WO2006136197A1 - Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule - Google Patents

Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule Download PDF

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Publication number
WO2006136197A1
WO2006136197A1 PCT/EP2005/008503 EP2005008503W WO2006136197A1 WO 2006136197 A1 WO2006136197 A1 WO 2006136197A1 EP 2005008503 W EP2005008503 W EP 2005008503W WO 2006136197 A1 WO2006136197 A1 WO 2006136197A1
Authority
WO
WIPO (PCT)
Prior art keywords
capsule
shell
anyone
smoking device
breakable
Prior art date
Application number
PCT/EP2005/008503
Other languages
French (fr)
Inventor
Didier Hartmann
Jean-Michel Hannetel
Nathalie Coursieres
Original Assignee
V. Mane Fils
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=35527447&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2006136197(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by V. Mane Fils filed Critical V. Mane Fils
Priority to PCT/EP2005/008503 priority Critical patent/WO2006136197A1/en
Priority to PL06808983T priority patent/PL1906775T3/en
Priority to AU2006271321A priority patent/AU2006271321B2/en
Priority to KR1020167033016A priority patent/KR20160138325A/en
Priority to AP2007004283A priority patent/AP2372A/en
Priority to AT06808983T priority patent/ATE439772T1/en
Priority to MX2007016382A priority patent/MX2007016382A/en
Priority to UAA200800574A priority patent/UA90150C2/en
Priority to DE602006008624T priority patent/DE602006008624D1/en
Priority to KR1020157011182A priority patent/KR101700549B1/en
Priority to JP2008517631A priority patent/JP5616018B2/en
Priority to PT06808983T priority patent/PT1906775E/en
Priority to KR1020187012324A priority patent/KR102315198B1/en
Priority to CN2006800224487A priority patent/CN101203148B/en
Priority to EP06808983A priority patent/EP1906775B1/en
Priority to NZ564190A priority patent/NZ564190A/en
Priority to PCT/IB2006/002818 priority patent/WO2007010407A2/en
Priority to KR1020077030421A priority patent/KR20080022127A/en
Priority to US11/917,769 priority patent/US8820331B2/en
Priority to BRPI0611577A priority patent/BRPI0611577B1/en
Priority to DK06808983T priority patent/DK1906775T3/en
Priority to CA2612665A priority patent/CA2612665C/en
Priority to SI200630467T priority patent/SI1906775T1/en
Priority to RU2008102112/21A priority patent/RU2415618C2/en
Priority to ES06808983T priority patent/ES2331713T3/en
Priority to ZA200711059A priority patent/ZA200711059B/en
Publication of WO2006136197A1 publication Critical patent/WO2006136197A1/en
Priority to EGPCTNA2007001411A priority patent/EG26683A/en
Priority to HK08109879.9A priority patent/HK1115783A1/en
Priority to CY20091101199T priority patent/CY1109633T1/en
Priority to US14/058,746 priority patent/US9339060B2/en
Priority to JP2014110193A priority patent/JP5731045B2/en
Priority to JP2014227817A priority patent/JP6010090B2/en
Priority to US15/153,766 priority patent/US10278418B2/en

Links

Classifications

    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/061Use of materials for tobacco smoke filters containing additives entrapped within capsules, sponge-like material or the like, for further release upon smoking
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00Cigars; Cigarettes
    • A24D1/002Cigars; Cigarettes with additives, e.g. for flavouring
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/02Manufacture of tobacco smoke filters
    • A24D3/0204Preliminary operations before the filter rod forming process, e.g. crimping, blooming
    • A24D3/0212Applying additives to filter materials
    • A24D3/0216Applying additives to filter materials the additive being in the form of capsules, beads or the like
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/02Manufacture of tobacco smoke filters
    • A24D3/0275Manufacture of tobacco smoke filters for filters with special features
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/04Tobacco smoke filters characterised by their shape or structure
    • A24D3/048Tobacco smoke filters characterised by their shape or structure containing additives
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24DCIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06Use of materials for tobacco smoke filters
    • A24D3/14Use of materials for tobacco smoke filters of organic materials as additive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation

