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WO2023068213A1 - Matériau pour article d'inhalation d'arôme, article d'inhalation d'arôme de type à chauffage, et procédé de production de matériau pour article d'inhalation d'arôme - Google Patents

Matériau pour article d'inhalation d'arôme, article d'inhalation d'arôme de type à chauffage, et procédé de production de matériau pour article d'inhalation d'arôme Download PDF

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Publication number
WO2023068213A1
WO2023068213A1 PCT/JP2022/038508 JP2022038508W WO2023068213A1 WO 2023068213 A1 WO2023068213 A1 WO 2023068213A1 JP 2022038508 W JP2022038508 W JP 2022038508W WO 2023068213 A1 WO2023068213 A1 WO 2023068213A1
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WO
WIPO (PCT)
Prior art keywords
tobacco
flavor
nicotine
articles
segment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/038508
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English (en)
Japanese (ja)
Inventor
明弘 小出
公隆 打井
尚大 松田
彩香 橋本
裕介 七崎
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Japan Tobacco Inc
Original Assignee
Japan Tobacco Inc
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Filing date
Publication date
Application filed by Japan Tobacco Inc filed Critical Japan Tobacco Inc
Publication of WO2023068213A1 publication Critical patent/WO2023068213A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/10Chemical features of tobacco products or tobacco substitutes
    • A24B15/16Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B3/00Preparing tobacco in the factory
    • A24B3/14Forming reconstituted tobacco products, e.g. wrapper materials, sheets, imitation leaves, rods, cakes; Forms of such products
    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24FSMOKERS' REQUISITES; MATCH BOXES; SIMULATED SMOKING DEVICES
    • A24F40/00Electrically operated smoking devices; Component parts thereof; Manufacture thereof; Maintenance or testing thereof; Charging means specially adapted therefor
    • A24F40/20Devices using solid inhalable precursors

Definitions

  • the present invention relates to a material for flavor inhaling articles, a heating type flavor inhaling article, and a method for producing a material for flavor inhaling articles.
  • Flavor inhalation article materials that form heated flavor inhalation articles contain nicotine, and there are also materials to which menthol is added as a fragrance.
  • the material for the flavor inhalation article includes a cellulosic base, tobacco extract, and optionally a polyol as an aerosol base.
  • the temperature of a device that heats a heating type flavor inhalation article is generally 200° C. or higher, and there are many that enjoy inhaling smoke derived from polyols.
  • Patent Literature 1 discloses a heating type flavor inhaling article that heats a flavor inhaling article material based on a specific temperature profile including a temperature range of 200° C. or higher.
  • an object of the present invention is to provide a material for a heating type flavor inhaling article that can be used at a low heating temperature.
  • a material for flavor inhalation articles comprising a mixture of a cellulosic base material and nicotine.
  • the material for the flavor inhalation article is a tobacco sheet for a non-combustion heating type flavor inhaler, and the tobacco sheet is a cellulosic base material, and the cumulative 90% particles in a volume-based particle size distribution measured by a dry laser diffraction method.
  • the material for flavor inhaling articles according to aspect 1 comprising tobacco powder having a diameter (D90) of 200 ⁇ m or more.
  • Aspect 3 The material for flavor inhaling articles according to aspect 2, which has a density of 1.0 g/cm 3 or less.
  • a tobacco-containing segment comprising the material for flavor inhalation articles according to any one of aspects 1 to 3,
  • a non-combustion heated flavor inhaler comprising:
  • Aspect 5 A non-combustion heating flavor inhaler according to aspect 4; a heating device for heating the tobacco-containing segment;
  • a non-combustion heated flavor suction system
  • the material for flavor inhaling articles of the present invention can be used at a low heating temperature.
  • FIG. 1 is a cross-sectional schematic diagram showing an example of a non-combustion heating smoking system.
  • FIG. 2 is a schematic cross-sectional view showing an example of a non-combustion-heating flavor inhalation article.
  • FIG. 3 is a graph showing the relationship between the nicotine filling amount and the nicotine release efficiency in the examples.
  • FIG. 4 is a graph showing the relationship between the filling amount of menthol and the release efficiency of menthol in Examples.
  • the flavor inhalation article material comprises a mixture of a cellulosic-based substrate and nicotine.
  • the method of mixing the cellulosic base material and nicotine is not particularly limited, but it is preferable to mix by supplying nicotine from the outside of the cellulosic base material.
  • nicotine is more likely to be released to the outside of the material for flavor inhalation articles than when nicotine is present inside the cellulosic base material.
  • the cellulose-based substrate may have a large number of pores on its surface (has a porous shape), and in this case, the surface of the cellulose-based substrate includes the inner portion of the pores. .
  • Cellulose-based substrates are not particularly limited, but include tobacco leaves, aged tobacco leaves, processed tobacco leaves, tobacco fillers, non-tobacco materials, or combinations of two or more of these.
  • non-tobacco-derived cellulose materials are preferable from the viewpoint of preventing impurities, but tobacco-derived cellulose is also acceptable as long as it contains few impurities.
  • tobacco leaf is a general term for harvested tobacco leaves before ripening, which will be described later.
  • One mode of aging includes curing.
  • aged tobacco leaves before being processed into various forms used in tobacco products are referred to as “aged tobacco leaves.” ”.
  • processed tobacco leaves are referred to as “processed tobacco leaves”.
  • tobacco in which matured tobacco leaves are chopped into a predetermined size
  • tobacco sheet obtained by molding a composition containing matured tobacco leaves pulverized to a predetermined particle size (hereinafter also referred to as "tobacco fine powder") into a sheet shape
  • tobacco fine powder a composition containing matured tobacco leaves pulverized to a predetermined particle size
  • Mention may also be made of "tobacco granules” obtained by molding into granular form.
  • tobacco powder is also one form of processed tobacco leaves.
  • Tobacco filling refers to a material filled with processed tobacco leaves in a predetermined manner.
  • "Filled material” is the object into which the processed tobacco leaves are filled and is a part of the tobacco product.
  • the stuff to be filled include, but are not limited to, a roll of paper rolled into a cylinder, a container having an air inlet and an air outlet, and the like.
