DE2157370A1 - Smoking mixture - based on cellulose and metal chelate cpds - Google Patents

Abstract

Smoking mixts. are made based on a mixt of a combustible cellulosic material and an alkaline earth and/or manganese -II-metal-III-chelate cpd consisting of a complex anion with Fr(III) or Al as central atom and anions of chelate-forming org. carboxylic acids as ligands. Prefd chelate cpds have the formyla Kz MexRy where K=Mg, Ca or Mn (II), Me=Fe(III) or Al and R= chelate forming org. carboxylic acid. Typical cpd is Mg3- Al2(citrate)3 . Generally the cellulose in the form of a paper-like material is treated with an aqs. soln of the chelate, opt. together with fillers, ammonia-splitting materials, oxidising agents, proteins and polygalacturonic acids, dried and shredded and opt. mixed with tobacco. The chelate improves the burning qualities of the cellulose and eliminates the sharp taste of burning cellulose from the smoke.

Description

Smokable - Products The invention relates to smokable products with cellulosic components in combination with metal chelates, ammonia-releasing agents Compounds and inorganic fillers and processes for the production of the same.

It is in making a smokable material that is not more natural Tobacco is known to be either pure tobacco waste products or mixtures thereof with other plant materials as well as with non-tobacco own, e.g. synthetic ones Products that are processed into paper-like sheets, foils or fibers be0 The processing of the manufacture of cigarettes, cigars or cut tobacco accumulating waste such as dust, grit, ribs or stalks to a film of reconstructed Tobacco is also known.

The principle underlying many processes is a grinding of the Waste products with the same or different fiber length or grain size, which contain Water and a binder mixed into a pulp and, for example, by method paper production or film casting, processed into a web or film will.

This known method can be used as a binder for the foils reconstructed tobacco tobacco pectin (US Patent 3,483,874), methyl cellulose (DOS 1 812,601), nitrocellulose (U.S. Patent 3,534,743), acylated methyl or hydroxyethyl cellulose (British Patent 1 203 940) and mineral fillers (US Patent 3,529,602) such as Clays, alkali and alkaline earth chlorides, sulfates, nitrates and phosphates added will.

When using blowing agents or by mechanical creping such Films can be used to produce particularly high-volume products. Reconstructed tobacco in thread form has also already been described (Usterr. Patent 262 125).

Furthermore, there are processes for the production of a smokable material, which are not based on any components of the tobacco plant or only their flavorings, known. Here, according to French patent specification 1 567 974 vegetable Substances such as lettuce, wild cabbage, spinach and melon tree leaves, according to US patent specification 3,106,209 are peanut and potato greens, corn and cereals, as well as according to US patent specification 2 809 904 the sugar cane press residues as starting material for a tobacco substitute used. Another option is the use of synthetic or semi-synthetic polymeric substances, for example condensed ketones (DOS-2 020 552), of degraded carbohydrates (French patent specification 1 523 686) or of oxidized cellulose (U.S. Patent 3,447,539) as a smoking material. Also for foils from synthetic materials is the addition of a variety of fillers such as Asbestos, fiberglass, clays, alkali and alkaline earth carbonates, metal oxides and hydroxides as well as sparingly soluble salts of organic acids are known.

In many cases show the synthetic or semi-synthetic products Glirnin behavior corresponding to tobacco, with unpleasant as a major disadvantage organoleptic properties, like sharpness and bad flavors occur in the main and secondary flow. So is tobacco substitutes with only a small Sulfur content, e.g. B. in the form of sulfates, a sulfidic taste of the smoke established. Certain alkaline earth ions give the smoke a dull, musty note. Cellulose products such as cellulose, regenerated cellulose, carboxymeth, oil cellulose, oxidized or ethoxylated cellulose, when smoldering under smoking conditions, provide hot, acrid smoke components which, among other things, have a lasting astringent effect in the oral cavity Leave an impact.

So far it has been difficult to deal with smoldering and burning processes to significantly reduce the sharpness of cellulosic products.

