EP2761086B1 - Cigarette paper comprising a lamellar filler - Google Patents

Description

FIELD OF THE INVENTION

The present invention relates to a cigarette paper containing pulp fibers and filler particles. The term "contain" does not exclude that the cigarette paper contains other ingredients. In particular, it relates to a cigarette paper which makes it possible to reduce the amount of carbon monoxide in cigarette smoke and an associated cigarette.

BACKGROUND AND PRIOR ART

It is well known that cigarette smoke contains many harmful substances, including carbon monoxide. There is therefore a great interest in the industry to produce cigarettes whose smoke contains significantly less harmful substances. To reduce the amount of such substances, cigarettes are often equipped with filters, typically cellulose acetate. However, these filters are not suitable for reducing the content of carbon monoxide in the smoke of the cigarette, since cellulose acetate can not absorb the carbon monoxide. Various proposals to incorporate catalysts into the filter to convert carbon monoxide into the less harmful carbon dioxide have been unsuccessful, partly for functional reasons and partly for economic reasons.

It is also known to dilute the smoke produced in the cigarette, for example, by a stream of air flowing through a perforation of the tipping paper. As a result, although the content of carbon monoxide in the cigarette smoke can be reduced, but at the price that the substances determining the taste of the cigarette are diluted and thus the taste impression of the cigarette and the customer acceptance are deteriorated.

The substances in the cigarette smoke are determined by a method in which the cigarettes are smoked to standardized specifications. Such a method is described for example in ISO 4387. The cigarette is first at the beginning of the The first train was lit and then every minute, a train at the mouth end of the cigarette with a duration of 2 seconds and a volume of 35 cm ³ with a sinusoidal Zugprofil performed on the cigarette. The moves are repeated until the cigarette falls below a certain, given in the standard length. The smoke flowing from the mouth end of the cigarette during traction is collected in a Cambridge Filter Pad and this filter is thereafter chemically analyzed for its content of various substances, such as nicotine. The gas phase flowing from the mouth end of the cigarette through the Cambridge Filter Pad during trains is collected and also chemically analyzed, for example to determine the level of carbon monoxide in the cigarette smoke.

During standardized smoking, the cigarette is therefore in two fluidically different states. During the draw, there is a significant pressure difference, typically in the range of 200 Pa to 1000 Pa, between the tobacco facing inside and the outside of the cigarette paper. By this pressure difference, air flows through the cigarette paper in the tobacco part of the cigarette and dilutes the resulting smoke during the move. During this phase, which lasts 2 seconds per puff, the extent of dilution of the cigarette smoke is determined by the air permeability of the paper. The air permeability is determined according to ISO 2965 and indicates which air volume per unit time, per unit area and per pressure difference flows through the cigarette paper and therefore has the unit cm ³ / (min cm ² kPa). It is often referred to as CORESTA unit (CU, CORESTA unit) (1 CU = 1 cm ³ / (min cm ² kPa)). With this value, the strand ventilation of a cigarette is controlled, ie the air flow, which flows in a train on the cigarette through the cigarette paper into the cigarette. Typically, the air permeability of cigarette papers is in the range of 0 CU to 200 CU, with the range of 20 CU to 120 CU being generally preferred.

In the period between trains, however, the cigarette will glow without any appreciable pressure difference between the interior of the tobacco part of the cigarette and the environment, so that the gas transport is determined by the gas concentration difference between the tobacco part and the environment. In this case, carbon monoxide can also diffuse through the cigarette paper from the tobacco part into the ambient air. In this phase, which lasts 58 seconds per train per train, as described in ISO 4387, the diffusion capacity is the relevant parameter for the reduction of carbon monoxide.

The diffusion capacity is a transfer coefficient and describes the permeability of the cigarette paper to a gas flow caused by a concentration difference. More specifically, the diffusion capacity refers to the gas volume passing through the paper per unit time, per unit area and per concentration difference, and therefore has the unit cm ³ / (s cm ² ) = cm / s. The diffusion capacity of a cigarette paper for CO ₂ can be determined, for example, with the CO ₂ Diffusivity Meter from Sodim and is closely related to the diffusion capacity of a cigarette paper for CO.