  • the processed tobacco leaves are wrapped in wrapping paper so that the processed tobacco leaves are on the inside (hereinafter also referred to as "tobacco rod”).
  • a mode in which processed tobacco leaves are filled into a flow path of a container having an air inlet and an air outlet hereinafter also referred to as a "tobacco cartridge"
  • Tobacco fillings include tobacco fillings composed of shredded tobacco filled in a material to be filled (hereinafter also referred to as "first tobacco filling"), and tobaccos composed of tobacco sheets filled in a material to be filled. Fillings (hereinafter also referred to as “second tobacco fillings”), tobacco fillings composed of tobacco granules filled in a filling material (hereinafter also referred to as “third tobacco fillings”), etc. be done.
  • Non-tobacco materials include plant roots (including scales (bulbs), tuberous roots (potatoes), bulbs, etc.), stems, tubers, skins (including stem bark, bark, etc.), leaves, flowers (petals, pistils, etc.). , stamens, etc.), seeds, or tree trunks and branches.
  • the content of the cellulosic base material with respect to the entire material for flavor inhaling articles is not particularly limited, but from the viewpoint of shape stability, it is preferably 0.1 to 80% by weight, more preferably 1 to 75% by weight, and 5 to 50% by weight. Weight percent is most preferred.
  • Nicotine is not particularly limited, but can be selected from the group consisting of synthetic nicotine, isolated nicotine, and combinations thereof.
  • the content of nicotine in the entire material for flavor inhalation articles is not particularly limited, but from the viewpoint of nicotine concentration in general cigarettes, the lower limit is preferably 2% by weight or more, and the upper limit is 10% by weight. 8% by weight or less, or 7% by weight or less.
  • the numerical range of the nicotine content can be applied to the content of nicotine added from the outside, the content of nicotine derived from tobacco, or the sum of these contents.
  • the material for flavor inhaling articles can further include menthol.
  • menthol By further including menthol in the material for flavor inhaling articles, a refreshing and cooling sensation can be obtained.
  • the content of menthol in the entire flavor inhaling article material is not particularly limited, but from the viewpoint of the concentration in general tobacco products, the lower limit is 6% by weight or more.
  • the upper limit may be 25% by weight or less, 23% by weight or less, or 20% by weight or less.
  • the material for flavor inhaling articles can further contain myristic acid, palmitic acid, or a mixture thereof as other components.
  • the form of the material for flavor inhalation articles is not particularly limited, but it can be granules or sheets (tobacco granules or tobacco sheets), and among these, granules are preferable from the viewpoint of stabilizing the filling weight. Further, since it is preferable to use a raw material derived from tobacco as the cellulosic base material, the material for flavor inhalation articles is more preferably tobacco granules or tobacco sheets, and particularly preferably tobacco granules. These will be described in detail below.
  • tobacco granules are obtained by molding a composition containing aged tobacco leaves into granules.
  • the method of forming tobacco granules is not particularly limited, but for example, tobacco powder, nicotine, a flavor development aid, a binder, and optionally an aerosol-generating base material and a flavoring agent are mixed, water is added to the mixture, and the mixture is kneaded.
  • the obtained kneaded product is granulated (long columnar) with a wet extrusion granulator, and then granulated into a short columnar or spherical shape.
  • Tobacco granules contain both nicotine from the tobacco-derived material and added nicotine.
  • extrusion granulation it is preferred to extrude the kneaded material at ambient temperature and at a pressure of 2 kN or more. Due to this high-pressure extrusion, the temperature of the kneaded material at the outlet of the extrusion granulator instantaneously rises sharply from the ambient temperature to, for example, 90° C. to 100° C., and 2 to 4% by weight of water and volatile components evaporate. . Therefore, the amount of water to be blended for making the kneaded product can be used in an amount larger than the desired water content in the final tobacco granules by the amount of evaporation described above. Tobacco granules obtained by extrusion granulation may be further dried for moisture adjustment, if necessary.
  • the loss on drying of tobacco granules obtained by extrusion granulation is measured, and if it is higher than the desired loss on drying (for example, 5% by weight or more and 17% by weight or less), tobacco is added to obtain the desired loss on drying.
  • Granules may be further dried.
  • the drying conditions (temperature and time) for obtaining the desired loss on drying should be determined in advance and set based on the drying conditions (temperature and time) required to reduce the loss on drying by a predetermined value. can be done.
  • the tobacco sheet is obtained by forming a composition containing aged tobacco leaves and the like into a sheet shape.
  • the aged tobacco leaf used for the tobacco sheet is not particularly limited, but examples thereof include those that have been deboned and separated into lamina and backbone.
  • sheet refers to a shape having a pair of substantially parallel main surfaces and side surfaces.
  • the method of forming the tobacco sheet is not particularly limited.
  • the resulting kneaded product can be molded by a known method such as a papermaking method, a casting method, a rolling method, or the like.
  • Various tobacco sheets formed by such a method are disclosed in detail in "Encyclopedia of Tobacco, Tobacco Research Center, March 31, 2009".
  • the particle size of the granules is not particularly limited, but from the viewpoint of improving the release efficiency of nicotine and/or menthol, which will be described later, it is preferably 250 ⁇ m or more, and 250 to 850 ⁇ m. More preferably, 250-500 ⁇ m is most preferable.
  • the average particle size (D50) of the granules is not limited to, but is preferably 250 to 450 ⁇ m, more preferably 250 to 400 ⁇ m, more preferably 250 to 300 ⁇ m, from the viewpoint of improving the release efficiency of nicotine and / or menthol described later. is most preferred.
  • the particle size and average particle size (D50) of the granules can be measured based on the laser diffraction method under dry conditions using a scattering particle size distribution analyzer (Partica, manufactured by Yamato Scientific Co., Ltd.). can.
  • the surface area of each granule is not particularly limited, but from the viewpoint of improving the nicotine and/or menthol release efficiency described later, it is 0.1-2. 5 mm 2 is preferred, 0.1-1.5 mm 2 is more preferred, and 0.1-0.8 mm 2 is most preferred.
  • the surface area of each granule can be calculated based on the following formula (1) assuming that the granule is a sphere.
  • the nicotine release efficiency per 10 suctions during heating suction at 55 ° C. of the material for flavor inhalation articles is not particularly limited, but the lower limit is preferably 0.6% or more, and The upper limit can also be 5.0% or less, 2.5% or less, or 2.1% or less.
