EP2868213A1 - Wrapping material for smoking products having controlled smouldering properties - Google Patents

Abstract

A smoking article wrapping material is described which comprises composite particles obtainable by a process in which
a) introducing an aqueous suspension containing calcium carbonate particles,
b) adding a metal salt comprising an aluminum cation,
wherein the metal salt
(i) is capable of forming a basic metal component in the suspension,
(ii) in water, measured at the pH of the charged suspension and a temperature of 20 ° C, having a solubility greater than 9.0 mg / l, and a process for the preparation thereof, the use of such a tobacco product wrapping material for the manufacture of tobacco products and derived tobacco products.

Description

The present invention relates to a smoking article wrapping material comprising composite particles based on mineral particles, to processes for their production and to their use in tobacco products. One focus of the present application is smoking articles with controlled glow properties.

Typically, filter cigarettes consist of a cylindrical, round, or oval tobacco rod wrapped in a cigarette paper, a similarly shaped filter plug surrounded by a filter wrap paper, and a tipping paper (base paper for the tipping pad, also referred to as tipping paper), commonly used is glued to the entire filter wrapping paper and a portion of the cigarette paper wrapping the tobacco rod, and so connects the filter plug with the tobacco rod. All of these papers are to be collectively referred to herein as smoking article wrapping materials.

Smoking article wrapping materials usually contain fillers. In addition, other additives may be included to provide specific properties, such as wet strength agents, burn rate retarding substances, and / or burn rate accelerating substances, etc.

As fillers are usually incorporated materials such as calcium carbonate, titanium dioxide, aluminum hydroxide, magnesium hydroxide, kaolin, calcined kaolin or talc and mixtures thereof in tobacco product wrapping materials, which can be controlled by appropriate choice of the type and amount of fillers, both the optical properties and the glow properties. However, smoking article wrapping materials that have no fillers or only a low filler content may have an enhanced smoking effect in smoking products, however, such smoking article wrapping materials do not have the desired optical properties, such as high whiteness or high opacity.

In the case of smoking article wrapping materials, however, there are also restrictions as to which fillers may be used in accordance with the applicable statutory provisions. Calcium carbonate can be fully used in all types of smoking article wrapping materials under current regulations. However, it is known that certain fillers for the optical properties and the glow properties are disadvantageous. Furthermore, it is known that tobacco product wrapping materials, which have a high content of fillers and additionally show controlled glow characteristics and a desired extinguishing behavior when used in tobacco products, in addition to calcium carbonate require a significant proportion of other fillers or mixtures of other fillers, and optionally other substances, eg the burn rate retarding substances that can be incorporated into these smoking article wrapping materials.

Furthermore, it is known in the art to apply substances such as polymers, silicates, polysaccharides and derivatives in aqueous or non-aqueous solutions or suspensions in sufficient quantity and geometrical distribution to a smoking article wrapping material, preferably cigarette paper, to thereby influence the glow characteristics of the tobacco product wrapping material ,

In recent years, further demands have been made on a smoking article, such as a cigarette. Thus, it has recently been demanded that a smoking article which continues to glow in the ordinary smoking without extinguishing extinguishes when the smoking article is placed on a combustible material to prevent the combustible material from catching fire. In other words, a controlled smoldering behavior is desired, in which the smoked goods, on the one hand, smolder unhindered with freely accessible air to the tobacco product wrapping material, and on the other hand extinguish themselves on documents, which in turn may be combustible, shortly after contact with these documents.

Japanese Patent Application No. Hei. 11-151082 A discloses a cigarette with controlled glow characteristics in which a plurality of annular regions (combustion control regions) are arranged separately from one another in the longitudinal direction of a cigarette. These annular regions are in turn coated with a suspension comprising an inorganic filler such as chalk, clay or titanium oxide in a cellulosic polymer.

The European patent application EP 1 321 048 A1 describes a smoking article with controlled glow characteristics comprising a cigarette paper coated with a burn control agent intended to adjust the smoking article's burning behavior. As examples of this Combustion control agents are proteins such. Gelatin, casein, albumin and gluten; thickening polysaccharides such as starch, echo gum, locust bean gum, guar gum, tragacanth gum, tare gum, tamarind seed polysaccharides (glyloid), karaya gum, gum arabic, pullulan, dextrin, cyclodextrin (Oligoseven), and ghatti gum; gelling polysaccharides such as carrageenan, Kurdlan, agar, furcellaran, pectin, "Jeram" gum and " Kelco "gel; Lipids such as lecithin; natural, high molecular weight derivatives such as carboxymethyl cellulose, methyl cellulose, propylene glycol alginate ester, and a processed starch such as starch phosphate; synthetic, high molecular weight compounds such as poly (sodium acrylate) and various high molecular weight emulsifiers; inorganic ammonium salts such as ammonium chloride, ammonium phosphate, ammonium hydrogenphosphate, ammonium dihydrogenphosphate, ammonium bromide and ammonium sulfate; inorganic hydroxides such as barium hydroxide, calcium hydroxide and aluminum hydroxide; and inorganic salt flame retardants such as sodium borate, boric acid, zinc chloride, magnesium chloride, calcium chloride and sodium sulfate. These combustion control agents are intended to be used singly or in the form of a mixture of at least two of these combustion control agents.

CN 101747909 B discloses a flame retardant additive comprising calcium carbonate and magnesium hydroxide which is obtainable by adding a magnesium sulfate solution, adding an alkaline calcium hydroxide suspension, adding a calcium chloride solution and separating the precipitate.

A disadvantage of the procedure described in this document is the time-consuming and expensive process, which comprises a total of 10 steps, where step 9 alone takes 2-3 days. In addition, step 4 involves an ultrasound treatment, which can only be realized with great difficulty on an industrial scale.

Furthermore, the product obtainable in this way is only above 200 ° C able to deliver significant amounts of water. X-ray diffraction spectra of the product show that the product is a physical mixture of calcium carbonate and magnesium hydroxide.

In the patent application US 2006/0162884 A1 describes mineral pigments containing a product which is obtained in situ by reaction of a calcium carbonate with a weak or a strong acid, gaseous CO ₂ and a certain salt. It should be used as the salt of aluminum silicate, synthetic silica, calcium silicate, a silicate of a monovalent salt, such as. As sodium silicate, potassium silicate and / or lithium silicate, aluminum hydroxide, sodium aluminate and / or potassium aluminate are used, wherein the content of monovalent silicate salts should be less than 0.1 wt .-%, based on the dry weight of the calcium carbonate. The mineral pigments obtainable in this way should have a pH, measured at 20 ° C., greater than 7.5.

The BET surface area of the mineral pigment of this document should preferably be between 25 m ² / g and 200 m ² / g.

In working example 10 of this patent application, aluminum hydroxide powder and then sodium silicate are added to a suspension of natural calcium carbonate in water and the resulting suspension is treated with phosphoric acid.

An addition of a metal salt to a calcium carbonate suspension, which in the suspension, measured at 20 ° C, a solubility greater than 9.0 mg / l, however, the publication is not apparent.

Furthermore, this application is not concerned with the technical field of the present invention, namely the making available of smokers with kotrollierten glow properties, but concerns the provision of fillers for inkjet papers and has the particular aim of improving the printability of conventional coated or uncoated papers.

Finally, for the purposes of the present invention, substances can not be used in which calcium silicates are formed as the main product or as a by-product, since silicates are not permissible according to relevant statutory provisions in cigarette papers.

Furthermore, the product obtainable in this way is only above 200 ° C able to deliver significant amounts of water. X-ray diffraction spectra of the product show that the product is a physical mixture of calcium carbonate and magnesium hydroxide.

WO-A-03/034845 describes cigarettes with increased self-quenching tendency, the cigarette paper having annular zones whose air permeability is lowered by the presence of a polymer. The polymers used are in particular polyvinyl acetate, partially hydrolyzed polyvinyl acetate or polyvinyl alcohol.

EP 1 933 651 A1 describes a smoking article wrapping material which is a base wrap material coated on at least discrete zones with a composition comprising a mechanically fragmented, chemically crosslinked polysaccharide having a particle size (weighted average) polysaccharide dry product in the range of 1 μm to 1000 μm ,

The fillers commonly used in smoking article wrapping materials are thus subject to limitations and disadvantages, in particular because they can not be controlled in a targeted manner, the glow behavior of the tobacco product wrapping material. However, it would be desirable to have a filler-containing smoking article wrapping material in which the glow behavior of the smoking article wrapping material can be selectively controlled by the filler.

Against this background, better ways of reducing the flammability of combustible articles should be demonstrated. In particular, better solutions for controlling the glow characteristics and extinguishing behavior of smoking articles are desired, especially better solutions for controlling the glow properties of smoking articles, where the smoking articles should smolder in normal smoking as possible without extermination, but in contact with another combustible material its inflammation best prevented, d. H. On the one hand, the smoked goods should smolder unhindered on free-flowing air and on the other hand go out on documents, which in turn can be combustible, themselves extinguish. The solution according to the invention should be as simple as possible and as cost-effective as possible and universally applicable.

