KR20040084959A - Low sidestream smoke cigarette with combustible paper having a modified ash characteristics - Google Patents

Abstract

Low live tobacco smoke cigarettes include conventional tobacco rods 54, and combustible treated papers 56, 58 having live tobacco smoke treatment compositions. The treatment composition comprises an oxygen storage and providing metal oxide oxide catalyst in combination with an essentially non-flammable particulate adduct for the catalyst. Improvements in addition to enhancement of the ash properties consist of the treatment composition and / or the addition of metal oxides or carbonates.

Description

LOW SIDESTREAM SMOKE CIGARETTE WITH COMBUSTIBLE PAPER HAVING A MODIFIED ASH CHARACTERISTICS

Various attempts have been made to reduce or eliminate live tobacco smoke from burning cigarettes. Applicants have disclosed their Canadian Patents 2,054,735 and 2,057,962; US Patents 5,462,073 and 5,709,228 and PCT Application Publication WO 96/22031; Several approaches have been developed for the control system of live tobacco smoke as described in WO 98/16125 and WO 99/53778.

Other live tobacco smoke control systems have been developed, which use filter materials or adsorbent materials in tobacco, filters or paper wrappers. Examples of such systems are described in US Pat. Nos. 2,755,207, 4,108,151 and 4,225,636; European Patent Applications 0 740 907 and 0 251254; And WO 97/27831 and WO 99/53778. U.S. Patent 2,755,207 describes a cigarette paper with low live tobacco smoke. Burning cigarette paper generally produces smoke free of toxic components. Cigarette paper is a cellulosic material in fibrous form. It is closely related to the siliceous catalyst material, which is a phase mineral type. Intrinsically non-flammable and fire-resistant cigarette papers remain substantially unchanged while the cigarette paper burns and function as a catalyst in modifying the burning of the paper. Suitable siliceous catalysts include natural and synthetic silicates comprising acid-treated clay, heat-treated montmorillonite and some relatively mobile hydrogen atoms. Properly mixed silica oxides include silica oxides with alumina, zirconia, titania, chromium oxide and magnesium oxide. Other silicas include silicon and aluminum oxide with a weight ratio of silica to alumina of 9: 1.

US Patent 4,108, 151 describes the use of gamma alumina fillers for cigarette paper to selectively reduce organic vapor phase components in tobacco smoke. There is at least 50% by weight of alumina filler in cigarette paper to reduce the organic vapor phase components of tobacco smoke. As a result, there is a reduction in the visibility of live tobacco smoke emitted from burning cigarettes. Gamma alumina is most commonly known as activated alumina finely ground to allow passage through a 300-mesh screen.

U. S. Patent 4,225, 636 describes the use of carbon in cigarette paper to reduce the organic vapor phase components and total particulate matter found in live tobacco smoke. Moreover, carbon results in a significant reduction in the visible live tobacco smoke emitted from burning cigarettes. Activated carbon is suitable as a carbon source. The use of activated charcoal results in a slight reduction in visible live tobacco smoke. Up to 50% of cigarette paper may be powdered carbon. Carbon-coated paper can be used as the inner wrapper of tobacco rods in combination with conventional cigarettes.

European Patent Application 0 740 907, published November 6, 1996, discloses the use of zeolites in cigarettes to change the characteristics of the mainstream smoke and to remove various components such as some tar from the direct smoke. Explain the use. In addition, the zeolites provided in tobacco obviously change the properties of live tobacco smoke. The zeolite used had a particle size of 0.5 mm to 1.2 mm.

European application 0 251 254 describes the use of surface area fillers in cigarette paper. Fillers are generally crystals or solids having a surface area of at least 20 m ² / g. Fillers are preferably peroxides, carbonates, phosphates, sulfates, aluminates and silicates. It teaches that porous fillers, such as zeolites, are undesirable for cigarette papers, and that they function similarly to conventional chalk.

Published PCT patent application WO 97/27831 describes the use of dealaluminate zeolites to adsorb nonpolar or weakly polar molecules from polar liquids or gases. An effective amount of dealaluminate zeolite can be bound to cigarette paper to reduce carbon monoxide in live tobacco smoke. Dealuminizing the aluminum zeolite imparts hydrophobicity to the zeolite to affect the adsorption and removal of nonpolar and weakly polar molecules that may occur even in the presence of water.

The published PCT patent application WO 99/53778 describes a non-combustible sheet of treated material which reduces the release of live tobacco smoke. The sheet is used as a roll paper and applied onto conventional cigarette paper of conventional cigarette. The wrapper has a very high porosity, which reduces the visibility of live tobacco smoke emissions while at the same time allowing the cigarette to be burned at or near conventional free combustion rates. Non-combustible wrappers include non-combustible ceramic fibers and non-combustible activated carbon fibers as well as other standard materials used to make the wrappers. The wrapper also includes zeolites or other similar adsorbent materials and oxygen providing / oxygen storage metal oxide catalysts. Non-combustible wrappers provide an acceptable control of live tobacco smoke, but due to the non-flammable nature of the wrappers, they remain tubular char.

U.S. Patents 4,433,697 and 4,915,117 describe the addition of ceramic fibers in cigarette paper manufacture. U.S. Patent 4,433,697 describes certain ceramic fibers in at least 1% by weight paper furnish in combination with magnesium oxide and / or magnesium hydroxide fillers that reduce the visible live tobacco smoke released from a burning cigarette. Furnishes, ceramic fibers and fillers of fiber pulp are used to make paper sheets in conventional paper making machines. The ceramic fiber may be selected from the group of polycrystalline alumina, aluminum silicate and amorphous alumina. Magnesium hydroxide or magnesium oxide fillers are used and coated or applied onto the fiber sheet.

US Patent 4,915,117 to Ito describes a non-combustible sheet that supports tobacco. The thin sheet is formed from a ceramic material that does not produce smoke upon combustion. The ceramic sheet consists of a woven or nonwoven fabric of ceramic fibers or a mixture of paper and pyrolyzed ceramic at high temperatures. The ceramic fibers may be selected from inorganic fibers such as silica fibers, silica-alumina fibers, alumina fibers, zirconia fibers or alumino borosilicates and glass fibers. The ceramic sheet is formed by the bonding of these materials by an inorganic binder such as silica gel or alumina gel. The fiber preferably has a diameter of 1 to 10 μm.

The published PCT patent application WO 01/41590 describes the use of cigarette wrap paper as a ceramic material to reduce live tobacco smoke. The ceramic filler bonded to the cigarette wrapper using a binder has a particle size in the range of 2-90 μm. The ceramic filler is a predetermined form, which is spherical, substantially spherical, ovoid, substantially ovoid or other atypical form similar thereto. Ceramic fillers can be alumina, silica, aluminum silicate, silicon carbide, stabilized or unstabilized zirconium oxide, zircon, garnet, feldspar and the like. Ceramic filler is provided to the cigarette wrapper in at least 40% by weight of the dry matter in the slurry used to produce the wrapper. The binder can be alginate, resin, cellulose, factin, starch or a Group I or II metal salt of such a binder. The resulting wrapper usually has a porosity less than 200 Coresta units, suitably in the range of 2-100 Coresta units. The wrapper has a density of 0.5-3. 0 g / cm ³ . The wrapper is suitable as a wrapper for tobacco rods with non-porous smoking plug wrappers having a porosity of about 12,000 Coresta units.

