JP2009050280A - Low sidestream smoke cigarette with combustible paper having modified ash characteristics - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a combustible treatment paper with an improved ash characteristics by adding a metal oxide or a carbonate to a treatment composition and/or in the composition. <P>SOLUTION: The low sidestream smoke cigarette comprises a conventional tobacco rod (54), and a combustible treatment paper (56, 58) having a sidestream smoke treatment composition. The treatment composition comprises in combination, an oxygen storage and donor metal oxide oxidation catalyst and an essentially non-combustible particulate adjunct for the catalyst. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to the reduction of sidestream smoke in burning cigarettes and other smoking products. More specifically, the present invention reduces cigarette paper, cigarette wrappers, or cigars or other similar tobacco leaves to reduce visible sidestream smoke and at the same time provide modified ash. (Tobacco) relates to product wrappers.

  Various attempts have been made to reduce or eliminate sidestream smoke generated from burning cigarettes. The present applicants are described in Patent Documents 1 and 2 (Canadian Patent Nos. 2054735 and 2057962); Patent Documents 3 and 4 (U.S. Pat. Various approaches to cigarette sidestream smoke control systems have been developed as described in WO 98/16125 and WO 99/53778).

  Other cigarette sidestream smoke control systems have been developed that use filter or adsorbent materials in tobacco leaves, filters, or paper wrappers. Examples of these systems are described in U.S. Pat. Nos. 5,048,086 (U.S. Pat. Nos. 2,755,207, 4,108,151 and 4,225,636); U.S. Pat. Nos. 7,140,027 and 2,051,254; 27831 and WO 99/53778). Patent Document 15 (US Pat. No. 2,755,207) describes thin paper for low sidestream smoke cigarettes. When the cigarette paper burns, it produces smoke that is substantially free of unpleasant components. Cigarette paper is a cellulosic material in the form of fibers. This is intimately bonded with a finely divided mineral type siliceous catalyst material. Intrinsically non-flammable and refractory cigarette paper does not change substantially while the cigarette paper is burning, and functions as a catalyst that changes paper combustion. Suitable siliceous catalysts include acid-treated clays, heat-treated montmorillonite, and natural and synthetic silicates containing several relatively mobile hydrogen atoms. Suitable mixed silica oxides include silica oxides having alumina, zirconia, titania, chromium oxide and magnesium oxide. Other silicas include silicon and aluminum oxides with a silica to alumina weight ratio of 9: 1.

  US Pat. No. 4,810,151 describes the use of a gamma alumina filler for thin cigarette paper that selectively reduces organic vapor phase components in tobacco leaf smoke. There is at least 50 weight percent alumina filler in the cigarette paper that reduces the organic vapor phase component in the tobacco leaf smoke. As a result, visible sidestream smoke generated from the burning cigarette is reduced. Gamma alumina is most commonly known as activated alumina and is comminuted until it passes through a 300 mesh sieve.

  U.S. Patent No. 4,225,636 describes the use of carbon in thin cigarette paper to reduce the organic vapor phase components and total particulate matter found in sidestream smoke. In addition, the carbon substantially reduces visible sidestream smoke generated from the burning cigarette. Activated carbon is preferred as the carbon source. The use of activated carbon reduces some of the visible sidestream smoke. The cigarette paper may be up to 50% finely ground carbon. Carbon coated paper can be used as an inner wrap for a tobacco leaf rod in combination with a conventional cigarette.

  Patent Document 18 (European Patent Application No. 0740907) published on November 6, 1996 describes a cigarette that changes the characteristics of mainstream smoke and in particular removes various components such as tar from mainstream smoke. The use of zeolite in tobacco tobacco leaves is described. When fed into tobacco leaves, zeolites also clearly change the characteristics of sidestream smoke. The zeolite used was of a particle size between 0.5 mm and 1.2 mm.

Patent document 19 (European application 0512254) describes the use of high apparent surface area fillers in thin cigarette paper. Fillers are generally crystals and solids having a surface area of at least 20 m ² / g. The filler is preferably a peroxide, carbonate, phosphate, sulfate, aluminate and silicate. It is taught that porous fillers such as zeolite are not preferred in thin cigarette papers and that they function similarly to conventional chalk.

  Patent document 20 (published PCT patent application WO 97/27831) describes that polar liquids or gases are formed by the use of dealuminated zeolites to absorb nonpolar or weakly polar molecules. . An effective amount of enhanced dealuminated zeolite can be incorporated into the cigarette paper to reduce carbon monoxide in sidestream smoke. The step of dealuminating the alumina zeolite renders the zeolite hydrophobic so that it has the effect of absorbing and removing nonpolar or weakly polar molecules, and the effect occurs even in the presence of water.

  Patent Document 21 (published PCT patent application WO99 / 53778) describes a non-combustible sheet made of a processing material for reducing the emission of sidestream smoke. This sheet is used as a wrap and applied over a conventional cigarette paper. Because this wrap has a very high porosity, the cigarette can burn at or near the traditional free-burn rate and at the same time reduce visible sidestream smoke emissions. . This non-combustible wrap includes non-combustible ceramic fibers, non-combustible activated carbon fibers, and other standard materials used in the manufacture of wraps. The wrap also includes zeolite or other similar sorption material, and oxygen donating / oxygen storage metal oxide oxidation catalyst. Incombustible wrap provides acceptable sidestream smoke control, but charred tubes remain due to the non-combustible nature of the wrap.

  U.S. Pat. Nos. 4,036,036 and U.S. Pat. Nos. 4,433,697 and 4,915,117 describe incorporating ceramic fibers in the manufacture of cigarette paper. US Pat. No. 4,433,697 discloses a finished paper in combination with magnesium oxide and / or magnesium hydroxide filler to reduce visible sidestream smoke generated from burning cigarettes. At least 1% by weight of specific ceramic fibers in the furnish are described. A paper sheet is manufactured by a conventional papermaking machine using a furnish made of fiber pulp, ceramic fibers, and a filler. The ceramic fibers can be selected from the group of polycrystalline alumina, aluminum-silicate, and amorphous alumina. Magnesium hydroxide or magnesium oxide filler is used and is coated or applied to the fibers of the sheet.

  Ito, in US Pat. No. 4,915,117, describes a non-combustible sheet for holding cigarettes. The thin sheet is formed from a ceramic material that does not produce smoke when burned. This ceramic sheet includes a woven or non-woven ceramic fiber that is decomposed by heat at high temperature, or a mixture of paper and ceramics. The ceramic fibers can be selected from inorganic fibers such as silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers, or alumino-borosilicate and glass fibers. By bonding these materials with an inorganic binder such as silica gel or alumina gel, a ceramic sheet is formed. The fibers are preferably 1-10 micrometers in diameter.

U.S. Patent No. 6,057,059 (published PCT patent application WO 01/41590) describes the use of ceramic materials in cigarette wrappers to reduce sidestream smoke. The ceramic filler incorporated into the cigarette wrapper using the binder has a particle size in the range of 2 to 90 μm. The ceramic filler is of a predefined shape that is spherical or substantially spherical, oval or substantially oval, or other irregular shapes similar to them. The ceramic filler can be alumina, silica, alumino-silicate, silicon carbide, stabilized or unstabilized zirconium oxide, zircon, garnet, feldspar, and the like. The ceramic filler is provided in the cigarette wrapper in excess of 40% by weight of the slurry-like dry material used to make the wrapper. The binder can be alginate, gum, cellulose, pectin, starch, or a Group I or II metal salt of these binders. The resulting wrapper has a porosity that is usually less than 200 Coresta units, and preferably in the range of 2-100 Coresta units. The wrapper has a density of 0.5 to 3.0 g / cm ³ . The wrapper is preferably used as an overlap for a porous, non-smoking plugwrap tobacco leaf rod having a porosity of about 12,000 Coresta units.

