EP1470761B1 - Smoking filter and smoking article - Google Patents
Smoking filter and smoking article Download PDFInfo
- Publication number
- EP1470761B1 EP1470761B1 EP03701015.4A EP03701015A EP1470761B1 EP 1470761 B1 EP1470761 B1 EP 1470761B1 EP 03701015 A EP03701015 A EP 03701015A EP 1470761 B1 EP1470761 B1 EP 1470761B1
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- EP
- European Patent Office
- Prior art keywords
- filter
- acid
- cigarette
- hydrotalcite
- hydrotalcite compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
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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
- A24D3/062—Use of materials for tobacco smoke filters characterised by structural features
- A24D3/063—Use of materials for tobacco smoke filters characterised by structural features of the fibers
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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
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
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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
- A24D3/12—Use of materials for tobacco smoke filters of ion exchange materials
Definitions
- the present invention relates to a smoking filter and a smoking article.
- the adsorbent used in the past also adsorbs the components other than formaldehyde, with the result that it was possible for adverse effects to be given to the flavor and taste of the smoking article.
- JP 2001 300220 A discloses an air cleaning filter apparatus constituted of a first filter obtained by supporting acidic phosphate and a copper compound on a base material and a second filter obtained by supporting a hydrotalcite compound and a sulfite on a base material.
- EP-A-0 532 329 discloses cigarettes including a filter element which have a gathered web of paper incorporating a carbonaceous material. The paper is gathered so as to include a plurality of longitudinally extending channels, and the channels provide a cross-sectional void area of about 5 to about 30 percent of the filter element.
- An object of the present invention is to provide a smoking filter and a smoking article capable of selectively removing formaldehyde contained in mainstream smoke.
- the present invention is directed to a cigarette, characterized by comprising:
- a smoking filter for a cigarette i.e. a cigarette filter containing a hydrotalcite compound exhibiting a lamellar structure in which a large number of octahedral layers of a metal hydroxide are laminated one upon the other.
- the hydrotalcite compound used in the present invention is represented by a general formula: M 2+ 1-x M 3+ x (OH) 2 (A n- ) x/n • mH 2 O
- M 2+ represents a divalent metal ion selected from the group consisting of a Mg ion, a Zn ion, a Ni ion and a Ca ion
- M 3+ represents an Al ion
- the cigarette filter is prepared by dispersing a hydrotalcite compound having an average particle diameter falling within a range of between 200 ⁇ m and 800 ⁇ m in, for example, the fiber tow or an unwoven fabric sheet.
- the typical fiber used in the present invention is formed of cellulose acetate.
- the cigarette filter prefferably be prepared by forming a paper sheet added with a hydrotalcite compound having an average particle diameter not larger than 10 ⁇ m.
- the cigarette filter prefferably includes a plurality of filter segments, at least one filter segment containing a hydrotalcite compound.
- a charcoal filter segment in addition to the filter segment containing the hydrotalcite compound.
- the cigarette filter prefferably includes a plurality of filter segments and hydrotalcite particles filled in the space present between the adjacent filter segments.
- a smoking article including the cigarette filter referred to above and a tobacco rod connected to the smoking filter.
- hydrotalcite compounds permit effectively removing formaldehyde.
- the hydrotalcite compound exhibits a lamellar structure in which a large number of octahedral layers of a divalent or trivalent metal hydroxide are laminated one upon the other, and an anion is intercalated in the octahedral layers.
- the octahedral layer is referred to as a host and exhibits basicity. It is considered reasonable to understand that the removal of formaldehyde achieved by the hydrotalcite compound results from contribution of the basicity of the host and from the ion exchange function performed by the intercalated anions.
- hydrotalcite compound is represented by a general formula: M 2+ 1-x M 3+ x (OH) 2 (A n- ) x/n • mH 2 O.
- a Mg ion constitutes the divalent metal ion M 2+ included in the general formula given above
- an Al ion constitutes the trivalent metal ion M 3+
- CO 3 2- or SO 4 2- constitutes the anion A n- .
- a Zn ion, a Ni ion or a Ca ion to constitute the divalent metal ion M 2+ in addition to the Mg ion.
- the anion is selected from the group consisting of OOC-COO, Cl, Br, F, NO 3 , Fe(CN) 6 3- , Fe(CN) 6 4- , phthalic acid, isophthalic acid, terephthalic acid, maleic acid, alkenyl acid and its derivative, malic acid, salicylic acid, acrylic acid, adipic acid, succinic acid, citric acid and sulfonic acid in addition to CO 3 2- and SO 4 2- .
- the symbol x in the general formula is larger than 0.1 and smaller than 0.4, i.e., 0.1 ⁇ x ⁇ 0.4, and the symbol m is larger than 0 and smaller than 2, i.e., 0 ⁇ m ⁇ 2.
- the Mg-Al-based hydrotalcite compound is stable in the case where the value of x falls within a range of between 0.20 and 0.33.
- a reaction is carried out by adding an alkali carbonate or both an alkali carbonate and a caustic alkali to an aqueous solution containing a water-soluble aluminum salt selected from the group consisting of aluminum sulfate, aluminum acetate and aluminum potassium sulfate or aluminic acid and a water-soluble magnesium salt while maintaining the pH value of the reaction mixture at 8.0 or more.
- a water-soluble aluminum salt selected from the group consisting of aluminum sulfate, aluminum acetate and aluminum potassium sulfate or aluminic acid and a water-soluble magnesium salt
- hydrotalcite compound it is possible to control a micro pore size of the hydrotalcite compound by, for example, the size of the anion intercalated in the hydrotalcite compound. It is also possible for the hydrotalcite compound to perform various functions depending on the nature of the anion and on the state of the interlayer water.
- the hydrotalcite compound it is desirable to control the particle diameter of the hydrotalcite compound as follows.
- the hydrotalcite compound it is desirable for the hydrotalcite compound to have a particle diameter of 200 to 800 ⁇ m, more desirably 400 to 600 ⁇ m.
- the hydrotalcite compound it is desirable for the hydrotalcite compound to have a particle diameter not larger than 10 ⁇ m.
- a hydrotalcite compound represented by Mg 6 Al 2 (OH) 16 CO 3 •4H 2 O was used.
- the particle diameter of the hydrotalcite compound was controlled to 250 to 500 ⁇ m by pulverization and sieving.
- a filter 1 shown in FIG. 1 was prepared by using the hydrotalcite compound.