Sol gels have been applied to conventional cigarette papers to reduce live tobacco smoke, in particular sol gels from magnesium aluminate, calcium aluminate, titania, zirconia and aluminum oxide as described in Canadian Patent 1,180,968 and Canadian Patent Application 2,010,575. Made. Canadian Patent 1,180,968 describes the application of magnesium hydroxide in the form of an amorphous gel as a cigarette paper filler composition to enhance ash form and reduced live tobacco smoke. Magnesium hydroxide is coated or applied onto the fibrous sheet of cigarette paper. Canadian patent application 2,010, 575 describes the use of gels produced by solution gelling or sol-gel processes to control the burning of wraps for smoking products. The gel can be applied by coating the paper fibers before the paper is formed into a roll of paper. Wedges are useful for reducing the visibility of live tobacco smoke. The metal oxide for the sol gel can be an oxide of aluminum, titanium, zirconium, sodium, potassium or calcium.

Published German patent application DE 3 508 127 describes a new type of cigarette in which many sparks are produced when smoking. This is accomplished by the bonding of granular misch metal in the form of cerium ferrite or silico-cerium to cigarette paper. When smoking in particularly dark places, the burning cigarette emits sparks with the effect of bright light. Cerium ferrite molecules bound to cigarette paper usually have a particle size of about 20 μm.

As described in Canadian Patent 604,895 and US Patent 5,386,838, the catalyst can also be applied directly to cigarette paper. Canadian patent 604,895 describes the use of platinum, osmium, iridium, palladium, rhodium and ruthenium in cigarette paper. These metals function as oxidation catalysts for the treatment of steam arising from the combustion of cigarette paper. The optimum catalytic effect is provided by the palladium metal. Metal particles in a suitable medium are sprayed onto the surface of the cigarette wrapper before the cigarette wrapper is applied to the cigarette.

U.S. Patent 5,386,838 describes the use of sol solutions comprising iron and magnesium mixtures as smoke suppressing compositions. Smoke suppressing compositions are made by co-precipitation of iron and magnesium from an aqueous solution of base. The iron magnesium composition exhibits a high surface area from about 100 m ² / g to about 225 m ² / g when heated to a temperature of 100 ° C. to about 500 ° C. The iron magnesium composition may be added to the pulp pulp used to make smoke suppressed cigarette paper. The iron magnesium composition apparently functions as an oxidation catalyst and reduces the amount of smoke generated by cigarette combustion. As described in US Pat. No. 4,248,251, the catalyst can also be applied to tobacco, for example palladium in metal form or as a salt can be applied to tobacco. The presence of palladium in tobacco reduces polycyclic aromatic hydrocarbons in direct drinking smoke. Palladium is used in combination with an inorganic salt or nitric acid or nitrous acid. Such nitrates are lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, lanthanum, cerium, neodymium, samarium, europium, gadolinium, terbium, disphosphorium, erbium, scandium, manganese, iron, rhodium, palladium Contains copper, zinc, aluminum, gallium, tin, bismuth, their hydrates and mixtures thereof. Catalysts are also used in the tubes to reduce live tobacco smoke as described in published PCT application WO 98/16125.

US Patent 6 228 799 describes a composition comprising cerium oxide and zirconium oxide in particulate form and generally having a high surface area in excess of 35 m ² / g. The composition is prepared by coprecipitation of cerium and zirconium species from solution at elevated temperature, then separated and dried at a temperature between 80-300 ° C. and calcined at a temperature between 200-1200 ° C.

The catalytic material does not originally produce live tobacco smoke or direct smoke, but instead is used in aromatic aerosol type cigarettes. Examples of such aerosol castings include those described in US Pat. Nos. 5,040,551, 5,137,034 and 5,944,025, wherein the catalyst is used to provide the heat generation necessary to generate the aerosol. Such catalyst systems include oxides of cerium, palladium or platinum.

Various live tobacco smoke control systems have been attempted in the prior art, but none of them are combustible cigarette papers that have combustible and acceptable ashes as conventional cigarettes without affecting the taste of the cigarettes.

The present invention relates to the reduction of sidestream smoke and other smoking products in burning cigarettes. More specifically, the present invention relates to cigarette paper, cigarette wrappers, or wrappers for cigar or other similar tobacco products to provide a modified ash while at the same time reducing visible live tobacco smoke.

Preferred embodiments of the invention are shown in the drawings:

1 is a schematic of a spraying technique for applying a treatment composition to a cigarette paper;

2 is a schematic view of extruding a film of treatment composition onto a cigarette paper;

3 is a schematic view of roll coating a treatment composition onto a cigarette paper;

4 is a schematic diagram of impregnating a coating of a treatment composition on a cigarette paper;

5 is a schematic diagram of mixing a treatment composition with paper-pulp in the manufacture of cigarette paper;

6 is a perspective view of a tobacco rod having a treated paper to which the present invention is applied;

FIG. 7 shows another embodiment of FIG. 6;

8 is a perspective view of a tobacco rod having a treatment composition sandwiched between two layers of cigarette paper when applied to the tobacco rod; And

Fig. 9 is a perspective view of a treatment paper applied on a conventional cigarette paper in a double wrap for tobacco paper.

Detailed Description of the Preferred Embodiments

In view of the present invention, the live tobacco smoke treatment composition provides a suitable ash with the desired characteristics while providing control of the desired degree of visible live tobacco smoke. The live tobacco smoke treatment composition of the present invention comprises an oxygen storage and providing metal oxide catalyst used in combination with a non-flammable powdery porous particulate adduct for the catalyst. As known from US patent application Ser. No. 09 / 954,432 filed on September 18, 2001, filed by Applicant, when these two components are used alone or in combination with other elements, very surprisingly visible live tobacco smoke control is achieved. It was discovered by chance that it was provided. Along with certain types of catalytic materials and / or adducts, re-characteristics have been found, such as sometimes lesser appearance than should be taken for granted, for example of discoloration, breaking into pieces and falling off. In the present invention, for example, compositions which modify the properties of the ash in order to provide an acceptable appearance, acceptable strength, color, bonding strength and reduction and fall of ash and the like and especially catalysts and / or Or improvements were made in the adducts.

The adduct may be any suitable inherently non-flammable, powdery particulate material that does not affect the aroma and taste of direct smoke smoke and does not emit any unwanted odor in the live tobacco vapor. Particulate matter is physically stable at elevated temperatures of a burning cigarette. The adduct usually has a low surface area of less than 20 m ² / g, preferably 1 m ² / g to 15 m ² / g, and most preferably 3 m ² / g to 10 m ² / g. For low surface area materials the fines are finely ground and usually not porous. However, when the surface area is increased to 20 m ² / g, it is natural that the particulate matter becomes porous. Conversely, adducts may also have a surface area usually greater than 20 m ² / g and this level of surface area is usually porous in particulate material. The porous adduct has pores smaller than 100 nm (1000 mm 3) in average diameter. More preferably, pores having an average diameter of less than 20 nm (200 mm 3) and pores having an average diameter of 0.5 to 1.0 nm (5-100 mm 3) are more preferred. For zeolite based materials, the pores range from about 0.5 to 1.3 nm (5-13 mm 3) in average diameter.