  In order to reduce sidestream smoke, as described in U.S. Patent Nos. 5,028,028 (Canadian Patent 1180968 and Canadian Patent Application No. 2010575), sol-gels, particularly magnesium aluminate, calcium aluminate, titania, zirconia, and Sol gels made from aluminum oxide have been applied to conventional cigarette paper. U.S. Patent No. 5,098,086 (Canada Patent 1180968) describes the use of magnesium hydroxide in the form of an amorphous gel as a thin paper filler component for cigarettes that improves ash appearance and sidestream smoke reduction. . Magnesium hydroxide gel is coated on or applied to the fibers of a sheet of cigarette paper. U.S. Patent No. 5,099,075 (Canadian Patent No. 2010575) describes the use of gels made by solution gelling or sol-gel methods to control the burning of wrappers for smoking articles. Before forming the paper as a wrapper, the gel can be applied as a coating on the paper fibers. This wrapper is useful for reducing visible sidestream smoke. The metal oxide for sol-gel may be an oxide of aluminum, titanium, zirconium, sodium, potassium or calcium.

  Patent document 31 (published German patent application DE 3508127) describes a new type of cigarette that produces a series of sparks when smoked. This is achieved by incorporating granular misch metal in the form of cerium ferrite or silicon-cerium into the cigarette paper. Especially when cigarettes are applied in dark spaces, the burning cigarettes generate a spark with a bright light effect. The cerium ferrite particles incorporated in the thin paper for cigarettes usually have a particle size of about 20 μm.

  Catalysts, such as those described in US Pat. Nos. 6,028,036 and 6,058,895 and US Pat. No. 5,386,838, are also applied directly to the cigarette paper. Patent Document 34 (Canadian Patent 604895) describes the use of platinum, osmium, iridium, palladium, rhodium, and ruthenium in thin paper for cigarettes. These metals function as an oxidation catalyst that treats the steam resulting from the combustion of the paper wrapper. The optimum catalytic effect is obtained by metallic palladium. Metal particles in a suitable medium are dispersed on the surface of the paper wrapper and then applied to the cigarette.

US Pat. No. 5,386,838 describes the use of a sol solution containing a mixture of iron and magnesium as a smoke suppression composition. A smoke suppression composition is made by co-precipitation of iron and magnesium from an aqueous solution in the presence of a base. The iron magnesium composition is heated to a temperature between about 100 ° C. ~ about 500 ° C., it shows a high surface area of about 100 m ² / g to about 225 m ² / g. The iron magnesium composition can be added to paper pulp and used to make a smoke-suppressed cigarette paper. The iron magnesium composition clearly functions as an oxidation catalyst, reducing the amount of smoke produced by the burning cigarette. The catalyst can also be applied to tobacco leaves, for example palladium can be applied to the tobacco leaves either in metal form or as a salt as described in US Pat. No. 4,248,251. The presence of palladium in tobacco leaves reduces polycyclic aromatic hydrocarbons in mainstream smoke. Palladium is used in combination with an inorganic salt or nitric acid or nitrous acid. Such nitrates include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, scandium, manganese, iron, rhodium, palladium, Copper, zinc, aluminum, gallium, tin, bismuth, hydrates thereof, and mixtures thereof are included. Catalysts are also used in the tubes to reduce sidestream smoke, such as those described in US Pat.

US Pat. No. 6,228,799 describes a composition comprising cerium oxide and zirconium oxide in the form of particles and having a high surface area usually exceeding 35 m ² / g. This composition is obtained by co-precipitation of cerium and zirconium species from the solution at high temperature, then separating, drying at a temperature between 80-300 ° C, and then calcining at a temperature between 200 and 1200 ° C. Things are made.

Catalytic materials are used in aerosol-type cigarettes that do not themselves produce sidestream or mainstream smoke, but instead provide a flavored aerosol. Examples of these aerosol-type cigarettes are described in U.S. Pat. Nos. 5,040,551, 5,137,034, and 5,944,025, which provide the heat generation necessary to produce an aerosol using a catalyst. Is included. Such catalyst systems include cerium, palladium, or platinum oxides.
Canadian Patent No. 2054735 Canadian Patent No. 2057962 US Pat. No. 5,462,073 US Pat. No. 5,709,228 International Publication No. 96/22031 Pamphlet International Publication No. 98/16125 Pamphlet WO99 / 53778 pamphlet US Pat. No. 2,755,207 US Pat. No. 4,108,151 US Pat. No. 4,225,636 European Patent Application No. 0740907 European Patent Application 0512254 WO 97/27831 Pamphlet WO99 / 53778 pamphlet US Pat. No. 2,755,207 US Pat. No. 4,108,151 US Pat. No. 4,225,636 European Patent Application No. 0740907 European Patent Application 0512254 WO 97/27831 Pamphlet WO99 / 53778 pamphlet U.S. Pat. No. 4,433,697 US Pat. No. 4,915,117 U.S. Pat. No. 4,433,697 US Pat. No. 4,915,117 International Publication No. 01/41590 Pamphlet Canadian Patent No. 1180968 Specification Canadian Patent Application No. 2010575 Specification Canadian Patent No. 1180968 Specification Canadian Patent No. 2010575 German Patent Application No. 3508127 Canadian Patent No. 604895 Specification US Pat. No. 5,386,838 Canadian Patent No. 604895 Specification US Pat. No. 5,386,838 U.S. Pat. No. 4,248,251 International Publication No. 98/16125 Pamphlet US Pat. No. 6,228,799 US Pat. No. 5,040,551 US Pat. No. 5,137,034 US Pat. No. 5,944,025

  Various sidestream smoke control systems are contemplated in the prior art, all of which are combustible like ordinary cigarettes and have acceptable ash without significantly affecting the taste of the cigarette. It does not contemplate thin paper for sex cigarettes.

  Cigarette paper, cigarette wrappers, cigars or other similar tobacco leaves with improved or modified ash and reduced visible sidestream smoke in accordance with various aspects of the invention Provide product wrappers.

  In accordance with one aspect of the present invention, a low sidestream cigarette cigarette having a conventional tobacco leaf rod and flammable treated paper, wherein the treated paper comprises an oxygen storage and donor metal oxide oxidation catalyst and an essence for the catalyst. And a non-combustible finely pulverized particle auxiliary material, and the improvement is that a solid solution of particle mixed metal oxide is used as the catalyst and the auxiliary material. Including cigarettes.

  The oxygen storage and donor metal oxide oxidation catalyst as part of the solid solution is preferably selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. The auxiliary material which is also part of the solid solution is preferably selected from the group of metal oxides consisting of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof.

  The solid solution of the mixed metal oxide may further include a metal catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof in the solid solution. Preferred mixed oxides of the solid solution are cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / zirconium / lanthanum mixed oxide, cerium / zirconium / praseodymium mixed oxide, cerium / zirconium / lanthanum / praseodymium mixed oxide. Cerium / zirconium / neodymium mixed oxides and mixtures thereof.

