AEROSOL-GENERATING ARTICLES SUITABLE FOR USE IN AEROSOL-GENERATING DEVICES

Abstract

An aerosol-generating article may include: an aerosol-forming substrate; and/or at least one element including at least one polyhydroxyalkanoate (PHA). The at least one element may be downstream with respect to the aerosol-forming substrate. An aerosol-generating article may include: an aerosol-forming substrate; a support element immediately downstream of the aerosol-forming substrate; an aerosol-cooling element downstream of the support element; and/or an outer wrapper circumscribing the aerosol-forming substrate, the support element, and the aerosol-cooling element. The aerosol-cooling element may include at least one PHA. A method for quenching reactive oxygen species (ROS) in an aerosol produced by an aerosol-generating article comprising an aerosol-forming substrate may include: providing the aerosol-generating article with at least one element including at least one PHA. The at least one element is downstream with respect to the aerosol-forming substrate.

Claims

1. An aerosol-generating article, comprising: an aerosol-forming substrate; and at least one element including at least one polyhydroxyalkanoate (PHA); wherein the at least one element is downstream with respect to the aerosol-forming substrate.

2. An aerosol-generating article, comprising: an aerosol-forming substrate; a support element immediately downstream of the aerosol-forming substrate; an aerosol-cooling element downstream of the support element; and an outer wrapper circumscribing the aerosol-forming substrate, the support element and the aerosol-cooling element; wherein the aerosol-cooling element includes at least one polyhydroxyalkanoate (PHA).

3. The article of claim 2, wherein the aerosol-cooling element is formed by a sheet of polymeric composition that is pleated to define a plurality of longitudinally extending channels, and wherein the polymeric composition comprises the at least one PHA.

4. The article of claim 2, wherein the aerosol-cooling element is formed by a sheet of polymeric composition that is pleated to define a plurality of longitudinally extending channels, and wherein the sheet is coated with the at least one PHA.

5. The article of claim 2, wherein the support element is a hollow tubular element made from fibers bonded together to form a filtering element.

6. The article of claim 5, wherein the fibers comprise the at least one PHA.

7. The article of claim 5, wherein the fibers comprise cellulose acetate fibers bonded together using the at least one PHA surrounding the cellulose acetate fibers.

8. The article of claim 2, further comprising: a mouthpiece filter at an extreme downstream end of the aerosol-generating article; wherein the mouthpiece filter comprises fibers bonded together to form a filtering element, and wherein the fibers comprise the at least one PHA.

9. The article of claim 2, further comprising: a mouthpiece filter at an extreme downstream end of the aerosol-generating article, wherein the mouthpiece filter comprises fibers bonded together to form a filtering element, and wherein the fibers are cellulose acetate fibers bonded together using the at least one PHA surrounding the cellulose acetate fibers.

10. The article of claim 1, wherein the aerosol-forming substrate comprises a gathered sheet of crimped homogenized tobacco material circumscribed by a wrapper.

11. The article of claim 1, wherein the at least one PHA comprises a polymer containing repeating units of formula (I):
OCHR.sub.1(CH.sub.2).sub.nCO(I) where R.sub.1 is selected from: C.sub.1-C.sub.12 alkyls, C.sub.4-C.sub.16 cycloalkyls, C.sub.2-C.sub.12 alkenyls, optionally substituted with at least one group selected from: halogen (F, Cl, Br), CN, OH, OOH, OR, or COOR (RC.sub.1-C.sub.4 alkyl, benzyl), and where n is zero or is an integer from 1 to 6.

12. The article of claim 11, wherein the at least one PHA is selected from: polyhydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxyhexanoate (PHH), poly-3-hydroxyoctanoate (PHO), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxyoctanoate-co-3-hydroxyundecen-10-enoate) (PHOU), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-4-hydroxyvalerate) (PHBVV), polyhydroxybutyrate-hydroxyvalerate copolymer, or mixtures thereof.