The particulate adduct has an average particle size of less than about 30 μm, more preferably less than about 20 μm, most preferably in the range from about l μm to about 10 μm. Non-combustible materials may be porous clays of various categories, such as bentonite clays or treated clays having high surface areas commonly used in cigarette paper manufacture. Non-combustible carbon materials can also be used, including ground porous carbon fibers and particulates. Zirconium fibers and pulverized materials with porous single minerals 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 Various metal oxides and / or carbonates can be used, such as metal oxide fibers such as porous ceramic fibers and other ceramics such as mixtures thereof. With respect to cerium oxide, it has been found that it can function as a powder adduct and as an oxygen storage and providing cerium oxide oxidation catalyst. Other accessory materials include materials such as activated carbon and zeolites at high surface areas.

Adducts may also include high surface area highly adsorptive materials that are non-combustible, inorganic powdery particulates such as molecular sieves containing zeolites and such as silica / alumina, zirconium oxide, zirconium hydrate and the like. And amorphous materials. Zeolites such as silicalite zeolites, paujasite X, Y and L zeolites, beta zeolites, mordenite zeolites and ZSM zeolites are acceptable. Preferred zeolites include hydrophobic zeolites and more or less hydrophobic zeolites, which have affinity for the hydrophobic and somewhat hydrophobic organic compounds of such live tobacco smoke and thus eliminate water vapor. Zeolite materials provide a highly porous structure that selectively absorbs and adsorbs compositions of live tobacco smoke. Highly porous structures generally include macropores between the microparticles and micropores in the microparticles branched into macropores. Compositions trapped in the macropores and micropores in the presence of cerium oxide or other suitable oxidation catalysts in the high temperature firing furnace are converted into oxidized compounds, which are either enclosed in the adsorbent or have a sufficiently low level of tar and nicotine. It is therefore believed that live tobacco smoke is emitted as an invisible or desired low level of invisible gas.

Zeolite materials can be characterized by the formula: MmM'nM "p [aAlO ₂ .b SiO ₂ .cTO ₂ ]

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 the stoichiometric ratio,

c, m, n or p can also be zero,

Al and Si are tetragonal Al and Si atoms, and

T is a metal atom that interacts as a tetrahedron to replace Al or Si, wherein the b / a ratio of the zeolite or zeolite-like material has a value of about 5 to 300, and the micropore size is about 0.5 to 1.3 nm. In the range (5 to 13 kV).

Preferred zeolites of the above formula are _pauzasite ((Na ₂ , Ca, Mg) ₂₉ [AI ₅₈ Si _l34 0 ₃₈₄ ] .240H ₂ 0; cube), β-zeolite (Na _n [Al _n Si _64-n O _l28). ], n <7; tetragonal system), mordenite zeolite (Na ₈ [Al ₈ Si ₄₀ 0 ₉₆ ] .24H ₂ 0; tetragonal system), ZSM zeolite (Na _n [Al _n Si _96-n O ₁₉₂ ]. ~ 16H ₂ O, n <27; orthorhombic), and mixtures thereof.

It has been recognized that various grades of adsorptive materials can be used. This is particularly evident that it can be designed with a gradient of zeolites, for example, high boiling point material, medium boiling point material and low boiling point material for selective adsorption. This can be layers of zeolite composition, where cerium oxide or other suitable catalyst as observed by the present invention can be appropriately sprayed through these layers. The layers are then bonded to the cigarette paper to the tobacco rod using a binder or an adhesive, for example polyvinylacetate, polyvinyl alcohol, carboxymethyl cellulose, starch and casein or soy protein, and mixtures thereof.

Oxygen donor and oxygen storage metal oxide catalysts may be selected from transition metal oxides, rare earth metal oxides (such as scandium, yttrium, and lanthanide metals such as lanthanum and the like) and mixtures thereof. The catalyst is present in its metal oxide form or as a precursor of the metal oxide, which is recognized to be converted to a metal oxide to carry out its catalytic activity at the combustion temperature of the cigarette. The transition metal oxides may be selected from oxides of the metal group and mixtures thereof from the periodic table consisting of Group IVB, VB, VIB, VIIB, VIII and Group IB metals. Metals selected from transition metal groups are oxides of iron, copper, silver, manganese, titanium, zirconium, vanadium and tungsten, and metals selected from rare earth groups are lanthanides such as oxides of lanthanum, cerium, praseodymium, neodymium and mixtures thereof Oxides of metals. For example, cerium may be used in admixture with any one transition metal, such as Ce / Zr mixed oxides. Other metal oxide oxide catalysts can be used with catalysts in the form of oxygen storage and oxygen providing. Such other metal catalysts include precious metals and metals from Groups IIA, IVA and mixtures thereof. For example, palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof.

Cerium catalyst precursors are applied in the form of cerium salts such as cerium nitrate or in adsorbent material or paper as a solution or in a sol coating and are converted to cerium oxide at high temperatures of cigarette combustion and act as a catalyst (or it is referred to as cerium hydroxide). Other sprayable forms of cerium, such as cerium sol. Naturally, the sol becomes a low cerium nitrate hydroxide sol. For the purpose of illustrating the invention, the term catalyst is intended to include any catalyst precursor.

Catalysts such as cerium oxide are used in combination with the adducts. It has been found that the ability to control live tobacco smoke is greatly reduced when the two are used apart or in spaces separated by non-adjacent layers. In any arrangement, some live tobacco smoke control can be achieved. Preferably the catalyst is substantially adjacent to the adduct. This is a surprising and surprising tobacco smoke control characteristic that is caused by co-mixing the particulate catalyst in admixture with the adduct, contacting the catalyst layer with the adjunct layer, coating the catalyst in the adduct or inserting the catalyst onto or into the porous surface of the adduct. Can be achieved. Many other compositions can be used with the addition of oxygen storage and oxygen providing metal oxide oxide catalysts and adducts. Additional additives may be used to further improve the treatment of live tobacco smoke or to change other features of the cigarette. Such additional additives may be mixed with the treatment composition or used anywhere in the cigarette composition, providing that the additives do not affect the treatment composition's ability to treat live tobacco smoke.

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

As a general criterion for selecting catalyst particle size and surface area, those skilled in the art will understand that the selected catalyst has a surface area which ensures that the catalytically active sites are useful for transporting live tobacco smoke components. If the catalyst particulates are properly distributed to achieve the required degree of live tobacco smoke component oxidation, this will in some embodiments be a catalyst particle size of at least 30 μm.

It has been surprisingly found that cerium oxides, especially high surface area cerium oxides, are one of the rare metal oxides capable of performing both functions of the present invention as well as adducts as well as oxygen storage and oxygen providing catalysts. Porous cerium oxide fine particles can be made to the average particle size required for high surface area and additives. Cerium oxide is used in cigarette paper in the treatment composition as the first amount as catalyst and the second amount as adduct. Such amounts of cerium oxide are generally consistent with the amounts used as catalysts and adducts in accordance with other aspects of the present invention that make up the total loading. Optionally high surface area cerium oxides can be used as adducts such as zeolites or other high surface metal oxides such as zirconium oxide or zirconium hydroxide.

