WO2015062730A1

WO2015062730A1 - Article with low flammability

Info

Publication number: WO2015062730A1
Application number: PCT/EP2014/002921
Authority: WO
Inventors: Christoph Nover; Marijan Vucak; Thomas Fritzsching
Original assignee: Schaefer Kalk Gmbh & Co. Kg
Priority date: 2013-10-31
Filing date: 2014-10-31
Publication date: 2015-05-07
Also published as: DE112014004958A5

Abstract

The invention relates to composite particles obtained according to a method, in which a) an aqueous suspension containing mineral particles is produced, b) a metal salt comprising a cation that is not calcium is added, said metal salt (i) being capable of forming an alkaline metal component in the suspension and (ii) having a solubility in water of greater than 9.0 mg/l, measured at the pH value of the suspension that has been provided and at a temperature of 20°C.

Description

Article with lower flammability

The present invention relates to composite particles based on mineral particles, processes for their preparation and their use in smoking products, in particular in tobacco product wrapping materials, and in articles with lower flammability. 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) which is commonly used with the whole

Filter wrapping paper and a part of the tobacco rod enveloping

Cigarette paper is bonded, 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 that retard burn rate

Substances and / or the burning rate accelerating substances, etc.

As fillers are usually substances such as calcium carbonate,

Titanium dioxide, aluminum hydroxide, magnesium hydroxide, kaolin, calcined kaolin or talc, and mixtures thereof incorporated into smoking article wrapping materials, where by suitable choice of the type and amount of fillers both optical and glow properties can be controlled. Smoking article wrapping materials which have no fillers or only a low filler content can be reinforced

Extinguishing effect of tobacco products, such

However, 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 products according to current regulations

Tobacco products wrapping materials. However, it is known

CONFIRMATION COPY that certain fillers for the optical properties and the

Glowing properties are disadvantageous. Furthermore, it is known that

Smoking article wrapping materials which have a high content of fillers and additionally controlled for use in smoking products

Glowing properties as well as a desired extinguishing behavior, in addition to calcium carbonate require a significant proportion of other fillers or mixtures of other fillers, and optionally other substances, e.g. the burn rate retarding substances that can be incorporated into these smoking article wrapping materials.

Furthermore, it is known in the art, substances such as polymers, silicates, polysaccharides and derivatives in aqueous or

nonaqueous solutions or suspensions in a sufficient amount and in a suitable geometric distribution on a tobacco product wrapping material, preferably cigarette paper, to thereby apply the

To influence the glow characteristics of the tobacco product wrapping material.

In recent years, various requirements have now been made on one

Smoking article such as a cigarette. Thus, it is recently demanded that a smoking article which continues to glow in the ordinary smoking without extinguishing extinguishes, however, when the smoking article is placed on a combustible material to prevent the combustible material from catching fire. In other words, a controlled glow behavior

desired, in which the smoking goods on the one hand with the

Smoke product wrapping material freely smoldering on freely flowing air and on the other hand on documents, which in turn may be flammable, extinguished itself shortly after contact with these documents.

Japanese Patent Application No. 11-151082 A discloses a cigarette having controlled glow characteristics in which a plurality of annular regions (combustion control regions) are separated from each other

Longitudinal direction of a cigarette are arranged. 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.

However, the application of the annular regions is extremely complicated and requires an additional process step in the production of such cigarettes. Furthermore, the fire behavior of the cigarette produced according to this document is in need of improvement. European patent application EP 1 321 048 A1 describes a smoking article with controlled glow characteristics comprising a cigarette paper coated with a combustion control agent intended to adjust the fire behavior of the smoking article. As examples of this combustion control agent, proteins such as e.g. 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 "e / co"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 hydrogen phosphate, ammonium dihydrogen phosphate,

Ammonium bromide and ammonium sulfate; inorganic hydroxides, such as

for example, barium hydroxide, calcium hydroxide and aluminum hydroxide; and flame retardants of inorganic salts, such as

Sodium borate, boric acid, zinc chloride, magnesium chloride, calcium chloride and sodium sulfate, called. 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.

However, the application of the combustion control agent is extremely expensive and requires an additional process step in the production of such smoking articles. Furthermore, the fire behavior of the smoking article manufactured according to this document is in need of improvement.

Better and more efficient ways of reducing the fire diffusion of smoking articles are therefore desired before use.

CN 101747909 B discloses a flame retardant additive comprising

Calcium carbonate and magnesium hydroxide 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 includes a very expensive to implement on an industrial scale

Sonication.

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 a physical mixture of calcium carbonate and magnesium hydroxide.

The patent application US 2006/0162884 A1 discloses mineral pigments

described containing a product which is obtained in situ by reacting a calcium carbonate with a weak or a strong acid, gaseous CO2 and a certain salt. It should as a salt

Aluminum silicate, synthetic silica, calcium silicate, a silicate of a

monovalent salt, such as. For example, 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 articles with lower flammability, 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, solutions are disadvantageous in which calcium silicates are formed as main product or as by-product, since in particular for tobacco product coating materials with controlled

Glowing properties Substances which can not be used are those in which calcium silicates are formed as the main product or as a by-product, since silicates are not permitted according to the relevant statutory provisions in cigarette papers.

It should also be noted that the described in this document

Procedure comprises several sub-steps and therefore is very time-consuming and expensive.

X-ray diffraction spectra of the product show a physical mixture of the components used.

WO-A-03/034845 describes cigarettes with increased self-quenching tendency, wherein the cigarette paper has 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 tobacco product wrapping material which is a base wrapping material on which, at least in discrete zones, a composition having a mechanical properties is applied

fragmented, chemically crosslinked polysaccharide having a particle size (weighted average) of Polysaccharidtrockenprodukts in the range of 1 pm to 1000 μητι comprises.

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 should be better ways to reduce the

Flammability of combustible articles are shown. In particular, better solutions for controlling the glow characteristics and extinguishing behavior of smoking articles were desired, especially better solutions for controlling the smoldering behavior of smoking articles, which smokers should smolder with as little extinction as possible during normal smoking, but upon contact with another combustible material Inflammation should be prevented as best as possible 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 should

Solution according to the invention in the simplest possible way as well as

be realized as inexpensively and universally applicable as possible. In addition to improving the fire behavior of smoking articles were in particular ways to reduce the flammability of other combustible items such. As paper and plastic, searched.

These are solved as well as further tasks, which result from those in the

Description of the invention immediately revealed by the provision of composite particles with all the features of

Present claim 1. The dependent claims on claim 1 describe preferred embodiments of Kompositteilchen. In the remaining claims, particularly advantageous processes for preparing the Kompositteilchen invention and particularly favorable

Fields of application of the composite particles according to the invention are protected.

By providing composite particles obtainable by a process in which

a) introducing an aqueous suspension containing mineral particles, and b) a metal salt comprising one different from calcium, preferably

polyvalent cation, admits,

wherein the metal salt

(i) is capable of containing a basic metal component in the suspension

form,

(ii) in water, measured at the pH of the suspension presented and

a temperature of 20 ° C, a solubility greater than 9.0 mg / l, succeeds in not easily foreseeable manner, an additive for

To provide the flammability, the glow characteristics and the extinguishing behavior of combustible articles can be controlled specifically. The use of the inventive allows Composite particles, in particular an excellent control of the smoldering properties of smoking articles, wherein the smoking article in the

smolder ordinary smoking if possible without extinction, but in contact with another combustible material whose inflammation is best prevented, d. H. The present invention makes it possible to provide smoking products, which, on the one hand, radiate freely on free-flowing air and, on the other hand, extinguish themselves on documents which in turn may be flammable. The solution according to the invention can be realized extremely inexpensively in the simplest way and can be used universally. In addition to improving the fire behavior of smoking articles, it is due to the

Use of the composite according to the invention furthermore also possible, the flammability of other combustible articles such. As paper and plastic, targeted to control and even significantly reduce.