These and other objects, which result directly from the contexts discussed in the description of the invention, are achieved by providing a tobacco product wrapping material having all the features of present claim 1. The dependent claims referring to claim 1 describe preferred embodiments of the invention tobacco product wrapping material according to the invention. In the other claims, particularly advantageous methods for producing the tobacco product wrapping material according to the invention, the use of the tobacco product wrapping material according to the invention as well as tobacco products made using the tobacco product wrapping material according to the invention are put under protection.

1. a) eine wässrige Suspension vorlegt, die Calciumcarbonat-Partikel enthält, und
2. b) ein Metallsalz, umfassend ein Aluminiumkation, zugibt,
   wobei das Metallsalz
   1. (i) in der Lage ist, in der Suspension eine basische Aluminiumkomponente zu bilden, und
   2. (ii) in Wasser, gemessen bei dem pH-Wert der vorgelegten Suspension und einer Temperatur von 20°C, eine Löslichkeit größer 9,0 mg/l aufweist,
   wird auf nicht ohne Weiteres vorhersehbare Weise ein Additiv zur Verfügung gestellt, mit welchem die Entflammbarkeit, die Glimmeigenschaften und das Verlöschungsverhalten des Rauchwarenumhüllungsmaterials gezielt gesteuert werden können. Dabei ermöglicht die Verwendung der erfindungsgemäß verwendeten Kompositteilchen insbesondere eine ausgezeichnete Steuerung der Glimmeigenschaften von Rauchartikeln, wobei die Rauchartikel beim gewöhnlichen Rauchen möglichst ohne Verlöschung glimmen, aber bei Kontakt mit einem weiteren Material, dessen Entzündung bestmöglich verhindert wird, d.h. die vorliegende Erfindung ermöglicht die Bereitstellung von Rauchwaren, die einerseits unbehindert an frei zutretender Luft abglimmen und andererseits auf Unterlagen, die ihrerseits brennbar sein können, selbst erlöschen. Die erfindungsgemäße Lösung kann auf einfachste Art und Weise äußerst kostengünstig realisiert werden und ist universell einsetzbar.

By the composite particles used according to the invention, which are obtainable by a process in which man

1. a) presents an aqueous suspension containing calcium carbonate particles, and
2. b) adding a metal salt comprising an aluminum cation,
   wherein the metal salt
   1. (i) is capable of forming a basic aluminum component in the suspension, and
   2. (ii) has a solubility greater than 9.0 mg / l in water, measured at the pH of the suspension submitted and at a temperature of 20 ° C,
   In a manner which is not readily foreseeable, an additive is provided with which the flammability, the glowing properties and the extinguishing behavior of the tobacco product wrapping material can be controlled in a targeted manner. In particular, the use of the composite particles used in accordance with the invention makes it possible to control the smoldering properties of smoking articles in an excellent manner, with the smoking articles smoldering as far as possible without quenching during normal smoking, but in contact with another material whose ignition is prevented as best as possible, ie the present invention makes possible the provision of Smoke products which, on the one hand, smolder freely on free-flowing air and, on the other hand, extinguish themselves on documents which themselves may be flammable. The solution according to the invention can be realized extremely inexpensively in the simplest way and can be used universally.

Compared with those in the prior art, in particular in the patent applications JP 11-151082 A and EP 1 321 048 A1 described methods for controlling the glow properties of conventional smoking articles, the advantages of the present invention, in particular be seen in the fact that the composite particles used in the invention can substitute the filler to be used in any case in a tobacco product wrapping material. Ideally, only one additive, namely the composite particles used according to the invention is used, with the corresponding procedural advantages.

Compared with powders comprising a physical mixture of calcium carbonate and a basic metal component, such as. For example, aluminum hydroxide or magnesium hydroxide, the Kompositteilchen used in the invention have several advantages. In particular, they allow better and more efficient control of the smoldering properties of smoking articles.

The manufacture of smoking articles benefits from the fact that essentially the same filler as before, namely CaCO ₃ , can be used, with the result that the already existing processes for the production of smoking articles, if any, have to be modified only slightly. The composite particles used according to the invention are easy to handle and show a very good compatibility and an excellent mixing behavior, in particular with long fiber pulps.

1. a) eine wässrige Suspension vorlegt, die Calciumcarbonat-Partikel enthält, und
2. b) ein Metallsalz, umfassend ein Aluminiumkation, zugibt.

The present invention accordingly provides smoking article wrapping materials comprising composite particles used in the invention obtainable by a process comprising:

1. a) presents an aqueous suspension containing calcium carbonate particles, and
2. b) adding a metal salt comprising an aluminum cation.

In the context of the present invention, calcium carbonate particles are initially charged in an aqueous suspension.

The suspension to be prepared in step a) which contains calcium carbonate particles preferably has a pH in the range from 6.0 to 13.0, preferably in the range from 6.0 to 11.0, in each case measured at 20 ° C. ,

Furthermore, the suspension to be prepared in step a), which contains calcium carbonate particles, in each case based on their total weight, preferably at least 1.0 wt .-%, preferably at least 5.0 wt .-%, especially 8.0 wt .-% to 22.0% by weight, calcium carbonate. With the addition of suitable and per se known viscosity improvers but much higher proportions of up to 75.0 wt .-% calcium carbonate are conceivable.

In addition, the suspension may contain other mineral substances, such as talc, kaolin, titanium dioxide, magnesium oxide, these mineral substances being suitably inert in the suspension at temperatures in the range from 10 ° C. to 90 ° C. and the pH of the suspension. The proportion of this mineral substances in the suspension, based on the total weight of the suspension, but is preferably less than 25.0 wt .-%, preferably less than 10.0 wt .-%, more preferably less than 5.0 wt .-%, advantageously less than 1, 0 wt .-%, in particular less than 0.1 wt .-%. In a particularly preferred embodiment of the present invention, apart from the essential components mentioned in this application, the suspension contains no further mineral substances. According to the invention, mineral substances are understood to be chemical elements or chemical compounds which are crystallized constituents which contain the smallest building blocks which are periodically arranged three-dimensionally irrespective of any crystal defects and irregularities present and which have been formed by geological processes.

The origin of the calcium carbonate used is of minor importance to the present invention and both natural ground calcium carbonate particles (GCC) and precipitated calcium carbonate particles (PCC) can be used, but the use of precipitated calcium carbonate particles is particularly advantageous.

The shape of the calcium carbonate particles preferably used, in particular the precipitated calcium carbonate particles, according to the invention is subject to no further restrictions and can be tailored to the specific application. However, scalenohedral, rhombohedral, needle-shaped, platelet-shaped or spherical (spherical) particles are preferably used. Within the scope of a very particularly preferred embodiment of the present invention, needle-shaped (preferably aragonitic), rhombohedral (preferably calcitic) and / or scalenohedral (preferably calcitic) calcium carbonate particles, suitably acicular (preferably aragonitic) and / or scalenohedral (preferably calcitic) calcium carbonate particles, in particular precipitated Calcium carbonate particles, the use of scalenohedral (preferably calcitic) calcium carbonate particles, especially precipitated scalenohedral (preferably calcitic) calcium carbonate particles, being most preferred.

The mean diameter of the calcium carbonate particles used, especially the precipitated calcium carbonate particles, can in principle be chosen freely. It is preferably in the range from 0.05 μm to 30.0 μm, in particular in the range from 0.1 μm to 15.0 μm.

For scaleneohedral calcium carbonate particles, the average diameter of the calcium carbonate particles is desirably in the range of 0.05 μm to 5.0 μm, preferably less than 3.0 μm, more preferably less than 1.8 μm, in particular less than 1.6 μm. Furthermore, the average particle diameter in this case is favorably greater than 0.1 .mu.m, preferably greater than 0.3 .mu.m, more preferably greater than 0.6 .mu.m, advantageously greater than 0.8 .mu.m, in particular greater than 1.0 .mu.m.

The abovementioned average particle sizes (by weight) of the calcium carbonate particles used are expediently determined in the context of the present invention by means of sedimentation analysis methods, the use of a Sedigraph 5100 (Micromeritics GmbH) being particularly advantageous in this connection. The determination of this measurand takes place as well as for all other parameters mentioned in this application, unless otherwise stated, preferably at 20 ° C.

The preparation of the aqueous suspension can be carried out in a manner known per se by mixing the components. Alternatively, it is also possible to produce the aqueous suspension in situ, for example by introducing CO ₂ -containing gas into aqueous milk of lime.

