NO131152B - - Google Patents

Description

Smokeable cellulose-based products containing metal chelates.

The invention relates to smokable products containing combustible cellulose-based materials and metal chelates.

In the production of a smokable material that is not natural tobacco, it is known both to start from tobacco waste products or mixtures of these with other plant materials or also from natural or synthetic non-tobacco products, which are processed into paper-like webs, foils or fibers . For example, it can - according to BRD off. document 1,900,491, smokable materials are produced from cellulose, cellulose derivatives or starch using specific inorganic fillers, which maintain combustion as an annealing process. Furthermore, according to US patent no. 3,461,879, hydrated magnesium citrate and calcium tartrate can be added to certain cellulose derivatives as combustion support substances.

The non-tobacco-specific smokable products produced according to previously known methods show no satisfactory organoleptic properties, but more or less unfavorable organoleptic properties such as pungency or bad aromas in the main and by-stream. For example, tobacco substitute products with only a low sulfur content, e.g. in the form of sulphates an unpleasant sulphidic taste of the smoke. Tobacco substitute products with a high cellulose content, which usually contain alkali, alkaline earth and iron salts used in smoking products, give a sharp and biting smoke with a cellulose taste when heated and leave a persistent astringent effect in the oral cavity. Furthermore, the known non-tobacco smokable products usually have an organoleptic incompatibility with a number of tobacco types when mixed.

For example, the use of substances which according to the state of the art can be added to improve the glow ratio, such as magnesium citrate or calcium tartrate, leads to smoking products whose organoleptic properties are completely unsatisfactory. An insufficient reduction in sharpness is achieved. Particularly disturbing is the burning of the cellulosic material of such smoking products, an unpleasant taste (cellulose taste) and the smell of paper burning, which is practically not reduced compared to the smoke and taste properties of pure cellulose. Thus, such products do not prove to be usable as smoking products or as additives to smoking products.

Unfortunate with the known, non-tobacco-like, smokable products is also the poor filling volume, a usually insufficient wet strength and low mechanical strength, which leads to the formation of large amounts of dust during processing.

The invention relates to a smokable product with a combustible material on a cellulose basis, the product being characterized in that it contains a chelate compound of formula (I)

in which

K means hydrogen, magnesium, calcium or manganese (II), with at least one K being magnesium, calcium or manganese,

Me means trivalent iron or aluminum,

R means an anion of a chelating carboxylic acid with 2-8 carbon atoms, which, in addition to the carboxyl group, contains at least one hydroxyl or keto group, or additional carboxyl groups,

z is 1/2, 1, 3/2, 2 or 3,

x is 1 or 2,

y is 1-4.

As alkaline earth/metal (III) chelate compounds7 that find use in the products according to the invention, mention should be made, for example, of the calcium or magnesium compounds.

The chelate compounds that find use in the products according to the invention are referred to below as chelates.

The term chelate is therefore understood to mean complex salts with a chelate structure, which contain magnesium, calcium or manganese(II) ions as cations and which anion contains a chelate complex, consisting of iron (III)- or aluminum ions as central atom and chelating organic carboxylic acids as ligands (compare e.g. A.E. Martell, M. Calvin, Die Chemie der Metall-Chelat-Verbindungen, page 204, Verlag Chemie, Weinheim 1958).

In many cases, it has proven appropriate to partially replace the cations in the chelates with hydrogen, so that the corresponding acidic salts are formed. Thereby, the hydrogen ion-containing acidic chelate compounds are preferred.

Chelating organic carboxylic acids, hereinafter called "chelat danne re" (see A.E.' Martell, M. Calvin Die Chemie der Metallchelatverbindungen (pages 462 - 517) Verlag Chemie, Weinheim 1958), are organic carboxylic acids with 2-8 carbon atoms, which besides the carboxyl group contains at least one hydroxyl group, keto group or additional carboxyl groups.

Chelatants can therefore e.g. be dicarboxylic acids. Examples of dicarboxylic acids should be mentioned: Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and itaconic acid. Particularly preferred dicarboxylic acids are oxalic acid, malonic acid and succinic acid. Chelatants can also be hydroxy acids such as, for example, hydroxymono-, hydroxydi- and hydroxytricarboxylic acids. Examples of hydroxymonocarboxylic acids should be mentioned: Lactic acid, glycolic acid, 3-hydroxyprbionic acid, glycerol acid and hydroxypivalic acid. Particularly preferred hydroxymonocarboxylic acids are glycolic acid and glycerol acid. Examples of hydroxydi- and hydroxytricarboxylic acids include: Hydroxylmalonic acid, malic acid, tartaric acid, 2-hydroxyglutaric acid, 3-hydroxyglutaric acid, 3-methylmalic acid, 2,5-dihydroxyadipic acid, 2,4-dihydroxyadipic acid

and citric acid, preferably malic acid, tartaric acid and citric acid.

Chelatants can further e.g. be those from pentoses

and hexoses derived mono- and dicarboxylic acids. As examples of this, the isomeric monocarboxylic acids known as uronic acids, such as glucuronic acid, galacturonic acid and mannuronic acid, the compounds known as sugar acids, such as e.g. sugar acid, manno- resp. isosugar-acid, as well as the isomeric mucilaginous acids (galactaric acids). Furthermore, pentaric acids, ribotrioxyglutaric acid and xylotrioxyglutaric acid derived from the pentoses should be mentioned as examples. As chelating agents, which contain a keto group, ketocarboxylic acids with 3-8 C atoms can be used. Examples of ketocarboxylic acids include pyruvic acid, acetoacetic acid, levulinic acid and mesoxalic acid.