  In accordance with another aspect of the invention, a low sidestream cigarette comprises a conventional tobacco leaf rod and a combustible treated paper having a sidestream smoke treatment composition, the treatment composition comprising an oxygen storage and donor. A metal oxide oxidation catalyst, an essentially non-flammable auxiliary for the catalyst, and a metal oxide for modifying the ash properties.

According to another aspect of the invention, the auxiliary material comprises a mixed metal oxide or carbonate filler used with a zeolitic material. The amount of zeolitic material can be increased, but is preferably in an amount ranging from about 0.1% to 35% by weight of the total dry weight of the composition. The metal oxide mixture includes a mixture of zirconium oxide, tin oxide, titanium oxide, magnesium oxide, alumina, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and mixtures thereof. May be included. Metal oxides may be of various surface areas, and most preferably having a low surface area in the range of about 5 to 15 m ² / g, and 20 m ² / g may be any more than the high surface area of those Can do. A cerium oxide hydrate sol can be applied to an auxiliary material, such as a metal oxide, to provide increased catalytic activity.

  In accordance with another aspect of the present invention, the oxygen storage and donor metal oxide oxidation catalyst material preferably includes lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, and mixtures thereof. Precious metal and transition metal type oxidation catalysts such as palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof may also be included. These catalysts can be fixed to the auxiliary material or ash modifying material, or can be part of a mixed oxide solid solution.

  The sidestream smoke treatment composition may be incorporated into the combustible treated paper, coated on the combustible treated paper, impregnated into the treated paper, or a combination of the above steps It may be a thing. The treated paper can be double wrapped and of the same or different composition. One of the double wraps can be conventional paper. Alternatively, one of the double wraps may have a composition primarily for reducing sidestream smoke and the other double wrap paper may contain a composition for ash modification.

  In accordance with another aspect of the present invention, a low sidestream cigarette includes a conventional tobacco leaf rod and a combustible treated paper having a sidestream smoke treating composition. The treatment composition comprises an oxygen storage and donor metal oxide oxidation catalyst and an essentially non-flammable high surface area adsorbent aid for the catalyst incorporated into the treated paper. A coating of calcium carbonate is provided on the outer surface of the treated paper to modify the ash characteristics.

  For ease of description, whenever cigarette terminology is used, cigarettes are not only cigarettes that can be smoked, but also any form of wrapped cigarette tobacco products that can be smoked, etc. Is also included. Whenever treated paper terminology is used, it is understood that the treated paper includes combustible wrappers and the like that can be used on cigarettes, cigars and the like. The wrapper can be used as a single layer cigarette paper or as a multilayer cigarette paper. The wrapper can be applied as a single layer of cigarette paper or as a wrap on a conventional cigarette paper of cigarettes. The treated paper may include conventional cigarette paper as its substrate, or similar flammable products having a wide range of porosity. Conventional tobacco leaf rods include tobacco leaf compositions commonly used in cigarettes that can be smoked. These rods should be distinguished from the tobacco leaf components used in aerosol cigarettes.

  According to one aspect of the present invention, the sidestream smoke treatment composition provides the desired degree of visible sidestream smoke control while at the same time providing suitable ash with the desired properties. The sidestream smoke treatment composition of the present invention comprises an oxygen storage and donor metal oxide oxidation catalyst along with a non-flammable finely divided porous particle aid for the catalyst. As taught in Applicant's co-pending US patent application Ser. No. 09 / 95,432, filed Sep. 18, 2001, these two components can be combined when used alone or in combination with other components. Was unexpectedly found to provide a surprising degree of visible sidestream smoke control. According to certain types of catalyst materials and / or adjuncts, it has been found that ash characteristics such as appearance can sometimes be below acceptable characteristics due to, for example, fading, delamination and delamination. Has been. Strengthen the composition, and in particular the catalyst and / or adjuncts according to the present invention to modify the ash properties, eg acceptable appearance, acceptable strength, color, integrity, and ash flaking, flaking, etc. Has been reduced or eliminated.

The auxiliary material may be any suitable essentially non-flammable finely divided particulate material that does not affect the scent and taste of mainstream smoke and does not release any undesirable odor in the sidestream steam. it can. The particulate material is physically stable at the high burnout temperature of the burning cigarette. The auxiliary material, usually less than 20 m ² / g, preferably from 1m ² / g~15m ² / g, and most preferably may have a low surface area of 3m ² / g~10m ² / g. With low surface area materials, it is understood that the particles are pulverized and are not usually porous. However, it is understood that as the surface area increases towards 20 m ² / g, the particles can become porous. Conversely, adjuvants can also have a high surface area, usually greater than 20 m ² / g, at which level the particles are usually porous. The porous auxiliary material can have pores having an average diameter of less than 100 nm (1000 mm). More preferably, the pores have an average diameter of less than 20 nm (200 Å), and even more preferred are pores having an average diameter of 0.5 to 10 nm (5 to 100 Å). For zeolitic materials, the pores have an average diameter in the range of about 0.5-1.3 nm (5-13 cm).

  The particle aid can have an average particle size that is less than about 30 μm, more preferably less than about 20 μm, and most preferably in the range of about 1 μm to about 10 μm. The non-flammable material can be various categories of porous clays commonly used in the manufacture of cigarette paper such as bentonite clay or treated clay with high surface area. It is also possible to use a non-combustible carbon material comprising ground porous carbon fibers and particles. Porous monolithic mineral materials such as zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and mixtures thereof, such as zirconium fiber Various metal oxides and / or carbonates such as metal oxide fibers and ground porous ceramic fibers and mixtures thereof can be used. With regard to cerium oxide, it has been found that it can function as a finely divided auxiliary and as an oxygen storage and donor cerium oxide oxidation catalyst. Other adjunct materials include high surface area materials such as activated carbon and zeolite.

  Adjuncts can also include high surface area, high sorption materials that are non-flammable, inorganic finely divided particles such as molecular sieves containing zeolite, and also include silica / alumina, zirconium oxide, hydroxylated Amorphous materials such as zirconium can also be included. Zeolites such as silicalite zeolite, faujasite X, Y, and L zeolite, beta zeolite, mordenite zeolite, and ZSM zeolite are acceptable. Preferred zeolites include hydrophobic and weakly hydrophobic zeolites that have an affinity for such sidestream smoke hydrophobic and weakly hydrophobic organic compounds, thereby avoiding water vapor. The zeolitic material provides a highly porous structure that selectively absorbs and adsorbs sidestream smoke components. Highly porous structures generally include macropores between particles and micropores within the particles that branch off from the macropores. Ingredients trapped in macropores and micropores are present in the presence of cerium oxide or other suitable oxidation catalyst that converts such trapped components to oxidized compounds at the high temperatures of burning cigarettes. It is believed that it remains trapped in the adsorbent material or has a sufficiently low tar and nicotine level so that the sidestream is released as an invisible gas, invisible or at the desired low level.

Zeolites can be characterized by the following _{formula: M m M 'n M "} p [aAlO 2 · bSiO 2 · cTO 2]
(Where
M is a monovalent cation,
M ′ is a divalent cation,
M "is a trivalent cation,
a, b, c, n, m, and p are numbers that reflect stoichiometric ratios;
c, m, n, and p can also be zero;
Al and Si are Al and Si atoms coordinated as tetrahedra,
T is a metal atom coordinated as a tetrahedron that can replace Al or Si, provided that the ratio b / a of zeolite and zeolite-like material has a value of about 5-300, and The pore size is in the range of about 0.5 to 1.3 nm (5 to 13 cm). ).