Compared with those in the prior art, especially in the

Patent applications JP 11-151082 A and EP 1 321 048 A1 for controlling the glow properties of conventional smoking articles, the advantages of the present invention are primarily to be seen in that the composite particles according to the invention can substitute in any case to be used filler. Ideally, only one additive, namely the

used composite particles according to the invention, with the corresponding procedural advantages.

By adding the Kompositteilchen invention as an additive additional process steps to improve the fire behavior of the resulting products are generally no longer required, especially when adding the composite according to the invention instead of conventional additives in the production of papers for the smoking article is the desired improvement in fire behavior directly and without additional

Process steps achieved. The desired effect, d. H. the improvement of the fire behavior, then occurs later while enjoying the smoking article

Impact of a hot zone on the composite particles is controllable in terms of intensity and thus extremely effective.

Compared with powders comprising a physical mixture of

Calcium carbonate and a basic metal component, such as. B.

Aluminum hydroxide or magnesium hydroxide, the composite particles of the invention have several advantages. On the one hand, they enable a better and more efficient control of the fire behavior of smoking articles. About that In addition, the composite particles of the invention are easier to prepare and easier to handle than corresponding physical mixtures.

In particular, in the manufacture of smoking articles, it is benefited that basically the same filler as before, CaCO3, can be used, with the result that existing, if any, smoking article manufacturing processes need only be slightly modified. The composite particles 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. This results in a very good logistics of

Manufacturing process, since the previous filler can be replaced by the Kompositteilchen invention and therefore only one filler must be processed. Problems in the processing of the invention

Composite particles are not observed, since the composite particles according to the invention can be incorporated very well homogeneously into polymeric, in particular fibrous, materials and segregation does not occur. In addition, a very good compatibility of the invention

Composite particles are added with the conventionally used further additives, so that they can be used in addition as before.

The subject of the present invention are accordingly

Composite particles obtainable by a process comprising a) introducing an aqueous suspension containing mineral particles, and b) adding a metal salt comprising a calcium derivative, preferably a polyvalent cation other than calcium.

"Mineral particles" in the context of the present invention denote particles containing at least one mineral.

In turn, "minerals" refer to materially uniform, natural (as a result of geological processes) constituents of the earth and / or other celestial bodies, preferably crystallized constituents that contain the smallest building blocks that are periodically arranged three-dimensionally regardless of any crystal defects and irregularities present . In the

In the context of the present invention, the term "minerals" is also intended to include synthetic equivalents of natural constituents of the earth and / or other celestial bodies, since the use of synthetic equivalents of natural constituents of the soil and / or other celestial bodies is particularly advantageous for the purposes of the present invention. Mineral particles preferred according to the invention include particles comprising calcium carbonate, talc, kaolin, titanium dioxide and / or magnesium oxide,

especially naturally occurring or synthetic calcium carbonate. The proportion of calcium carbonate, talc, kaolin, titanium dioxide and / or magnesium oxide, in particular of calcium carbonate, based on the

Total weight of the mineral particles is preferably at least 10.0 wt .-%, preferably at least 25.0 wt .-%, advantageously at least 50.0 wt .-%, especially. preferably at least 75.0% by weight, more preferably at least 90.0% by weight, most preferably

at least 95.0% by weight, in particular at least 99.0% by weight.

In a very particularly preferred variant of the present invention, only calcium carbonate particles are used as mineral particles.

The suspension to be prepared in step a), the mineral particles,

especially calcium carbonate particles, preferably has a pH in the range of 6.0 to 13.0, preferably in the range of 6.0 to 11, 0, each measured at 20 ° C, on.

Furthermore, the suspension to be prepared in step a), which contains mineral particles, in each case based on their total weight, preferably at least 1, 0 wt .-%, preferably at least 5.0 wt .-%, in particular 8.0 wt .-% to 22.0 wt .-%, 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. However, the proportion of these mineral substances in the suspension, based on the total weight of the suspension, is preferably less than 25.0% by weight, preferably less than 10.0% by weight, particularly preferably less than 5.0% by weight, expediently 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. The origin of the preferred calcium carbonate is of minor importance to the present invention and may be both natural ground calcium carbonate particles (GCC) and precipitated

Caiciumcarbonatpartchen (PCC) are used, but the

Use of precipitated calcium carbonate particles is particularly advantageous.

The form of the Caiciumcarbonatteilchen preferably used, in particular the precipitated Caiciumcarbonatteilchen, according to the invention is subject to no further restrictions and can be tailored to the specific application. However, preference is given to scalenohedral, rhombohedral,

acicular, platy or spherical (spherical) particles used. Within the scope of a very particularly preferred embodiment of the present invention, acicular (preferably aragonitic), rhombohedral (preferably calcitic) and / or scalenoedric

(preferably calcitic) calcium carbonate particles, preferably acicular (preferably aragonitic) and / or scalenoedric

(preferably calcitic) Caiciumcarbonatpartchen, in particular precipitated Caiciumcarbonatteilchen used, wherein the use of scalenoedric (preferably calcite) Caiciumcarbonatteilchen, in particular of precipitated scalenoedric (preferably calcite) Caiciumcarbonatteilchen, on

Most people are preferred.

The mean diameter of the mineral particles, especially the

preferably used Caiciumcarbonatteilchen, especially the precipitated

Caiciumcarbonatpartchen, can be chosen freely in principle. He is lying

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 scalenohedral Caiciumcarbonatteilchen the average diameter of the Caiciumcarbonatteilchen is favorably in the range of 0.05 pm to 5.0 pm, preferably less than 3.0 pm, more preferably less than 1, 8 pm, in particular less than 1, 6 pm. Furthermore, the average particle diameter in this case is advantageously greater than 0.1 μm, preferably greater than 0.3 μm, particularly preferably greater than 0.6 μm, advantageously greater than 0.8 μm, in particular greater than 1.0 μm.

The abovementioned mean particle sizes of the mineral particles, in particular of the calcium carbonate particles preferably used, are expediently used in the context of the present invention by means of

Sedimentation analysis method determined, in which context the Use of a Sedigraph 5100 (Micromeritics GmbH) is particularly advantageous. 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 prepare the aqueous suspension in situ, for example by introducing CO2-containing gas into aqueous milk of lime.

In step b), a metal salt comprising a monovalent or polyvalent cation other than calcium is added to the aqueous suspension, preferably to an aqueous calcium carbonate-containing suspension. This is preferably a polyvalent cation.

In the context of the present invention, "metal salts" denote heteropolar compounds whose crystal lattice involves at least one metal species as cation and at least one anion species other than hydroxide ions.

According to the invention, the metal salt is characterized by the ability to form a basic metal component in the suspension virtually in situ. Preferred metal salts in this context are able to form a basic metal component which satisfies the general formula (I)

MetnAx (OH) _y (I) where

Met represents a preferably polyvalent cation other ^than Ca ²⁺ ,

A represents a monovalent or polyvalent anion other than OH ^" ,

n represents a preferably integer greater than zero,

x represents a preferably integer greater than or equal to zero,

- y represents a preferably integer greater than zero.

Very particularly preferred basic metal components in the context of the present invention include magnesium hydroxide and aluminum hydroxide, in particular aluminum hydroxide.