13. The article of claim 1, wherein the at least one PHA has a weight-average molecular weight (M.sub.w) greater than or equal to 10,000 daltons (Da) and less than or equal to 1,000,000 Da.

14. A method for quenching reactive oxygen species (ROS) in an aerosol produced by an aerosol-generating article comprising an aerosol-forming substrate, the method comprising: providing the aerosol-generating article with at least one element including at least one polyhydroxyalkanoate (PHA); wherein the at least one element is downstream with respect to the aerosol-forming substrate.

15. The article of claim 10, wherein the tobacco material contains glycerin as an aerosol-former.

16. The article of claim 11, where n is 1.

17. The article of claim 11, where n is 2.

18. The article of claim 11, where R.sub.1 is methyl or ethyl.

19. The article of claim 11, where R.sub.1 is methyl, and where n is 1 or 2.

20. The article of claim 11, where R.sub.1 is ethyl, and where n is 1 or 2.

Description

DRAWINGS

[0026] The above and/or other aspects and advantages will become more apparent and more readily appreciated from the following detailed description of examples, taken in conjunction with the accompanying drawings, in which:

[0027] FIG. 1 shows an image of a pleated sheet, taken using an optical microscope;

[0028] FIG. 2 shows images of a surface of the pleated sheet of FIG. 1 coated with PHB, taken using a SEM electronic microscope;

[0029] FIG. 3 shows a schematic cross-sectional diagram of an embodiment of an aerosol-generating article suitable for use with an aerosol generating-device; and

[0030] FIG. 4 shows an embodiment of an experimental sampling system.

DETAILED DESCRIPTION

[0031] As regards the aerosol-forming substrate, it preferably comprises tobacco, more preferably a gathered sheet of crimped homogenised tobacco material circumscribed by a wrapper. Preferably, the crimped sheet of homogenised tobacco material comprises glycerin as an aerosol-former.

[0032] As regards the PHA to be used in the present invention, it is preferably a polymer containing repeating units of formula (I):

OCHR.sub.1(CH.sub.2).sub.nCO(I)

[0033] where:

[0034] R.sub.1 is selected from: C.sub.1-C.sub.12 alkyls, C.sub.4-C.sub.16 cycloalkyls, C.sub.2-C.sub.12 alkenyls, optionally substituted with at least one group selected from: halogen (F, Cl, Br), CN, OH, OOH, OR, COOR (RC.sub.1-C.sub.4 alkyl, benzyl);

[0035] n is zero or is an integer from 1 to 6, preferably is 1 or 2.

[0036] Preferably, R.sub.1 is methyl or ethyl, and n is 1 or 2.

[0037] The PHAs can either be homopolymers, copolymers, or terpolymers. In the case of copolymers or terpolymers, they can consist of different repeating units of formula (I), or of at least one repeating unit of formula (I) in combination with at least one repeating unit deriving from comonomers that are able to copolymerize with hydroxyalkanoates, such as lactones or lactams. In the latter case, the repeating units of formula (I) are present in an amount equal to at least 10% in moles with respect to the total moles of repeating units.

[0038] Particularly preferred repeating units of formula (I) are those deriving from: 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxyhexanoate, 3-hydroxyoctanoate, 3-hydroxyundec-10-enoate, 4-hydroxyvalerate.

[0039] Particularly preferred PHAs are: polyhydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxyhexanoate (PHH), poly-3-hydroxyoctanoate (PHO), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBH), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxyoctanoate-co-3-hydroxyundecen-10-enoate) (PHOU), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-4-hydroxyvalerate) (PHBVV), polyhydroxybutyrate-hydroxyvalerate copolymer, or mixtures thereof.

[0040] According to the purposes of the present invention, particularly preferred PHAs are polyhydroxybutyrate (PHB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV).

[0041] Preferably, the PHA has a weight-average molecular weight (M.sub.w) ranging from 10,000 to 1,000,000 Da.

