WO2012066656A1 - Adsorbent-supported granules and process for production thereof, cigarette filter, and cigarette - Google Patents

Adsorbent-supported granules and process for production thereof, cigarette filter, and cigarette Download PDF

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Publication number
WO2012066656A1
WO2012066656A1 PCT/JP2010/070489 JP2010070489W WO2012066656A1 WO 2012066656 A1 WO2012066656 A1 WO 2012066656A1 JP 2010070489 W JP2010070489 W JP 2010070489W WO 2012066656 A1 WO2012066656 A1 WO 2012066656A1
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Prior art keywords
adsorbent
core material
fine
cigarette
carrying
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PCT/JP2010/070489
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French (fr)
Japanese (ja)
Inventor
朋広 小林
憲俊 藤田
正人 宮内
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日本たばこ産業株式会社
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Priority to PCT/JP2010/070489 priority Critical patent/WO2012066656A1/en
Publication of WO2012066656A1 publication Critical patent/WO2012066656A1/en

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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/327—Polymers obtained by reactions involving only carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers

Definitions

  • the present invention relates to an adsorbent-carrying granule, a production method thereof, a cigarette filter, and a cigarette.
  • the activated charcoal that adsorbs the components in the smoke during smoking is used for the cigarette charcoal filter.
  • Activated carbon uses a specific surface area of 1000 to 1100 g / m @ 2 by carbonization and activation of coconut shells and an acetone adsorption capacity of 26%, and 20-50 mg per cigarette is attached to the filter.
  • the charcoal filter containing activated carbon can adsorb and remove the vapor phase (VOC) component in the smoke, and can provide its unique taste and aroma.
  • the specific surface area of the activated carbon is increased or the amount of the activated carbon added to the filter is increased. It can be mentioned. Further, in order to increase the contact area between the activated carbon and the cigarette smoke flow, it is possible to reduce the particle size of the activated carbon.
  • a porous inorganic material (core material) is mixed with a carbonized material and an inorganic binder, and the core material is coated with the carbonized material together with the inorganic binder, followed by firing.
  • Japanese Patent Application Laid-Open No. 11-241871 has a predetermined particle size, specific surface area and JIS hardness obtained by adding a water-soluble binder to powdered activated carbon and stirring granulation, and has a high adsorption rate and can prevent scattering.
  • a granulated activated carbon for an adsorption-type refrigerator is disclosed.
  • the present invention provides, for example, an adsorbent-carrying granule that adsorbs a VOC component in smoke well and has a larger particle size than activated carbon used in current charcoal filters, and a method for producing the same.
  • the present invention also provides a cigarette filter capable of adsorbing VOC components in smoke well and reducing the airflow resistance.
  • the present invention provides a cigarette that can suppress or prevent the adsorption of flavor during storage, can adsorb the VOC component in the smoke well, and can reduce the ventilation resistance.
  • At least the surface of the non-porous core material is finer adsorbent finer than polyvinyl alcohol, and the blending ratio of polyvinyl alcohol is 6 with respect to the total amount of fine adsorbent and polyvinyl alcohol.
  • An adsorbent-carrying granule supported so as to be 7% by weight or less is provided.
  • a desired amount of a non-porous core material is placed on a rotating dish in a chamber; and the rotating dish is rotated so that the chamber inner surface and the outer peripheral edge of the rotating dish While supplying the air from below to above to cause planetary movement of the core material, spray an aqueous polyvinyl alcohol solution toward the core material, and spray finer particulate adsorbent than the core material.
  • a method for producing an adsorbent-carrying granule is provided.
  • a cigarette filter having the adsorbent-carrying granules of the first aspect.
  • a cigarette provided with the cigarette filter of the third aspect is provided.
  • FIG. 1 is a schematic view showing a centrifugal rolling granulation coating apparatus used for production of an adsorbent-carrying granule according to an embodiment.
  • FIG. 2 is a cross-sectional view showing a cigarette filter according to the embodiment.
  • FIG. 3 is a cross-sectional view showing another cigarette filter according to the embodiment.
  • FIG. 4 is a cross-sectional view showing a cigarette according to the embodiment.
  • FIG. 5 is a cross-sectional view showing another cigarette according to the embodiment.
  • FIG. 6 is a diagram showing the particle size distribution of fine-grained coal and normal coal.
  • FIG. 7 is a graph showing the initial VOC component adsorption rates of evaluation cigarettes equipped with filters containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and fine coal of Example 1-4.
  • FIG. 8 is a graph showing the adsorption rate of the VOC component after the acceleration conditions described above of the cigarette provided with the filter containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4.
  • FIG. 9 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 2-1 to 2-3, the fine coal of Example 2-4, and the normal coal of Example 2-5.
  • FIG. FIG. 10 is a graph showing the adsorption rate of the initial VOC component of the evaluation cigarette provided with the filter containing the adsorbent-carrying granules of Examples 3-1 to 3-3 and the fine coal of
  • the adsorbent-carrying granule according to the embodiment has a fine particle adsorbent finer than polyvinyl alcohol supported on at least a non-porous core material, and the blending ratio of polyvinyl alcohol is the sum of the fine particle adsorbent and polyvinyl alcohol. It is 6.7% by weight or less based on the amount.
  • At least the surface of the non-porous core material means a core material having no open pores on the surface.
  • This core material allows to have pores (closed pores, independent pores) inside.
  • a preferable core material is non-porous inside including the surface.
  • the core material is preferably hygroscopic. Examples of such core materials include granulated sugar, lactose, tri-warm sugar, fine sugar and starch.
  • the core material is preferably spherical.
  • the adsorbent-supporting granules obtained by making the core material spherical to support the fine particle adsorbent on the surface of the core material while moving the planetary planetary motion while supporting the fine particle adsorbent on the core material.
  • the sphericity can be improved. If the spherical adsorbent-carrying granules are selected with a vibration sieve, the particle size distribution can be sharpened.
  • Such adsorbent-carrying granules can improve the filter quality such as adsorption performance and ventilation resistance. It is also possible to increase the filling rate of the adsorbent-carrying granules when filling the filter cavity and to improve the quantitative accuracy of supplying the adsorbent-carrying granules when manufacturing the filter.
  • the fine-grain adsorbent adsorbs the VOC component in the smoke.
  • fine sorbents include activated carbon, hydrotalcite, zeolite, alumina, sepiolite, silica and their surface modifiers, and combinations thereof.
  • activated carbon is preferable.
  • the activated carbon preferably has a specific surface area of 1780 to 1900 m 2 / g by BET method.
  • the blending ratio of polyvinyl alcohol (PVA) By controlling the blending ratio of polyvinyl alcohol (PVA) to 6.7% by weight or less with respect to the total amount of the fine-grain adsorbent and PVA, it is possible to prevent the pores that are the adsorbing portions of the fine-grain adsorbent from being blocked by PVA. Thus, the original adsorption performance of the fine-grain adsorbent can be maintained.
  • the lower limit of the blending ratio of PVA is preferably 0.7% by weight with respect to the total amount of the fine particle adsorbent and PVA from the viewpoint of favorably adhering and supporting the fine particle adsorbent on the surface of the core material.
  • the most preferable blending ratio of PVA is 4.0 wt% or more and 6.3 wt% or less with respect to the total amount of the fine-grain adsorbent and PVA.
  • the adsorbent-carrying granule according to the embodiment is too small, the passage resistance when cigarette smoke passes is increased, and if it is too large, the amount of adhering to the filter is limited, and the adsorption performance of the VOC component in the smoke May decrease. For this reason, it is desirable that the adsorbent-carrying granules have an appropriate size, for example, a particle size of 1000 ⁇ m or less.
  • the core material serving as the core of the adsorbent-carrying granules desirably has a size corresponding to the granules, for example, a particle size of 200 to 900 ⁇ m, more preferably 600 to 900 ⁇ m.
  • the fine particle adsorbent supported on the surface of the core material desirably has a particle size of 50 to 350 ⁇ m, more preferably 75 to 350 ⁇ m in order to adsorb the VOC component in the smoke well.
  • the method for producing an adsorbent-carrying granule includes a step of placing a desired amount of a non-porous core material on a rotating plate of a chamber, a rotating plate, rotating the chamber inner surface and the rotating plate While supplying air from below to above between the outer peripheral edges of the core material to cause planetary movement of the core material, the PVA aqueous solution is sprayed toward the core material, and finer particulate adsorbent is sprayed from the core material. Then, the fine particle adsorbent is supported on the core material so that the blending ratio of PVA is 6.7% by weight or less based on the total amount of the fine particle adsorbent and PVA.
  • centrifugal rolling granulation coating apparatus In such a method for producing an adsorbent-carrying granule, a centrifugal rolling granulation coating apparatus can be used. Centrifugal rolling granulation coating apparatuses are well known in the art and can be obtained, for example, under the name of CF granulator from Freund Sangyo Co., Ltd., Japan.
  • the centrifugal rolling granulation coating apparatus 10 includes a rotating dish (rotor) 11 that rotates in the horizontal direction and a rotating dish 11 that surrounds the rotating dish 11.
  • a cylindrical fixed wall (stator) 12 is provided.
  • the upper opening of the fixed wall 12 is closed by the upper wall 13.
  • the lower opening of the fixed wall 12 is closed by the lower wall 14.
  • a space 16 is provided between the rotating dish 11 and the lower wall 15, and an air supply pipe 17 is provided on the fixed wall 12 so as to communicate with the space 16.
  • a centrifugal rolling chamber 18 is configured by the rotating dish 11 and the fixed wall portion on the upper part of the rotating dish 11.
  • the central part of the rotating dish 11 is raised in a truncated cone shape, and this raised part 31 can move the core particles near the center of the rotating dish 11 to the outer peripheral part and roll the core material on the inclined side surface. .
  • the peripheral edge of the rotating dish 11 is slightly curved upward. The rotating dish 11 is rotated by driving the motor 25 via the shaft 25a.
  • a nuclear material supply pipe (not shown) is provided in the centrifugal rolling chamber 18 through the upper portion of the fixed wall 12, and a nuclear material storage tank (not shown) installed outside the fixed wall 12.
  • the core material 19 is supplied onto the rotating dish 11 through the supply pipe.
  • a fine-particle adsorbent spraying pipe 20 is provided in the centrifugal rolling chamber 18, and the fine-grain adsorbent 21 is sprayed from the storage tank 22 of the fine-grain adsorbent 21 installed outside the fixed wall 12. Is spread on the rotating dish 11.
  • a spray nozzle 24 for spraying the aqueous PVA solution 23 onto the core material 19 on the rotating dish 11 through the upper wall 13 is provided in the centrifugal rolling chamber 18.
  • the core material 19 is placed on the rotating dish 11 from a core material supply pipe (not shown), and the rotating dish 11 is driven to rotate by the motor 25.
  • air 26 is supplied from the air supply pipe 17 into the space 16.
  • the air 26 flows into the centrifugal rolling chamber 18 through a gap 27 between the rotating dish 11 and the fixed wall 12 (slit air 26a). Due to the centrifugal force generated by the rotation of the rotating dish 11 and the action of the slit air 26 a, the core material 19 performs planetary movement (circulating flow) on the rotating dish 11.
  • a PVA aqueous solution 23 is sprayed from the spray nozzle 24 onto the nuclear material 19 in a planetary motion state, and then the fine-particle adsorbent 21 is sprayed from the spray tube 20. That is, spraying of the PVA aqueous solution 23 and spraying of the fine-grain adsorbent 21 are performed intermittently.
  • the coating temperature of PVA on the surface of the core material 19 corresponds to the temperature of the slit air 26a.
  • the PVA aqueous solution penetrates into the core material, and while the spraying of the PVA aqueous solution suppresses the excessive state of moisture on the surface of the core material, the PVA aqueous solution is applied to the core material surface.
  • the uniform adhesion of the dispersed fine particle adsorbent 21 which is uniformly large is promoted.
  • spray conditions such as the number of rotations of the rotating pan 11, the flow rate and temperature of the slit air 26a, the spray amount per spray of the PVA aqueous solution 23, and the spray interval are set so that the core materials do not aggregate. It is preferable to set.
  • the rotational speed of the rotating pan 11 is set to 100 to 1000 rpm
  • the flow rate of the slit air 26a is set to 10 to 100 NL / min
  • the temperature of the slit air 26a is set to 30 to 70 ° C.
