AU2010243337A1

AU2010243337A1 - Aerosol generating material for a smoking article

Info

Publication number: AU2010243337A1
Application number: AU2010243337A
Authority: AU
Inventors: Martin Coleman; Edward Dennis John; Anastasia Plakidis; Dominic Woodcock
Original assignee: British American Tobacco Investments Ltd
Current assignee: British American Tobacco Investments Ltd
Priority date: 2009-04-29
Filing date: 2010-04-28
Publication date: 2011-11-10
Also published as: EP2424393A1; GB2469842A; WO2010125386A1; CN102421307A; JP2012525137A; GB0907368D0; NZ595757A; BRPI1015534A2; KR20120005043A; AR078037A1; RU2011148251A; CL2011002671A1; CA2759075A1; US20120312314A1; MX2011011313A; ZA201107451B

Abstract

The invention provides an aerosol generating material (6) for a smoking article, comprising particles (1) that consist essentially of diluent (2) encapsulated by barrier material (3).

Description

WO 2010/125386 PCT/GB2010/050691 Aerosol generating material for a smoking article Description The present invention relates to an aerosol generating material for a smoking article. 5 In particular, the present invention relates to an aerosol generating material for a smoking article comprising particulate sorbent material coated and/or impregnated with diluent, and products comprising the same. The particulate material has a high BET specific surface area, or is calcium carbonate. 10 It is known to include diluents in smoking articles such as cigarettes. Diluents are compounds that are vapourised during smoking and transfer to the mainstream smoke in aerosol form. They are generally selected such that they transfer to the smoke substantially intact. Other components of the smoke (tobacco-derived components in the case of tobacco-containing smoking articles, or nicotine and/or 15 flavour components in the case of non-tobacco-containing smoking articles) are therefore diluted by this means. A cigarette can comprise a filter at the mouth end, a tobacco rod comprising smokable filler material, and cigarette paper wrapped around the rod. When diluent 20 is present in the smokable filler material, this may be as a simple mixture with the other ingredients (particularly for diluents in solid form), or the diluent may be carried on one or more of the other ingredients (particularly if the diluent is in liquid form). If incorporated into the filler material as a simple mixture, this may present disadvantages during manufacturing, and the diluent may be easily dislodged 25 from the finished product, especially if it is in fine powder form. Accordingly, it is preferred for the diluent to be held in intimate contact with another ingredient of the filler material. It has been discovered that, although the diluent is vapourised during smoking in 30 the course of performing its function, vapourisation of the diluent at lower temperatures can cause problems during storage of the cigarettes. Specifically, the diluent can migrate during storage and subsequently be lost to the atmosphere or interact with other parts of the product such as the cigarette paper. This may also WO 2010/125386 PCT/GB2010/050691 -2 lead to staining or marking of the cigarette paper, either by the diluent itself or by compounds released from the diluent interaction. Those in the art have therefore sought to immobilize the diluent until it is required. 5 US 2008/0110470 describes the immobilization of a diluent in a porous sorbent, which is then incorporated into a tobacco rod. It focuses on silica gel as the sorbent. However, the smoke data disclosed in this document reveals that the use of the silica gels therein caused an increase in the acrolein, B[a]A and B[a]P content of the smoke. Furthermore, the diluent loading capacity for a free-flowing sample 10 is relatively low; for instance, this document states that glycerol can be loaded at about 120 % by weight of the silica gel, whereas propylene glycol can be loaded at about 100 % by weight of the silica gel. There is therefore a need in the art to carry diluents on alternative sorbents in a 15 manner that overcomes one or more of the problems outlined above. Accordingly, the present inventors have devised the invention defined in the claims. Figure 1 is a schematic illustration of a precipitated calcium carbonate particle 20 carrying and/or impregnated with a diluent in accordance with an embodiment of the invention, and a similar precipitated calcium carbonate particle additionally coated with a barrier material in accordance with another embodiment of the invention. 25 Figure 2 is a schematic illustration of a cigarette containing an aerosol generating material in accordance with another embodiment of the invention. In the first aspect of the invention, the particulate porous material having a BET specific surface area of at least 1200 m 2 /g is a sorbent material, preferably an 30 adsorbent material. Such materials are known to the skilled person and, in many cases, commercially available. For instance, examples of sorbent resins having a BET specific surface area of at least 1200 m 2 /g include the polystyrene divinylbenzene resin Chromabond@ HR-P from Macherey-Nagel GmbH & Co., WO 2010/125386 PCT/GB2010/050691 -3 KG, Diiren, Germany and the styrene-based resin Sepabeads from Sorbent Technologies Inc., Atlanta, US. Preferably, the particulate porous material is a carbon material, a resin or a metal 5 organic framework, preferably carbon, preferably activated carbon. The activation level can be measured by standard techniques in the art. For instance, activated carbon can be weighed, exposed to carbon tetrachloride (CTC) and then reweighed, and the percentage weight increase determined. In an embodiment, the CTC activation level of the particulate porous material before loading with the diluent is 10 at least 50 %, 60 %, 