Dicarboxylic acids and hydroxyl acids are preferably used as chelating agents, especially oxalic acid, glyceric acid, glycolic acid, malic acid, tartaric acid, galactaric acid, sugar acid and citric acid.

For example, it has proven particularly advantageous to use chelates corresponding to the general formula I with the following composition: Magnesium-iron-III-glycolate, magnesium-iron-III-oxalate, magnesium-iron-III-citrate, magnesium-iron-III-tartrate , magnesium iron III galactarate, magnesium iron III saccharate, magnesium aluminum glycolate, magnesium aluminum oxalate, magnesium aluminum citrate, magnesium aluminum tartrate, magnesium aluminum galactarate, magnesium aluminum -saccharate, manganese-iron-III-glycolate, manganese-iron-III-oxalate, manganese-iron-III-citrate, manganese-iron-III-tartrate, manganese-iron-III-galactarate, manganese-iron-III-saccharate , manganese aluminum glycolate, manganese aluminum oxalate, manganese aluminum citrate, manganese aluminum tartrate, manganese aluminum galactarate, manganese aluminum

saccharate.

Chelates, which are used in the smokable products according to the invention, can for example have the composition listed in table 1. The compounds listed in Table 1 correspond to the general formula 1 (K /—Me R /), where K means magnesium, calcium or manganese(II) z x y

and Me means iron(III) or aluminum and R means a chelating carboxylic acid. The stated values for x, y and z are used each time in the general formula 1 and thus give the sum formula of the example mentioned chelates.

Tartaric acid, citric acid and galactaric acid are particularly preferably used as chelating agents.

As particularly preferred chelates, magnesium iron III tartrate, magnesium iron III citrate, magnesium aluminum tartrate, magnesium aluminum citrate, manganese iron III galactarate, manganese iron III citrate are mentioned.

The chelates contained in the smokable products according to the invention can be prepared in a known manner in aqueous solution, e.g. by reacting iron or aluminum salts of the relevant chelating carboxylic acids with calcium, magnesium or manganese salts, the latter being added as hydroxides, carbonates or salts of the corresponding gel-forming carboxylic acids (compare German patent no. 514,504, Hanus and Quadat Z. Anorg. Chem. 63, page 314 (1909) and W. Franke, Liebig Ann.'Chem. 486, page 248 (1931).

Combustible cellulose-based materials are e.g. cellulose-containing plant material, especially tobacco, tobacco waste products, such as stems, nerves or dust, entangled cellulose-containing plant material such as e.g. hay, straw, lupins or ferns as well as cellulose or cell substances or cellulose derivatives alone or in mixtures. As cellulose derivatives, it can e.g. find use carboxymethyl cellulose, hydroxyethyl cellulose or methyl cellulose.

Furthermore, the polymer homologues of low molecular weight fragments of the cellulose formed by thermal decomposition of cellulose as well as the cellulose derivatives produced by chemical processes, especially by alkaline or acid oxidation, can also be used as combustible materials.

Particularly good results are obtained when using tobacco, as well as paper-like webs made from tobacco waste products or from cellulose or cell substances.

The smokeable products according to the invention usually contain approx. 0.5 to 70% by weight chelate referred to the total weight of the combustible material that finds use in the smokable products according to the invention. It has proven advantageous to match the amount of chelate to the cellulose content of the combustible material that is used. For example, with amounts of approx. 10% by weight of cellulose in the combustible material is preferably used at approx. 1-15 weight of chelate referred to the total weight, particularly preferably approx. 5-10% by weight. In the case of an amount of more than 70 weight?2 cellulose in the combustible material, approx. 10 - 70% by weight of chelate, referred to the total weight, particularly preferred 25 - 50 weight 5?.

In a preferred embodiment of the invention, the smokable products contain a filler. Under smoking conditions, fillers are understood to mean palatable, inert minerals, inorganic salts and oxides, such as for example diatomaceous earth, silicates, mica, clay, dolomite, magnesite and chalk respectively. carbonates, phosphates and oxides of. aluminium, iron, magnesium, calcium. Furthermore, such inert fillers can also be used, which release water under smoking conditions. The water separation can on the one hand take place due to a high content of crystal water in the filler, on the other hand by chemical separation, e.g. of metal hydroxides. The hydroxides of the oxyhydrates of aluminum and iron, natural silicates such as vermiculite and kaolin, precipitated silicates such as silicic acid, silica gel, silica sol, alkaline earth and alkali silicates have proven to be particularly advantageous as fillers, preferably using the oxyhydrates of aluminum and/or silicic acid. The fillers are suitably used usually in amounts of approx. 1-70% by weight referred to the total weight of the smokable product, preferably approx.

15 - 50% by weight.

Thereby, it has proven particularly advantageous to use the fillers in proportions from 9"-l to 1:9 to the chelate used.

In a further preferred embodiment according to the invention, the smokable products contain compounds which, under smoking conditions, release ammonia. As compounds which split off ammonia under smoking conditions, ammonium salts of inorganic acids, organic carboxylic acids and salts of amino acids and acid amides are particularly used.

Preferably, the acidic and neutral ammonium salts of inorganic acids such as carbonic acid, nitric acid, phosphoric acid, especially the ammonium salts of phosphoric acid should be mentioned as compounds which split off ammonia under the smoking conditions.