- a hydrotalcite powder 3 was filled in the space present between two acetate filter segments 2, 2 each wrapped with a plug wrapper and, then, the resultant structure was wrapped with a forming paper 4 so as to prepare the filter 1 of the plug-space-plug structure.
- filters of the plug-space-plug structure as shown in FIG. 1 were prepared by using following adsorbents: charcoal, charcoal having a high specific surface area, alkali metal salt impregnated charcoal, amine impregnated charcoal, active alumina, magnesium oxide, aluminum oxide, magnesium silicate, zinc oxide, silica gel, zeolite, construction material pulp for formalin, a column packing material for gas chromatography (GC), and water-absorbing resin.
- adsorbents charcoal, charcoal having a high specific surface area, alkali metal salt impregnated charcoal, amine impregnated charcoal, active alumina, magnesium oxide, aluminum oxide, magnesium silicate, zinc oxide, silica gel, zeolite, construction material pulp for formalin, a column packing material for gas chromatography (GC), and water-absorbing resin.
- the amount of formaldehyde contained in cigarette mainstream smoke was measured according to "Health Canada - Official Method" (2,4-DNPH-HPLC method) so as to provide the removal rate of formaldehyde.
- DNPH 2,4-dinitrophenyl hydrazine
- a DNPH trapping solution 12 is put in a Drechsel-type trap 11.
- the Drechsel-type trap 11 has an inner volume of 100 mL, and an amount of the DNPH trapping solution 12 is 80 mL.
- the trap 11 is put in an ice water bath 13 so as to be cooled.
- the lower end of a glass pipe 14 to which a cigarette 10 is attached is dipped in the trapping solution 12 within the trap 11.
- a glass pipe 15 having a Cambridge pad 16 mounted thereto is arranged to communicate with the dead volume of the trap 11, and a smoking machine 17 was connected to the Cambridge pad 16.
- the cigarette 10 was attached to the glass pipe 14 so as to permit the cigarette 10 to be automatically smoked under the standard smoking conditions specified in ISO standards. To be more specific, the operation of sucking 35 mL of the smoke in a single puff for two seconds for a single cigarette was repeated at an interval of 58 seconds. While the mainstream smoke was being bubbled, formaldehyde was converted into a derivative of DNPH. Two cigarettes were used for the measurement. In this case, the cigarettes using the different adsorbents were controlled to exhibit the same pressure loss.
- the formaldehyde derivative thus formed was measured by high-performance liquid chromatography (HPLC).
- HPLC high-performance liquid chromatography
- the trapping solution was filtered, followed by diluting the filtered trapping solution with a Trizma Base solution (4 mL of trapping solution : 6 mL of Trizma Base solution). Then, the diluted solution was measured by the HPLC.
- the measuring conditions of the HPLC were as follows:
- FIG. 3 is a graph showing the removal rates of formaldehyde in the case of using various adsorbents. As apparent from FIG. 3 , formaldehyde was most effectively removed in the case of using hydrotalcite as the adsorbent.
- the removal rate of the vapor phase components contained in cigarette mainstream smoke was measured by using as an adsorbent a hydrotalcite compound or charcoal constituting the most general adsorbent for a cigarette.
- a filter similar to that shown in FIG. 1 was manufactured as in Example 1 by preparing a hydrotalcite compound having a particle diameter of 250 to 500 ⁇ m or charcoal as an adsorbent and loading the adsorbent in an amount of 50 mg. Then, a cigarette was prepared by connecting a tobacco section containing 12 mg of tar to the filter thus manufactured.
- FIG. 4 shows the trapping method of the vapor phase components.
- a cigarette 10 was attached to a smoking machine 17 so as to permit the cigarette 10 to be automatically smoked under the standard smoking conditions specified in the ISO standards.
- the particle phase in the mainstream smoke was removed by a Cambridge filter, and the vapor phase was trapped by a gas bag 20.
- the operation of sucking 35 mL of the smoke in 2 seconds in a single puff for each cigarette was repeated at an interval of 58 seconds.
- 10 conditioned cigarettes (conditioned under temperature of 22°C and humidity of 60%) were automatically smoked.
- FIG. 5 shows gas chromatography.
- a prescribed amount of the vapor phase components trapped in the gas bag 20 is stored in a sample loop 21.
- the vapor phase components are injected into a gas chromatograph 22.
- the components are separated in a column (DB-WAX) and detected in a detector. Further, the amounts of the components are analyzed by using a program installed in a personal computer 23. The analytical value was obtained by dividing the peak area of each of the vapor phase components by the peak area of the standard gas.
- FIG. 6 is a graph showing the relationship between the vapor pressure of the vapor phase component and the removal rate of the component.
- the removal rate is increased with increase in the vapor pressure of the vapor phase component in the case of using charcoal as an adsorbent.
- the removal rate is specifically high in respect of formaldehyde, supporting that the hydrotalcite compound permits selectively removing formaldehyde.
- the hydrotalcite compound is granulated, it is possible to prepare samples differing from each other in the particle size distribution. In this case, the samples are classified depending on the average particle diameter of the hydrotalcite compound.
- FIG. 7A shows three types of samples having the average particle diameters of 250 ⁇ m, 500 ⁇ m, and 800 ⁇ m, respectively.
- Filters of the construction as shown in FIG. 1 were prepared by using hydrotalcite particles differing from each other in the average particle diameter. These filters differed from each other in the loading amount of the hydrotalcite particles.
- filters of the construction shown in FIG. 1 were also prepared by using charcoal. These filters also differed from each other in the loading amount of the charcoal.
- the resistance to draw was examined in respect of these filters under the sucking flow rate of 1050 mL/min.
- the resistance to draw was calculated by excluding the resistance to draw due to the two acetate filter segments 2, 2 shown in FIG. 1 .
- FIG. 7B is a graph showing the relationship between the average particle diameter and the resistance to draw. As apparent from FIG. 7B , the resistance to draw is high in the case of using the adsorbent particles having the average particle diameter of 250 ⁇ m and is low in the case of using the adsorbent particles having the average particle diameter of 800 ⁇ m. FIG. 7B also indicates that it is reasonable to use hydrotalcite particles having the average particle diameter falling within a range of between 400 ⁇ m and 600 ⁇ m in designing cigarettes.
- hydrotalcite particles having a desired size it is possible to provide hydrotalcite particles having a desired size by employing any granulating method such as rolling granulation, compression molding, coating granulation, or extrusion molding. It should be noted in this connection that, in order to avoid the breakage of the hydrotalcite particles in the manufacturing process of the filter, it is desirable to employ a granulating method that permits manufacturing granulated hydrotalcite particles having an appropriate hardness. The present inventor found that it is possible to prevent the hydrotalcite particles from being broken in the manufacturing process of the filter if the hydrotalcite particles have a hardness falling within a range of between 300 g/mm 2 and 3,000 g/mm 2 .