Furthermore, the metal salt which is capable of a basic

Metal component, in water, measured at the pH of the suspension submitted and a temperature of 20 ° C, a solubility greater 9.0 mg / l, preferably greater than 100.0 mg / l, more preferably greater than 500.0 mg / l, expediently greater than 1.0 g / l, advantageously 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%, favorably 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 silicates is minimized for the purposes of the present invention.

In the light of those summarized in the following list

Water solubility of some salts, therefore, the use of ΑΙ (Νθ3) 3, Mg (CI) 2 and Mg (NO3) 2 is particularly preferred for the purposes of the present invention, whereas the use of Al (OH) 3 and Mg (OH) 2 as

Water-soluble metal salt is not possible according to the invention.

Salt Water solubility at 20 ° C

[Mg / l]

AI (NO ₃ ) ₃ 419,000

Mg (CI) ₂ 542,000

Mg (NO ₃ ) ₂ 420,000

Al (OH) ₃ 1, 5

Mg (OH) ₂ 9

CaCl ₂ 740,000

Ca (NO ₃ ) ₂ > 1470,000

CaSiO3 practically insoluble

Ca (OH) ₂ 1,700

CaCOs 14

Other particularly suitable for the purposes of the present invention

Metal salts capable of forming a basic metal component include aluminum chloride, polyaluminium chloride, aluminum sulfate, Aluminum nitrate sulfate and polyaluminum (Nicasol ^® from

Sachtleben water chemistry).

In addition, aluminates have proven to be particularly suitable as metal salts.

These are salts of aluminum acid ΗΑΙΟ2Ή2Ο, 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 ion. Particularly preferred aluminates satisfy the general formula Met [Al (OH) 4] with met as monovalent cation, especially sodium aluminate (NaAl (OH) ₄ ) and potassium aliminate (KAI (OH) ₄ ).

According to the invention, the addition of a metal salt of a metal having a smaller atomic mass than 40, preferably less than 30, in particular in

Range of 23 to 28, especially the addition of an aluminum salt or a magnesium salt, in particular an aluminum salt, proved to be particularly favorable.

The addition amount of the water-soluble metal salt is preferably selected such that the weight ratio of metal of the water-soluble

Metal salt to the mineral of the mineral particles, preferably the

Weight ratio of metal of the water-soluble metal salt to

Calcium carbonate, in the range from 0.01 to 25.0, preferably in the range from 0.1 to 20.0, particularly preferably in the range from 0.2 to 15.0, in particular in the range from 2.0 to 7.5, lies.

The addition of the water-soluble metal salt can be carried out as a pure substance or in a mixture with other components, for example as a solution.

However, for the purposes of the present invention, the addition of the metal salt in solid form, in particular as a powder, especially in the case of polyaluminum chloride (CAS: 1327-41-9), has proven particularly useful.

The reaction of the components in step b) is preferably carried out at a temperature in the range of 5 ° C to 90 ° C, preferably in the range of 15 ° C to 30 ° C, and preferably leads to the in situ formation of

basic composite particles according to the invention.

The composite according to the invention fall under the above conditions from the reaction mixture and can in known manner, for. B. by filtration or centrifugation, separated from the mother liquor become. 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 according to the invention is used directly, in particular in the paper process.

It is also possible to add a metal salt during the

Preparation of a calcium carbonate suspension from aqueous Ca (OH) 2 suspension (milk of lime) by introduction of CO2. Preferred in this context is a method in which

a) presents an aqueous Ca (OH) 2 suspension,

b) initiating a first amount of CO2-containing gas into the aqueous Ca (OH) 2 suspension,

c) a metal salt comprising one different from calcium, preferably

polyvalent cation, admits,

d) introducing a second amount of CO2-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 mineral particles, preferably in calcium carbonate particles. With respect to the pure basic metal components are the invention

Composite particles preferably X-ray amorphous, d. H. the

Distance range of the added basic metal components is below the coherence length of the X-radiation used, in particular below the coherence length of Cu Κα radiation (wavelength 154 pm).

X-ray diffraction studies on the composite particles according to the invention therefore preferably show no Bragg reflections of the pure basic

Metal components, in particular magnesium hydroxide or

Aluminum hydroxide, but, if any, only so-called signal hump, which represent the usual Gaussian distribution of the average atomic distances of the pure basic metal component.

Accordingly, X-ray diffraction spectra can usually be used to make the composite particles of the invention of conventional

Mixtures of mineral particles and a basic metal component, in particular of conventional mixtures of calcium carbonate and a basic metal component.

Thus, especially in aluminum-containing composite particles containing calcitic calcium carbonate, in an X-ray diffraction of the

composite particles of the invention, the signal intensity at 2Θ = 18.3 ± 1, 0, preferably at 2Θ = 18.3 ± 0.5, in particular at 29 = 18.3, usually less than 100.0%, preferably less than 75.0%, especially preferably less than 50.0%, advantageously less than 25.0%, advantageously less than 10.0%, even more preferably less than 5.0%, very preferably less than 1.0%, in particular less than 0.1%, the intensity of Signal at 29 = 29, 5 ± 1, 0, preferably at 29 = 29, 5 ± 0, 5, in particular at 29 = 29.5, in the same

X-ray diffraction is defined as 100%.

For aluminum-containing Kompositteilchen containing aragonitic calcium carbonate, the signal intensity at 29 = 18.3 ± 1, 0, in an X-ray diffraction recording of composite particles according to the invention preferably at

29 = 18.3 ± 0.5, in particular at 29 = 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%, very particularly preferably less than 1.0%, in particular less than 0.1%, the intensity of the signal being 29 = 26.2 ± 1.0, preferably 29 = 26 , 2 ± 0.5, in particular at 29 = 26.2, in the same X-ray diffraction recording is defined as 100%.

Furthermore, in particular with magnesium-containing composite particles containing calcitic calcium carbonate, the signal intensity at 29 = 38, 0 ± 1, 0, preferably at 29 = 38, 0 ± 0, 5, in particular at 29 = 38 in an X-ray diffraction recording of Kompositteilchen invention , 0, 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%, especially preferably less than 1.0%, in particular less than 0.1%, the intensity of the signal being 29 = 29, 5 ± 1, 0, preferably 29 = 29, 5 ± 0, 5, in particular 29 = 29.5, in the same

X-ray diffraction is defined as 100%.

For magnesium-containing Kompositteilchen containing aragonitic calcium carbonate, the signal intensity at 29 = 38, 0 ± 1, 0, in an X-ray diffraction pattern of the composite according to the invention preferably at

29 = 38, 0 ± 0, 5, in particular at 29 = 38.0, 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%, very particularly preferably less than 1.0%, in particular less than 0 , 1%, wherein the intensity of the signal at 2Θ = 26.2 ± 1, preferably at 2Θ = 26.2 ± 0.5, in particular at 29 = 26.2, in the same X-ray diffraction recording is defined as 100%.

The structural difference between the composite particles of the invention and conventional mixtures of mineral particles and basic metal component, in particular between the inventive

Composite particles and conventional mixtures of calcium carbonate particles and basic metal component, further leads to a different behavior of the composite according to the invention in comparison with

conventional mixtures of mineral particles and basic

Metal component, especially in comparison with conventional mixtures of mineral particles and basic metal component, at

thermogravimetric investigations. The invention

Composite particles give off when heated from room temperature (20 ° C) to over 200 ° C, preferably up to about 300 ° C, in particular up to about 450 ° C continuously from water, whereas a mixture of mineral

Particles and Al (OH) 3 or from mineral particles and Mg (OH) 2,

in particular from PCC and Al (OH) 3 or from PCC and Mg (OH) 2, only from a minimum temperature of greater than 200 ° C gives off significant amounts of water.

