EP2871982A1 - Degradable filter for smoking articles - Google Patents
Degradable filter for smoking articlesInfo
- Publication number
- EP2871982A1 EP2871982A1 EP13747361.7A EP13747361A EP2871982A1 EP 2871982 A1 EP2871982 A1 EP 2871982A1 EP 13747361 A EP13747361 A EP 13747361A EP 2871982 A1 EP2871982 A1 EP 2871982A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- filter
- filtration material
- fibres
- regenerated cellulose
- segment
- 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.)
- Withdrawn
Links
- 230000000391 smoking effect Effects 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000001914 filtration Methods 0.000 claims abstract description 61
- 239000004627 regenerated cellulose Substances 0.000 claims abstract description 33
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 28
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 24
- 239000001087 glyceryl triacetate Substances 0.000 claims abstract description 15
- 235000013773 glyceryl triacetate Nutrition 0.000 claims abstract description 15
- 229960002622 triacetin Drugs 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 229920000433 Lyocell Polymers 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- -1 linen Polymers 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 210000002268 wool Anatomy 0.000 claims description 2
- 241000208125 Nicotiana Species 0.000 description 16
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 16
- 239000000443 aerosol Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 5
- 238000006065 biodegradation reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229960002715 nicotine Drugs 0.000 description 5
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009264 composting Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 239000002054 inoculum Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000019613 sensory perceptions of taste Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035923 taste sensation Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
- 239000002023 wood 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
- A24D3/06—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
- A24D3/062—Use of materials for tobacco smoke filters characterised by structural features
- A24D3/063—Use of materials for tobacco smoke filters characterised by structural features of the fibers
-
- 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
-
- 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
- A24D3/06—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
-
- 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
- A24D3/18—Mouthpieces for cigars or cigarettes; Manufacture thereof
Definitions
- the present invention relates to a filter for a smoking article, the filter comprising a segment of filtration material comprising regenerated cellulose fibres, cellulose acetate fibers, and triacetin.
- the present invention also relates to a filter for a smoking article, the filter comprising a segment of filtration material comprising regenerated cellulose fibers and a low molecular weight polyether.
- the present invention also extends to smoking articles comprising such filters.
- Filter cigarettes typically comprise a cylindrical rod of tobacco cut filler surrounded by a paper wrapper and a cylindrical filter axially aligned in an abutting end-to-end relationship with the wrapped tobacco rod.
- the cylindrical filter typically comprises a filtration material, usually cellulose acetate tow, circumscribed by a paper plug wrap.
- the wrapped tobacco rod and the filter are joined by a band of tipping wrapper, normally formed of an opaque paper material, which circumscribes the entire length of the filter and an adjacent portion of the wrapped tobacco rod.
- a number of smoking articles in which tobacco is heated rather than combusted have also been proposed in the art.
- heated smoking articles an aerosol is generated by heating a flavour generating substrate, such as tobacco.
- Known heated smoking articles include, for example, electrically heated smoking articles and smoking articles in which an aerosol is generated by the transfer of heat from a combustible fuel element or heat source to a physically separate aerosol forming material.
- volatile compounds are released from the aerosol forming substrate by heat transfer from the fuel element and entrained in air drawn through the smoking article. As the released compounds cool they condense to form an aerosol that is inhaled by the consumer.
- Smoking articles in which a nicotine-containing aerosol is generated from a tobacco material, tobacco extract or other nicotine source, without combustion or heating are also known.
- a filter for a smoking article comprising a segment of filtration material, wherein the filtration material comprises randomly oriented regenerated cellulose fibres and cellulose acetate fibers.
- the filtration material further comprises triacetin, and the filter also includes a wrapper circumscribing the segment of filtration material.
- regenerated cellulose fibres is used herein to mean cellulose fibres which have been formed by processing a naturally occurring cellulose material to provide cellulose fibres having a desired physically property.
- a typical process for forming regenerated cellulose fibres includes the steps of: pulping a naturally occurring cellulose material, such as wood chips, to form a pulp; subjecting the pulp to one or more treatment steps to alter the physical properties of the cellulose; and forming fibers of regenerated cellulose from the treated pulp, for example by spinning cellulose fibres by passing the pulp through a spinneret.
- a filtration material that comprises randomly oriented regenerated cellulose improves the degradation of the filtration material. This is because the randomly oriented fibres can more easily disperse after the filter has been discarded, particularly when compared with the substantially continuous filaments of traditional cellulose acetate tow filters. Increased dispersion of the fibres increases the exposure of the individual fibres to the environment, thus increasing the rate at which the filtration material degrades.
- filters in accordance with the present invention deliver a similar taste to the consumer when compared with traditional cellulose acetate tow filters.
- the similar taste sensation is due to the cellulose acetate fibers and the triacetin binder present in the filtration material of filters in accordance with the present invention.