  • the spray amount per one time of the aqueous PVA solution is set to 1.
  • the desired spray interval can be set to 0.2 to 5 parts by weight per 100 parts by weight of the core material per minute.
  • the fine particle adsorbent is PVA on each surface of the core material, and the blending ratio of PVA is 6.7% by weight with respect to the total amount of the fine particle adsorbent and PVA.
  • the granules are dried. This drying is preferably performed while the adsorbent-carrying granules are maintained in the planetary motion state described above so that the prepared adsorbent-carrying granules are not aggregated. Drying is preferably performed until the water content of the PVA carrying the fine-grain adsorbent is 1% by weight or less.
  • the pore structure of the fine-grain adsorbent (for example, activated carbon) is covered with the PVA aqueous solution, which may reduce the adsorbent adsorption performance.
  • a fine particle adsorbent (for example, activated carbon) having a minimum particle size of 50 ⁇ m, more preferably 75 ⁇ m, is used during the production of the adsorbent-carrying granules. It is desirable.
  • the upper limit particle size of the fine particle adsorbent is preferably 350 ⁇ m.
  • the cigarette filter according to the embodiment has a structure in which the aforementioned adsorbent-carrying granules are attached to a filter material.
  • cellulose acetate fiber tow can be used as the filter material.
  • a bundle of cellulose acetate fibers can be bound by treating with triacetin.
  • the cigarette filter 41 shown in FIG. 2 is a dual type.
  • One filter material 42 has a structure in which, for example, a filter material 43 formed by bundling or folding acetate fiber or non-woven fabric of pulp is wound into a cylindrical shape with an individual winding paper (not shown).
  • the other filter material 44 has a structure in which a plurality of adsorbent-carrying granules 45 are attached to the same filter material 43 as a whole and wound in a cylindrical shape with an individual web (not shown).
  • These filter materials 42 and 44 are end-butted with each other, and are wound into a cylindrical shape by a common web 46.
  • the cigarette filter 41 shown in FIG. 3 includes two filter materials 47a and 47b in which a filter material 43 formed by bundling or folding non-woven fabrics of acetate fibers or pulp, for example, is wound in a cylindrical shape with individual winding paper (not shown). ing. These filter materials 47a and 47b are arranged at a predetermined interval from each other, and a plurality of adsorbent-carrying granules 45 are filled in the cavity between the filter materials 47a and 47b. Filter members 47 a and 47 b in which the filling portion of the adsorbent-carrying granule 45 is arranged in the middle are wound in a cylindrical shape by a common web 46.
  • the cigarette according to the embodiment includes the filter described above.
  • the cigarette 51 shown in FIG. 4 abuts the end of the cigarette rod 52 and the end of the filter material 44 (attached with the adsorbent-carrying granules 45) of the cigarette filter 41 shown in FIG.
  • the cigarette rod 52 and the filter 41 are integrated by encapsulating the entire outer peripheral surface and the outer peripheral surface portion of the tobacco rod 52 in the vicinity of the butt with a chip paper 53.
  • the tobacco rod 52 is formed by enclosing a tobacco cut 54 in a cylindrical shape with a wrapping paper 55.
  • the cigarette 51 shown in FIG. 5 abuts the end of the cigarette rod 52 and the end of the filter material 47a of the cigarette filter 41 shown in FIG.
  • the outer peripheral surface portion is encapsulated with chip paper 53, and the tobacco rod 52 and the filter 41 are integrated.
  • the surface of the non-porous core material is a fine adsorbent finer than polyvinyl alcohol, and the blending ratio of the polyvinyl alcohol is that of the fine adsorbent and polyvinyl alcohol.
  • the adsorbent-carrying granules of the embodiment show excellent adsorption performance in the fine adsorbent layer on the surface of the core material by supporting the fine particle adsorbent with polyvinyl alcohol (PVA) on the surface of the core material, It has a larger particle size than activated carbon used in charcoal filters.
  • PVA polyvinyl alcohol
  • the adsorbent-supporting granule of the embodiment regulates the upper limit amount of polyvinyl alcohol as a binder, thereby suppressing the pores that are the adsorbing part of the fine adsorbent from being blocked by PVA, and the fine adsorbent It becomes possible to maintain the original adsorption performance.
  • the VOC component in the smoke can be favorably adsorbed.
  • the VOC component in the smoke can be favorably adsorbed.
  • the adsorbent-supported granules contained in the filter have a core-shell structure in which fine adsorbent is supported by PVA on the surface of the core material, and can be made larger in particle size than activated charcoal used in current charcoal filters. Ventilation resistance can be reduced.
  • the cigarette according to the embodiment includes the filter including the adsorbent-carrying granules described above, the VOC component in the smoke can be favorably adsorbed, and the particle size can be increased as compared with the activated carbon used in the current charcoal filter. Ventilation resistance during smoking can be reduced.
  • the adsorbent-carrying granules contained in the filter can be adsorbed by supporting fine adsorbent with polyvinyl alcohol (PVA) at least on the surface of the non-porous core material, that is, the core material that does not have its own adsorption performance.
  • PVA polyvinyl alcohol
  • the field can be limited to the fine sorbent layer on the surface of the core material.
  • the adsorbing ability of the entire adsorbent-supporting granule containing the core material is not expressed, and the adsorbing ability of only the fine-grain adsorbent layer is maintained, thereby exhibiting a high adsorbing ability from the surface of the known example to the entire interior.
  • Adsorption of cigarette flavor during adsorption storage like granulated activated carbon can be suppressed or prevented.
  • Pulverized coal (average particle size 14 ⁇ m, specific surface area 1780 m 2 / g by BET method), 70-200 mesh (75-212 ⁇ m sieve mesh) fine coal (coconut shell activated carbon obtained from Kuraray Chemical Co., Ltd. as an adsorbent. Prepared normal charcoal (average particle size 390 ⁇ m, specific surface area 1800 m 2 / g by BET method) with average particle size 195 ⁇ m, specific surface area 1900 m 2 / g by BET method, and 28-70 mesh (screen interval 212-600 ⁇ m) did.
  • FIG. 6 shows the particle size distribution (A) of the fine coal and the particle size distribution (B) of the normal coal. From FIG. 6, it can be seen that the fine coal has a particle size distribution of 50 to 350 ⁇ m.
  • the average particle diameter and the specific surface area by the BET method were measured by the following methods.
  • ⁇ Particle size distribution of activated carbon, average particle size measurement> The particle size distribution of the powdered activated carbon without pretreatment was measured from the measurement of laser scattering in water by HORIBA LA-920 (manufactured by HORIBA, Ltd.), and the 50% median diameter of the sphere equivalent diameter was calculated as the average particle diameter.
  • Examples 1-1 to 1-3 Using a centrifugal fluid coating device (CF granulator, CF-LABO; manufactured by Freund Sangyo Co., Ltd.), an aqueous binder solution having a concentration of 5% by weight is intermittently injected onto 100 g of granulated sugar (manufactured by Mitsui Sugar Co., Ltd., average particle size 560 ⁇ m) as a core material. Then, 15 g of the above-mentioned three kinds of activated carbon were gradually sprayed to produce adsorbent-carrying granules.
  • CF granulator CF-LABO; manufactured by Freund Sangyo Co., Ltd.
  • Examples 1-1 to 1-3 fine coal was used as activated carbon, and polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) and tamarind gum (TG) were used as binders, respectively.
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • TG tamarind gum
  • the operating conditions of the centrifugal flow coating apparatus are as follows: the slit air temperature is 55 ° C., the slit air flow rate is 20 NL / min, the rotating plate (rotor) rotational speed is 200 ppm, did.
  • the amount of binder in the adsorbent layer on the surface of the core material of the adsorbent-supported granules obtained under such conditions is shown in Table 1 below. Further, in order to prevent granulation between the adsorbent-carrying granules, the operation was continued for 5 minutes or more after the spraying of the activated carbon, and the granules were sufficiently dried. Table 1 below shows the finished water content and average particle size of the adsorbed and supported granules.
  • Example 2-1 Pulverized coal (Example 2-1), fine coal (Example 2-2), ordinary charcoal (Example 2-3) are used as the activated carbon, PVA is used as the binder, and the spraying speed and spray integration time of the binder aqueous solution are as follows.
  • Adsorbent-carrying granules were produced in the same manner as in Examples 1-1 to 1-3 except that the drying time was changed under the conditions shown in Table 1.
  • Table 1 below shows the ratio of PVA in the adsorbent layer on the surface of the core material of each adsorbent-supported granule, the finished moisture of the adsorbent-supported granule, and the average particle diameter.
  • Example 1-1 Example 1-1, except that fine coal (Example 2-2) was used as the activated carbon, PVA was used as the binder, and the drying time was changed under the conditions shown in Table 1 below for the spray rate and spray integration time of the aqueous binder solution.
  • Adsorbent-carrying granules were produced by the same method as in 1-3. Table 1 below shows the ratio of PVA in the adsorbent layer on the surface of the core material of each adsorbent-supported granule, the finished moisture of the adsorbent-supported granule, and the average particle diameter.
  • the ratio of the binder was calculated from the amount of the binder with respect to the total amount of the adsorbent (activated carbon) and the binder.
  • support granule were measured with the following method.
  • adsorbent-carrying granules were calculated using CAMSIZER (manufactured by HORIBA, Ltd.) or using an incremental-architecture type particle distribution measuring device, and the 50% median diameter of the equivalent sphere diameter was calculated as the average particle diameter.
  • the evaluation cigarette was produced according to the following method.
  • An acetate filter material without addition of triacetin having a length of 5 mm was inserted into a paper tube having an outer diameter of 7.7 mm and a length of 27 mm, and the above-described Examples 1-1 to 1-3 and Examples 2-1 to 2- 3 and the adsorbent-carrying granules obtained in Examples 3-1 to 3-3 were each inserted and filled with 30 mg of activated carbon, and then a 9 mm plasticizer-free acetate filter material was inserted to evaluate 9 types. Filter. Subsequently, the filter of the Salem Alaska menthol product was removed, and this filter was connected to one end of each evaluation filter with an adhesive tape to produce an evaluation cigarette.
  • two acetate filter materials with a length of 5 mm that are not filled with activated carbon and no plasticizer are inserted into the paper tube at a predetermined interval, and the filter of the Salem Alaska menthol product is bonded to one end of the filter for evaluation.
  • Control cigarettes were prepared by connecting with tape.
  • Ventilation Resistance Test The ventilation resistance of the filter was measured according to ISO 6565: 2002 (ISO 6565: 2002 Tobacco and tobacco product “Draw resistance of cigarettes and pressure drop of filter rods” Standard conditions and measurement).
  • Adsorption performance test of nicotine and tar in smoke under accelerated conditions An evaluation cigarette filled with granules of Examples 1-1 to 1-3 was held at a temperature of 22 ° C. and a humidity of 60% for 14 hours, and then a temperature of 55 ° C. and a humidity of 25 After repeating the operation of holding at 10% for 10 hours, it was stored for 1 week. These evaluation cigarettes after the acceleration test were subjected to the adsorption test of 2 above, and the adsorption performance of nicotine and tar in the smoke (nicotine and tar amount per cigarette after passing through the filter) was tested.
  • Table 2 below shows the ventilation resistance of these filters and the adsorption performance of nicotine and tar in low smoke.
  • Examples 1-4, 2-4, and 3-4 are evaluation cigarettes in which fine charcoal is filled in a paper tube instead of granules, and Example 2-5 is ordinary charcoal in paper tubes instead of granules. This is an example using a filled evaluation cigarette.
  • Examples 1-5, 2-6, and 2-5 are examples using control cigarettes.
  • GC was performed using an Agilent 7890 (Agilent Technologies Inc.). MSD was performed using Agilent 5975B (Agilent Technologies Inc.).
  • the adsorption rate (E i ) of the VOC component by each evaluation cigarette was obtained by the following formula by comparing the peak area of the chromatogram of the evaluation cigarette with the peak area of the chromatogram of the control cigarette.
  • E i (A i, in ⁇ A i, out ) / A i, in
  • a i, in and A i, out indicate the peak areas of the VOC component i in the smoke of the evaluation cigarette and the control cigarette, respectively.