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 according to the invention, the

preferably have a humidity, measured at 130 ° C, less than 5%, preferably less than 4%, in particular less than 3%, show in the thermogravimetric analysis in the range of 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%.

The composition of the composite particles 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% by weight, preferably at least 0.5% by weight, especially

preferably at least 1, 0 wt .-%, in particular at least 2.5 wt .-%, of a non-calcium, preferably polyvalent metal cation and

d) at least 0.1% by weight, preferably at least 0.7% by weight, especially

preferably at least 1, 3 wt .-%, in particular at least 3.5 wt .-%, comprise hydroxide.

The respective proportions of calcium, carbonate and calcium

different, preferably polyvalent metal cations 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 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

Range from 5.0 m / 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.

The composite particles according to the invention are preferably after one

Obtainable method in which the reaction of the aqueous suspension with the metal salt as possible in the absence of potentially interfering

Performs substances. The proportion of pulp in the reaction mixture (aqueous suspension and metal salt), in each case based on the total weight of water, mineral particles and metal salt in the reaction mixture, is preferably less than 100.0% by weight, preferably less than 50.0% by weight. , particularly preferably less than 25.0 wt .-%, advantageously less than 10.0 wt .-%, even more preferably less than 5.0 wt .-%, advantageously less than 1, 0 wt .-%, even more preferably less than 0 , 5 wt .-%, in particular less than 0.1 wt .-%. In the context of a whole

particularly preferred variant of the present invention contains the

Reaction mixture no pulp at all.

Furthermore, the proportion of substances in the reaction mixture which are neither water, nor mineral particles, nor the above-described metal salt, in each case based on the total weight of water, mineral particles and metal salt in the reaction mixture, preferably less than 100 , 0% by weight, preferably less than 50.0% by weight, particularly preferably less than 25.0% by weight, advantageously less than 10.0% by weight, even more preferably less than 5.0% by weight , Advantageously less than 1, 0 wt .-%, even more preferably less than 0.5 wt .-%, in particular less than 0.1 wt .-%.

Pulp refers in this context to the resulting in the digestion of wood or other plant fibers, fine-grained, consisting mainly of cellulose mass. For further details on this technical term, reference is made to general knowledge, in particular to Römpp-Lexikon Chemie Editor: Jürgen Falbe; Manfred Regitz, edit. by Eckard Amelingmeier - Stuttgart; New York; Thieme; Volume 6 T-Z; 10th edition; 1999; Reference is made to "pulp" and the references cited here.

In a very particularly preferred embodiment of the

present invention, the composite particles according to the invention are obtainable by a process in which

a) introducing an aqueous suspension containing mineral particles,

b) adding a metal salt comprising a cation other than calcium, wherein the metal salt

(i) is capable of containing a basic metal component in the suspension

form,

(ii) in water, measured at the pH of the suspension submitted and at a temperature of 20 ° C, a solubility greater than 9,0 mg / l, the suspension to be presented in step (a) containing mineral particles, in particular calcium carbonate Particle, has a pH in the range of 6.0 to 13.0, preferably in the range of 6.0 to 11.0, in each case measured at 20 ° C,

wherein the proportion of pulp in the reaction mixture, in each case based on the total weight of water, mineral particles and metal salt in the

Reaction mixture, preferably less than 100.0 wt .-%, preferably less than 50.0 wt .-%, particularly preferably less than 25.0 wt .-%, advantageously less than 10.0 wt .-%, even more preferably less than 5, 0% by weight,

advantageously less than 1.0% by weight, even more preferably less than 0.5% by weight, in particular less than 0.1% by weight, most preferably 0.0% by weight,

wherein the composite particles are X-ray amorphous with respect to the basic metal component,

wherein the composite particles continuously release water when heated from room temperature (20 ° C) to over 200 ° C,

wherein the average diameter of the mineral particles, in particular of the preferably used calcium carbonate particles, especially the precipitated

Calcium carbonate particles, in the range of 0.05 pm to 30.0 pm, in particular in the range of 0.1 pm to 15.0 pm.

Possible fields of application of the composite particles according to the invention are immediately obvious. They are particularly suitable as an additive for combustible substances to their fire behavior, preferably their glow behavior,

especially their flammability, to control. They are therefore used in particular as Addtiv for controlling the glow characteristics and as a flame retardant additive.

Furthermore, by adding the Kompositteilchen invention, the fire diffusion of burning objects can be improved because at contact of the burning object with another combustible material, such. As fiber pulp-containing materials, especially paper, and / or plastic, the risk of spreading the fire is significantly reduced to this combustible material.

In addition, an addition of the composite according to the invention has a strong self-extinguishing effect, since the composite according to the invention continuously release water in a fire and extinguish the fire itself in this way.

The application of the composite particles according to the invention is therefore

in particular in smoking articles, in particular in cigarettes; in

Wall coatings, in particular in decorative wall coatings; in floor coverings, especially in the back of carpets; in furniture, in garland paper, in melamine paper, in wallpaper, in construction panels for roof, wall and door areas, in bodywork, in particular in panels for vehicle, rail vehicle, ship and aircraft construction, in air conditioning and ventilation systems, in packaging of sensitive goods as well as in coating materials, in particular in paints and varnishes, particularly advantageous.

The amount of the composite particles to be added according to the invention can in principle be chosen freely and matched to the specific application. Typical levels of use in reduced flammability articles range from 0.1% to 35.0% by weight. For cigarette papers, tipping papers and filter wrapping papers, it is preferred to use additional amounts which correspond to the content of the fillers commonly used, the additional amounts preferably being in the range from 0.1% by weight to 85.0% by weight, particularly preferably in the range from 0, 15% by weight to 50.0% by weight,

in particular in the range from 0.2% to 35.0% by weight to ensure control of the glow properties.

Very particularly favorable is the use of the invention

Composite particles in articles with reduced flammability, comprising at least 10.0% by weight, preferably at least 20.0% by weight, in particular at least 50.0% by weight of fiber pulp, in particular paper, and / or polymer,

in particular at least one thermoplastic or thermosetting

Polymers.

If necessary, the flame retardant effect of the invention

Kompositteilchen by addition of known flame retardants on be improved. In this context, the use of the composite particles according to the invention together with special inorganic compounds, such as aluminum oxide hydrate, zinc borate, ammonium phosphate, antimony oxide, has proven particularly advantageous. halogenated organic compounds, such as chloroparrafines, hexabromobenzene, brominated diphenyl ethers, etc.

bromine compounds; organic phosphorus compounds such as phosphates, phosphites, phosphonates; and / or with halogenated organic

Phosphorus compounds, such as. B. tri- (2,3-dibromopropyl) phosphate and / or tris (2-bromo-4-methylphenyl) phosphate, wherein, in each case based on the total weight of the composite according to the invention and the other flame retardants, preferably

a) from 0.1% by weight to 99.9% by weight, preferably from 50.0% by weight to 99.9% by weight,

in particular from 75.0% by weight to 99.9% by weight, according to the invention

Composite particles and

b) from 0.1% by weight to 99.9% by weight, preferably from 0.1% by weight to 50.0% by weight,

in particular from 0.1% by weight to 25.0% by weight, further flame retardants are used.

In the context of a further particularly preferred embodiment of the present invention, an addition of further flame retardants, in particular of the abovementioned substances, is dispensed with as far as possible. The proportion of other flame retardants, in particular of the abovementioned substances, based on the total weight of the composite particles and the other flame retardants, in this case is preferably less than 5.0% by weight, preferably less than 1.0% by weight, more preferably less than zero , 5% by weight, in particular 0.0% by weight.