- the triacetin whilst the triacetin binds to the cellulose acetate fibers to improve the structural integrity of the filtration material, the triacetin does not bind to the regenerated cellulose fibers, thus maintaining the improved degradation of the filtration material.
- filters in accordance with the present invention address this problem by incorporating cellulose acetate fibers and triacetin into the filter with the regenerated cellulose fibers.
- the triacetin is preferably present in an amount of about 1 % to about 15% by weight of the filtration material in the filter segment, more preferably about 5% to about 10% by weight of the filtration material in the filter segment, most preferably about 3% to about 5% by weight of the filtration material in the filter segment.
- the filtration material further comprises a low molecular weight polyether to further increase the ability of the filter to selectively retain phenols during smoking of the smoking article.
- a suitable polyether is polyethylene glycol.
- the polyethylene glycol has a number average molecular weight of between about 200 and about 3600, preferably between about 400 and about 1600.
- the use of a low molecular weight polyether to increase the selective phenol retention of a filtration material comprising randomly oriented regenerated cellulose fibers is itself a novel and inventive arrangement.
- a filter for a smoking article comprising a segment of filtration material, the filtration material comprising randomly oriented regenerated cellulose fibres and a low molecular weight polyether.
- the filter further comprises a wrapper circumscribing the segment of filtration material.
- incorporating a low molecular weight polyether into the filtration material improves the selective phenol retention of the filtration material. This may be important where a regenerated cellulose filter is used to replace a traditional cellulose acetate tow filter, for example, since regenerated cellulose fibers exhibit less selective phenol retention when compared to traditional cellulose acetate.
- the use of a low molecular polyether to improve the selective phenol retention of a regenerated cellulose filter is illustrated in the examples shown in Table 1 below:
- Table 1 Comparison of retention of different phenols by a traditional cellulose acetate filter, a regenerated cellulose (Lyocell) filter, and a regenerated cellulose (Lyocell) + polyethylene glycol (PEG) filter.
- the data represents the amount of each phenol which passes through the filter (that is, the amount of phenol not retained by the filter) when the article is smoked.
- the data is normalised with respect to the amount of nicotine which is also passes through the filter during smoking of the article.
- the data was collected using a smoking test in accordance with ISO 4387: Determination of total and nicotine-free dry particulate matter using a routine analytical smoking machine.
- a suitable polyether is polyethylene glycol.
- the polyethylene glycol has a number average molecular weight of between about 200 and about 3600, preferably between about 400 and about 1600.
- the filtration material may include triacetin.
- Including triacetin also helps to increase filter stiffness, which reduces the likelihood of filter collapse during handling of the smoking article and during smoking.
- the triacetin is preferably present in an amount of about 1 % to about 15% by weight of the filtration material in the filter segment, more preferably about 5% to about 10% by weight of the filtration material in the filter segment, most preferably about 3% to about 5% by weight of the filtration material in the filter segment.
- filtration materials in accordance with both aspects of the present invention will degrade by at least about 30%, more preferably at least about 40%, more preferably at least about 50%, within less than about 40 days, preferably less than about 30 days, when measured in accordance with either of the following tests:
- Graph 1 Comparison of the degradation of various filters under the conditions of ISO 14851- 2004. Test filters are 100% regenerated cellulose (Lyocell) fibres and a traditional cellulose acetate filter. For reference, the degradation of a pure cellulose sample under the same conditions is also shown.
- the random orientation of the fibres in filters according to the present invention advantageously provides the required resistance of the filtration material to mechanical deformation, such that the filter can withstand being grasped by the consumer during smoking of the smoking article.
- the random orientation of the fibres also provides the required resistance to draw such that the smoking experience using filters in accordance with the present invention is substantially the same as the smoking experience using a traditional cellulose acetate tow filter.
- Filters in accordance with both aspects of the present invention may have a resistance to draw of between about 40 mm WG and about 250 mm WG for a filter length of 27 millimetres, preferably from about 75 mm WG to about 175 mm WG for a filter length of 27 millimetres, and most preferably from about 100 mm WG to about 150 mm WG for a filter length of 27 millimetres. Resistance to draw is measured using the test procedure described in ISO 6565:2002.
- the regenerated cellulose fibres are crimped staple fibres, which helps to reduce mechanical degradation of the fibres during processing of the filtration material to form the filter, and during subsequent assembly of the smoking article.
- the fibres can be crimped using a known method for crimping textile fibres, such as the method described in US 2,647,285.
- the crimped staple fibres preferably have a stretched length of between about 10 mm and about 30 mm under a tension of between about 5 cN/denier and about 10 cN/denier. This provides an optimum balance between the mechanical integrity of the filter during use and the rate of dispersion of the filtration material after the filter has been discarded.
