WO2001037684A2

WO2001037684A2 - Aromatized items for smoking

Info

Publication number: WO2001037684A2
Application number: PCT/EP2000/011610
Authority: WO
Inventors: Thomas Pienemann; Gunther Peters; Hans Noe
Original assignee: H.F. & Ph.F.Reemtsma Gmbh
Priority date: 1999-11-23
Filing date: 2000-11-22
Publication date: 2001-05-31
Also published as: AU2358701A; HK1048419A1; DE19957486A1; EP1231849B1; DE50010531D1; ATE297136T1; DE19957486C2; ES2240224T3; EP1231849A2; JP2003530827A; TW568754B; HK1048419B; WO2001037684A3

Abstract

The invention relates to aromatized items for smoking. Said items contain a glycoside of a di- or polysaccharide and an aroma component in the wrapping, which consists especially of paper or tobacco. Said glycosides can be applied in a more varied and improved way and when the item is smoked, release an aroma component which aromatizes the secondary stream of smoke.

Description

Flavored smokable items

The present invention relates to smokable articles which contain special aroma substances in their wrapping in order to aromatize the by-pass smoke, as well as a wrapping for smokable articles.

When using smokable items, e.g. Cigarettes, cigars and cigarillos, the so-called sidestream smoke arises from the smoldering of the tobacco during breaks in the train. This is often perceived - especially by non-smokers - as unpleasant and annoying.

Numerous ways have been proposed to overcome this problem. In the case of conventional cigarettes, these methods are based either on a reduction in the amount of sidestream smoke or an improvement in odor by aromatizing the sidestream smoke. The aroma substances required for the latter method are preferably applied to the wrapping of the tobacco product. This application is preferable to an aroma treatment of tobacco, since it leads to a more effective transition of the aroma substances into the by-pass smoke and to less influence of the smoke taste. Because of the volatility of most of the effective aroma substances, it has proven to be advantageous to use them in chemically or physically bound form. This avoids loss of aroma during storage and a noticeable smell of the unlit smokable article. The bond must be thermolytically cleavable so that the aroma component is released by the heating when smoking.

For example, US Pat. No. 4,804,002 proposes treating the wrapper of a smokable article with glycosides of an aroma component, only glucosides being specifically examined. When the article is burned off, the aroma component is released from the glucoside and can thereby have a positive effect on the smell of the bypass smoke without the taste of the mainstream smoke being changed appreciably. Among the proposed glucosides, the ethylvanillyl-β-D-glucopyranoside (ethylvanillin glucoside) primarily shows the desired effect. The glucosides of maltol and menthol, which are also described, on the other hand only have a weak effect.

A method which can also be used on a production scale for applying the glucosides to the casing of a smokable product is, however, not apparent from US Pat. No. 4,804,002. Rather, only small quantities of test cigarettes are produced by applying an ethanolic solution of the glucosides to the casing with the aid of a microliter syringe.

A cigarette is also known from US Pat. No. 4,941,486, the wrapper of which is in close contact with a bound flavoring agent. Ethylvanillin glucoside is used primarily as a bound flavoring agent. Impregnation, application of a film, introduction via a size press, electrostatic deposition, printing and incorporation into the seam glue of the cigarette are mentioned as possible methods for applying flavor to the wrapper. However, there is no information about made the concrete procedure when loading, e.g. type and concentration of the solutions used or their technical implementation. Only the size press technology is used in the exemplary embodiments.

In addition to the methods listed in US Pat. No. 4,941,486 for impregnating wrapping materials for smokable articles with glycosides, the two following methods would be particularly advantageous:

1. Wrapping materials for smokable articles, such as cigarette paper or foil tobacco, are usually manufactured using common paper-making processes. Such methods often provide for one-sided spraying of the paper or tobacco fleece with the aid of a spray bar, which could be used to apply a solution of the glycoside. The possible one-sided application of the glycoside either on the inside or outside of the casing could also enable more targeted control of the pyrolytic decomposition.