Definitions

  • This invention relates to a smoking device incorporating a breakable capsule, more particularly to a filtered smoking device incorporating such a capsule in its filter element.
  • US2004/0261807 describes a cigarette comprising a tobacco rod and a filter element connected to the tobacco rod, said filter having a cavity wherein a capsule is disposed.
  • Said capsule comprises an outer gelatin shell, and an inner liquid composition including flavoring agents.
  • the goal of US2004/0261807 is to make it possible for the smoker to break the capsule, during the combustion of the cigarette, to allow the release of the content stored in the capsule.
  • the gelatin capsule is a good storage capsule, but is sensitive to moisture, and may soften during the smoking time. Because of this softening, the gelatin shell loses its breakability, i.e. its ability of being ruptured under the pressure imposed by the smoker' s fingers when the smoker wants to release the content of the capsule. The ability to rupture is measured through the crush strength to be exerted to rupture the capsule and through the deformation of the capsule when pressure is applied.
  • said crush strength must not be too high at a dry state to be suitable in such an application.
  • a crush strength of more than 2.5 kp appears too high to achieve the expected results.
  • the gelatin capsule of the prior art has a very important deformation when placed in smoking moisture conditions, which prevents the smoker from breaking it through a pressure of his/her fingers. There is therefore a need to build up new capsules which present a crush strength of at most 2.5kp and which keep their breakability even when exposed to the moisture brought into the filter during the smoking.
  • the invention relates to a smoking device comprising:
  • a recipient including or able to receive burning products, preferably tobacco, a filter element which is connected to the recipient, wherein said filter comprises at least one breakable capsule, said capsule
  • the recipient may be the rod of a cigarette, wherein the burning product is tobacco.
  • the initial crush strength Ci of the capsule is measured before smoking, by continuously applying a load vertically onto one particle until rupture using a LLOYD - CHATILLON Digital Force Gauge, Model DFIS 50, having a capacity of 25Kg, a resolution of 0.02 Kg, and an accuracy of +/- 0,15 %.
  • the force gauge is attached to a stand; the capsule is positioned in the middle of a plate that is moved up with a manual thread screw device. Pressure is then applied manually and the gauge records the maximum force applied at the very moment of the rupture of the capsule, (measured in Kg or in Lb) . Rupture of the capsule results in the release of the core.
  • the smoking test A is performed on the smoking
  • the cigarette containing breakable capsule is positioned on the smoking machine as standard position used for other type of analysis.
  • the adjustable parameters are set up as follows :
  • Puff volume 35ml (as defined in internationally standard method for smoking machine)
  • Puff period 60 s
  • Puff duration 2 s
  • Puff sweep time 1.8s
  • Exhaust sweep time Is
  • the test is finished when the cigarette is completely smoked or after 7 or 8 puffs.
  • the final crush strength Cf is measured after said smoking Test A following the same procedure as used for Ci.
  • the deformation of the capsule is also measured after smoking test A, just before the rupture of the capsule.
  • the smoking device includes a capsule having a crush strength Ci of 0.6 to 2 kp, preferably of 0.8 to 1.2 kp and keeping a crush strength Cf in the range of 0.6 to 2 kp, preferably in the range of 0.8 to 1.2 kp when submitted to the smoking test A.
  • the deformation of the breakable capsule within the smoking device prior to rupture, before and after its submission to the smoking test A is less than 2 mm, preferably less than 1 mm.
  • the capsule is such that it claps or makes an audible "pop", when ruptured.
  • the shell thickness of the capsule is 10-500 microns, preferably 30-150 microns, more preferably 50-60 microns;
  • the outer diameter of the capsule is in the range of 2 to 8 mm, preferably 3 to 5 mm, more preferably 3, 5 to 4 mm;
  • the ratio diameter of the capsule / thickness of the shell is in the range of 10 to 100, preferably 50 to 70.
  • the shell comprises at least one hydrocolloid selected from gellan gum, agar, carrageenans, pullulan gum or modified starch, alone or as a mixture thereof or in combination with gelatin.
  • the selected hydrocolloid is gellan
  • the amount of gellan present in the shell is 1.5 to 50 % w/w of the total weight of the shell.
  • the shell contains less than 80 % gelatin, preferably less than 75 % gelatin.
  • the capsule includes a moisture barrier coating.
  • the shell of the capsule is coated with at least one moisture barrier layer comprising at least one moisture barrier agent dispersed in an organic solvent.
  • the shell can be made of any hydrocolloid, including gelatin which can even constitutes in that case the only gelling agent of the shell. But preferably, even with the presence of the hydrophobic coating, the shell comprises also an amount of gellan, or agar, or carragheenan or pullulan gum sufficient to bring a certain resistance to moisture .
  • the at least one moisture barrier agent is at least one hydrophobic agent selected from those suitable for confectionery or pharmaceutical products, preferably selected from the group consisting of waxes, especially carnauba wax, candelilla wax or beeswax, carbowax, shellac (in alcoholic or aqueous solution) , ethyl cellulose or a combination thereof. More preferably, the at least one moisture barrier agent is ethyl cellulose or a mixture of ethyl cellulose and shellac.
  • the hydrophobic moisture barrier agent is a filmogen gelling agent, preferably gellan gum itself.
  • the shell may further comprise at least one plasticizer, which may be glycerol, sorbitol, maltitol, triacetine or polyethylene glycol, or another polyalcohol with plasticizing properties, and optionally one acid of the monoacid, diacid or triacid type, in particular citric acid, fumaric acid, malic acid, etc.
  • the shell can notably comprises a coloring agent which renders easier the location of the capsule in the filter during the manufacturing process of filters. Fillers can also be included in the composition of the shell.
  • the core of the capsule included within the smoking device of the invention is preferentially composed of a mixture of materials or products which are lipophilic or partially soluble in ethanol, or of molecules formulated as oil/water/oil emulsions.
  • the core of a breakable capsule according to the invention represents by weight 50 to 92% of said capsule, preferably 80 to 92%, more preferably 85 to 92%.
  • the core of the capsule may be composed of one or more lipophilic solvents conventionally used in the food, pharmaceutical or cosmetic industries.
  • these lipophilic solvents may be triglycerides, especially medium chain triglycerides, and in particular triglycerides of caprylic and capric acid, or mixtures of triglycerides such as vegetable oil, olive oil, sunflower oil, corn oil, groundnut oil, grape seed oil, wheat germ oil, mineral oils and silicone oils.
  • the amount of lipophilic solvent in the core of a capsule according to the invention is of the order of 0.01 to 90%, preferentially 25 to 75%, of the total weight of the capsule.
  • the core may also comprise one or more aromatic or fragrance molecules as conventionally used in the formulation of flavoring or fragrance compositions. Mention will in particular be made of aromatic, terpenic and/or sesquiterpenic hydrocarbons, and more particularly essential oils, alcohols, aldehydes, phenols, carboxylic acids in their various forms, aromatic acetals and ethers, nitrogenous heterocycles, ketones, sulfides, disulfides and mercaptans which may be aromatic or non aromatic. It may also comprise one or more molecules or extracts for cosmetic use.