- stretched length is used herein to mean the average length of the crimped regenerated cellulose staple fibres when stretched under a given tensional load.
- the crimped staple fibres have a denier of between about 0.5 and about 8.0, preferably between about 1.5 and about 5.5, most preferably between about 2.0 and about 3.2.
- the staple fibres have a crimped rate of between about 3 curves and about 10 curves per 10 mm of fibre length, more preferably between about 6 curves and about 8 curves per 10 mm of fibre length.
- the regenerated cellulose fibres may comprise Lyocell fibres.
- Lyocell fibres are defined as a regenerated cellulose fibre that is obtained by an organic solvent spinning process.
- Lyocell fibres suitable for use in filters according to the present invention are commercially available from Lenzing Aktiengesellschaft under the trademark Tencel®.
- the process of manufacturing Lyocell fibres is more environmentally friendly when compared with the manufacture of traditional cellulose acetate, as well as other regenerated cellulose materials such as rayon, viscose, and such like.
- the manufacture of cellulose acetate uses catalytic agents containing cobalt or manganese.
- the manufacture of cellulose acetate also produces a strong, unpleasant odour.
- the cellulose or ground pulp used to form Lyocell is treated in a closed-loop process in which non-toxic solvents are recycled with a recovery rate of up to 99.5%.
- bleaching agents are not required in the production of Lyocell fibres. Any remaining emissions from the manufacture of Lyocell can be decomposed in biological purification plants.
- the filtration material may include other fibres in addition to the regenerated cellulose fibres. Such additional fibres can be incorporated into the filter by mixing the additional fibres with the regenerated cellulose fibres during manufacture of the filtration material.
- the additional fibres may be bound to the regenerated cellulose fibres using a suitable water-soluble binder, such as those discussed above.
- the filtration material of filters in accordance with the second aspect of the present invention may include cellulose acetate fibres to increase the mechanical strength of the filter.
- the filtration material may include additional fibres which alter the appearance of the filtration material.
- the appearance of the filtration material of filters in accordance with both aspects of the present invention may be altered to more closely resemble the appearance of a traditional cellulose acetate tow filter.
- Exemplary fibres for altering the appearance of the filtration material include silk, cotton, polyester, linen, nylon and wool.
- the wrapper may comprise a dissolvable plug wrap.
- dissolvable is used herein to mean that the plug wrap is capable of dissolving into a solution with water.
- a dissolvable plug wrap will break open and disperse upon contact with water after the filter has been discarded, therefore exposing the underlying filtration material to the environment and increasing the rate of dispersion and degradation of the filtration material.
- the plug wrap may be biodegradable.
- the plug wrap comprises or consists of a sheet of polymeric film, wherein the polymeric film includes at least one water-soluble polymer.
- a polymeric film to form the plug wrap reduces cost and simplifies the manufacture of the plug wrap.
- a polymeric film can be formed to inherently posses the required properties of a plug wrap, such as low gas permeability, without the need for any further processing steps during manufacture.
- it is desirable for the plug wrap to be transparent it is easier to provide a transparent polymeric film than a transparent paper.
- a 5 mm by 5 mm square sample of the polymeric film will dissolve in less than 72 hours when placed in 25 ml of distilled water at a temperature of 22°C.
- the test is carried out in a container sized such that the depth of water is sufficient to completely submerge the square sample (although the buoyancy of the sample may be such that it floats on the surface of the water during the test). The sample is deemed to have dissolved when the water-soluble material is no longer visible to the naked eye.
- Suitable polymeric materials for forming the polymeric film include, but are not limited to, polyvinyl alcohol, cellophane, starch, hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose and combinations thereof.
- Suitable polymeric films may be made entirely of one or more water-soluble polymers or may include additional polymers or inert inorganic fillers, which may or may not be dissolvable.
- the polymeric film may be single-layered or multi-layered. Where the film comprises multiple layers, the layers may be formed from the same polymeric materials or they may be formed from different polymeric materials. Where the layers are formed from different polymeric materials, each polymeric material comprises at least one water-soluble polymer.
- a smoking article comprising an aerosol-forming substrate and a mouthpiece secured in axial alignment with the aerosol-forming substrate, the mouthpiece comprising a filter according to either aspect of the present invention.
- the term 'aerosol-forming substrate' is used to describe a substrate capable of releasing upon heating volatile compounds, which can form an aerosol.
- the aerosols generated from aerosol-forming substrates of smoking articles described herein may be visible or invisible and may include vapours (for example, fine particles of substances, which are in a gaseous state, that are ordinarily liquid or solid at room temperature) as well as gases and liquid droplets of condensed vapours.
- Smoking articles according to the present invention may be filter cigarettes or other smoking articles in which the aerosol-forming substrate comprises tobacco material or another combustible material that is combusted to form smoke.