Cerium may be formulated as a solution dispersion such as cerium oxide sol or the like and applied to an adsorbent material such as zeolite. It is then combusted to provide cerium oxide fine particles that are dried and fixed to the surface of the adsorbent material. When the cerium oxide fine particles are fixed to an adduct surface such as zeolite surfaces, the average particle size becomes less than about 1.0 μm. The relative amount of cerium oxide fixed to the zeolite ranges from about 1% to 75% by weight based on the total equivalent cerium oxide and zeolite content. Preferred relative amounts of cerium oxide fixed to the zeolite range from about 5% to 75% by weight based on the total equivalent cerium oxide and zeolite content.

One possible method of preparing a combination product of cerium oxide immobilized on the surface of a zeolite is a series of co-pending applications, filed and published by the US Patent Office on September 14, 2001, entitled Preparation of Metal Oxide-Coated Porous Materials. No. 60 / 318,878, the contents of which are hereby incorporated by reference.

The method generally relates to preparing zeolite particulate materials coated with catalytic cerium having at least 1% by weight of cerium oxide coated on the outer surface of the zeolite particulate material based on total equivalent cerium oxide and zeolite content. From one point of view, the method generally

i) zeolite particulates having a mean pore size of at least 20% by weight of cerium oxide, up to 20 GPa when thermally treated according to step (ii) to form a slurry and thereby place the colloidal dispersion on the zeolite outer surface Combining the colloidal dispersion of the cerium oxide hydrate (cerium hydroxide) and the compatible zeolite particulate material in an amount sufficient to provide a material and a colloidal dispersion having an average particle size of at least 20 GPa; And

ii) fixing the resulting cerium oxide to the outer surface of the zeolite particulate material, and first heat treating the slurry to a temperature below about 200 ° C. and then to a temperature above about 400 ° C. to provide flowing bulk particulates:

Several combinations of treatment compositions can result in what can be considered an unacceptable reappearance. Unacceptable ash appearance features include shattering, falling off, ash staining, oily appearance and color. It is contemplated that various ash modifiers may be added to the paper to enhance the ash appearance. Such remodifiers include carbonates such as metal oxides and / or zirconium oxides, titanium oxides, magnesium oxides, aluminum oxides, cerium oxides, tin oxides, iron oxides, manganese oxides, calcium carbonates, zirconium carbonates, magnesium carbonates and mixtures thereof. do.

The treatment composition is known to require modifications to enhance the re-characteristics. Such modifications include the selection of a particular chemical or physical type of oxygen providing / oxygen storage catalyst and / or adduct. It is known that reduced amounts of zeolite salt material as adducts are particularly suitable to enhance the color of ash to be whiter or grayer than dark coal. The reduced amount of zeolitic material based on 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 has been found that other types of fillers must be added to compensate for the reduced amount of zeolite base adduct. Suitable substituted 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 mixtures thereof. Low or high surface area cerium / zirconium mixed oxides are suitable as solid solutions. Such adducts are produced, for example, by co-precipitation of zirconium and cerium species, drying of precipitates and burning to form crystallized solid solution products of high surface area cerium oxides and zirconium oxides. The ratio of cerium oxide and zirconium oxide in the present crystal structure may range from about 5:95 to 95: 5. Optionally, the ratio may range from about 20:80 to 80:20, with the range of about 50:50 to 80:20 being most preferred. In its high surface area form this material also has catalyst characteristics and also provides oxygen storage and provision characteristics, where zirconium oxide functions as an addition to cerium oxide.

With regard to catalyst selection, it has also been found that the combination with cerium oxide contributes to a further improved reappearance. For example, cerium oxide can be placed on high surface area cerium oxide, cerium oxyhydrate can be placed on high surface area cerium / zirconium oxide, cerium oxyhydrate precipitate, and dried on high surface area cerium oxide fine particles. Moreover, the oxidation catalyst of the noble metal or transition metal type described above may be combined with cerium based materials such as palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof.

Solid solutions of mixed metal oxides are particularly suitable as oxygen providing catalysts because of improved lighter colored ash. Solid solutions of mixed metal oxides include oxygen providing oxygen storage oxidation catalysts and adducts. Preferred metal oxides of the solid solution as the oxygen providing oxygen storage material include lantin oxide, cerium oxide, placeodymium oxide, neodymium oxide and mixtures thereof. Preferred metal oxides as adducts include zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof. Examples of such solid solutions include cerium / lanthanum mixed oxides, cerium / zirconium mixed oxides, cerium / zirconium / lantinium mixed oxides, cerium / zirconium / plasedionium mixed oxides, cerium / zirconium / lantinium / placeocidinium mixtures. Oxides. Solid solutions of these mixed oxides and other mixed oxides are readily available as industrial grade catalysts and from any catalyst supplier. Other choices of solid solutions include, for example, physical mixtures of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide with a solid solution such as cerium / zirconium mixed oxide solid solution. Other solid solutions and mixed oxides envisioned by the present invention include cerium / aluminum mixed oxides, cerium / magnesium mixed oxides, and cerium / titanium mixed oxides.

Oxidation catalysts that can be included in solid solutions are generally present in trace amounts. Such catalysts include palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof. They are usually included in solid solutions at less than 1% by weight of the total solid solution. Preferred combinations for solid solutions with trace amounts of other oxidation catalysts are combinations of these catalysts with cerium / zirconium mixed oxides. The oxidation catalysts, individually or as a mixture thereof, are preferably included in solid solution. It is natural that the catalyst or mixtures thereof, although optional, may be applied to cerium / zirconium mixed oxide solid solution particulate molecules.

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

It has also been found that the wrapper coating of calcium carbonate fine particles is useful for enhancing the properties of the ash. As previously described, the treatment composition may be integrated or coated on a single wrapper for tobacco rods. As mentioned above, one approach to improving ash is to reduce large amounts of adsorbent adducts such as substitutes for zeolites and selected metal oxides. It has been found that the coating of calcium carbonate on the outside of the wrapper, optionally with a single wrapper, particularly with the integration of the treatment composition, greatly improves the ash in particular in terms of appearance. It is quite surprising that the coating of particulate calcium carbonate has this effect of improving the properties of the ash. Perhaps calcium carbonate binds chemically or physically to the components in the wrapper to produce a more uniform brightness into grayish ash. Particulate calcium carbonate can be suspended in a binder with a suitable binder for coating. Suitable binders include those commonly used to coat calcium carbonate on wrapper materials such as polyvinylalcohol, starch, CMC, casein, soybeans, bonded clay and other acceptable binders or glues. Particulate calcium carbonate has a particle size normally associated with its use as filler in the manufacture of cigarette paper. Therefore, the particle size is usually 10 μm or less, preferably 3 μm or more. Even some grades of calcium carbonate smaller than 1 μm may also be useful.

The surprising activity of the live tobacco smoke treatment composition allows its use in cigarette paper having a wide range of porosity. The composition should not be used for cigarette papers with only high porosity. The treatment composition works equally well on paper with very high porosity of about 1,000 Coresta units from very low porosity of about 0.5. Suitable porosity is typically less than 200 Coresta units, and the most preferred porosity is usually in the range of about 15 to 60 Coresta units. It is understood that paper can be used in double or multiple rolls. The paper may be applied as an outer wrapper on a cigarette having a conventional cigarette paper. Depending on the porosity, certain combinations of catalysts and adducts may work better than others.