70 %, 80 %, 90 %, or 100 %. Preferably, the particulate porous material has a BET specific surface area of at least 1300 m 2 /g, preferably at least 1400, 1500, 1600, 1700 or 1800 m 2 /g. In general, the greater the BET specific surface area, the greater the amount of diluent that can be 15 carried by the particles. However, the brittleness can increase if the surface area is too high. Preferably, the BET specific surface area is 3000 m 2 /g or less, preferably 2500 m 2 /g or less, preferably 2000 m 2 /g or less. In an embodiment, the particles of the porous material have an average particle size 20 in the range 3 - 45 m, preferably 5 - 30 pLm, preferably 6 - 20 rim, preferably 8 15 rm. In an embodiment, the pore volume of the porous material is at least 0.5 cc/g, preferably at least 0.6, 0.7 or 0.8 cc/g. 25 In the second aspect of the invention in which the aerosol generating material comprises particulate calcium carbonate carrying and/or impregnated with a diluent, any suitable calcium carbonate particles may be used. The calcium carbonate is preferably precipitated calcium carbonate, which is crystalline. 30 Preferably, the particles have a surface morphology with a plurality of indentations and/or protrusions, in or between which a substantial quantity of the diluent can reside. For example, each particle may be an agglomeration of scalenohedral calcite WO 2010/125386 PCT/GB2010/050691 -4 and/or acicular aragonite crystals. Figure 1 illustrates one suitable structure schematically: a precipitated calcium carbonate particle (1) formed by an agglomeration of scalenohedral calcite crystals has crystalline protrusions (2) on its surface. Although not wishing to be limited by theory, it is thought that, upon 5 exposure to the diluent, the diluent (3) may become trapped between these protrusions, in addition to entering the pores of the material. A further advantage of this type of structure is that the protrusions may interlock effectively in the aerosol generating material of the invention to form a strongly bound entity. 10 In an embodiment, the calcium carbonate has an average particle size in the range 0.05 - 200 jim, preferably 0.5 - 50 jim, 1 - 45 jim, 1.5 - 30 [im, 1.8 - 20 jim or 2 10 jim. In both these aspects of the invention, application of the diluent to the sorbent is 15 by any suitable method known to the skilled person or described herein. The diluent may be applied in pure form or in a vehicle of, or mixture with, one or more other materials, which may include a barrier material as described below but, in an embodiment, do not include a barrier material. 20 In an embodiment, the diluent is comprised in a liquid in which the sorbent is washed or soaked. Alternatively, the sorbent can be sprayed with the diluent in a liquid or gel format. For instance, diluents that are solid at room temperature may be melted, or incorporated into a liquid vehicle such as methanol or ethanol, and those that are liquid at room temperature may be applied in pure form or dissolved 25 or emulsified with another liquid. Simple admixture may also be suitable, for instance admixture of the liquid with the sorbent, allowing the liquid to seep into the pores of the material. Further processing steps may be employed such as curing or pressure treatment. 30 When using calcium carbonate, such methods may result in a surface covering of the diluent, and/or the diluent may seep into its pores. When using the material specified in the first aspect of the invention, however, it is required for the diluent WO 2010/125386 PCT/GB2010/050691 -5 to enter the pores of the particulate porous material to take advantage of the high BET surface area of the particles, thereby allowing a higher loading of the diluent. The diluent is at least one aerosol forming agent which may be, for instance, a 5 polyol aerosol generator or a non-polyol aerosol generator, preferably a non-polyol aerosol generator. It may be a solid or liquid at room temperature, but preferably is a liquid at room temperature. Suitable polyols include sorbitol, glycerol, and glycols like propylene glycol or triethylene glycol. Suitable non-polyols include monohydric alcohols, high boiling point hydrocarbons, acids such as lactic acid, and esters such 10 as diacetin, triacetin, triethyl citrate or isopropyl myristate. A combination of diluents may be used, in equal or differing proportions. Triacetin, triethyl citrate and isopropyl myristate are particularly preferred. There may be several factors influencing the stability and migration of diluents 15 under ambient conditions. These factors may include hydrophobicity or hydrophilicity, viscosity, saturated vapour pressure at room temperature, boiling point, molecular structure (such as hydrogen bonding or Van der Waals forces) and the absorptive/adsorptive interaction between diluent and the substrate. Some diluents will suffer from migration problems to a greater extent than others; for 20 instance, it has been found that triacetin, isopropyl myristate and triethyl citrate particularly benefit from immobilisation as in the present invention. Another relevant factor is the loading level of the diluent. For instance, if a diluent such as glycerol is included in a large amount, migration problems can still be 25 significant. The diluent loading level in the present invention may depend upon the specific diluent. In an embodiment of the first aspect of the invention, however, the particulate porous material is loaded with up to 500 % by weight of the diluent, 30 preferably 80 - 450 %, 130 - 400 %, 140 - 350 %, 150 - 300 % or 160 - 250 % by weight of the diluent, preferably triacetin. In an embodiment of the second aspect of the invention, the calcium carbonate is loaded with 20 - 100 %, preferably 30 95 % or 50 - 90 %, by weight of the diluent.