  • the nicotine release efficiency per 10 suctions during heating suction at 70° C. of the material for flavor inhalation articles is not particularly limited, but the lower limit is preferably 1.8% or more, and The upper limit can also be 6.0% or less, 5.5% or less, or 5.0% or less.
  • the release efficiency of menthol per 10 times of heat suction at 55 ° C. of the material for flavor inhalation articles is not particularly limited, but the lower limit is preferably 4% or more, and the upper limit is can also be 15.0%, 13.0%, or 10.2%.
  • the release efficiency of menthol per 10 times of heat suction at 70 ° C. of the material for flavor inhalation articles is not particularly limited, but the lower limit is preferably 7% or more, and the upper limit is can be 20.0% or less, 18.0% or less, or 16.6% or less.
  • the total particulate matter (TPM) of the material for flavor inhalation articles when heated and inhaled at 55° C. is not particularly limited, but from the viewpoint of filling amount, it is 0.5 to 10.5. It can be 0 mg, 0.7-7.0 mg, or 0.8-5.0 mg.
  • the total particulate matter (TPM) of the material for flavor inhalation articles when heated and inhaled at 70° C. is not particularly limited, but from the viewpoint of filling amount, 0.8 to 15.0 mg, 1. It can also be 0-10.0 mg, or 1.3-7.8 mg.
  • the above 1.
  • a tobacco-derived material is used as the cellulosic base material, which is preliminarily molded into tobacco granules or tobacco sheets.
  • the finally obtained material for flavor inhalation articles can be in the form of tobacco granules or tobacco sheets.
  • Supply of nicotine from the outside of the cellulosic base material is not particularly limited, but can be carried out, for example, by spraying under a pressure condition of 0.1 MPa.
  • the pressure conditions when nicotine is supplied by spraying are not particularly limited, but are preferably 0.05 to 2.5 MPa, more preferably 0.05 to 2.0 MPa, and most preferably 1.00 to 1.50 MPa.
  • the pressure at the time of nicotine supply is within the above numerical range, nicotine can be efficiently adhered to the surface of the cellulosic substrate, and as a result, the above-mentioned nicotine and/or menthol release efficiency is further improved. can be done.
  • Flavor Inhalation Articles In some embodiments, the method described in 1. above.
  • flavor inhaling article means an inhaling article that allows the user to taste the flavor by inhaling.
  • Flavor inhaling articles can be broadly classified into burning type flavor inhaling articles typified by conventional cigarettes and non-burning type flavor inhaling articles.
  • Combustion-type flavor-inhaling articles include, for example, cigarettes, pipes, pipes, cigars, and cigarillos.
  • the non-combustion heating type flavor inhaling article may be heated by a heating device separate from the article, or may be heated by a heating device integrated with the article.
  • the non-combustion heating flavor inhalation article and the heating device are collectively referred to as a "non-combustion heating smoking system".
  • An example of a non-combustion heating smoking system will now be described with reference to FIGS. 1 and 2.
  • FIG. 1 An example of a non-combustion heating smoking system will now be described with reference to FIGS. 1 and 2.
  • FIG. 1 is a cross-sectional schematic diagram showing an example of a non-combustion heating smoking system, showing a state before the heater 12 is inserted into the smoking segment 20A of the non-combustion heating flavor inhalation article 20.
  • FIG. 1 is a cross-sectional schematic diagram showing an example of a non-combustion heating smoking system, showing a state before the heater 12 is inserted into the smoking segment 20A of the non-combustion heating flavor inhalation article 20.
  • FIG. 2 is a cross-sectional view of a non-combustion heated flavor inhalation article 20. As shown in FIG.
  • the non-combustion heating smoking system includes a non-combustion heating flavor inhalation article 20 and a heating device 10 that heats the smoking segment 20A from the inside.
  • the non-combustion heating smoking system is not limited to the configuration of FIG.
  • a heating device 10 shown in FIG. 1 includes a body 11 and a heater 12 .
  • body 11 may include a battery unit and a control unit.
  • Heater 12 which can be an electrical resistance heater, is inserted into smokable segment 20A to heat smokable segment 20A.
  • the smoking segment 20A is heated from the inside in FIG. 1, the aspect of the non-combustion heating flavor inhalation article 20 is not limited to this, and in another aspect, the smoking segment 20A is heated from the outside.
  • the heating temperature of the heating device 10 is not particularly limited, it is preferably 400°C or less, more preferably 50 to 400°C, and even more preferably 150 to 350°C.
  • the heating temperature refers to the temperature of the heater 12 of the heating device 10 .
  • the non-combustion heating type flavor inhaling article 20 (hereinafter simply referred to as "flavor inhaling article 20") has a cylindrical shape.
  • the length of the circumference of the flavor inhaling article 20 is preferably 16 mm to 27 mm, more preferably 20 mm to 26 mm, even more preferably 21 mm to 25 mm.
  • the overall length (horizontal length) of the flavor inhaling article 20 is not particularly limited, but is preferably 40 mm to 90 mm, more preferably 50 mm to 75 mm, and even more preferably 50 mm to 60 mm.
  • the flavor inhaling article 20 is composed of a smoking segment 20A, a filter portion 20C forming a mouthpiece, and a connecting portion 20B connecting them.
  • the smoking segment 20A has a cylindrical shape, and its total length (length in the axial direction) is, for example, preferably 5 to 100 mm, more preferably 10 to 50 mm, even 10 to 25 mm. More preferred.
  • the cross-sectional shape of the smoking segment 20A is not particularly limited, but may be circular, elliptical, polygonal, or the like, for example.
  • the smoking segment 20A has a smoking composition sheet or material 21 derived therefrom and a wrapper 22 wrapped around it.
  • the filter part 20C has a cylindrical shape.
  • the filter part 20C has a rod-shaped first segment 25 filled with cellulose acetate fibers and a rod-shaped second segment 26 similarly filled with cellulose acetate fibers.
  • the first segment 25 is positioned on the smoking segment 20A side.
  • the first segment 25 may have a hollow portion.
  • the second segment 26 is located on the mouthpiece side.