In a very particularly preferred embodiment of the

In the present invention, the composite particles according to the invention, in particular the composite particles obtainable from an aqueous calcium carbonate-containing suspension, are used in tobacco product wrapping materials. Here, the composite particles according to the invention are preferably able, in addition to their function as filler, to impart controlled glow characteristics to the tobacco product wrapping material.

Usually, the composite particles of the invention are for these

Application an average particle size of 0.1 pm to 10 μιτι, preferably from 0.5 pm to 5 μιτι, in particular from 1 μητι to 3 pm. Furthermore, the BET surface area of the composite particles according to the invention for this application is preferably in the range of 0.1 m ² / g to 100 m ² / g, preferably in the range of 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 according to the invention to fillers is usually 1 wt .-% to 70 wt .-%, preferably 10 wt .-% to 50 wt .-%, preferably 25 wt .-% to 40 wt .-%, in particular 25 wt .-% to 35 wt .-%, based on the total weight of

Smoking article wrapping material.

In addition to the composite particles according to the invention, the

Tobacco wrap material optionally contain other fillers such as calcium carbonate, titanium dioxide, aluminum hydroxide, magnesium hydroxide, kaolin, calcined kaolin or talc. 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% by weight, more preferably less than 5.0% by weight, advantageously less than 1, 0 wt .-%, in particular less than 0.1 wt .-%.

The smoking article wrapping paper may be a cigarette paper wrapping the tobacco rod, a filter wrapping paper surrounding the filter, or a tipping paper (base paper for the tipping pad, which is also referred to as a filter paper)

Tippingpapier is called) act. Furthermore, it may be

Act cigarette paper filterless cigarettes, which envelops the tobacco rod. In a preferred embodiment, the

Smoking ware wrapping material around a cigarette paper. In a further preferred embodiment, the

Tobacco wrapping material around a tipping paper.

Further, the smoking article wrapping material may optionally contain other ingredients such as a burn rate retarding substance and / or a burning rate accelerating substance at 0.1% to 6%,

preferably 0.3% to 3% by weight.

Further preferred optional ingredients are binders based on

Polysaccharides such as guar, galactomannan, starch and their derivatives,

Carboxylmethyl cellulose and wet strength agent for a temporary or permanent Wet strength and sizing agent for hydrophobizing and controlling the penetrability of the smoking article wrapping material.

As the burning rate accelerating substance, if necessary, alkali or alkaline earth metal salts such as sodium, potassium and magnesium salts, or carboxylic acid salts such as acetic, citric, malic,

Lactic acid and tartaric acid salts, in particular citric acid salts, use.

The proportions of the respective constituents in the tobacco product wrapping material are in each case based on the total weight of the tobacco

Tobacco product wrapping material, usually - if present - 0 to 6 wt .-%, preferably 0.5 wt .-% to 3 wt .-% of a

Burning rate retarding and / or accelerating substance.

Preferred base wrapper materials for the smoking article wrapping material are usually made from pulp fibers obtained, for example, from flax, softwood or hardwood. To the properties of

If desired, basic pulp material may also be mixed with various mixtures of pulp fibers as the base wrap material.

The pulp fibers used for papermaking are usually distinguished into long and short fibers, with long fibers

typically pulp fibers from 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 and typically have a length of less than 2 mm, often less than 1 mm.

The tobacco product wrapping material has in the absence of

Composite particles of the invention usually have an air permeability of from 5 CU to 200 CU (= Coresta units), preferably from 20 CU to 130 CU. Additional perforations of different kinds, which are in the

Tobacco wrap material can be incorporated

Tobacco wrapping materials with air permeabilities of more than 200 CU lead.

The surface mass of the smoking article wrapping material is usually 10 g / m ² to 120 g / m ² , preferably 15 g / m ² to 80 g / m ² , more preferably 18 g / m ² to 40 g / m ² . The manufacture of the tobacco product wrapping material is usually carried out on paper machines, for example on a wire-screening machine.

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 the measurement of 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 determined in degrees according to Schopper's method. Riegler (° SR) stated.

Typically, long fiber pulp is suitable for use in

Smokers wrapping materials to a freeness of 50-90 ° SR, preferably ground to 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 produced pulp suspension is from a headbox of

Paper machine led to a drainage screen and can there with

various means are drained, for example by gravity or vacuum. Thereafter, the wet fiber network through a

Run press section in which it is further dehydrated by mechanical pressure against a press felt. Finally, the fiber network can still pass through a dryer section and through dry felts or dryer fabrics containing the

Press fiber network against a hot - heated for example with steam - drying cylinder surface and thereby dry the fiber network. Instead of the dryer section with drying cylinders can also be a

Throughdrying or Impallsströmtrocknung and / or another type of convection drying can be used. Then the finished

Are rolled up tobacco products wrapping material. 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 according to the invention can either be

Pulp suspension mixed before dewatering and / or pulp after dewatering, for example, a size press or by

Sprayed on and / or onto the surface of as described above manufactured tobacco product wrapping material by application, such as watering, spraying, printing, brushing applied.

For the purposes of the present invention, a method for producing a tobacco product wrapping material is particularly preferred, which is a

Producing a smoking article wrapping material on a paper machine using a pulp suspension containing composite particles of the invention.

Furthermore, a method for producing a

Tobacco product wrapping material, which comprises producing a tobacco product wrapping material on a paper machine, wherein the cellulose pulp after dewatering via a size press and / or by any other application devices according to the invention

Composite particles are added.

In addition, a method of producing a

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

In a preferred embodiment, the inventive

Composite particles added to the pulp suspension. In another

In a preferred embodiment, the composite particles according to the invention are applied to the surface of a tobacco product wrapping material produced, for example, by means of a paper machine, either over the entire surface or only in the surface

special zones, preferably only in special zones such as

described below applied.

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

In a further embodiment, when the

Tobacco wrap material around a filter wrapping paper may be based on the use of further fillers in addition to the composite particles according to the invention dispensed in the filter wrapping paper. The amount of

Composite particles according to the present invention in such a filter wrap paper containing them as a filler may usually contain 0.1% by weight to 50% by weight, usually 0.2% by weight to 45% by weight, preferably 10% by weight. to 45 wt .-% amount.

In a further embodiment, when the

Tobacco product wrapping material around a cigarette paper, the composite particles according to the invention as sole filler in amounts of usually 0.1 wt .-% to 50 wt .-%, usually 0.2 wt .-% to 45 wt .-%, preferably 10 wt. % to 45% by weight, based on the weight of the

Cigarette paper, or as a constituent of a filler mixture, the total amount of filler usually being from 0.1% by weight to 50% by weight, usually from 0.2% by weight to 45% by weight, preferably 10% by weight. % to 45% by weight, based on the weight of the cigarette paper, and the proportion of the composite material 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. The filler mixture may be a mixture of the composite particles according to the invention and a further filler, preferably precipitated calcium carbonate, which has been prepared, for example, by means of a precipitation reaction of calcium hydroxide and carbon dioxide.

By incorporation of such a filler mixture in the

It is possible to make tobacco products usually

Glimmfördernde 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 according to the invention, which have a glow retardant effect, based on the weight of the filler mixture to modify, for example, a glow-promoting Effect, wherein according to the invention it was found that this effect is usually at levels greater than 30% of the invention

Composite particles, based on the weight of the filler mixture, begins. Thus, it is possible the glow characteristics of

Tobacco wrapping material, such as the smoldering speed of cigarette paper and thus the number of train smoking products, such as cigarettes to control targeted without having to change other parameters of the cigarette paper such as basis weight, air permeability, Glimmsalzmenge and - art. This can be used for a balanced sensory result of the smoking product. In a further embodiment, it may be in the

Tobacco wrap material around 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, to which the discrete zones mentioned above are applied, in which the air permeability of the

Base wrap material is changed, in one embodiment it may be a smoking article wrapping material into which the composite particles of the invention have been incorporated, or alternatively in another

Embodiment to act a tobacco product wrapping material that does not contain the composite particles according to the invention. In a preferred

Embodiment are applied to a tobacco product wrapping material discrete zones containing composite particles according to the invention in an amount of 5 wt .-% to 20 wt .-%, based on the total weight of the applied discrete zones, wherein the tobacco product wrapping material to which the discrete zones are applied , the composite particles according to the invention in an amount of 15% - 40%, based on the total weight of

Smoking article wrapping material, included.