The invention now relates to new smokable products with cellulosic Ingredients, consisting of cellulosic plant material, Cellulose or cellulose derivatives and / or mixtures thereof and 0.5-70 wt, ß, based on the consumable product, an ammonium or alkaline earth metal chelate of carboxylic acids with iron or aluminum as the central atom.

Chelate complexes such as ammonium, magnesium and aluminum are particularly suitable and / or contain iron, the carboxylic acids being dicarboxylic acids such as oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid and hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxypivalic acid, tartaric acid, citric acid, malic acid, Carboxylic acids derived from pentoses and hexoses and ketocarboxylic acids are used Find.

The chelate complexes are preferably used as ammonium metal chelates or used as alkaline earth metal chelates in which an earth metal or iron forms the complex-bound central atom.

On the one hand, one can use salts of these metals of different stoichiometric Composition according to the formula for ammonium or alkaline earth metal chelates apply like: ammonium iron (III) glycolate, ammonium iron (III) oxalate, ammonium iron (II) - or iron (III) citrate, magnesium iron (III) citrate, ammonium iron (III) tartrate, Ammonium aluminum citrate, ammonium aluminum oxalate, magnesium aluminum oxalate, magnesium aluminum citrate, on the other hand, non-stoichiometric formulas that do not correspond to these formulas can also be found Use mixtures made by dissolving ammonium or alkaline earth salts organic acids can be obtained in solutions of earth metal salts of these acids. For example, neutral magnesium citrate, which is normally sparingly soluble in water, dissolves is, even at room temperature in an aluminum citrate solution in high concentration on.

The products according to the invention are organoleptic when consumed a reduced sharpness with an improved smell and taste character. With tobacco with cellulosic sharpness, the aroma is emphasized more clearly by reducing it.

Another object of the invention relates to new smokable products with cellulosic components, consisting of smokable cellulosic Plant material, cellulose or cellulose derivatives and / or mixtures thereof and 0.5-70% by weight of a metal chelate of carboxylic acids in combination with one at smoking temperature ammonia-releasing compound in a ratio of 9: 1 to 3 s 7, based on the consumable product.

Compounds which release ammonia under smoking conditions are special suitable: the acidic and neutral ammonium salts of organic acids, such as oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glycolic acid, Lactic acid, hydroxypivalic acid, tartaric acid, citric acid, malic acid, mono- and Dicarboxylic acids, which are derived from pentoses or hexoses and from ketocarboxylic acids, Acid amides such as urea, succinic acid mono- or diamide, propionic acid amide, etc. and / or Mg salts of amino acids such as Mg olutamate etc. and / or ammonium salts of Polygalacturonic acid and oligomeric galacturonic acids such as pectins, hydrolyzed Pectin, alginic acid and gum arabic and / or ammonium salts of carboxymethyl cellulose used. Ammonia itself can be used by making acidic chelating solutions adjusts to neutral to weakly ammoniacal with ammonia. It is essential that the Amount of ammonia-releasing compounds used at smoking temperature as above is measured that it only contains the acids formed during the smoldering in the smoke neutralizes, which can be easily checked by measuring the pH in the smoke.

The products according to the invention show organoleptically when roughened no more sharpness, are without astringent effect and have a tobacco-like effect Smell and taste character.

Another object of the invention relates to new useful products with cellulosic components, consisting of smokable cellulosic Plant material, cellulose or cellulose derivatives and / or mixtures thereof and 0.5-70% by weight, based on the consumable product, of a combination of Metal chelates of carboxylic acids smell under smoke.

require ammonia-releasing compounds in a ratio of 9 s 1 up to 3: 7 and taste-neutral inorganic waxes that are used under smoking conditions Split off water, in relation to the salt combination from 9: l to 1: 9.