  • the second segment 26 is solid.
  • the first segment 25 is composed of a first filling layer (cellulose acetate fiber) 25a and an inner plug wrapper 25b wound around the first filling layer 25a.
  • the second segment 26 is composed of a second packing layer (cellulose acetate fiber) 26a and an inner plug wrapper 26b wrapped around the second packing layer 26a.
  • the first segment 25 and second segment 26 are connected by an outer plug wrapper 27 .
  • the outer plug wrapper 27 is adhered to the first segment 25 and the second segment 26 with a vinyl acetate emulsion adhesive or the like.
  • the length of the filter portion 20C is 10 to 30 mm
  • the length of the connecting portion 20B is 10 to 30 mm
  • the length of the first segment 25 is 5 to 15 mm
  • the length of the second segment 26 is 5 to 15 mm. can do.
  • the length of each of these segments is an example, and can be changed as appropriate according to manufacturability, required quality, length of smoking segment 20A, and the like.
  • the first segment 25 (center hole segment) is composed of a first filling layer 25a having one or more hollow portions and an inner plug wrapper 25b covering the first filling layer 25a.
  • the first segment 25 has the function of increasing the strength of the second segment 26 .
  • the first filling layer 25a of the first segment 25 is filled with, for example, cellulose acetate fibers at a high density.
  • a plasticizer containing triacetin is added to the cellulose acetate fibers in an amount of, for example, 6 to 20% by weight based on the weight of the cellulose acetate, and hardened.
  • the hollow portion of the first segment 25 has an inner diameter of ⁇ 1.0 to ⁇ 5.0 mm, for example.
  • the first packing layer 25a of the first segment 25 may, for example, be configured with a relatively high fiber packing density, or have a fiber packing density equivalent to that of the second packing layer 26a of the second segment 26, which will be described later. good too. Therefore, air and aerosol flow only through the hollow portion during suction, and hardly any air or aerosol flows through the first filling layer 25a.
  • the length of the second segment 26 can be shortened and the first segment 25 can be lengthened accordingly.
  • Replacing the shortened second segment 26 with the first segment 25 is effective for increasing the delivery amount of the aerosol component. Since the first filling layer 25a of the first segment 25 is a fiber filling layer, the feeling of touch from the outside during use does not make the user feel uncomfortable.
  • the second segment 26 is composed of a second filling layer 26a and an inner plug wrapper 26b covering the second filling layer 26a.
  • the second segment 26 (filter segment) is packed with cellulose acetate fibers at a typical density and has typical aerosol component filtering performance.
  • the first segment 25 and the second segment 26 may have different filtration performances for filtering the aerosol (mainstream smoke) released from the smoking segment 20A. At least one of the first segment 25 and the second segment 26 may contain perfume.
  • the structure of the filter part 20C is arbitrary, and may be a structure having a plurality of segments as described above, or may be composed of a single segment. Alternatively, the filter section 20C may be composed of one segment. In this case, the filter section 20C may be composed of either the first segment or the second segment.
  • the connecting part 20B has a cylindrical shape.
  • the connecting portion 20B has a cylindrical paper tube 23 made of, for example, thick paper.
  • the connecting portion 20B may be filled with a cooling member for cooling the aerosol.
  • the cooling member include a sheet of a polymer such as polylactic acid, and the sheet can be folded and filled.
  • a support portion may be provided between the smoking segment 20A and the connecting portion 20B to prevent the position of the smoking segment 20A from fluctuating.
  • the support can be constructed of known materials such as center hole filters such as the first segment 25 .
  • the wrapper 28 is cylindrically wound around the smoking segment 20A, the connecting portion 20B, and the filter portion 20C to integrally connect them.
  • One surface (inner surface) of the wrapper 28 is coated with a vinyl acetate emulsion-based adhesive over the entire surface or substantially the entire surface except for the vicinity of the air hole portion 24 .
  • the air hole portion 24 has two or more through holes so as to pass through the connecting portion 20B in the thickness direction.
  • the two or more through-holes are formed so as to be radially arranged when viewed from the extension of the central axis of the flavor inhaling article 20 .
  • the ventilation hole portion 24 is provided in the connecting portion 20B, but may be provided in the filter portion 20C.
  • the two or more through holes of the ventilation hole portion 24 are arranged in a row on one circular ring at regular intervals. Alternatively, one or two rows of vent holes 24 may be arranged discontinuously or irregularly. When the user holds the mouthpiece and inhales, outside air is taken into the mainstream smoke through the ventilation hole portion 24 . However, the ventilation hole portion 24 may not be provided.
  • the heating type flavor inhaling article is the above 1.
  • a pouch containing the material for the flavor inhaling article described in section 1 above can be included.
  • the pouch is not limited, and any known pouch can be used as long as it can pack the filling, does not dissolve in water, and can permeate liquids (water, saliva, etc.) and water-soluble components in the filling.
  • non-woven pouches can be used.
  • Materials for the pouch include, for example, cellulose-based nonwoven fabrics, and commercially available nonwoven fabrics may be used.
  • a pouch product can be produced by forming a sheet made of such a material into a bag shape, filling the bag with a filler, and sealing the bag by means of heat sealing or the like.
  • the basis weight of the sheet is not particularly limited, and is usually 12 gsm or more and 54 gsm or less, preferably 24 gsm or more and 30 gsm or less.
  • the thickness of the sheet is not particularly limited, and is usually 100 ⁇ m or more and 300 ⁇ m or less, preferably 175 ⁇ m or more and 215 ⁇ m or less.
  • At least one of the inner and outer surfaces of the pouch may be partially coated with a water-repellent material.
  • a water-repellent fluorine-based resin is suitable as the water-repellent material.
  • this type of water-repellent fluorine-based resin includes Asahi Guard (registered trademark) manufactured by Asahi Glass Co., Ltd.
  • Water-repellent fluorine-based resins are applied to packaging materials for foods and products containing oils and fats, such as confectionery, dairy products, side dishes, fast food, and pet food. Therefore, this type of water-repellent fluororesin is safe even when applied to pouches placed in the oral cavity.
  • the water-repellent material is not limited to the fluorine-based resin, and may be, for example, a material having a water-repellent action such as a paraffin resin, a silicon-based resin, or an epoxy-based resin.