  • the core may also comprise one or more fillers as used in aromatic emulsions. Mention will be made of dammar gum, wood resins of the ester gum type, sucrose acetate isobutyrate (SAIB) or brominated vegetable oils. The function of these weighting agents is to adjust the density of the liquid core.
  • the core or the shell may also comprise one or more sweeteners, which may be provided in the form of a solution or suspension in ethanol. Examples of suitable sweeteners may be, but is not limited to, aspartame, saccharine, NHDC, sucralose, acesulfame, neotame, etc.
  • the core may also comprise one or more "sensate" aromatic agents, which provide either a freshening effect or a hot effect in the mouth.
  • Suitable freshening agents may be, but are not limited to, menthyl succinate and derivatives thereof, in particular Physcool® marketed by the Applicant.
  • a suitable hot effect agent may be, but is not limited to, vanillyl ethyl ether.
  • the flavoring agents that can be solubilized in the solvent of the core of the capsule include, but are not limited to, natural or synthetic aromas and/or fragrances.
  • suitable fragrances are fruity, confectionery, floral, sweet, woody fragrances.
  • suitable aromas are vanilla, coffee, chocolate, cinnamon, mint.
  • the invention also relates to a breakable capsule suitable for being incorporated in the filter of a smoking device, which is substantially moisture stable.
  • substantially moisture stable means that the outer shell or outer coating of the capsule has the ability to retard degradation of the capsule by means of the water brought into the smoking device by a smoker.
  • the breakable capsule according to the invention comprises a core as described hereinbefore, and a shell, said capsule presents a crush strength from 0.5 to 2.5 kp, and keeps a crush strength from 0.5 to 2.5 kp and a deformation of less than two third of its diameter after having been submitted to the smoking test A.
  • the capsule of the invention is a seamless capsule, obtained trough a co- extrusion process.
  • the co-extrusion process is a synchronous extrusion of two liquids: the external and hydrophilic liquid phase, and the internal and lipophilic liquid phase.
  • the co- extrusion process consists of three main stages: compound drop formation, shell solidification and capsule collection.
  • the compound drop is a sphere of the liquid fill phase inside the shell phase.
  • the liquid fill phase is hereinafter referred to as "the core”.
  • the shell phase is hereinafter referred to as "the shell”.
  • the capsules of the invention may be produced by any suitable co-extrusion process.
  • the capsules are produced by an apparatus and a process as described in EP 513603, the disclosure of which is herein incorporated by reference.
  • the solidification step is performed by keeping cold the capsules in order to ensure correct gelling of the shell for example by contacting them with a cold bath.
  • the cold bath is preferably cold oil.
  • the capsules may then be centrifuged in order to remove the surplus oil, optionally washed with organic solvent (such as acetone, ethyl acetate, ethanol, petroleum ether, etc.) also to remove the surplus oil, and dried.
  • organic solvent such as acetone, ethyl acetate, ethanol, petroleum ether, etc.
  • the capsules are co-extruded, centrifuged and optionally immersed into a solution or an emulsion containing a curing agent.
  • the curing agent may also be ethanol or any other anhydrous organic solvent, such as ethyl acetate or isopropanol, maintained at a temperature of between 0 and 25°C, more particularly between 10 and 20 0 C.
  • the curing agent can alternatively or also be a bath of calcium ions, for example of calcium chloride, dicalcium phosphate or calcium sulfate or a bath of acid containing calcium ions of pH less than 5, preferably of 3 to 4.
  • acids may be adipic acid, fumaric acid, gluconic acid or glucono-delta-lactone.
  • the calcium ion or acid bath is preferably at a temperature of 0 to 25 °C, preferably 10 to 20 0 C.
  • the effect of the immersion step is to wash out the oil remaining at the periphery of the capsule, and to gradually strengthen the shell, notably through dehydration and osmotic equilibrium.
  • the capsules after immersion, are dried in a current or air at controlled temperature and humidity.
  • the relative humidity of the drying air is 20% to 60%, preferably 30 to 50%; the temperature of the drying air is of 15 to 60 0 C, preferably 35 to 45 "C.
  • the capsules can be obtained using the following method: co- extrusion of the external and hydrophilic liquid phase on the one hand, and of the internal and lipophilic liquid phase and components of the core on the other hand, optionally centrifugation, optionally immersion of the capsules so obtained in a bath of calcium ions or acid, followed by drying.
  • the process according to the invention further comprises a coating step during which the moisture barrier outer layer is applied on the capsules.
  • said coating step is performed by dipping the capsules in a coating solution, or by spraying a coating solution onto the capsules.
  • Said coating step is preferably performed after the drying step.
  • the capsules manufactured through the process of the invention are essentially or perfectly spherical and very homogeneous in size.
  • composition of capsules according to the present invention referenced as 1004/H11 (having less than 80 % gelatin and including gellan gum) is given in Table 1 below, and the composition of prior art capsules containing 80% gelatin, referenced 1004/C30, is given in Table 2 below.
  • weight of each capsule 20.56mg in which weight of the shell: 3.68 mg (17,89' weight of the core: 16.88 mg (82.11%)
  • Capsules 1004/C30 and capsules 1004/H11 present a diameter of respectively 3489 +/- 40 and 3394 +/- 35 ⁇ m.
  • the crush strength of the capsules is measured as follows using a LLOYD-CHATILLON Digital Force Gauge - Model DFIS 50
  • the capsule is positioned in the middle of a plate that is moved up with a manual thread screw device. Pressure is then applied manually and once the capsule wall fails, the gauge records the maximum force applied prior to rupture (measure in Kg or in Ib) . Sample of 10 to 20 capsules is measured.
  • Capsules are prepared according to example 1.
  • Core content is about 89 % and shell content is about 11 %, corresponding to a thickness of dried shell of about 50 microns.
  • Capsules are then dried to obtain 3.5 mm spherical capsules with a crush-strength of 1 kp. Average weight of capsule is about 20 mg.
  • a prior art capsule containing gelatin (ref 1004/Cl) containing 72 % gelatin and a capsule as described in example 1 above are incorporated into a cavity filter of a cigarette.
  • Crush strength value Ci is measured for both capsules according to the herein described method.
  • the obtained cigarettes are then smoked on a smoking machine (smoking test A) according to international standard procedure.
  • Filters containing the capsules are collected and capsules are extracted from the filter to measure crush strength value Cf after smoking process.
  • capsules In the case of gelatin capsules, capsules have melted into the filter during the smoking process and crush strength value is not measurable. Capsules are deformed and cannot burst when press on them. Gellan-including capsule, on the contrary, still burst when pressure on the filter. Instrumentation :
  • the cigarettes containing breakable capsules are positioned on the smoking machine as standard position used for other type of analysis.
  • the adjustable parameters are set up as follows :
  • weight of each capsule 20.57 mg in which weight of the shell: 2.37 mg (11,51%) weight of the core: 18.20 mg (88.49%)
  • Example 3 Capsules are prepared according to example 1, using the following composition: Capsules 1004/H6
  • weight of each capsule 20.9 ⁇ mg in which, weight of the shell: 3.72 mg (17,74%) weight of the core: 17.24 mg (82.26%)
  • Ci 0.80 +/- 0.20 Kp
  • the capsule breaks with an audible ⁇ pop' .