Good results are also obtained with the acidic and neutral ammonium salts of organic carboxylic acids, which have a carbon-oxygen ratio in the general formula from 2:1 to 1:2, preferably 1:1 to 1:2. Consequently, ammonium salts of monocarboxylic acids such as formic acid and acetic acid, of dicarboxylic acids such as oxalic acid, malonic acid and succinic acid, of hydroxymono-, hydroxydi- and hydroxytricarboxylic acids such as glycolic acid, lactic acid, B-hydroxy-propionic acid, glyceric acid, malic acid, tartaric acid and citric acid1 as well as the ammonium salts of the mono- and dicarboxylic acids derived from pentoses and hexoses such as glucuronic acid, galacturonic acid, mannuronic acid, the sugar acid and especially the mucilaginous acids. Preferably, ammonium tartrate and ammonium citrate are used.

Particularly advantageously, it is also possible to use ammonium salts corresponding to the gels according to the invention as ammonia-releasing compounds (since in the general formula I "K" means ammonium). Preferably, the following ammonium gel compounds are used: Ammonium iron III glycolate, ammonium iron III oxali, ammonium iron III citrate, ammonium iron III tartrate, ammonium iron III galactarate and ammonium iron III saccharate as well as ammonium aluminum glycolate, ammonium aluminum oxalate, ammonium aluminum citrate, ammonium aluminum tartrate, ammonium aluminum galactarate and ammonium aluminum saccharate.

Particularly preferred are ammonium iron III citrate, ammonium iron III tartrate and ammonium iron III galactarate and ammonium aluminum citrate and ammonium aluminum tartrate.

It has also proven advantageous to use acid amides as ammonia-releasing compounds. Examples can be mentioned: Acetamide, propionamide, succinic acid monoamide and -diamide and particularly preferred urea, furthermore, the ammonium, magnesium or manganese (II) salts of amino acids can also be used as ammonia-releasing compounds, with glycine being preferably used as amino acids, serine, lysine, arginine, leucine, proline, valine, aspartic acid or glutamic acid. Magnesium and manganese glutamate are particularly preferably used as the ammonia-decomposing compound.

The ammonia-releasing compounds are used, for example, in amounts of from 1 to 25% by weight, referred to the smokable product, preferably 5 to 15% by weight

It has proven appropriate to dimension the quantity

of the compounds which, under the smoke conditions, split off ammonia so that the acids formed during charring are neutralized in the smoke, which can be checked by pH measurement in the main stream smoke. Preferably, such amounts are added to ammonia-decomposing compounds that a pH of 5 to 8, preferably 6 to 7.5 is set in the main stream smoke.

In a further special embodiment according to the invention, the smokable products refer to the total weight of the smokable product contain 0.01 - 7, preferably 1-5 weight$ of an oxidizing agent, with oxidizing agent being understood as substances which improve the smokable product glow ratio.

Salts of nitric acid, especially alkali or alkaline earth nitrates, can for example be used as oxidising agents. As nitrate, which is preferably used, mention should be made of potassium and/or sodium nitrate.

It has proved particularly advantageous as an oxidizing agent in the smokable products according to the invention to use compounds of manganese of oxidation stage VII, especially alkali permanganates, e.g. potassium permanganate.

In a further preferred perform Isesform contains

the smokeable products approx. 0.01 to 10% by weight, preferably 0.1 to 5% by weight, referred to the smokable product of ammonium salts of polygalacturonic acids such as pectin, alginic acid or gum arabic and/or ammonium salts of carboxymethylcellulose.

Good organoleptic results are also achieved by using 0.01 to 5% by weight, preferably 0.1 to 3% by weight, referred to smokable products of low-sulphur egg whites,

like for example. zein, hordein or gliadin as well as those by fractional extraction with alcohol, e.g. by extracting with ethanol from these egg whites recovering extracts. In addition to the ammonia release in the smokable products, the aforementioned compounds cause a lucky plant flavor with a tobacco-like taste. The smokable products obtained by this embodiment are fully compatible in aroma in arbitrary mixtures with tobacco.

In a further preferred embodiment contains

the smokable products 0.1 - 50% by weight, referred to the total weight of the smokable product of tobacco-containing substances. Such substances or groups of substances which can be produced from tobacco according to known methods apply to substances contained in tobacco. Tobacco-containing substances can e.g. produced by extortion, distillation and extraction. Preferably, tobacco-containing substances that were formed by extraction are used, as the extraction e.g. took place with water or organic solvents. The combustible materials that form the basis of the smokable products according to the invention can be in the form of a paper-like web, a web, a foil, a thread or string, cut or uncut. The paper-like webs, flor etc. can be produced according to known technical methods (compare Ullmann's Enzyklopadie der techn. Chemie, 3rd edition, volume 13, page

122 - 130 (1962) and volume 17, pages 288 - 296 (1966).

It has proven particularly advantageous to produce the products according to the invention in the form of paper-like webs with a basis weight of 10 - 250 g/m 2 , preferably 15 - 60 g/m 2 and in sheet thicknesses that are usually in the range of . 10 - 120 µm, preferably 20 - 60 µm, particularly preferred 30 - 45 µm.

The production of the smokable products according to the invention can, for example, take place in such a way that the combustible cellulose-based material is in the form of a paper-like web, a flor, a foil, a thread or string, cut or uncut, and applied to the gelates which, according to the invention, find use in a solution, preferably in aqueous solution. The application can e.g. takes place by immersing the combustible material in a bath with the solution of the chelate compound and then drying it, with temperatures of 50 - 120°C suitably used. However, the combustible material can also be sprayed with the chelate solution or coated with it. Furthermore, the chelates can also be introduced directly into the starting mixture from which the combustible material is produced, e.g. in the form of paper-like webs, a flor, a foil, a thread or string.