Preferred zeolites of the above formula are faujasite ((Na ₂ , Ca, Mg) ₂₉ [Al ₅₈ Si ₁₃₄ O ₃₈₄ ] · 240H ₂ O: cubic), β-zeolite ( _{N n} [Al _n Si _64-n O ₁₂₈ ], where n <7: tetragonal, mordenite zeolite (Na ₈ [Al ₈ Si ₄₀ O ₉₆ ] · 24H ₂ O: orthorhombic), ZSM zeolite (Na _n [Al _n Si _96-n O ₁₉₂ ] to 16 H ₂ O, where n <27: orthorhombic) and mixtures thereof.

  It is understood that various grades of sorption material can be used. This is especially true for gradient zeolites that are custom designed to selectively adsorb high, medium and low boiling materials. This results in a layer of zeolite composition in which the cerium oxide or other suitable catalyst contemplated by the present invention is preferably dispersed throughout these layers. The cigarette for tobacco leaf rods is then used using a binder or adhesive, which can be, for example, polyvinyl acetate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, and casein or soy protein, and mixtures thereof. These layers can be bonded onto the application paper.

  The oxygen donor and oxygen storage metal oxide oxidation catalyst can be selected from transition metal oxides, rare earth metal oxides (such as scandium, yttrium, and lanthanide metal series, ie, lanthanum), and mixtures thereof. It is understood that the catalyst can be in the form of its metal oxide, or it can be converted to a metal oxide at the temperature of the burning cigarette and exhibit its catalytic activity. Is done. The transition metal oxide can be selected from oxides of the group of metals from the periodic table consisting of Group IVB, VB, VIB, VIIB, VIII, and IB metals, and mixtures thereof. Preferred metals from the transition metal group are oxides of iron, copper, silver, manganese, titanium, zirconium, vanadium, and tungsten, and from the rare earth group, oxides of lanthanide metals such as lanthanum, cerium, praseodymium, neodymium, As well as mixtures thereof. For example, cerium can be used as a mixture with any one transition metal, such as a Ce / Zr mixed oxide. It is understood that other metal oxide oxidation catalysts can be used with oxygen storage and oxygen donor type catalysts. Such other metal catalysts include noble metals and metals from IIA, Group IVA, and mixtures thereof. Examples include palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof.

  The cerium catalyst precursor is applied to the sorbent material as a solution or sol, or as a coating on paper, converted to cerium oxide at the high temperature of a burning cigarette, and then in the form of a cerium salt such as cerium nitrate that functions as a catalyst. Or other dispersible forms of cerium, such as cerium sol made of cerium oxide hydrate or cerium hydroxide. It is understood that the sol can be a low cerium nitrate hydrate sol. For purposes of describing the present invention, the term catalyst is intended to include any catalyst precursor.

  A catalyst such as cerium oxide is used in combination with the auxiliary material. It has been found that the ability to control sidestream smoke is greatly reduced when the two are used as non-adjacent layers that are separated from each other or spaced apart. However, in some arrangements, some sidestream smoke control can be achieved. The catalyst is preferably substantially adjacent to the auxiliary material. This can be achieved by mixing the particulate catalyst with each other as a mixture with the adjunct, bringing the adjunct layer into contact with the catalyst layer, and catalyst on the adjunct to provide the desired surprising sidestream smoke control properties. Or by impregnating the catalyst in or on the porous surface of the auxiliary material. It should be understood that many other components can be used in addition to the oxygen storage and oxygen donor metal oxide oxidation catalyst and auxiliary combinations. Additional additives can be used to further facilitate sidestream smoke processing or to further alter other properties of the cigarette. Such additional additives can, of course, be mixed with the treatment composition or used elsewhere in the cigarette structure if no adverse effects are observed in the treatment composition's ability to treat sidestream smoke. it can.

  The composition may be formulated in a variety of ways to achieve intermixing of cerium with the adsorbent material. For example, a cerium salt solution such as cerium nitrate or cerium oxide hydrate sol can be sprayed on the adsorbing material, or the adsorbing material can be immersed in the cerium salt solution to impregnate the surface of the adsorbing material with the cerium material. Cerium oxide can be prepared as a separate fine powder that is mixed with the fine powder of the adsorbent material. The catalyst powder has an average particle size of less than about 30 μm, preferably less than 20 μm, most preferably about 1.0-10 μm, more preferably about 6-10 μm to ensure intimate mixing and intermixing of the materials. It is particularly preferred.

  In accordance with the general guidelines for selecting catalyst particle size and surface area, those skilled in the art will appreciate that the selected catalyst has a surface area that ensures a catalytic active site that is available to the moving sidestream smoke component. The Thus, in certain embodiments, the catalyst particle size may exceed 30 μm if the catalyst particles are properly distributed to achieve the required degree of sidestream smoke component oxidation.

  Cerium oxide, especially high surface area cerium oxide, is surprisingly one of the few metal oxides that can perform both functions of the present invention, ie as an oxygen storage and oxygen donor catalyst and as an adjunct. Has been found to be one of the following. Porous cerium oxide particles having a high surface area and an average particle size required for the auxiliary material can be produced. Cerium oxide is used in a first amount as a catalyst for cigarette paper and in a second amount as an adjunct in the treatment composition. The amount of such cerium oxide constitutes the total addition amount, generally corresponding to the amount used as a catalyst and the amount of auxiliary material according to other embodiments of the present invention. Alternatively, high surface area cerium oxide can be used with an auxiliary material such as zeolite, or other high surface area metal oxides such as zirconium oxide or zirconium hydroxide.

  Cerium can be formulated as a solution dispersion such as a cerium oxide sol and applied to a sorption material such as zeolite. This is then dried to provide cerium oxide particles immobilized on the surface of the sorption material. When cerium oxide particles are fixed on the surface of an auxiliary material such as the surface of zeolite, the average particle size can be less than about 1.0 μm. The relative amount of cerium oxide immobilized on the zeolite can range from about 1% to 75% by weight relative to the total equivalent cerium oxide and zeolite content. The preferred relative amount of cerium oxide immobilized on the zeolite can range from about 5% to 70% by weight relative to the total equivalent cerium oxide and zeolite content.

  One possible method of making a combination product of cerium oxide immobilized on the surface of a zeolite is described in “Metal,” filed on Sep. 14, 2001, U.S. Patent Office application, the subject matter of which is incorporated herein by reference. Published in co-pending application 60/318878 entitled "A Process For Making Metal Oxide-Coated Microporous Materials".

The method generally includes producing a catalytic cerium oxide coated zeolite particulate material having a total equivalent cerium oxide and at least 1 wt% cerium oxide based on the zeolite content coated on the outer surface of the zeolite particulate material. . In one aspect, the method comprises:
i) combining an amount of a colloidal dispersion of cerium oxide hydrate (cerium hydroxide) with a compatible zeolite particulate material to form a slurry, wherein the amount of colloidal dispersion is an amount sufficient to provide greater than 20% by weight of cerium oxide when heat treated according to ii), the zeolitic particulate material has an average particle size of less than 20 mm, and the colloidal dispersion has an average particle size of at least 20 mm. Having a colloidal dispersion in position on the outer surface of the zeolite, and
ii) heat treating the slurry first at a temperature below about 200 ° C. and secondly at a temperature above about 400 ° C., and fix the resulting cerium oxide on the outer surface of the zeolite particulate material, free flowing Generally resulting in bulk particles.