In step b), a metal salt comprising an aluminum cation is added to the aqueous suspension, preferably to an aqueous calcium carbonate-containing suspension. In this case, the metal salt used is further characterized in that it is capable of being able to form a basic aluminum component in the suspension virtually in situ.

In the present invention, the metal cation-containing metal salt capable of forming a basic metal component has a solubility of greater than 9.0 mg in water, measured at the pH of the charged suspension and at a temperature of 20 ° C / l, preferably greater than 100.0 mg / l, more preferably greater than 500.0 mg / l, suitably greater than 1.0 g / l, favorably greater than 5.0 g / l, even more preferably greater than 100.0 g / l , in particular greater than 400.0 g / l, on. In the following, therefore, it is sometimes referred to as "water-soluble metal salt" .

Moreover, the metal salt capable of forming a basic metal component preferably comprises less than 10.0 mol%, preferably less than 5.0 mol%, more preferably less than 1.0 mol%, more preferably less than 0.1 mol%, especially none of hydroxide various anions which are capable of forming salts with Ca ²⁺ ions which, in water, measured at the pH of the suspension submitted and at a temperature of 20 ° C., have a solubility of less than 5.0 g / l, preferably less than 2.5 g / l, more preferably less than or equal to 2.0 g / l, in particular less than 1.0 g / l. Above all, the proportion of metal salts comprising sulfate and / or silicate is as low as possible for the purposes of the present invention.

Therefore, in view of the water solubilities of some salts summarized in the following list, the use of Al (NO ₃ ) _{3 is} particularly preferred for the purposes of the present invention, whereas the use of Al (OH) ₃ as the water-soluble metal salt is not possible according to the invention. salt Water solubility at 20 ° C [mg / l] Al (NO ₃ ) ₃ 419000 Al (OH) ₃ 1.5 CaCl ₂ 740000 Ca (NO ₃ ) ₂ > 1470.000 CaSiO ₃ practically insoluble Ca (OH) ₂ 1700 CaCO ₃ 14

Further particularly suitable for the purposes of the present invention, metal salts which are able to form a basic metal component include aluminum chloride, polyaluminum chloride, aluminum sulfate, aluminum nitrate, sulfate, polyaluminum (Nicasol ^® Sachtleben water chemistry), aluminum hydroxide chloride, Aluminiumhydroxidchloridsulfat and Aluminiumhydroxidnitratsulfat a.

In addition, aluminates have proven to be particularly suitable as metal salts. These are salts of the aluminum acid HAlO ₂ · H ₂ O, in which aluminum forms a complex anion [Al (OH) ₄ ] ^- with hydroxide ions as ligands, and salts in which the anion is present as a condensate of the aluminate. Particularly preferred aluminates satisfy the general formula Met [Al (OH) ₄ ] with Met equal to a monovalent cation, in particular sodium aluminate (NaAl (OH) ₄ ) and potassium aluminate (KAl (OH) ₄ ).

According to the invention, the addition of an aluminum salt has proven to be particularly favorable.

The addition amount of the water-soluble metal salt is preferably selected such that the weight ratio of aluminum of the water-soluble metal salt to the mineral of the calcium carbonate particles is in the range of 0.01 to 25.0, preferably 0.1 to 20.0, more preferably Range of 0.2 to 15.0, in particular in the range of 2.0 to 7.5, is located.

The reaction of the components in step b) is preferably carried out at a temperature in the range from 5 ° C. to 90 ° C., preferably in the range from 15 ° C. to 30 ° C., and preferably leads to in situ formation of the basic composite particles used according to the invention.

The composite particles used according to the invention precipitate out of the reaction mixture under the abovementioned conditions and can be prepared in a manner known per se, for. B. by filtration or centrifugation, are separated from the mother liquor. For further purification, the composite particles can be washed, if necessary, with water, acetone and / or other suitable substances.

Within the scope of a further preferred variant of the present invention, the suspension of the composite particles without isolation of the composite particles used according to the invention is used directly in the papermaking process.

• a) eine wässrige Ca(OH)₂-Suspension vorlegt,
• b) eine erste Menge CO₂ enthaltendes Gas in die wässrige Ca(OH)₂-Suspension einleitet,
• c) ein Metallsalz, umfassend ein Aluminiumkation, zugibt,
• d) eine zweite Menge CO₂ enthaltendes Gas in das Reaktionsgemisch einleitet und
• c) die sich bildenden Kompositteilchen isoliert.

It is also possible to add a metal salt during the production of a calcium carbonate suspension from aqueous Ca (OH) ₂ suspension (milk of lime) by introducing CO ₂ . Preferred in this context is a method in which

• a) presents an aqueous Ca (OH) ₂ suspension,
• b a first amount of CO ₂ containing gas (in the aqueous Ca OH) ₂ suspension initiates)
• c) adding a metal salt comprising an aluminum cation,
• d) introducing a second amount of CO ₂ -containing gas into the reaction mixture and
• c) isolated the composite particles forming.

The processes described above lead to incorporation of the preferably in situ forming basic metal component in the submitted calcium carbonate particles. With regard to the pure basic metal components, the composite particles used according to the invention are preferably X-ray amorphous, ie the range of the basic metal components added is below the coherence length of the X-radiation used, in particular below the coherence length of Cu K _α radiation (wavelength 154 pm).

X-ray diffraction studies on the composite particles used according to the invention therefore preferably show no Bragg reflections of the pure basic metal components, in particular of aluminum hydroxide, but, if at all, only so-called signal humps which represent the usual Gaussian distribution of the average atomic distances of the pure basic metal component.

Accordingly, X-ray diffraction spectra typically can be used to distinguish the composite particles used in the present invention from conventional mixtures of mineral particles and a basic metal component, especially conventional mixtures of calcium carbonate and a basic metal component.

Thus, in particular in the case of aluminum-containing composite particles which contain calcitic calcium carbonate, the signal intensity at 2θ = 18.3 ± 1.0, preferably 2θ = 18.3 ± 0.5, in particular 2θ = in an X-ray diffraction recording of the composite particles used according to the invention 18.3, usually less than 100.0%, preferably less than 75.0%, more preferably less than 50.0%, favorably less than 25.0%, advantageously less than 10.0%, even more preferably less than 5.0%, quite particularly preferably less than 1.0%, in particular less than 0.1%, the intensity of the signal being 2θ = 29.5 ± 1.0, preferably 2θ = 29.5 ± 0.5, in particular 2θ = 29.5 is defined as 100% in the same X-ray diffraction image.

For aluminum-containing composite particles containing aragonitic calcium carbonate, the X-ray diffraction pattern of the composite particles used according to the invention shows the signal intensity at 2θ = 18.3 ± 1.0, preferably 2θ = 18.3 ± 0.5, in particular 2θ = 18, 3, usually less than 100.0%, preferably less than 75.0%, more preferably less than 50.0%, favorably less than 25.0%, advantageously less than 10.0%, even more preferably less than 5.0%, most preferably less than 1.0%, in particular less than 0.1%, wherein the intensity of the signal at 2θ = 26.2 ± 1.0, preferably at 2θ = 26.2 ± 0.5, in particular at 2θ = 26.2, in the same X-ray diffraction recording is defined as 100%.

The structural difference between the composite particles used according to the invention and conventional mixtures of mineral particles and basic metal component, in particular between the composite particles used according to the invention and conventional mixtures of calcium carbonate particles and basic metal component, furthermore leads to a different behavior of the composite particles used according to the invention in comparison with conventional mixtures of mineral ones Particles and basic metal component, especially in comparison with conventional mixtures of mineral particles and basic metal component, in thermogravimetric investigations. The composite used in the invention give when heated from room temperature (20 ° C) to over 200 ° C, preferably up to about 300 ° C, especially up to about 450 ° C continuously from water, whereas a mixture of mineral particles and Al (OH ) ₃ , in particular from PCC and Al (OH) ₃ , releases significant amounts of water only from a minimum temperature of greater than 200 ° C.

The thermogravimetric investigations in this context are preferably carried out in the range of 40 ° C to 1000 ° C. The heating rate is preferably 20 ° C / min. The composite particles used according to the invention, which preferably have a moisture, measured at 130 ° C., less than 5%, preferably less than 4%, in particular less than 3%, show in the thermogravimetric analysis in the range from 40 ° C. to 200 ° C. at a heating rate of 20 ° C preferably a weight loss of at least 0.4%, preferably of at least 5.0%, in particular of at least 10.0%.