For example, the chelates can be introduced directly into a casting solution, which contains the combustible material. Appropriately, such casting solutions can, in addition to any fillers that are used, contain ammonia-decomposing compounds, oxidizing agents and substances contained in tobacco approx. 0.1 to 2.0 wt/5 of a binder. As a binder, it can e.g. find application polysaccharides or their derivatives, gum arabic, starch, alkali-poor carboxymethyl cellulose and/or ammonium carboxymethyl cellulose. If the binder forms a combustible material on a cellulose basis, the binder in the products according to the invention naturally takes over the function of combustible material. For the production of the products according to the invention, one can e.g. proceed in such a way that the pouring solution or casting solution is poured onto an endless belt and dried at 50 - 120°C.

For the smokable products according to the invention, paper-like webs or flor are particularly used.

The uptake of chelate by means of the foil or fleece can also be controlled by means of the processing parameter by the structure of the foil and by the viscosity and concentration of the solution of the relevant chelate. The viscosity setting can, for example, be achieved by changing the concentration of solutions of chelates or by addition of thickeners, such as low-alkali carboxymethyl cellulose, hydroxyethyl cellulose, pectins, gum arabic, alginates, galactomannan, starch or their derivatives. Concentrated high-viscosity solutions cause, for example, a high absorption of salts in the smokable product.

The fillers which are used in a preferred embodiment according to the invention can be incorporated simultaneously with the gels in the combustible material. However, the incorporation of the fillers can also take place in whole or in part in a separate process step before or after the treatment with the chelates. The fillers can be incorporated according to the known technological methods for the production of filler-containing paper-like webs, fleeces or foils.

The ammonia-splitting compounds which further find use can be introduced simultaneously with the chelates or also in a separate process step before or after the incorporation of the chelates into the combustible material. The introduction takes place e.g. by spraying, dipping or coating the combustible material with aqueous solutions of the ammonia-releasing compounds and subsequent drying.

The oxidizing agents which are used according to the preferred embodiment can be introduced simultaneously with the chelates and before or after their incorporation into the combustible material. The introduction takes place e.g. by spraying, dipping or coating the combustible material with an aqueous alcoholic or acetone solution of the oxidizing agent.

The ammonium salts of polygalacturonic acids, which find use according to the further embodiment, as well as the low-sulphur egg whites or their alcoholic extracts and furthermore the tobacco-containing substances which find use according to a further embodiment, can be introduced simultaneously with the chelates and before or after their incorporation into the combustible material. Preferably, the mentioned substances are incorporated simultaneously with or after the gels in the smokable material.

In all embodiments, it is also possible to introduce, in the same or separate process steps, the additions that are common in tobacco processing, such as e.g. humectants as well as "Flavor" and nicotine.

Of course, the preferred embodiments can take place in the production of the smokable products according to the invention in the desired combination.

The products according to the invention have, in relation to the combustible material used, to which combustion modifying substances are mixed according to the state of the art, when smoked organoleptically a reduced sharpness, a pleasant mild taste without astringent effect and improved smell. For example, by mixing the smokable products according to the invention into tobaccos with a cellulose-like sharpness or by treating such tobaccos to reduce the sharpness, the aroma of such tobaccos is clearly highlighted. The smokable products according to the invention are distinguished by a particularly low condensate value and furthermore show an excellent glow ratio. The smokeable products according to the invention are particularly distinguished by a smoke without cellulose taste and thus without organoleptic irritating components.

The smoke analysis of the smokable products according to the invention showed a partial considerable reduction of physiologically harmful substances compared to tobacco. Thus, per cigarette containing the products according to the invention compared to a cigarette with tobacco a significantly lower phenol content and prussic acid content as well as significantly lower condensate values. For example, when using filler-containing cellulose foils with chelates in relation to tobacco per cigarette achieved a reduction of the phenol content of around over 90% and of the prussic acid content of around approx. h0% and of the benzpyrene content around approx. 25%. Compared to tobacco, the amount of dry condensate could be reduced by around 80 - 90%.

Mixtures of the smokable products according to the invention with tobacco can affect the combustion conditions of the tobacco in a beneficial way by achieving a greater decrease in physiologically harmful substances

in the smoke than was to be expected from the individual components of this mixture.

By varying the chelates, as well as the components which according to the present embodiments find additional use, e.g. by tuning the amount of the chelate compound to ammonia-releasing compounds under smoking conditions, the smell and taste of the smokable products can vary and e.g. also set taste-wise neutrality. Furthermore, a strong adaptation to tobacco and artificial aroma components can be achieved. With the help of the method according to the invention, it is therefore possible to match the smokable products both in terms of aroma components either with synthetic substances or substances obtained by extracting tobacco, as well as with different tobacco types such as Burley, Virginia and Orient in a mixture. In any case, it is possible to reproducibly realize an unchanged, harmonious taste impression with respect to the tobacco aroma.

The use of the chelates contained in the products according to the invention proves particularly advantageous, as these compounds are usually very soluble in water. This makes it possible to achieve a homogeneous distribution of the chelates in the smokeable products in a simple way in a work process. Due to the small tendency to crystallization and due to the hygroscopic condition, the products obtained by the method are flexible and elastic and thus particularly easy to process.