2. A very flexible way of impregnation could also be to apply a solution of the glycoside in the form of traces to the wrapping directly on the cigarette machine. A device required for this is e.g. offered by the company KAYMICH, Sheffield, UK, under the designation FAS or MAS, which is why this process is referred to below as the KAYMICH process. The device works with a series of nozzles, which are supplied with the solution by a dosing pump.

However, the latter two processes have the disadvantage that the amount of solvent that can be applied is very small. In the first process, the high level of moisture caused by a large amount of solvent would severely impair the processing of the nonwoven. With the KAYMICH The contact of the over-moistened paper with the tobacco could lead to undesirable stains on the cigarette. It is known that the KAYMICH process only allows the application of a maximum of 20% aqueous solution, based on the weight of the cigarette paper. With larger quantities, stains appear on the finished cigarettes.

In order to work with the known glucosides, i.e. Glycosides of a simple sugar, in order to achieve sufficient aromatization of the secondary stream, however, usually amounts of 1% glucoside, based on the weight of the coating, are required. In order to avoid the problems described above with large amounts of solvent, a total of solutions with a content of at least 5% by weight of glucoside must be used.

The water solubility of the known flavorings is too low for this. The solubility of ethylvanillin glucoside at 20 ° C is only about 2% by weight. Since this is far from sufficient, a warm solution would have to be used. However, in a corresponding test carried out to impregnate the coating using the KAYMICH process, the ethyl vanillin glucoside crystallized at the nozzle tips, which led to blockage of the nozzles and thus to the test being stopped. The need to use warm solutions also has considerable further disadvantages, such as significantly increased equipment expenditure and reduced storage life of the solutions.

The invention is therefore based on the object to provide smokable articles with flavorings in their wrapping for aromatizing the sidestream smoke, which can be obtained in a simple manner by means of various processes in large quantities and using aqueous solutions with an increased concentration of flavoring material, and in particular also by application of the aroma substance can be produced by means of nozzles. This object is surprisingly achieved by the flavored and smokable articles according to the invention. The smokable articles according to the invention have a casing which contains at least one aroma substance for aromatizing the side-stream smoke, and are characterized in that the aroma substance is a glycoside of a two- or multiple sugar and an aroma component.

The invention also relates to the wrapper for smokable articles, which is characterized by a glycoside content of a double or multiple sugar and an aroma component as an aroma substance.

Maltose, lactose or cellobiose is preferably used as the double or multiple sugar and thus the sugar component of the glycoside.

All flavoring compounds which can be linked to the double or multiple sugar via a glycosidic linkage can be used as the flavor component of the glycoside. Preferred aroma components are vanillin, ethylvanillin, eugenol, menthol or maltol.

It is preferred that the amount of all glycosides present in the casing is 0.1 to 5% by weight, based on the weight of the casing.

The special glycosides present in the smokable articles according to the invention allow, due to their special sugar component, simple application by means of different processes and thus mass production of the articles according to the invention. They can be used in the form of highly concentrated aqueous solutions for impregnating the wrapper of the smokable article. It is particularly advantageous that, when applied by means of nozzles, in contrast to the known glycosides, the nozzles are not clogged. Furthermore, it surprisingly shows that when a solution of glycoside used according to the invention, such as ethylvanillin maltoside, is cooled in the warm, the tendency to crystallize is significantly reduced in comparison to ethylvanillin glucoside, which means that even more concentrated solutions can be used and the impregnation of the coating is thus made even easier.

The smokable articles according to the invention preferably contain tobacco as the smokable material. They are therefore particularly in the form of cigars, cigarillos and cigarettes.

Investigations showed that when the articles according to the invention are smoked, the applied glycoside is decomposed with the release of the aroma component, which in turn led to an excellent aromatization of the bypass smoke.