The discrete zones can be obtained by applying a glowing salt,

for example, the above, and / or the invention

Composite particles and / or a mixture of inventive

Composite particles and another filler, such as

Calcium carbonate, and / or a mechanically fragmented, chemically crosslinked polysaccharide optionally in conjunction with the

composite particles according to the invention are formed.

In a preferred embodiment, discrete zones become one

Smoking products serving material, the one the burning speed

retarding substance and optionally the inventive

Composite containing particles applied, wherein the discrete zones forming substance to be applied also contains a burning rate retarding substance, so that the discrete zones having

A tobacco product wrapping material is characterized in that the content of retarding substance in the burning rate 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 smoking article wrapping material, which is a burning rate

applied substance and optionally composite particles according to the invention, applied, wherein the discrete zones forming substance to be applied contains a burning rate-changing substance, which contained in the tobacco product wrapping material

Burning rate retarding substance is different, so that the discrete zones having tobacco product wrapping material is characterized in that the type of 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 containing composite particles according to the invention, the substance to be applied forming the discrete zones likewise containing composite particles according to the invention, so that the tobacco product wrapping material having the discrete zones is characterized in that the content of inventive Composite particles 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 smoking article wrapping material containing composite particles according to the invention, the substance to be applied forming the discrete zones containing a mechanically fragmented, chemically crosslinked polysaccharide such that it has the discrete zones

Characterized in that the content of composite particles according to the invention in the areas in the discrete zones and outside the discrete zones is not different.

By incorporating the Kompositteilchen invention in the

Smoke wrapping material before application of 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 crosslinked polysaccharide in the discrete zones in smaller amounts than previously used to reduce the air permeability to, for example, 3 CU to 15 CU. Thus, there is a discrete zones of reduced air permeability

Tobacco wrap material also characterized in that the discrete zones are no longer or significantly less visible to the human eye. Moreover, in such a tobacco product wrapping material having discrete zones of reduced air permeability, there is less sensory difference in smoker smoking when comparing the discrete zone and the non-discrete zone areas over conventional cigarette papers without composite particles of the present invention and correspondingly large differences between the discrete zone and the outside areas perceived the discrete zone.

As a mechanically fragmented chemically crosslinked polysaccharide, one may include a mechanical fragmentation and a 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 as meaning a polysaccharide which is produced by a shearing action and

subsequent expansion is crushed 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 following

Cationization or anionization agents in the substitution range between 0.02-0.1 (DS) are carried out: 3-chloro-2-hydroxypropyltrimethylammonium chloride, 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyldimethyldodecylammonium chloride, 3-chloro-2-one 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

Polysaccharides in grain form, which can react with at least two free hydroxyl groups of the polysaccharide molecules, reacted with the starch granules. The usable bifunctional or polyfunctional agent is hereby customary selected from the group consisting of aliphatic epoxyhalogen or dihalogen compounds, phosphoroxyhalides, 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 tubers 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 under 2 mm grain size, preferably less than 1 mm, with an average particle size of about 500 pm.

The mechanical and thermal comminution of the networked

Polysaccharide grains lead 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 smoking article wrapping material may optionally be in addition to the air permeability of the

Tobacco wrapping material causing agent containing a solvent. 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.

i

Furthermore, the applied to the tobacco product wrapping material

Composition optionally further components such as other air permeability of the base wrapping material changing substances, fillers, the burning rate retarding substances and / or the burning rate accelerating substances containing.

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 on the

For example, from 20% to 100%, preferably from 45% to 100%, especially preferably from 70% to 100% of chemically cross-linked, mechanically fragmented polysaccharide, in particular starch, optionally from 0% to 1% by weight, based on the weight of the solids content of the composition 40%, preferably 0% to 20% of a conventionally used polysaccharide, optionally 0% - 50%, preferably 0% - 30% filler, and optionally 0% - 6%, preferably 0% - 3% retarding and / or accelerating the burning rate Substance.

The application of the composition to the tobacco product wrapping material is usually carried out after the preparation of the

Base smoking article wrapping material, for example by means of a spraying or printing technique, preferably a gravure printing technique. These processes are well known to those skilled in the art and are well known in the art

Patent literature described in detail, so here on a detailed

Description of the applicable application method can be omitted.

In a further, particularly preferred embodiment of the present invention, the application of the composition to the

Tobacco wrapping material by application by means of a pressure nozzle with a generally transverse to the running direction exit slot. The usable 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 adapted to the desired application of nozzle and

Exit slot.

The use of such a pressure nozzle allows either one

continuous or discontinuous material application on the

Tobacco product wrapping material 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 spraying process, none occur

unwanted sporadic splashes of the applied material outside of the discrete area.

The application of the composition to be applied to the

A smoking article wrapping material according to any one of the above

Application methods are 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 on the

The smoking article wrapping material 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 is not or hardly visible and the treated areas have a smooth and flat structure, which in

Substantially corresponds to that of the untreated zones. The width and spacing of the applied zones will depend on a number of variables, such as the air permeability of the smoking article wrapping material, the density of the composition of the tobacco rod, the cigarette design and so forth. 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 wrapper paper (in the rolled form) contains 1 to 3 treated annular zones which are spaced as stated above.

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

Generally, the smoking article wrapping material has reduced air permeability in the region of these zones, thereby extinguishing the cigarette in that area, as far as 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 according to the invention, in particular those obtainable starting from an aqueous calcium carbonate-containing suspension

Composite particles can be used in smoking article wrapping materials of any air permeability, as the particle size, shape and other important parameters of the composite particles of the present invention can be matched with those of commonly used fillers, particularly 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 exemplified by and

Comparative examples further illustrated, without thereby a

Restriction of the inventive concept should take place. measurement methods

electron microscope

The scanning electronical recordings were made with a

High voltage electron microscope (Zeiss, DSM 962) performed 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

Brand 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 oil, 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 in which the combustion of a vertically arranged test specimen among the

Test conditions stops.

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 particle size distribution with the Sedigrafen 5100. Test procedure

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 on the beginning of sedimentation the jet can better penetrate the "thinner" suspension, i.e. the weakening decreases.

Devices, chemicals

- general laboratory equipment

- Sedigraf 5100 with Master-Tech 51 from Micromeritics

Dispersing solutions 0.5% and 0.1% sodium polyphosphate (NPP) in

completely desalinated 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 weight of dispersant

Powder 3.0 g 0.1% NPP

PCC suspension, 20.0 g 0.5% NPP

Concentration about 160g

CaCOs / l *

PCC suspension, 25.0 g 0.5% NPP

Concentration about 120g

Cacoa / l *

* 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. Determination of ash content in paper (based on ISO2144)

preparation

A porcelain crucible is annealed at 1000 ° C for one hour and then cooled in a desiccator over dry silica gel. The crucible is weighed.

execution

About 2 g of the paper sample are folded so that the sample fits completely into the crucible. The weighing-in is determined.

The crucible is heated with the gas flame so carefully that no flame is produced. The sample burns up.

The crucible with the sample is annealed in the muffle furnace for one hour at 575 ° C and then cooled in a desiccator on dry silica gel.