  Some combinations of treatment compositions can result in what can be considered an unacceptable ash appearance. Unacceptable ash appearance characteristics include flaking, flaking, ash smear, oily appearance, and color. It was thought that the appearance of ash could be improved by adding various ash modifiers to the paper. Such ash modifiers include metals such as zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and mixtures thereof. Oxides and / or carbonates are included.

  It has been found that treatment compositions may need to be modified to improve ash properties. Such reforming may include selection of a specific chemical or physical type of oxygen donor / oxygen storage catalyst and / or selection of auxiliary material type. It has been found that a reduced amount of zeolitic material for the adjunct is appropriate, especially for improving the color of ash to white or gray rather than dark coal color. The reduced amount of zeolitic material relative to the dry weight of the paper is preferably less than 35% by weight, more preferably less than 25% by weight and most preferably less than 15% by weight. It will be appreciated that other types of fillers must be added to make up for the reduced amount of zeolitic aid. Suitable alternative metal oxides and / or carbonates include zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and the like A mixture of A low or high surface area cerium / zirconium mixed oxide as a solid solution is preferred. Such adjuvants can be made, for example, by co-precipitating zirconium and cerium species, drying the precipitate and then calcining to form a crystalline solid solution product of high surface area cerium oxide and zirconium oxide. The ratio of cerium oxide to zirconium oxide in this crystalline structure can range from about 5:95 to 95: 5. Alternatively, this ratio can range from about 20:80 to 80:20, and most preferably from about 50:50 to 80:20. This material in high surface area form also has catalytic properties and also provides oxygen storage and donor properties, with zirconium oxide serving as an adjunct for cerium oxide.

  With regard to the choice of catalyst, it has also been found that the combination with cerium oxide contributes to a better ash appearance. For example, cerium oxide can be deposited on high surface area cerium oxide, cerium oxide hydrate can be deposited on high surface area cerium oxide / zirconium, and cerium oxide hydrate is deposited on high surface area cerium oxide particles and dried. Furthermore, the aforementioned noble or transition metal type oxidation catalysts such as palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof can be combined with cerium-based materials.

  A mixed metal oxide solid solution is particularly preferred as the oxygen donor catalyst because improved lighter ash is obtained. The mixed metal oxide solid solution includes an oxygen donor oxygen storage oxidation catalyst and auxiliary materials. Preferred metal oxides forming solid solutions as oxygen donor oxygen storage materials include lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. Preferred metal oxides as auxiliary materials include zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof. Examples of these solid solutions include cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / zirconium / lanthanum mixed oxide, cerium / zirconium / praseodymium mixed oxide, cerium / zirconium / lanthanum / praseodymium mixed oxide. , Cerium / zirconium / neodymium mixed oxide. These mixed oxides and other mixed oxide solid solutions are readily available as commercial grade catalysts and are also available from any of a number of catalyst suppliers. Other alternatives to solid solutions include physical mixtures of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide with solid solutions such as, for example, cerium / zirconium mixed oxide solid solutions. Other solid solutions and mixed oxides contemplated by the present invention include cerium / aluminum mixed oxides, cerium / magnesium mixed oxides, and cerium / titanium mixed oxides.

  The oxidation catalyst that may be included in the solid solution is usually present in a very small amount. Such catalysts include palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof. These catalysts are usually included in the solid solution at a level of less than 1% by weight of the total solid solution. A preferred combination for a solid solution with a small amount of another oxidation catalyst is a combination of the above catalyst with a solid solution of a mixed cerium / zirconium oxide. The above oxidation catalysts are preferably included in the solid solution individually or as a mixture thereof. However, it is understood that the catalyst or catalyst mixture described above can alternatively be applied to the surface of the cerium / zirconium mixed oxide solid solution particulate material.

  Multipurpose solid solutions of mixed oxides include ceria / zirconia / magnesia / titania where ceria constitutes from about 5% to about 75% of the solid solution.

  It has also been found that a coating of particulate calcium carbonate on the wrapper is useful to improve ash properties. As described above, the treatment composition can be incorporated into the wrapper, which is a single wrapper for the tobacco leaf rod, or the wrapper can be coated with the treatment composition. As mentioned above, one approach to improving ash is to reduce the amount of adsorption aids such as zeolite and substitute selected metal oxides. Alternatively, particularly for a single wrapper incorporating the treatment composition, it has been found that the coating of calcium carbonate on the outside of the wrapper greatly improves the ash, particularly from an appearance point of view. Regarding the improvement of ash properties, it is quite surprising that a coating of particulate calcium carbonate can have this effect. Presumably calcium carbonate chemically or physically combines with the ingredients in the wrapper to produce a more uniform light to gray ash. To coat the wrapper, the particulate calcium carbonate can be slurried with a suitable binder. Suitable binders include those commonly used to coat with calcium carbonate, such as polyvinyl alcohol, starch, CMC, casein, soy, binder clay and other acceptable binders or adhesives. Particulate calcium carbonate has a particle size commonly associated with its use as a filler in the manufacture of cigarette paper. Accordingly, the particle size is usually less than 10 μm and preferably more than 3 μm. However, some grades of calcium carbonate below 1 μm may also be useful.

  The surprising activity of the sidestream smoke treatment composition has made it possible to use it in cigarette paper having a wide range of porosity. It has also been found that it is not necessary to use the composition in cigarette paper that actually has a high porosity. The treatment composition works equally well from paper having a very low porosity of about 0.5 Cresta units to paper having a very high porosity of about 1,000 Cresta units. The preferred porosity is usually less than 200 Cresta units, and the most preferred porosity is usually in the range of 15-60 Cresta units. It is understood that the paper can be used as a double or multiple wrap. The paper can be applied as an outer wrap on a cigarette with conventional cigarette paper. It is understood that certain combinations of catalyst and auxiliary material work better than others, depending on the porosity.

  The composition can simply be sprayed on either or both sides of the cigarette paper and absorbed into the paper. As shown in FIG. 1, the paper 10 is conveyed in the direction of the arrow 12. The treatment composition 14 as a slurry is sprayed onto the paper 10 by a spray nozzle 16 to provide a coating 18 that is dried on the paper. Alternatively, the composition can be extruded as a film on the surface of paper and used as single or multiple wraps. As shown in FIG. 2, the film coating apparatus 20 contains the processing composition 14 made into a slurry. The film coater 20 lays a thin film 22 on the paper 10, and the paper 10 is conveyed in the direction of arrow 12. The film is dried, resulting in a coating 24 on the paper 10. It is quite surprising that these treatments effectively eliminate visible sidestream smoke from the burning cigarette. The treatment composition can be applied to the outside of a conventional cigarette paper.

  As shown in FIG. 3, painting can be achieved by the roller applicator 26. The treatment composition 14 is applied as a layer 28 on the roller 30. The thickness of the layer 34 is determined by the doctor knife 32, and then the layer 34 is laid on the paper 10 and the paper 10 is conveyed in the direction of arrow 12. The layer is then dried to form a coating 36 on the paper 10.

  Impregnation is achieved by using the coating roller 24 of FIG. By passing the paper 10 in the direction of arrow 12, the resulting layer 36 passes through pressure rollers 38 and 40, which pushes the material layer into the paper 10 and thereby the components of the treatment composition into the paper. Impregnate.

  It will also be appreciated by those skilled in the art that various other coating methods, including transfer coating methods, can be used to make the treated paper of the present invention. In the transfer coating process, the coating composition can be transferred from the Mylar ™ sheet to the surface of the cigarette paper using a Mylar ™ sheet, or other suitable continuous sheet. This type of transfer coating is useful when the substrate sheet is not readily acceptable for roll coating of the composition, such as due to the physical strength properties of the paper.