- This Example is intended to support that the reduction rate of the formaldehyde content in mainstream smoke achieved by the hydrotalcite particle is dependent on the surface area of the hydrotalcite particle.
- Various granulated hydrotalcite particles were prepared by means of (A) rolling granulation, (B) compression molding, and (C) extrusion molding.
- the average surface area per unit weight of the hydrotalcite particles was calculated by using a laser scattering type particle size distribution measuring apparatus.
- FIG. 8 is a graph showing the result.
- This Example is intended to examine the reduction rate of formaldehyde contained in mainstream smoke, which is achieved by a paper filter to which hydrotalcite particles are added, and by a cellulose acetate filter to which granulated hydrotalcite particles are added.
- a paper sheet was made while adding hydrotalcite particles having an average particle diameter not larger than 10 ⁇ m. Then, the paper filter 7 shown in FIG. 9 was prepared by using the resultant paper sheet. For comparison, a filter was prepared by forming a paper sheet to which hydrotalcite particles were not added.
- a filter was also prepared by dispersing granulated hydrotalcite particles in the cellulose acetate tow.
- a cellulose acetate filter was prepared without using hydrotalcite particles.
- the filters thus prepared were 25 mm long and were made as uniform as possible in the resistance to draw.
- the ratio of formaldehyde outflow to tar outflow was decreased in the paper filter containing the hydrotalcite particles, compared with the acetate filter containing the hydrotalcite particles. It is considered reasonable to understand that the result was achieved by the large contact surface area of the hydrotalcite particles having an average particle diameter not larger than 10 ⁇ m dispersed in the paper filter.
- This Example is intended to support that the reduction rate of the organic vapor components can be increased by the combination of a hydrotalcite filter and a charcoal filter.
- Filters I, II, III of the triple segment structure including an acetate filter segment, a hydrotalcite (HT) filter segment and a charcoal filter segment as shown in Table 2 were prepared.
- the acetate filter segment was prepared by bundling cellulose acetate tow and was 7 mm long.
- the hydrotalcite (HT) filter segment was prepared by bundling cellulose acetate tow having 70 mg of hydrotalcite particles dispersed therein and was 10 mm long.
- the charcoal filter segment was prepared by bundling cellulose acetate tow having 70 mg of charcoal particles dispersed therein and was 10 mm long.
- FIG. 10 shows the construction of the filter III shown in Table 2.
- a charcoal filter segment 5 is arranged on the side of the cut tobacco
- an acetate filter segment is arranged on the inhaling side
- an HT filter segment 6 is arranged intermediate between the charcoal filter segment 5 and the acetate filter segment 2.
- the filter III permits lowering the content of the total organic vapor because of the function of the charcoal filter and also permits lowering the formaldehyde content because of the function of the hydrotalcite (HT) filter.
- Table 2 Cut tobacco side Center Inhaling side TOV reduction rate (%) FA reduction rate (%) I charcoal filter acetate filter acetate filter 62.7 67.2 II acetate filter HT filter acetate filter 20.8 69.3 III charcoal filter HT filter acetate filter 64.8 71.9 Weight of additives: 70 mg/10 mm Filter length: 10mm, 10mm, and 7mm Ventilation resistance of filter tip: 72 mmWG/27 mm Ventilation hole: no
- the filter of the construction as shown in FIG. 1 it is possible to use another filter segment in place of at least one of the acetate filter segments 2.
- a hydrotalcite filter segment or a charcoal filter segment in place of at least one of the acetate filter segments 2.
- the cellulose acetate tow having a hydrotalcite compound dispersed therein were used for forming the hydrotalcite filter segment.
- a hydrotalcite filter segment prepared by forming a paper sheet made by adding hydrotalcite compound was also possible.
- a filter comprising a charcoal filter segment 5, a space filled with hydrotalcite particles 3, a hydrotalcite (HT) filter segment 6 and an acetate filter segment 2, as shown in FIG. 11 .
- the hydrotalcite filter segment 6 it is possible for the hydrotalcite filter segment 6 to be acetate filter-based or paper filter-based in this case, too. It is possible for the arrangement of the space filled with the HT particles 3 and the HT filter segment 6 to be opposite to that shown in FIG. 11 . In FIG. 11 , the space is filled with HT particles. Alternatively, it is possible for the space to be filled with charcoal particles.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Filtering Materials (AREA)
Description
- The present invention relates to a smoking filter and a smoking article.
- Various chemical components are contained in mainstream smoke that is inhaled by the smoker in smoking a smoking article. Among these chemical components, the lower aldehydes represented by formaldehyde are difficult to remove by adsorption on an ordinary smoking filter. Naturally, it is desirable to remove the aldehydes from the mainstream smoke.
- It was customary to use a filter having activated carbon added thereto as an adsorbent for removing formaldehyde from the mainstream smoke. In addition, it was attempted to use various other adsorbents.
- However, the adsorbent used in the past also adsorbs the components other than formaldehyde, with the result that it was possible for adverse effects to be given to the flavor and taste of the smoking article.
-
JP 2001 300220 A EP-A-0 532 329 discloses cigarettes including a filter element which have a gathered web of paper incorporating a carbonaceous material. The paper is gathered so as to include a plurality of longitudinally extending channels, and the channels provide a cross-sectional void area of about 5 to about 30 percent of the filter element. - An object of the present invention is to provide a smoking filter and a smoking article capable of selectively removing formaldehyde contained in mainstream smoke.
- The present invention is directed to a cigarette, characterized by comprising:
- a tobacco rod; and
- a cigarette filter connected to the tobacco rod, the cigarette filter comprising a cellulose acetate tow or an unwoven fabric made of cellulose acetate and particles of hydrotalcite compound dispersed in the cellulose acetate tow or unwoven fabric made of cellulose acetate,
- or comprising filter segments of cellulose acetate tow and particles of hydrotalcite compound filled in a space present between the adjacent filter segments,
- the hydrotalcite compound having an average particle diameter in a range of between 200 µm and 800 µm.
- Described is a smoking filter for a cigarette, i.e. a cigarette filter containing a hydrotalcite compound exhibiting a lamellar structure in which a large number of octahedral layers of a metal hydroxide are laminated one upon the other.