The residue is determined.

evaluation

Residue (g) / weight (g) ^* 100 = filler content (%) moisture

The moisture is determined by drying at 130 ° C to constant weight

example 1

Raw materials used: 700 ml_ calcium carbonate suspension

Crystal structure: Calcite / Scalenoeder

Particle size (sedimentation analysis, Sedigraph): dso = about 2.0 pm; <1 pm = ca. 7% pH-value: 8 - 9

Solids content (gravimetric): 12.9%

Specific surface area (BET): 7 m ² / g

210 ml of magnesium nitrate hexahydrate solution (c = 1 mol / L)

210 ml_ potassium hydroxide solution (c = 2 mol / L) Equipment: 2000 mL beaker

IKA laboratory stirrer with laboratory stirrer

700 ml of a 13% strength by weight calcium carbonate suspension in water are initially charged and stirred vigorously. Then, with stirring, 210 ml of magnesium nitrate-hexahydrate solution (c = 1 mol / L) and 210 ml

Potassium hydroxide solution (c = 2 mol / L) added quickly at the same time. The Suspension is stirred for 20 min. At the end of the precipitation, the pH is between 10 and 1 1.

analysis

The suspension is filtered and the filter cake obtained in

Circulating air drying oven dried at 30 ° C overnight. The dry filter cake is then ground (Alpine "ye // ow line") and the analysis data of the starting calcium carbonate and the resulting powder are summarized in the following table, with the moisture being determined at 130 ° C using a Mettler Toledo infrared flash dryer HB43.

Analytical data of the powder

Fig. 1 shows the diffractogram of the Ausgangssccciumcarbonates, Fig. 2 shows the diffractogram of the composite pigment. 3 shows a SEM image of the composite pigment.

Example 2

Raw materials used: 20 kg of calcium carbonate suspension in water

Crystal structure: Calcite / Scalenoeder

Particle size (sedimentation analysis, Sedigraph): dso = ca. 1, 5 pm; <1 pm = approx. 19% pH value: 8 - 9

Solids content (gravimetric): 17%

Specific surface area (BET): 9 m ² / g

1, 12 kg of polyaluminium 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. Then 20 g of PAX-XL 19 are added rapidly while 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 washed with a suction filter (d = 26 cm) and with a

Blue filter (,, 42 "quantitative) is filtered and the filter cake is washed with demineralized water until by precipitation with silver nitrate in a known manner no more chloride ions in the filtrate are observed

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

Fig. 4 shows the diffractogram of Ausgangssccciumcarbonates, Fig. 5 shows the diffractogram of the composite pigment. 6 shows a SEM image of composite pigment. Fig. 7 shows the TGA curve of the composite pigment.

Comparative Example 1

750 g of calcium carbonate suspension of Example 2 were mixed with 15.2 g

Aluminum hydroxide (Alfrimal, Alpha) mixed, stirred for 15 minutes and dried as previously described.

Fig. 8 shows the diffractogram of the aluminum hydroxide, Fig. 9 shows the diffractogram of the resulting mixture. Fig. 10 shows an SEM photograph of the resulting mixture. In contrast to the composite pigment according to the invention, the diffractogram of the mixture of calcium carbonate and aluminum hydroxide shows signals, for example at about 20 = 18.3, for aluminum hydroxide and in the SEM image the aluminum hydroxide can be clearly recognized.

Fig. 11 shows the TGA curve of the resulting mixture. In contrast to the composite pigment according to the invention, the mixture of calcium carbonate and aluminum hydroxide releases significant amounts of water only above 200 ° C.

Example 3

Procedure as in Example 2 using 0.09 kg of PAX-XL 19.

Analytical data of the powder

Comparative Example 2

Calcium carbonate suspension:

Crystal structure: Calcite / Scalenoeder

Particle size (sedimentation analysis, Sedigraph): dso = ca. 1, 5 pm; <1 μιη = about 19%

pH value: 8 - 9

Solids content (gravimetric): 17%

Specific surface area (BET): 9 m ² / g

Example 4

Carry out as in Example 2 using the following

Calcium carbonate suspension

Crystal structure: Calcite / Scalenoeder

Particle size (sedimentation analysis, Sedigraph): dso = about 2.95 pm; <1 pm = approx. 0.47%

pH value: 8 - 9

Solids content (gravimetric): 17%

Specific surface area (BET): 6 m ² / g Analytical data of the powder

Example 5

Procedure as in Example 4, 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

Example 6

Raw materials used: 6 kg of calcium carbonate suspension in water

Crystal structure: Calcite / Scalenoeder

Solids content (gravimetric): 13.8%

Specific surface area (BET): 7 m ² / g

0.964 kg aluminum sulphate solution (4.3% AI;

Merchandise ALS of 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. In the Visible decrease in viscosity, the speed is reduced again to 450 rev / min. The suspension is stirred for 20 minutes. At the end of the precipitation, the pH is between 6 and 7.

analysis

The suspension is washed with a suction filter (d = 26 cm) and with a

Blue filter (,, 42 "quantitative) is filtered and the filter cake is washed with demineralized water until by 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

Analytical data of the powder

Fig. 12 shows the diffractogram of the composite pigment. Fig. 13 shows an SEM photograph of the composite pigment.

Example 7

Procedure as in Example 6, but instead of 0.964 kg of aluminum sulfate solution 0.767 kg of aluminum nitrate sulfate solution (5.4% AI, commercial goods Nicasal Sachtleben) were used.

Analytical data of the powder

Fig. 14 shows the diffractogram of the composite pigment. Fig. 15 shows an SEM photograph of the composite pigment. Example 8

Procedure as in Example 6, except that instead of 0.964 kg of aluminum sulfate solution, 0.796 kg of aluminum chloride solution (5.2% AI, Sachtoklar P commercial goods from Sachtleben) were used.

Analytical data of the powder

Examples 10 and 11 and Comparative Example 10

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

Smoking article wrapping paper containing composite particles in an amount of 25% by weight, based on the total weight of the wrapping paper. Further, in 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 paper. In the

Comparative smoking article wrapping paper of Comparative Example 10, the calcium carbonate suspension prepared in Comparative Example 2 was incorporated in such an amount that the proportion of calcium carbonate, based on the total weight of the wrapping material, was 25% by weight. The basis weight of the manufactured tobacco wrapper paper was 30 g / m ² . Glimmsalzmenge in the papers, the glow time and the results of the fire piercing test are summarized in the following overview.

Pigment Glimmsalz Glimmzeit Brandloch

[% By weight] [s] [mm]

VB 10 Comparative Example 2 1, 17 63 7-oo

B 10 Example 3 1, 09 72.5 4

B 11 Example 2 1, 15 76 2

The sample VB 10 achieves a burn hole increase of more than 5 mm, in some samples the entire paper smoldered (infinite burn hole growth). By adding the composite pigments according to the invention in sample B10 and B11, the burn hole increase is increasingly reduced and kept smaller than 5 mm (mean value of 5 tests) ). These 5 mm are considered on the relevant The art recognized border to designate a smoking article wrapping paper as reduced in glow (less than or equal to 5 mm). With a Brandlochzuwachs greater than 5 mm, the tobacco wrapper paper is called not glimmreduziert.

Examples 12-13 and Comparative Examples 12-13

Analogous to Example 10, tobacco wrapper papers were the

Composite particles of Example 2 produced.

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 is 75% by weight of the

Made up of milled tobacco products

Long fiber pulp with a freeness of 65 to 84 degrees Schopper Riegler to represent the o.g. Air permeability range. Glimmersalzmenge in the papers, the glow time and the results of the fire test are summarized in the following overview.