Abstract

A smoking device comprising a recipient including or able to receive burning products, preferably tobacco, and a filter element connected to the recipient, wherein said filter comprises at least one breakable capsule, said capsule having a initial crush strength from 0.5 to 2.5 kp, and keeping a crush strength from 0.5 to 2.5 kp and a deformation of less than two third of its diameter prior to rupture after having been submitted to a smoking test. The invention is also relating to the capsule suitable for being incorporated in a smoking device, and to the process of manufacture of said capsule.

Description

SMOKING DEVICE INCORPORATING A BREAKABLE CAPSULE, BREAKABLE CAPSULE AND PROCESS FOR MANUFACTURING SAID CAPSULE
This invention relates to a smoking device incorporating a breakable capsule, more particularly to a filtered smoking device incorporating such a capsule in its filter element.
In the prior art, some smoking devices incorporating a breakable capsules are known. For example, US2004/0261807 describes a cigarette comprising a tobacco rod and a filter element connected to the tobacco rod, said filter having a cavity wherein a capsule is disposed. Said capsule comprises an outer gelatin shell, and an inner liquid composition including flavoring agents. The goal of US2004/0261807 is to make it possible for the smoker to break the capsule, during the combustion of the cigarette, to allow the release of the content stored in the capsule.
The gelatin capsule is a good storage capsule, but is sensitive to moisture, and may soften during the smoking time. Because of this softening, the gelatin shell loses its breakability, i.e. its ability of being ruptured under the pressure imposed by the smoker' s fingers when the smoker wants to release the content of the capsule. The ability to rupture is measured through the crush strength to be exerted to rupture the capsule and through the deformation of the capsule when pressure is applied.
It is to be noted that said crush strength must not be too high at a dry state to be suitable in such an application. As a matter of fact, a crush strength of more than 2.5 kp appears too high to achieve the expected results. Typically, the gelatin capsule of the prior art has a very important deformation when placed in smoking moisture conditions, which prevents the smoker from breaking it through a pressure of his/her fingers. There is therefore a need to build up new capsules which present a crush strength of at most 2.5kp and which keep their breakability even when exposed to the moisture brought into the filter during the smoking.
The Applicant has now found that the incorporation of selected hydrocolloids in the outer shell of the capsule, and/or the coating of the outer shell by a moisture barrier layer, result in capsules keeping their ability to rupture within a smoking device even after exposition to the moisture brought in the smoking device by the smoker. Thus, the invention relates to a smoking device comprising:
-a recipient including or able to receive burning products, preferably tobacco, a filter element which is connected to the recipient, wherein said filter comprises at least one breakable capsule, said capsule
- having a crush strength Ci of 0.5 to 2.5 kp,
- keeping a crush strength Cf of 0.5 to 2.5 kp and presenting a deformation of less than two third of its diameter prior to rupture after having been submitted to a smoking test A. (It is known from one skilled in the art that 1 kp is 9.8 N) .
The recipient may be the rod of a cigarette, wherein the burning product is tobacco.
The initial crush strength Ci of the capsule is measured before smoking, by continuously applying a load vertically onto one particle until rupture using a LLOYD - CHATILLON Digital Force Gauge, Model DFIS 50, having a capacity of 25Kg, a resolution of 0.02 Kg, and an accuracy of +/- 0,15 %. The force gauge is attached to a stand; the capsule is positioned in the middle of a plate that is moved up with a manual thread screw device. Pressure is then applied manually and the gauge records the maximum force applied at the very moment of the rupture of the capsule, (measured in Kg or in Lb) . Rupture of the capsule results in the release of the core.
The smoking test A is performed on the smoking
Machine HEINR BORGWALDT RM 4/cs. The cigarette containing breakable capsule is positioned on the smoking machine as standard position used for other type of analysis. The adjustable parameters are set up as follows :
Puff volume: 35ml (as defined in internationally standard method for smoking machine) Puff period : 60 s Puff duration : 2 s Puff sweep time : 1.8s Exhaust sweep time : Is
The test is finished when the cigarette is completely smoked or after 7 or 8 puffs.
The final crush strength Cf is measured after said smoking Test A following the same procedure as used for Ci.
The deformation of the capsule is also measured after smoking test A, just before the rupture of the capsule.
The deformation corresponds to the ratio between the capsule diameter and the width of the capsule once pressed at the very moment of the rupture. According to one embodiment of the invention, the smoking device includes a capsule having a crush strength Ci of 0.6 to 2 kp, preferably of 0.8 to 1.2 kp and keeping a crush strength Cf in the range of 0.6 to 2 kp, preferably in the range of 0.8 to 1.2 kp when submitted to the smoking test A.
According to another embodiment of the invention, the deformation of the breakable capsule within the smoking device prior to rupture, before and after its submission to the smoking test A, is less than 2 mm, preferably less than 1 mm.
According to a preferred embodiment of the invention, the capsule is such that it claps or makes an audible "pop", when ruptured. Advantageously, the shell thickness of the capsule is 10-500 microns, preferably 30-150 microns, more preferably 50-60 microns; the outer diameter of the capsule is in the range of 2 to 8 mm, preferably 3 to 5 mm, more preferably 3, 5 to 4 mm; the ratio diameter of the capsule / thickness of the shell is in the range of 10 to 100, preferably 50 to 70.