The composition can simply be sprayed onto one or both sides of the cigarette paper and absorbed into the paper. As shown in FIG. 1, the paper 10 is moved in the direction of the arrow 12. The treating composition 14 as a slurry provides a coating 18 that is sprayed on the paper 10 by a spray jet 16 and dried on the paper. Alternatively, the composition may be extruded as a film on the surface of the paper and used as single or multiple wrappers. As shown in FIG. 2, the membrane coating apparatus 20 includes a suspended composition 14. The film coater 20 places the thin film 22 on the paper 10 which is moved in the direction of the arrow 12. The film is dried to provide a coating 24 on the paper 10. With such a device, visible live tobacco smoke substantially disappears from the burning of cigarettes. The treatment composition may be applied to the exterior of conventional cigarette cigarette paper.

As shown in FIG. 3, the coating is made by a roller spatula 26. The treating composition 14 is applied to the roller 30 in layer 28. Doctor knife 32 determines the thickness of layer 34 that is placed on paper 10 that is moved in the direction of arrow 12. The layer is then dried in the form of a coating 36 on the paper 10.

Injection is achieved by using the coating roller 24 of FIG. 4, with the paper 10 and the resulting layer 36 forcing the material layer onto the paper 10 to inject the components of the treatment composition into the paper. It passes through the compression rollers 38 and 40 in the direction of the arrow 12.

It will also be apparent to those skilled in the art that various other coating procedures, including transfer coating processes, can be used to make the treatment paper of the present invention. In the transfer coating process, a Mylar ^™ sheet or other suitable continuous sheet can be used to transfer the coating composition from the Mylar ^™ sheet to the surface of the cigarette paper. Such transfer coating forms are useful when the substrate sheet cannot readily accept the components of the roll coating due to the physical strength of the paper or the like.

A further approach is to integrate the treatment composition into paper making. The composition can be introduced into the paper furnish as a slurry. As mentioned in FIG. 5, the treatment composition in furnish 42 is stirred by stirrer 44 to form a slurry in tank 46. The slurry is transferred as a layer 48 on a conveyor 50 that is transferred in a conventional paper making manner and moves to form the resulting cigarette paper 52. As a result, the treatment composition is incorporated into the final paper product.

Another alternative is to sandwich the treatment composition between the paper layers to form a double cigarette paper wrapper on the tobacco rod. For example, the composition may be applied as by the spraying technique of Figure 1 on the inner side of the outer paper and / or on the outer side of the inner paper. Once two sheets of paper are applied to the tobacco rod, the composition as a layer is It will be sandwiched between two pieces of paper. Since each paper is half the thickness of a conventional cigarette paper, the double wrapper does not increase the overall diameter of the cigarette to the extent that it can be easily manipulated by a cigarette making machine.

As mentioned in FIG. 6, for example, the tobacco rod 54 has a cigarette paper 10 surrounded by a coating 18 on the outer side of the paper. Conversely, as shown in FIG. 7, cigarette paper 10 may be applied with a coating 18 on the inner side of the paper adjacent the tobacco rod 54.

As shown in FIG. 8, another alternative is to sandwich the coating 18 between the cigarette paper 56 and 58. Papers 56 and 58 with intermediate coating 18 may be formed as one cigarette wrapper applied to tobacco rod 54. A further alternative is shown in FIG. 9, wherein the tobacco rod 54 is covered with a conventional cigarette paper 60. The top of a conventional paper 60 is the cigarette paper 52 of FIG. 5 with the treatment composition integrated therein. It is also recognized that the paper 52 incorporating the treatment composition can be applied directly to the tobacco rod 54.

Nevertheless, in another alternative embodiment, various combinations for live tobacco smoke treatment paper may be provided in a double wrapper structure, for example, the coated paper of FIG. 7 may be used as an inner layer of paper. Other paper may be used as the outer layer of the double wrapper, which may be a conventional paper. The inner layer paper can also be a paper having a treatment composition integrated therein as in FIG. 9. The inner layer paper can be designed to include all necessary configurations of the composition, such as oxygen storage and providing metal oxide oxide catalysts and non-combustible adducts to the catalyst to provide live tobacco smoke reduction. Preferred examples of this composition form include cerium / zirconium mixed oxides that contain a high surface area, zeolite and optionally enhanced oxidation catalyst such as platinum or palladium. In a double wound system, the amount of zeolite is above 30%, for example in the weight range of 50 to 60%.

The outer layer of the double wrapper can have a different composition and can be designed to provide re-deformation to achieve the desired characteristics. For example, the outer paper can be designed not only to improve the appearance of the ash, but also to modify the burning rate of the cigarette and to minimize it, although not necessarily to ignite the cigarette or to eliminate burning in smoking. For example, the outer layer includes ground surface area cerium oxide, solid solution of cerium / zirconium oxide, alumina, zirconium oxide, titanium oxide, tin oxide, and metal oxides such as these. In addition, cerium oxyhydrate can be coated on the metal oxide of the outer layer to assist in burning the outer layer of the cigarette in the presence of sufficient oxygen. When combined into a double wrapper, the two layers provide effective control of visible live tobacco smoke. Adjacent papers are burned evenly to produce the desired ash and the outer paper functions to remove or minimize the high active oxygen providing material from the blazing cause.

The dual wrapper feature of the present invention provides important flexibility in the design of low live tobacco smoke cigarettes. Each sheet of the double wrap design has a selected treatment composition that is permeated, coated or integrated on each sheet. Selected sheets incorporating treatment compositions may be coated with the same or different treatment compositions to further enhance live tobacco smoke control and / or re-deformation. To demonstrate such flexibility in the design of low live tobacco smoke cigarettes, exemplary treatment compositions for the inner and outer paper are as follows:

Outer paper

i) high surface area + low surface area zirconium oxide of cerium / zirconium mixed oxide (75:25);

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 oxides (25:75).

Inside paper

i) a high surface area cerium / zirconium mixed oxide (75:25) + zeolite reinforced with a palladium catalyst;

ii) zeolites reinforced with high surface area cerium / zirconium mixed oxides (75:25) + palladium;

iii) a high surface area cerium / zirconium mixed oxide (75:25) + zeolite, where the cerium / zirconium mixed oxide is reinforced with a palladium catalyst; or

iv) a high surface area cerium / zirconium mixed oxide (75:25) + zeolite, where the cerium / zirconium mixed oxide is reinforced with a palladium and tin catalyst.

These various compositions for the inner and outer paper can be combined in various combinations provided for live tobacco smoke control and ash improvement.

Preferred combinations are solid solutions of high surface area cerium / zirconium mixed oxides (75:25) and zirconium oxides of the outer paper. For the inner paper, the preferred treatment composition is a solid solution of a high surface area cerium / zirconium mixed oxide (75:25) reinforced with a palladium catalyst and a zeolite reinforced with a palladium catalyst. In outer paper based on dry weight the coating formula has 25% high surface area cerium / zirconium mixed oxide and 75% low surface area zirconium oxide. The dry paper based on dry weight has about 44% high surface area cerium / zirconium mixed oxide and about 56% zeolite, both of which are promoted by palladium.

As will be appreciated by one of ordinary skill in the art, the foregoing procedures for providing a live tobacco smoke composition in or on a desired cigarette paper vary depending on the number of loadings and wraps used on the tobacco rod. Can be. For example, two or more papers with various loadings of the composition on both sides of the papers can be used as the loading on one side is reduced which makes coating application easier.