  A further option is to incorporate the treatment composition into the manufacture of paper. The composition can be introduced into the paper furnish as a slurry. Referring to FIG. 5, the processing composition in the furnish 42 is stirred by the stirrer 44 to form a slurry in the tank 46. The slurry is moved by a conventional papermaking method and laid on a conveyor 50 that moves as a layer 48, resulting in the formation of a thin cigarette paper 52. As a result, the treatment composition is incorporated into the final paper product.

  Another option is to sandwich the treatment composition between the paper layers to form a double cigarette paper wrap on the tobacco leaf rod. For example, the composition can be applied to the inside of the outer paper and / or on the outside of the inner paper, such as by the spraying technique of FIG. As soon as two sheets of paper are applied to the tobacco leaf rod, the composition as a layer is sandwiched between the two sheets. Each paper can be half the thickness of a conventional cigarette paper, so the overall diameter of the double-wrapped cigarette can be kept from increasing so much that the cigarette making machine is easier to handle.

  Referring to FIG. 6, the tobacco leaf rod 54 is wrapped around, for example, a cigarette paper 10 having a coating 18 on the outside of the paper. Conversely, as shown in FIG. 7, in the thin cigarette paper 10, the coating 18 can be applied to the inner surface of the paper adjacent to the tobacco leaf rod 54.

  Another option is to sandwich the coating 18 between the cigarette paper 56 and 58, as shown in FIG. The papers 56 and 58 with the intermediate coating 18 can be formed as a single cigarette wrapper applied to the tobacco leaf rod 54. A further option is shown in FIG. 9, in which the tobacco leaf rod 54 is coated with a conventional cigarette paper 60. There is a thin cigarette paper 52 of FIG. 5 covering the thin cigarette paper 60 and incorporating the treatment composition therein. It will also be appreciated that the paper 52 incorporating the treatment composition therein can be applied directly to the tobacco leaf rod 54.

  In yet another alternative embodiment of the invention, for example, the coated paper of FIG. 7 can be used as the inner layer of the paper, and another paper, which can be conventional paper, can be used as the outer layer of the double wrap. Various combinations of sidestream smoke treated paper in a double wrap configuration can be provided. The inner layer paper can also be paper having incorporated therein a treatment composition such as that of FIG. The inner layer paper should be designed to provide sidestream smoke reduction by including all necessary components of the composition, such as oxygen storage and donor metal oxide oxidation catalysts and non-flammable aids for the catalyst. Can do. Preferred examples of this type of composition include a high surface area, cerium / zirconium mixed oxide with zeolite and optionally reinforced with an oxidation catalyst such as platinum or palladium. In a double wrap system, the amount of zeolite can exceed 30% by weight, for example in the range of 50% to 60% by weight.

  The double wrap outer layer can have different compositions and can be designed to provide ash modification that achieves the desired properties. For example, the outer paper not only improves the appearance of the ash, but also modifies the cigarette's burning rate and minimizes the flare up when the cigarette is ignited and blown off. It can be limited. The outer layer may include, for example, metal oxides such as low surface area cerium oxide, cerium oxide / zirconium oxide solid solution, alumina, zirconium oxide, titanium oxide, tin oxide. Furthermore, cerium oxide hydrate can be coated on the outer layer metal oxide material to ensure that there is sufficient oxygen to support the burning of the outer layer of the cigarette. When combined as a double wrap, the two layers provide effective control of visible sidestream smoke. Adjacent paper burns uniformly to produce the desired ash, and the outer paper prevents or minimizes burning due to highly active oxygen donor materials. Can function.

The double wrap feature of the present invention provides significant freedom in the design of low sidestream cigarettes. Individual sheets in a double wrap design have each sheet impregnated, coated, or incorporated with a selected treatment composition. Alternatively, the sheet having the treatment composition incorporated therein may be coated with the same or different treatment composition to further enhance sidestream smoke control and / or ash modification. Illustrative treatment compositions for the inner and outer papers to demonstrate this degree of freedom in low sidestream cigarette designs are as follows:
Outer paper i) high surface area cerium / zirconium mixed oxide (75:25) + low surface area zirconium oxide;
ii) high surface area alumina coated with cerium hydrate;
iii) low surface area cerium oxide coated with cerium hydrate;
iv) high surface area zirconium oxide coated with cerium hydrate; or v) high surface area cerium / zirconium mixed oxide (25:75).

Inner paper i) High surface area cerium / zirconium mixed oxide reinforced with palladium catalyst (75:25) + zeolite reinforced with palladium catalyst;
ii) high surface area cerium / zirconium mixed oxide (75:25) + palladium reinforced zeolite;
iii) high surface area cerium / zirconium mixed oxide (75:25) + zeolite; cerium / zirconium mixed oxide reinforced with palladium catalyst; or iv) cerium / zirconium mixed oxide reinforced with platinum and tin catalyst High surface area cerium / zirconium mixed oxide (75:25) + zeolite.

  These various compositions of the inner and outer papers can be combined into various combinations that provide sidestream smoke control and ash improvement.

  A preferred combination is a high surface area cerium / zirconium mixed oxide (75:25) and zirconium oxide solid solution for the outer paper. For the inner paper, the preferred treatment composition is a solid solution of palladium surface enhanced cerium / zirconium mixed oxide (75:25) reinforced with palladium catalyst plus zeolite reinforced with palladium catalyst. In the outer paper on a dry weight basis, the coating formulation has 25% high surface area cerium / zirconium mixed oxide and 75% low surface area zirconium oxide. The inner paper, on a dry weight basis, has about 44% high surface area cerium / zirconium mixed oxide, both reinforced with a palladium catalyst, and 56% zeolite.

  As will be appreciated by those skilled in the art, the foregoing procedure for providing a sidestream smoke treatment composition in or on the desired cigarette paper includes the amount provided and the wrap used on the tobacco leaf rod. You can change the number of. For example, two or more papers having different addition amounts of the present composition on both sides of the paper can be used with less addition on one side and easier application of the coating.

  It has been surprisingly found that for any of these combinations, visible sidestream smoke is virtually eliminated. At the same time, the cigarette paper exhibits conventional ashing properties. It is particularly surprising that by simply applying the composition to the outside of the cigarette paper, visible sidestream smoke can be minimized to an almost undetectable level.

  It is understood that depending on how the composition is used and applied to the cigarette, various processing aids and mixtures thereof may be required to facilitate specific application of the treatment composition. Is done. Such processing aids include laminate materials such as polyvinyl alcohol, starch, CMC, casein, soy, and other types of acceptable adhesives, various types of binding clays, inert fillers, white extender pigments. , A viscosity modifier, U.S. Application No. 60 / 318,614, filed September 13, 2001, named Zirconium / Metal Oxide Fibers, the subject matter of which is incorporated herein by reference. Inert fiber materials such as zirconium fibers and zirconium / cerium fibers such as those described in the issue.

  A penetrant can also be used to bring the composition into the paper. Water spray coating, curtain coating, air knife coating, rod coating, blade coating, print coating, size press coating, roller coating, slot die coating, transfer coating techniques, etc. on conventional thin cigarette paper. Suitable diluents such as are also used to dilute the composition.