  • the non-combustion heating type flavor inhaler can include a tobacco-containing segment filled with tobacco sheets or the like, a cooling segment, and a filter segment.
  • Flavor inhaler is synonymous with flavor inhaling article and both are used interchangeably.
  • the axial length of the tobacco-containing segment of the non-combustion-heating flavor inhaler is generally shorter than the axial length of the tobacco-containing segment of the normal combustion-type flavor inhaler in relation to the heater. Therefore, in the non-combustion heating type flavor inhaler, a large amount of tobacco sheets are filled in the short tobacco-containing segments in order to secure the amount of aerosol generated during heating.
  • non-combustion heating type flavor inhalers In order to fill a large amount of tobacco sheets in a short section, non-combustion heating type flavor inhalers usually use tobacco sheets with low swelling, that is, high density tobacco sheets.
  • the swelling property is a value indicating the volume of a tobacco sheet having a predetermined weight when notches are compressed under a constant pressure for a certain period of time.
  • the inventors of the present invention believe that if a tobacco sheet with low swelling (high density) is used, the total heat capacity of the tobacco-containing segment increases. It was found that the tobacco sheet filled in the tobacco-containing segment did not contribute sufficiently to aerosol generation, depending on the method and heater capacity. In order to solve this problem, it is conceivable to reduce the total heat capacity of the tobacco-containing segment.
  • the present inventors (1) reduce the specific heat of the tobacco raw material contained in the tobacco sheet, and (2) use a highly bulky (low-density) tobacco sheet. I considered using it.
  • the specific heat of the tobacco raw material it is difficult to reduce the specific heat of the tobacco raw material itself, so it was considered effective to reduce the total heat capacity of the tobacco-containing segment by (2). Therefore, as a preferred first embodiment, a mode in which the material for flavor inhalation articles is a highly bulky (low density) tobacco sheet suitable for use in non-combustion heating type flavor inhalers will be described below.
  • tobacco sheet for non-combustion heating type flavor inhaler The tobacco sheet for a non-combustion heating type flavor inhaler according to the present embodiment (hereinafter also referred to as "tobacco sheet”) has a cellulosic base material with a cumulative volume-based particle size distribution measured by a dry laser diffraction method of 90%. Tobacco powder with a particle size (D90) of 200 ⁇ m or more is included.
  • the tobacco sheet according to the present embodiment since the D90 of the tobacco powder measured by the dry laser diffraction method is 200 ⁇ m or more, the gaps between the tobacco powders in the tobacco sheet are large, and the gaps contribute to the bulkiness of the tobacco sheet. presumed to have contributed to the improvement.
  • the tobacco sheet according to the present embodiment preferably further contains an aerosol-generating base material and a molding agent. By setting the blending ratio of these materials within a predetermined range, the swelling property of the tobacco sheet is further improved.
  • the tobacco powder contained in the tobacco sheet according to the present embodiment is one of the aforementioned cellulosic base materials, and contains tobacco-derived cellulose.
  • tobacco-derived cellulose include tobacco leaves, aged tobacco leaves, processed tobacco leaves, tobacco fillers, and the like, as described above. These may be used alone or in combination of two or more. By chopping these into a predetermined size, they can be used as tobacco powder.
  • the cumulative 90% particle size (D90) in the volume-based particle size distribution measured by the dry laser diffraction method is 200 ⁇ m or more, preferably 350 ⁇ m or more, and 500 ⁇ m or more. is more preferred.
  • the upper limit of the range of D90 is not particularly limited, it can be, for example, 2000 ⁇ m or less.
  • the cumulative 50% particle size (D50) in the volume-based particle size distribution measured by the dry laser diffraction method is 40 ⁇ m or more from the viewpoint of further improving the swelling property of the tobacco sheet. , more preferably 100 ⁇ m or more, and even more preferably 200 ⁇ m or more.
  • the upper limit of the range of D50 is not particularly limited, it can be, for example, 1000 ⁇ m or less.
  • D90 and D50 can be measured by a dry laser diffraction method using, for example, Mastersizer (trade name, manufactured by Spectris Co., Ltd., Malvern Panalytical Division).
  • the ratio of tobacco powder contained in 100% by weight of the tobacco sheet is preferably 45-95% by weight.
  • a sufficient tobacco aroma can be generated during heating.
  • by setting the tobacco powder content to 95% by weight or less a sufficient amount of the aerosol-generating base material and molding agent can be contained.
  • the tobacco powder content is more preferably 50 to 93% by weight, even more preferably 55 to 90% by weight, and particularly preferably 60 to 88% by weight.
  • a nicotine-containing tobacco extract may be used as nicotine.
  • the tobacco extract for example, leaf tobacco is crushed, mixed and stirred with a solvent such as water to extract a water-soluble component from the leaf tobacco, and the resulting water extract is dried under reduced pressure and concentrated. Tobacco extract obtained in.
  • the tobacco sheet according to this embodiment preferably further contains an aerosol-generating substrate.
  • Aerosol-forming substrates include, for example, glycerin, propylene glycol, 1,3-butanediol, and the like. These may be used alone or in combination of two or more.
  • the ratio of the aerosol-generating base material contained in 100% by weight of the tobacco sheet is preferably 4 to 50% by weight.
  • the proportion of the aerosol-generating base material is 4% by weight or more, sufficient aerosol can be generated upon heating from the viewpoint of quantity.
  • the proportion of the aerosol-generating base material is 50% by weight or less, sufficient aerosol can be generated during heating from the viewpoint of heat capacity.
  • the proportion of the aerosol-generating substrate is more preferably 6-40% by weight, even more preferably 8-30% by weight, and particularly preferably 10-20% by weight.
  • the tobacco sheet according to the present embodiment preferably further contains a molding agent from the viewpoint of shape retention.
  • Molding agents are one type of the aforementioned binders. Molding agents include, for example, polysaccharides, proteins, synthetic polymers and the like. These may be used alone or in combination of two or more. Examples of polysaccharides include cellulose derivatives and naturally occurring polysaccharides.