Pigment Glimmsalz Glimmzeit Brandloch

[%] [s] [mm]

VB 12 Comparative Example 2 0 O oo

VB 13 Comparative Example 2 1 60 oo

B 12 Example 2 0 O ¹ <5

B 13 Example 2 1 70 <5

¹ : not measurable, goes out

Examples 14-16 and Comparative Example 14

Those described in Comparative Example VB 13 and Example B 13

Envelope papers are made with special bands (LIP bands) for the

Self-extinguishing test on cigarettes provided, 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-ply filter paper (see ASTM values) and the tendency of the cigarette to self-quenching in free glowing (surrounded only 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

The composition of the investigated materials as well as the observed FASE values are summarized in the following overview: Pigment in cigarette paper Pigment in LIP order FASE

[%]

VB 14 Comparative Example 2 - 60

B 14 Comparative Example 2 Example 2 (8% by weight) 40

B 15 Example 2 - 100

B 16 Example 2 Example 2 (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 more than 75%, the more advantageous such cigarettes are from the

Cigarettes manufacturer and the smoker rated.

The paper sample of example B 16 with composite pigment in the cigarette paper and as a constituent of the LIP strip material achieves the best result here compared to standard PCC, followed by the paper sample of example B 14 (composite pigment in LIP order).

Examples P 1 to P 4 and Comparative Example VP 1

Paper sheets based on waste paper were produced according to the following recipe:

Designation VP 1 P 1 P 2 P 3 P 4

Waste paper 99.48 67.98 47.98 17.97 47.97

Strength 0,50 0,50 0,50 0,50 0,50

Example 5 - 30.00 50.00 80.00 -

Example 4 - - - - 50.00

Latex - 1, 50 1, 50 1, 50 1, 50

Retention aids 0.02 0.020 0.025 0.035 0.035

The basis weight was about 130 g / m ² . Different filler contents (composite particle content) were obtained:

Designation VP 1 P 1 P 2 P 3 P 4

Basis weight [g / m ² ] 113 135 129 134 128

Ash content is [%] 7.66 28.24 43.16 72.67 45.81

Thickness [pm] 204 239 235 247 n. B. n. b .: not determined

The papers were subjected to the LOI (Limiting Oxygen Index) test: The LOI test shows that as the content of the composite particles increases, the combustibility (flammability) decreases. This applies equally to Example 4 and Example 5.

Example 100 and Comparative Examples 100 and 101

On a fourdrinier machine different ones became

Smoking article wrapping paper containing 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 100, 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 smoking confectionery wrapping paper of Comparative Example 01, 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, an amount of 1.2% by weight of mullet salt (sodium / potassium citrate = 1: 1) based on the total weight of the

Tobacco product wrapping material, incorporated. The basis weight of the manufactured tobacco wrapper paper was 30 g / m ² . The glow time and the results of the burn test are shown in the following overview

summarized:

Pigment Glimmsalz Glimmzeit Brandloch

[% By weight] [s] [mm]

VB 100 Comparative Example 2 1, 17 63 7-oo

VB 101 90% Comparative Example 2 + 1, 20 69 6

0% aluminum hydroxide

(Afrimal, Fa. Alpha)

B 100 Example 2 1, 15 76 2 The mixture of 90% calcium carbonate and 10% aluminum hydroxide in

Tobacco wrapper papers (VB 101) is efficient compared to VB 00 with only calcium carbonate as the pigment in increasing the smoldering time (reducing the smoldering rate) and reducing the burnout, but significantly less efficient compared to Example 100 comprising composite particles of the invention. The air permeability is 100 CU.

Claims

claims:

1. Composite particles, obtainable by a process in which

a) introducing an aqueous suspension containing mineral particles, b) adding a metal salt comprising a cation other than calcium, 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.

2. Composite particles according to claim 1, obtainable using a

Calcium carbonate-containing aqueous suspension.

A composite particle according to claim 1 or 2, obtainable using a metal salt comprising a polyvalent cation other than calcium.

4. Composite particles according to claim 1, 2 or 3, obtainable using a metal salt of a metal having a smaller atomic mass than 40, preferably less than 30, in particular in the range of 23 to 28.

5. Composite particles according to claim 4, obtainable using a

Aluminum salt or a magnesium salt, in particular a

Aluminum salt.

6. Kompositteilchen according to at least one of the preceding claims, characterized in that the metal salt in water, measured at the pH of the charged suspension and a temperature of 20 ° C, a solubility greater than 100.0 mg / l.

7. Composite particles according to at least one of the preceding claims, characterized in that the metal salt comprises less than 10.0 mol% of anions other than hydroxide which are capable of forming salts with Ca ²⁺ ions which are dissolved in water, measured at the pH of the submitted suspension and a temperature of 20 ° C, have a solubility less than 5.0 g / l.

8. Composite particles according to at least one of the preceding claims, obtainable using Al (NO 3) 3, Mg (CI) 2, Mg (NO 3) 2,

Polyaluminum chloride, aluminum sulfate and / or aluminum nitrate sulfate.

9. Kompositteilchen according to at least one of the preceding claims, characterized in that in an X-ray diffraction recording of Kompositteilchen the signal intensity at 2Θ = 18.3 ± 1, 0 is less than 100.0%, wherein the intensity of the signal at 29 = 29, 5 ± 1, 0 is defined as 100.0%.

10. Composite according to at least one of the preceding claims 1 to 8, characterized in that in an X-ray diffraction recording of the Kompositteilchen the signal intensity at 2Θ = 18.3 ± 1, 0 is less than 100.0%, wherein the intensity of the signal at 2Θ = 26 , 2 ± 1, 0 is defined as 100.0%.

11. Kompositteilchen according to at least one of the preceding claims 1 to 8, characterized in that in an X-ray diffraction recording of the Kompositteilchen the signal intensity at 2Θ = 38.0 ± 1, 0 is less than 100.0%, wherein the intensity of the signal at 29 = 29 , 5 ± 1, 0 is defined as 100%.

12. Kompositteilchen according to at least one of the preceding claims 1 to 8, characterized in that in an X-ray diffraction recording of the Kompositteilchen the signal intensity at 29 = 38, 0 ± 1, 0 is less than 100.0%, wherein the intensity of the signal at 29 = 26 , 2 ± 1, 0 is defined as 100%.

13. Kompositteilchen according to at least one of the preceding claims, characterized in that the composite particles continuously give off water when heated in the range of 40 ° C to 200 ° C at a heating rate of 20 ° C / min.

14 composite particles according to at least one of the preceding claims, characterized in that the composite particles have a BET surface area in the range of 0.1 m ² / g to 100 m ² / g.

15. Composite particles according to at least one of the preceding claims, characterized in that the composite particles, in each case based on the total weight of the composite particles,

a) at least 23.2% by weight of calcium,

b) at least 34.8% by weight of carbonate, c) at least 0.1% by weight of a metal cation other than calcium, and

d) at least 0.1 wt .-% hydroxide include.

16. A process for the preparation of Kompositteilchen, in which one

a) presenting a calcium hydroxide suspension,

b) introducing a first quantity of CO2-containing gas into the calcium hydroxide suspension,

c) adding a metal salt comprising a cation other than calcium, d) a second amount of CO2-containing gas in the reaction mixture

initiates and

e) isolates the forming Kompositteilchen.

17. Use of the composite according to one of claims 1 to 15 as a flame retardant additive.

18. An article with reduced flammability, comprising from 0.1% to 85.0% by weight of composite particles according to any one of claims 1 to 15.

19. Article according to claim 18, comprising at least 10.0% by weight

Fiber pulp and / or plastic.