- smoking articles according to the present invention may be articles in which the aerosol-forming substrate comprises material that is heated to form an aerosol, rather than combusted.
- tobacco material or another aerosol forming material is heated by one or more electrical heating elements to produce an aerosol.
- an aerosol is produced by the transfer of heat from a combustible or chemical heat source to a physically separate aerosol forming material, which may be located within, around or downstream of the heat source.
- the present invention further encompasses smoking articles in which a nicotine-containing aerosol is generated from a tobacco material, tobacco extract or other nicotine source, without combustion or heating. Test procedures
- the controlled composting biodegradation test is an optimised simulation of an intensive aerobic composting process where the biodegradability of a test under dry aerobic conditions is determined.
- the inoculum consists of stabilised and mature compost derived from the organic fraction of municipal solid waste.
- the test item is mixed with the inoculum and introduced into static reactor vessels where it is intensively composted under optimum oxygen, temperature and moisture conditions.
- the test is performed according to ISO 14855 (2005) method "Determination of the Ultimate Aerobic Biodegradability and Disintegration of Plastics under Controlled Composting Conditions", but in duplicate instead of in triplicate.
- Figure 1 shows a smoking article in accordance with an embodiment of the present invention.
- FIG 2 shows the smoking article of Figure 1 with the filter unwrapped.
- the filter cigarette 10 shown in Figures 1 and 2 comprises a wrapped rod 12 of tobacco cut filler which is attached at one end to an axially aligned filter 14 in accordance with the present invention.
- the filter 14 comprises a single segment of filtration material 16, the filtration material 16 comprising randomly oriented regenerated cellulose fibres and cellulose acetate fibers, and triacetin.
- the filtration material 16 may also include other fibres to alter the appearance of the filtration material 16, such as silk fibres.
- the filtration material 16 may also comprise one or more binders and may include one or more additives to improve selective phenol retention.
- the segment of filtration material 16 is circumscribed by a plug wrap 18, which may be dissolvable and may consist of a sheet of polymeric film comprising at least one water-soluble polymer.
- the wrapped tobacco rod 12 and the filter 14 are joined by a band 20 of tipping paper, which circumscribes the entire length of the filter 14 and an adjacent portion of the wrapped tobacco rod 12.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Nonwoven Fabrics (AREA)
- Filtering Materials (AREA)
- Woven Fabrics (AREA)
Abstract
A filter (14) for a smoking article (10) comprises a segment of filtration material (16), the filtration material (16) comprising randomly oriented regenerated cellulose fibres and cellulose acetate fibers. The filtration material (16) further comprises triacetin. The filter (14) also includes a wrapper (18) circumscribing the segment of filtration material (16).
Description
DEGRADABLE FILTER FOR SMOKING ARTICLES
The present invention relates to a filter for a smoking article, the filter comprising a segment of filtration material comprising regenerated cellulose fibres, cellulose acetate fibers, and triacetin. The present invention also relates to a filter for a smoking article, the filter comprising a segment of filtration material comprising regenerated cellulose fibers and a low molecular weight polyether. The present invention also extends to smoking articles comprising such filters.
Filter cigarettes typically comprise a cylindrical rod of tobacco cut filler surrounded by a paper wrapper and a cylindrical filter axially aligned in an abutting end-to-end relationship with the wrapped tobacco rod. The cylindrical filter typically comprises a filtration material, usually cellulose acetate tow, circumscribed by a paper plug wrap. Conventionally, the wrapped tobacco rod and the filter are joined by a band of tipping wrapper, normally formed of an opaque paper material, which circumscribes the entire length of the filter and an adjacent portion of the wrapped tobacco rod.
A number of smoking articles in which tobacco is heated rather than combusted have also been proposed in the art. In heated smoking articles, an aerosol is generated by heating a flavour generating substrate, such as tobacco. Known heated smoking articles include, for example, electrically heated smoking articles and smoking articles in which an aerosol is generated by the transfer of heat from a combustible fuel element or heat source to a physically separate aerosol forming material. During smoking, volatile compounds are released from the aerosol forming substrate by heat transfer from the fuel element and entrained in air drawn through the smoking article. As the released compounds cool they condense to form an aerosol that is inhaled by the consumer. Smoking articles in which a nicotine-containing aerosol is generated from a tobacco material, tobacco extract or other nicotine source, without combustion or heating, are also known.
After a smoking article has been smoked and the remainder of the article has been discarded, it is desirable that the filter section degrade as quickly as possible. It would be desirable to provide a filter for a smoking article which facilitates this.
According to a first aspect of the present invention, there is provided a filter for a smoking article, the filter comprising a segment of filtration material, wherein the filtration material comprises randomly oriented regenerated cellulose fibres and cellulose acetate fibers. The filtration material further comprises triacetin, and the filter also includes a wrapper circumscribing the segment of filtration material.