The preferred amount of treatment composition cigarette thin, into the upper or their like wrapper, preferably in the range of about 2.5 g / m ² ~ about 125 g / m ^2. Most preferably, the loading is in the range of about 2.5 g / m ² to about 100 g / m ² . Expressed in weight percent, the paper can have a treatment composition of from about 10% to 500%, and most preferably from about 10% to 400%. Although these additions are shown for a single paper, it will be understood by those skilled in the art that for two or more sheets, these total additions can be provided.

  The sidestream smoke reducing composition is typically used as a water slurry of the composition. The composition of the dry composition, which can be a slurry, can be altered by use as a paper coating, incorporation, or impregnation. For example, the embedded formulation can contain about 10% to 33% by weight cerium-based catalyst, 20% to 62% by weight auxiliary material, and 10% to 75% by weight ash modifier. Other alternatives can contain about 10% to 25% by weight cerium-based catalyst, 40% to 55% by weight auxiliary material, and 20% to 50% by weight zeolite other than auxiliary material. .

  Slurry can be incorporated into the paper furnish during the paper manufacturing process, and the slurry is coated on the paper by various coating methods, or the slurry is impregnated into the paper by various impregnation methods. The preferred average particle size of the catalyst and auxiliary material for the slurry is in the range of about 1 μm to about 30 μm, and most preferably about 1 μm to about 10 μm. The preferred relative amount of catalyst fixed to the adjunct is about 1% to 75%, more preferably about 10% to 70%, and even more preferred for cerium, based on the total equivalent catalyst and adjunct content. Can be in the range of about 20% to 70% by weight. Other catalysts, such as noble metal catalysts, of less than 1% by weight can be fixed to the auxiliary material.

  While preferred embodiments of the present invention have been described in detail herein, those skilled in the art will recognize that variations can be made therein without departing from the spirit of the invention or the appended claims. Will be understood.

FIG. 1 is a schematic diagram of a spray technique for applying the treatment composition to a thin cigarette paper. FIG. 2 is a schematic diagram of the steps of extruding a film of the treatment composition onto a thin cigarette paper. FIG. 3 is a schematic diagram of the steps of roll coating the treatment composition onto a thin cigarette paper. FIG. 4 is a schematic diagram of impregnation of a coating of the present treatment composition into a thin cigarette paper. FIG. 5 is a schematic diagram of the steps of mixing the treatment composition with paper pulp in the manufacture of cigarettes. FIG. 6 is a perspective view of a tobacco leaf rod having treated paper of the present invention applied thereon. FIG. 7 shows another embodiment of FIG. FIG. 8 is a perspective view of a tobacco leaf rod sandwiching the treatment composition between two layers of thin cigarette paper applied to the tobacco leaf rod. FIG. 9 is a perspective view of a double wrap for a tobacco leaf rod applying treated paper onto a conventional cigarette paper.

Explanation of symbols

10 Paper 14 Treatment Composition 16 Spray Nozzle 18 Coating 20 Film Coater 22 Thin Film 24 Coating 26 Roller Applicator 28 Layer 30 Roller 32 Doctor Knife 34 Layer 36 Layer 38 Pressure Roller 40 Pressure Roller 42 Finished Paper 44 Stirrer 46 Tank 48 Layer 50 Conveyor 52 Cigarette Paper 54 Cigarette Leaf Rod 56 Cigarette Paper 58 Cigarette Paper 60 Cigarette Paper

Claims (59)