Hydroxides and hydrated oxides are used as dehydrating compounds of aluminum and iron, natural silicates such as vermiculite, kaolin or precipitated Silicates, such as silicic acid and alkaline earth metal silicates, show the products according to the invention by dilution of the combustible organic substances and, due to the result Dehydration, reduced glow temperature, an aromatically improved organoleptic Impression. Also, smoking products that contain alkali salts show through the joint Use of compounds with metal chelates that release water at smoking temperature and compounds that release ammonia at smoke temperature show a strong reduction the severity of burns increased by the alkalis.

The smokable products according to the invention are produced by that plant leaf material such as tobacco, smokable plant materials Cellulose and / or cellulose derivatives and / or mixtures thereof in Borm of paper-like webs, fleeces, foils or threads in the form of a strand, uncut or cut with aqueous solutions of the metal complexes, the ammonia-releasing ones Connections and ssr. with suspensions of the water-repellent fillers and one Treated binder and then dried at temperatures between 50 and 120 ° C.

The paper-like webs, fleeces, foils or threads are made of cellulose, their derivatives, tobacco waste products such as extracted ribs, stems or grits, digested plant material from straw, hay, lupine and fern alone or in Mixtures produced according to the customary technical processes. In the manufacturing process can be a part or the entire amount, preferably 10-50 GewO «, of the smoking dehydrating filler are introduced. In addition, during the manufacturing process some or all of the amount, preferably 10-40% by weight, of the fillers described in the form of cellulose fibers with precipitated dehydrating when smoked Fillers are used.

Paper webs or fleeces are preferably used for the impregnation by spraying, dipping or brushing with the salt combination according to the invention used.

Films are preferably produced in such a way that the metal chelate compounds, the substances that release ammonia under smoke conditions and, if applicable, inorganic, When smoking, dehydrating compounds in a casting solution that act as a binder a polysaccharide and / or its derivatives, such as gum arabic, low-alkali carboxymethyl cellulose and / or containing ammonium carboxymethylcellulose, introduces them onto an endless belt pours and dries at 50 - 120 0C. In addition, the casting solution can contain tobacco ingredients be admitted.

The uptake of salt and filler can not only be influenced by the processing parameters, can be controlled by the structure of the film and by the viscosity of the salt solution. The viscosity can be adjusted by changing the salt concentration or by adding thickeners such as low-alkali carboxymethyl cellulose, Hydroxyethyl cellulose, pectins, gum arabic, alginates, galactomannans, starch and derivatives. It is also possible to use some or all of the salt and the filler to be incorporated into the film during the manufacturing process. Leave in all cases themselves in the same or a separate process step preparations such as humectants, flavorings, tobacco extract, treated or untreated.

By varying the components of the metal chelate, by changing it the ratio of chelate to compounds which release ammonia under smoking conditions and by changing the total amount of compounds you can be smokable Set a taste neutrality for products and tobacco own and artificial ones Adjust aroma components in a wide range. It is thus achieved that the Foil with the help of the salt-chelate combination against both aroma components there are synthetic substances or substances obtained by extracting tobacco, if applicable by treatment with ion exchangers or by distribution between not Miscible solvents were freed from fiber, as well as opposite various tobacco locations, such as Burley, Virginia and. Orient, compatible when mixed is. In any case, an unchanged, more harmonious one with regard to tobacco flavors can be achieved Realize taste impression.

The paper-like ones made by the methods described above Sheets, fleeces and foils have a weight per unit area of between 10 and 250 g / m². You own a tobacco-like handle and their processing properties (cutting behavior, Mixing behavior and filling volume) comparable to natural tobacco. Through attitudes corresponding basis weights of the carrier can be compared to filling volumes an equal amount of tobacco, and thus one when mixed with tobacco achieve a lower initial weight. This also reduces the total substance to be smoked and finally the amount of condensate when smoking is reduced. By type and amount of the filler the puff count for a puff article, e.g.

decrease, increase or keep a cigarette constant.

The smokable products of the invention are used alone or as a component in cigarette tobacco, cigar tobacco and pipe tobacco. They can also be used as cigar wrappers or wrappers or as cigarette paper insert.