The shell comprises at least one hydrocolloid selected from gellan gum, agar, carrageenans, pullulan gum or modified starch, alone or as a mixture thereof or in combination with gelatin. Advantageously, the selected hydrocolloid is gellan, and the amount of gellan present in the shell is 1.5 to 50 % w/w of the total weight of the shell. According to an embodiment of the invention, the shell contains less than 80 % gelatin, preferably less than 75 % gelatin. In an alternative embodiment of the invention, the capsule includes a moisture barrier coating. In this embodiment, the shell of the capsule is coated with at least one moisture barrier layer comprising at least one moisture barrier agent dispersed in an organic solvent. In this embodiment, the shell can be made of any hydrocolloid, including gelatin which can even constitutes in that case the only gelling agent of the shell. But preferably, even with the presence of the hydrophobic coating, the shell comprises also an amount of gellan, or agar, or carragheenan or pullulan gum sufficient to bring a certain resistance to moisture . Advantageously, the at least one moisture barrier agent is at least one hydrophobic agent selected from those suitable for confectionery or pharmaceutical products, preferably selected from the group consisting of waxes, especially carnauba wax, candelilla wax or beeswax, carbowax, shellac (in alcoholic or aqueous solution) , ethyl cellulose or a combination thereof. More preferably, the at least one moisture barrier agent is ethyl cellulose or a mixture of ethyl cellulose and shellac.
According to another embodiment of the invention, the hydrophobic moisture barrier agent is a filmogen gelling agent, preferably gellan gum itself.
The shell may further comprise at least one plasticizer, which may be glycerol, sorbitol, maltitol, triacetine or polyethylene glycol, or another polyalcohol with plasticizing properties, and optionally one acid of the monoacid, diacid or triacid type, in particular citric acid, fumaric acid, malic acid, etc. The shell can avantageously comprises a coloring agent which renders easier the location of the capsule in the filter during the manufacturing process of filters. Fillers can also be included in the composition of the shell. The core of the capsule included within the smoking device of the invention is preferentially composed of a mixture of materials or products which are lipophilic or partially soluble in ethanol, or of molecules formulated as oil/water/oil emulsions.
The core of a breakable capsule according to the invention represents by weight 50 to 92% of said capsule, preferably 80 to 92%, more preferably 85 to 92%.
The core of the capsule may be composed of one or more lipophilic solvents conventionally used in the food, pharmaceutical or cosmetic industries. In a preferred embodiment, these lipophilic solvents may be triglycerides, especially medium chain triglycerides, and in particular triglycerides of caprylic and capric acid, or mixtures of triglycerides such as vegetable oil, olive oil, sunflower oil, corn oil, groundnut oil, grape seed oil, wheat germ oil, mineral oils and silicone oils. The amount of lipophilic solvent in the core of a capsule according to the invention is of the order of 0.01 to 90%, preferentially 25 to 75%, of the total weight of the capsule.
The core may also comprise one or more aromatic or fragrance molecules as conventionally used in the formulation of flavoring or fragrance compositions. Mention will in particular be made of aromatic, terpenic and/or sesquiterpenic hydrocarbons, and more particularly essential oils, alcohols, aldehydes, phenols, carboxylic acids in their various forms, aromatic acetals and ethers, nitrogenous heterocycles, ketones, sulfides, disulfides and mercaptans which may be aromatic or non aromatic. It may also comprise one or more molecules or extracts for cosmetic use.
The core may also comprise one or more fillers as used in aromatic emulsions. Mention will be made of dammar gum, wood resins of the ester gum type, sucrose acetate isobutyrate (SAIB) or brominated vegetable oils. The function of these weighting agents is to adjust the density of the liquid core. The core or the shell may also comprise one or more sweeteners, which may be provided in the form of a solution or suspension in ethanol. Examples of suitable sweeteners may be, but is not limited to, aspartame, saccharine, NHDC, sucralose, acesulfame, neotame, etc. The core may also comprise one or more "sensate" aromatic agents, which provide either a freshening effect or a hot effect in the mouth. Suitable freshening agents may be, but are not limited to, menthyl succinate and derivatives thereof, in particular Physcool® marketed by the Applicant. A suitable hot effect agent may be, but is not limited to, vanillyl ethyl ether.
The flavoring agents that can be solubilized in the solvent of the core of the capsule include, but are not limited to, natural or synthetic aromas and/or fragrances. Examples of suitable fragrances are fruity, confectionery, floral, sweet, woody fragrances. Examples of suitable aromas are vanilla, coffee, chocolate, cinnamon, mint.
The invention also relates to a breakable capsule suitable for being incorporated in the filter of a smoking device, which is substantially moisture stable. "Substantially moisture stable " means that the outer shell or outer coating of the capsule has the ability to retard degradation of the capsule by means of the water brought into the smoking device by a smoker. The breakable capsule according to the invention comprises a core as described hereinbefore, and a shell, said capsule presents a crush strength from 0.5 to 2.5 kp, and keeps a crush strength from 0.5 to 2.5 kp and a deformation of less than two third of its diameter after having been submitted to the smoking test A.
According to a preferred embodiment, the capsule of the invention is a seamless capsule, obtained trough a co- extrusion process.
All the characteristics described hereabove in relation with the consitution of the capsule of the smoking device also apply to the breakable capsules according to the invetion.
The co-extrusion process is a synchronous extrusion of two liquids: the external and hydrophilic liquid phase, and the internal and lipophilic liquid phase. The co- extrusion process consists of three main stages: compound drop formation, shell solidification and capsule collection. The compound drop is a sphere of the liquid fill phase inside the shell phase. The liquid fill phase is hereinafter referred to as "the core". The shell phase is hereinafter referred to as "the shell". The capsules of the invention may be produced by any suitable co-extrusion process. Preferably, the capsules are produced by an apparatus and a process as described in EP 513603, the disclosure of which is herein incorporated by reference.
According to an embodiment of the invention, after the co-extrusion step, the solidification step is performed by keeping cold the capsules in order to ensure correct gelling of the shell for example by contacting them with a cold bath. The cold bath is preferably cold oil.
