EP1470761B1 - Rauchfilter und rauchartikel - Google Patents
Rauchfilter und rauchartikel 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
- Authority
- 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.)
- Expired - Lifetime
Links
- 230000000391 smoking effect Effects 0.000 title description 18
- 229960001545 hydrotalcite Drugs 0.000 claims description 106
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 106
- 239000002245 particle Substances 0.000 claims description 67
- 235000019504 cigarettes Nutrition 0.000 claims description 55
- -1 hydrotalcite compound Chemical class 0.000 claims description 51
- 239000003610 charcoal Substances 0.000 claims description 29
- 229920002301 cellulose acetate Polymers 0.000 claims description 23
- 241000208125 Nicotiana Species 0.000 claims description 10
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 96
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 57
- 239000003463 adsorbent Substances 0.000 description 23
- 239000000779 smoke Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000012808 vapor phase Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 238000010276 construction Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 229910020038 Mg6Al2 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- QANIADJLTJYOFI-UHFFFAOYSA-K aluminum;magnesium;carbonate;hydroxide;hydrate Chemical compound O.[OH-].[Mg+2].[Al+3].[O-]C([O-])=O QANIADJLTJYOFI-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000011361 granulated particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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.
Landscapes
- 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)
- Filtering Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Claims (4)
- Zigarette, dadurch gekennzeichnet, dass sie enthält:eine Tabakstange; undeinen Zigarettenfilter, der mit der Tabakstange verbunden ist, wobei der Zigarettenfilter ein Zelluloseacetatkabel oder ein aus Zelluloseacetat hergestelltes Faservlies und Teilchen einer Hydrotalcitverbindung, die in dem Zelluloseacetatkabel oder dem aus Zelluloseacetat hergestellten Faservlies verteilt sind, enthält,oder Filterabschnitte aus einem Zelluloseacetatkabel und Teilchen einer Hydrotalcitverbindung, die in einen zwischen benachbarten Filterabschnitten vorhandenen Raum eingefüllt sind, enthält, wobei die Hydrotalcitverbindung einen mittleren Teilchendurchmesser in einem Bereich von zwischen 200 µm und 800 µm aufweist.
- Zigarette nach Anspruch 1, dadurch gekennzeichnet, dass die Hydrotalcitverbindung durch die allgemeine Formel:
M2+ 1-xM3+ x(OH)2(A-n)x/n·mH2O
wiedergegeben ist, in der M2+ für ein zweiwertiges Metallion steht, das ausgewählt ist aus der Gruppe, bestehend aus einem Mg-Ion, einem Zn-Ion, einem Ni-Ion und einem Ca-Ion, M3+ für ein Al-Ion steht, An- für ein Anion mit einer Wertigkeit n steht, das ausgewählt ist aus der Gruppe, bestehend aus CO3, SO4, OOC-COO, Cl, Br, F, NO3, Fe(CN)6 3-, Fe(CN)6 4-, Phthalsäure, Isophthalsäure, Terephthalsäure, Maleinsäure, Alkenylsäure und dessen Derivate, Äpfelsäure, Salicylsäure, Acrylsäure, Adipinsäure, Bernsteinsäure, Zitronensäure und Sulfonsäure, und 0,1 < x < 0,4 und 0 < m < 2 ist. - Zigarette nach Anspruch 1, wobei der Zigarettenfilter Filterabschnitte aus einem Zelluloseacetatkabel und Teilchen einer Hydrotalcitverbindung, die in einen zwischen benachbarten Filterabschnitten vorhandenen Raum eingefüllt sind, enthält und dadurch gekennzeichnet ist, dass er neben dem die Hydrotalcitverbindung enthaltenden Filterabschnitt ferner einen Filterabschnitt aus Aktivkohle enthält.