The term "regenerated cellulose fibres" is used herein to mean cellulose fibres which have been formed by processing a naturally occurring cellulose material to provide cellulose fibres having a desired physically property. A typical process for forming regenerated cellulose fibres includes the steps of: pulping a naturally occurring cellulose material, such as wood chips, to form a pulp; subjecting the pulp to one or more treatment steps to alter the physical properties of the cellulose; and forming fibers of regenerated cellulose from the treated pulp, for example by spinning cellulose fibres by passing the pulp through a spinneret.
Advantageously, using a filtration material that comprises randomly oriented regenerated cellulose improves the degradation of the filtration material. This is because the randomly oriented fibres can more easily disperse after the filter has been discarded, particularly when compared with the substantially continuous filaments of traditional cellulose acetate tow filters. Increased dispersion of the fibres increases the exposure of the individual fibres to the environment, thus increasing the rate at which the filtration material degrades.
Furthermore, despite using regenerated cellulose fibers in the filtration material, filters in accordance with the present invention deliver a similar taste to the consumer when compared with traditional cellulose acetate tow filters. The similar taste sensation is due to the cellulose acetate fibers and the triacetin binder present in the filtration material of filters in accordance with the present invention. Moreover, whilst the triacetin binds to the cellulose acetate fibers to improve the structural integrity of the filtration material, the triacetin does not bind to the regenerated cellulose fibers, thus maintaining the improved degradation of the filtration material.
The inventors have also recognised that filters consisting of only regenerated cellulose fibers do not exhibit the same levels of selective phenol retention during smoking of the smoking article when compared to traditional cellulose acetate filters. Therefore, filters in accordance with the present invention address this problem by incorporating cellulose acetate fibers and triacetin into the filter with the regenerated cellulose fibers.
The triacetin is preferably present in an amount of about 1 % to about 15% by weight of the filtration material in the filter segment, more preferably about 5% to about 10% by weight of the filtration material in the filter segment, most preferably about 3% to about 5% by weight of the filtration material in the filter segment.
In some embodiments, the filtration material further comprises a low molecular weight polyether to further increase the ability of the filter to selectively retain phenols during smoking of the smoking article. A suitable polyether is polyethylene glycol. Preferably, the polyethylene glycol has a number average molecular weight of between about 200 and about 3600, preferably between about 400 and about 1600.
The use of a low molecular weight polyether to increase the selective phenol retention of a filtration material comprising randomly oriented regenerated cellulose fibers is itself a novel and inventive arrangement. Therefore, according to a second aspect of the present invention, there is provided a filter for a smoking article, the filter comprising a segment of filtration material, the filtration material comprising randomly oriented regenerated cellulose fibres and a low molecular weight polyether. The filter further comprises a wrapper circumscribing the segment of filtration material.
As discussed above, incorporating a low molecular weight polyether into the filtration material improves the selective phenol retention of the filtration material. This may be important where a regenerated cellulose filter is used to replace a traditional cellulose acetate tow filter, for example, since regenerated cellulose fibers exhibit less selective phenol retention when compared to traditional cellulose acetate. The use of a low molecular polyether to improve the selective phenol retention of a regenerated cellulose filter is illustrated in the examples shown in Table 1 below:
Table 1: Comparison of retention of different phenols by a traditional cellulose acetate filter, a regenerated cellulose (Lyocell) filter, and a regenerated cellulose (Lyocell) + polyethylene glycol (PEG) filter. The data represents the amount of each phenol which passes through the filter (that is, the amount of phenol not retained by the filter) when the article is smoked. The data is normalised with respect to the amount of nicotine which is also passes through the filter during smoking of the article. The data was collected using a smoking test in accordance with ISO 4387: Determination of total and nicotine-free dry particulate matter using a routine analytical smoking machine.
A suitable polyether is polyethylene glycol. Preferably, the polyethylene glycol has a number average molecular weight of between about 200 and about 3600, preferably between about 400 and about 1600.
To further improve the function of the filter to selectively remove phenols during the smoking of the smoking article, the filtration material may include triacetin. Including triacetin also helps to increase filter stiffness, which reduces the likelihood of filter collapse during
handling of the smoking article and during smoking. In embodiments comprising triacetin, the triacetin is preferably present in an amount of about 1 % to about 15% by weight of the filtration material in the filter segment, more preferably about 5% to about 10% by weight of the filtration material in the filter segment, most preferably about 3% to about 5% by weight of the filtration material in the filter segment.