WO 2010/125386 PCT/GB2010/050691 -6 The particulate sorbent material, once impregnated and/or loaded with diluent, may be encapsulated in a barrier material, which provides further hindrance to migration of the diluent during storage of the smoking article but allows release of the diluent 5 during smoking of the smoking article. This is particularly advantageous for the second aspect of the invention, since calcium carbonate tends to bind diluents relatively weakly. Figure 1 shows the barrier material (4) encapsulating a calcium carbonate particle loaded with diluent. Use of a barrier material also assists in hindering dislodging of powder in the finished cigarette. 10 The barrier material may be one that melts, decomposes, reacts, degrades, swells or deforms to release the diluent at a temperature above room temperature but at or below the temperature reached inside a smoking article during smoking. For instance, the physical expansion occurring with vapourisation of sufficient levels of 15 diluent may break down the structure of the barrier material. In embodiments of the invention, the barrier material releases substantial amounts of the diluent above 50 "C, preferably above 60 'C, 70 'C, 80 'C or 90 'C. The barrier material may be, for example, a polysaccharide or cellulosic barrier 20 material, a gelatin, a gum, a gel or a mixture thereof. Suitable polysaccharides include an alginate, dextran, maltodextrin, cyclodextrin and pectin. Suitable cellulosic materials include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and cellulose ethers. Suitable gums include gum Arabic, gum ghatti, gum tragacanth, Karaya, locust bean, acacia, 25 guar, quince seed and xanthan gums. Suitable gels include agar, agarose, carrageenans, furoidan and furcellaran. In a preferred embodiment of the invention, the barrier material comprises a polysaccharide. An alginate is especially preferred, due to its encapsulation 30 properties. The alginate may be, for instance, a salt of alginic acid, an esterified alginate or glyceryl alginate. Salts of alginic acid include ammonium alginate, triethanolamine alginate, and group I or II metal ion alginates like sodium, WO 2010/125386 PCT/GB2010/050691 -7 potassium, calcium and magnesium alginate. Esterified alginates include propylene glycol alginate and glyceryl alginate. In an embodiment, the barrier material is sodium alginate and/or calcium alginate. 5 Calcium alginate provides a greater inhibition of migration of the diluent at ambient temperature than sodium alginate, but also may release the diluent at a higher temperature than the latter. Application of the barrier material to the particulate sorbent material carrying the 10 diluent is by any suitable method known to the skilled person or described herein, which does not cause complete loss of the diluent in the process. Preferably, substantially no diluent is lost due to the step of applying the barrier material. In an embodiment, the barrier material or a precursor thereto is sprayed onto the particulate sorbent material. 15 For instance, the particulate sorbent material carrying the diluent can be sprayed with an aqueous sodium alginate solution and dried to form a water-soluble film of sodium alginate on the surface. Alternatively, the particulate material can be sprayed with sodium alginate and then treated with a source of calcium ions, to 20 form a water-insoluble film or gel covering of calcium alginate. In the resulting product of the invention, individual diluent-carrying particles are surrounded by barrier material and migration of the diluent is further hindered under ambient conditions. This should be contrasted with a comparative situation 25 in which the diluent is combined with "barrier" material before application to the sorbent, such that in the resulting product the barrier material resides only in homogeneous admixture with the diluent, or the diluent has been pre-encapsulated with the barrier material before application to the sorbent (and so is not in intimate contact with the sorbent). 