From the above considerations it can be seen that the diffusion capacity should have an independent, important importance for the carbon monoxide content in the cigarette smoke and that the values of carbon monoxide in the cigarette smoke should be reduced by increasing the diffusion capacity. This is particularly important in view of the self-extinguishing cigarettes known from the prior art, in which comparatively high levels of carbon monoxide are observed. In such cigarettes, fire retardant streaks are applied to the cigarette paper for self extinguishment in a standardized test (ISO 12863). This or a similar test, for example, is part of legal regulations in the US, Canada, Australia and the European Union. The increased levels of carbon monoxide are due to the fact that the carbon monoxide can diffuse from the cigarette only to a very small extent by the fire-retardant strip. It would therefore be of great advantage to have cigarette papers available that compensate for this undesirable side effect.

In practice, however, it is extremely difficult to adjust the diffusion capacity regardless of the air permeability of the paper in the papermaking process. However, air permeability, in turn, is in most cases the subject of the paper specifications given by the cigarette manufacturers, so that - under this requirement - the diffusion capacity is practically derived from the papermaking process and can be varied only in a very small range ( see also BE: The influence of the pore size distribution of cigarette paper on its diffusion constant and air permeability, SSPT17, 2005, CORESTA meeting, Stratford-upon-Avon, UK ) . For both the air permeability and the diffusion capacity are determined by the pore structure of the cigarette paper, wherein there is an association between these sizes, which is approximately given by D * ~Z ^(1/2) , where D * denotes the diffusion capacity and Z the air permeability. This relationship is especially in very good Approximation, if the air permeability of the paper is adjusted primarily by the grinding of the pulp fibers.

Various approaches are known from the prior art in order to increase the diffusion constant of the cigarette paper, for example by adding thermally unstable substances (US Pat. WO 2012013334 ) or by choosing the average size of the filler particles ( EP 1450632 . EP 1809128 ). Despite such attempts, there is still a lack of opportunity to substantially increase the diffusion capacity at a given air permeability.

The US 5,253,660 discloses a cigarette paper in which a novel filler is used which reacts strongly endothermically upon combustion to produce non-combustible, non-toxic and non-corrosive gases. The filler consists of a mixture of huntite (Mg ₃ Ca (CO ₃ ) ₄ ) and hydromagnesite (Mg ₄ (CO ₃ ) ₃ (OH) ₂ .3H ₂ O). The filler with this chemical composition can occur in five different variants, one of which is described as "platelet-shaped".

SUMMARY OF THE INVENTION

The present invention has for its object to provide a cigarette paper, which allows a selective reduction of the carbon monoxide content in cigarette smoke at a given air permeability.

This object is achieved by a cigarette paper according to claim 1. Advantageous developments are specified in the dependent claims.

According to the invention, the cigarette paper contains pulp fibers and filler particles, wherein at least a part of the filler particles has a platelet-shaped form. The inventors have found that the diffusion capacity of the cigarette paper - while maintaining the air permeability - can be substantially increased if at least a portion of the filler particles has a platelet-like shape. Particularly high diffusion capacities can be achieved if the entire filler is formed from platelet-shaped particles. Nevertheless, one can occasionally use a smaller proportion of platelet-shaped filler for cost reasons. However, according to the invention at least 20%, preferably at least 40%, particularly preferably at least 55% and in particular at least 70% of the filler particles, based on the mass or on the particle number, have a platelet-like shape. Such different proportions of platelet-shaped and non-platelet-shaped particles can be achieved, for example, by adding different filler types in mixture to the paper.

In a preferred embodiment, the platelet-shaped filler particles have a length 1, a width b and a thickness d, which correspond to the respective maximum dimensions in three mutually orthogonal spatial directions, both the length 1 and the width b at least twice as large, preferably at least four times are as big as the thickness d.

The length 1 and the width b will usually be different from each other, but should differ by a factor of less than 5, preferably less than 3 and more preferably less than 2.

In the idealized idea of a nearly cuboid geometry, the length 1, the width b and the thickness d could correspond, for example, to the edge lengths of the cuboid, i. H. it is by no means necessary for the length 1 to correspond to the longest dimension of the particle, which in the case of an idealized cuboid would correspond to the spatial diagonal. In general, however, the length 1 will be greater than or equal to the width b, and in turn will differ by a factor of 2.5 or less from the longest spatial direction of the particle.

