-07-13 | 2002-08-19 | ダイセル化学工業株式会社 | Tobacco filter and method for producing the same |
TW241198B (en) * | 1993-09-06 | 1995-02-21 | Daicel Chem | A tobacco filter material and a method of producing the same |
DE69520816T2 (en) * | 1994-10-31 | 2001-09-13 | Daicel Chemical Industries, Ltd. | Tobacco smoke filter material and tobacco smoke filter made from this material |
EP0783841A4 (en) * | 1995-08-04 | 1998-08-26 | Mitsubishi Rayon Co | Filter medium and cigarette filter made with the use of the same |
US5709227A (en) * | 1995-12-05 | 1998-01-20 | R. J. Reynolds Tobacco Company | Degradable smoking article |
DE19605863A1 (en) * | 1996-02-16 | 1997-08-21 | Reemtsma H F & Ph | Cigarette filter |
JPH09316420A (en) * | 1996-05-27 | 1997-12-09 | Daicel Chem Ind Ltd | Water-soluble hot melt adhesive, cigarette filter using the same and their production |
US5817159A (en) * | 1996-12-31 | 1998-10-06 | Cahill; Scott A. | Filter with interpenetrating polymer network that biodegrades |
US6305382B1 (en) * | 1997-04-07 | 2001-10-23 | Schweitzer-Mauduit International, Inc. | Reduced basis weight cigarette paper |
US5911224A (en) * | 1997-05-01 | 1999-06-15 | Filtrona International Limited | Biodegradable polyvinyl alcohol tobacco smoke filters, tobacco smoke products incorporating such filters, and methods and apparatus for making same |
CA2305356C (en) * | 1997-10-10 | 2004-07-13 | Union Carbide Chemicals & Plastics Technology Corporation | Spray application of an additive composition to sheet materials |
WO2002017738A1 (en) * | 2000-08-31 | 2002-03-07 | Japan Tobacco Inc. | Filter manufacturing machine |
AU2002228901A1 (en) * | 2000-11-10 | 2002-05-21 | Vector Tobacco (Bermuda) Ltd. | Method and product for removing carcinogens from tobacco smoke |
US20090065012A1 (en) * | 2001-08-14 | 2009-03-12 | Pankaj Patel | Materials and Methods for Manufacturing Cigarettes |
EP1441603A2 (en) * | 2001-11-09 | 2004-08-04 | Vector Tobacco Inc. | Method and composition for mentholation of charcoal filtered cigarettes |
TWI324049B (en) * | 2002-01-08 | 2010-05-01 | Japan Tobacco Inc | Smoking filter and smoking article |
DE10217410A1 (en) * | 2002-04-18 | 2003-10-30 | Hauni Maschinenbau Ag | Cigarette filter and method of making the same |
RU2290047C2 (en) * | 2002-09-04 | 2006-12-27 | Джапан Тобакко Инк. | Filter for smoking |
DE10252823A1 (en) * | 2002-11-13 | 2004-06-09 | Biotec Biologische Naturverpackungen Gmbh & Co. Kg | filter element |
US7281540B2 (en) * | 2002-12-20 | 2007-10-16 | R.J. Reynolds Tobacco Company | Equipment and methods for manufacturing cigarettes |
US6998009B2 (en) * | 2003-06-10 | 2006-02-14 | Ut-Battelle, Llc | Filter and method of fabricating |
ATE361004T1 (en) * | 2003-09-03 | 2007-05-15 | Hauni Maschinenbau Ag | METHOD AND DEVICE FOR PRODUCING A FILTER STRING |
US7381277B2 (en) * | 2004-07-29 | 2008-06-03 | R.U. Reynolds Tobacco Company | Flavoring a cigarette by using a flavored filter plug wrap |
GB0404324D0 (en) * | 2004-02-27 | 2004-03-31 | British American Tobacco Co | Smoking article and apparatus and process for manufacturing a smoking article |
DE102004048651A1 (en) * | 2004-10-06 | 2006-04-13 | Rhodia Acetow Gmbh | Tobacco smoke filters or filter elements containing additives |
US7856989B2 (en) * | 2004-12-30 | 2010-12-28 | Philip Morris Usa Inc. | Electrostatically produced fast dissolving fibers |
DE102005009608A1 (en) * | 2005-02-28 | 2006-08-31 | Hauni Maschinenbau Ag | Filter for articles of the tobacco processing industry |
DE102005015877A1 (en) * | 2005-04-06 | 2006-10-12 | Hauni Maschinenbau Ag | Method and device for applying triacetin to a filter material web |
RU2413438C2 (en) * | 2005-09-05 | 2011-03-10 | Родиа Ацетов Гмбх | Filter or filtering element for tobacco smoke, cigarette with such filter or filtering element and method to manufacture such filter or filtering element |
US8381736B2 (en) * | 2006-01-27 | 2013-02-26 | British America Tobacco (Investments) Limited | Method of preparing a rod for use in the preparation of a smoking article |
PL1993389T3 (en) * | 2006-03-10 | 2010-09-30 | British American Tobacco Investments Ltd | Smoking article filter |
DE102006047098A1 (en) * | 2006-09-28 | 2008-04-03 | Hauni Maschinenbau Ag | Method and device for heating and curing filter rods |