30 In addition to or instead of encapsulation with barrier material as described above, the particulate sorbent material carrying the diluent may be combined with other materials to form a slurry that is cast and dried to form a sheet, which is then cut or WO 2010/125386 PCT/GB2010/050691 shredded to form the aerosol generating material of the invention. The other materials may comprise a filler material such as ground chalk, a binder such as alginate, and/or a plasticizer such as glycerol. For instance, the use of up to around 25 % glycerol by weight of the sheet renders the sheet suitably flexible. This 5 glycerol may have the advantage of being transferred to the smoke along with the triacetin upon smoking, providing an additional diluent effect. Preferably, the sheet is cut or shredded so as to have dimensions similar to those of cut tobacco. For instance, the sheet may be cut at 35 - 40 cuts per inch, preferably 10 36 - 39, 37 or 38 cuts per inch. The shredded portions may have a width of 0.5 - 2 mm and a length of 5 mm - 5 cm. This has the advantage that the aerosol generating material may be processed using the same apparatus as cut tobacco. In addition, when the aerosol generating material is incorporated into the smokable filler material of the invention, the presence of the aerosol generating material is not 15 readily apparent. In a preferred embodiment, the CTC activation level of the particulate porous material in the first aspect of the invention after loading with the diluent is less than 20 %, preferably less than 10 %, 5 % or 3 %. This affords substantial advantages 20 when forming a sheet material from the impregnated material, including improved processing. Alternatively, the slurry may be extruded to form lengths of material, which may then be cut into pieces, e.g. having the dimensions described above. Further, the 25 aerosol generating material may be in the form of flakes. The aerosol generating material of the invention may comprise a mixture of the impregnated particulate porous material, described above in connection with the first aspect, with the particulate calcium carbonate carrying and/or impregnated 30 with the diluent, described above in connection with the second aspect. The third aspect of the invention relates to a smokable filler material. This smokable filler material comprises smoking material and the aerosol generating WO 2010/125386 PCT/GB2010/050691 -9 material of the invention, preferably a blend of these substances. The smoking material may be tobacco, a tobacco-containing material or a non-tobacco-containing material such as a non-tobacco reconstituted material. Preferably, the smoking material is a tobacco-containing material, but more preferably the smoking material 5 is tobacco. The tobacco may be, for example, stem, lamina, dust or a mixture thereof. Suitable tobacco materials include the following tobacco types: Virginia or flue-cured tobacco, Burley tobacco, Oriental tobacco, or a blend of tobacco materials. The 10 tobacco may be expanded, such as dry ice expanded tobacco (DIET), or processed by any other means such as extrusion. Tobacco or other smoking materials can also or alternatively be incorporated in the sheet material described above. 15 Preferably, the aerosol generating material is present in the smokable filler material in an amount of 1 - 95 % by weight, and preferably 3 - 80 %, 5 - 60 %, 10 - 30 % or 15 - 25 % by weight. 20 The fourth aspect of the invention relates to a smoking article comprising the aerosol generating material of the invention. The aerosol generating material can be incorporated into the smoking article by conventional means. As used herein, the term "smoking article" includes smokeable products such as cigarettes, cigars and cigarillos whether based on tobacco, tobacco derivatives, reconstituted tobacco or 25 tobacco substitutes. The term also includes so-called "heat-not-burn" products, which produce smoke or a smoke-like aerosol. The smoking article may be provided with a filter for the particulate and gaseous flow drawn by the smoker. Preferably, the smoking article is a cigarette. 