  • Cellulose derivatives include, for example, cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, benzylcellulose, tritylcellulose, cyanoethylcellulose, carboxymethylcellulose, carboxyethylcellulose, aminoethylcellulose; Organic acid esters such as cellulose, cellulose formate, cellulose propionate, cellulose butyrate, cellulose benzoate, cellulose phthalate, and tosyl cellulose; and inorganic acid esters such as cellulose nitrate, cellulose sulfate, cellulose phosphate, and cellulose xanthate. be done.
  • cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, benzylcellulose, tritylcellulose
  • Naturally-derived polysaccharides include guar gum, tara gum, roasted bean gum, tamarind seed gum, pectin, arabic gum, tragacanth gum, karaya gum, gutti gum, arabinogalactan, amaseed gum, cascha gum, psyllium seed gum, and mugwort seed gum.
  • plant-derived polysaccharides agar, alginic acid, propylene glycol alginate, furcelleran, algae-derived polysaccharides such as fukuronori extract; xanthan gum, gellan gum, curdlan, pullulan, Agrobacterium succinoglycan, welan gum, macro Microorganism-derived polysaccharides such as homopsis gum and rhamzan gum; crustacean-derived polysaccharides such as chitin, chitosan, and glucosamine; and starches such as starch, sodium starch glycolate, pregelatinized starch, and dextrin.
  • proteins examples include grain proteins such as wheat gluten and rye gluten.
  • Synthetic polymers include, for example, polyphosphoric acid, sodium polyacrylate, polyvinylpyrrolidone, and the like.
  • the proportion of the molding agent contained in 100% by weight of the tobacco sheet is preferably 0.1 to 15% by weight.
  • the ratio of the molding agent is 0.1% by weight or more, the raw material mixture can be molded into a sheet. Further, since the ratio of the molding agent is 15% by weight or less, it is possible to sufficiently use other raw materials for securing the functions required for the tobacco-containing segment of the non-combustion heating type flavor inhaler.
  • the ratio of the molding agent is more preferably 0.2 to 13% by weight, even more preferably 0.5 to 12% by weight, and particularly preferably 1 to 10% by weight.
  • the tobacco sheet according to this embodiment may further contain a reinforcing agent from the viewpoint of further improving physical properties.
  • reinforcing agents include fibrous substances such as fibrous pulp, insoluble fibers and fibrous synthetic cellulose, and liquid substances such as pectin suspension having a surface coating function that forms a film when dried. These may be used alone or in combination of two or more.
  • the ratio of the reinforcing agent contained in 100% by weight of the tobacco sheet is preferably 4 to 60% by weight. Within this range, other raw materials can be sufficiently used to secure the functions required for the tobacco-containing segment of the non-combustion-heating flavor inhaler.
  • the ratio of the reinforcing agent is more preferably 4.5 to 55% by weight, more preferably 5 to 50% by weight.
  • the tobacco sheet according to this embodiment may further contain a humectant from the viewpoint of maintaining quality.
  • moisturizing agents include sugar alcohols such as sorbitol, erythritol, xylitol, maltitol, lactitol, mannitol, and reduced maltose starch syrup. These may be used alone or in combination of two or more.
  • the ratio of the humectant contained in 100% by weight of the tobacco sheet is preferably 1 to 15% by weight. Within this range, other raw materials can be sufficiently used to secure the functions required for the tobacco-containing segment of the non-combustion-heating flavor inhaler.
  • the ratio of the moisturizing agent is more preferably 2 to 12% by weight, more preferably 3 to 10% by weight.
  • the tobacco sheet according to the present embodiment may contain a flavoring agent such as a flavoring agent and a flavoring agent, and a coloring agent, if necessary. , wetting agents, preservatives, diluents such as inorganic substances, and the like.
  • the tobacco sheet according to the present embodiment has a swelling property of 190 cc/100 g or more.
  • the swelling property is 190 cc/100 g or more, the total heat capacity of the tobacco-containing segment of the non-combustion heating type flavor inhaler can be sufficiently reduced, and the tobacco sheet filled in the tobacco-containing segment is generated by aerosol generation. be able to contribute.
  • the swelling property is more preferably 210 cc/100 g or more, more preferably 230 cc/100 g or more.
  • the upper limit of the swelling range is not particularly limited, it can be, for example, 800 cc/100 g or less.
  • the swelling property was measured by cutting a tobacco sheet into a size of 0.8 mm x 9.5 mm, leaving it in a conditioned room at 22°C and 60% for 48 hours, and measuring DD-60A (trade name, manufactured by Borgwald). ) is the value measured by The measurement is carried out by placing 15 g of cut tobacco sheets in a cylindrical container with an inner diameter of 60 mm and compressing the container with a load of 3 kg for 30 seconds to obtain the volume.
  • the “tobacco sheet” is formed by forming a tobacco sheet component such as tobacco powder into a sheet shape.
  • sheet refers to a shape having a pair of substantially parallel main surfaces and side surfaces.
  • the length and width of the tobacco sheet are not particularly limited, and can be appropriately adjusted according to the manner of filling.
  • the thickness of the tobacco sheet is not particularly limited, but is preferably 100 to 1000 ⁇ m, more preferably 150 to 600 ⁇ m, in terms of heat transfer efficiency and strength.
  • the tobacco sheet according to this embodiment can be produced by a known method such as a rolling method or a casting method.
  • a known method such as a rolling method or a casting method.
  • Various tobacco sheets manufactured by such a method are disclosed in detail in "Encyclopedia of Tobacco, Tobacco Research Center, March 31, 2009".
  • Examples of methods for producing tobacco sheets by rolling include methods including the following steps. (1) Mixing water, tobacco powder as a cellulosic base material, an aerosol-generating base material, a molding agent, and a reinforcing agent to obtain a mixture. (2) A step of rolling the mixture by putting it into rolling rollers. (3) A step of drying the rolled product with a dryer. When a tobacco sheet is produced by this method, the surface of the pressure roller may be heated or cooled, and the rotation speed of the pressure roller may be adjusted depending on the purpose. Also, the interval between the rolling rollers may be adjusted. One or more rolling rollers can be used to obtain tobacco sheets of desired basis weight. Between steps (1) and (2), between (2) and (3), or after (3), the nicotine is externally supplied to the cellulosic substrate to at least partially A step of applying to the surface of the cellulosic base material may be provided.