A low sidestream cigarette cigarette comprising a conventional tobacco leaf rod and a combustible treated paper having a sidestream smoke treating composition;
The treatment composition comprises an oxygen storage and donor metal oxide oxidation catalyst, an essentially non-flammable particle aid for the catalyst, and a metal oxide or carbonate to modify ash properties. Low sidestream smoke cigarette.   The low sidestream smoke cigarette of claim 1, wherein the auxiliary material is high surface area particles.   Zeolite in which the particle aid ranges from about 0.1% by weight of the total dry weight of the composition to about 60% by weight of the total dry weight of the composition, preferably less than 25%, most preferably less than 15%. The low sidestream smoke cigarette according to claim 2, which is a system material.   The metal oxide or carbonate for modifying the ash is zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and their The low sidestream cigarette of claim 2 selected from the group consisting of a mixture.   The low sidestream cigarette of claim 1, wherein the auxiliary material is a carrier for the ceria sol applied and dried thereon.   6. The low sidestream cigarette of claim 5, wherein the auxiliary material is high surface area cerium oxide.   A transition wherein the catalyst is selected from the group consisting of (a) a Group VB metal oxide, a Group VIB metal oxide, a Group VIIB metal oxide, a Group VIII metal oxide, and a Group IB metal oxide. The metal oxide, (b) rare earth metal oxide, and (c) selected from the group consisting of a mixture of the transition metal oxide and the rare earth metal oxide according to any one of claims 1-6. Low sidestream smoke cigarette. The catalyst is a mixture of transition metal oxide and rare earth metal oxide;
The transition metal oxides include Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, and the like. The low sidestream smoke cigarette according to any one of claims 1 to 6, selected from the group consisting of:   The low sidestream smoke cigarette according to claim 7 or 8, wherein the rare earth metal oxide is selected from the group consisting of oxides of scandium, yttrium, lanthanide metals, and mixtures thereof.   The low sidestream smoke cigarette of claim 9, wherein the lanthanide metal oxide is selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, and mixtures thereof.   The oxygen storage and donor metal oxide oxidation catalyst and the catalyst auxiliary material are mixed metal oxide solid solutions, wherein the auxiliary material is zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide, and 11. The low sidestream cigarette of claim 10 selected from the group consisting of:   The low sidestream smoke cigarette of claim 11, wherein the mixed metal oxide solid solution comprises a catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide and manganese oxide.   For mixed metal oxide solid solutions, cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / aluminum mixed oxide, cerium / magnesium mixed oxide, cerium / titanium mixed oxide, cerium / zirconium / lanthanum mixed Oxide, cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / zirconium / lanthanum mixed oxide, cerium / zirconium / praseodymium mixed oxide, cerium / zirconium / lanthanum / praseodymium mixed oxide, cerium / zirconium / The low sidestream smoke cigarette of claim 1, comprising a neodymium mixed oxide.   2. The low of claim 1, wherein the auxiliary material is selected from the group consisting of clay, an essentially non-flammable mill fiber, a monolithic mineral-based material, an essentially non-flammable carbon, a zeolite, and mixtures thereof. Sidestream smoke cigarette.   The auxiliary material is zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, metal oxide fiber, pulverized porous ceramic fiber 15. The low sidestream cigarette of claim 14 selected from the group consisting of and mixtures thereof.   14. A low sidestream smoke cigarette according to claim 10, 11, 12, or 13, wherein the solid solution is a high surface area porous particle.   14. A low sidestream smoke cigarette according to claim 10, 11, 12, or 13, wherein the solid solution is a low surface area particle.   The low sidestream smoke cigarette of claim 4, wherein the ash modifying particles are zirconium oxide. An oxidation catalyst is used with the oxygen storage and donor metal oxide oxidation catalyst;
11. The low sidestream smoke cigarette of claim 10, wherein the oxidation catalyst is selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof.   The low sidestream smoke cigarette according to claim 3, wherein the zeolite is a Y-type zeolite, a ZSM-5 type zeolite, or a beta type zeolite.   11. The low sidestream smoke cigarette of claim 10, wherein the oxygen storage and donor metal oxide oxidation catalyst is a cerium / zirconium porous particulate solid solution, preferably a mixed oxide high surface area material.   The low sidestream smoke cigarette of claim 21, wherein zirconium oxide and / or zeolite is used in combination with the cerium / zirconium mixed oxide.   23. A low sidestream cigarette according to claim 22, wherein an oxidation catalyst is used with the cerium / zirconium metal oxide, zirconium oxide and / or zeolite. The oxidation catalyst is selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof;
24. The selected oxidation catalyst is incorporated into the cerium / zirconium mixed oxide solid solution or applied to the surface of the cerium / zirconium mixed oxide, zirconium oxide, and / or zeolite of the particles. The low sidestream smoke cigarette described in 1.   24. The low sidestream cigarette of claim 23, wherein the zeolite is a Y-type zeolite. The treatment composition is applied as a coating to a cigarette paper,
The coating composition is selected from the group consisting of zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, zirconium carbonate, magnesium carbonate, and mixtures thereof. The low sidestream smoke cigarette of claim 1, comprising a metal oxide or carbonate. The combustible treated paper comprises an inner sheet and an outer sheet;
The inner sheet comprises the treatment composition for reducing sidestream smoke;
The low sidestream cigarette of claim 1, wherein the outer layer comprises a treatment composition for modifying ash properties.   28. The low sidestream cigarette of claim 27, wherein the inner paper has a zeolitic material greater than 35% by weight.   28. The low sidestream smoke cigarette of claim 27, wherein the inner paper and outer paper are coated with, incorporated into, or impregnated on or within the treatment composition.   28. The low sidestream smoke cigarette of claim 27, wherein the sidestream smoke reducing composition is incorporated into the inner paper.   28. The low sidestream smoke cigarette of claim 27, wherein the inner paper is coated with the sidestream smoke reducing composition.   28. The low sidestream smoke cigarette of claim 27, wherein the sidestream smoke reducing composition is incorporated and coated on the inner paper.   28. The low sidestream smoke cigarette of claim 27, wherein the sidestream smoke reducing composition is incorporated into the outer paper.   28. The low sidestream smoke cigarette of claim 27, wherein the outer paper is coated with the sidestream smoke reducing composition.   28. The low sidestream smoke cigarette of claim 27, wherein the sidestream smoke reducing composition is incorporated into and coated on the outer paper. The inner paper comprises an oxygen storage and donor metal oxide oxidation catalyst with auxiliary materials and a high surface area adsorbent material;
28. The low sidestream smoke cigarette of claim 27, wherein the outer layer includes an oxygen storage and donor metal oxide oxidation catalyst with auxiliary materials and a metal oxide for modifying ash properties.   37. The low of claim 36, wherein the treatment composition for reducing sidestream smoke and the treatment composition for modifying ash are applied as coatings to the inner sheet and the outer sheet, respectively. Sidestream smoke cigarette.   38. The low sidestream smoke cigarette of claim 37, wherein the oxygen storage and donor metal oxide oxidation catalyst is a porous, particulate, high surface area solid solution of cerium / zirconium mixed oxide.   40. The low sidestream cigarette of claim 38, wherein the cerium oxide and the zirconium oxide in the solid solution are in a ratio of about 5:95 to about 95: 5.   40. The low sidestream smoke cigarette of claim 39, wherein the coating is applied to the inner and outer sheets on either or both sides of the respective sheet. A low sidestream cigarette cigarette comprising a conventional tobacco leaf rod and a combustible treated paper having a sidestream smoke treating composition;
The treatment composition comprises an oxygen storage and donor metal oxide oxidation catalyst, an essentially non-flammable high surface area aid for the catalyst incorporated in the treated paper, and for modifying ash properties A low sidestream smoke cigarette comprising a calcium carbonate coating on the exterior surface of the treated paper.   42. The low sidestream smoke cigarette of claim 41, wherein the auxiliary material comprises a zeolitic material.   The zeolitic material is in an amount ranging from about 0.1% by weight of the total dry weight of the composition to about 60% by weight of the total dry weight of the composition, preferably less than 25%, most preferably less than 15%. 43. The low sidestream smoke cigarette of claim 42.   The catalyst is a transition selected from the group consisting of (a) a Group VB metal oxide, a Group VIB metal oxide, a Group VIIB metal oxide, a Group VIII metal oxide, and a Group IB metal oxide. 44. The metal oxide according to any one of claims 41 to 43, selected from the group consisting of a metal oxide, (b) a rare earth metal oxide, and (c) a mixture of the transition metal oxide and the rare earth metal oxide. Low sidestream smoke cigarette. The catalyst is a mixture of transition metal oxide and rare earth metal oxide;
The transition metal oxides include Group IVB metal oxides, Group VB metal oxides, Group VIB metal oxides, Group VIIB metal oxides, Group VIII metal oxides, Group IB metal oxides, and the like. 44. The low sidestream smoke cigarette of any one of claims 41 to 43, selected from the group consisting of:   46. The low sidestream smoke cigarette of claim 44 or 45, wherein the rare earth metal oxide is selected from the group consisting of oxides of scandium, yttrium, and lanthanide metals, and mixtures thereof.   47. The low sidestream smoke cigarette of claim 46, wherein the lanthanide metal oxide is selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, and mixtures thereof.   The oxygen storage and donor metal oxide oxidation catalyst and the catalyst auxiliary material are mixed metal oxide solid solutions, wherein the auxiliary material is zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide, 48. The low sidestream cigarette of claim 47, selected from the group consisting of: and a mixture thereof.   49. The low sidestream cigarette of claim 48, wherein the solid solution comprises a metal catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof. .   The mixed metal oxide solid solution includes cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / aluminum mixed oxide, cerium / magnesium mixed oxide, cerium / titanium mixed oxide, cerium / zirconium / lanthanum mixed. Oxide, cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / zirconium / lanthanum mixed oxide, cerium / zirconium / praseodymium mixed oxide, cerium / zirconium / lanthanum / praseodymium mixed oxide, cerium / zirconium / 50. The low sidestream smoke cigarette of claim 49, comprising a neodymium mixed oxide.   51. The low sidestream cigarette of claim 47, 48, 49 or 50, wherein the solid solution is high surface area porous particles. An oxidation catalyst is used with the oxygen storage and donor metal oxide oxidation catalyst;
48. The low sidestream smoke cigarette of claim 47, wherein the oxidation catalyst is selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof.   43. The low sidestream smoke cigarette of claim 42, wherein the zeolite is a Y-type zeolite, a ZSM-5 type zeolite, or a beta type zeolite.   54. The low sidestream cigarette of claim 53, wherein the oxygen storage and donor metal oxide oxidation catalyst is a porous particulate cerium / zirconium mixed oxide high surface area material.   55. A low sidestream cigarette according to claim 54, wherein an oxidation catalyst is used with the cerium / zirconium mixed oxide, zirconium oxide and / or zeolite. The oxidation catalyst is selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof;
Either the selected oxidation catalyst is incorporated into the cerium / zirconium mixed oxide solid solution or is applied to the surface of particulate cerium / zirconium mixed oxide, zirconium oxide, and / or zeolite. 56. The low sidestream smoke cigarette of claim 55.   57. The low sidestream cigarette of claim 56, wherein the zeolite is a Y-type zeolite.   42. The low of claim 41, wherein the binder for the calcium carbonate coating is selected from the group consisting of polyvinyl alcohol, starch, CMC, casein, soy, binding clay, mineral binder, and mixtures thereof. Sidestream smoke cigarette.   42. The low sidestream cigarette of claim 1 or 41, wherein the catalyst is a precursor of the catalyst.

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