- Zigarette nach Anspruch 1, dadurch gekennzeichnet, dass die Hydrotalcitverbindung in einem Bereich von zwischen 50 und 146,7 mg/Zigarette enthalten ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP2002001509 | 2002-01-08 | ||
JP2002001509 | 2002-01-08 | ||
PCT/JP2003/000036 WO2003056947A1 (fr) | 2002-01-08 | 2003-01-07 | Filtre anti-fumee et article a fumer |
Publications (3)
Publication Number | Publication Date |
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EP1470761A1 EP1470761A1 (de) | 2004-10-27 |
EP1470761A4 EP1470761A4 (de) | 2009-05-27 |
EP1470761B1 true EP1470761B1 (de) | 2015-12-30 |
Family
ID=19190626
Family Applications (1)
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EP03701015.4A Expired - Lifetime EP1470761B1 (de) | 2002-01-08 | 2003-01-07 | Rauchfilter und rauchartikel |
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US (1) | US20040237983A1 (de) |
EP (1) | EP1470761B1 (de) |
JP (1) | JP3895327B2 (de) |
KR (1) | KR100912311B1 (de) |
CN (2) | CN1612701A (de) |
AU (1) | AU2003202479A1 (de) |
CA (1) | CA2472385C (de) |
DK (1) | DK1470761T3 (de) |
ES (1) | ES2563032T3 (de) |
MY (1) | MY146655A (de) |
PT (1) | PT1470761E (de) |
RU (1) | RU2291657C2 (de) |
TW (1) | TWI324049B (de) |
UA (1) | UA77052C2 (de) |
WO (1) | WO2003056947A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110639283A (zh) * | 2019-09-16 | 2020-01-03 | 江苏清荷材料科技有限公司 | 一种采用凹土复合材料制备空气滤网的方法 |
RU2739544C1 (ru) * | 2017-06-19 | 2020-12-25 | Джапан Тобакко Инк. | Фильтр курительного изделия и способ его изготовления |
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DE102004048651A1 (de) * | 2004-10-06 | 2006-04-13 | Rhodia Acetow Gmbh | Tabakrauchfilter oder -filterelemente mit einem Gehalt an Zusatzstoffen |
JP4556026B2 (ja) * | 2004-12-28 | 2010-10-06 | 富田製薬株式会社 | ホルムアルデヒドガス処理剤及びホルムアルデヒドガス処理方法 |
JP2008131856A (ja) * | 2005-02-28 | 2008-06-12 | Japan Tobacco Inc | 多重フィルタロッドの検査装置 |
JP5126868B2 (ja) * | 2006-12-25 | 2013-01-23 | 株式会社ダイセル | 多孔質体からなるフィルタ素材およびそれを用いたたばこフィルタ |
JP5800460B2 (ja) | 2010-02-01 | 2015-10-28 | 株式会社ダイセル | メタ珪酸アルミン酸マグネシウムを含有するたばこフィルタ |
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 (ja) | 2010-11-11 | 2014-11-12 | 株式会社ダイセル | 複合粒子、タバコフィルター及びその製造方法並びにタバコ |
EP2540174B1 (de) * | 2011-06-29 | 2017-06-21 | Daicel Corporation | Tabakfilter mit Magnesiumaluminiummetallsilikat |
CN103987284B (zh) * | 2011-12-06 | 2019-01-11 | 日本烟草产业株式会社 | 香烟过滤嘴及香烟 |
CN102551206A (zh) * | 2012-01-04 | 2012-07-11 | 安徽中烟工业有限责任公司 | 一种可降低卷烟主流烟气有害成分释放量的含层状双氢氧化物的卷烟滤嘴 |
JP6575993B2 (ja) * | 2015-05-25 | 2019-09-18 | 住江織物株式会社 | アンモニアガス、二酸化硫黄ガス及び二酸化窒素ガス除去フィルター |
EP3400814A4 (de) * | 2016-03-28 | 2019-08-21 | Japan Tobacco Inc. | Filter für rauchartikel, rauchartikel und verfahren zur herstellung eines filters für rauchartikel |
JP7150719B2 (ja) * | 2016-12-29 | 2022-10-11 | フィリップ・モーリス・プロダクツ・ソシエテ・アノニム | 非晶質炭酸マグネシウムを有する喫煙物品フィルター |
CN113347895A (zh) | 2019-01-25 | 2021-09-03 | 日本烟草产业株式会社 | 吸烟物品用滤嘴 |
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DE2740011A1 (de) * | 1977-09-06 | 1979-03-08 | Bat Cigarettenfab Gmbh | Verfahren zur entfernung von stickstoffmonoxid und kohlenmonoxid aus tabaksrauch sowie tabakmaterial, rauchfilter und cigarettenpapier zu seiner durchfuehrung |
JPS63248380A (ja) * | 1987-04-06 | 1988-10-14 | 三井東圧化学株式会社 | 煙草煙用ラジカル捕捉剤 |