[0042] As for the production of PHA, this is preferably achieved by microbial fermentation of an organic substrate (for example carbohydrates or other fermentable substrates, such as glycerol) through a strain of microorganisms capable of producing PHA, and subsequent recovery of PHA from the cell mass. For further details see, for example patent applications WO 99/23146, WO 2011/045625 and WO 2015/015395. Substrates suitable for the production of PHA by fermentation can be obtained in particular from the processing of vegetables, for example juices, molasses, pulps derived from the processing of sugar beet, sugar cane. These substrates generally contain, in addition to sucrose and other carbohydrates, organic growth factors, nitrogen, phosphorus and/or other minerals useful as nutrients for cell growth. An alternative is glycerol, a low-cost organic carbon source, being a by-product of biodiesel production, which can optionally be used in a mixture with levulinic acid (see, for example, U.S. Pat. No. 8,956,835 B2).

[0043] As reported hereinabove, the PHA is preferably included in the aerosol-cooling element. This can be achieved according to two different embodiments.

[0044] In a first embodiment, the aerosol-cooling element is formed by a sheet of a polymeric composition that is pleated to define a plurality of longitudinally extending channels, wherein the polymeric composition comprises at least one PHA.

[0045] The polymeric composition comprising the at least one PHA can be formulated according to known techniques, and can include as polymeric base 100% by weight of PHA, or preferably a mixture of from 60% to 90% by weight of PHA and from 10% to 40% by weight of at least one different biodegradable/compostable polymer, such as polylactide (PLA), poly(butylene-co-adipate-co-terephthalate) (PBAT), poly(butylene-co-succinate) (PBS), poly(butylene-co-succinate-co-adipate) (PBSA), polycaprolactone (PCL), and mixtures thereof), the percentage being expressed with respect to the total weight of the polymeric base.

[0046] The polymeric composition may further comprise at least one plasticizer, usually in an amount of from 2 to 15% by weight, based on the total weight of the polymeric base. Preferably, the plasticizer may be selected from natural or biobased plasticizers, such as natural oils (e.g. linseed, castor, palm, flax and coconut oil, hydrogenated and non-hydrogenated derivatives thereof, glycerol and citric esters, and mixtures thereof).

[0047] Other possible additives of the polymeric composition may be e.g.: processing aids; fillers (e.g. kaolin, talc, chalk, silica, montmorillonite and mixtures thereof); primary or secondary antioxidants.

[0048] The sheet may be produced according to known techniques, for instance by extruding the polymeric composition through a die to form the sheet, that is then recovered and wound by means of a chill roll. To form the aerosol-cooling element, the sheet is then pleated and cut to the desired length according to known techniques.

[0049] In FIG. 1 an image of the pleated sheet is reported, taken by means of an optical microscope.

[0050] In a second embodiment, the aerosol-cooling element is formed by a sheet of a polymeric material that is pleated to define a plurality of longitudinally extending channels, wherein the sheet is coated with at least one PHA. In this case, the sheet may be made from any suitable polymeric composition, preferably from a biodegradable/compostable polymer material, such as: polylactide (PLA), poly(butylene-co-adipate-co-terephthalate) (PBAT), poly(butylene-co-succinate) (PBS), poly(butylene-co-succinate-co-adipate) (PBSA), polycaprolactone (PCL), and mixtures thereof). The pleated sheet is then coated with the PHA. The coating may be carried out by known techniques. Preferably, the coating is carried out by spraying an aqueous suspension of the PHA onto the pleated sheet. The spraying may be performed on only one side of the pleated sheet, or on both sides. After spraying, the coated pleated sheet is dried, e.g. at room temperature or in an oven at a temperature not exceeding 80 C. (e.g. at 40 C. for 1 hour).

[0051] In FIG. 2 images of the surface of the pleated sheet coated with PHB is reported, taken by means of a SEM electronic microscope. The white spots and particles in the images are formed by the PHB which adheres to the sheet material.

[0052] FIG. 3 is a schematic cross-sectional diagram of an embodiment of an aerosol-generating article according to the present invention suitable for use with an aerosol generating-device.