Thermogravimetric investigations of the ethylvanillinmal, tosids, which are preferably used in the smokable articles according to the invention, and the sensory properties of the secondary flow smoke impregnated therewith are described in the exemplary embodiments. It was shown that both the decomposition temperature and the sensory assessment of the sidestream smoke corresponded to the values determined for the ethylvanillin glucoside conventionally used.

The smokable articles according to the invention therefore offer the advantage, with the same aromatization of the sidestream smoke, that because of the improved solution behavior of the glycosides of two or multiple sugars used, the spectrum of the exposure methods available could be expanded significantly. In particular, it is possible to select the advantageous application of the glycoside by means of nozzles by the KAYMICH process for the manufacture of the smoking articles directly on the cigarette machine. The wrapping of the articles according to the invention has in particular paper or tobacco. It is particularly advantageously made of paper or film tobacco. The wrapping can also be multi-layered, whereby combinations of paper and tobacco can also be used. A natural cover sheet can also be used as the outer layer.

The use of wrapping materials, such as e.g. of papers that contain substances to reduce the particle mass of the sidestream smoke. As such, special fillers, e.g. cigarette papers provided with magnesium oxide, magnesium hydroxide or a mixture thereof.

Usually, when using cigarette paper as wrapping, it is used in one or two layers. The glycoside is advantageously applied directly to the paper in the case of a single-layer form and to the outer layer in the case of a two-layer form. In the latter embodiment, it is preferred to use the sidestream-reducing paper for the inner layer and conventional cigarette paper for the outer layer.

Furthermore, the wrapping of the article according to the invention can in particular also consist of one or two layers of film tobacco. If two-layer film tobacco is used, it is preferred that the outer layer contain the glycoside. Accordingly, in the case of cigars and cigarillos, the cover sheet is usually provided with the glycoside.

In addition to using the impregnation process mentioned above for paper, wrappings made of film tobacco can also be produced using the so-called slurry process. Here, ground tobacco dust is mixed with an aqueous solution of binders, scraped onto a heated belt and then dried. In this case, the glycoside can be added to the aqueous binder solution, which results in impregnated film tobacco. In general, the smokable articles according to the invention can be produced by providing the coating, in particular in sheet form, with the glycoside. The glycoside is preferably used in the form of an aqueous solution which contains the glycoside in an amount of greater than or equal to 5% by weight.

The glycoside is preferred by

(a) spraying a solution of the glycoside on the outside or inside of the casing,

(b) using a size press, or

(c) direct application of a solution of the glycoside by means of nozzles

upset,

If film tobacco is used as the wrapper, it can be produced either by the paper or by the slurry process. In the first case, the application takes place according to the procedures already mentioned above under (a) to (c). In the second case, the glycoside can be added to the aqueous binder solution.

In the event that the articles according to the invention are cigars or cigarillos provided with a natural cover sheet, they can be applied either by spraying the cover sheet with an aqueous solution of the glycoside or by dissolving the glycoside in the adhesive for the gluing between the surrounding and Cover sheet used glue. In this case too, the increased water solubility of the glycosides used according to the invention proves to be advantageous.

Finally, it has proven to be particularly advantageous to use the glycosides of two or multiple sugars used according to the invention together with a furaneyl glycoside and in particular Use furaneyl glucoside. The furaneyl glycosides release furaneol when they smoke, which due to its aroma is able to mask the aroma which is sometimes perceived as tobacco-foreign, for example ethyl vanillin, without reducing its positive effects, such as less irritating or stale smoke.

The invention is explained in more detail below with the aid of examples.

Examples

Example 11 Preparation of ethylvanillirunaltoside

To a solution of 1.54 g (2.2 mmol) of acetobromomaltose in 9 ml of absolute dichloroethane is a solution of 332 mg (2.0 mmol) of ethyl vanillin in 4.4 ml of a 0.45 molar solution of potassium hydroxide in absolute methanol slowly added dropwise. The mixture is stirred for 13 hours at room temperature and then poured into 20 ml of ice water. The aqueous phase is extracted twice with dichloromethane and the combined organic phases are dried over magnesium sulfate. The solvent is removed and the residue is purified by column chromatography on silica gel (mobile phase petroleum ether / ethyl acetate 1: 1). Yield: 341 mg (0.43 mmol, 22%) of ethylvanillin maltoside protected with acetyl groups.