Preferably, filtration materials in accordance with both aspects of the present invention will degrade by at least about 30%, more preferably at least about 40%, more preferably at least about 50%, within less than about 40 days, preferably less than about 30 days, when measured in accordance with either of the following tests:
ISO 14855-2005, TEST1 : aerobic biodegradation under controlled composting conditions ISO 14851 -2004, TEST2: aquatic aerobic respirometric biodegradation test
To illustrate the improved degradation of a filter including regenerate cellulose fibers when compared to a traditional cellulose acetate filter, a comparison of the degradation of different filters under ISO 14851-2004, TEST2 is shown in Graph 1 below:
Cellulose 100% Lyocell • Cellulose acetate
Graph 1: Comparison of the degradation of various filters under the conditions of ISO 14851- 2004. Test filters are 100% regenerated cellulose (Lyocell) fibres and a traditional cellulose
acetate filter. For reference, the degradation of a pure cellulose sample under the same conditions is also shown.
The random orientation of the fibres in filters according to the present invention advantageously provides the required resistance of the filtration material to mechanical deformation, such that the filter can withstand being grasped by the consumer during smoking of the smoking article. The random orientation of the fibres also provides the required resistance to draw such that the smoking experience using filters in accordance with the present invention is substantially the same as the smoking experience using a traditional cellulose acetate tow filter. Filters in accordance with both aspects of the present invention may have a resistance to draw of between about 40 mm WG and about 250 mm WG for a filter length of 27 millimetres, preferably from about 75 mm WG to about 175 mm WG for a filter length of 27 millimetres, and most preferably from about 100 mm WG to about 150 mm WG for a filter length of 27 millimetres. Resistance to draw is measured using the test procedure described in ISO 6565:2002.
Preferably, the regenerated cellulose fibres are crimped staple fibres, which helps to reduce mechanical degradation of the fibres during processing of the filtration material to form the filter, and during subsequent assembly of the smoking article. The fibres can be crimped using a known method for crimping textile fibres, such as the method described in US 2,647,285.
The crimped staple fibres preferably have a stretched length of between about 10 mm and about 30 mm under a tension of between about 5 cN/denier and about 10 cN/denier. This provides an optimum balance between the mechanical integrity of the filter during use and the rate of dispersion of the filtration material after the filter has been discarded. The term "stretched length" is used herein to mean the average length of the crimped regenerated cellulose staple fibres when stretched under a given tensional load.
Preferably the crimped staple fibres have a denier of between about 0.5 and about 8.0, preferably between about 1.5 and about 5.5, most preferably between about 2.0 and about 3.2.
Preferably the staple fibres have a crimped rate of between about 3 curves and about 10 curves per 10 mm of fibre length, more preferably between about 6 curves and about 8 curves per 10 mm of fibre length.
The regenerated cellulose fibres may comprise Lyocell fibres. Lyocell fibres are defined as a regenerated cellulose fibre that is obtained by an organic solvent spinning process. Lyocell fibres suitable for use in filters according to the present invention are commercially available from Lenzing Aktiengesellschaft under the trademark Tencel®. Advantageously, the process of
manufacturing Lyocell fibres is more environmentally friendly when compared with the manufacture of traditional cellulose acetate, as well as other regenerated cellulose materials such as rayon, viscose, and such like.
In particular, the manufacture of cellulose acetate uses catalytic agents containing cobalt or manganese. The manufacture of cellulose acetate also produces a strong, unpleasant odour. In contrast, the cellulose or ground pulp used to form Lyocell is treated in a closed-loop process in which non-toxic solvents are recycled with a recovery rate of up to 99.5%. Furthermore, bleaching agents are not required in the production of Lyocell fibres. Any remaining emissions from the manufacture of Lyocell can be decomposed in biological purification plants.
The filtration material may include other fibres in addition to the regenerated cellulose fibres. Such additional fibres can be incorporated into the filter by mixing the additional fibres with the regenerated cellulose fibres during manufacture of the filtration material. The additional fibres may be bound to the regenerated cellulose fibres using a suitable water-soluble binder, such as those discussed above. For example, the filtration material of filters in accordance with the second aspect of the present invention may include cellulose acetate fibres to increase the mechanical strength of the filter. Alternatively, or in addition, the filtration material may include additional fibres which alter the appearance of the filtration material. For example, the appearance of the filtration material of filters in accordance with both aspects of the present invention may be altered to more closely resemble the appearance of a traditional cellulose acetate tow filter. Exemplary fibres for altering the appearance of the filtration material include silk, cotton, polyester, linen, nylon and wool.
To further improve the rate of dispersion and degradation of the filter after it has been discarded, the wrapper may comprise a dissolvable plug wrap. The term "dissolvable" is used herein to mean that the plug wrap is capable of dissolving into a solution with water. Advantageously, a dissolvable plug wrap will break open and disperse upon contact with water after the filter has been discarded, therefore exposing the underlying filtration material to the environment and increasing the rate of dispersion and degradation of the filtration material. In addition to being dissolvable, the plug wrap may be biodegradable.