With these combinations, it has been surprisingly found that visible live tobacco smoke is substantially eliminated. At the same time, cigarette paper exhibits conventional ash properties. It is particularly surprising that a simple application of the composition to the outside of the cigarette paper can minimize the visible live tobacco smoke to an almost undetectable level.

Depending on the manner in which the compositions are used and applied to cigarettes, it is recognized that the aids of the various processes and their mixtures are required to facilitate the particular application of the treatment composition. Auxiliaries of such processes are 2001, named polyvinyl alcohol, starch, CMC, casein, soybeans and other types of acceptable adhesives, various types of bonding clays, inert fillers, bleaches, viscosity modifiers, zirconium / metal oxide fibers. U. S. Patent Application 60/318, 614, which is incorporated herein by reference, includes fragmented materials such as zirconium fibers and inert fiber materials such as zirconium / cerium fibers.

Penetrations may also be applied to carry the composition into the paper. Suitable diluents, such as water, are also used to dilute the composition, which is a transfer coating technique and conventional spray coating, curtain coating, air knife coating, rod coating, blade coating, print coating, size compression coating, on conventional cigarette paper, Roller coated, slot die coated.

The desired loading of the treatment composition on or into a cigarette puper, wrapper or the like is preferably in the range of about 2.5 g / m ² to about 125 g / m ² . The most preferred loading is in the range of about ^2.5 g / m ² to about 100 g / m ² . Expressed in weight percentages, the paper has a weight of about 10% to about 500%, most preferably about 10% to 400% of the weight of the treatment composition. While such loading is typical for a single piece of paper, it is natural for a person skilled in the art that this total loading can be provided for the use of two or more pieces of paper.

The live tobacco smoke reducing composition is normally used as a slurry of water and the composition. The composition of the dry composition, which can be made into a slurry, varies depending on its use in paper coating, incorporation or infiltration. For example, the integrated formula comprises about 10% to 33% by weight of a cerium based catalyst, 20% to 62% adduct and 10% to 75% re variant. Other choices include zeolites different from about 10% to 25% by weight cerium based catalyst, 40% to 55% adduct and 20% to 50% adduct.

The slurry can be incorporated into the paper furnish during the paper making process, coated on the paper by various coating processes, or penetrated into the paper by various permeation methods. Preferred average particle sizes of catalyst and adducts for the slurry range from about 1 μm to about 30 μm, most preferably from about 1 μm to about 10 μm. The amount of preferred relative catalyst fixed to the adduct ranges from about 1% to 75% by weight relative to cerium, more preferably from about 10% to 70% by weight, most preferably the total equivalent catalyst and adduct content From about 20% to 70% by weight.

While preferred embodiments of the invention have been described in detail herein, it will be apparent to those skilled in the art that changes may be made without departing from the spirit of the invention or the scope of the appended claims.

Summary of the Invention

With respect to various aspects of the present invention, cigarette paper, cigarette wrappers, cigars, or wrappers for other similar tobacco products are provided to reduce visible live tobacco smoke while having improved or modified ash.

With respect to various aspects of the present invention, for small live tobacco smoke cigarettes having conventional tobacco rods and combustible treated papers, the treated paper is an oxygen storage and providing metal oxide oxide catalyst and a particulate particulate adduct that is essentially non-flammable to the catalyst. And has a refinement comprising the use of a solid solution of particulate mixed metal oxides as said catalyst and said adduct.

Oxygen storage and provision as part of the solid solution The metal oxide catalyst is preferably selected from the group consisting of lantin oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. The adduct is also part of a solid solution and 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 solid solution metal catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof. Properly mixed solid oxide oxides include cerium / lanthanum mixed oxides, cerium / zirconium mixed oxides, cerium / zirconium / lanthanum mixed oxides, cerium / zirconium / praseodynium mixed oxides, cerium / zirconium / lantinium / prase It is an odynium mixed oxide, a cerium / zirconium / neodymium mixed oxide and mixtures thereof.

With respect to another aspect of the present invention, a low live tobacco smoke cigarette comprises a combustible treatment paper having a conventional tobacco rod and a live tobacco smoke treatment composition, wherein the treatment composition comprises an oxygen storage and providing metal oxide catalyst, an essentially non- Combustible adducts and metal oxides for modifying ash properties.

With respect to another aspect of the invention, the adduct may include a mixed metal oxide or carbonate filler used with the zeolite base material. The zeolite base material is preferably in an amount ranging from about 0.1% to 35% by weight of the total dry weight of the composition, but may be higher. The mixture of metal oxides may include 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. The metal oxides can be of various surface areas and most suitably selected from a low surface area in the range of about 5 to 15 m ² / g and a high surface area of at least 20 m ² / g. Cerium oxide hydrate sol can be applied to adducts such as metal oxides to increase the catalytic activity.

With respect to another aspect of the invention, the oxygen storage and providing metal oxide oxide catalytic material preferably comprises lantin oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. Oxidation catalysts of noble and transition metal types may also include such as palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof. Such catalysts may also be immobilized on adducts or reforming materials or may be part of a solid solution of mixed oxides.

The live tobacco smoke treatment composition may be incorporated into or coated on the combustible treatment paper, impregnated into the treatment paper, or a combination of the above steps. The treatment paper may be double wrapped in the same or different compositions. One of the double rolls is a conventional paper. Alternatively, one of the double rolls may preferentially have a composition for reducing live tobacco smoke, and the remaining double rolls of paper may comprise a composition for reshaping.

With respect to another aspect of the present invention, less live tobacco smoke cigarettes include combustible treated papers having conventional tobacco rods and live tobacco smoke treatment compositions. The treatment composition comprises an essentially non-flammable, high surface area adsorption adduct for oxygen storage and providing metal oxide oxide catalysts and catalysts incorporated in the treatment paper. A coating of calcium carbonate is provided on the outer surface of the treated paper to modify the ash properties.

For convenience of explanation, whenever the term cigarette is used, it is natural that it refers to a flammable cigarette as well as a wrapped combustible tobacco product of any form, such as cigars or the like. Whenever the term treatment paper is used, it is natural that it refers to flammable wraps and cigarettes, cigars, and the like, including those that can be used in such. The wrapper may be a single layer of cigarette paper or a multilayer of cigarette paper. The wrapper may be applied as a single layer of cigarette paper or as a wrapper on a conventional cigarette paper of a cigarette. The treated paper may include, as its substrate, conventional cigarette paper or similar combustible products having a wide range of porosity. Conventional tobacco rods include tobacco compositions used in common combustible cigarettes. These rods are distinguished from the tobacco compositions used in aerosol cigarettes.