US5360023A (en) * | 1988-05-16 | 1994-11-01 | R. J. Reynolds Tobacco Company | Cigarette filter |
US5362457A (en) * | 1992-08-13 | 1994-11-08 | Aluminum Company Of America | Direct synthesis of anion substituted hydrotalcite |
DE4322966C2 (de) * | 1993-07-09 | 1995-10-26 | Rhodia Ag Rhone Poulenc | Aus Celluloseacetat geformte Gebilde und ihre Verwendung als Filtertow und Tabakrauchfilterelement |
US5509430A (en) * | 1993-12-14 | 1996-04-23 | American Filtrona Corporation | Bicomponent fibers and tobacco smoke filters formed therefrom |
JP3745857B2 (ja) * | 1996-06-04 | 2006-02-15 | ゼオン化成株式会社 | 脱臭剤、それを用いた脱臭フィルタおよび脱臭装置 |
JPH10280298A (ja) * | 1997-04-03 | 1998-10-20 | Toagosei Co Ltd | 消臭性シート |
JPH11553A (ja) * | 1997-06-13 | 1999-01-06 | Nippon Steel Corp | 脱臭材およびその製造方法 |
JP2001300220A (ja) * | 2000-04-20 | 2001-10-30 | Zeon Kasei Co Ltd | 空気清浄用フィルタ装置 |
ITPI20010014A1 (it) * | 2001-03-05 | 2002-09-05 | Ivo Pera | Composto per filtri per sigarette,o altri articoli da fumo,a base di sostanze antiossidanti ed il filtro cosi'ottenuto |
JP2003155696A (ja) * | 2001-11-16 | 2003-05-30 | Oji Paper Co Ltd | たばこ用巻紙 |
-
2002
- 2002-12-31 TW TW091137960A patent/TWI324049B/zh not_active IP Right Cessation
-
2003
- 2003-01-03 MY MYPI20030015A patent/MY146655A/en unknown
- 2003-01-07 DK DK03701015.4T patent/DK1470761T3/en active
- 2003-01-07 EP EP03701015.4A patent/EP1470761B1/de not_active Expired - Lifetime
- 2003-01-07 RU RU2004124060/12A patent/RU2291657C2/ru active
- 2003-01-07 CA CA2472385A patent/CA2472385C/en not_active Expired - Lifetime
- 2003-01-07 ES ES03701015.4T patent/ES2563032T3/es not_active Expired - Lifetime
- 2003-01-07 KR KR1020047010408A patent/KR100912311B1/ko active IP Right Grant
- 2003-01-07 CN CNA038019744A patent/CN1612701A/zh active Pending
- 2003-01-07 PT PT3701015T patent/PT1470761E/pt unknown
- 2003-01-07 CN CN2010105256143A patent/CN102028307A/zh active Pending
- 2003-01-07 AU AU2003202479A patent/AU2003202479A1/en not_active Abandoned
- 2003-01-07 WO PCT/JP2003/000036 patent/WO2003056947A1/ja active Application Filing
- 2003-01-07 JP JP2003557319A patent/JP3895327B2/ja not_active Expired - Fee Related
- 2003-07-01 UA UA20040806603A patent/UA77052C2/uk unknown
-
2004
- 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 (ru) * | 2017-06-19 | 2020-12-25 | Джапан Тобакко Инк. | Фильтр курительного изделия и способ его изготовления |
CN110639283A (zh) * | 2019-09-16 | 2020-01-03 | 江苏清荷材料科技有限公司 | 一种采用凹土复合材料制备空气滤网的方法 |
Also Published As
Publication number | Publication date |
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CN102028307A (zh) | 2011-04-27 |
KR100912311B1 (ko) | 2009-08-14 |
JPWO2003056947A1 (ja) | 2005-05-12 |
CA2472385A1 (en) | 2003-07-17 |
CN1612701A (zh) | 2005-05-04 |
UA77052C2 (en) | 2006-10-16 |
EP1470761A4 (de) | 2009-05-27 |
JP3895327B2 (ja) | 2007-03-22 |
MY146655A (en) | 2012-09-14 |
AU2003202479A1 (en) | 2003-07-24 |
DK1470761T3 (en) | 2016-02-15 |
EP1470761A1 (de) | 2004-10-27 |
RU2004124060A (ru) | 2006-01-27 |
CA2472385C (en) | 2011-08-02 |
TW200301681A (en) | 2003-07-16 |
KR20040073534A (ko) | 2004-08-19 |
RU2291657C2 (ru) | 2007-01-20 |
ES2563032T3 (es) | 2016-03-10 |
TWI324049B (en) | 2010-05-01 |
PT1470761E (pt) | 2016-03-18 |
WO2003056947A1 (fr) | 2003-07-17 |
US20040237983A1 (en) | 2004-12-02 |
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