They have a tobacco-like grip and are comparable to natural tobacco in their processing properties, such as cutting conditions and mixing conditions. When setting the surface weight of the carrier, e.g. between 15 and 60 g/m, the filling volume can be increased in relation to a corresponding amount of tobacco, for a predetermined smoking article such as a cigarette, cigar or pipe tobacco and thus, when mixed with tobacco, to achieve a smaller weighting for the smoking article. Thereby, the total smokable substances and finally the amount of condensate during smoking are further reduced.

The smokable products according to the invention are used alone or as a mixed component in cigarette tobacco, cigar tobacco and pipe tobacco. In addition, it can be conveniently used as a cigar cover or wrapper or as cigarette paper.

Examples.

The smokable products formed according to the examples below were processed into filter cigarettes with cellulose acetate filters. The filter cigarettes had a length of 8.2 mm, a diameter of 8 mm and

a string length of 67 mm. The cigarettes were smoked to an average stub length of 23 mm.

To characterize the filling density of the cigarettes, the draw resistance was indicated. The draw resistance was determined with a draw resistance measuring device for single cigarettes from the company Filtrona, London, which indicated the pressure drop in "mm H^O".

Generally, the filter cigarettes produced with the smokable products had a draft resistance of between 100 and 125 mm H^O.

The amounts of condensate indicated for the examples are dry condensate in mg/cigarette. The condensate was obtained according to Coresta standard no. 10. The test cigarettes were thereby smoked with a puff volume of 35 ml, a puff duration of 2 seconds and a puff frequency of 60 seconds.

The condensate formed was precipitated on a Cambridge filter and weighed. The amount of water was determined titrimetrically according to the Karl-Fischer method and subtracted from the total condensate.

The smokable products obtained according to the examples were

which follows the assessment of the stage in the organoleptic properties.

a) Sharpness: (++) normal cellulose sharpness (+) slight sharpness, above all at the beginning of smoking

(-) almost no sharpness, corresponding to tobacco material

(--„), completely without sharpness.

b) Smoky taste: (++) strong, usual cellulose taste, paper fire, strong astringent

(+) light cellulose taste, not astringent

(-) no cellulose taste, little taste influence

(--) mild, no taste impact.

Example la.

100 g of a paper-like film of bleached sulfate cellulose with a basis weight of 58 g/m and a thickness of 60 µm and an ash content of 0.06% was sprayed with a 25% aqueous solution of magnesium aluminum citrate Mg/. Al^ icitrate)^_/ and dried in such a way that the resulting dry foil' contained 20% by weight of chelate. The foil was cut into strips of approx. 0.9 mm width and different lengths (cigarette fine section) and using commercial cigarette paper sleeves with cellulose acetate filter processed into cigarettes with an average draw resistance of 113 mm H2O.

When smoked, the cigarettes showed an even glow without the smokable product igniting. The ash was grey-white and self-supporting.

Organoleptic assessment:

Sharpness: (+)

Smoky taste: (-)...

Dry condensate-: 7.3 mg. Example lb.

100 g of a paper-like film of bleached sulfate cellulose with a basis weight of 25 g/m 2 , a density of 32 µm and an ash content of 0.08% was sprayed with a 25% aqueous solution of magnesium aluminum citrate Mg -^/. AI2 (citrate) ^_/ and dried so that the resulting dry film contained 20% by weight of chelate. The treated foil was cut into strips of approx. 0.9 mm width and different length (cigarette fine section) and prepared using commercial cigarette paper sleeves with cellulose acetate filter for cigarettes with an average draw resistance of 102 mm H^O.

When smoked, the cigarettes showed an even glow - without the smokable product flaming. The ashes were self-supporting.

Organoleptic assessment:

Sharpness: (+)

Smoke flavor: (-)

Dry condensate: 5.0 mg.

Example lc.

100 g of a paper-like foil made from approx. 60% by weight ground tobacco ribs, 30% by weight tobacco leaf waste (gravel and dust) and 10% by weight unground sulphate cellulose produced in a known manner on a longwire paper machine, had a basis weight of 70 g/m p and a thickness of 60^u, was sprayed with a 25% solution of magnesium aluminum citrate Mg^/_ Alg (citrate) ^_/ and dried so that the impregnated foil contained 5% by weight of chelate. The product thus formed was cut according to example 1 and processed into filter cigarettes with an average draw resistance of 109 ml H 2 O.

The cigarettes showed an even glow ratio. The main and side stream smoke was rated as distinctly aromatic.

Organoleptic evaluation:

Sharpness: (-)

Smoke flavor :■(-)'

Condensate: 6.2 mg.-

Example 2. (Comparison example)

A product corresponding to example 1a was produced, which instead of magnesium-aluminum citrate as an additive contained magnesium citrate. It was then proceeded in such a way that 100 g of a paper-like foil according to example 1 consisting of bleached sulphate cellulose with a basis weight of 58 g/m 2 and a thickness of 60 µm, which contained 11.3% by weight magnesium carbonium as filler, at 30°C was dipped in a 10% aqueous citric acid solution, so that magnesium citrate formed in the product. After washing out excess citric acid and drying, the weight gain of the foil amounted to 19 g, which corresponds to a magnesium citrate content of 22 by weight. The product thus formed was cut according to example 1 and processed into filter cigarettes with an average tensile strength of 102 mm ^0.

Organoleptic assessment:

Sharpness: (++)

Smoky flavor : (++)

Condensate: 9.3 mg/cigarette.

Example 3a.

100 g of a paper-like foil according to example 1 was sprayed with a 25 µg aqueous solution of magnesium-iron-III-citrate Mg-j/_~Fe (citrate) 2- J 2 °^ dried so that the dried foil contained 20 wt? chelate. The product thus formed was cut into strips of approx. 0.9 mm width and different lengths and processed according to example 1 into cigarettes with a draw resistance of 115 mm H^O.