The capsules may then be centrifuged in order to remove the surplus oil, optionally washed with organic solvent (such as acetone, ethyl acetate, ethanol, petroleum ether, etc.) also to remove the surplus oil, and dried. According to one embodiment of the invention, after the co-extrusion step, and eventually the solidification step, the capsules are centrifuged.
According to another embodiment of the invention, the capsules are co-extruded, centrifuged and optionally immersed into a solution or an emulsion containing a curing agent.
The curing agent may also be ethanol or any other anhydrous organic solvent, such as ethyl acetate or isopropanol, maintained at a temperature of between 0 and 25°C, more particularly between 10 and 200C.
The curing agent can alternatively or also be a bath of calcium ions, for example of calcium chloride, dicalcium phosphate or calcium sulfate or a bath of acid containing calcium ions of pH less than 5, preferably of 3 to 4. Examples of acids may be adipic acid, fumaric acid, gluconic acid or glucono-delta-lactone. The calcium ion or acid bath is preferably at a temperature of 0 to 25 °C, preferably 10 to 200C. The effect of the immersion step is to wash out the oil remaining at the periphery of the capsule, and to gradually strengthen the shell, notably through dehydration and osmotic equilibrium.
According to an embodiment of the invention, after immersion, the capsules are dried in a current or air at controlled temperature and humidity. The relative humidity of the drying air is 20% to 60%, preferably 30 to 50%; the temperature of the drying air is of 15 to 60 0C, preferably 35 to 45 "C. According to an embodiment of the invention, the capsules can be obtained using the following method: co- extrusion of the external and hydrophilic liquid phase on the one hand, and of the internal and lipophilic liquid phase and components of the core on the other hand, optionally centrifugation, optionally immersion of the capsules so obtained in a bath of calcium ions or acid, followed by drying.
According to another embodiment, the process according to the invention further comprises a coating step during which the moisture barrier outer layer is applied on the capsules. Preferably, said coating step is performed by dipping the capsules in a coating solution, or by spraying a coating solution onto the capsules. Said coating step is preferably performed after the drying step.
The capsules manufactured through the process of the invention are essentially or perfectly spherical and very homogeneous in size.
The invention is hereunder illustrated by the following examples, which should not be considered as limiting the scope of the invention.
EXAMPLES
Example 1
Two types of capsules presenting the same size are prepared by co-extrusion as disclosed in patent EP 513603. The composition of capsules according to the present invention, referenced as 1004/H11 (having less than 80 % gelatin and including gellan gum) is given in Table 1 below, and the composition of prior art capsules containing 80% gelatin, referenced 1004/C30, is given in Table 2 below. Table 1 - Capsules 1004/H11
Figure imgf000012_0001
weight of each capsule: 20.56mg in which weight of the shell: 3.68 mg (17,89' weight of the core: 16.88 mg (82.11%)
Table 2 - Capsules 1004/C30
Figure imgf000012_0002
Figure imgf000013_0001
Capsules 1004/C30 and capsules 1004/H11 present a diameter of respectively 3489 +/- 40 and 3394 +/- 35 μm.
The crush strength of the capsules is measured as follows using a LLOYD-CHATILLON Digital Force Gauge - Model DFIS 50
Capacity = 25 Kgf (501b)
Resolution = 0.02Kgf (0.051b)
Accuracy = +/- 0.15%
Sampling Rate = 1000 times per second
Methodology:
Force Gauge is attached to a stand.
The capsule is positioned in the middle of a plate that is moved up with a manual thread screw device. Pressure is then applied manually and once the capsule wall fails, the gauge records the maximum force applied prior to rupture (measure in Kg or in Ib) . Sample of 10 to 20 capsules is measured.
The results are as follows: capsules Crush strength (Kp) Standard deviation
1004/C30 4.60 1.11
1004/H11 1.70 0.26
The results are also represented on Figure 1.
Example 2
Capsules are prepared according to example 1.
Core content is about 89 % and shell content is about 11 %, corresponding to a thickness of dried shell of about 50 microns. Capsules are then dried to obtain 3.5 mm spherical capsules with a crush-strength of 1 kp. Average weight of capsule is about 20 mg.
A prior art capsule containing gelatin (ref 1004/Cl) containing 72 % gelatin and a capsule as described in example 1 above are incorporated into a cavity filter of a cigarette.
Crush strength value Ci is measured for both capsules according to the herein described method.
The obtained cigarettes are then smoked on a smoking machine (smoking test A) according to international standard procedure. Filters containing the capsules are collected and capsules are extracted from the filter to measure crush strength value Cf after smoking process.
In the case of gelatin capsules, capsules have melted into the filter during the smoking process and crush strength value is not measurable. Capsules are deformed and cannot burst when press on them. Gellan-including capsule, on the contrary, still burst when pressure on the filter. Instrumentation :
• Smoking Machine HEINR BORGWALDT RM 4/cs
The cigarettes containing breakable capsules are positioned on the smoking machine as standard position used for other type of analysis.
The adjustable parameters are set up as follows :
Puff volume : 35ml (as defined in internationally standard method for smoking machine)
Puff period : : 60 s
Puff duration : 2 s
Puff sweep time : 1.8s
Exhaust sweep time : Is
Crush strength are measured according to the procedure described in example 1 above. Capsules 1004/Cl
Figure imgf000015_0001
Figure imgf000016_0001
weight of each capsule: 20.57 mg in which weight of the shell: 2.37 mg (11,51%) weight of the core: 18.20 mg (88.49%)
The results are as follows :
Figure imgf000016_0002
After smoking, prior art capsules are no longer breakable. The results are also presented on Figure 2.
Example 3 Capsules are prepared according to example 1, using the following composition: Capsules 1004/H6
Figure imgf000017_0001
weight of each capsule: 20.9βmg in which, weight of the shell: 3.72 mg (17,74%) weight of the core: 17.24 mg (82.26%)
One capsule was introduced in a cavity of a cigarette filter. Crush strength Ci was measured according to the procedure described in example 1 above. Ci = 0.80 +/- 0.20 Kp
Then the cigarette was submitted to Test A as described in example 2 above, for 8 puffs.
After 8 puffs, the capsule breaks with an audible Λpop' .