  • Examples of methods for producing tobacco sheets by casting include methods including the following steps. (1) Mixing water, tobacco powder as a cellulosic base material, an aerosol-generating base material, a molding agent, and pulp to obtain a mixture. (2) A step of thinly spreading (casting) the mixture and drying to form a tobacco sheet.
  • a slurry obtained by mixing water, tobacco powder, an aerosol-generating base material, a molding agent, and pulp is irradiated with ultraviolet rays or X-rays to remove some components such as nitrosamines. You may add the process of removing. Between the steps (1) and (2) or after (2), the nicotine is supplied from the outside of the cellulosic substrate and at least part of it is applied to the surface of the cellulosic substrate. You may provide a process.
  • the resulting kneaded product is put into a wet extrusion granulator (TDG-80A-1, manufactured by Dalton Co., Ltd.) and granulated into long columns under the conditions of pressure: 250 kN and temperature: 80 ° C., and then spherically. After sizing, tobacco granules (spherical) (particle size: 250-500 ⁇ m, average particle size (D50): 352 ⁇ m) were obtained.
  • TDG-80A-1 wet extrusion granulator
  • Tobacco granules (spherical) (particle size: 500 to 850 ⁇ m, average particle size (D50): 643 ⁇ m) were prepared in the same manner as described above, except that the granulation conditions of the wet extrusion granulator were changed to pressure: 200 kN and temperature: 75°C. ).
  • the particle size of the above granules was dried at 100° C. for 2 hours, and then measured by laser diffraction under dry conditions using a scattering particle size distribution analyzer (Partica, manufactured by Yamato Scientific Co., Ltd.). .
  • each tobacco granule obtained as described above was sprayed with nicotine (( -)-nicotine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): a solution of 1 g dissolved in 10 g of water, and menthol (l-menthol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 10 g of propylene glycol (PG) and 10 g
  • nicotine (( -)-nicotine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): a solution of 1 g dissolved in 10 g of water
  • menthol l-menthol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • PG propylene glycol
  • tobacco granules A particle size 250-500 ⁇ m, average particle size (D50) 352 ⁇ m)
  • tobacco granules B 2.125 mg nicotine and 6.584 mg menthol per 100 mg of tobacco attached to its surface Granules (with respect to the total tobacco granules, the nicotine content and menthol content are 2.125% by weight and 6.584% by weight, respectively, particle size 500 to 850 ⁇ m, average particle size (D50) 643 ⁇ m) (hereinafter “tobacco granules B ) was obtained.
  • the surface area per tobacco granules A and B is calculated to be 0.196 to 0.785 mm 2 (average value 0.442 mm 2 ) and 0.785 to 2.270 mm 2 (average value 1.431 mm 2 ).
  • a cylindrical body containing tobacco granules was externally heated by a heater (set temperature: 55° C. or 70° C.) to generate steam and aerosol, and the generated steam and aerosol were inhaled with a smoking device.
  • a heater set temperature: 55° C. or 70° C.
  • 1 puff was 55 ml/2 seconds (1 puff is an interval of 30 seconds, i.e., suction for 2 seconds and waiting for 28 seconds), and a total of 10 puffs were performed.
  • the amount of nicotine and menthol collected by the glass fiber filter was quantified to obtain the amount of nicotine or menthol collected (inhaled amount) per 10 puffs.
  • the quantification was carried out by extracting the collected components with 10 ml of isopropanol (IPA) as an extraction solvent with shaking at 200 rpm for 20 minutes, and subjecting the resulting extract to GC analysis under the following conditions.
  • IPA isopropanol
  • the weight of the glass fiber filter before smoking is subtracted from the weight of the glass fiber filter after smoking to calculate the difference in weight of the glass fiber filter before and after smoking, and the weight difference is transferred to the vapor and aerosol inhaled by the smoking device. It is the amount of total particulate matter (TPM) contained.
  • TPM total particulate matter
  • the ratio of the amount captured per 10 puffs to the filling amount of nicotine or menthol was calculated. The results obtained are shown in Table 1 and FIGS.
  • the materials for flavor inhaling articles of Examples 1 to 12 are materials for flavor inhaling articles obtained by mixing a cellulosic base material and nicotine. From the results in Table 1 and FIGS. 3 and 4, the materials for flavor inhalation articles of Examples 1 to 12 were heated to 70° C., which is lower than the conventional heating temperature of 200° C. or higher. The nicotine release efficiency was 1.8% or higher, indicating that nicotine is easily released. In addition, the materials for flavor inhalation articles of Examples 1 to 12 have a menthol release efficiency of 7% or more per 10 inhalations even when the heating temperature is as low as 70°C, indicating that menthol is easily released. have understood.
  • the materials for flavor inhalation articles of Examples 1 to 12 had a nicotine release efficiency of 0.6% or more per 10 inhalations even when the heating temperature was further lowered from 70°C to an extremely low temperature of 55°C. , and it was found that nicotine is still easily released.
  • the materials for flavor inhalation articles of Examples 1 to 12 had a menthol release efficiency of 4% or more per 10 inhalations, even when the heating temperature was set to an extremely low temperature of 55°C, and menthol is still easily released. I understand.
  • the materials for flavor inhalation articles of Examples 1 to 12 were formed by supplying nicotine and menthol from the outside of tobacco granules, nicotine and menthol were formed on the surface of the material for flavor inhalation articles and on the surface. It is believed that they adhere to the inside of the pores. Nicotine and menthol adhering to the surface of the material for flavor inhalation articles and the inside of the pores are closer to the external surface than nicotine, etc. existing inside due to the original ingredients of the material for flavor inhalation articles. It is thought that it is more easily released because it exists in Therefore, even when the heating temperature is low, nicotine and menthol are sufficiently released to the outside, and the release efficiency is considered to be high.
  • tobacco granules A which have a smaller particle size, have a higher nicotine release efficiency per 10 inhalations than tobacco granules B, which have a larger particle size. It was found that there is a tendency In this regard, it is considered that the total surface area of all the tobacco granules increases as the particle size of the tobacco granules decreases when the tobacco granules have the same filling amount. Such an increase in surface area is thought to increase the amount of nicotine present on the surface of the tobacco granules to be released, thereby increasing the nicotine release efficiency. Furthermore, it was found that the lower the nicotine loading, the higher the nicotine release efficiency per 10 puffs.