When smoked, the cigarettes showed a tobacco-like glow without the smokable product igniting. The ash was brownish gray and self-supporting.

Organoleptic assessment:

Sharpness:

Smoke flavor : (+)

Dry condensate: 4.5 mg.

Example 3b.

300 g of dried and cut worm fern stalks (Dryopteris filix-mas) were heated in a 10 liter pressure vessel with 6 liters of a 5% aluminum sulphate solution for 4 hours at 105°C. The plant material thus absorbed was filtered off and washed sulfate-free with water. It was then defibrated in a Hollender and prepared on a longwire paper machine into a web with a basis weight of 68 g/m and a thickness of 60 µm. 90 g of the foil thus formed was sprayed with a 10 µg magnesium iron citrate solution and dried, so that the foil's content of chelate amounted to 10 µg by weight. The product thus formed was similarly cut and processed into filter cigarettes with an average draw resistance of 120 mm H2O in accordance with example 1. The cigarettes were mild in the mainstream smoke and of a pleasant herbal taste. Organoleptic evaluation:

Sharpness: (-)

Smoke flavor : (-)

Condensate: 5.2 mg/cigarettes.

Example 3c.

100 g of a paper-like foil, made from approx.

60 weight? ground tobacco ribs, 30 weight? tobacco waste (gravel and dust)

and 10 weight? unmilled sulfate cellulose, which was produced in a known manner on a longwire paper machine and had a basis weight of 70 g/m 2 and a thickness of 60 µm, was sprayed with a 5 µg aqueous solution of magnesium iron III citrate Mg^/_ Fe (citrate)2_/2°^ dried so that the increase in weight after drying amounted to 5?, i.e. it was obtained

a chelate content of 5 wt?. The cigarettes produced according to example 1, which have a draft resistance of 115 mm H 2 O, showed a uniform glow ratio. The ash was brownish red and se.lv-bearing. When smoked, the product showed a light and aromatic flavor impression without cellulose sharpness. Organoleptic assessment:

Sharpness: (-)

Smoke flavor: (--)

Condensate: 4.4 mg/cigarette.

Example 4.

A paper-like foil according to example 1b was impregnated for a long time alternating in a saturated calcium hydroxide solution and then in a 10% tartaric acid solution, then washed out and dried until the increase in weight amounted to 25.3% by weight, i.e. the foil contained approx. 20 weight? calcium tartrate. The thus produced product was cut according to example 1 (cigarette fine section) and processed into filter cigarettes with a draft resistance of 117 mm H₂O.

The cigarettes have a dull, mature aftertaste and a distinctly high cellulosic sharpness.

Organoleptic assessment:

Sharpness: "(++)

Smoky taste: (++)

Condensate: 8.4 mg/cigarette.

Example 5.

A paper-like foil according to example 1 was treated

in an aqueous immersion bath, which contained 12.6 wt? magnesium-aluminium-tartrate Mg^/_ Al (tartrate) -^ U 2 squeezed out^ between steel rollers and dried so that the impregnated' web has a weight increase of 24.8?, which corresponded to a chelate content of 20 weight?. The product thus formed was cut according to example 1 and processed into filter cigarettes, which had an average draft resistance of 115 mm H^O. The cigarettes showed a slow and constant glow and formed a light self-supporting ash.

Organoleptic evaluation:

Sharpness: (+)

Smoke flavor : (-)

Condensate: 6.8 mg/cigarette.

Example 6.

100 g of a paper-like foil corresponding to example 1a was sprayed with a 25 µg manganese iron (III) oxalate solution

Mn-j/<->Fe (oxalate) - yj 2 °S dried - in such a way that the foil thus treated contained 20 wt?chelate. The product formed was cut analogously to example 1 and processed into filter cigarettes. Tensile strength 123 mm i^O. The cigarettes glowed very evenly and formed a brown self-supporting ash.

Organoleptic assessment:

Sharpness: (-)

Smoke flavor : (+)

Condensate: 4.2 mg/cigarette.

Example 7.

100 g of a paper-like foil according to example 1 was sprayed several times with a total of 250 ml of a 10 µg magnesium-aluminum glycolate solution Mg^/_ Al (glycolate) ^_/ ^ and dried, so that the chelate content amounted to 20 wt.

The product thus formed was processed as in example 1 into filter cigarettes, which had a draft resistance of 122 mm H2O. The cigarettes glowed evenly, forming a light white ash. Organoleptic assessment:

Sharpness': ( + )

Smoke flavor: (+)

Condensate: 7.0 mg/cigarette.

Example. 8.

100 g of a paper-like foil according to example 1 was sprayed with a 12 µg manganese-iron-galactarate solution Mn^/_Fe (galactarate)j_72 and dried. The film contained 19.5% by weight of chelate.

The material corresponding to example 1 was cut and processed into filter cigarettes with a tensile strength of 121 mm 1^0 had a uniform glow ratio and formed a brown-grey ash.

Organoleptic evaluation:

Sharpness: (-)

Smoke flavor : (+)

Condensate: 4.9 mg/cigarette.

Example 9»

A mixture of 30 weight? of the impregnated foil according to example 1 and 70 weight? of an American Virginia tobacco with a condensate of 28 mg/cigarette was processed into filter cigarettes with a draw resistance of 126 mm H^O. The aromas and sweetness characteristic of Virginia tobacco were completely retained when the mixture was smoked. The nicotine reaction on the airway was clearly weakened.