Claims (77)

For small live tobacco smoke cigarettes having conventional tobacco rods and combustible treated papers, the treated paper comprises an oxygen storage and providing metal oxide oxide catalyst and an inherently non-flammable powdery particulate adduct for the catalyst. And have an improvement comprising the use of a solid solution of a particulate mixed metal oxide as said catalyst and said adduct. The small live tobacco smoke cigarette according to claim 1, wherein the oxygen storage and providing metal oxide catalyst for solid solution is selected from the group consisting of lantin oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. 2. The small live tobacco smoke cigarette of claim 1, wherein the adduct is selected from the group of metal oxides consisting of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof. 4. The catalyst of claim 1, 2 or 3 wherein the solid solution of mixed metal oxides further comprises an oxidation catalyst selected from the group comprising palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof. It is characterized in that less live tobacco smoke cigarettes. The solid solution of mixed metal oxides according to claim 1, 2, 3 or 4, wherein the solid solution of mixed metal oxides is cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / zirconium / lantinium mixed oxide, cerium / zirconium / praseodynium mixed. A small live tobacco smoke cigarette, characterized in that it is selected from the group consisting of oxides, cerium / zirconium / lantinium / praseodynium mixed oxides, cerium / zirconium / neodymium mixed oxides and mixtures thereof. The small live tobacco smoke cigarette according to any one of claims 1 to 5, wherein the solid solution is a high surface area porous particulate. 7. The small live tobacco smoke cigarette of claim 6, wherein the solid solution is low surface area particulates. 7. The low live tobacco smoke cigarette of claim 6, wherein said catalyst and said adduct are said high surface area cerium / zirconium mixed oxide. The catalyst of claim 1 wherein the catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof is included in the solid solution of cerium / zirconium mixed oxide or the high surface area. Small live tobacco smoke cigarette, characterized in that applied to the surface of the cerium / zirconium mixed oxide. 10. The small live tobacco smoke cigarette of claim 9, wherein the cerium / zirconium mixed oxide has a particle size of at least about 1 μm. The low live tobacco smoke cigarette of claim 10, wherein the cerium / zirconium mixed oxide has a particle size of less than about 30 μm. 9. The small live tobacco smoke cigarette of claim 8, wherein the cerium / zirconium mixed oxide has a ratio in the range of about 5:95 to 95: 5. The small live tobacco smoke cigarette of claim 12, wherein the ratio is about 75:25 and the particle size is about 6 μm to 10 μm. The low live tobacco smoke cigarette of claim 1, wherein the treatment composition is incorporated into the treatment paper at a loading rate of about 2.5 g / m ² to about 125 g / m ² . 2. The small live tobacco smoke cigarette of claim 1, wherein the treatment composition is coated onto the treatment paper. 9. The process of claim 8 wherein the treatment composition comprises particulate 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. Features a little live cigarette smoke cigarette. 10. The small live tobacco smoke cigarette of claim 8, wherein the treatment composition comprises particulate zeolite. 18. The small live tobacco smoke of claim 17, wherein the zeolite is a support for an oxidation catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide and mixtures thereof. cigarette. 10. The small live tobacco smoke cigarette of claim 8, wherein the treatment composition comprises zirconium oxide. A small live tobacco smoke cigarette comprising a combustible treatment composition having a conventional tobacco rod and a live tobacco smoke treatment composition, the treatment composition comprising an oxygen storage and providing metal oxide oxide catalyst, an essentially non-combustible particulate additive and ash for the catalyst. Small live tobacco smoke cigarettes comprising metal oxides or carbonates to modify properties. 21. The small live tobacco smoke cigarette of claim 20, wherein the adduct is high surface area particulates. The zeolite base material of claim 21 wherein the particulate adduct is in the range of from about 0.1% to about 60%, preferably less than 25%, most preferably less than 15% by weight of the total dry weight composition. Little tobacco smoke cigarettes made with. 22. The method of claim 21, wherein the reformed metal oxide or carbonate is 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. Small live tobacco smoke cigarette, characterized in that selected from the group consisting of. 21. The small live tobacco smoke cigarette of claim 20, wherein the adduct is a support that allows cerium oxide sol to be applied and dried thereon. The low live tobacco smoke cigarette of claim 24, wherein the adduct is high surface area cerium oxide. 21. The small live tobacco smoke cigarette of claim 20, wherein the oxygen storage and provision metal oxide catalyst is selected from the group consisting of transition metal oxides, rare earth metal oxides, and mixtures thereof. 27. The low live tobacco smoke cigarette of claim 26, wherein the transition metal oxide is selected from the group consisting of oxides of Group IVB, VB, VIB, VIIB, VIIIB, Group IB metals and mixtures thereof. 28. The small live tobacco smoke cigarette of claim 27, wherein the rare earth metal oxide is selected from the group consisting of scandium, yttrium and lanthanide metals and mixtures thereof. 21. The small live tobacco smoke cigarette according to claim 20, wherein said lanthanum series metal is selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide and mixtures thereof. 30. The group of claim 29 wherein the oxygen storage and providing metal oxide catalyst and adduct therefor is a solid solution of mixed metal oxides, wherein the adduct consists of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof. Small live tobacco smoke cigarettes, characterized in that is selected from. 31. The low live tobacco smoke cigarette of claim 30, wherein the solid solution of mixed metal oxides comprises a catalyst selected from the group consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide. 21. The method of claim 20, wherein the solid solution of the mixed metal oxide is cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / aluminum mixed oxide, cerium / magnesium mixed oxide, cerium / titanium mixed oxide, cerium / zirconium / lanthanum Mixed oxides, cerium / lanthanum mixed oxides, cerium / zirconium mixed oxides, cerium / zirconium / lanthanum mixed oxides, cerium / zirconium / praseodynium mixed oxides, cerium / zirconium / lantin / praseodynium mixed oxides, Little live tobacco smoke cigarettes characterized by containing cerium / zirconium / neodymium mixed oxides. 21. The low live tobacco smoke cigarette of claim 20, wherein the adduct is selected from the group consisting of clay, essentially non-combustible comminuted fibers, single mineral base material, essentially non-combustible carbon, zeolites, and mixtures thereof. . The method of claim 33, wherein the adducts are 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, metal oxide fibers and Low live tobacco smoke cigarettes, characterized in that it is selected from the group consisting of ground porous ceramic fibers and mixtures thereof. 33. The low live tobacco smoke cigarette of claim 29, 30, 31 or 32, wherein the solid solution is a high surface area porous particulate. 33. The low live tobacco smoke cigarette of claim 29, 30, 31 or 32, wherein the solid solution is a low surface area particulate. 24. The small live tobacco smoke cigarette of claim 23, wherein the remodified particulate is zirconium oxide. 30. The method of claim 29, wherein an oxidation catalyst is used in conjunction with the oxygen storage and providing metal oxide catalyst, wherein the oxidation catalyst is from the group consisting of palladium, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof. Little live tobacco smoke cigarette, characterized in that selected. 23. The small live tobacco smoke cigarette of claim 22, wherein the zeolite is a Y-type zeolite, a ZSM-5 type zeolite or a beta type zeolite. 30. The low live tobacco smoke cigarette of claim 29, wherein the oxygen storage and provision metal oxide catalyst is a porous particulate solid solution of cerium / zirconium, which is preferably a mixed oxide high surface area material. 