For illustration, see the attached FIG. 1 which illustrates a platelet-shaped filler particle in which the length 1, width b and thickness d are drawn.

auf eine erwartete Diffusionskapazität bei 50 CU normieren, indem man sie mit einem Faktor $\sqrt{50}/\sqrt{x}$

multipliziert, also $D_{50}^{*}=D_x^{*}\cdot \sqrt{50}/\sqrt{x}\mathrm{.}$

As mentioned above, the diffusion capacity D * in conventional papers is, to a good approximation, proportional to the root of the air permeability Z in CU, that is, D * ~ Z ^(1/2) . A typical value for the diffusion capacity for CO2 with an air permeability of Z = 50 CU is z. B. 1.65 cm / s. Until now, it has been technically extremely difficult to vary the diffusion capacity D * independently of the air permeability Z such that, given a given air permeability Z, an increased diffusion capacity D * results. However, by using platelet-shaped filler according to the invention, it is possible to increase the diffusion capacity D * for CO ₂ to D * ≥ 1.80 cm / s for an otherwise identical paper having an air permeability of Z = 50 CU. A similar relative increase in the diffusion capacity D * due to the platelet-shaped filler also results at air permeabilities Z which differ from Z = 50 CU. To quantify this effect also for general air permeabilities of x CU, the diffusion capacity D * for CO ₂ can be exploited using the relationship $D_x^{*}~{\mathrm{Z}}^{\left(1/2\right)}$

to an expected Normalize diffusion capacity at 50 CU by adding one factor $\sqrt{50}/\sqrt{x}$

multiplied, so $D_{50}^{*}=D_x^{*}\cdot \sqrt{50}/\sqrt{x}\mathrm{,}$

für CO₂ eines Zigarettenpapiers mit einer Luftdurchlässigkeit von x CU daher: $D_x^{*}\cdot \sqrt{50}/\sqrt{x}\ge 1,80\mathrm{cm}/\mathrm{s},$

vorzugsweise ≥ 1,85 cm/s . Dies gilt insbesondere für Luftdurchlässigkeitswerte x aus dem Bereich 20 ≤ x ≤ 120, vorzugsweise 30 ≤ x ≤ 100, betragen, und zumindest für Papiere mit Füllstoffgehalten zwischen 20 und 40 Gew.-%.In an advantageous embodiment of the invention applies to the diffusion capacity $D_x^{*}$

for CO _{2 of} a cigarette paper with an air permeability of x CU, therefore: $D_x^{*}\cdot \sqrt{50}/\sqrt{x}\ge 1.80\mathrm{cm}/\mathrm{s}.$

preferably ≥ 1.85 cm / s. This applies in particular to air permeability values x from the range 20 ≦ x ≦ 120, preferably 30 ≦ x ≦ 100, and at least for papers with filler contents between 20 and 40 wt .-%.

It turns out that for the effect according to the invention, the geometry, that is to say the platelet shape, is significantly more decisive than the mean particle size, ie the desired effect is achieved within certain limits independently of the average particle size. In a preferred embodiment, the mass-median value d _{50 of} the particle size distribution measured according to ISO 13317-3 is between 0.2 μm and 4.0 μm, preferably between 0.5 μm and 3.0 μm.

Since, according to investigations of the inventors, the particle geometry or shape is primarily decisive for increasing the diffusion capacity, the filler material is initially not further limited as long as the filler is permitted for cigarette paper for toxicological or legal reasons. Preferably, however, the filler contains platelet-shaped calcium carbonate, which is completely safe in terms of health and legal considerations. However, as mentioned above, it is not necessary for the filler to be completely formed by platelet-shaped calcium carbonate, but calcium carbonates without platelet-shaped geometry or completely different fillers may also be added.

In a preferred embodiment, the calcium carbonate is a calcite, a vaterite, or a mixture thereof, which are preferred over aragonite or other modifications of the calcium carbonate. Preferably, the mixture consists of 50 wt% to 70 wt% calcite and 30 wt% to 50 wt% vaterite.

The filler according to the invention can be added to the paper in the usual way, as is known to the person skilled in the art in papermaking. Also, in the production of the paper requires no additional, special measures after the addition of the filler according to the invention.