  • FIG. 7 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4.
  • FIG. 8 shows the adsorption rate of the VOC components after the acceleration conditions described above of cigarettes equipped with filters containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4.
  • FIG. 9 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 2-1 to 2-3, the fine coal of Example 2-4, and the normal coal of Example 2-5. Indicates.
  • FIG. 10 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 3-1 to 3-3 and the fine coal of Example 3-4.
  • the adsorbent-carrying granules of Examples 1-1 to 1-3 using PVA, CMC, and TG as binders are more effective than the fine coal of Example 1-4. It can be seen that the resistance can be reduced.
  • the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder are the adsorbent-carrying examples of Examples 1-2 and 1-3 using CMC and TG as the binder.
  • the adsorption performance of nicotine and tar is higher than that of the granules, and that the adsorption performance of nicotine and tar is almost the same as that of the fine coal of Example 1-4.
  • the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder are the adsorbent-carrying granules of Examples 1-2 and 1-3 using CMC and TG as the binder. It can be seen that the adsorption performance of the VOC component is higher than that of Example 1, and that the adsorption performance of the VOC component is as high as that of the fine coal of Example 1-4 alone. As is apparent from the results of FIG.
  • the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder have a high VOC component adsorption performance equivalent to that of the fine coal of Example 1-4 alone. It can be seen that
  • Example 2-4 As is apparent from the results in Table 2, the adsorbent-carrying granules of Examples 2-1 to 2-3 using PVA as the binder and pulverized coal, fine-grained coal, and ordinary charcoal as the activated carbon were obtained in Example 2-4. It can be seen that the ventilation resistance of the filter can be reduced as compared with fine-grained charcoal alone, and high nicotine and tar adsorption performance is exhibited. As is apparent from the results of FIG. 9, the adsorbent-carrying granules of Example 2-2 using PVA as the binder and fine coal with a particle size of 50 to 350 ⁇ m as the activated carbon are equivalent to the fine coal alone of Example 2-4.
  • the adsorption performance of the VOC component in smoke with a high level of smoke is exhibited.
  • the adsorbent-carrying granules of Example 2-1 using pulverized coal as the activated carbon hardly show the adsorption performance of the VOC component in the smoke. This is presumably because the pores on the surface of the pulverized coal supported on the core material were covered with PVA.
  • the adsorbent-carrying granules of Example 2-3 carrying normal charcoal have a slightly lower adsorption performance of the VOC component in the smoke than the normal charcoal alone of Example 2-5. Since the particle size of normal charcoal is close to that of granulated sugar, which is the core material, there is no merit of supporting normal charcoal on the core material.

Abstract

The present invention provides adsorbent-supported granules which can adsorb a VOC component or the like in smoke satisfactorily and each of which has a larger grain diameter than that of active carbon that has been used in conventional charcoal filters. According to the present invention, adsorbent-supported granules can be provided, which comprise a fine particulate adsorbent that is supported on a core material through polyvinyl alcohol, wherein at least the surface of the core material is non-porous, and the fine particulate adsorbent is smaller than the core material and is supported on the core material in such a manner that the content ratio of polyvinyl alcohol becomes 6.7 wt% or less relative to the total amount of the fine particulate adsorbent and polyvinyl alcohol.

Description

吸着剤担持顆粒、その製造方法、シガレットフィルタおよびシガレットAdsorbent-carrying granules, production method thereof, cigarette filter and cigarette
　本発明は、吸着剤担持顆粒、その製造方法、シガレットフィルタおよびシガレットに関する。 The present invention relates to an adsorbent-carrying granule, a production method thereof, a cigarette filter, and a cigarette.
　シガレットのチャコールフィルタには、喫煙時の煙中の成分を吸着する活性炭が用いられている。活性炭は、ヤシガラを炭化、賦活したＢＥＴ法による比表面積が１０００から１１００ｇ／ｍ2、アセトン吸着能が２６％を使用し、フィルタにシガレット１本当たり２０～５０ｍｇ添着している。この活性炭を含むチャコールフィルタは、煙中の蒸気相（ＶＯＣ）成分を吸着、除去でき、その独特の味、香りを提供できる。 The activated charcoal that adsorbs the components in the smoke during smoking is used for the cigarette charcoal filter. Activated carbon uses a specific surface area of 1000 to 1100 g / m @ 2 by carbonization and activation of coconut shells and an acetone adsorption capacity of 26%, and 20-50 mg per cigarette is attached to the filter. The charcoal filter containing activated carbon can adsorb and remove the vapor phase (VOC) component in the smoke, and can provide its unique taste and aroma.
　このようなチャコールフィルタで煙中のＶＯＣ成分の吸着量を増大させる（煙中のＶＯＣ成分量を低減させる）には、活性炭の比表面積を増大させる、またはフィルタに添加する活性炭の量を増大させる、ことが挙げられる。さらに、活性炭とたばこ煙の気流との接触面積を増大させるには、活性炭の粒径を小さくすることが挙げられる。 In order to increase the adsorption amount of the VOC component in the smoke (reducing the VOC component amount in the smoke) with such a charcoal filter, the specific surface area of the activated carbon is increased or the amount of the activated carbon added to the filter is increased. It can be mentioned. Further, in order to increase the contact area between the activated carbon and the cigarette smoke flow, it is possible to reduce the particle size of the activated carbon.
　しかしながら、活性炭の粒径は小さいほど、煙中のＶＯＣ成分の吸着性能が向上するものの、例えばフィルタの通気抵抗が増大する等のフィルタ品質に悪影響を及ぼし、かつフィルタの製造時の取り扱いが面倒になる問題がある。 However, the smaller the particle size of the activated carbon, the better the adsorption performance of the VOC component in the smoke, but it has an adverse effect on the filter quality, for example, increases the ventilation resistance of the filter, and the handling at the time of manufacturing the filter becomes troublesome. There is a problem.
　一方、特開平１１－１５７８１７号公報には多孔質の無機物（核材）に被炭化材および無機質粘結材を混合して前記核材に被炭化材を無機質粘結材と共に被覆した後、焼成して核材の多孔に炭化物を充填した吸着作用を持つ難燃炭の製造方法が記載されている。 On the other hand, in Japanese Patent Application Laid-Open No. 11-157817, a porous inorganic material (core material) is mixed with a carbonized material and an inorganic binder, and the core material is coated with the carbonized material together with the inorganic binder, followed by firing. Thus, there is described a method for producing flame retardant coal having an adsorption action in which the core material is filled with carbides.
　特開平１１－２４１８７１号公報には、粉末活性炭に水溶性バインダを添加し、攪拌造粒した所定の粒径、比表面積およびＪＩＳ硬さを有し、吸着速度が大きく、飛散を防ぐことが可能な吸着式冷凍機用造粒活性炭が開示されている。 Japanese Patent Application Laid-Open No. 11-241871 has a predetermined particle size, specific surface area and JIS hardness obtained by adding a water-soluble binder to powdered activated carbon and stirring granulation, and has a high adsorption rate and can prevent scattering. A granulated activated carbon for an adsorption-type refrigerator is disclosed.
　前記文献の難燃炭、造粒活性炭をフィルタにそれぞれ添着し、これらのフィルタをシガレットに適用した場合、喫煙時の煙中のＶＯＣ成分を良好に吸着することが可能である。しかしながら、これらの炭は表面から内部の全体に亘って高い吸着能を持つために、パッケージに収納、保存する蔵置中にシガレットに添着した香料をも吸着して香味を低減する課題があった。 When flame retardant charcoal and granulated activated carbon of the above-mentioned literature are respectively attached to a filter and these filters are applied to a cigarette, it is possible to satisfactorily adsorb the VOC component in the smoke during smoking. However, since these charcoals have a high adsorbing ability from the surface to the entire inside, there is a problem of reducing the flavor by adsorbing the fragrance attached to the cigarette during storage in a package.
　本発明は、例えば煙中のＶＯＣ成分を良好に吸着すると共に、現行のチャコールフィルタで用いられる活性炭に比べて粒径の大きい吸着剤担持顆粒およびその製造方法を提供する。 The present invention provides, for example, an adsorbent-carrying granule that adsorbs a VOC component in smoke well and has a larger particle size than activated carbon used in current charcoal filters, and a method for producing the same.
　また、本発明は煙中のＶＯＣ成分を良好に吸着すると共に、通気抵抗を低減することが可能なシガレットフィルタを提供する。 The present invention also provides a cigarette filter capable of adsorbing VOC components in smoke well and reducing the airflow resistance.
　また、本発明は蔵置中に香味の吸着を抑制ないし防止し、かつ煙中のＶＯＣ成分を良好に吸着すると共に、通気抵抗を低減することが可能なシガレットを提供する。 In addition, the present invention provides a cigarette that can suppress or prevent the adsorption of flavor during storage, can adsorb the VOC component in the smoke well, and can reduce the ventilation resistance.
　本発明の第１態様によると、少なくとも表面が無孔の核材にそれより微細な細粒吸着剤をポリビニルアルコールでポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下になるように担持した吸着剤担持顆粒が提供される。 According to the first aspect of the present invention, at least the surface of the non-porous core material is finer adsorbent finer than polyvinyl alcohol, and the blending ratio of polyvinyl alcohol is 6 with respect to the total amount of fine adsorbent and polyvinyl alcohol. An adsorbent-carrying granule supported so as to be 7% by weight or less is provided.
　本発明の第２態様によると、チャンバ内の回転皿上に少なくとも表面が無孔の核材を所望量載置する工程；および
　前記回転皿を回転させ、前記チャンバ内面と前記回転皿の外周縁の間に空気を下から上方に向けて供給して前記核材を遊星運動させながら、前記核材に向けてポリビニルアルコール水溶液を噴霧し、前記核材より微細な細粒吸着剤を散布して前記核材に前記細粒吸着剤をポリビニルアルコールでポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下になるように担持する工程；
を含む吸着剤担持顆粒の製造方法が提供される。 According to a second aspect of the present invention, a desired amount of a non-porous core material is placed on a rotating dish in a chamber; and the rotating dish is rotated so that the chamber inner surface and the outer peripheral edge of the rotating dish While supplying the air from below to above to cause planetary movement of the core material, spray an aqueous polyvinyl alcohol solution toward the core material, and spray finer particulate adsorbent than the core material. A step of supporting the fine particle adsorbent on the core material with polyvinyl alcohol so that the blending ratio of polyvinyl alcohol is 6.7% by weight or less with respect to the total amount of the fine particle adsorbent and polyvinyl alcohol;
A method for producing an adsorbent-carrying granule is provided.
　本発明の第３態様によると、前記第１態様の吸着剤担持顆粒を有するシガレットフィルタが提供される。 According to the third aspect of the present invention, there is provided a cigarette filter having the adsorbent-carrying granules of the first aspect.
　本発明の第４態様によると、前記第３態様のシガレットフィルタを備えるシガレットが提供される。 According to the fourth aspect of the present invention, a cigarette provided with the cigarette filter of the third aspect is provided.
図１は、実施形態に係る吸着剤担持顆粒の製造に用いられる遠心転動型造粒コーティング装置を示す概略図である。FIG. 1 is a schematic view showing a centrifugal rolling granulation coating apparatus used for production of an adsorbent-carrying granule according to an embodiment. 図２は、実施形態に係るシガレットフィルタを示す断面図である。FIG. 2 is a cross-sectional view showing a cigarette filter according to the embodiment. 図３は、実施形態に係る別のシガレットフィルタを示す断面図である。FIG. 3 is a cross-sectional view showing another cigarette filter according to the embodiment. 図４は、実施形態に係るシガレットを示す断面図である。FIG. 4 is a cross-sectional view showing a cigarette according to the embodiment. 図５は、実施形態に係る別のシガレットを示す断面図である。FIG. 5 is a cross-sectional view showing another cigarette according to the embodiment. 図６は、細粒炭および通常炭の粒度分布を示す図である。FIG. 6 is a diagram showing the particle size distribution of fine-grained coal and normal coal. 図７は、例１－１～１－３の吸着剤担持顆粒、例１－４の細粒炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す図である。FIG. 7 is a graph showing the initial VOC component adsorption rates of evaluation cigarettes equipped with filters containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and fine coal of Example 1-4. 図８は、例１－１～１－３の吸着剤担持顆粒、例１－４の細粒炭を含むフィルタを備えたシガレットの前述した加速条件後のＶＯＣ成分の吸着率を示す図である。FIG. 8 is a graph showing the adsorption rate of the VOC component after the acceleration conditions described above of the cigarette provided with the filter containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4. . 図９は、例２－１～２－３の吸着剤担持顆粒、例２－４の細粒炭、例２－５の通常炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す図である。FIG. 9 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 2-1 to 2-3, the fine coal of Example 2-4, and the normal coal of Example 2-5. FIG. 図１０は、例３－１～３－３の吸着剤担持顆粒、例３－４の細粒炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す図である。FIG. 10 is a graph showing the adsorption rate of the initial VOC component of the evaluation cigarette provided with the filter containing the adsorbent-carrying granules of Examples 3-1 to 3-3 and the fine coal of Example 3-4.