• a) mindestens 23,2 Gew.-%, bevorzugt mindestens 30,3 Gew.-%, besonders bevorzugt mindestens 34,8 Gew.-%, insbesondere mindestens 37,3 Gew.-%, Calcium,
• b) mindestens 34,8 Gew.-%, bevorzugt mindestens 45,4 Gew.-%, besonders bevorzugt mindestens 52,0 Gew.-%, insbesondere mindestens 55,8 Gew.-%, Carbonat,
• c) mindestens 0,1 Gew.-%, bevorzugt mindestens 0,5 Gew.-%, besonders bevorzugt mindestens 1,0 Gew.-%, insbesondere mindestens 2,5 Gew.-%, eines Aluminiumkations und
• d) mindestens 0,1 Gew.-%, bevorzugt mindestens 0,7 Gew.-%, besonders bevorzugt mindestens 1,3 Gew.-%, insbesondere mindestens 3,5 Gew.-%, Hydroxid umfassen.

The composition of the composite particles used according to the invention can in principle be chosen freely and adapted to the specific application. For the purposes of the present invention, however, composite particles have proved particularly suitable which, based in each case on the total weight of the composite particles,

• a) at least 23.2% by weight, preferably at least 30.3% by weight, particularly preferably at least 34.8% by weight, in particular at least 37.3% by weight, of calcium,
• b) at least 34.8% by weight, preferably at least 45.4% by weight, particularly preferably at least 52.0% by weight, in particular at least 55.8% by weight, of carbonate,
• c) at least 0.1 wt .-%, preferably at least 0.5 wt .-%, particularly preferably at least 1.0 wt .-%, in particular at least 2.5 wt .-%, of an aluminum cation and
• d) at least 0.1 wt .-%, preferably at least 0.7 wt .-%, particularly preferably at least 1.3 wt .-%, in particular at least 3.5 wt .-%, comprise hydroxide.

The respective proportions of calcium, carbonate and aluminum cation are preferably determined by means of X-ray fluorescence analysis. The hydroxide fraction is preferably determined from the difference to 100% by weight.

For the purposes of the present invention, the BET surface area of the composite particles used according to the invention is preferably in the range from 0.1 m ² / g to 100 m ² / g, preferably in the range from 1.0 m ² / g to less than 25.0 m ² / g, more preferably in the range of 2.5 m ² / g to less than 20.0 m ² / g, in particular in the range of 5.0 m ² / g to 12.0 m ² / g.

The specific surface area (BET surface area) of the composite particles is preferably determined by nitrogen adsorption using the BET method. The use of a Micromeritics Gemini 2360 analyzer has proven particularly useful in this context. Expediently, the samples are degassed before the adsorption measurement at 130 ° C. for at least 3 hours, in particular for at least 12 hours, for which purpose the use of a FlowPrep 060 degasser is particularly advantageous.

Possible fields of application of the composite particles used according to the invention are immediately apparent. They are particularly suitable as an additive for combustible substances to control their glow characteristics. They are therefore used in particular as an additive for controlling the glow properties.

Moreover, an addition of the composite particles used according to the invention has a strong self-extinguishing effect, since the composite particles used according to the invention continuously release water and in this way extinguish the embers themselves.

The use of the composite particles used according to the invention is therefore particularly advantageous especially in smoking articles, in particular in cigarettes.

For cigarette papers, tipping papers and filter wrapping papers, addition amounts of the composite particles used according to the invention are usually selected which correspond to the content of the fillers commonly used, the additional amounts preferably in the range of 0.1 wt .-% to 50.0 wt .-%, in particular in the range from 0.2% to 45.0% by weight to ensure control of glow properties.

In one embodiment of the present invention, the composite particles used in the invention are used in tobacco product wrapping materials. Here, the composite particles used in the present invention are preferably capable of imparting, in addition to their function as a filler, controlled glow characteristics to the tobacco product wrapping material.

The composite particles used according to the invention usually have an average particle size of from 0.1 μm to 10 μm, preferably from 0.5 μm to 5 μm, in particular from 1 μm to 3 μm, for this application.

Furthermore, the BET surface area of the composite particles used according to the invention for this application is preferably in the range from 0.1 m ² / g to 100 m ² / g, preferably in the range from 1.0 m ² / g to less than 25.0 m ² / g, more preferably in the range of 2.5 m ² / g to less than 20.0 m ² / g, in particular in the range of 5.0 m ² / g to 12.0 m ² / g.

The total content of fillers of the present invention to fillers is usually 0.1 wt .-% to 50 wt .-%, usually 0.2 to 45 wt .-%, preferably 10 wt .-% to 45 wt .-%, preferably 15 wt .-% to 40 wt .-%, in particular 25 wt .-% to 35 wt .-%, based on the total weight of the tobacco product wrapping material.

In addition to the composite particles used according to the invention, the tobacco product wrapping material according to the invention may optionally contain further fillers such as calcium carbonate, titanium dioxide, aluminum hydroxide, magnesium hydroxide, kaolin, calcined kaolin or talcum. However, the proportion of these further fillers, based on the total weight of the tobacco product wrapping material, is preferably less than 25.0% by weight, preferably less than 10.0 Wt .-%, more preferably less than 5.0 wt .-%, advantageously less than 1.0 wt .-%, in particular less than 0.1 wt .-%.

The smoking article wrapping material may be a cigarette paper wrapping the tobacco rod, a filter wrapping paper surrounding the filter, or a tipping paper (tipping paper base paper, also referred to as a tipping paper). Furthermore, it may be cigarette paper filterless cigarettes, which envelops the tobacco rod. In a preferred embodiment, the tobacco product wrapping material according to the invention is a cigarette paper. In a further preferred embodiment, the tobacco product wrapping material according to the invention is a tipping paper.

Further, the tobacco product wrapping material of the present invention may optionally contain other ingredients such as a burning rate retarding substance and / or a burning rate accelerating substance at 0.1% to 6%, preferably 0.3% to 3% by weight.

Other preferred optional ingredients are polysaccharide-based binders such as guar, galactomannan, starch and its derivatives, carboxylmethyl cellulose and wet strength temporary or permanent wet strength agents and sizing agents for hydrophobizing and controlling the penetrability of the smoking article wrapping material.

As the burning rate accelerating substance, alkali or alkaline earth metal salts such as sodium, potassium and magnesium salts, or carboxylic acid salts such as acetic, citric, malic, lactic and tartaric salts, especially citric acid salts, may be used as required.

The proportions of the respective constituents in the tobacco product wrapping material according to the present invention are usually from 0 to 6% by weight, preferably from 0.5% to 3% by weight, of a burning rate retarding amount, based on the total weight of the smoking article wrapping material and / or accelerating substance.

Preferred base wrapping materials for the tobacco product wrapping material of the present invention are usually made from pulp fibers obtained, for example, from flax, softwood or hardwood. To change the properties of the base wrapping material, if desired, For example, various blends of pulp fibers may also be used as the base wrapping material.

The pulp fibers used for papermaking are usually distinguished into long and short fibers, with long fibers typically being pulp fibers of softwoods, such as spruce or pine, with a length of more than 2 mm, while the short fibers of hardwoods, such as birch, Beech or eucalyptus are derived and typically have a length of less than 2 mm, often less than 1 mm.

In the absence of the composite particles used according to the invention, the tobacco product wrapping material according to the invention usually has an air permeability of from 5 CU to 200 CU (= Coresta units), preferably from 20 CU to 130 CU, in particular from 30 CU to 90 CU. Additional perforations of various types incorporated into the smoking article wrapping material of the present invention may result in smoking article wrapping materials having air permeabilities greater than 200 CU.

The surface mass of the tobacco product wrapping material according to the invention is usually 10 g / m ² to 120 g / m ² , preferably 15 g / m ² to 80 g / m ² , more preferably 15 g / m ² to 70 g / m ² , even more preferably 18 g / m ² to 40 g / m ² .

The production of the tobacco product wrapping material according to the invention is usually carried out on paper machines, for example on wire-screening machines.

In a first step of the production, the pulp is usually suspended in water and then ground in a grinding unit, a so-called refiner. It is common for short and long fibers to be ground separately. The intensity with which the pulp was ground is determined by measuring the degree of grinding, for example according to ISO 5267 ("Pulps. Determination of drainability Part 1: Schopper-Riegler method"). The result of this measurement is given in degrees according to Schopper-Riegler (° SR).

Typically, long fiber pulp is ground for use in tobacco product wrapping materials of the invention to a freeness of 50-90 ° SR, preferably 70-80 ° SR.

Short fiber pulp is usually ground much less strongly and reaches a freeness of 20 ° SR to 60 ° SR, preferably 40 ° SR to 60 ° SR. The grinding of short fiber pulps can be completely eliminated.

The prepared pulp suspension is fed from a head box of the paper machine to a dewatering screen and can be dewatered there by various means, for example by gravity or vacuum. Thereafter, the wet fiber network can pass through a press section where it is further dewatered by mechanical pressure against a press felt. Finally, the fiber network may still pass through a dryer section and through dry felts or dryer screens which force the fiber network against a hot, for example steam heated, drying cylinder surface and thereby dry the fiber network. Instead of the dryer section with drying cylinders, throughflow drying or impingement drying and / or another type of convection drying can also be used. Subsequently, the finished tobacco product wrapping material can be rolled up. If desired, further processing steps may be performed in the paper machine, for example, sizing in a size or film press, application of watermarks, embossing, etc.