In embodiments including a dissolvable plug wrap, the plug wrap comprises or consists of a sheet of polymeric film, wherein the polymeric film includes at least one water-soluble polymer. Using a polymeric film to form the plug wrap reduces cost and simplifies the manufacture of the plug wrap. Specifically, in contrast to a paper material, a polymeric film can be formed to inherently posses the required properties of a plug wrap, such as low gas permeability, without the need for any further processing steps during manufacture.
Furthermore, where it is desirable for the plug wrap to be transparent, it is easier to provide a transparent polymeric film than a transparent paper.
Preferably, a 5 mm by 5 mm square sample of the polymeric film will dissolve in less than 72 hours when placed in 25 ml of distilled water at a temperature of 22°C. The test is carried out in a container sized such that the depth of water is sufficient to completely submerge the square sample (although the buoyancy of the sample may be such that it floats on the surface of the water during the test). The sample is deemed to have dissolved when the water-soluble material is no longer visible to the naked eye.
Suitable polymeric materials for forming the polymeric film include, but are not limited to, polyvinyl alcohol, cellophane, starch, hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose and combinations thereof.
Suitable polymeric films may be made entirely of one or more water-soluble polymers or may include additional polymers or inert inorganic fillers, which may or may not be dissolvable. The polymeric film may be single-layered or multi-layered. Where the film comprises multiple layers, the layers may be formed from the same polymeric materials or they may be formed from different polymeric materials. Where the layers are formed from different polymeric materials, each polymeric material comprises at least one water-soluble polymer.
According to the present invention, there is also provided a smoking article comprising an aerosol-forming substrate and a mouthpiece secured in axial alignment with the aerosol-forming substrate, the mouthpiece comprising a filter according to either aspect of the present invention.
As used herein, the term 'aerosol-forming substrate' is used to describe a substrate capable of releasing upon heating volatile compounds, which can form an aerosol. The aerosols generated from aerosol-forming substrates of smoking articles described herein may be visible or invisible and may include vapours (for example, fine particles of substances, which are in a gaseous state, that are ordinarily liquid or solid at room temperature) as well as gases and liquid droplets of condensed vapours.
Smoking articles according to the present invention may be filter cigarettes or other smoking articles in which the aerosol-forming substrate comprises tobacco material or another combustible material that is combusted to form smoke. Alternatively, smoking articles according to the present invention may be articles in which the aerosol-forming substrate comprises material that is heated to form an aerosol, rather than combusted. In one type of heated smoking article, tobacco material or another aerosol forming material is heated by one or more electrical heating elements to produce an aerosol. In another type of heated smoking article, an aerosol is produced by the transfer of heat from a combustible or chemical heat source to a physically separate aerosol forming material, which may be located within, around or
downstream of the heat source. The present invention further encompasses smoking articles in which a nicotine-containing aerosol is generated from a tobacco material, tobacco extract or other nicotine source, without combustion or heating. Test procedures
ISO 14855-2005
The controlled composting biodegradation test is an optimised simulation of an intensive aerobic composting process where the biodegradability of a test under dry aerobic conditions is determined. The inoculum consists of stabilised and mature compost derived from the organic fraction of municipal solid waste. The test item is mixed with the inoculum and introduced into static reactor vessels where it is intensively composted under optimum oxygen, temperature and moisture conditions. The test is performed according to ISO 14855 (2005) method "Determination of the Ultimate Aerobic Biodegradability and Disintegration of Plastics under Controlled Composting Conditions", but in duplicate instead of in triplicate.
ISO 14851-2004 This test determines the aquatic, aerobic biodegradation under laboratory conditions. The test material is placed in a chemically defined liquid medium and spiked with micro-organisms. During the aerobic degradation, oxygen is consumed and carbonaceous material is converted to gaseous C02. NaOH pellets trap the C02 released and the induced-pressure drop is directly related to the consumed oxygen and the biodegradation of the test material.
The invention will now be further described, by way of example only, with reference to the accompanying drawings in which:
Figure 1 shows a smoking article in accordance with an embodiment of the present invention; and
Figure 2 shows the smoking article of Figure 1 with the filter unwrapped.
The filter cigarette 10 shown in Figures 1 and 2 comprises a wrapped rod 12 of tobacco cut filler which is attached at one end to an axially aligned filter 14 in accordance with the present invention. The filter 14 comprises a single segment of filtration material 16, the filtration
material 16 comprising randomly oriented regenerated cellulose fibres and cellulose acetate fibers, and triacetin. The filtration material 16 may also include other fibres to alter the appearance of the filtration material 16, such as silk fibres. The filtration material 16 may also comprise one or more binders and may include one or more additives to improve selective phenol retention. The segment of filtration material 16 is circumscribed by a plug wrap 18, which may be dissolvable and may consist of a sheet of polymeric film comprising at least one water-soluble polymer. The wrapped tobacco rod 12 and the filter 14 are joined by a band 20 of tipping paper, which circumscribes the entire length of the filter 14 and an adjacent portion of the wrapped tobacco rod 12.