Claims

1. A smoking device comprising:
- a recipient including or able to receive burning products, preferably tobacco, a filter element connected to the recipient , wherein said filter comprises at least one breakable capsule, said capsule having a initial crush strength Ci from 0.5 to 2.5 kp,
- keeping a crush strength Cf from 0.5 to 2.5 kp and presenting a deformation of less than two third of its diameter prior to rupture after having been submitted to the smoking test A.
2. The smoking device according to claim 1, wherein the breakable capsule is an essentially spherical seamless capsule.
3. The smoking device according to anyone of claims 1 or 2, wherein the crush strengths Ci and Cf are comprised between 0.8 to 1.2 kp.
4. The smoking device according to anyone of claims 1 to 3, wherein the deformation of the breakable capsule prior to rupture, after submission to the smoking test A, is less than 2 mm, preferably less than 1 mm.
5. The smoking device according to anyone of claims 1 to 4, wherein the capsule claps when ruptured.
6. The smoking device according to anyone of claims 1 to 5, wherein the shell thickness of the capsule is 10-500 microns, preferably 30-150 microns, more preferably 50-60 microns.
7. The smoking device according to anyone of claims 1 to 6, wherein the outer diameter of the capsule is from 2 to 8 mm, preferably 3 to 5 mm, more preferably 3.5 to 4 mm.
8. The smoking device according to anyone of claims 1 to 7, wherein the ratio (diameter of the capsule / thickness of the shell) is in the range of 10 to 100.
9. The smoking device according to anyone of claims 1 to 8, wherein the breakable capsule includes, in a core surrounded by a shell, fragrances or aromas dispersed or solubilized in a medium chain triglyceride solvent.
10. The smoking device according to anyone of claims 1 to 9, wherein the capsule comprises a core and a shell, said shell comprising at least one hydrocolloid selected from gellan gum, agar, carrageenans, pullulan gum or modified starch, alone or as a mixture thereof or in combination with gelatin.
11. The smoking device according to anyone of claims 1 to 10, wherein the hydrocolloid is gellan, and the amount of gellan present in the shell is 1.5 to 50 % w/w of the shell.
12. The smoking device according to anyone of claims 1 to 11, wherein the shell is coated with at least one moisture barrier outer layer.
13. The smoking device according to anyone of claims 1 to 9, wherein the shell comprises gelatin alone or in combination with at least one hydrocolloid selected from gellan gum, agar, carrageenans, pullulan gum or modified starch or a mixture thereof, said shell being coated with at least one moisture barrier outer layer.
14. The smoking device according to anyone of claims 12 to 13, wherein the moisture barrier layer comprises at least a hydrophobic agent suitable for confectionery or pharmaceutical products, preferably selected from the group consisting of waxes, especially carnauba wax, candelilla wax or beeswax, shellac, ethylcellulose or a combination thereof.
15. The smoking device according to anyone of claims 12 to 14, wherein the hydrophobic moisture barrier agent is a filmogen gelling agent, preferably gellan gum.
16. A breakable capsule suitable for being incorporated in the filter of a smoking device, comprising a core and a shell, said capsule: - having an initial crush strength Ci from 0.5 to 2.5 kp and keeping a crush strength Cf from 0.5 to 2.5 kp after having been submitted to the smoking test A, and presenting a deformation of less than two third of its diameter prior to rupture after having been submitted to the smoking test A.
17. A breakable capsule according to claim 16, wherein the capsule is a seamless capsule.
18. A breakable capsule according to anyone of claims 16 or 17, wherein the capsule comprises a core and a shell, said shell comprising at least one hydrocolloid selected from gellan gum, agar, carraghenan, or modified starch, alone or as a mixture thereof or in combination with gelatin.
19. A breakable capsule according to claim 18, wherein the hydrocolloid is gellan, and the amount of gellan present in the shell is 1.5 to 50 % w/w of the shell.
20. A breakable capsule according to anyone of claims 16 to 19, wherein the capsule comprises a core and a shell, said shell being coated with at least one moisture barrier outer layer.
21. A breakable capsule according to anyone of claims 16 or 17, wherein the shell comprises gelatin alone or in combination with at least one hydrocolloid selected from gellan gum, agar, carraghenan, or modified starch or a mixture thereof, said shell being coated with at least one moisture barrier outer layer.
22. A breakable seamless capsule according to claim 21, wherein the moisture barrier layer comprises at least a hydrophobic agent suitable for confectionery or pharmaceutical products, preferably selected from the group consisting of waxes, especially carnauba wax, candelilla wax or beeswax, shellac, ethylcellulose or a combination thereof.
23. A breakable seamless capsule according to claim 22, wherein the hydrophobic moisture barrier agent is a filmogen gelling agent, preferably gellan gum.
24. A filter for smoking device comprising at least a breakable capsule as defined in anyone of claims 16 to 23.
25. Use of a breakable capsule according to anyone of claims 16 to 23 in a smoking device.
26. Process for manufacturing a breakable capsule according to anyone of claims 16 to 23, comprising:
- co-extruding an external and hydrophilic liquid phase, and an internal and lipophilic liquid phase, in order to form a capsule constituted of a core comprising the internal and lipophilic phase and a shell comprising the external and hydrophilic phase,
- solidifying and/or gellifying the surface of the shell by keeping the capsule under cold conditions, eventually washing the so-obtained capsule with an organic solvent,
- drying the capsule, - optionally coating the obtained capsule with at least one moisture barrier outer layer.
27. Process for manufacturing a breakable capsule according to claim 26, wherein after the co-extrusion step, the capsules are centrifuged, after or before the solidication step.
28. Process for manufacturing a breakable capsule according to anyone of claims 26 or 27, comprising a further step of immersion of the capsules into an organic liquid or an emulsion containing a curing agent.
29. Process for manufacturing a breakable capsule according to claim 28, wherein the curing agent is a solution comprising bivalent ions, preferably calcium ions.
PCT/EP2005/008503 2005-06-21 2005-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule WO2006136197A1 (en)