30 The smoking article may contain a smokable filler material that consists of the aerosol generating material of the invention, i.e. no other smoking or aerosol generating material is incorporated into the smoking article. This may be WO 2010/125386 PCT/GB2010/050691 - 10 particularly suitable for heat-not-burn smoking articles. Alternatively, the smoking article may contain the aerosol generating material as an additive. Figure 2 illustrates an embodiment of the invention in which the smoking article is a 5 cigarette (5) that contains a filter (6) and a smoking rod (7). The aerosol generating material (8) is in shredded sheet form and is incorporated in the rod together with other components of the smokable filler material. The invention will now be illustrated by way of the following examples. 10 Example 1 Triacetin diluent was admixed with Picactif@ PNC100 carbon particles from Pica Carbons, France, which were activated to 100 % CTC and had a surface area of 1800 m 2 /g and mean particle diameter of 8 - 15 yim. Separately, an aqueous 15 solution of sodium alginate binder was prepared and glycerol was added. The diluent-impregnated carbon particles were then added to this liquid and formed into a slurry along with a ground chalk filler, which had a particle size of around 170 pLm. This was then cast to form a sheet and shredded to 37 cuts per inch to form an aerosol generating material of the invention. Various shredded sheet formulations 20 were prepared by this method, having the compositions (given in percentage by weight) shown in Table 1. Table 1. Formulations used for sheet manufacture (percentage by weight) Sheet Carbon Triacetin Ground Alginate Glycerol No. (adsorbent) (diluent) chalk (filler) (binder) (plasticiser) 1 7.5 17.6 62.4 7.5 5.0 2 7.5 17.6 60.9 9.0 5.0 3 4.0 12.0 70.0 9.0 5.0 25 The shredded sheet was blended with lamina tobacco at two levels, 20% sheet / 80% tobacco and 50% sheet / 50% tobacco. These blends were then used in the manufacture of cigarettes. A control cigarette with 100% lamina tobacco blend was also manufactured. The compositions are shown in Table 2. The cigarettes were made with a 27 mm cellulose acetate filter, cork on white tipping paper, and 50 WO 2010/125386 PCT/GB2010/050691 - 11 Coresta Unit wrapper. The cigarettes were tip ventilated to give a target tar yield of 7 mg. Table 2. Cigarette formulations Cigarette Sheet number Sheet inclusion Lamina tobacco in blend in blend (%) inclusion in blend (%) 1A 1 20 80 1B 1 50 50 2A 2 20 80 2B 2 50 50 3A 3 20 80 3B 3 50 50 Control - 100% 5 The cigarettes were smoked under ISO conditions (35 ml puff of 2 second duration every minute). The results are shown in Table 3. Table 3 shows that the control cigarette with no triacetin in the blend had a small 10 yield of triacetin in the smoke of 0.3 mg/cigarette. This is likely to be the result of elution of triacetin from the filter where it is used as a plasticiser. The results also clearly show that triacetin incorporated as a diluent in and on carbon particles in the tobacco rod is effectively transferred to the smoke. Increasing the triacetin inclusion level increases the dilution. 15 Further analysis of smoke analytes revealed that the test cigarettes exhibited no increase in benzo[a]pyrene (B[a]P) or acrolein levels in their smoke compared with the control. 20 WO 2010/125386 PCT/GB2O1O/050691 -12 .4 4-4 4.4 (U v *b0 o- cq C\ C C C Lo Cl 44 M (UU '--4 00 .4 4 S 4-a u (U 4. 75 U0 4 4 0 m u (L 4) .0 41 -a '' WO 2010/125386 PCT/GB2010/050691 - 13 Example 2 Triacetin diluent is admixed with precipitated calcium carbonate particles having an agglomerated scalenohedral calcite crystal structure (Sturcal@ L), obtained from Speciality Minerals Inc., Separately, an aqueous solution of sodium alginate binder 5 is prepared, and glycerol and colorant are added. The diluent-carrying calcium carbonate particles are then added to this liquid and formed into a slurry. In this instance, the calcium carbonate serves a dual role as diluent carrier and filler; no additional chalk filler is required. The slurry is cast to form a sheet and shredded to form an aerosol generating material of the invention. Various shredded sheet 10 formulations are prepared by this method, having the compositions (given in percentage by weight) shown in Table 4. Table 4. Sheet formulations (percentage by weight) Sheet Calcium Triacetin Alginate Glycerol E150a No. carbonate (diluent) (binder) (plasticiser) (colourant) (adsorbent and filler) 4 78.5 7.5 7.5 5 1.5 5 71.5 15 7.5 5 1.5 6 71.5 7.5 7.5 12.5 1.5 7 71 17 7.5 3 1.5