It will be appreciated that whilst the specific embodiment described above relates to conventional smoking articles comprising a filter and a tobacco rod, a similar arrangement of a filter in accordance with the present invention could also be used on a heated smoking article.
Claims
1. A filter for a smoking article, the filter comprising:
a segment of filtration material, the filtration material comprising randomly oriented regenerated cellulose fibres and cellulose acetate fibers, the filtration material further comprising triacetin; and
a wrapper circumscribing the segment of filtration material.
2. The filter of claim 1 , wherein the filtration material further comprises a low molecular weight polyether.
3. The filter of claim 1 or 2, wherein the filtration material comprises additional fibres selected from the group consisting of silk, cotton, polyester, linen, nylon, wool and combinations thereof.
4. The filter of any preceding claim, wherein the triacetin is present in an amount of 1 % to 15% by weight of the filtration material.
5. A filter for a smoking article, the filter comprising:
a segment of filtration material, the filtration material comprising randomly oriented regenerated cellulose fibres and a low molecular weight polyether; and
a wrapper circumscribing the segment of filtration material.
6. The filter of claim 2 or 5, wherein the low molecular weight polyether comprises polyethylene glycol.
7. The filter of claim 6, wherein the polyethylene glycol has a number average molecular weight of between 200 and 3600.
8. The filter of any preceding claim, wherein the regenerated cellulose fibres are crimped staple fibres.
9. The filter of claim 8, wherein the crimped staple fibres have a stretched length of between 10 mm and 30 mm under a tension of between 5 cN/denier and 10 cN/denier.
10. The filter of claim 8 or 9, wherein the crimped staple fibres have a denier of between 0.5 and 8.0 and a crimped rate of between 3 and 10 curves per 10 mm fibre length.
1 1. The filter of any preceding claim, wherein the regenerated cellulose fibres are Lyocell fibres.
12. The filter of any preceding claim, wherein the wrapper comprises a dissolvable plug wrap consisting of a sheet of polymeric material, wherein the polymeric material comprises at least one water-soluble polymer.
13. A smoking article comprising:
an aerosol-forming substrate; and
a mouthpiece secured in axial alignment with the aerosol-forming substrate, the mouthpiece comprising a filter according to any preceding claim.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13747361.7A EP2871982A1 (en) | 2012-07-13 | 2013-07-11 | Degradable filter for smoking articles |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12176441 | 2012-07-13 | ||
EP13747361.7A EP2871982A1 (en) | 2012-07-13 | 2013-07-11 | Degradable filter for smoking articles |
PCT/EP2013/064739 WO2014009498A1 (en) | 2012-07-13 | 2013-07-11 | Degradable filter for smoking articles |
Publications (1)
Publication Number | Publication Date |
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EP2871982A1 true EP2871982A1 (en) | 2015-05-20 |
Family
ID=48949121
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP13747361.7A Withdrawn EP2871982A1 (en) | 2012-07-13 | 2013-07-11 | Degradable filter for smoking articles |
Country Status (10)
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US (1) | US20150189913A1 (en) |
EP (1) | EP2871982A1 (en) |
JP (1) | JP2015523079A (en) |
KR (1) | KR20150035800A (en) |
CN (1) | CN104411189A (en) |
MX (1) | MX2014015903A (en) |
RU (1) | RU2634810C2 (en) |
SG (1) | SG11201408777WA (en) |
UA (1) | UA115062C2 (en) |
WO (1) | WO2014009498A1 (en) |
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- 2013-07-11 WO PCT/EP2013/064739 patent/WO2014009498A1/en active Application Filing
- 2013-07-11 KR KR20147036907A patent/KR20150035800A/en not_active Application Discontinuation
- 2013-07-11 EP EP13747361.7A patent/EP2871982A1/en not_active Withdrawn
- 2013-07-11 SG SG11201408777WA patent/SG11201408777WA/en unknown
- 2013-07-11 US US14/412,086 patent/US20150189913A1/en not_active Abandoned
- 2013-07-11 UA UAA201413596A patent/UA115062C2/en unknown
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CN104411189A (en) | 2015-03-11 |
WO2014009498A1 (en) | 2014-01-16 |
MX2014015903A (en) | 2015-12-15 |
KR20150035800A (en) | 2015-04-07 |
SG11201408777WA (en) | 2015-01-29 |
US20150189913A1 (en) | 2015-07-09 |
RU2634810C2 (en) | 2017-11-03 |
RU2014153532A (en) | 2016-09-10 |
UA115062C2 (en) | 2017-09-11 |
JP2015523079A (en) | 2015-08-13 |
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