　以下、本発明の実施形態に係る吸着剤担持顆粒およびその製造方法を詳細に説明する。 Hereinafter, the adsorbent-carrying granules and the manufacturing method thereof according to the embodiment of the present invention will be described in detail.
　実施形態に係る吸着剤担持顆粒は、少なくとも表面が無孔の核材にそれより微細な細粒吸着剤をポリビニルアルコールで担持し、かつポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下である。 The adsorbent-carrying granule according to the embodiment has a fine particle adsorbent finer than polyvinyl alcohol supported on at least a non-porous core material, and the blending ratio of polyvinyl alcohol is the sum of the fine particle adsorbent and polyvinyl alcohol. It is 6.7% by weight or less based on the amount.
　少なくとも表面が無孔の核材は、表面に開気孔が存在しない核材を意味する。この核材は、内部に気孔（閉気孔、独立気孔）を有することを許容する。好ましい核材は、表面を含む内部が無孔のものである。核材は吸湿性を有することが好ましい。このような核材の例は、グラニュー糖、乳糖、三温糖、上質糖および澱粉を含む。 At least the surface of the non-porous core material means a core material having no open pores on the surface. This core material allows to have pores (closed pores, independent pores) inside. A preferable core material is non-porous inside including the surface. The core material is preferably hygroscopic. Examples of such core materials include granulated sugar, lactose, tri-warm sugar, fine sugar and starch.
　核材は、球状であることが好ましい。後述するように核材への細粒吸着剤の担持は核材を遊星運動させながらその表面に細粒吸着剤を担持するために核材を球状にすることにより得られた吸着剤担持顆粒の真球度を向上できる。球状の吸着剤担持顆粒は振動篩器で選別すれば粒度分布をシャープにすることができる。このような吸着剤担持顆粒は吸着性能および通気抵抗のようなフィルタ品質を向上できる。また、フィルタのキャビティ充填時において吸着剤担持顆粒の充填率の増大およびフィルタ製造時の吸着剤担持顆粒供給の定量精度の向上を図ることが可能になる。 The core material is preferably spherical. As will be described later, the adsorbent-supporting granules obtained by making the core material spherical to support the fine particle adsorbent on the surface of the core material while moving the planetary planetary motion while supporting the fine particle adsorbent on the core material. The sphericity can be improved. If the spherical adsorbent-carrying granules are selected with a vibration sieve, the particle size distribution can be sharpened. Such adsorbent-carrying granules can improve the filter quality such as adsorption performance and ventilation resistance. It is also possible to increase the filling rate of the adsorbent-carrying granules when filling the filter cavity and to improve the quantitative accuracy of supplying the adsorbent-carrying granules when manufacturing the filter.
　細粒吸着剤は、煙中のＶＯＣ成分を吸着するものである。細粒吸着剤の例は、活性炭、ハイドロタルサイト、ゼオライト、アルミナ、セピオライト、シリカそれらの表面改質材、およびそれらの組合せを含む。これらの細粒吸着剤の中で活性炭が好ましい。活性炭は、ＢＥＴ法による比表面積が１７８０～１９００ｍ2／ｇであることが好ましい。 The fine-grain adsorbent adsorbs the VOC component in the smoke. Examples of fine sorbents include activated carbon, hydrotalcite, zeolite, alumina, sepiolite, silica and their surface modifiers, and combinations thereof. Among these fine-grain adsorbents, activated carbon is preferable. The activated carbon preferably has a specific surface area of 1780 to 1900 m 2 / g by BET method.
　ポリビニルアルコール（ＰＶＡ）の配合割合を細粒吸着剤とＰＶＡの合計量に対して６．７重量％以下にすることにより細粒吸着剤の吸着部である気孔がＰＶＡにより塞がれるのを抑制して、細粒吸着剤本来の吸着性能を維持することが可能になる。ＰＶＡの配合割合の下限値は、核材表面に細粒吸着剤を良好に接着、担持する観点から、細粒吸着剤とＰＶＡの合計量に対して０．７重量％にすることが好ましい。最も好ましいＰＶＡの配合割合は、細粒吸着剤とＰＶＡの合計量に対して４．０重量％以上６．３重量％以下である。 By controlling the blending ratio of polyvinyl alcohol (PVA) to 6.7% by weight or less with respect to the total amount of the fine-grain adsorbent and PVA, it is possible to prevent the pores that are the adsorbing portions of the fine-grain adsorbent from being blocked by PVA. Thus, the original adsorption performance of the fine-grain adsorbent can be maintained. The lower limit of the blending ratio of PVA is preferably 0.7% by weight with respect to the total amount of the fine particle adsorbent and PVA from the viewpoint of favorably adhering and supporting the fine particle adsorbent on the surface of the core material. The most preferable blending ratio of PVA is 4.0 wt% or more and 6.3 wt% or less with respect to the total amount of the fine-grain adsorbent and PVA.
　実施形態に係る吸着剤担持顆粒は、小さすぎると喫煙時のたばこ煙が通過するときの通過抵抗が増大し、大きすぎるとフィルタへの添着量が制限されて、煙中のＶＯＣ成分の吸着性能が低下するおそれがある。このため、吸着剤担持顆粒は適切な大きさ、例えば１０００μｍ以下の粒径を有することが望ましい。 If the adsorbent-carrying granule according to the embodiment is too small, the passage resistance when cigarette smoke passes is increased, and if it is too large, the amount of adhering to the filter is limited, and the adsorption performance of the VOC component in the smoke May decrease. For this reason, it is desirable that the adsorbent-carrying granules have an appropriate size, for example, a particle size of 1000 μm or less.
　吸着剤担持顆粒の核となる核材は、顆粒に対応した大きさ、例えば２００～９００μｍ、より好ましくは６００～９００μｍの粒径を有することが望ましい。 The core material serving as the core of the adsorbent-carrying granules desirably has a size corresponding to the granules, for example, a particle size of 200 to 900 μm, more preferably 600 to 900 μm.
　核材表面に担持される細粒吸着剤は、煙中のＶＯＣ成分を良好に吸着するために粒径が５０～３５０μｍ、より好ましくは７５～３５０μｍであることが望ましい。 The fine particle adsorbent supported on the surface of the core material desirably has a particle size of 50 to 350 μm, more preferably 75 to 350 μm in order to adsorb the VOC component in the smoke well.
　次に、実施形態に係る吸着剤担持顆粒の製造方法を説明する。 Next, a method for producing an adsorbent-carrying granule according to the embodiment will be described.
　実施形態に係る吸着剤担持顆粒の製造方法は、チャンバの回転皿上に少なくとも表面が無孔の核材を所望量載置する工程と、前記回転皿を回転させ、前記チャンバ内面と前記回転皿の外周縁の間に空気を下から上方に向けて供給して前記核材を遊星運動させながら、前記核材に向けてＰＶＡ水溶液を噴霧し、前記核材より微細な細粒吸着剤を散布して前記核材に前記細粒吸着剤をＰＶＡでＰＶＡの配合割合が細粒吸着剤とＰＶＡの合計量に対して６．７重量％以下になるように担持する工程を含む。 The method for producing an adsorbent-carrying granule according to the embodiment includes a step of placing a desired amount of a non-porous core material on a rotating plate of a chamber, a rotating plate, rotating the chamber inner surface and the rotating plate While supplying air from below to above between the outer peripheral edges of the core material to cause planetary movement of the core material, the PVA aqueous solution is sprayed toward the core material, and finer particulate adsorbent is sprayed from the core material. Then, the fine particle adsorbent is supported on the core material so that the blending ratio of PVA is 6.7% by weight or less based on the total amount of the fine particle adsorbent and PVA.
　このような吸着剤担持顆粒の製造方法において、遠心転動型造粒コーティング装置を用いることができる。遠心転動型造粒コーティング装置は、当該分野でよく知られており、例えば日本国のフロイント産業社からＣＦグラニュレータの名称の下で入手することができる。 In such a method for producing an adsorbent-carrying granule, a centrifugal rolling granulation coating apparatus can be used. Centrifugal rolling granulation coating apparatuses are well known in the art and can be obtained, for example, under the name of CF granulator from Freund Sangyo Co., Ltd., Japan.
　概略を述べると、図１に示すように、遠心転動型造粒コーティング装置１０は、水平方向に回転する回転皿（ロータ）１１と、回転皿１１と離間して回転皿１１を囲むように設けられた円筒状の固定壁（ステータ）１２を備える。固定壁１２の上部開口は上部壁１３により閉鎖されている。固定壁１２の下部開口は下部壁１４により閉鎖されている。回転皿１１と下部壁１５との間にはスペース１６が設けられ、固定壁１２には、このスペース１６と連通してエアー供給管１７が設けられている。回転皿１１と、回転皿１１の上部の固定壁部分とにより遠心転動室１８が構成される。回転皿１１の中央部は円錐台状に隆起しており、この隆起部３１は、回転皿１１の中心付近の核粒子を外周部に移動させ、その傾斜した側面で核材を転動させ得る。回転皿１１の周縁部は上方に向かってやや湾曲している。回転皿１１は、シャフト２５ａを介してモータ２５の駆動により回転される。 Briefly, as shown in FIG. 1, the centrifugal rolling granulation coating apparatus 10 includes a rotating dish (rotor) 11 that rotates in the horizontal direction and a rotating dish 11 that surrounds the rotating dish 11. A cylindrical fixed wall (stator) 12 is provided. The upper opening of the fixed wall 12 is closed by the upper wall 13. The lower opening of the fixed wall 12 is closed by the lower wall 14. A space 16 is provided between the rotating dish 11 and the lower wall 15, and an air supply pipe 17 is provided on the fixed wall 12 so as to communicate with the space 16. A centrifugal rolling chamber 18 is configured by the rotating dish 11 and the fixed wall portion on the upper part of the rotating dish 11. The central part of the rotating dish 11 is raised in a truncated cone shape, and this raised part 31 can move the core particles near the center of the rotating dish 11 to the outer peripheral part and roll the core material on the inclined side surface. . The peripheral edge of the rotating dish 11 is slightly curved upward. The rotating dish 11 is rotated by driving the motor 25 via the shaft 25a.
　固定壁１２の上方部分を貫通して遠心転動室１８内には、核材の供給管（図示せず）が設けられ、固定壁１２の外部に設置された核材の貯蔵タンク（図示せず）から核材１９が供給管を通して回転皿１１上に供給される。 A nuclear material supply pipe (not shown) is provided in the centrifugal rolling chamber 18 through the upper portion of the fixed wall 12, and a nuclear material storage tank (not shown) installed outside the fixed wall 12. The core material 19 is supplied onto the rotating dish 11 through the supply pipe.
　また、遠心転動室１８内には細粒吸着剤の散布管２０が設けられ、固定壁１２の外部に設置された細粒吸着剤２１の貯蔵タンク２２から細粒吸着剤２１が散布管２０を通して回転皿１１上に散布される。上部壁１３を貫通して、ＰＶＡ水溶液２３を回転皿１１上の核材１９に噴霧するための噴霧ノズル２４が遠心転動室１８内に設けられている。 Further, a fine-particle adsorbent spraying pipe 20 is provided in the centrifugal rolling chamber 18, and the fine-grain adsorbent 21 is sprayed from the storage tank 22 of the fine-grain adsorbent 21 installed outside the fixed wall 12. Is spread on the rotating dish 11. A spray nozzle 24 for spraying the aqueous PVA solution 23 onto the core material 19 on the rotating dish 11 through the upper wall 13 is provided in the centrifugal rolling chamber 18.