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PCT/EP2005/008503 WO2006136197A1 (en) 2005-06-21 2005-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
ZA200711059A ZA200711059B (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
PCT/IB2006/002818 WO2007010407A2 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
US11/917,769 US8820331B2 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
KR1020167033016A KR20160138325A (en) 2005-06-21 2006-06-21 Smoking Device Incorporating a Breakable Capsule, Breakable Capsule and Process for Manufacturing Said Capsule
KR1020077030421A KR20080022127A (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
AT06808983T ATE439772T1 (en) 2005-06-21 2006-06-21 SMOKING DEVICE HAVING A CRUSHABLE CAPSULE, CRUSHABLE CAPSULE AND METHOD FOR PRODUCING SAID CAPSULE
MX2007016382A MX2007016382A (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule.
UAA200800574A UA90150C2 (en) 2005-06-21 2006-06-21 Smoking device comprising breakable capsule
AU2006271321A AU2006271321B2 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
KR1020157011182A KR101700549B1 (en) 2005-06-21 2006-06-21 Smoking Device Incorporating a Breakable Capsule, Breakable Capsule and Process for Manufacturing Said Capsule
JP2008517631A JP5616018B2 (en) 2005-06-21 2006-06-21 Smoking device incorporating a collapsible capsule, collapsible capsule, and method of manufacturing the capsule
PT06808983T PT1906775E (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
KR1020187012324A KR102315198B1 (en) 2005-06-21 2006-06-21 Smoking Device Incorporating a Breakable Capsule, Breakable Capsule and Process for Manufacturing Said Capsule
CN2006800224487A CN101203148B (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
BRPI0611577A BRPI0611577B1 (en) 2005-06-21 2006-06-21 smoking device, brittle capsule, filter for smoking device, use of a brittle capsule and process for making brittle capsules
NZ564190A NZ564190A (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
PL06808983T PL1906775T3 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
AP2007004283A AP2372A (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule.
DE602006008624T DE602006008624D1 (en) 2005-06-21 2006-06-21 SMOKING DEVICE WITH A BREAKABLE CAPSULE, BREAKABLE CAPSULE AND METHOD FOR PRODUCING SAID CAPSULE
EP06808983A EP1906775B1 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
DK06808983T DK1906775T3 (en) 2005-06-21 2006-06-21 Smoking device containing a breakable capsule, breakable capsule and a process for making the capsule
CA2612665A CA2612665C (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
SI200630467T SI1906775T1 (en) 2005-06-21 2006-06-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
RU2008102112/21A RU2415618C2 (en) 2005-06-21 2006-06-21 Smoking device with fragile capsule, fragile capsule and its production method
ES06808983T ES2331713T3 (en) 2005-06-21 2006-06-21 SMOKING DEVICE THAT INCLUDES A FRANGIBLE CAPSULE, FRANGIBLE CAPSULA AND PROCEDURE FOR MANUFACTURING THE CAPSULA.
EGPCTNA2007001411A EG26683A (en) 2005-06-21 2007-12-13 Smoking device incorporating a breakable capsule breakable capsule and process for manufacturing said capsule
HK08109879.9A HK1115783A1 (en) 2005-06-21 2008-09-05 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
CY20091101199T CY1109633T1 (en) 2005-06-21 2009-11-16 SMOKING DEVICE INCORPORATING FRAGRANCES, FRAGRANCES AND CONSTRUCTION PROCEDURE OF THIS LOGIC
US14/058,746 US9339060B2 (en) 2005-06-21 2013-10-21 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule
JP2014110193A JP5731045B2 (en) 2005-06-21 2014-05-28 Disintegratable capsule, filter enclosing a disintegratable capsule, and smoking device incorporating the disintegratable capsule
JP2014227817A JP6010090B2 (en) 2005-06-21 2014-11-10 Smoking device incorporating a collapsible capsule, collapsible capsule, and method of manufacturing the capsule
US15/153,766 US10278418B2 (en) 2005-06-21 2016-05-13 Smoking device incorporating a breakable capsule, breakable capsule and process for manufacturing said capsule

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