[0053] In FIG. 3, the aerosol-generating article (10) comprises four elements arranged in coaxial alignment: an aerosol-forming substrate (20), a support element (30), an aerosol-cooling element (40), and a mouthpiece filter (50). These four elements are arranged sequentially and are circumscribed by an outer wrapper (60) to form the aerosol-generating article (10). The aerosol-generating article (10) has a proximal or mouth end (70), which a user inserts into his or her mouth during use, and a distal end (80) located at the opposite end of the aerosol-generating article (10) to the mouth end (70).

[0054] In use air is drawn through the aerosol-generating article by a user from the distal end (80) to the mouth end (70).

[0055] The aerosol-forming substrate (20) is located at the extreme distal or upstream end of the aerosol-generating article (10). The support element (30) is located immediately downstream of the aerosol-forming substrate (20) and abuts the aerosol-forming substrate (20). In the embodiment shown in FIG. 3, the support element (30) is a hollow tube of cellulose acetate fibers. The support element (30) locates the aerosol-forming substrate (20) at the extreme distal end (80) of the aerosol-generating article (10) so that it can be penetrated by a heating element of an aerosol-generating device. The support element (30) acts to prevent the aerosol-forming substrate (20) from being forced downstream within the aerosol-generating article (10) towards the aerosol-cooling element (40) when a heating element of an aerosol-generating device is inserted into the aerosol-forming substrate (20). The support element (30) also acts as a spacer to space the aerosol-cooling element (40) of the aerosol-generating article 10 from the aerosol-forming substrate (20).

[0056] The aerosol-cooling element (40) is located immediately downstream of the support element (30) and abuts the support element (30). In use, volatile substances released from the aerosol-forming substrate (20) pass along the aerosol-cooling element (40) towards the mouth end (70) of the aerosol-generating article (10). The volatile substances may cool within the aerosol-cooling element (40) to form an aerosol that is inhaled by the user. In the embodiment illustrated in FIG. 3, the aerosol-cooling element comprises a pleated sheet circumscribed by a wrapper (90). The pleated sheet defines a plurality of longitudinal channels that extend along the length of the aerosol-cooling element (40). The mouthpiece filter (50) is located immediately downstream of the aerosol-cooling element (40) and abuts the aerosol-cooling element (40).

[0057] To assemble the aerosol-generating article (10), the four elements described above are aligned and tightly wrapped within the outer wrapper (60). The outer wrapper may be a conventional cigarette paper.

[0058] As disclosed hereinabove, at least one element of the aerosol-generating article (10), which is placed downstream with respect to the aerosol forming substrate, includes at least one PHA. With reference to FIG. 3, such element may be the aerosol-cooling element (40). Alternatively, it may be the support element (30) and/or the mouthpiece filter (50). Advantageously, the PHA may be included both in the aerosol-cooling element (40) and in at least one element selected from the support element (30) and the mouthpiece filter (50).

[0059] Further details about the structure, manufacturing and use of an aerosol-generating article as described above are reported in WO 2013/098410 and WO 2013/098405.

[0060] The Applicant wishes to underline that the use of at least one PHA for manufacturing at least one element of the the aerosol-generating article improves biodegradability and environmental sustainability of the article, since it is well known that PHAs are biodegradable materials which are produced from renewable sources.

[0061] As regards the embodiments wherein the PHA is used as bonding agent for cellulose acetate fibers to form a filtering element, the Applicant has found that at least one PHA can be advantageously used as bonding agent for cellulose acetate fibers, instead of triacetin or other bonding agents, commonly used in the art. The PHA is able to bond the cellulose acetate fibers when applied on the fiber surface, causing the formation of random connection points to retain a space between the fibers suitable for a correct pressure drop during smoking and to impart a suitable hardness to the filter element. Moreover, since the PHA has a relatively high melting point and is substantially insoluble in water, it does not soften or melt when it is subjected to the warm and humid smoke produced during cigarette smoking, so as to prevent softening or collapsing of the filter element during smoking.