- The hydrotalcite compound used in the present invention is represented by a general formula:
M2+ 1-xM3+ x(OH)2(An-)x/n • mH2O
where M2+ represents a divalent metal ion selected from the group consisting of a Mg ion, a Zn ion, a Ni ion and a Ca ion, M3+ represents an Al ion, Anrepresents an anion having a valency of n, which is selected from the group consisting of CO3, SO4, OOC-COO, Cl, Br, F, NO3, Fe(CN)6 3-, Fe(CN)6 4-, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, alkenyl acid and its derivative, malic acid, salicylic acid, acrylic acid, adipic acid, succinic acid, citric acid and sulfonic acid, 0.1 < x < 0.4, and 0 < m < 2. - The cigarette filter is prepared by dispersing a hydrotalcite compound having an average particle diameter falling within a range of between 200 µm and 800 µm in, for example, the fiber tow or an unwoven fabric sheet. The typical fiber used in the present invention is formed of cellulose acetate.
- It is possible for the cigarette filter to be prepared by forming a paper sheet added with a hydrotalcite compound having an average particle diameter not larger than 10 µm.
- It is possible for the cigarette filter to include a plurality of filter segments, at least one filter segment containing a hydrotalcite compound. In this case, it is possible to use a charcoal filter segment in addition to the filter segment containing the hydrotalcite compound.
- It is possible for the cigarette filter to include a plurality of filter segments and hydrotalcite particles filled in the space present between the adjacent filter segments.
- Further described is a smoking article including the cigarette filter referred to above and a tobacco rod connected to the smoking filter.
-
-
FIG. 1 is a perspective view showing a filter manufactured in the Examples of the present invention; -
FIG. 2 shows the construction of an apparatus used in the Examples of the present invention for measuring formaldehyde contained in cigarette mainstream smoke; -
FIG. 3 is a graph showing the removal rate of formaldehyde achieved by various adsorbents; -
FIG. 4 shows a collecting method of the vapor phase components from cigarette mainstream smoke, which was employed in the Examples of the present invention; -
FIG. 5 shows gas chromatography of the vapor phase components contained in cigarette mainstream smoke, which was used in the Examples of the present invention; -
FIG. 6 is a graph showing the relationship between the vapor pressure of the vapor phase components and the removal rate of the vapor phase components, covering the case where hydrotalcite or charcoal was used as the adsorbent; -
FIG. 7A is a graph showing the particle size distribution of the hydrotalcite particles; -
FIG. 7B is a graph showing the relationship between the average particle diameter of the hydrotalcite particles and the resistance to draw; -
FIG. 8 is a graph showing the relationship between the surface area of the hydrotalcite particle and the formaldehyde reduction rate; -
FIG. 9 is a perspective view showing the construction of the paper filter prepared in Example 5; -
FIG. 10 is a perspective view showing the construction of the triple segment type filter prepared in Example 6; and -
FIG. 11 is a perspective view showing the construction of a filter in another Example of the present invention. - As a result of extensive research conducted from various viewpoints in an attempt to find an adsorbent effective for lowering the formaldehyde content in mainstream smoke, the present inventor has found that hydrotalcite compounds permit effectively removing formaldehyde.
- The hydrotalcite compound exhibits a lamellar structure in which a large number of octahedral layers of a divalent or trivalent metal hydroxide are laminated one upon the other, and an anion is intercalated in the octahedral layers. The octahedral layer is referred to as a host and exhibits basicity. It is considered reasonable to understand that the removal of formaldehyde achieved by the hydrotalcite compound results from contribution of the basicity of the host and from the ion exchange function performed by the intercalated anions.
- In the present invention, it is possible to use a natural or synthetic hydrotalcite compound. The hydrotalcite compound is represented by a general formula:
M2+ 1-xM3+ x(OH)2(An-)x/n • mH2O.
- In the most general hydrotalcite compound, a Mg ion constitutes the divalent metal ion M2+ included in the general formula given above, an Al ion constitutes the trivalent metal ion M3+, and CO3 2- or SO4 2- constitutes the anion An-. It is possible for a Zn ion, a Ni ion or a Ca ion to constitute the divalent metal ion M2+ in addition to the Mg ion. Also, it is possible for the anion to be selected from the group consisting of OOC-COO, Cl, Br, F, NO3, Fe(CN)6 3-, Fe(CN)6 4-, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, alkenyl acid and its derivative, malic acid, salicylic acid, acrylic acid, adipic acid, succinic acid, citric acid and sulfonic acid in addition to CO3 2- and SO4 2-. The symbol x in the general formula is larger than 0.1 and smaller than 0.4, i.e., 0.1 < x < 0.4, and the symbol m is larger than 0 and smaller than 2, i.e., 0 < m < 2. The Mg-Al-based hydrotalcite compound is stable in the case where the value of x falls within a range of between 0.20 and 0.33.
- In order to manufacture the hydrotalcite, a reaction is carried out by adding an alkali carbonate or both an alkali carbonate and a caustic alkali to an aqueous solution containing a water-soluble aluminum salt selected from the group consisting of aluminum sulfate, aluminum acetate and aluminum potassium sulfate or aluminic acid and a water-soluble magnesium salt while maintaining the pH value of the reaction mixture at 8.0 or more.
- It is possible to control a micro pore size of the hydrotalcite compound by, for example, the size of the anion intercalated in the hydrotalcite compound. It is also possible for the hydrotalcite compound to perform various functions depending on the nature of the anion and on the state of the interlayer water.
- Various types are conceivable as given below in respect of a cigarette filter having a hydrotalcite compound added thereto:
- (1) A cigarette filter in which the hydrotalcite compound is dispersed in the fiber tow or an unwoven fabric made of cellulose acetate.
- (2) A cigarette filter prepared by forming a paper sheet added with a hydrotalcite compound.
- (3) A cigarette filter formed of at least two segments comprising at least one segment, which is formed of the smoking filter referred to in item (1) or (2) given above, and the other segment, which is formed of the conventional cellulose acetate filter or a charcoal filter.
- (4) A cigarette filter prepared by filling the space of the plug-space-plug structure with the hydrotalcite compound. In this case, the plug is selected from the conventional cellulose acetate filter or charcoal filter, or the filter referred to in item (1) or (2) given above. Also, where there are two or more spaces, it suffices to fill at least one space with the hydrotalcite compound, and it is possible to fill the other space with charcoal.