For deacetylation, 982 mg (1.25 mmol) of the protected maltoside are suspended in 15 ml of absolute methanol and 1.5 ml of a 1% sodium methoxide solution are added. After stirring for ten minutes, the maltoside is completely dissolved and neutralized with A berlite IR-120 (H). The ion exchanger is filtered off and the solvent is removed in vacuo. The purification is carried out by recrystallization from 95% ethanol. 520 mg (1.06 mmol, 85%) of ethylvanillin maltoside are obtained as a white solid.

(4-Formyl-2-ethoxyphenyl) -4-Q- -D-qlucopyranosyl-ß-D-qlucopy-ranoside (ethylvanillin maltoside): C ₂₁ H ₃₀ O ₁₃ (490.46 g / mol)

[<*] ^_20/57 8 = + A2 ° (c 0.1, H ₂ 0) m.p .: 199 ° C

Elemental analysis calculated: C 51.43 H 6.17 found: C 50.97 H 6.22 Mass spectrum: MALDI-TOF-MS: m / z = 513.2 [M + Na] ⁺ , 529.2

[M + K] ⁺

H-NMR (400 MHz, D, Q δ = 9.67 (s, 1 H, CHO), 7.49 (dd, 1 H, aryl H-5), 7.43 (d, 1 H, aryl H-3), 7.21 ( d, 1 H, aryl H-6),

5.38 (d, 1 H, Hl '), 5.19 (d, 1 H, Hl), 4.08-4.17 (m, 2H, O-CHz- CH ₃ ), 3.62-3.89 (m, 10 H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-3 ', H-5A H-6', H-6'b), 3.53 (dd, 1 H, H-2 '), 3.37 (dd ~ t, 1 H, H-4'), 1-36 (t, 3H, O-CHz-CH _j ) ppm. J _lι2 = 7.6, Jj., ₂ . = 4.1, J ₂ . _{ι3 <} = 9.7, J ₃ . _{) 4} . = 9.7, J ₄ , _{> 5} . = 9.7,

Jar-3, ar-5 ⁼ i «5, J _a r-5, ar- ₆ ⁼ 8.1, J _0Et: = 7.1 HZ.

¹³ C-NMR (100.6 MHz, d, MeOH) δ = 195.11 (CHO), 151.62, 148.36 (2 x C, aryl C-1, aryl C-2), 131.31 (aryl C-4), 126.94 ( aryl C-5), 115.34 (aryl C-6), 112.99 (aryl C-3), 100.07 (C-1 '), 99.78 (C-1), 76.74 (C-5), 76.21 (C-3) , 75.24 (C-4), 73.23 (C-2), 73.11 (C-5 '), 72.86 (C-3'), 72.06 (C-2 '), 69.69 (C- 4'), 65.68 (0 -CH ₂ -CH ₃ ), 60.85, 60.80 (2 x C, C-6, C-6 '), 15.37 (0-CH ₂ -CH ₃ ) ppm.

Example 2: Thermogravimetric examination

The figure below shows the decomposition curve of the ethyl vanillin maltoside used in smokable articles according to the invention, obtained with the aid of thermography (heating rate: 5 ° C./min).

Fig. 1: Thermogravimetry of ethylvanillin maltoside m / m ₀ [%]

200 400 600 800

Are there

m - mass at measuring temperature m ₀ - initial mass (initial weight)

TG - thermogravimetry

DTG - differential thermogravimetry (1st derivative of TG)

The thermolytic cleavage of the glycosidic bond with the release of ethyl vanillin results in a theoretical mass loss of 34%. A loss of mass of 31% in a temperature range of 160-260 ° C could be determined using the experimentally determined curve.