Preferably, the total filler content of the paper between 10 wt .-% and 45 wt .-%, particularly preferably between 20 wt .-% and 40 wt .-%. Further, the cigarette paper preferably has a basis weight of from 10 g / m ² to 60 g / m ² , particularly preferably from 20 g / m ² to 35 g / m ² .

In a particularly preferred embodiment, the paper is treated in areas with fire retardant materials that are capable of imparting self extinguishing properties to a cigarette made from the paper. As previously mentioned, such fire retardant areas hinder the diffusion of CO out of the cigarette between two consecutive trains. This is the reason why such self-extinguishing cigarettes are typically observed to have elevated CO levels. This is a significant problem because increased fire safety should not be at the expense of the harmfulness of cigarette smoke. With the cigarette paper according to the invention, the typical increase in the CO content in cigarette smoke due to the fire-retardant regions can be at least partially compensated by the increased diffusion capacity of the paper in the untreated sections. Therefore, the invention in connection with such treated paper unfolds a special technical effect.

BRIEF DESCRIPTION OF THE FIGURES

Fig. 1

is a schematic representation of a platelet-shaped filler particle, in which the length 1, the width b and the thickness d are drawn.

DESCRIPTION OF PREFERRED EMBODIMENTS example 1

Starting point for Example 1 is a non-inventive cigarette paper consisting of wood pulp fibers and 25.5 wt .-% of a conventional, non-platelet, precipitated calcium carbonate, which served as a comparative example. However, other substances could be provided, for example brand salts. The cigarette paper had a basis weight of 28.2 g / m ² and an air permeability of 46.9 CU. The CO ₂ diffusion capacity was measured with the CO ₂ Diffusity Meter from Sodim after conditioning the paper according to ISO 187 and was $D_{46.9}^{*}=1.59\mathrm{cm}/\mathrm{s}\mathrm{,}$

Another identical cigarette paper was prepared, but in which instead of the conventional calcium carbonate, a calcium carbonate with platelet-shaped particles was used. X-ray diffraction analysis revealed that this is a mixture of about 60% by weight of calcite and about 40 % by weight of vaterite. The average particle diameter was about 1.1 μm. A method for producing such platelet-shaped calcium carbonate is in EP 1 151 966 B1 described.

während sich für das Zigarettenpapier des Beispiels 1 mit dem erfindungsgemäßen plättchenförmigen Kalk eine normierte Diffusionskapazität $D_{50}^{*}$

von $1,81\mathrm{cm}/\mathrm{s}\cdot \sqrt{\mathrm{50}}/\sqrt{\mathrm{41},\mathrm{7}}=\mathrm{1},\mathrm{98}\mathrm{cm}/\mathrm{s}$

ergibt.It can be seen that by replacing the lime with practically identical paper properties an increase in the diffusion capacity from 1.59 cm / s to 1.81 cm / s can be achieved, ie by 13.8%. It should be noted that the air permeability of the paper with the inventive plate-like lime 41.7 CU is slightly lower than that of the paper of the comparative example of 46.9 CU. This small difference in air permeability can be easily compensated, for example, by changing the grinding intensity of the pulp, and it is to be expected that, with identical air permeability, the increase in the diffusion capacity will be even greater. Namely, if the diffusivity is normalized in the above-described manner to an air permeability of 50 CU, a normalized diffusion capacity results for the comparative example $D_{50}^{*}=1.59\mathrm{cm}/\mathrm{s}\cdot \sqrt{\mathrm{50}}/\sqrt{\mathrm{46}.\mathrm{9}}=\mathrm{1}.\mathrm{64}\mathrm{cm}/\mathrm{s}.$

while for the cigarette paper of Example 1 with the platelet-shaped lime according to the invention a normalized diffusion capacity $D_{50}^{*}$

from $1.81\mathrm{cm}/\mathrm{s}\cdot \sqrt{\mathrm{50}}/\sqrt{\mathrm{41}.\mathrm{7}}=\mathrm{1}.\mathrm{98}\mathrm{cm}/\mathrm{s}$

results.