Organoleptic assessment:

Sharpness: (-)

Smoke flavor: (--)

Condensate: 15 mg/cigarette.

Example 10.

A mixture of 30 weight? of the foil according to example 3 and -vi 70 weight? of an Italian Burley tobacco with a condensate of 22 mg/cigarette was processed into filter cigarettes with an average draw resistance of 121 mm H^O. When smoked, the cigarettes completely returned the characteristic cigar-like taste of Burley tobacco. Organoleptic assessment:

Sharpness: (-)

Smoke flavor: (--)

Condensate: 12 mg/cigarette.

Example 11.

A mixture of 30 weight? of the foil according to example 6 and 70 weight? of a commercially available tobacco mixture of a light character (flavor type American blend) with condensate of 15 mg/cigarette was processed into filter cigarettes. When smoked, the cigarettes showed a pleasant and mild taste. In relation to the tobacco mixture used, the smoke appeared highly diluted. The glow ratio corresponded in uniformity and speed to that of natural tobacco.

Tensile strength: 118 mm H^O.

Organoleptic evaluation:

Sharpness: (-)

Smoke flavor : (-)

Condensate: 9.3 mg.

Example 12.

As combustible material, a tobacco was used which was characterized as raw "Burley" with a strong cigar-like character. This tobacco was sprayed with a solution of ammonium iron(III) citrate (NH^)jl<_> Fe (citrate) 2— °& acidic magnesium aluminum tartrate Mg H

/JAI (tartrate)^_7 in a weight ratio of 1:1, so that the dry absorption amounted to 2.5 wt?, i.e. both compounds were present in the treated tobacco material to 1.25 wt?.

In relation to the material used, the Burley tobacco treated by the method according to the invention, when smoked, showed a weakened sharpness, however a root-aromatic overall impression. The Burley characteristic was completely retained.

Rating:

Sharpness: (--)

Smoky taste : (—).

Example 13.

A paper-like foil of a mixture (1:1) of ground tobacco ribs and sulphate cellulose with a basis weight of 45 g/m 2 and a thickness of 55/U was used as combustible material. This material was treated in a dipping bath containing

15 parts magnesium aluminum citrate Mg^/_ Al ( citrate) 2- J 2

6 parts ammonium aluminum citrate (NH^^/-Al (citrate) 2^

4 parts aluminum hydroxide

4 parts silicic acid

11 parts tobacco extract and

60 parts water.

The thus treated foil was pressed off and dried in an air stream at 95°C. This resulted in a weight increase of 55 weight?. The dissolved components of the dipping bath were incorporated in different equal concentration ratios in the foil, i.e. the foil contained 13.6 wt? Mgj/fAK citrate)2_72 and 5 weight? (NH^)^ _/~Al (citrate) 2_7.

Compared to a product which was prepared without the addition of chelate, the smokable product formed was without astringent action, showed no pungency and gave a light aromatic smell. When mixed with commercial cigarette tobacco, it proves to be completely compatible. Rating:

Sharpness:

Smoky taste : (-).

Examples 14 - 22. Chelate complexes on cellulose webs.

As starting material for the smokable products, paper-like foils or lanes with and without filler. The resulting foils are listed in Table II.

The foils A to D were each prepared in a dipping bath, which consisted of the aqueous solution of the chelate together with the compound which releases ammonia by smoking. In examples 15, 17, 18 and 19, a filler and a binder were also present in the dipping bath.

The dipped foil was pressed off by passing on a roll chair and dried in an air stream at 95°C on an endless belt.

In table III it is indicated for examples 14 to 22

the type of foil used as combustible material, the composition of the dipping bath, dry weight increase of the treated foil (total or chelate) and assessment of the organoleptic properties of the smokable product formed as well as the condensate value. The amount of solids taken up by the foil (ammonia-decomposing compounds, fillers) is shown by the weight gain, as the individual components are taken up in the foil in the weight ratio, as they were in the dipping bath. The amount of the chelates used is indicated separately.

Example 23 - 25 - Tobacco mixtures.

The cut foils according to examples 15, 16 and 18 were mixed with a commercial cigarette tobacco with a light character and processed into filter cigarettes.

Example 23.

A 30% mixture of the foil according to example 15 with a commercially available cigarette tobacco of light type gave a round soft aroma impression without any cellulose sharpness. With the overall mixture's low nicotine content, only the reaction when inhaling the main stream smoke was weakened.

Rating:

Sharpness:

Smoke flavor :

Condensate: 13.6 mg.

Example 24.

A 30% mixture of the foil in example 16 gave a slightly weakened aroma impression of the tobacco mixture with little residual sharpness (-). With regard to the nicotine reaction when inhaling the main stream smoke, the same effect was present as in example 13. Assessment:

Sharpness: (-)

Smoke flavor : (-)

Condensate: 14.1 mg.

Example 25.

A 30% by weight mixture of the foil according to example 18 is assessed organoleptically with regard to aroma weaker, however, with regard to sharpness completely indifferent.

A cellulosic aftertaste was not detected in either the main or by-stream smoke. The nicotine reaction when inhaling the mainstream smoke was further weakened compared to examples 23 and 24. Assessment:

Sharpness: (--)

Smoke flavor : (--)

Condensate: 15.0 mg.

Example 26 - 31.

Foils according to examples 14 - 22 were, according to the following examples 26 to 31, dipped in a solution of aqueous tobacco extract, which contained approx. 30 weight? soluble tobacco-containing substances or sprayed with this solution, so that the dry increase amounted to up to 50 weight?. The drying took place with hot air at 60-100°C. Example 26.