The composite particles used in the present invention may be added either to the pulp suspension prior to dewatering and / or to the pulp after dewatering, for example via a size press or by spraying and / or applied to the surface of the tobacco product wrapping material of the invention as described above by application, for example, soaking, spraying, imprinting , Painting, be applied.

For the purposes of the present invention, a method for producing a tobacco product wrapping material according to the invention is particularly preferred, which comprises producing a tobacco product wrapping material according to the invention on a paper machine using a pulp suspension containing composite particles used according to the invention.

Furthermore, a method for producing a tobacco product wrapping material according to the invention is particularly preferred, which comprises producing a tobacco product wrapping material on a paper machine, wherein the cellulose pulp after dewatering via a size press and / or be added by any other application devices according to the invention Kompositteilchen used.

Moreover, a method for producing a tobacco product wrapping material according to the invention is particularly preferred, which comprises applying composite particles used according to the invention to a tobacco product wrapping material produced by means of a paper machine.

In a preferred embodiment, the composite particles used according to the invention are added to the pulp suspension. In a further preferred embodiment, the composite particles used according to the invention are applied to the surface of a tobacco product wrapping material according to the invention, for example by means of a paper machine, either over the entire surface or only in special zones, preferably only in special zones, as described below.

In one embodiment, when the tobacco product wrapping material according to the invention is a tipping paper, the use of further fillers in addition to the composite particles used according to the invention in the tipping paper can be dispensed with. The amount of composite particles used in the invention in such a tipping paper containing it as a filler may usually be 0.1% to 50% by weight, usually 0.2 to 45% by weight, preferably 10% by weight. to 45 wt .-% amount.

In a further embodiment, when the tobacco product wrapping material according to the invention is a filter wrapping paper, it is possible to dispense with the use of further fillers in addition to the composite particles used according to the invention in the filter wrapping paper. The amount of composite particles used in the present invention in such a filter wrapping paper containing them as a filler may usually be 0.1 wt% to 50 wt%, usually 0.2 to 45 wt%, preferably 10 wt%. to 45 wt .-%, amount.

In another embodiment, when the tobacco product wrapping material of the present invention is a cigarette paper, the composite particles used in the present invention may be used as the sole filler in amounts of usually 0.1% to 50% by weight, usually 0.2 to 45% by weight .-%, preferably 10 wt .-% to 45 wt .-% "based on the weight of the cigarette paper, or used as a component of a filler mixture wherein the total amount of filler is usually 0.1% by weight to 50% by weight, usually 0.2 to 45% by weight, preferably 10% by weight to 45% by weight "based on the weight of the The proportion of the composite particles to be used according to the invention is 20% to 99%, preferably 50% to 99%, in particular 60% to 99%, based on the weight of the filler mixture Kompositteilchen used according to the invention and a further filler, preferably precipitated calcium carbonate, which was prepared for example by means of a precipitation reaction of calcium hydroxide and carbon dioxide, act.

By incorporating such a filler mixture into the tobacco product wrapping material according to the invention, it is possible to reduce the usually glow-promoting effect of the further filler, for example the precipitated calcium carbonate, by adding suitable proportions of more than 20%, preferably more than 50%, of the composite particles used according to the invention Have effect, based on the weight of the filler mixture to modify, for example, abolish a glow-promoting effect, it was found according to the invention that this effect usually starts at proportions of greater than 30% of the composite particles according to the invention, based on the weight of the filler mixture. Thus, it is possible to improve the glow characteristics of the tobacco article wrapping material of the present invention, for example the smoldering speed of cigarette paper and thus the number of smoking article traits, e.g. Controlling cigarettes, without having to change further parameters of the cigarette paper such as basis weight, air permeability, amount of bleaching salt and type. This can be used for a balanced sensory result of the smoking product.

In a further embodiment, the tobacco product wrapping material according to the invention may be a cigarette paper containing discrete zones in which the air permeability of the base wrapping material is changed (so-called LIP cigarette papers). In one embodiment, the discrete zones with altered air permeability are zones with an air permeability of 0 CU to 30 CU, preferably 3 CU to 15 CU, in particular 3 CU to 10 CU.

In the tobacco product wrapping material according to the invention, to which the above-mentioned discrete zones are applied, in which the air permeability of the base wrapping material is changed, it may be in one Embodiment be a tobacco product wrapping material into which the composite particles used in the invention were incorporated, or alternatively act in another embodiment to a tobacco product wrapping material that does not contain the composite particles according to the invention. In a preferred embodiment, discrete zones are applied to a tobacco product wrapping material according to the invention containing composite particles used in the invention in an amount of 5 wt .-% to 20 wt .-%, based on the total weight of the applied discrete zones, wherein the inventive tobacco product wrapping material, on the discrete zones are applied containing the composite particles used in the invention in an amount of 15% -40%, based on the total weight of the tobacco product wrapping material according to the invention.

The discrete zones may be obtained by application of a glow salt, for example those mentioned above, and / or the composite particles used according to the invention and / or a mixture of composite particles used according to the invention and a further filler, such as calcium carbonate, and / or a mechanically fragmented, chemically crosslinked polysaccharide, if appropriate be formed in conjunction with the composite particles used in the invention.

In a preferred embodiment, discrete zones are applied to a smoking article wrapping material according to the invention which contains a burning rate retarding substance and optionally the composite particles used according to the invention, wherein the substance to be administered forming the discrete zones likewise contains a substance retarding the burning rate, so that the discrete one Characterized in that the content of retarding substance in the areas in the discrete zones and outside the discrete zones is different.

In a further preferred embodiment, discrete zones are applied to a tobacco product wrapping material according to the invention containing a burn rate altering substance and composite particles optionally used in the invention, the substance to be applied forming the discrete zones containing a burn rate altering substance from that in the smoking article wrapping material contained the burning speed delaying substance is different, so that the discrete zones having tobacco product wrapping material according to the invention is characterized in that the type of the burning rate-changing substance is different in the areas in the discrete zones and outside the discrete zones.

In a further preferred embodiment, discrete zones are applied to a tobacco product wrapping material according to the invention which contains composite particles used in accordance with the invention, the substance to be applied forming the discrete zones likewise containing composite particles used according to the invention, so that the tobacco product wrapping material according to the invention having the discrete zones is characterized in that the content of composite particles used according to the invention is different in the regions in the discrete zones and outside the discrete zones.

In a further preferred embodiment, discrete zones are applied to a tobacco product wrapping material according to the invention which contains composite particles used in accordance with the invention, the substance to be applied forming the discrete zones containing a mechanically fragmented, chemically crosslinked polysaccharide so that the tobacco product wrapping material according to the invention having the discrete zones is characterized is that the content of composite particles used in the invention is not different in the regions in the discrete zones and outside the discrete zones.

By incorporating the composite particles used according to the invention into the smoke enveloping material according to the invention before applying discrete zones, it is possible, in particular if, for example, a mechanically fragmented, chemically cross-linked polysaccharide is applied in discrete zones, that the mechanically fragmented, chemically cross-linked polysaccharide in the discrete zones in smaller quantities can be used so far to reduce the air permeability to, for example, 3 CU to 15 CU. Thus, a discrete zones of reduced air permeability inventive tobacco product wrapping material also characterized by the fact that the discrete zones are no longer or significantly less recognizable to the human eye.

Moreover, with such a discrete zone tobacco product wrapping material of the present invention, it is reduced Air permeability A smaller sensory difference in the smokiness of the smoking product when comparing the discrete zone and the areas outside the discrete zone compared to conventional cigarette papers without composite particles used according to the invention and correspondingly pronounced differences between the discrete zone and the areas outside the discrete zone perceived.

As the mechanically fragmented, chemically crosslinked polysaccharide may be a mechanical fragmentation and chemical crosslinking starch, modified starch, starch derivative, cellulose, cellulose derivative, chitosan, chitosan derivative, chitin, chitin derivative, alginate, alginate derivative or a combination of these compounds , preferably a mechanically fragmented, chemically crosslinked starch.

A mechanically fragmented, chemically cross-linked polysaccharide is understood to mean a polysaccharide which is comminuted by shearing and subsequent expansion using, for example, an extruder, which polysaccharide can also be subjected to various chemical reactions, such as oxidation or reduction.

Thus, in the case of using a starch as granular starting starch, for example, a native or an oxidatively, thermally or hydrolytically degraded starch or a chemically modified ether or ester derivative thereof can be used.