　図示しない核材供給管から回転皿１１上に核材１９を載せ、モータ２５により回転皿１１を回転駆動させると同時に、エアー供給管１７から、エアー２６をスペース１６内に供給する。このエアー２６は、回転皿１１と固定壁１２との間の隙間２７を通して遠心転動室１８内に流入する（スリットエアー２６ａ）。回転皿１１の回転による遠心力とスリットエアー２６ａの作用により、核材１９は回転皿１１上で遊星運動（循環流）する。この遊星運動状態にある核材１９に、噴霧ノズル２４からＰＶＡ水溶液２３を噴霧し、その後散布管２０から細粒吸着剤２１を散布する。つまり、ＰＶＡ水溶液２３の噴霧と細粒吸着剤２１の散布を間欠的に行う。核材１９表面へのＰＶＡのコーティング温度は、スリットエアー２６ａの温度に相当する。 The core material 19 is placed on the rotating dish 11 from a core material supply pipe (not shown), and the rotating dish 11 is driven to rotate by the motor 25. At the same time, air 26 is supplied from the air supply pipe 17 into the space 16. The air 26 flows into the centrifugal rolling chamber 18 through a gap 27 between the rotating dish 11 and the fixed wall 12 (slit air 26a). Due to the centrifugal force generated by the rotation of the rotating dish 11 and the action of the slit air 26 a, the core material 19 performs planetary movement (circulating flow) on the rotating dish 11. A PVA aqueous solution 23 is sprayed from the spray nozzle 24 onto the nuclear material 19 in a planetary motion state, and then the fine-particle adsorbent 21 is sprayed from the spray tube 20. That is, spraying of the PVA aqueous solution 23 and spraying of the fine-grain adsorbent 21 are performed intermittently. The coating temperature of PVA on the surface of the core material 19 corresponds to the temperature of the slit air 26a.
　実施形態において、核材１９が吸湿性を有する場合、ＰＶＡ水溶液が核材に浸透し、ＰＶＡ水溶液の噴霧中に核材表面での水分の過剰状態を抑制しながら、ＰＶＡ水溶液を核材表面に均一に多い、散布した細粒吸着剤２１の均一な付着を促進する。 In the embodiment, when the core material 19 has hygroscopicity, the PVA aqueous solution penetrates into the core material, and while the spraying of the PVA aqueous solution suppresses the excessive state of moisture on the surface of the core material, the PVA aqueous solution is applied to the core material surface. The uniform adhesion of the dispersed fine particle adsorbent 21 which is uniformly large is promoted.
　このコーティング時において、核材同士が凝集することがないように、回転皿１１の回転数、スリットエアー２６ａの流量および温度、ＰＶＡ水溶液２３の１回当たりの噴霧量、噴霧間隔等の噴霧条件を設定することが好ましい。例えば、回転皿１１の回転数を１００～１０００ｒｐｍに、スリットエアー２６ａの流量を１０～１００ＮＬ／分に、スリットエアー２６ａの温度を３０～７０℃に、ＰＶＡ水溶液の１回当たりの噴霧量を１分間当たり核材１００重量部にあたり０．２～５重量部に、所望の噴霧間隔に、それぞれ設定することができる。 At the time of coating, spray conditions such as the number of rotations of the rotating pan 11, the flow rate and temperature of the slit air 26a, the spray amount per spray of the PVA aqueous solution 23, and the spray interval are set so that the core materials do not aggregate. It is preferable to set. For example, the rotational speed of the rotating pan 11 is set to 100 to 1000 rpm, the flow rate of the slit air 26a is set to 10 to 100 NL / min, the temperature of the slit air 26a is set to 30 to 70 ° C., and the spray amount per one time of the aqueous PVA solution is set to 1. The desired spray interval can be set to 0.2 to 5 parts by weight per 100 parts by weight of the core material per minute.
　前記ＰＶＡ水溶液の噴霧および細粒吸着剤の散布により、核材のそれぞれの表面上に細粒吸着剤がＰＶＡでＰＶＡの配合割合が細粒吸着剤とＰＶＡの合計量に対して６．７重量％以下になるように付着、担持された吸着剤担持顆粒が得られる。 By spraying the PVA aqueous solution and spraying the fine particle adsorbent, the fine particle adsorbent is PVA on each surface of the core material, and the blending ratio of PVA is 6.7% by weight with respect to the total amount of the fine particle adsorbent and PVA. % Adsorbent-carrying granules adhered and supported so as to be less than or equal to%.
　前記細粒吸着剤の担持後、顆粒を乾燥する。この乾燥は、調製された吸着剤担持顆粒同士が凝集しないように、吸着剤担持顆粒を前述した遊星運動状態に維持したままで行うことが好ましい。乾燥は、細粒吸着剤を担持するＰＶＡの水分が１重量％以下となるまで行うことが好ましい。 After the fine adsorbent is supported, the granules are dried. This drying is preferably performed while the adsorbent-carrying granules are maintained in the planetary motion state described above so that the prepared adsorbent-carrying granules are not aggregated. Drying is preferably performed until the water content of the PVA carrying the fine-grain adsorbent is 1% by weight or less.
　このような吸着剤担持顆粒の製造において、ＰＶＡ水溶液により細粒吸着剤（例えば活性炭）の細孔構造が覆われ、吸着剤の吸着性能を低下するおそれがある。細粒吸着剤の細孔構造へのＰＶＡ水溶液の被覆を回避するために、吸着剤担持顆粒の製造時に細粒吸着剤（例えば活性炭）として最小粒径を５０μｍ、より好ましくは７５μｍのものを用いることが望ましい。なお、細粒吸着剤の上限粒径は３５０μｍにすることが好ましい。 In the production of such adsorbent-carrying granules, the pore structure of the fine-grain adsorbent (for example, activated carbon) is covered with the PVA aqueous solution, which may reduce the adsorbent adsorption performance. In order to avoid covering the pore structure of the fine particle adsorbent with the aqueous PVA solution, a fine particle adsorbent (for example, activated carbon) having a minimum particle size of 50 μm, more preferably 75 μm, is used during the production of the adsorbent-carrying granules. It is desirable. The upper limit particle size of the fine particle adsorbent is preferably 350 μm.
　次に、実施形態に係るシガレットフィルタを説明する。 Next, the cigarette filter according to the embodiment will be described.
　実施形態に係るシガレットフィルタはフィルタ素材に前述した吸着剤担持顆粒を添着した構造を有する。 The cigarette filter according to the embodiment has a structure in which the aforementioned adsorbent-carrying granules are attached to a filter material.
　フィルタ素材は、例えば、セルロースアセテート繊維のトウを用いることができる。セルロースアセテート繊維の束はトリアセチンで処理することにより結束できる。 For example, cellulose acetate fiber tow can be used as the filter material. A bundle of cellulose acetate fibers can be bound by treating with triacetin.
　実施形態の係るシガレットフィルタを図２、図３を参照して具体的に説明する。 The cigarette filter according to the embodiment will be specifically described with reference to FIGS.
　図２に示すシガレットフィルタ４１は、デュアルタイプでる。一方のフィルタ材４２は例えばアセテート繊維またはパルプの不織布を束ねたり、折畳んだりして成形したフィルタ素材４３を図示しない個別巻取紙で円柱状に巻いた構造を有する。他方のフィルタ材４４は同様なフィルタ素材４３全体に複数の吸着剤担持顆粒４５を添着し、図示しない個別巻取紙で円柱状に巻いた構造を有する。これらのフィルタ材４２、４４は端部を互いに突合せ、共通巻取紙４６で円柱状に巻かれている。 The cigarette filter 41 shown in FIG. 2 is a dual type. One filter material 42 has a structure in which, for example, a filter material 43 formed by bundling or folding acetate fiber or non-woven fabric of pulp is wound into a cylindrical shape with an individual winding paper (not shown). The other filter material 44 has a structure in which a plurality of adsorbent-carrying granules 45 are attached to the same filter material 43 as a whole and wound in a cylindrical shape with an individual web (not shown). These filter materials 42 and 44 are end-butted with each other, and are wound into a cylindrical shape by a common web 46.
　図３に示すシガレットフィルタ４１は、例えばアセテート繊維またはパルプの不織布を束ねたり、折畳んだりして成形したフィルタ素材４３を図示しない個別巻取紙で円柱状に巻いた２つのフィルタ材４７ａ，４７ｂを備えている。これらのフィルタ材４７ａ，４７ｂは互いに所定の間隔をあけて配置され、フィルタ材４７ａ，４７ｂ間のキャビティに複数の吸着剤担持顆粒４５が充填されている。吸着剤担持顆粒４５の充填部を中間に配置したフィルタ材４７ａ，４７ｂは共通巻取紙４６で円柱状に巻かれている。 The cigarette filter 41 shown in FIG. 3 includes two filter materials 47a and 47b in which a filter material 43 formed by bundling or folding non-woven fabrics of acetate fibers or pulp, for example, is wound in a cylindrical shape with individual winding paper (not shown). ing. These filter materials 47a and 47b are arranged at a predetermined interval from each other, and a plurality of adsorbent-carrying granules 45 are filled in the cavity between the filter materials 47a and 47b. Filter members 47 a and 47 b in which the filling portion of the adsorbent-carrying granule 45 is arranged in the middle are wound in a cylindrical shape by a common web 46.
　次に、実施形態に係るシガレットを説明する。 Next, the cigarette according to the embodiment will be described.
　実施形態に係るシガレットは前述したフィルタを備える。 The cigarette according to the embodiment includes the filter described above.
　実施形態の係るシガレットを図４、図５を参照して具体的に説明する。 The cigarette according to the embodiment will be specifically described with reference to FIGS.
　図４に示すシガレット５１は、たばこロッド５２の端部と前述した図２に示すシガレットフィルタ４１のフィルタ材４４（吸着剤担持顆粒４５が添着されている）の端部とを互いに突合せ、フィルタ４１の外周面全体および突合せ近傍のたばこロッド５２の外周面部分をチップペーパー５３で被包してたばこロッド５２とフィルタ４１とを一体化した構造を有する。たばこロッド５２は、たばこ刻み５４を巻紙５５で円柱状に被包することにより形成される。 The cigarette 51 shown in FIG. 4 abuts the end of the cigarette rod 52 and the end of the filter material 44 (attached with the adsorbent-carrying granules 45) of the cigarette filter 41 shown in FIG. The cigarette rod 52 and the filter 41 are integrated by encapsulating the entire outer peripheral surface and the outer peripheral surface portion of the tobacco rod 52 in the vicinity of the butt with a chip paper 53. The tobacco rod 52 is formed by enclosing a tobacco cut 54 in a cylindrical shape with a wrapping paper 55.
　図５に示すシガレット５１は、たばこロッド５２の端部と前述した図３に示すシガレットフィルタ４１のフィルタ材４７ａの端部とを互いに突合せ、フィルタ４１の外周面全体および突合せ近傍のたばこロッド５２の外周面部分をチップペーパー５３で被包してたばこロッド５２とフィルタ４１とを一体化した構造を有する。 The cigarette 51 shown in FIG. 5 abuts the end of the cigarette rod 52 and the end of the filter material 47a of the cigarette filter 41 shown in FIG. The outer peripheral surface portion is encapsulated with chip paper 53, and the tobacco rod 52 and the filter 41 are integrated.
　以上説明した実施形態に係る吸着剤担持顆粒によれば、少なくとも表面が無孔の核材にそれより微細な細粒吸着剤をポリビニルアルコールでポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下になるように担持することによって、例えばシガレットフィルタへの適用において、煙中のＶＯＣ成分を良好に吸着できる。 According to the adsorbent-carrying granule according to the embodiment described above, at least the surface of the non-porous core material is a fine adsorbent finer than polyvinyl alcohol, and the blending ratio of the polyvinyl alcohol is that of the fine adsorbent and polyvinyl alcohol. By supporting the amount so as to be 6.7% by weight or less with respect to the total amount, for example, in application to a cigarette filter, the VOC component in the smoke can be favorably adsorbed.