[0062] The above filter element may be produced by a process which comprises:

[0063] embedding a bundle of cellulose acetate fibers with an aqueous suspension of at least one PHA to obtain a wet bundle of cellulose acetate fibers covered by the PHA suspension;

[0064] shaping the wet bundle in the form of a continuous elongated element;

[0065] heating the continuous elongated element to a temperature of from 140 C. to 180 C. for a time sufficient to melt the PHA and evaporate the water;

[0066] cooling the heated continuous elongated element to obtain crystallization of the PHA;

[0067] cutting the so obtained continuous elongated element into segments of a predetermined length.

[0068] The following examples are provided to further illustrate the invention.

EXAMPLE 1

[0069] A polymeric composition was produced having the following ingredients:

TABLE-US-00001 PHB (polyhydroxybutyrate) 60.70% by weight PLA (polylactide) 30.00% by weight Plasticizer 6.00% by weight Processing aid 2.40% by weight Antioxidant 0.90% by weight

[0070] The PHB had Mw of about 500 KDa.

[0071] The composition was produced in a LabTech LMX5-VS highspeed mixer applying speeds ranging from 100 rpm to 900 rpm.

[0072] The so obtained composition, in the form of powder, was extruded in a twin-screw extruder (LabTech LTE 16-40) with a volumetric hopper feeder. The extruded material was formed in the form of a sheet by means of a chill roll unit (LabTech LBCR-150) connected to the extruder head. The sheet had a thickness of about 150 m.

[0073] The sheet was cut into strips of 11 mm length, 1.8 mm height, each having a weight of about 0.260-0.360 g.

[0074] The strips were pleated by a mechanical tool and then folded and rolled to obtain aerosol-cooling elements having the same dimensions of those which were found in HEETs cigarettes for I-QOS (Philip Morris). Such cigarettes (or, more precisely, aerosol-generating articles) had the structure as shown in FIG. 3. The aerosol-cooling elements in the HEETs cigarettes are made from PLA (polylactide).

EXAMPLE 2-3

[0075] The aerosol-cooling elements found in the HEETs cigarettes, made from PLA (polylactide), were extracted, unfolded and then sprayed with an aqueous suspension of PHB (Mw: 443 KDa) (Example 2) or of poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) (Mw: 700 KDa) (Example 3). The concentration of PHB and PHBV in the aqueous suspensions was 10% w/v. The suspensions were sprayed on only one side of the PLA pleated strips or on both sides. The sprayed strips were then dried in an oven at 40 C. for 1 hour.

EXAMPLE 4

Determination of ROS

[0076] (a) Sampling System.

[0077] A computer-controlled Single Cigarette Smoking Machine (SCSM, CH Technologies) was used to generate mainstream smoke under standard smoking conditions (cigarettes burn for 5 min with a 2-s puff duration, puff interval 2-s and 65-mL puff volume). To generate e-cigarette vapor an I-QOS (2.4 Plus) Heat-Not-Burn device was used. Three impingers were filled with 20 mL of a 2,7-dichlorofluorescin-horseradish peroxidase (DCFH-HRP) solution and used to collect gas-phase ROS from mainstream smoke.

[0078] The experimental system is shown schematically in FIG. 4. Commercially available HEETS Marlboro (Gold) cigarettes were used to collect ROS from mainstream smoke. In FIG. 4, the SCSM (1) is connected to the three impingers (2) containing the DCFH-HRP solution which receives the smoke produced by the cigarette (3) connected to the impingers by means of a filter holder (4). The exhaust smoke exits the SCSM through a pipe (5). The SCSM is connected to a laptop (6) in order to control puff duration and puff interval of the cigarette smoking.

[0079] (b) Sample Preparation and Analysis.