The preparation of ionised polysaccharide derivatives may e.g. with the following cationization or anionization agents in the substitution range between 0.02-0.1 (DS): 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxy-propyldimethyldodecylammonium chloride, 3-chloro 2-hydroxypropyldimethyloctadecylammonium chloride, sodium monochloroacetate, acetic anhydride and / or maleic anhydride.

For crosslinking, preferably 0.1% by weight to 0.8% by weight of a bifunctional or polyfunctional agent, calculated on the basis of the weight of the polysaccharide in granular form which can react with at least two free hydroxyl groups of the polysaccharide molecules, is reacted with the starch granules. The bifunctional or polyfunctional agent which can be used is usually selected from the group consisting of aliphatic epoxyhalogen or dihalogen compounds, Phosphoroxyhalogeniden, alkali metal metaphosphates, aldehydes, including aldehyde-containing resins, acid anhydrides and polyfunctional reagents such as cyanuric chloride selected.

Chemical modification reactions can be carried out both before extrusion and in the extruder. It may be useful to perform these before extrusion, because then, after fragmentation in the extruder and subsequent dispersion of the ground product in the water dispersions are formed with smaller fragments.

The starches may preferably be derived from tuber and root starches as well as cereal starches as starting material. Typical tuber and root strengths are potato starch, tapioca starch; where readily available cereal starches are corn starch or wheat starch. However, the useful starch is by no means limited to these starches - the advantage of the foregoing is merely that they are readily available on the market today. It is of course also possible to use mixtures of one or more starches selected from the group consisting of native, oxidatively, thermally or hydrolytically degraded and chemically modified tuber, root or grain starches. In addition, tuber, root or grain flours can be used as raw material. By means of an extruder (both single-screw and twin-screw extruders), starting from e.g. Potato starch granules, a defined fragmentation can be achieved, wherein the finished dry product is ground below 2 mm grain size, preferably below 1 mm, with an average particle size of about 500 microns.

The mechanical and thermal comminution of the crosslinked polysaccharide grains leads to fragments whose surface does not consist of ordered molecular districts, but is formed by loose, partially hydrolyzed polysaccharide strands. This "soft" layer after swelling in water allows for larger contact areas when attached to fibers and thus stronger binding of the polysaccharide particles to fibers.

The composition to be applied to the tobacco product wrapping material according to the invention may optionally contain a solvent in addition to the agent causing the air permeability of the tobacco product wrapping material. As the solvent, water and / or an organic solvent can be used. Suitable organic solvents are, for example, isopropanol, ethanol, dimethylacetamide, N-methylpyrrolidone and / or N-methylmorpholine N-oxide.

Further, the composition to be applied to the tobacco product wrapping material of the present invention may optionally contain other ingredients such as other substances which change the air permeability of the base wrapping material, fillers, burn rate retarding substances and / or burn rate accelerating substances.

Substances which alter the air permeability of the base wrapping material can be mentioned in particular not polysaccharides subjected to mechanical fragmentation and chemical crosslinking, such as starch, modified starch, starch derivatives, cellulose, cellulose derivatives, chitosan, chitosan derivatives, chitin, chitin derivatives, alginate, alginate derivatives or a combination of these compounds ,

The proportions of the respective constituents in the composition to be applied to the tobacco product wrapping material according to the invention are, for example, 20% to 100%, preferably 45% to 100%, especially preferably 70% to 100% chemically cross-linked, in each case based on the weight of the solids content of the composition fragmented polysaccharide, in particular starch, optionally 0% to 40%, preferably 0% to 20% of a conventionally used polysaccharide, optionally 0% -50%, preferably 0% -30% filler, and optionally 0% -6%, preferably 0% - 3% of the burning rate retarding and / or accelerating substance.

The application of the composition to the tobacco product wrapping material is usually carried out after the preparation of the basic smoking article wrapping material, for example by means of a spraying or printing technique, preferably a gravure printing technique. These methods are well known to those skilled in the art and described in detail in the patent literature, so that a detailed description of the applicable application methods can be dispensed with here.

In a further, particularly preferred embodiment of the present invention, the application of the composition to the tobacco product wrapping material according to the invention by application by means of a pressure nozzle with a generally transverse to the running direction exit slot. The insertable pressure nozzle is usually a nozzle with an inner chamber under a pre-pressure, controlled and rapidly responding valves which control the outlet into a nozzle slot, and a geometry of nozzle and exit slot adapted to the desired application.

The use of such a pressure nozzle allows either a continuous or discontinuous application of material to the tobacco product wrapping material according to the invention in the discrete areas required for the application described or over the entire surface of the tobacco product wrapping material. For the desired application also several separately controllable individual nozzles can be combined in modular form.

With sufficient viscosity of the application medium, the process provides uniform coatings with clear and precisely offset front and rear edges. Since it is not a spray process, no unwanted sporadic splashes of the applied material occur outside the discrete area.

The application of the composition to be applied to the tobacco product wrapping material according to the invention according to one of the above-described application methods is usually carried out at least in discrete zones of the tobacco product wrapping material, if desired also on the entire tobacco product wrapping material.

The application amount of the composition to the smoking article wrapping material of the present invention is usually in a range of 0.1 g / m ² - 10 g / m ² , preferably 0.3 g / m ² - 5 g / m ^{2 of} the smoking article wrapping material.

The application is usually carried out so that the application on the resulting tobacco product wrapping material according to the invention is not or hardly visible and the treated zones have a smooth and flat structure, which substantially corresponds to that of the untreated zones. The width and spacing of the applied zones depend on a number of variables, such as the air permeability of the tobacco product wrapping material, the density of the composition of the tobacco Tobacco strands, the cigarette design, etc. from. The zones usually have a width of at least 3 mm, preferably 5 mm to 10 mm.

The distance between the zones also depends on a number of variables. Usually, the spacing of the zones should be 1 mm to 35 mm, preferably 10 mm to 25 mm.

Usually, the tobacco article wrapper paper (in the rolled form) of the present invention contains 1 to 3 treated annular zones spaced as noted above.

In another aspect of the present invention, the above-described tobacco product wrapping material of the present invention is used to make smoking products.

In general, the tobacco product wrapping material according to the invention has a reduced air permeability in the region of these zones, whereby the cigarette extinguishes in this area, if there is a hindrance to the free access of air. To measure the self-extinction tendency, a commonly accepted standard, the NIST test according to NIST Technical Note 1436, is commonly used. Further, a general glow test may be performed in which a cigarette is once lighted after being mounted in a holder while allowing free access of air. In a successful free glow test, the cigarette glows after lighting in the holder completely without going out. If this is not the case and the cigarette is extinguished before completely glowing, this test is not or only partially fulfilled.

The composite particles used in the present invention can be used in tobacco product wrapping materials of any air permeability according to the present invention because the particle size, shape and other important parameters of the composite particles of the present invention can be matched with those of commonly used filler materials, especially precipitated calcium carbonate. Other fillers, which also have a glow-reducing effect, can not cover this wide range of air permeability of cigarette paper or are not permitted under applicable legislation. In the following, the present invention is further illustrated by Examples and Comparative Examples, without this being intended to limit the inventive concept.

measurement methods electron microscope

The scanning electron images were taken with a high voltage electron microscope (Zeiss, DSM 962) at 15 kV. The samples were sprayed with a gold-palladium layer.

Thermogravimetry (TGA)

Thermogravimetry was performed with a PerkinElmer STA 6000 under nitrogen (nitrogen flow rate: 20 ml / min) in the range of 40 ° C to 1000 ° C at a heating rate of 20 ° C / min.

Brandloch test

An approximately 1 mm thin wire loop, which in turn is heated to 550 ° C temperature, is horizontally inserted into a vertically stretched paper strip, which is the tobacco product wrapping paper to be tested and left in this position during the measurement. The temperature of the hot wire loop is measured with a temperature sensor and controlled to 550 ° C. The hot wire loop burns the paper, forms a burn hole and initiates a glowing process. The horizontal magnification of the burn hole diameter minus the wire loop diameter gives the burn hole gain and is expressed in mm. The fire test was carried out 5 times with each paper sample.

oxygen Index

The oxygen index (abbreviated to OI, or LOI = Limiting Oxygen Index) is a parameter used to describe the fire behavior of plastics. It is the minimum oxygen concentration of an oxygen-nitrogen mixture at which the combustion of a vertically arranged specimen stops under the test conditions.

The sample whose oxygen index is to be determined is ignited from above in a stationary glass tube through which an oxygen-nitrogen mixture flows. After removal of the pilot flame, the fire behavior is observed. If the flame burns for more than 180 seconds or reaches a mark 50 mm below the upper edge, the Oxygen concentration reduced in the following experiment, in the other case increased. This is done until 50% of the specimens burn at a certain concentration.

sedimentation

Determination of the particle size distribution with the Sedigrafen 5100.