　すなわち、シガレットフィルタで用いる吸着剤の吸着サイトは空間速度と物質移動速度から考察すると、吸着剤表面近傍の寄与度が大きいものと推定される。実施形態の吸着剤担持顆粒は、核材表面に細粒吸着剤をポリビニルアルコール（ＰＶＡ）で担持することによって、核材の表面の細粒吸着剤層で優れた吸着性能を示すと共に、現行のチャコールフィルタで用いられる活性炭に比べて大きな粒径を有する。また、実施形態の吸着剤担持顆粒はバインダとしてのポリビニルアルコールの上限量を規定することによって、細粒吸着剤の吸着部である気孔がＰＶＡにより塞がれるのを抑制して、細粒吸着剤本来の吸着性能を維持することが可能になる。その結果、例えば煙中のＶＯＣ成分を良好に吸着することができる。 That is, when the adsorption site of the adsorbent used in the cigarette filter is considered from the space velocity and the mass transfer velocity, it is estimated that the contribution in the vicinity of the adsorbent surface is large. The adsorbent-carrying granules of the embodiment show excellent adsorption performance in the fine adsorbent layer on the surface of the core material by supporting the fine particle adsorbent with polyvinyl alcohol (PVA) on the surface of the core material, It has a larger particle size than activated carbon used in charcoal filters. Further, the adsorbent-supporting granule of the embodiment regulates the upper limit amount of polyvinyl alcohol as a binder, thereby suppressing the pores that are the adsorbing part of the fine adsorbent from being blocked by PVA, and the fine adsorbent It becomes possible to maintain the original adsorption performance. As a result, for example, the VOC component in the smoke can be favorably adsorbed.
　実施形態に係る吸着剤担持顆粒の製造方法によれば、前述した特性を有する吸着剤担持顆粒を容易に製造することができる。 According to the method for producing an adsorbent-carrying granule according to the embodiment, it is possible to easily produce an adsorbent-carrying granule having the characteristics described above.
　実施形態に係るシガレットフィルタは、前述した吸着剤担持顆粒を含むため、煙中のＶＯＣ成分を良好に吸着できる。 Since the cigarette filter according to the embodiment includes the adsorbent-carrying granules described above, the VOC component in the smoke can be favorably adsorbed.
　また、フィルタに含まれる吸着剤担持顆粒は核材表面に細粒吸着剤をＰＶＡで担持したコアーシェル構造を有し、現行のチャコールフィルタで用いられる活性炭に比べて粒径を大きくできるため、喫煙時の通気抵抗を低減できる。 In addition, the adsorbent-supported granules contained in the filter have a core-shell structure in which fine adsorbent is supported by PVA on the surface of the core material, and can be made larger in particle size than activated charcoal used in current charcoal filters. Ventilation resistance can be reduced.
　実施形態に係るシガレットは、前述した吸着剤担持顆粒を含むフィルタを備えるため、煙中のＶＯＣ成分を良好に吸着でき、さらに現行のチャコールフィルタで用いられる活性炭に比べて粒径を大きくできるため、喫煙時の通気抵抗を低減できる。 Since the cigarette according to the embodiment includes the filter including the adsorbent-carrying granules described above, the VOC component in the smoke can be favorably adsorbed, and the particle size can be increased as compared with the activated carbon used in the current charcoal filter. Ventilation resistance during smoking can be reduced.
　また、フィルタに含まれる吸着剤担持顆粒は少なくとも表面が無孔の核材、つまりそれ自身吸着性能を持たない核材表面に細粒吸着剤をポリビニルアルコール（ＰＶＡ）で担持することによって、吸着の場を核材の表面の細粒吸着剤層に制限できる。すなわち、核材を含む吸着剤担持顆粒全体による吸着能を発現させず、細粒吸着剤層のみでの吸着能に留めることによって、公知例の表面から内部の全体に亘って高い吸着能を示す造粒活性炭のように吸着蔵置中にシガレットの香味の吸着するのを抑制ないし防止することができる。 Also, the adsorbent-carrying granules contained in the filter can be adsorbed by supporting fine adsorbent with polyvinyl alcohol (PVA) at least on the surface of the non-porous core material, that is, the core material that does not have its own adsorption performance. The field can be limited to the fine sorbent layer on the surface of the core material. In other words, the adsorbing ability of the entire adsorbent-supporting granule containing the core material is not expressed, and the adsorbing ability of only the fine-grain adsorbent layer is maintained, thereby exhibiting a high adsorbing ability from the surface of the known example to the entire interior. Adsorption of cigarette flavor during adsorption storage like granulated activated carbon can be suppressed or prevented.
　以下、本発明の実施例を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
　吸着剤としてクラレケミカル株式会社から入手したヤシガラ活性炭である微粉炭（平均粒径１４μｍ、ＢＥＴ法による比表面積１７８０ｍ2／ｇ），７０～２００メッシュ（篩目間隔７５～２１２μｍ）の細粒炭（平均粒径１９５μｍ、ＢＥＴ法による比表面積１９００ｍ2／ｇ）、および２８～７０メッシュ（篩目間隔２１２～６００μｍ）の通常炭（平均粒径３９０μｍ、ＢＥＴ法による比表面積１８００ｍ2／ｇ）を用意した。図６は前記細粒炭の粒径分布（Ａ）および通常炭の粒径分布（Ｂ）を示す。図６から細粒炭は粒径が５０～３５０μｍに分布していることがわかる。 Pulverized coal (average particle size 14 μm, specific surface area 1780 m 2 / g by BET method), 70-200 mesh (75-212 μm sieve mesh) fine coal (coconut shell activated carbon obtained from Kuraray Chemical Co., Ltd. as an adsorbent. Prepared normal charcoal (average particle size 390 μm, specific surface area 1800 m 2 / g by BET method) with average particle size 195 μm, specific surface area 1900 m 2 / g by BET method, and 28-70 mesh (screen interval 212-600 μm) did. FIG. 6 shows the particle size distribution (A) of the fine coal and the particle size distribution (B) of the normal coal. From FIG. 6, it can be seen that the fine coal has a particle size distribution of 50 to 350 μm.
　なお、平均粒径およびＢＥＴ法による比表面積は次の方法で測定した。 In addition, the average particle diameter and the specific surface area by the BET method were measured by the following methods.
　＜活性炭の粒度分布、平均粒径測定＞
　前処理なしの粉末活性炭の粒度分布はHORIBA　LA-920（堀場製作所社製）による水中でのレーザ散乱の測定から測定し、球相当径の５０％メジアン径を平均粒径として算出した。 <Particle size distribution of activated carbon, average particle size measurement>
The particle size distribution of the powdered activated carbon without pretreatment was measured from the measurement of laser scattering in water by HORIBA LA-920 (manufactured by HORIBA, Ltd.), and the 50% median diameter of the sphere equivalent diameter was calculated as the average particle diameter.
　＜活性炭の比表面積測定＞
　活性炭の比表面積は、Autsorb-1-MP(Quantachrome社製）による７７Ｋでの窒素の吸脱着等温線測定データから相対圧Ｐ／Ｐ0＝０．０１～０．１間でのMulti Point BET法により算出した。この測定は、約０．０１０ｇの活性炭試料を0.1Ｐａ，５７３Ｋ，１５時間前処理した後行った。 <Specific surface area measurement of activated carbon>
The specific surface area of the activated carbon was determined by the Multi Point BET method with relative pressure P / P0 = 0.01 to 0.1 based on nitrogen adsorption and desorption isotherm measurement data at 77K by Autsorb-1-MP (manufactured by Quantachrome). Calculated. This measurement was performed after pre-treatment of about 0.010 g of activated carbon sample for 0.1 Pa, 573 K, 15 hours.
　（例１－１～１－３）
　遠心流動コーティング装置（ＣＦグラニュレータ、ＣＦ－ＬＡＢＯ；フロイント産業社製）を用い、核材としてグラニュー糖（三井製糖製、平均粒径５６０μｍ）１００ｇに濃度５重量％のバインダ水溶液を間欠的に噴射しながら、前述した３種の活性炭１５ｇを徐々に散布して吸着剤担持顆粒を製造した。 (Examples 1-1 to 1-3)
Using a centrifugal fluid coating device (CF granulator, CF-LABO; manufactured by Freund Sangyo Co., Ltd.), an aqueous binder solution having a concentration of 5% by weight is intermittently injected onto 100 g of granulated sugar (manufactured by Mitsui Sugar Co., Ltd., average particle size 560 μm) as a core material. Then, 15 g of the above-mentioned three kinds of activated carbon were gradually sprayed to produce adsorbent-carrying granules.
　例１－１～１－３では、いずれも活性炭として細粒炭を用い、バインダとしてそれぞれポリビニルアルコール（ＰＶＡ）、カルボキシメチルセルロース（ＣＭＣ）およびタマリンドガム（ＴＧ）を用いた。 In Examples 1-1 to 1-3, fine coal was used as activated carbon, and polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC) and tamarind gum (TG) were used as binders, respectively.
　遠心流動コーティング装置の運転条件は、スリットエアー温度を５５℃、スリットエアー流量を２０ＮＬ／分、回転皿（ロータ）回転数を２００ｐｐｍとし、下記表１に示すバインダ水溶液の噴霧速度および噴霧積算時間とした。このような条件で得られた吸着剤担持顆粒の核材表面の吸着剤層中のバインダ量を下記表１に示す。また、吸着剤担持顆粒同士の造粒を防ぐために活性炭の散布終了後に５分間以上運転を続行し、顆粒を十分に乾燥させた。このときの吸着担持顆粒の仕上げ水分および平均粒径を下記表１に示す。 The operating conditions of the centrifugal flow coating apparatus are as follows: the slit air temperature is 55 ° C., the slit air flow rate is 20 NL / min, the rotating plate (rotor) rotational speed is 200 ppm, did. The amount of binder in the adsorbent layer on the surface of the core material of the adsorbent-supported granules obtained under such conditions is shown in Table 1 below. Further, in order to prevent granulation between the adsorbent-carrying granules, the operation was continued for 5 minutes or more after the spraying of the activated carbon, and the granules were sufficiently dried. Table 1 below shows the finished water content and average particle size of the adsorbed and supported granules.
　（例２-１～２－３）
　活性炭としてそれぞれ微粉炭（例２－１）、細粒炭（例２－２）、通常炭（例２－３）を用い、バインダとしてＰＶＡを用い、バインダ水溶液の噴霧速度および噴霧積算時間を下記表１に示す条件で、乾燥時間を変えた以外、例１－１～１－３と同様な方法により吸着剤担持顆粒を製造した。得られた各吸着剤担持顆粒の核材表面の吸着剤層中のＰＶＡの割合、吸着担持顆粒の仕上げ水分および平均粒径を下記表１に示す。 (Examples 2-1 to 2-3)
Pulverized coal (Example 2-1), fine coal (Example 2-2), ordinary charcoal (Example 2-3) are used as the activated carbon, PVA is used as the binder, and the spraying speed and spray integration time of the binder aqueous solution are as follows. Adsorbent-carrying granules were produced in the same manner as in Examples 1-1 to 1-3 except that the drying time was changed under the conditions shown in Table 1. Table 1 below shows the ratio of PVA in the adsorbent layer on the surface of the core material of each adsorbent-supported granule, the finished moisture of the adsorbent-supported granule, and the average particle diameter.
　（例３-１～３－３）
　活性炭としてそれぞれ細粒炭（例２－２）を用い、バインダとしてＰＶＡを用い、バインダ水溶液の噴霧速度および噴霧積算時間を下記表１に示す条件で、乾燥時間を変えた以外、例１－１～１－３と同様な方法により吸着剤担持顆粒を製造した。得られた各吸着剤担持顆粒の核材表面の吸着剤層中のＰＶＡの割合、吸着担持顆粒の仕上げ水分および平均粒径を下記表１に示す。 (Examples 3-1 to 3-3)
Example 1-1, except that fine coal (Example 2-2) was used as the activated carbon, PVA was used as the binder, and the drying time was changed under the conditions shown in Table 1 below for the spray rate and spray integration time of the aqueous binder solution. Adsorbent-carrying granules were produced by the same method as in 1-3. Table 1 below shows the ratio of PVA in the adsorbent layer on the surface of the core material of each adsorbent-supported granule, the finished moisture of the adsorbent-supported granule, and the average particle diameter.