During the measurement, the smell of the released aromatic alcohol ethyl vanillin was clearly perceptible in the decomposition area. Example 3: Production and sensory evaluation of the sidestream smoke of a cigarette with ethylvanillinmaltoside

Filter cigarettes were used on a conventional cigarette machine in KS format (25 mm monoacetate filter with a 59 mm long tobacco rod, tobacco weight 630 mg, filter ventilation 40%, smoke data according to the ISO standard with a draft of 7.5 are 6 mg dry condensate and 0 , 6 mg smoke nicotine). A commercially available American blend mixture was used as the tobacco mixture. Commercially available cigarette paper (porosity 40 CU) was used to wrap the tobacco rod.

The ethylvanillin maltoside was applied to the paper using an application device from Kaymich, Sheffield, UK, during the manufacture of the tobacco rod on the cigarette machine. Different doses of 0.15 and 0.6 mg glycoside per cigarette were tested. For this purpose, a solution of the glycoside in warm water (temperature of 50 ° C) with a concentration of 75 g / 1 was added to the storage container of the device, which is equipped with a heater to keep the solution temperature at 40 ° C. The application to the paper was carried out shortly before the formation of the strand, in that the paper was drilled with holes, i.e. with a metal block provided with nozzles. The control of the dosing quantity was adjusted via the pump pressure in such a way that based on the weight of the cigarette paper (40 mg / cigarette) 5% by weight for the low dosage and 28% by weight of the glycoside solution on the wrapper for the high dosage were applied.

The sensory evaluation of the sidestream smoke of the test samples was carried out by a trained panel of smokers and non-smokers in comparison to similar cigarettes without flavoring glycoside in the cigarette paper. The test samples were machine-smoked in a room of known size and defined equipment (eg 5 cigarettes in one Room with a volume of 20 m). The evaluation was made immediately on the fresh smoke and also after 6 hours on the aged smoke. The subjects had to indicate on a scaled questionnaire, among other things, how intense the smell of the aroma (here ethyl vanillin) and how strong the unpleasant properties associated with cigarette smoke, such as burning eyes, are perceptible. The evaluation was carried out according to the statistical methods customary for sensory tests.

At a dose of 0.15 mg glycoside / cigarette, a significant reduction in the irritant effects of the smoke was achieved without the flavor ethyl vanillin itself being recognized. At the higher dose of 0.6 mg glycoside / cigarette, the aroma released when smoked was perceived more clearly (smells sweet, smells of vanilla). In addition, the irritant effects of the smoke were felt to be even more reduced.

If the evaluation was not carried out immediately, but only after 6 hours, the smell in the test room after the smoking of commercially available comparative cigarettes without glycoside used according to the invention was described as stale, "smells of ashtray" and musty. The aged smoke of the cigarettes with ethyl vanillin maltoside was said to be significantly less uncomfortable.

Example 4: Production and sensory evaluation of the sidestream smoke of a cigarette with ethylvanillin glucoside

For comparison purposes, cigarettes were produced and evaluated in accordance with Example 3, but which contained the conventional ethylvanin glucoside in different dosages of 0.1 and 0.4 mg / cigarette as a flavoring on the wrapping of the tobacco rod. Due to its poorer solubility in water and the higher dilution required, this glycoside was applied in a separate operation by brushing on the substance and then drying the paper.

The evaluation of the cigarettes obtained was carried out in the same way by a trained panel, which described the effect on the sidestream smoke identical to that of the ethylvanillin maltoside.

Example 5: Production and sensory evaluation of the secondary flow smoke of cigarettes with a mixture of ethyl vanillin maltoside and furaneyl glucoside

Furaneyl glucoside ((2,5-dimethyl-4-oxo-dihydrofuran-3-yl) -ß-D-glucopyranoside) was first used according to a literature specification by R. RÖSCHER et al. , in Phytochemistry 43 (1), 155 (1996).