- It is desirable to control the particle diameter of the hydrotalcite compound as follows. In the case of using a cigarette filter in which the hydrotalcite compound is dispersed in the cellulose acetate tow or unwoven fabric, or in which the hydrotalcite compound is filled in the space of the plug-space-plug, it is desirable for the hydrotalcite compound to have a particle diameter of 200 to 800 µm, more desirably 400 to 600 µm. On the other hand, in the case of using a cigarette filter prepared by forming a paper sheet made by adding the hydrotalcite compound, it is desirable for the hydrotalcite compound to have a particle diameter not larger than 10 µm.
- A hydrotalcite compound represented by Mg6Al2(OH)16CO3•4H2O was used. The particle diameter of the hydrotalcite compound was controlled to 250 to 500 µm by pulverization and sieving. A
filter 1 shown inFIG. 1 was prepared by using the hydrotalcite compound. To be more specific, ahydrotalcite powder 3 was filled in the space present between twoacetate filter segments paper 4 so as to prepare thefilter 1 of the plug-space-plug structure. - For comparison, filters of the plug-space-plug structure as shown in
FIG. 1 were prepared by using following adsorbents: charcoal, charcoal having a high specific surface area, alkali metal salt impregnated charcoal, amine impregnated charcoal, active alumina, magnesium oxide, aluminum oxide, magnesium silicate, zinc oxide, silica gel, zeolite, construction material pulp for formalin, a column packing material for gas chromatography (GC), and water-absorbing resin. - These filters were made equal to each other in the amount of the adsorbent. Also, a test cigarette was prepared by connecting a tobacco section containing 12 mg of tar to each of the filters.
- The amount of formaldehyde contained in cigarette mainstream smoke was measured according to "Health Canada - Official Method" (2,4-DNPH-HPLC method) so as to provide the removal rate of formaldehyde.
- To be more specific, 9.51 g of 2,4-dinitrophenyl hydrazine (DNPH) was dissolved in 1L of acetonitrile under heating, followed by adding 5.6 mL of a 60% perchloric acid to the solution and subsequently adding ultra pure water to the solution, thereby preparing 2L of a trapping solution.
- The construction of the measuring apparatus will now be described with reference to
FIG. 2 . As shown in the drawing, aDNPH trapping solution 12 is put in a Drechsel-type trap 11. The Drechsel-type trap 11 has an inner volume of 100 mL, and an amount of theDNPH trapping solution 12 is 80 mL. Thetrap 11 is put in anice water bath 13 so as to be cooled. The lower end of aglass pipe 14 to which acigarette 10 is attached is dipped in thetrapping solution 12 within thetrap 11. Further, aglass pipe 15 having aCambridge pad 16 mounted thereto is arranged to communicate with the dead volume of thetrap 11, and asmoking machine 17 was connected to theCambridge pad 16. - The
cigarette 10 was attached to theglass pipe 14 so as to permit thecigarette 10 to be automatically smoked under the standard smoking conditions specified in ISO standards. To be more specific, the operation of sucking 35 mL of the smoke in a single puff for two seconds for a single cigarette was repeated at an interval of 58 seconds. While the mainstream smoke was being bubbled, formaldehyde was converted into a derivative of DNPH. Two cigarettes were used for the measurement. In this case, the cigarettes using the different adsorbents were controlled to exhibit the same pressure loss. - The formaldehyde derivative thus formed was measured by high-performance liquid chromatography (HPLC). In the first step, the trapping solution was filtered, followed by diluting the filtered trapping solution with a Trizma Base solution (4 mL of trapping solution : 6 mL of Trizma Base solution). Then, the diluted solution was measured by the HPLC. The measuring conditions of the HPLC were as follows:
- Column: HP LiChrospher 100RP-18(5µ)250 × 4 mm
- Guard column: HP LiChrospher 100RP-18(5µ)4 × 4 mm
- Column temperature: 30°C
- Detecting wavelength: DAD 356 nm
- Injection amount: 20 µL
- Mobile phase: Gradients by three phases (solution A: ultra pure aqueous solution containing 30% of acetonitrile, 10% of tetrahydrofuran and 1% of isopropanol; solution B: ultra pure aqueous solution containing 65% of acetonitrile, 1% of tetrahydrofuran and 1% of isopropanol; solution C: 100% of acetonitrile).
- The removal rate of formaldehyde is represented by:
where E represents the removal rate of formaldehyde, W represents the amount of formaldehyde measured in the case of using a cigarette containing no adsorbent, and W' represents the amount of formaldehyde measured in the case of using a cigarette containing an adsorbent. -
FIG. 3 is a graph showing the removal rates of formaldehyde in the case of using various adsorbents. As apparent fromFIG. 3 , formaldehyde was most effectively removed in the case of using hydrotalcite as the adsorbent. - The removal rate of the vapor phase components contained in cigarette mainstream smoke was measured by using as an adsorbent a hydrotalcite compound or charcoal constituting the most general adsorbent for a cigarette.
- A filter similar to that shown in
FIG. 1 was manufactured as in Example 1 by preparing a hydrotalcite compound having a particle diameter of 250 to 500 µm or charcoal as an adsorbent and loading the adsorbent in an amount of 50 mg. Then, a cigarette was prepared by connecting a tobacco section containing 12 mg of tar to the filter thus manufactured. - The method of measuring the removal rate of the vapor phase components from cigarette mainstream smoke will now be described with reference to
FIGS. 4 and 5 . -
FIG. 4 shows the trapping method of the vapor phase components. As shown in the drawing, acigarette 10 was attached to asmoking machine 17 so as to permit thecigarette 10 to be automatically smoked under the standard smoking conditions specified in the ISO standards. In this case, the particle phase in the mainstream smoke was removed by a Cambridge filter, and the vapor phase was trapped by agas bag 20. Also, the operation of sucking 35 mL of the smoke in 2 seconds in a single puff for each cigarette was repeated at an interval of 58 seconds. Further, 10 conditioned cigarettes (conditioned under temperature of 22°C and humidity of 60%) were automatically smoked. -
FIG. 5 shows gas chromatography. As shown in the drawing, a prescribed amount of the vapor phase components trapped in thegas bag 20 is stored in asample loop 21. After a standard gas is injected, the vapor phase components are injected into agas chromatograph 22. The components are separated in a column (DB-WAX) and detected in a detector. Further, the amounts of the components are analyzed by using a program installed in a personal computer 23. The analytical value was obtained by dividing the peak area of each of the vapor phase components by the peak area of the standard gas. - The removal rate E of each of the vapor phase components is represented by:
where E represents the removal rate of each of the vapor phase components, A represents the analytical value of the component measured by using a cigarette containing no adsorbent, and A' represents the analytical value of the component measured by using a cigarette containing an adsorbent. -
FIG. 6 is a graph showing the relationship between the vapor pressure of the vapor phase component and the removal rate of the component. As apparent fromFIG. 6 , the removal rate is increased with increase in the vapor pressure of the vapor phase component in the case of using charcoal as an adsorbent. On the other hand, in the case of using a hydrotalcite compound as an adsorbent, the removal rate is specifically high in respect of formaldehyde, supporting that the hydrotalcite compound permits selectively removing formaldehyde. - In the case of using a hydrotalcite compound in a cigarette filter constructed as shown in, for example,
FIG. 1 , it is necessary to control appropriately the size of the hydrotalcite compound in order to control the resistance to draw and the outflow of tar/nicotine. - If the hydrotalcite compound is granulated, it is possible to prepare samples differing from each other in the particle size distribution. In this case, the samples are classified depending on the average particle diameter of the hydrotalcite compound.