　なお、バインダの割合は吸着剤（活性炭）とバインダの合計量に対するバインダ量から算出した。また、吸着剤担持顆粒中の水分および平均粒径は以下の方法で測定した。 In addition, the ratio of the binder was calculated from the amount of the binder with respect to the total amount of the adsorbent (activated carbon) and the binder. Moreover, the water | moisture content and average particle diameter in adsorbent carrying | support granule were measured with the following method.
　＜吸着剤担持顆粒中の水分測定＞
　吸着剤担持顆粒１００ｇを内部標準物質としたエタノールを含むメタノール溶液約１０ｍＬで１時間以上振盪し、顆粒中の水分を抽出した。振盪後、約３０分間静置し、顆粒が沈殿したことを目視で確認した時点で上澄みを約１．５ｍＬ分取した。分取したメタノール溶液をＧＣ／ＴＣＤで水分分析し、内部標準法で定量した。ＧＣは、Agilent 7890（Agilent Technologies Inc.）を用いて行った。 <Measurement of moisture in adsorbent-supported granules>
The water in the granules was extracted by shaking with about 10 mL of a methanol solution containing ethanol using 100 g of the adsorbent-supported granules as an internal standard substance for 1 hour or more. After shaking, the mixture was allowed to stand for about 30 minutes, and when it was visually confirmed that granules were precipitated, about 1.5 mL of the supernatant was collected. The separated methanol solution was subjected to moisture analysis by GC / TCD and quantified by an internal standard method. GC was performed using an Agilent 7890 (Agilent Technologies Inc.).
　＜吸着剤担持顆粒の平均粒径測定＞
　吸着剤担持顆粒はCAMSIZER（堀場製作所社製）によるか増加遺跡式の粒子分布測定装置を用い、球相当径の５０％メジアン径を平均粒径として算出した。
Figure JPOXMLDOC01-appb-T000001
 <Measurement of average particle size of adsorbent-supported granules>
The adsorbent-carrying granules were calculated using CAMSIZER (manufactured by HORIBA, Ltd.) or using an incremental-architecture type particle distribution measuring device, and the 50% median diameter of the equivalent sphere diameter was calculated as the average particle diameter.
Figure JPOXMLDOC01-appb-T000001
　＜煙成分評価シガレットの作製＞
　評価シガレットは、以下の方法に従って作製した。外径７．７ｍｍ、長さ２７ｍｍの紙管に長さ５ｍｍのトリアセチン無添加のアセテートフィルタ材を挿入し、さらに紙管に前述した例１－１～１－３、例２－１～２－３および例３－１～３－３で得た吸着剤担持顆粒を活性炭量で３０ｍｇをそれぞれ挿入、充填した後、長さ５ｍｍの可塑剤無添加のアセテートフィルタ材を挿入して９種の評価用フィルタとした。つづいて、セーラムアラスカメンソール製品のフィルタを取り除き、このフィルタを各評価用フィルタの一端に接着テープで接続して評価シガレットを作製した。 <Production of smoke component evaluation cigarette>
The evaluation cigarette was produced according to the following method. An acetate filter material without addition of triacetin having a length of 5 mm was inserted into a paper tube having an outer diameter of 7.7 mm and a length of 27 mm, and the above-described Examples 1-1 to 1-3 and Examples 2-1 to 2- 3 and the adsorbent-carrying granules obtained in Examples 3-1 to 3-3 were each inserted and filled with 30 mg of activated carbon, and then a 9 mm plasticizer-free acetate filter material was inserted to evaluate 9 types. Filter. Subsequently, the filter of the Salem Alaska menthol product was removed, and this filter was connected to one end of each evaluation filter with an adhesive tape to produce an evaluation cigarette.
　また、前記紙管に長さ５ｍｍの活性炭無充填、可塑剤無添加のアセテートフィルタ材を２つ所定の間隔をあけて挿入し、この評価用フィルタの一端に前記セーラムアラスカメンソール製品のフィルタを接着テープで接続してコントロールシガレットを作製した。 Also, two acetate filter materials with a length of 5 mm that are not filled with activated carbon and no plasticizer are inserted into the paper tube at a predetermined interval, and the filter of the Salem Alaska menthol product is bonded to one end of the filter for evaluation. Control cigarettes were prepared by connecting with tape.
　＜評価シガレットによるフィルタの通気抵抗および低煙中のニコチン、タールの吸着性能試験＞
　１．通気抵抗試験
　フィルタの通気抵抗は、ISO 6565:2002（ISO 6565:2002 Tobacco and tobacco product "Draw resistance of cigarettes and pressure drop of filter rods" Standard conditions and measurement）に従って測定した。 <Evaluation cigarette filter ventilation resistance and low-smoke nicotine and tar adsorption performance test>
1. Ventilation Resistance Test The ventilation resistance of the filter was measured according to ISO 6565: 2002 (ISO 6565: 2002 Tobacco and tobacco product “Draw resistance of cigarettes and pressure drop of filter rods” Standard conditions and measurement).
　２．初期条件での煙中ニコチン、タールの吸着性能試験
　自動喫煙器（Borgwaldt KC Inc製のRM20D）を用いて各評価シガレット１０本を流量１７．５ｍＬ／秒、吸煙時間２秒／回、吸煙頻度１回／分の条件にて自動喫煙し、ケンブリッジフィルタ（Borgwaldt KC Inc製のCM-133）に粗タールを捕集した。ケンブリッジフィルタをメタノール１０ｍＬで振盪、抽出した後、ＧＣ－ＦＩＤでニコチンを、ＧＣ－ＴＣＤで水を分析した。ＧＣはAgilent 7890（Agilent Technologies Inc.）を用いて行った。得られた粗タールの値から水およびニコチンの値を引いてタールの値を求めた。すなわち、フィルタ通過後のシガレットあたりのニコチン、タール量を求めた。 2. Adsorption performance test of nicotine and tar in the smoke under initial conditions Using an automatic smoker (RM20D manufactured by Borgwaldt KC Inc), each evaluation cigarette was flowed at 17.5 mL / second, smoke absorption time 2 seconds / time, smoke absorption frequency 1 Automatic smoking was performed under conditions of times / minute, and crude tar was collected on a Cambridge filter (CM-133 manufactured by Borgwaldt KC Inc). After shaking and extracting the Cambridge filter with 10 mL of methanol, nicotine was analyzed by GC-FID and water was analyzed by GC-TCD. GC was performed using an Agilent 7890 (Agilent Technologies Inc.). The tar value was determined by subtracting the water and nicotine values from the crude tar value obtained. That is, the amount of nicotine and tar per cigarette after passing through the filter was determined.
　３．加速条件での煙中ニコチン、タールの吸着性能試験
　例１－１～１－３の顆粒を充填した評価シガレットを、温度２２℃、湿度６０％で１４時間保持し、その後温度５５℃、湿度２５％で１０時間保持する操作を繰り返した後、１週間保存した。これらの加速試験後の評価シガレットを前記２の吸着試験に供して煙中ニコチン、タールの吸着性能（フィルタ通過後のシガレットあたりのニコチン、タール量）を試験した。 3. Adsorption performance test of nicotine and tar in smoke under accelerated conditions An evaluation cigarette filled with granules of Examples 1-1 to 1-3 was held at a temperature of 22 ° C. and a humidity of 60% for 14 hours, and then a temperature of 55 ° C. and a humidity of 25 After repeating the operation of holding at 10% for 10 hours, it was stored for 1 week. These evaluation cigarettes after the acceleration test were subjected to the adsorption test of 2 above, and the adsorption performance of nicotine and tar in the smoke (nicotine and tar amount per cigarette after passing through the filter) was tested.
　これらのフィルタの通気抵抗および低煙中のニコチン、タールの吸着性能を下記表２に示す。なお、表２中の例１－４，２－４，３－４は顆粒に代えて細粒炭を紙管に充填した評価シガレット、例２－５は顆粒に代えて通常炭を紙管に充填した評価シガレット、を用いた例である。例１－５，２－６，２－５はコントロールシガレットを用いた例である。
Figure JPOXMLDOC01-appb-T000002
 Table 2 below shows the ventilation resistance of these filters and the adsorption performance of nicotine and tar in low smoke. In Table 2, Examples 1-4, 2-4, and 3-4 are evaluation cigarettes in which fine charcoal is filled in a paper tube instead of granules, and Example 2-5 is ordinary charcoal in paper tubes instead of granules. This is an example using a filled evaluation cigarette. Examples 1-5, 2-6, and 2-5 are examples using control cigarettes.
Figure JPOXMLDOC01-appb-T000002
　また、自動喫煙器（Borgwaldt KC Inc製のRM20D）を用いて例１－１～１－４、例２－１～２－５、例３－１～３－４の評価シガレット１０本を流量１７．５ｍＬ／秒、吸煙時間２秒／回、吸煙頻度１回／分の条件にて自動喫煙した。ケンブリッジフィルタ（Borgwaldt KC Inc製のCM-133）を通過した煙をドライアイス－イソプロパノールの冷媒にて－７０℃に冷却したメタノールに捕集した。捕集したメタノール１ｍＬをマイクロシリンジで定量し、ＧＣ－ＭＳＤで煙中の蒸気相（ＶＯＣ）成分を分析した。ＧＣはAgilent 7890（Agilent Technologies Inc.）を用いて行った。ＭＳＤはAgilent 5975B（Agilent Technologies Inc.）を用いて行った。各評価シガレットによるＶＯＣ成分の吸着率（Ｅi）は、評価シガレットのクロマトグラムのピーク面積をコントロールシガレットのクロマトグラムのピーク面積と比較し、次式により求めた。 In addition, using an automatic smoker (RM20D manufactured by Borgwaldt KC Inc), the evaluation cigarettes of 10 examples 1-1 to 1-4, examples 2-1 to 2-5, and examples 3-1 to 3-4 were flowed to 17 Automatic smoking was performed under the conditions of 5 mL / second, smoke absorption time 2 seconds / time, and smoke absorption frequency 1 time / minute. The smoke that passed through the Cambridge filter (CM-133 manufactured by Borgwaldt KC Inc) was collected in methanol cooled to -70 ° C. with a dry ice-isopropanol refrigerant. 1 mL of the collected methanol was quantified with a microsyringe, and the vapor phase (VOC) component in the smoke was analyzed by GC-MSD. GC was performed using an Agilent 7890 (Agilent Technologies Inc.). MSD was performed using Agilent 5975B (Agilent Technologies Inc.). The adsorption rate (E i ) of the VOC component by each evaluation cigarette was obtained by the following formula by comparing the peak area of the chromatogram of the evaluation cigarette with the peak area of the chromatogram of the control cigarette.
　　　　　Ｅi＝（Ａi,in－Ａi,out）／Ａi,in
　ここで、Ａi,inおよびＡi,outはそれぞれ評価シガレット、コントロールシガレットの煙中のＶＯＣ成分ｉのピーク面積を示す。 E i = (A i, in −A i, out ) / A i, in
Here, A i, in and A i, out indicate the peak areas of the VOC component i in the smoke of the evaluation cigarette and the control cigarette, respectively.
　図７は、例１－１～１－３の吸着剤担持顆粒、例１－４の細粒炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す。図８は、例１－１～１－３の吸着剤担持顆粒、例１－４の細粒炭を含むフィルタを備えたシガレットの前述した加速条件後のＶＯＣ成分の吸着率を示す。 FIG. 7 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4. FIG. 8 shows the adsorption rate of the VOC components after the acceleration conditions described above of cigarettes equipped with filters containing the adsorbent-carrying granules of Examples 1-1 to 1-3 and the fine coal of Example 1-4.
　図９は、例２－１～２－３の吸着剤担持顆粒、例２－４の細粒炭、例２－５の通常炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す。 FIG. 9 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 2-1 to 2-3, the fine coal of Example 2-4, and the normal coal of Example 2-5. Indicates.
　図１０は、例３－１～３－３の吸着剤担持顆粒、例３－４の細粒炭を含むフィルタを備えた評価シガレットの初期のＶＯＣ成分の吸着率を示す。 FIG. 10 shows the adsorption rate of the initial VOC component of the evaluation cigarette equipped with the filter containing the adsorbent-carrying granules of Examples 3-1 to 3-3 and the fine coal of Example 3-4.