Claims

1. An aerosol generating material (8) for a smoking article (5), comprising 5 particulate porous material impregnated with a diluent (3), wherein said particulate porous material has a BET specific surface area of at least 1200 m 2 /g.

2. An aerosol generating material (8) as claimed in claim 1, wherein said material is a particulate porous carbon material, 10

3. An aerosol generating material (8) as claimed in claim 1 or 2, wherein said particulate porous material has a BET specific surface area of at least 1300 m 2 /g, preferably at least 1400, 1500, 1600, 1700 or 1800 m 2 /g, and preferably 3000 m 2 /g or less, 2500 m 2 /g or less, or 2000 m 2 /g or less. 15

4. An aerosol generating material (8) as claimed in any of the preceding claims, wherein the pore volume of said particulate porous material is at least 0.5 cc/g, preferably at least 0.6, 0.7 or 0.8 cc/g. 20

5. An aerosol generating material (8) as claimed in any of the preceding claims, wherein said particulate porous material is activated carbon, preferably having a CTC activation level prior to impregnation with the diluent of at least 50 %, 60 %, 70 %, 80 %, 90 % or 100 %. 25

6. An aerosol generating material (8) as claimed in any of the preceding claims, wherein the diluent is impregnated into said particulate porous material in an amount of 150 - 200 % by weight of the particulate porous material.

7. An aerosol generating material (8) for a smoking article (5), comprising 30 particulate calcium carbonate (1) carrying and/or impregnated with a diluent (3).

8. An aerosol generating material (8) as claimed in claim 7, wherein the calcium carbonate is precipitated calcium carbonate. WO 2010/125386 PCT/GB2010/050691 -15

9. An aerosol generating material (8) as claimed in any of the preceding claims, wherein the diluent (3) is a liquid at room temperature. 5

10. An aerosol generating material (8) as claimed in any of the preceding claims, wherein the diluent (3) is triacetin, triethyl citrate, and/or isopropyl myristate.

11. An aerosol generating material (8) as claimed in any of the preceding claims, wherein the impregnated particulate porous material, or calcium carbonate carrying 10 and/or impregnated with the diluent, is encapsulated in a barrier material.

12. An aerosol generating material (8) as claimed in any of the preceding claims, which is a cut or shredded sheet material. 15

13. An aerosol generating material (8) substantially as hereinbefore described with reference to the Examples.

14. A smokable filler material, comprising smoking material and an aerosol generating material (8) as claimed in any of the preceding claims. 20

15. A smoking article (5) comprising an aerosol generating material (8) as claimed in any of claims 1 to 13, or a smokable filler material as claimed in claim 14.