Test carried out

The determination of the particle size distribution is carried out by measuring the sedimentation rate of the test substance. The measurement itself is done by attenuating an X-ray beam that is sent through the suspension. Initially, the weakening is high, later at the beginning of sedimentation, the beam can better penetrate the " thinner " suspending suspension, ie the weakening decreases.

• allgemeine Laborausrüstung
• Sedigraf 5100 mit Master-Tech 51 der Firma Micromeritics
• Dispergierlösungen 0,5% und 0,1% Natriumpolyphosphat(NPP) in vollentsalztes-Wasser;

Devices, chemicals

• general laboratory equipment
• Sedigraf 5100 with Master-Tech 51 from Micromeritics
• Dispersing solutions 0.5% and 0.1% sodium polyphosphate (NPP) in deionized water;

execution 1st preparation

First, the sample is prepared by tare the sample cup on the balance, weighs the sample amount according to Table 1 or pipetted and filled with the dispersing solution according to Table 1 to a total of about 80 g. Table 1: sample weighing dispersants powder 3.0 g 0.1% NPP PCC suspension, 20.0 g 0.5% NPP Concentration approx. 160g CaCO ₃ / I * PCC suspension, concentration approx. 120g CaCO ₃ / I * 25.0 g 0.5% NPP * The initial weight always refers to 3 g atro, in case of strong deviations of the solids content the weight has to be adjusted.

2. Measurement and evaluation

The measurement and the evaluation takes place by means of the Sedigrafen. The software calculates the particle size distribution.

example 1

Used raw materials: 20 kg calcium carbonate suspension in water Crystal structure: Calcite / Scalenoeder Particle size (sedimentation analysis, Sedigraph): d ₅₀ = approx. 1.5 μm; <1 μm = approx. 19% pH value: 8 - 9 Solids content (gravimetric): 17% Specific surface area (BET): 9 m ² / g 1.12 kg of polyaluminum chloride solution (12.5% Al ± 0.3%, commercial product PAX-XL 19 from Kemira) Equipment: Dissolver Dispermat from the company Emod with propeller stirrer Stirring tank approx. 25 L without baffle

20.0 kg of a 14% strength by weight aqueous calcium carbonate suspension are initially charged and stirred at 450 rpm. Subsequently, 1120 g of PAX-XL 19 are added rapidly with stirring and the speed is increased to 1000 rpm. When the viscosity decreases visibly, the speed is reduced again to 450 rpm. The suspension is stirred for 20 minutes. At the end of the precipitation, the pH is between 6 and 7.

analysis

The suspension is filtered with a suction filter (d = 26 cm) and with a blue ribbon filter ("42" quantitative) and the filter cake is washed with demineralized water until flocculation with silver nitrate in a known manner no more chloride ions in the filtrate are observed. The moist filter cake is dried in a circulating air dryer at 100 ° C to constant mass. The dry filter cake is then ground with a pin mill (UPZ from ALPINE at 220 V). Analytical data of the powder powder spec. surface humidity [m ² / g] [%] Starting calcium carbonate 9 0.4 composite 21 2.9

Fig. 1 shows the diffractogram of the starting calcium carbonate, Fig. 2 shows the diffractogram of the composite particle. Fig. 3 shows an SEM image of the composite particle. Fig. 4 shows the TGA curve of the composite particle.

Comparative Example 1

750 g of calcium carbonate suspension of Example 1 were mixed with 15.2 g of aluminum hydroxide (Alfrimal, Alpha), stirred for 15 minutes and dried at 130 ° C. as described above.

Fig. 5 shows the diffractogram of the aluminum hydroxide, Fig. 6 shows the diffractogram of the resulting mixture. Fig. 7 shows an SEM image of the resulting mixture.

In contrast to the composite particles used according to the invention, the diffractogram of the mixture of calcium carbonate and aluminum hydroxide shows signals, for example at about 2θ = 18.3, for aluminum hydroxide and in the SEM image the aluminum hydroxide can be clearly recognized.

Fig. 8 shows the TGA curve of the resulting mixture. In contrast to the composite particles used according to the invention, the mixture of calcium carbonate and aluminum hydroxide releases water only above 200 ° C.

Example 2

Procedure as in Example 1 using 0.09 kg of PAX-XL 19. Analytical data of the powder powder spec. surface humidity [m ² / g] [%] Starting calcium carbonate 9 0.4 composite 10 0.6

Comparative Example 2

• Kristallstruktur: Calcit / Skalenoeder
• Teilchengröße (Sedimentationsanalyse, Sedigraph): d₅₀ = ca. 1,5 µm; < 1 µm = ca. 19 %
• pH-Wert: 8 - 9
• Feststoffgehalt (gravimetrisch): 17 %
• Spez. Oberfläche (BET): 9 m²/g

Calcium carbonate suspension:

• Crystal structure: Calcite / Scalenoeder
• Particle size (sedimentation analysis, Sedigraph): d ₅₀ = approx. 1.5 μm; <1 μm = approx. 19%
• pH value: 8 - 9
• Solids content (gravimetric): 17%
• Specific surface area (BET): 9 m ² / g

Example 3

Carry out as in Example 1 using the following calcium carbonate suspension
Crystal structure: Calcite / Scalenoeder
Particle size (sedimentation analysis, Sedigraph): d ₅₀ = approx. 2.95 μm; <1 μm = approx. 0.47%
pH value: 8 - 9
Solids content (gravimetric): 17%
Specific surface area (BET): 6 m ² / g Analytical data of the powder powder spec. surface humidity [m ² / g] [%] Starting calcium carbonate 6 0.4 composite pigment 11 2.7

Example 4

Procedure as in Example 3, except that instead of 1.12 kg of polyaluminum chloride solution only 0.56 kg of polyaluminum chloride solution were used. Analytical data of the powder powder spec. surface humidity [m ² / g] [%] Starting calcium carbonate 6 0.4 composite pigment 9 1.8

Example 5

Used raw materials:

6 kg calcium carbonate suspension in water Crystal structure: Calcite / Scalenoeder particle size (sedimentation analysis, Sedigraph): d ₅₀ = approx. 2.0 μm; <1 μm = approx. 7% pH value: 8 - 9
Solids content (gravimetric): 13.8% Specific surface area (BET): 7 m ² / g
0.964 kg aluminum sulphate solution (4.3% Al, commercial product ALS from Kemira)

Equipment:

Dissolver Dispermat from the company Emod with propeller stirrer Stirring tank approx. 10 L without baffle

6 kg of a 14% strength by weight aqueous calcium carbonate suspension are initially charged and stirred at 450 rpm. Then, with stirring, 964 g of ALS are added rapidly and the speed is increased to 1000 rpm. When the viscosity decreases visibly, the speed is reduced again to 450 rpm. The suspension is stirred for 20 minutes. At the end of the precipitation, the pH is between 6 and 7.

analysis

The suspension is filtered with a suction filter (d = 26 cm) and with a blue ribbon filter ("42" quantitative) and the filter cake is washed with demineralized water until flocculation with silver nitrate in a known manner no more chloride ions in the filtrate are observed. The moist filter cake is in a convection oven at 100 ° C until Constant mass dried. The dry filter cake is then ground with a pin mill (UPZ from ALPINE at 220 V). Analytical data of the powder powder spec. surface humidity [m ² / g] [%] composite pigment 16 3.6

Example 6

The procedure was as in Example 5, except that instead of 0.964 kg of aluminum sulfate solution, 0.767 kg of aluminum nitrate sulfate solution (5.4% Al, commercial product Nicasal from Sachtleben) were used. Analytical data of the powder powder spec. surface humidity [m ² / g] [%] composite pigment 11 4.2

Example 7

The procedure was as in Example 5, except that instead of 0.964 kg of aluminum sulfate solution 0.796 kg of aluminum chloride solution (5.2% Al, Sachtoklar P commercial goods from Sachtleben) were used. Analytical data of the powder powder spec. surface humidity [m ² / g] [%] composite pigment 27 2.9

Examples 8 and 9 and Comparative Example 3 On a fourdrinier machine different ones became

Tobacco wrap wrapping papers made of a long fiber pulp (2/3 Aspa - 1/3 Stendal, freeness 75 degrees Schopper-Riegler). The composite particles were added to the headbox in such an amount that the tobacco wrapper paper contained the composite particles in an amount of 25% Wt .-%, based on the total weight of the wrapping paper contained. Further, into the tobacco wrapper papers was incorporated an amount of 1.1% by weight of glowing salt (sodium / potassium citrate = 1: 1) based on the total weight of the tobacco wrapper material. In the comparative smoking goods wrapping paper of Comparative Example 3, the calcium carbonate suspension prepared in Comparative Example 2 was incorporated in such an amount that the content of calcium carbonate based on the total weight of the wrapping material was 25% by weight. The basis weight of the manufactured tobacco wrapper papers was 30 g / m ² . Glimmersalzmenge in the papers, the glow time and the results of the fire test are summarized in the following overview. pigment Mulled salt [% by weight] Glimmzeit [s] Burn hole [mm] VB 3 Comparative Example 2 1.17 63 7-∞ B 8 Example 2 1.09 72.5 4 B 9 example 1 1.15 76 2

The sample of Comparative Example 3 achieves a burn hole increase of greater than 5 mm, in some samples the entire paper smoldered (infinitely increased burn hole growth). By adding the composite particles used in the invention in Examples 8 and 9, the burning hole increase is increasingly reduced and kept smaller than 5 mm (mean of 5 tests). These 5 mm are considered to be recognized in the art to qualify a smoking article wrapping paper to be reduced in smoothness (less than or equal to 5mm). With a Brandlochzuwachs greater than 5 mm, the tobacco wrapper paper is called not glimmreduziert.