US8739802B2 (en) * | 2006-10-02 | 2014-06-03 | R.J. Reynolds Tobacco Company | Filtered cigarette |
US7855261B2 (en) * | 2006-12-08 | 2010-12-21 | Eastman Chemical Company | Aldehyde removal |
CN101677926B (en) * | 2007-03-01 | 2012-06-06 | 高砂香料工业株式会社 | Lipid composition having excellent shape retention property and product |
GB0713905D0 (en) * | 2007-07-17 | 2007-08-29 | British American Tobacco Co | Cellulose acetate thread in filter |
EP2324721A3 (en) * | 2007-07-20 | 2011-09-07 | Köhl Maschinenbau GmbH | Device for applying aroma agents to a line of tobacco, cigarette paper or cigarette filters |
EP2025251A1 (en) * | 2007-08-17 | 2009-02-18 | Philip Morris Products S.A. | Multi-component filter for a smoking article |
JP5043127B2 (en) * | 2007-12-14 | 2012-10-10 | 日本たばこ産業株式会社 | Cigarette filter and cigarette with filter |
US8613284B2 (en) * | 2008-05-21 | 2013-12-24 | R.J. Reynolds Tobacco Company | Cigarette filter comprising a degradable fiber |
GB0903136D0 (en) * | 2009-02-25 | 2009-04-08 | British American Tobacco Co | Smoking articles and method for manufacturing smoking articles |
GB0910198D0 (en) * | 2009-06-12 | 2009-07-29 | British American Tobacco Co | Smoking article |
US8534294B2 (en) * | 2009-10-09 | 2013-09-17 | Philip Morris Usa Inc. | Method for manufacture of smoking article filter assembly including electrostatically charged fiber |
GB0920397D0 (en) * | 2009-11-20 | 2010-01-06 | Filtrona Int Ltd | Tobacco smoke filter |
US20110220130A1 (en) * | 2009-12-15 | 2011-09-15 | John-Paul Mua | Tobacco Product And Method For Manufacture |
GB0922253D0 (en) * | 2009-12-21 | 2010-02-03 | British American Tobacco Co | Sheet filter materials with additives |
RU93226U1 (en) * | 2010-01-11 | 2010-04-27 | Закрытое акционерное общество "Нево Табак" | CIGARETTE |
US20110180084A1 (en) * | 2010-01-27 | 2011-07-28 | R.J. Reynolds Tobacco Company | Apparatus and associated method for forming a filter component of a smoking article |
US20110271968A1 (en) * | 2010-05-07 | 2011-11-10 | Carolyn Rierson Carpenter | Filtered Cigarette With Modifiable Sensory Characteristics |
US8950407B2 (en) * | 2010-06-30 | 2015-02-10 | R.J. Reynolds Tobacco Company | Degradable adhesive compositions for smoking articles |
US8720450B2 (en) * | 2010-07-30 | 2014-05-13 | R.J. Reynolds Tobacco Company | Filter element comprising multifunctional fibrous smoke-altering material |
-
2010
- 2010-05-12 GB GBGB1007946.5A patent/GB201007946D0/en not_active Ceased
-
2011
- 2011-05-11 JP JP2013509623A patent/JP5872547B2/en active Active
- 2011-05-11 CA CA2798042A patent/CA2798042C/en not_active Expired - Fee Related
- 2011-05-11 UA UAA201213920A patent/UA106913C2/en unknown
- 2011-05-11 MX MX2012012474A patent/MX2012012474A/en not_active Application Discontinuation
- 2011-05-11 WO PCT/GB2011/050899 patent/WO2011141735A1/en active Application Filing
- 2011-05-11 EP EP11724440.0A patent/EP2568833B1/en active Active
- 2011-05-11 AU AU2011251791A patent/AU2011251791B2/en not_active Ceased
- 2011-05-11 CN CN201180023581.5A patent/CN102883629B/en not_active Expired - Fee Related
- 2011-05-11 KR KR1020157035004A patent/KR20150144820A/en not_active Application Discontinuation
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- 2011-05-11 BR BR112012028950A patent/BR112012028950B1/en active IP Right Grant
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2013
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ZA201208308B (en) | 2016-09-28 |
CN102883629A (en) | 2013-01-16 |
HK1176525A1 (en) | 2013-08-02 |
AR084386A1 (en) | 2013-05-15 |
RU2012153392A (en) | 2014-06-20 |
KR20150144820A (en) | 2015-12-28 |
GB201007946D0 (en) | 2010-06-30 |
JP5872547B2 (en) | 2016-03-01 |
KR20130028937A (en) | 2013-03-20 |
BR112012028950B1 (en) | 2019-12-03 |
AU2011251791B2 (en) | 2013-11-14 |
CA2798042A1 (en) | 2011-11-17 |
UA106913C2 (en) | 2014-10-27 |
WO2011141735A1 (en) | 2011-11-17 |
BR112012028950A2 (en) | 2016-07-26 |
NZ603222A (en) | 2014-06-27 |
EP2568833A1 (en) | 2013-03-20 |
US20130137561A1 (en) | 2013-05-30 |
CN102883629B (en) | 2015-05-20 |
CL2012003121A1 (en) | 2013-02-15 |
JP2013526272A (en) | 2013-06-24 |
MX2012012474A (en) | 2013-02-27 |
CA2798042C (en) | 2014-11-18 |
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