FIG. 7A shows three types of samples having the average particle diameters of 250 µm, 500 µm, and 800 µm, respectively. - Filters of the construction as shown in
FIG. 1 were prepared by using hydrotalcite particles differing from each other in the average particle diameter. These filters differed from each other in the loading amount of the hydrotalcite particles. For reference, filters of the construction shown inFIG. 1 were also prepared by using charcoal. These filters also differed from each other in the loading amount of the charcoal. - The resistance to draw was examined in respect of these filters under the sucking flow rate of 1050 mL/min. Here, the resistance to draw was calculated by excluding the resistance to draw due to the two
acetate filter segments FIG. 1 . -
FIG. 7B is a graph showing the relationship between the average particle diameter and the resistance to draw. As apparent fromFIG. 7B , the resistance to draw is high in the case of using the adsorbent particles having the average particle diameter of 250 µm and is low in the case of using the adsorbent particles having the average particle diameter of 800 µm.FIG. 7B also indicates that it is reasonable to use hydrotalcite particles having the average particle diameter falling within a range of between 400 µm and 600 µm in designing cigarettes. - In the case of using granulated particles, it is possible to provide hydrotalcite particles having a desired size by employing any granulating method such as rolling granulation, compression molding, coating granulation, or extrusion molding. It should be noted in this connection that, in order to avoid the breakage of the hydrotalcite particles in the manufacturing process of the filter, it is desirable to employ a granulating method that permits manufacturing granulated hydrotalcite particles having an appropriate hardness. The present inventor found that it is possible to prevent the hydrotalcite particles from being broken in the manufacturing process of the filter if the hydrotalcite particles have a hardness falling within a range of between 300 g/mm2 and 3,000 g/mm2.
- This Example is intended to support that the reduction rate of the formaldehyde content in mainstream smoke achieved by the hydrotalcite particle is dependent on the surface area of the hydrotalcite particle.
- Various granulated hydrotalcite particles were prepared by means of (A) rolling granulation, (B) compression molding, and (C) extrusion molding. The average surface area per unit weight of the hydrotalcite particles was calculated by using a laser scattering type particle size distribution measuring apparatus.
- Filters of the construction as shown in
FIG. 1 were prepared by using hydrotalcite particles having various surface areas. In this case, the total surface area of the hydrotalcite particles was adjusted by controlling the amount of the hydrotalcite particles. Then, the relationship between the total surface area of the hydrotalcite particles and the reduction rate of the formaldehyde content in the mainstream smoke was examined.FIG. 8 is a graph showing the result. - As apparent from
FIG. 8 , it has been found that the reduction rate of the formaldehyde content in the mainstream smoke can be increased with increase in the total surface area of the hydrotalcite particles. This tendency is exhibited regardless of the granulating method of the hydrotalcite particles. - This Example is intended to examine the reduction rate of formaldehyde contained in mainstream smoke, which is achieved by a paper filter to which hydrotalcite particles are added, and by a cellulose acetate filter to which granulated hydrotalcite particles are added.
- Specifically, a paper sheet was made while adding hydrotalcite particles having an average particle diameter not larger than 10 µm. Then, the
paper filter 7 shown inFIG. 9 was prepared by using the resultant paper sheet. For comparison, a filter was prepared by forming a paper sheet to which hydrotalcite particles were not added. - A filter was also prepared by dispersing granulated hydrotalcite particles in the cellulose acetate tow. For comparison, a cellulose acetate filter was prepared without using hydrotalcite particles.
- Incidentally, the filters thus prepared were 25 mm long and were made as uniform as possible in the resistance to draw.
- The reduction rate of the formaldehyde content in mainstream smoke was examined by using the filter thus prepared. Table 1 shows the result.
- As shown in Table 1, the ratio of formaldehyde outflow to tar outflow was decreased in the paper filter containing the hydrotalcite particles, compared with the acetate filter containing the hydrotalcite particles. It is considered reasonable to understand that the result was achieved by the large contact surface area of the hydrotalcite particles having an average particle diameter not larger than 10 µm dispersed in the paper filter.
Table 1 HT amount Length Resistance to draw Tar outflow FA outflow FA/Tar (mg) (mm) (mmWG) (mg/cigarette) (µg/cigarette) (-) Acetate filter 0 25 65.5 12.53 72.86 5.81 146.7 25 61.9 12.19 35.70 2.93 Paper filter 0 25 65.0 7.31 48.56 6.64 48.3 25 65.5 6.42 14.03 2.19 - This Example is intended to support that the reduction rate of the organic vapor components can be increased by the combination of a hydrotalcite filter and a charcoal filter.
- Filters I, II, III of the triple segment structure including an acetate filter segment, a hydrotalcite (HT) filter segment and a charcoal filter segment as shown in Table 2 were prepared. The acetate filter segment was prepared by bundling cellulose acetate tow and was 7 mm long. The hydrotalcite (HT) filter segment was prepared by bundling cellulose acetate tow having 70 mg of hydrotalcite particles dispersed therein and was 10 mm long. Further, the charcoal filter segment was prepared by bundling cellulose acetate tow having 70 mg of charcoal particles dispersed therein and was 10 mm long.
-
FIG. 10 shows the construction of the filter III shown in Table 2. As shown in the drawing, acharcoal filter segment 5 is arranged on the side of the cut tobacco, an acetate filter segment is arranged on the inhaling side, and anHT filter segment 6 is arranged intermediate between thecharcoal filter segment 5 and theacetate filter segment 2. - The reduction rate of the total organic vapor (TOV) and the reduction rate of formaldehyde (FA) from mainstream smoke were examined by using these filters. Table 2 shows the results.