Example 2

der also ähnlich demjenigen des Vergleichsbeispiels von Beispiel 1 ist.A non-inventive cigarette paper consisting of pulp fibers from 30.2 wt .-% of a conventional non-platelet precipitated calcium carbonate was prepared as a comparative example. The paper had a basis weight of 28.8 g / m ² , an air permeability of 60.6 CU and a diffusion capacity of 1.84 cm / s, again measured with the CO ₂ Diffusity Meter from Sodim after conditioning the paper according to ISO 187 This corresponds to a value normalized to 50 CU $D_{50}^{*}=1.84\cdot \sqrt{50}/\sqrt{60.6}=1.67\mathrm{cm}/\mathrm{s}.$

that is similar to that of Comparative Example of Example 1.

beträgt hierbei $2,17$

$\mathrm{cm}/\mathrm{s}\cdot \sqrt{\mathrm{50}}/\sqrt{\mathrm{59},\mathrm{5}}=\mathrm{1},\mathrm{99}\mathrm{cm}/\mathrm{s},$

ist also ähnlich wie beim Beispiel 1.This cigarette paper was modified by using again a mixture of calcite and vaterite having a platelet-like structure instead of the conventional calcium carbonate. The modified cigarette paper had a filler content of 31.0% by weight, a basis weight of 29.1 g / m ² and an air permeability of 59.5 CU. The diffusion capacity was 2.17 cm / s. Thus, with almost identical paper properties, it was possible to increase the diffusion capacity from 1.84 cm / s to 2.17 cm / s, ie by 17.9%. Such a high diffusion capacity, as achieved by the paper according to the invention according to Example 2, would be expected in conventional cigarette papers only at an air permeability of about 85 CU. The normalized to an air permeability of 50 CU diffusion capacity $D_{50}^{*}$

is hereby $2.17$

$\mathrm{cm}/\mathrm{s}\cdot \sqrt{\mathrm{50}}/\sqrt{\mathrm{59}.\mathrm{5}}=\mathrm{1}.\mathrm{99}\mathrm{cm}/\mathrm{s}.$

is therefore similar to Example 1.

Thus, the cigarette papers according to the invention allow a considerably improved diffusion of carbon monoxide from the tobacco rod of a cigarette made with this paper, without having to change the air permeability of the cigarette paper.

Claims (9)

1. Cigarette paper, which contains pulp fibers and filler particles, whereby at least 20%, preferably at least 40%, particularly preferably at least 55% and particularly 70% of the filler particles, by mass or by particle number, have a flaked shape, wherein the flaked filler particles have a length 1, a width b and a thickness d, which correspond to the respective maximum extension in three mutually orthogonal spatial directions, whereby the length 1 as well as the width b are at least twice as large, preferably at least four times as large, as the thickness d, wherein the mass-specific median value d₅₀ of the particle size distribution measured according to ISO 13317-3 is between 0.2 µm and 4.0 µm, preferably between 0.5 µm and 3.0 µm and wherein the flaked particles are formed by calcium carbonate.
2. Cigarette paper according to claim 1, which has an air permeability of x CU and a diffusion capacity $D_x^{*}$

   

   for CO₂ and whereby $D_x^{*}\cdot \sqrt{50}/\sqrt{x}\ge 1.80\mathrm{cm}/\mathrm{s}$

   

   holds, preferably ≥1.85 cm/s and particularly preferably ≥1.90 cm/s.
3. Cigarette paper according to claim 2, whereby 20 ≤ x ≤ 120 holds, preferably 30 ≤ x ≤ 100.
4. Cigarette paper according to claim 1, whereby the calcium carbonate comprises a calcite, a vaterite or a mixture thereof.
5. Cigarette paper according to claim 4, whereby the mixture consists of 50% by weight to 70% by weight calcite and 30% by weight to 50% by weight vaterite.
6. Cigarette paper according to one of the preceding claims, wherein the entire filler content of the paper is between 10% by weight and 45% by weight, preferably between 20% by weight and 35% by weight.
7. Cigarette paper according to one of the preceding claims, wherein the basis weight is between 10 g/m² and 60 g/m², preferably between 20 g/m² and 35 g/m².
8. Cigarette paper according to one of the preceding claims, wherein the paper is treated in areas with burn-retardant substances, which are suitable for providing a cigarette manufactured from the paper with self-extinguishing properties.
9. Cigarette, comprising a tobacco rod and a cigarette paper wrapping the tobacco rod, whereby the cigarette paper is a cigarette paper according to one of claims 1 to 8.

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