41. The low live tobacco smoke cigarette of claim 40, wherein zirconium oxide and / or zeolite are used in combination with the cerium / zirconium mixed oxide. 42. The small live tobacco smoke cigarette of claim 41, wherein an oxidation catalyst is used as the cerium / zirconium metal oxide, zirconium oxide, and / or zeolite. 43. The method of claim 42, 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, wherein the selected oxidation catalyst is selected from cerium / zirconium mixed oxides. Small live tobacco smoke cigarettes, characterized in that they are incorporated into the solid solution or applied to the surfaces of particulate cerium / zirconium mixed oxides, zirconium oxides and / or zeolites. 43. The small live tobacco smoke cigarette of claim 42, wherein the zeolite is a Y-type zeolite. 21. The method of claim 20, wherein the treatment composition is applied as a coating to cigarette paper, the coating composition comprising zirconium oxide, titanium oxide, magnesium oxide, aluminum oxide, cerium oxide, tin oxide, iron oxide, manganese oxide, calcium carbonate, carbonate A small live tobacco smoke cigarette, comprising a metal oxide or carbonate selected from the group consisting of zirconium, magnesium carbonate and mixtures thereof. 21. The method of claim 20, wherein the combustible treated paper comprises an inner sheet and an outer sheet, the inner sheet comprising the treatment composition for reducing live tobacco smoke and the outer layer comprising a treatment composition for modifying ash properties. Little live tobacco smoke cigarettes, characterized in that. 47. The small live tobacco smoke cigarette of claim 46, wherein the inner paper has at least 35 wt% zeolite material. 47. The small live tobacco smoke cigarette of claim 46, wherein the inner and outer papers are coated, integrated or impregnated thereon. 49. The small live tobacco smoke cigarette of claim 48, wherein the inner paper has the live tobacco smoke reduction composition incorporated therein. 49. The small live tobacco smoke cigarette of claim 48, wherein the inner paper has the live tobacco smoke reduction composition coated thereon. 49. The small live tobacco smoke cigarette of claim 48, wherein the inner paper has the live tobacco smoke reduction composition integrated and coated thereon. 49. The small live tobacco smoke cigarette of claim 48, wherein the outer paper has the live tobacco smoke reduction composition integrated thereon. 49. The small live tobacco smoke cigarette of claim 48, wherein the outer paper has the live tobacco smoke reduction composition coated thereon. 49. The small live tobacco smoke cigarette of claim 48, wherein the outer paper has the live tobacco smoke reduction composition integrated and coated thereon. 47. The method of claim 46, wherein the inner paper comprises an oxygen storage and providing metal oxide oxide catalyst with adducts and a high surface area adsorbent material, and the outer layer is characterized by an oxygen storage and providing metal oxide catalyst with adducts and ash properties. Small live tobacco smoke cigarette, characterized in that it comprises a metal oxide to deform. 56. The small live tobacco smoke cigarette of claim 55, wherein the treatment composition for reducing live tobacco smoke and the treatment composition for modifying ash are applied as a coating to the inner sheet and the inner sheet, respectively. 59. The small live tobacco smoke cigarette of claim 56, wherein the oxygen storage and provision metal oxide catalyst is a porous particulate high surface area solid solution cerium / zirconium mixed oxide. 59. The small live tobacco smoke cigarette of claim 57, wherein the cerium oxide and zirconium oxide in the solid solution are in a ratio of about 5:95 to about 95: 5. 59. A small live tobacco smoke cigarette according to claim 58, wherein said coating is applied to said inner and outer sheets on one or both sides of said sheet. A small live tobacco smoke cigarette comprising a combustible treated paper having a conventional tobacco rod and a live tobacco smoke treating composition, wherein the treating composition is an oxygen storage and providing metal oxide oxide catalyst, an essentially non- A low live tobacco smoke cigarette comprising a calcium carbonate coating on the outer surface of the treated paper for modifying flammable high surface area additives and ash properties. 61. The small live tobacco smoke cigarette of claim 60, wherein the adduct comprises a zeolite based material. 62. The method of claim 61, wherein the zeolite base material is in an amount ranging from about 0.1% by weight of the total dry weight composition to about 60% by weight, preferably less than 25%, most preferably less than 15% of the total dry weight composition. Features a little live cigarette smoke cigarette. 61. The low live tobacco smoke cigarette of claim 60, wherein the oxygen storage and providing metal oxide catalyst is selected from the group consisting of transition metal oxides, rare earth metal oxides, and mixtures thereof. 63. The low live tobacco smoke cigarette of claim 61, wherein the transition metal oxide is selected from the group consisting of oxides of Group IVB, VB, VIB, VIIB, VIIIB, Group IB metals and mixtures thereof. 63. The low live tobacco smoke cigarette of claim 62, wherein the rare earth metal oxide is selected from the group consisting of oxides consisting of scandium, yttrium, lanthanide series metals, and mixtures thereof. 61. The low live tobacco smoke cigarette of claim 60, wherein the lanthanum based metal oxide is selected from the group consisting of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, and mixtures thereof. 67. The method of claim 66, wherein the oxygen storage and provision metal oxide catalyst and adducts therefor are solid solutions of mixed metal oxides, wherein the adduct is from the group consisting of zirconium oxide, aluminum oxide, magnesium oxide, titanium oxide and mixtures thereof. Little live tobacco smoke cigarette, characterized in that selected. 68. The low live tobacco smoke cigarette of claim 67, 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. 69. The method of claim 68, wherein the solid solution of mixed metal oxide is cerium / lanthanum mixed oxide, cerium / zirconium mixed oxide, cerium / aluminum mixed oxide, cerium / magnesium mixed oxide, cerium / titanium mixed oxide, cerium / zirconium / lanthanum Mixed oxides, cerium / lanthanum mixed oxides, cerium / zirconium mixed oxides, cerium / zirconium / lanthanum mixed oxides, cerium / zirconium / praseodynium mixed oxides, cerium / zirconium / lanthanum / praseodynium mixed oxides, cerium / A small live tobacco smoke cigarette, comprising a zirconium / neodymium mixed oxide. 70. A low live tobacco smoke cigarette according to claim 66, 67, 68 or 69, wherein said solid solution is high surface area porous particulates. 67. The method of claim 66, wherein an oxidation catalyst is used in conjunction with the oxygen storage and providing metal oxide catalyst, the oxidation catalyst consisting of palladium, platinum, rhodium, tin oxide, copper oxide, iron oxide, manganese oxide, and mixtures thereof. Small live tobacco smoke cigarette, characterized in that selected from the group. 62. The small live tobacco smoke cigarette of claim 61, wherein the zeolite is a Y-type zeolite, a ZSM-5 type zeolite or a beta type zeolite. 73. The small live tobacco smoke cigarette of claim 72, wherein the oxygen storage and provision metal oxide catalyst is a porous particulate cerium / zirconium mixed oxide high surface area material. 74. The small live tobacco smoke cigarette of claim 73, wherein an oxidation catalyst is used in combination with the cerium / zirconium mixed oxide, zirconium oxide, and / or zeolite. 75. The method of claim 74, 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, wherein the selected oxidation catalyst is selected from cerium / zirconium mixed oxides. Small live tobacco smoke cigarettes, characterized in that they are incorporated into the solid solution or applied to the surfaces of particulate cerium / zirconium mixed oxides, zirconium oxides and / or zeolites. 76. The small live tobacco smoke cigarette of claim 75, wherein the zeolite is a Y-type zeolite. 61. The low live tobacco smoke cigarette of claim 60, wherein the calcium carbonate coating binder is selected from the group consisting of polyvinyl alcohol, starch, CMC, casein, soybean, bonded clay, inorganic binder and mixtures thereof.