- As shown in Table 2, the filter III permits lowering the content of the total organic vapor because of the function of the charcoal filter and also permits lowering the formaldehyde content because of the function of the hydrotalcite (HT) filter.
Table 2 Cut tobacco side Center Inhaling side TOV reduction rate (%) FA reduction rate (%) I charcoal filter acetate filter acetate filter 62.7 67.2 II acetate filter HT filter acetate filter 20.8 69.3 III charcoal filter HT filter acetate filter 64.8 71.9 Weight of additives: 70 mg/10 mm
Filter length: 10mm, 10mm, and 7mm
Ventilation resistance of filter tip: 72 mmWG/27 mm
Ventilation hole: no - Various modifications are conceivable as follows in respect of the filter used in the present invention.
- For example, in the filter of the construction as shown in
FIG. 1 , it is possible to use another filter segment in place of at least one of theacetate filter segments 2. To be more specific, it is possible to use a hydrotalcite filter segment or a charcoal filter segment in place of at least one of theacetate filter segments 2. In the case of using a charcoal filter segment, it is desirable to arrange the charcoal filter segment on the cut tobacco side as inFIG. 10 . - In the structure shown in
FIG. 10 , the cellulose acetate tow having a hydrotalcite compound dispersed therein were used for forming the hydrotalcite filter segment. Alternatively, it is also possible to use a hydrotalcite filter segment prepared by forming a paper sheet made by adding hydrotalcite compound. - It is also possible to prepare a filter of a four-segment structure by attaching an additional filter segment to the filter of the three segment structure shown in
FIG. 10 . - Further, it is possible to use a filter comprising a
charcoal filter segment 5, a space filled withhydrotalcite particles 3, a hydrotalcite (HT)filter segment 6 and anacetate filter segment 2, as shown inFIG. 11 . - It is possible for the
hydrotalcite filter segment 6 to be acetate filter-based or paper filter-based in this case, too. It is possible for the arrangement of the space filled with theHT particles 3 and theHT filter segment 6 to be opposite to that shown inFIG. 11 . InFIG. 11 , the space is filled with HT particles. Alternatively, it is possible for the space to be filled with charcoal particles. - According to the present invention, it is possible to provide a cigarette with a cigarette filter, which permit effectively lowering the formaldehyde content in mainstream smoke.
Claims (4)
- A cigarette, characterized by comprising:a tobacco rod; anda cigarette filter connected to the tobacco rod, the cigarette filter comprising a cellulose acetate tow or an unwoven fabric made of cellulose acetate and particles of hydrotalcite compound dispersed in the cellulose acetate tow or unwoven fabric made of cellulose acetate,or comprising filter segments of cellulose acetate tow and particles of hydrotalcite compound filled in a space present between the adjacent filter segments,the hydrotalcite compound having an average particle diameter in a range of between 200 µm and 800 µm.
- The cigarette according to claim 1, characterized in that the hydrotalcite compound is represented by a general formula:
M2+ 1-xM3+ x(OH)2(An-)x/n·mH2O
where M2+ represents a divalent metal ion selected from the group consisting of a Mg ion, a Zn ion, a Ni ion and a Ca ion, M3+ represents an Al ion, An- represents an anion having a valency of n, which is selected from the group consisting of CO3, SO4, OOC-COO, Cl, Br, F, NO3, Fe(CN)6 3-, Fe(CN)6 4-, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, alkenyl acid and its derivative, malic acid, salicylic acid, acrylic acid, adipic acid, succinic acid, citric acid and sulfonic acid, 0.1 < x < 0.4, and 0 < m < 2. - The cigarette according to claim 1, wherein the cigarette filter comprises filter segments of cellulose acetate tow and particles of hydrotalcite compound filled in a space present between the adjacent filter segments, characterized by further comprising a charcoal filter segment in addition to the fitter segment containing the hydrotalcite compound.
- The cigarette according to claim 1, characterized in that the hydrotalcite compound is contained in a range of between 50 and 146.7 mg/cigarette.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002001509 | 2002-01-08 | ||
JP2002001509 | 2002-01-08 | ||
PCT/JP2003/000036 WO2003056947A1 (en) | 2002-01-08 | 2003-01-07 | Smoking filter and smoking article |
Publications (3)
Publication Number | Publication Date |
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EP1470761A1 EP1470761A1 (en) | 2004-10-27 |
EP1470761A4 EP1470761A4 (en) | 2009-05-27 |
EP1470761B1 true EP1470761B1 (en) | 2015-12-30 |
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EP03701015.4A Expired - Lifetime EP1470761B1 (en) | 2002-01-08 | 2003-01-07 | Smoking filter and smoking article |
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US (1) | US20040237983A1 (en) |
EP (1) | EP1470761B1 (en) |
JP (1) | JP3895327B2 (en) |
KR (1) | KR100912311B1 (en) |
CN (2) | CN102028307A (en) |
AU (1) | AU2003202479A1 (en) |
CA (1) | CA2472385C (en) |
DK (1) | DK1470761T3 (en) |
ES (1) | ES2563032T3 (en) |
MY (1) | MY146655A (en) |
PT (1) | PT1470761E (en) |
RU (1) | RU2291657C2 (en) |
TW (1) | TWI324049B (en) |
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Cited By (2)
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CN110639283A (en) * | 2019-09-16 | 2020-01-03 | 江苏清荷材料科技有限公司 | Method for preparing air filter screen by adopting attapulgite composite material |
RU2739544C1 (en) * | 2017-06-19 | 2020-12-25 | Джапан Тобакко Инк. | Smoking article filter and method of manufacturing thereof |