[0080] Preparation of Fluorescent Probes and Standards for ROS in cigarette smoke. The fluorescent probe used to determine ROS in this study was DCFH. A 1 mM stock solution was prepared by dissolving 2,7-dichlorofluorescin diacetate (DCFH-DA; Calbiochem, USA) into ethyl alcohol (ACS grade, Pharmo, USA). A 10 mL solution was mixed with 40 mL 0.01 M sodium hydroxide (NaOH) and left in a dark room temperature for 30 min to hydrolyze. Then 200 mL of phosphate buffer, obtained by mixing sodium phosphate dibasic (Na.sub.2HPO.sub.4, Sigma Aldrich, MO, USA) with sodium phosphate dihydrogen phosphate anhydrous (NaH.sub.2PO.sub.4, Fluka, Germany) to achieve a pH of 7.2, was added to the solution. Horseradish peroxidase (HRP, Sigma Aldrich, USA) was used as the catalyst with a concentration of 0.5 units/mL. The final DCFH concentration of this working solution was 5 M.

[0081] Equivalent H.sub.2O.sub.2 concentration was used to express the ROS concentrations by converting fluorescence intensity using a standard H.sub.2O.sub.2 calibration curve. Four H.sub.2O.sub.2 standards with the concentrations of 1.0, 2.0, 3.0, and 4.010.sup.7 nmol were prepared by mixing 0.1 mL hydrogen peroxide (ACS grade, Sigma Aldrich, USA) with 3 mL DCFH-HRP working solution. Standard blanks were obtained by mixing 0.1 mL deionized Milli-Q water (resistivity>18.2 M) with probe. The standards were placed in cuvettes and incubated at 37 C. in a water bath. Formation of 2,7-dichlorofluorescin was monitored by measuring fluorescence (excitation wavelength: 504 nm; emission wavelength: 524 nm) using a Shimadzu Spectrophotometer (model: RF-5301 PC, Japan).

[0082] (c) Analysis of Reactive Oxygen Substances (ROS).

[0083] Subsequent to sampling, 3 mL of the reagent solution was removed from each impinger (each contains 20 mL), placed into a cuvette, and incubated for 15 min at 37 C. in water bath. Generally, the fluorescence intensities of the solutions in impingers were within the range of the standards. After using the volume of the solution to get the amount of ROS in each impinger, the contents of all three impingers were combined. An aliquot of the solution was taken and the fluorescence intensity was measured. Sampling blanks were obtained by operating the smoking system without any cigarette burning and analyzed in the same way. Sampling blank values were subtracted from sample results.

[0084] The amount of ROS was also measured from the smoke produced by commercial cigarettes as reported in Table 1.

[0085] Further details about ROS analysis can be found in: [0086] Jiayuan Zhao & Philip K. Hopke, Concentration of Reactive Oxygen Species (ROS) in Mainstream and Sidestream Cigarette Smoke, Aerosol Science and Technology, 46:191-197, 2012.

[0087] The results are reported in Table 1. The data are the mean values measured on 12 samples for each type of aerosol-cooling element.

TABLE-US-00002 TABLE 1 PHA amount Average ROS * Standard % ROS Samples PHA (mg) (nmol/cigarette) Deviation quenched HEETS as such 30.22 2.90 HEETS-Ex. 1 PHB 228 5.58 2.92 81% HEETS-Ex. 2 PHB 6.5 15.80 0.49 48% (single side coated) HEETS-Ex. 2 PHB 5.3 11.20 1.14 63% (double side coated) HEETS-Ex. 3 PHBV 4.4 14.53 0.83 52% (single side coated) HEETS-Ex. 2 PHBV 7.2 19.39 0.76 36% (double side coated) * Detection limit: 1.5 nmol

[0088] The PHA amount is the amount in each aerosol-cooling element according to the present invention.

[0089] From the above data, it is clear the remarkable effect of ROS quenching in the aerosol generated by the aerosol-generating articles according to the invention, which contain the PHA.

[0090] Without being bound to any theory, the positive effect on ROS quenching by contacting the generated aerosol with the PHA is believed to be mainly due to the structure of the monomer unit OCHR.sub.1(CH.sub.2).sub.nCO. The hydrogen linked to the ternary carbon atom CHR.sub.1 is particularly reactive with formation of a hydrogen radical that quenches the ROS, by inactivating the same via radical reaction.