Of a commercial tobacco mixture of the taste type "American Blend" 20? of the contained substances extracted with a cold methanol-water solution (70 volume/30 volume). This aqueous methanolic extract was additionally sprayed onto the smokable product prepared according to example 17, so that a dry uptake of

30 weight?. The product formed was processed as filter cigarettes

which in the main stream has an aromatic taste impression without any sharpness (rating: (—)) and without cellulose aftertaste (rating: (-)) when inhaled with a clearly observable nicotine reaction and a semi-aromatic by-stream. The smokable product thus formed is compatible in any quantity ratio with Virginia, Burley and Orient types of tobacco as well as their mixtures (condensate: 9.8 mg).

Example 27.

The foil formed according to example 19 was treated with the same extract of tobacco-containing substances as in example 26, so that there was an increase in the dry weight of 29 wt. The taste impression of the product processed as filter cigarettes was assessed as poor in aroma and indifferent, as only a slight sharpness was determined (assessment: (-)) at the beginning of smoking. Bistrøm smoke is aromatic and mild. (Assessment of smoke flavor: (-), condensate: 10.7 mg). Example 28.

The foil obtained according to example 20 was treated

with the same extract of substances contained in tobacco as in example 26, so that there was an increase in the dry weight of around 25 weight?. In relation to example 27, a rounder taste impression with a good reaction was determined, since even at the beginning of smoking no sharpness could be determined (assessment: (-)) or any cellulose aftertaste (assessment: (--)). Bistrøm smoke is pleasantly aromatic. (Condensate: 9.0 mg). Example 29.

From American Virginia tobacco, the contained substances were completely extracted with hot water. This aqueous extract was additionally sprayed onto the smokable product produced according to example 20, so that the increase in dry weight amounted to 31%. When smoking these cigarettes, unadulterated typical Virginia flavor was established, the spice of which was not affected by the foil.

v

Rating:

Sharpness:

Smoke flavor : (—) Condensate: 11.0 mg.

Example 30.

From Italian Burley tobacco it became by extraction

with a cold methanol-water solution (60 vol/40 vol) completely extracted the contained soluble substances. This extract was additionally sprayed onto the smokable product produced according to example 22 so that the total weight increase amounted to 20%. The taste impression corresponded to this of a good characteristic Burley tobacco with a sweet character. The smoking product shows less sharpness than the Burley tobacco used for extraction. The smokable product thus formed was, in any mixing ratio, compatible with Virginia, Burley and Orient types of tobacco and their blends.

Rating:

.Sharpness: (-)

Smoke flavor : (--)

Condensate: 11.3 mg. Example 31»

The foil listed in Table II was treated in an impregnation bath, which contained 160 g of ammonium citrate, 80 g of magnesium aluminum citrate Mg^_/ Al^ (citrate) ^_/ and 280 g of that according to Example 19

by extraction with water extracted tobacco substances and adjusted with ammonia to pH 7. The increase in the dry weight of the foil thereby amounted to 50%, the thus formed smokable product containing 5.1% by weight of chelate. When smoked, the product showed a light, aromatic, for aftertaste and pungency practically free smoke impression and is compatible with common types of tobacco in any ratio. Rating:

Sharpness: (-)

Smoke flavor : (-)

Condensate: 9.9 mg.

Example 32.

To a 5% aqueous casting solution of sodium carboxymethylcellulose/ammonium carboxymethylcellulose 3:1, the following was added:

15 parts ground pure Linter (99.8? a-cellulose)

15 parts aluminum hydroxide

5 parts. magnesium aluminum citrate Mg y/_ Al (citrate) 2- J 2

5 parts magnesium iron citrate Mg^/_ Fe (citrate) 2' The solution was poured onto a Teflon-coated metal band using a pressure pourer and dried at 130°C. The molding film had a weight of 15 g/m 2 . A 30 wt.g mixture of this product with a Virginia

Burley mixture (in a weight ratio of 3:1) showed, compared to the Virginia-Burley mixture without the product, a slight reduction in aroma, but no falsification of the aroma and no pungency (--). (Condensate: 12.4 mg). Example 33.

A commercial cigarette paper was sprayed with a 6-weight solution of magnesium aluminum citrate Mg^_/ Al2(citrate)^_/ and ammonium aluminum citrate (NHJJ Al (citrate)„_/ in a ratio of 2 : 1 and dried at 90 oC. The salt absorption amounted to 9 weight?. The taste and smell of the cigarettes produced from this were better expressed in comparison, as the treated paper no longer has any sharp

hot and some destructive cellulose aftertaste.

Examples 34 - 49.

Paper webs were used as combustible material

bleached sulphate cellulose with different filler content and basis weight. The composition of the starting foil that finds use as combustible material is listed in Table IV.

Table V lists examples for the production of smokable products by the method as well as the quantities of condensate formed by these products.

Table VI lists the production of smokable products according to table V, which also contain potassium permanganate as an oxidizing agent, as well as the quantities of condensate formed by these products.

Claims (1)

Smokeable product with a combustible material on a cellulose basis, characterized in that it contains a chelate compound of formula (I) in which K means hydrogen, magnesium, calcium or manganese (II), with at least one K being magnesium, calcium or manganese, Me means trivalent iron or aluminium, R means an anion of a chelating carboxylic acid with 2-8 carbon atoms, which besides the carboxyl group contains at least one hydroxyl or keto group, or additional carboxyl groups, z is 1/2, 1, 3/2, 2 or 3, x is 1 or 2, y is 1-4.