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DE102004048651A1 (en) * | 2004-10-06 | 2006-04-13 | Rhodia Acetow Gmbh | Tobacco smoke filters or filter elements containing additives |
JP4556026B2 (en) * | 2004-12-28 | 2010-10-06 | 富田製薬株式会社 | Formaldehyde gas treating agent and formaldehyde gas treating method |
JP2008131856A (en) * | 2005-02-28 | 2008-06-12 | Japan Tobacco Inc | Apparatus for inspecting multiple filter rod |
JP5126868B2 (en) * | 2006-12-25 | 2013-01-23 | 株式会社ダイセル | Filter material made of porous material and cigarette filter using the same |
JP5800460B2 (en) | 2010-02-01 | 2015-10-28 | 株式会社ダイセル | Cigarette filters containing magnesium metasilicate aluminate |
GB201004976D0 (en) * | 2010-03-24 | 2010-05-12 | Filtrona Int Ltd | Tobacco smoke filter |
US9034106B2 (en) * | 2010-03-26 | 2015-05-19 | Philip Morris Usa Inc. | Smoking article including alkanoylated glycoside |
GB201007946D0 (en) * | 2010-05-12 | 2010-06-30 | British American Tobacco Co | Filter additive |
JP5623875B2 (en) | 2010-11-11 | 2014-11-12 | 株式会社ダイセル | COMPOSITE PARTICLE, TOBACCO FILTER, ITS MANUFACTURING METHOD, AND TOBACCO |
EP2540174B1 (en) | 2011-06-29 | 2017-06-21 | Daicel Corporation | Tobacco Filter Containing Magnesium Aluminometasilicate |
WO2013084661A1 (en) * | 2011-12-06 | 2013-06-13 | 日本たばこ産業株式会社 | Cigarette filter and cigarette |
CN102551206A (en) * | 2012-01-04 | 2012-07-11 | 安徽中烟工业有限责任公司 | Cigarette filter containing layered double hydroxide and capable of reducing harmful ingredient emission in cigarette mainstream smoke |
JP6575993B2 (en) * | 2015-05-25 | 2019-09-18 | 住江織物株式会社 | Ammonia gas, sulfur dioxide gas and nitrogen dioxide gas removal filter |
JP6535810B2 (en) * | 2016-03-28 | 2019-06-26 | 日本たばこ産業株式会社 | Filter for smoking article, smoking article, and method of manufacturing filter for smoking article |
US20190343175A1 (en) * | 2016-12-29 | 2019-11-14 | Philip Morris Products S.A. | Smoking article filter with amorphous magnesium carbonate |
JPWO2020153491A1 (en) * | 2019-01-25 | 2021-11-18 | 日本たばこ産業株式会社 | Filter for smoking goods |
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DE2740011A1 (en) * | 1977-09-06 | 1979-03-08 | Bat Cigarettenfab Gmbh | METHOD FOR REMOVING NITROGEN MONOXIDE AND CARBON MONOXIDE FROM TOBACCO SMOKE AND TOBACCO MATERIAL, SMOKE FILTER AND CIGARETTE PAPER FOR ITS IMPLEMENTATION |
JPS63248380A (en) * | 1987-04-06 | 1988-10-14 | 三井東圧化学株式会社 | Radical catching agent for tobacco smoke |
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US5362457A (en) * | 1992-08-13 | 1994-11-08 | Aluminum Company Of America | Direct synthesis of anion substituted hydrotalcite |
DE4322966C2 (en) * | 1993-07-09 | 1995-10-26 | Rhodia Ag Rhone Poulenc | Cellulose acetate molded structures and their use as filter tow and tobacco smoke filter element |
US5509430A (en) * | 1993-12-14 | 1996-04-23 | American Filtrona Corporation | Bicomponent fibers and tobacco smoke filters formed therefrom |
JP3745857B2 (en) * | 1996-06-04 | 2006-02-15 | ゼオン化成株式会社 | Deodorizing agent, deodorizing filter and deodorizing device using the same |
JPH10280298A (en) * | 1997-04-03 | 1998-10-20 | Toagosei Co Ltd | Deodorizing sheet |
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JP2003155696A (en) * | 2001-11-16 | 2003-05-30 | Oji Paper Co Ltd | Cigarette paper |
-
2002
- 2002-12-31 TW TW091137960A patent/TWI324049B/en not_active IP Right Cessation
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- 2003-01-03 MY MYPI20030015A patent/MY146655A/en unknown
- 2003-01-07 CN CN2010105256143A patent/CN102028307A/en active Pending
- 2003-01-07 DK DK03701015.4T patent/DK1470761T3/en active
- 2003-01-07 ES ES03701015.4T patent/ES2563032T3/en not_active Expired - Lifetime
- 2003-01-07 EP EP03701015.4A patent/EP1470761B1/en not_active Expired - Lifetime
- 2003-01-07 JP JP2003557319A patent/JP3895327B2/en not_active Expired - Fee Related
- 2003-01-07 PT PT3701015T patent/PT1470761E/en unknown
- 2003-01-07 CN CNA038019744A patent/CN1612701A/en active Pending
- 2003-01-07 KR KR1020047010408A patent/KR100912311B1/en active IP Right Grant
- 2003-01-07 RU RU2004124060/12A patent/RU2291657C2/en active
- 2003-01-07 AU AU2003202479A patent/AU2003202479A1/en not_active Abandoned
- 2003-01-07 CA CA2472385A patent/CA2472385C/en not_active Expired - Lifetime
- 2003-01-07 WO PCT/JP2003/000036 patent/WO2003056947A1/en active Application Filing
- 2003-07-01 UA UA20040806603A patent/UA77052C2/en unknown
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- 2004-07-07 US US10/885,088 patent/US20040237983A1/en not_active Abandoned
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2739544C1 (en) * | 2017-06-19 | 2020-12-25 | Джапан Тобакко Инк. | Smoking article filter and method of manufacturing thereof |
CN110639283A (en) * | 2019-09-16 | 2020-01-03 | 江苏清荷材料科技有限公司 | Method for preparing air filter screen by adopting attapulgite composite material |
Also Published As
Publication number | Publication date |
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TW200301681A (en) | 2003-07-16 |
RU2004124060A (en) | 2006-01-27 |
WO2003056947A1 (en) | 2003-07-17 |
ES2563032T3 (en) | 2016-03-10 |
US20040237983A1 (en) | 2004-12-02 |
UA77052C2 (en) | 2006-10-16 |
MY146655A (en) | 2012-09-14 |
CA2472385C (en) | 2011-08-02 |
TWI324049B (en) | 2010-05-01 |
CA2472385A1 (en) | 2003-07-17 |
DK1470761T3 (en) | 2016-02-15 |
KR20040073534A (en) | 2004-08-19 |
EP1470761A4 (en) | 2009-05-27 |
CN1612701A (en) | 2005-05-04 |
KR100912311B1 (en) | 2009-08-14 |
CN102028307A (en) | 2011-04-27 |
EP1470761A1 (en) | 2004-10-27 |
RU2291657C2 (en) | 2007-01-20 |
JP3895327B2 (en) | 2007-03-22 |
PT1470761E (en) | 2016-03-18 |
AU2003202479A1 (en) | 2003-07-24 |
JPWO2003056947A1 (en) | 2005-05-12 |
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