  • the particle size of the tobacco granules when the particle size of the tobacco granules is the same, the lower the nicotine filling amount, the thinner the nicotine layer adhering to the surface of the tobacco granules. It is believed that if the nicotine layer is thick, the nicotine below the layer is less likely to be released. On the other hand, if the nicotine layer is thin, the nicotine is more likely to be released from the entire layer, which is thought to increase the nicotine release efficiency. These trends seen for nicotine were similarly seen for menthol release efficiency. It is believed that these trends in release efficiency of menthol are caused by the same cause as menthol.
  • the material for flavor inhaling articles of the present application can be used at a low heating temperature.
  • Tobacco lamina (leaf tobacco) was dry pulverized with a Hosokawa Micron ACM machine to obtain tobacco powder.
  • Mastersizer (trade name, manufactured by Spectris Co., Ltd., Malvern Panalytical Division) was used to determine the cumulative 50% particle size (D50) and the cumulative 90% particle size distribution of the volume-based particle size distribution according to the dry laser diffraction method.
  • Particle diameters (D90) were measured to be 57 ⁇ m and 216 ⁇ m, respectively.
  • a tobacco sheet was produced by a rolling method using the tobacco powder. Specifically, 87 parts by weight of the tobacco powder, 12 parts by weight of glycerin as an aerosol-generating base material, and 1 part by weight of carboxymethyl cellulose as a molding agent were mixed and kneaded by an extruder. The kneaded product was formed into a sheet by two pairs of metal rolls and dried in a hot air circulating oven at 80° C. to obtain a tobacco sheet. The tobacco sheet was shredded to a size of 0.8 mm ⁇ 9.5 mm using a shredder.
  • the swelling properties of the shredded tobacco sheets were measured. Specifically, the cut tobacco sheets were left in a conditioning room at 22° C. and 60% for 48 hours, and then measured for swelling with DD-60A (trade name, manufactured by Borgwald). The measurement was carried out by placing 15 g of cut tobacco sheets in a cylindrical container having an inner diameter of 60 mm and compressing the container with a load of 3 kg for 30 seconds to determine the volume. Table 2 shows the results. In addition, in Table 1, the swelling property is shown as an increase rate (%) of the swelling property with respect to the standard value of the swelling property value of Reference Comparative Example 1 described later.
  • tobacco powder having a cumulative 50% particle size (D50) and a cumulative 90% particle size (D90) in the volume-based particle size distribution according to the dry laser diffraction method was 121 ⁇ m and 389 ⁇ m, respectively.
  • a tobacco sheet was produced in the same manner as in Example 1 and evaluated. Table 2 shows the results.
  • the tobacco sheets of Reference Examples 1 to 3 which are the tobacco sheets according to the present embodiment, are more expanded than the tobacco sheet of Reference Comparative Example 1, in which the D90 of the tobacco powder measured by the dry laser diffraction method is less than 200 ⁇ m. Improved bulkiness.
  • the tobacco sheets were produced by the rolling method, but when the tobacco sheets were similarly produced by the casting method, the swelling property was improved.
  • a material for flavor inhalation articles which is obtained by mixing a cellulosic base material and nicotine.
  • [5] The material for flavor inhaling articles according to any one of [1] to [4], further comprising menthol.
  • [6] The material for flavor inhaling articles according to [5], wherein the content of the menthol relative to the entire material for flavor inhaling articles is 6% by weight or more.
  • [12] The material for flavor inhalation articles according to any one of [1] to [11], which has a nicotine release efficiency of 1.8% or more per 10 inhalations with heating at 70°C.
  • a heated flavor inhalation article comprising the material for flavor inhalation articles according to any one of [1] to [13].
  • the heated flavor inhalation article according to [14] further comprising a pouch containing the material for the flavor inhalation article.
  • the heated flavor inhalation article according to [15] wherein the pouch is a non-woven fabric pouch.
  • [17] A method for producing the material for flavor inhaling articles according to any one of [1] to [13], providing the cellulosic substrate and the nicotine; and supplying the nicotine from outside the cellulosic substrate and applying at least a portion of the nicotine to the surface of the cellulosic substrate.
  • a method for producing a material for flavor inhalation articles is any one of [1] to [13], providing the cellulosic substrate and the nicotine; and supplying the nicotine from outside the cellulosic substrate and applying at least a portion of the nicotine to the surface of the cellulosic substrate.
  • the tobacco sheet for a non-combustion heating flavor inhaler according to any one of (1) to (3), further comprising an aerosol-generating substrate.
  • a non-combustion heating flavor inhaler comprising a tobacco-containing segment including the tobacco sheet for a non-combustion heating flavor inhaler according to any one of (1) to (9).
  • heating device 11 body 12 heater 20 Non-combustion heating flavor inhalation article 20A Smoking segment 20B Connection part 20C Filter part 21 smoking composition sheet or material derived therefrom 22 wrapper 23 paper tube 24 vent 25 first segment 25a first packing layer 25b inner plug wrapper 26 second segment 26a second packing layer 26b inner plug wrapper 27 outer plug rapper 28 rapper

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Tobacco Products (AREA)

Abstract

Matériau pour un article d'inhalation d'arôme, ledit matériau étant obtenu par mélange d'un matériau de base cellulosique et de nicotine.
PCT/JP2022/038508 2021-10-18 2022-10-17 Matériau pour article d'inhalation d'arôme, article d'inhalation d'arôme de type à chauffage, et procédé de production de matériau pour article d'inhalation d'arôme Ceased WO2023068213A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5279096A (en) * 1975-12-26 1977-07-02 Daicel Chem Ind Ltd Preparation of improved smoking composition
WO2020074535A1 (fr) * 2018-10-08 2020-04-16 Philip Morris Products S.A. Substrat générateur d'aérosol contenant du clou de girofle

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5279096A (en) * 1975-12-26 1977-07-02 Daicel Chem Ind Ltd Preparation of improved smoking composition
WO2020074535A1 (fr) * 2018-10-08 2020-04-16 Philip Morris Products S.A. Substrat générateur d'aérosol contenant du clou de girofle

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