　前記表２の結果から明らかなようにバインダとしてＰＶＡ、ＣＭＣ，ＴＧを用いた例１－１～１－３の吸着剤担持顆粒は、例１－４の細粒炭単独に比べてフィルタの通気抵抗を低減できることがわかる。前記表２の結果から明らかなようにバインダとしてＰＶＡを用いた本発明の例１－１の吸着剤担持顆粒は、バインダとしてＣＭＣ，ＴＧを用いた例１－２、１－３の吸着剤担持顆粒に比べて高いニコチン、タールの吸着性能を示し、例１－４の細粒炭単独とほぼ同等の高いニコチン、タールの吸着性能を示すことがわかる。図７の結果から明らかなようにバインダとしてＰＶＡを用いた本発明の例１－１の吸着剤担持顆粒は、バインダとしてＣＭＣ，ＴＧを用いた例１－２、１－３の吸着剤担持顆粒に比べて高いＶＯＣ成分の吸着性能を示し、例１－４の細粒炭単独と同等の高いＶＯＣ成分の吸着性能を示すことがわかる。図８の結果から明らかなように加速条件でも、バインダとしてＰＶＡを用いた本発明の例１－１の吸着剤担持顆粒は例１－４の細粒炭単独と同等の高いＶＯＣ成分の吸着性能を示すことがわかる。 As is clear from the results in Table 2, the adsorbent-carrying granules of Examples 1-1 to 1-3 using PVA, CMC, and TG as binders are more effective than the fine coal of Example 1-4. It can be seen that the resistance can be reduced. As is apparent from the results in Table 2, the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder are the adsorbent-carrying examples of Examples 1-2 and 1-3 using CMC and TG as the binder. It can be seen that the adsorption performance of nicotine and tar is higher than that of the granules, and that the adsorption performance of nicotine and tar is almost the same as that of the fine coal of Example 1-4. As is apparent from the results of FIG. 7, the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder are the adsorbent-carrying granules of Examples 1-2 and 1-3 using CMC and TG as the binder. It can be seen that the adsorption performance of the VOC component is higher than that of Example 1, and that the adsorption performance of the VOC component is as high as that of the fine coal of Example 1-4 alone. As is apparent from the results of FIG. 8, even under acceleration conditions, the adsorbent-carrying granules of Example 1-1 of the present invention using PVA as the binder have a high VOC component adsorption performance equivalent to that of the fine coal of Example 1-4 alone. It can be seen that
　前記表２の結果から明らかなようにバインダとしてＰＶＡを用い、活性炭として微粉炭、細粒炭、通常炭を用いた例２－１～２－３の吸着剤担持顆粒は、例２－４の細粒炭単独に比べてフィルタの通気抵抗を低減でき、かつ高いニコチン、タールの吸着性能を示すことがわかる。図９の結果から明らかなようにバインダとしてＰＶＡを用い、活性炭として粒径５０～３５０μｍの細粒炭を用いた例２－２の吸着剤担持顆粒は例２－４の細粒炭単独と同等の高い煙中ＶＯＣ成分の吸着性能を示すことがわかる。これに対し、活性炭として微粉炭を用いた例２－１の吸着剤担持顆粒は、煙中のＶＯＣ成分の吸着性能を殆ど示さない。これは、核材に担持される微粉炭表面の気孔がＰＶＡで覆われたためと考えられる。また、通常炭を担持した例２－３の吸着剤担持顆粒は、例２－５の通常炭単独に比べて煙中のＶＯＣ成分の吸着性能が僅かに低下する。通常炭の粒径は核材であるグラニュー糖のそれに近似しているため、通常炭を核材に担持するメリットがない。 As is apparent from the results in Table 2, the adsorbent-carrying granules of Examples 2-1 to 2-3 using PVA as the binder and pulverized coal, fine-grained coal, and ordinary charcoal as the activated carbon were obtained in Example 2-4. It can be seen that the ventilation resistance of the filter can be reduced as compared with fine-grained charcoal alone, and high nicotine and tar adsorption performance is exhibited. As is apparent from the results of FIG. 9, the adsorbent-carrying granules of Example 2-2 using PVA as the binder and fine coal with a particle size of 50 to 350 μm as the activated carbon are equivalent to the fine coal alone of Example 2-4. It can be seen that the adsorption performance of the VOC component in smoke with a high level of smoke is exhibited. On the other hand, the adsorbent-carrying granules of Example 2-1 using pulverized coal as the activated carbon hardly show the adsorption performance of the VOC component in the smoke. This is presumably because the pores on the surface of the pulverized coal supported on the core material were covered with PVA. In addition, the adsorbent-carrying granules of Example 2-3 carrying normal charcoal have a slightly lower adsorption performance of the VOC component in the smoke than the normal charcoal alone of Example 2-5. Since the particle size of normal charcoal is close to that of granulated sugar, which is the core material, there is no merit of supporting normal charcoal on the core material.
　前記表２の結果から明らかなようにバインダとしてＰＶＡを用い、活性炭として細粒炭を用いた例３－１～３－３の吸着剤担持顆粒は、例３－４の細粒炭単独に比べてフィルタの通気抵抗を低減でき、かつ高いニコチン、タールの吸着性能を示すことがわかる。一方、図１０の結果から明らかなように活性炭として細粒炭を用い、ＰＶＡ量が６．７重量％以下である例３－１，３－２の吸着剤担持顆粒は、ＰＶＡ量が６．７重量％を超える例３－３の吸着剤担持顆粒に比べて高い煙中ＶＯＣ成分の吸着性能を示し、かつ例３－４の細粒炭単独と同等の高い煙中ＶＯＣ成分の吸着性能を示すことがわかる。 As is apparent from the results in Table 2, the adsorbent-carrying granules of Examples 3-1 to 3-3 using PVA as the binder and fine coal as the activated carbon are compared with the fine coal alone of Example 3-4. It can be seen that the ventilation resistance of the filter can be reduced, and that the high nicotine and tar adsorption performance is exhibited. On the other hand, as is clear from the results of FIG. 10, the adsorbent-carrying granules of Examples 3-1 and 3-2 in which fine coal is used as the activated carbon and the amount of PVA is 6.7% by weight or less have a PVA amount of 6. Exceeds 7% by weight of the adsorbent-carrying granule of Example 3-3, exhibits higher adsorption performance of the VOC component in the smoke, and has the same high adsorption performance of the VOC component in the smoke as the fine coal alone of Example 3-4. You can see that
　１１…回転皿（ロータ）、１２…固定壁（ステータ）、１７…エア供給管、１８…遠心転動室、１９…核材、２０…散布管、２１…細粒吸着剤、２４…噴霧ノズル、４１…シガレットフィルタ、４２，４４、４７ａ，４７ｂ…フィルタ材、４３…フィルタ素材、４５…吸着剤担持顆粒、５１…シガレット。 DESCRIPTION OF SYMBOLS 11 ... Rotating dish (rotor), 12 ... Fixed wall (stator), 17 ... Air supply pipe, 18 ... Centrifugal rolling chamber, 19 ... Nuclear material, 20 ... Spreading pipe, 21 ... Fine-grain adsorbent, 24 ... Spray nozzle 41 ... Cigarette filters, 42, 44, 47a, 47b ... Filter materials, 43 ... Filter materials, 45 ... Adsorbent-carrying granules, 51 ... Cigarettes.

Claims (10)

  1. 　少なくとも表面が無孔の核材にそれより微細な細粒吸着剤をポリビニルアルコールでポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下になるように担持した吸着剤担持顆粒。 At least the surface of the nonporous core material is finer adsorbent than polyvinyl alcohol, and the blending ratio of polyvinyl alcohol is 6.7% by weight or less based on the total amount of fine adsorbent and polyvinyl alcohol. Adsorbent-carrying granules supported.
  2. 　前記核材はグラニュー糖である請求項１記載の吸着剤担持顆粒。 The adsorbent-carrying granules according to claim 1, wherein the core material is granulated sugar.
  3. 　前記細粒吸着剤は粒径５０～３５０μｍである請求項１記載の吸着剤担持顆粒。 The adsorbent-carrying granules according to claim 1, wherein the fine adsorbent has a particle size of 50 to 350 µm.
  4. 　前記細粒吸着剤はＢＥＴ法による比表面積が１７８０～１９００ｍ2／ｇである請求項３記載の吸着剤担持顆粒。 The adsorbent-carrying granule according to claim 3, wherein the fine adsorbent has a specific surface area of 1780 to 1900 m 2 / g by BET method.
  5. 　チャンバ内の回転皿上に少なくとも表面が無孔の核材を所望量載置する工程；および
    　前記回転皿を回転させ、前記チャンバ内面と前記回転皿の外周縁の間に空気を下から上方に向けて供給して前記核材を遊星運動させながら、前記核材に向けてポリビニルアルコール水溶液を噴霧し、前記核材より微細な細粒吸着剤を散布して前記核材に前記細粒吸着剤をポリビニルアルコールでポリビニルアルコールの配合割合が細粒吸着剤とポリビニルアルコールの合計量に対して６．７重量％以下になるように担持する工程；
    を含む吸着剤担持顆粒の製造方法。     Placing a desired amount of at least a non-porous core material on a rotating dish in the chamber; and rotating the rotating dish to move air between the inner surface of the chamber and the outer peripheral edge of the rotating dish from below to above The fine particle adsorbent is sprayed on the core material by spraying a polyvinyl alcohol aqueous solution toward the core material and spraying fine particle adsorbent finer than the core material. A step of supporting polyvinyl alcohol so that the blending ratio of polyvinyl alcohol is 6.7% by weight or less with respect to the total amount of the fine particle adsorbent and polyvinyl alcohol;
    The manufacturing method of the adsorbent carrying | support granule containing this.
  6. 　前記核材はグラニュー糖である請求項５記載の吸着剤担持顆粒の製造方法。 The method for producing adsorbent-carrying granules according to claim 5, wherein the core material is granulated sugar.
  7. 　前記細粒吸着剤は粒径５０～３５０μｍである請求項５記載の吸着剤担持顆粒の製造方法。 The method for producing adsorbent-carrying granules according to claim 5, wherein the fine adsorbent has a particle diameter of 50 to 350 µm.
  8. 　前記細粒吸着剤はＢＥＴ法による比表面積が１７８０～１９００ｍ2／ｇである請求項７記載の吸着剤担持顆粒の製造方法。 The method for producing adsorbent-carrying granules according to claim 7, wherein the fine adsorbent has a specific surface area of 1780 to 1900 m 2 / g by BET method.
  9. 　請求項１～４いずれか１項記載の吸着剤担持顆粒を有するシガレットフィルタ。 A cigarette filter having the adsorbent-carrying granules according to any one of claims 1 to 4.
  10. 　請求項９項記載のシガレットフィルタを備えたシガレット。 A cigarette comprising the cigarette filter according to claim 9.
PCT/JP2010/070489 2010-11-17 2010-11-17 Adsorbent-supported granules and process for production thereof, cigarette filter, and cigarette WO2012066656A1 (en)

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WO2017168516A1 (en) * 2016-03-28 2017-10-05 日本たばこ産業株式会社 Filter for smoking article, smoking article, and process for producing filter for smoking article
CN113347895A (en) * 2019-01-25 2021-09-03 日本烟草产业株式会社 Filter tip for smoking article
CN113492001A (en) * 2020-04-03 2021-10-12 万华化学集团股份有限公司 Odor adsorbent and preparation method thereof, adhesive system and application thereof, aldehyde-free shaving board and preparation method thereof
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JPH08506048A (en) * 1993-01-27 1996-07-02 シラキュース ユニバーシティ Molecule designed activated carbon
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017168516A1 (en) * 2016-03-28 2017-10-05 日本たばこ産業株式会社 Filter for smoking article, smoking article, and process for producing filter for smoking article
JPWO2017168516A1 (en) * 2016-03-28 2018-08-02 日本たばこ産業株式会社 Filter for smoking article, smoking article, and method for producing filter for smoking article
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CN113347895A (en) * 2019-01-25 2021-09-03 日本烟草产业株式会社 Filter tip for smoking article
CN113492001A (en) * 2020-04-03 2021-10-12 万华化学集团股份有限公司 Odor adsorbent and preparation method thereof, adhesive system and application thereof, aldehyde-free shaving board and preparation method thereof
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