Examples 10 and 11 and Comparative Examples 4 and 5

Analogous to Example 8 , tobacco wrapper papers were made with the composite particle of Example 2.
There were produced tobacco wrapper papers with 25% filler content, a basis weight of 30 g / m ² and an air permeability of 15 to 150 CU. The pulp component, which constituted 75% by weight of the tobacco wrapper paper, consisted of ground long fiber pulp having a freeness of 65 to 84 degrees Schopper Riegler to represent the above air permeability range. The Glimmsalzmenge in the Papers, the glow time and the results of the burn test are summarized in the following overview. <sup> 1 </ sup>: not measurable, goes out pigment Glacial salt [%] Glimmzeit [s] Burn hole [mm] VB 4 Comparative Example 2 0 0 ¹ ∞ VB 5 Comparative Example 2 1 60 ∞ B 10 example 1 0 0 ¹ <5 B 11 example 1 1 70 <5

Examples 12 to 14 and Comparative Example 6

The wrapping papers described in Comparative Example 5 and Example 10 are provided with special bands (LIP bands) for the self-quenching test on cigarettes, the diffusion capacity of the bands is 0.16 cm / s. Experience has shown that this is an area in which the effect of the different fillers on the self-quenching of the cigarette on a 10-layer filter paper (see ASTM values) and the tendency of the cigarette to self-quenching with free glow (only surrounded by free air and not on lying under a pad) of the cigarette (see FASE values) can be worked out and a distinction in FASE values is to be expected. The specifications 100% ASTM with band diffusion of 0.16 cm / s are met by all samples tested. The composition of the investigated materials and the observed FASE values are summarized in the following overview: Pigment in cigarette paper Pigment in the LIP order BEECH [%] VB 6 Comparative Example 2 - 60 B 12 Comparative Example 2 Example 1 (8% by weight) 40 B 13 example 1 - 100 B 14 example 1 Example 1 (8% by weight) 20

The lower a FASE value (20% FASE means that 80% of all cigarettes continue to glow in the free environment) with a simultaneous ASTM value of greater than 75%, the more favorably such cigarettes are rated by the cigarette manufacturer and the smoker.

The paper sample of Example 14 with composite particles in the cigarette paper and as a constituent of the LIP tape material achieves the best result here compared to standard PCC, followed by the paper sample of Example 12 (composite particles in the LIP order).

Example 15 and Comparative Examples 8 and 9

On a fourdrinier machine, various tobacco wrapper papers were made from a long fiber pulp (2/3 Aspa - 1/3 Stendal, grind 75 degrees Schopper-Riegler). The composite particles were added to the headbox in such an amount that the tobacco wrapper paper contained the composite particles in an amount of 25% by weight based on the total weight of the wrapping paper. In the comparative smoking goods wrapping paper of Comparative Example 8, the calcium carbonate suspension prepared in Comparative Example 2 was incorporated in such an amount that the content of calcium carbonate based on the total weight of the wrapping material was 25% by weight. In the comparative tobacco confectionery wrapping paper of Comparative Example 9, a mixture of the calcium carbonate suspension and aluminum hydroxide prepared in Comparative Example 2 was incorporated in a ratio of 90:10 (by weight) in such an amount that the proportion of the mixture of calcium carbonate and aluminum hydroxide, based on the total weight of the wrapping material, 25 wt .-% was. Further, in the tobacco wrapper papers was incorporated an amount of 1.2% by weight of glowing salt (sodium / potassium citrate = 1: 1) based on the total weight of the tobacco wrapper material. The basis weight of the manufactured tobacco wrapper paper was 30 g / m ² . The glow time and the results of the fire test are summarized in the following overview: pigment Mulled salt [% by weight] Glimmzeit [s] Burn hole [mm] VB 8 Comparative Example 2 1.17 63 7-∞ VB 9 90% VB 2 + 10% aluminum hydroxide (Afrimal, Fa. Alpha) 1.20 69 6 B 15 example 1 1.15 76 2

The mixture of 90% calcium carbonate and 10% aluminum hydroxide in tobacco wrapper papers (VB 9) is efficient compared to VB 8 with excluding calcium carbonate as a pigment in increasing the smoldering time (reducing the smoldering rate) and reducing the burnout, but significantly less efficiently compared to Example 15 (composite particles). The air permeability is 100 CU.

Claims (20)

A smoking article wrapping material comprising composite particles obtainable by a process comprising: a) introducing an aqueous suspension containing calcium carbonate particles, b) adding a metal salt comprising an aluminum cation, wherein the metal salt (i) is capable of forming a basic metal component in the suspension, (ii) has a solubility greater than 9.0 mg / l in water, measured at the pH of the charged suspension and at a temperature of 20 ° C. The smoking article wrapping material of claim 1, wherein the composite particles are obtainable using Al (NO ₃ ) ₃ ,, polyaluminum chloride, aluminum sulfate and / or aluminum nitrate sulfate. A smoking article wrapping material according to claim 1 or 2, characterized in that in an X-ray diffraction recording of the composite particles, the signal intensity at 2θ = 18.3 ± 1.0 is less than 100.0%, the intensity of the signal at 2θ = 29.5 ± 1.0 is defined as 100.0%. A smoking article wrapping material according to claim 1 or 2, characterized in that in an X-ray diffraction recording of the composite particles, the signal intensity at 2θ = 18.3 ± 1.0 is less than 100.0%, the intensity of the signal at 2θ = 26.2 ± 1.0 is defined as 100.0%. A smoking article wrapping material according to at least one of the preceding claims, characterized in that the composite particles have a BET surface area in the range from 0.1 m ² / g to less than 25 m ² / g. A smoking article wrapping material according to at least one of the preceding claims, characterized in that the composite particles are present in proportions of 1 - 50 wt .-%, based on the total weight of the tobacco product wrapping material. A smoking article wrapping material according to any one of the preceding claims, characterized in that the tobacco product wrapping material is a tipping paper. A smoking article wrapping material according to claims 1 to 6, characterized in that the smoking article wrapping material is a filter wrapping paper. A smoking article wrapping material according to claims 1 to 6, characterized in that the smoking article wrapping material is a cigarette paper. A smoking article wrapping material according to claim 9, characterized in that the cigarette paper contains discrete zones of reduced air permeability. A smoking article wrapping material according to claim 10, characterized in that the discrete zones of the cigarette paper - in Glimmsalzgehalt or - in the content of the composite or - in the Glimmsalzgehalt and in the content of the composite or - in the Glimmsalzgehalt and in the content of the composite pigment in mixture with calcium carbonate compared to the paper outside the discrete zones differ. A smoking article wrapping material according to claim 10 or 11, characterized in that the discrete zones of the cigarette paper comprise a mechanically fragmented, chemically cross-linked polysaccharide having a particle size, defined as a weighted average of the dry product in the range of 1 to 1000 μm. The smoking article wrapping material of claim 12, wherein the mechanically fragmented and chemically crosslinked polysaccharide is mechanically fragmented and chemically crosslinked starch. A smoking article wrapping material according to claim 12 or 13, characterized in that the discrete zones of the cigarette paper in addition to the mechanically fragmented, chemically crosslinked polysaccharide having a particle size, defined as a weighted average of the dry product in the range of 1 to 1000 microns, in addition composite particles as defined in claim 1 and optionally contain further fillers. A method of making a smoking article wrapping material, the method comprising producing a smoking article wrapping material on a paper machine, the pulp after drainage is added via a size press or by another application apparatus composite particles as defined in claim 1. Use of a smoking article wrapping material according to any one of claims 1 to 14 for the manufacture of tobacco products. Use according to claim 16, characterized in that the tobacco product wrapping material is a tipping paper. Use according to claim 16, characterized in that the tobacco product wrapping material is a filter wrapping paper. Use according to claim 16, characterized in that the tobacco product wrapping material is a cigarette paper. A smoking article, characterized in that it comprises a smoking article wrapping material according to any one of claims 1 to 14.

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