Then filter cigarettes with a diameter of 7.9 mm and a total length of 84 mm (king size format) were produced (21 mm monoacetate filter, 63 mm strand length, tobacco weight 750 mg, mixture type: American blend, filter ventilation 20%, smoke data according to ISO -Normal with a train count of 8.0: 11.8 mg dry condensate and 0.86 mg smoke nicotine). A commercial cigarette paper was used as the strand wrapper, which was provided with a mixture of 0.15 mg of ethyl vanillin maltoside and 0.3 mg of furaneyl glucoside per cigarette.

The cigarettes were evaluated as described in Example 3. The sidestream smoke was described as significantly more pleasant with a reduced irritating effect (fresh smoke) and less stale (aged smoke) compared to a commercially available comparison cigarette. No smell or taste unrelated to tobacco was found.

Example 6; Production and sensory evaluation of the sidestream smoke of cigarillos with a mixture of ethyl vanillin maltoside and furaneyl glucoside

Filter cigarillos with a diameter of 7.9 mm and an overall length of 84 mm were produced. The cover sheet consisted of film tobacco produced by a paper process, which was impregnated with the mixture of ethyl vanillin maltoside and furaneyl glucoside mentioned in Example 5. This aroma mixture was applied during the production of the cover sheet in the size press.

The cigarillos obtained were evaluated as described in Example 3. By using the aroma mixture on the outer wrapper, the more pronounced olfactory notes "cigararry" and "alkaline" than cigarettes were perceived as significantly reduced.

Claims

claims

1. Smokable article with a covering which contains at least one flavoring agent for flavoring the bypass smoke, characterized in that the flavoring agent is a glycoside of a two or multiple sugar and a flavoring component.

2. Article according to claim 1, characterized in that the two or multiple sugar is maltose, lactose or cellobiose.

3. Article according to claim 1 or 2, characterized in that the flavor component is vanillin, ethylvanillin, eugenol, menthol or maltol.

4. Article according to one of claims 1 to 3, characterized in that the wrapping comprises paper or tobacco.

5. Article according to claim 4, characterized in that the paper contains substances for reducing the particle mass of the sidestream smoke.

6. Article according to one of claims 1 to 5, characterized in that the amount of all glycosides present in the casing is 0.1 to 5 wt .-% based on the weight of the casing.

7. Article according to one of claims 1 to 6, characterized in that the wrapping consists of a layer of paper.

8. Article according to one of claims 1 to 6, characterized in that the wrapping consists of two layers of paper and the outer layer contains the glycoside.

9. Article according to claim 8, characterized in that the inner layer has fillers for reducing the particle mass of the sidestream smoke.

10. Article according to claim 9, characterized in that magnesium hydroxide, magnesium oxide or a mixture thereof is present as a filler.

11. Article according to one of claims 1 to 6, characterized in that the covering consists of a layer of film tobacco.

12. Article according to one of claims 1 to 6, characterized in that the covering consists of two layers of film tobacco and the outer layer contains the glycoside.

13. Article according to one of claims 1 to 6, characterized in that the wrapping consists of an inner layer of film tobacco and an outer layer of paper and the outer layer contains the glycoside.

14. A method for producing the smokable article according to one of claims 1 to 13, characterized in that the covering is provided with the glycoside.

15. The method according to claim 13, wherein the glycoside is used in the form of an aqueous solution which contains the glycoside in an amount of greater than or equal to 5 wt .-%.

16. The method of claim 13 or 14, wherein the glycoside on the envelope

(b) using a size press, or

(c) direct application of a solution of the glycoside by means of nozzles

is applied.

17. The method of claim 14 or 15, wherein the coating is produced in sheet form by mixing ground tobacco dust with an aqueous binder solution containing the glycoside.

18. A wrapper for flavored smokable articles, characterized in that the wrapper contains a glycoside of a two or more sugar and an aroma component as the aroma substance.