Example 1.

A rough burley with a heavily cigarette nate was made with a solution of ammonium iron (III) citrate and acidic aluminum tartrate in a weight ratio 1 = 1 sprayed in such a way that the dry absorption was 5% by weight. Compared to the original the treated Burley shows a weakened heat, but spicy-aromatic Overall impression. The character of this type of tobacco is fully retained.

Example 2: Reconstructed tobacco, consisting of about 60% by weight tobacco ribs, 30% by weight of sheet waste and 10% by weight of sulphate pulp, which is mixed with.

a paper machine was made with a 5% solution so sprayed of magnesia iron citrate that its weight gain after drying 5%. Compared to the untreated sample, the one loaded with the complex salt gave Foil a lighter and more aromatic taste impression when smoked without cellulosic heat.

Example 3: A paper-like film made from a mixture (1: 1) of ground tobacco stems and sulphate pulp with a surface weight of 45 g / m² was applied in an immersion bath, the 15 parts magnesium aluminum citrate 6 parts Ammonium aluminum citrate 4 parts aluminum hydroxide 4 parts silica 11 parts tobacco extract and contained 60 parts of water.

After squeezing and drying at 95 ° C in a stream of air, a Obtained weight gain of approx. 55%. The smokable product was devoid of astringent Effect, no longer showed sharpness and gave a slightly aromatic smell and Flavor with a weakened response. When mixed with commercially available cigarette tobacco worth it as fully compatible.

Examples 4 - 12.

The starting material for the consumable products is based on a Paper machine-made foils or webs with and without filler used The various types are summarized in Table I.

Table I Foil Weight per unit area Ingredients Filler% Ash after g / m annealing A 45 bleached - 0.07 sulphate pulp B 16 "- 0.09 C 50" A1 (OH) » 29 D 68 "Vermiculite) 4 The paper-like foils A to D are placed in an immersion bath, that from the aqueous solution of the complex salt together with that when smoking ammonia-splitting compound exists, prepared. Furthermore, filler, ggr, in the presence of a binder, are present in the immersion bath. The dipped slide will squeezed when passing through a roller mill and in a stream of air at 95 ° C dried in an endless belt.

The composition of the immersion bath, the salt or filler absorption and the organoleptic properties of the film are given in Table II. To the Assessment of sharpness and cellulose taste are the following characteristics indicated0 a) sharpness ++ usual cellulose sharpness + slight sharpness, especially with Smoking - almost no sharpness, corresponding to the tobacco material - completely without sharpness b) cellulosic smoke taste ++ strong, usual cellulose taste, paper burn + slight cellulose taste - no cellulose taste, little smoke nuisance - No cellulose taste, completely neutral. Selected tobacco blends from the aforementioned Examples (Examples 13-15) The cut films of Examples 5, 6 and 8 were up to 50% by weight with a commercially available cigarette tobacco with a light note mixed and processed into filter cigarettes.

Example 13 A 70% blend of the film from Example 5 provided a round, soft aroma impression without any cellulose sharpness.

Due to the low nicotine content of the overall mixture was only the reaction weakened.

Table II Ex. Fol. Composition of the immersion bath Complex salt ammonia-releasing filler binder absorption * sharpness cellu- (g / l) conn. (g / l) (g / l) (g / l) wt.% loose- smeared 4 A 200 g magnesium aluminum 100 g ammonium - - - 29.6 - + minium citrate tartrate 5 A 100 g magnesium aluminum 100 g ammonium 250 g 10 g 25 - - aluminum citrate citrate Al (OH) 3 rubber arabic cum 6 A 200 g magnesium aluminum 50 g urea - - 36.4 - - minium citrate 7 B 19 g acidic aluminum - 30 g urea 200 g 30 g 56 - - nium tartrate Al (OH) 3 maize 84 ammonium aluminum starch minium tartrate 8 B 100 g magnesium egg 50 g urea 200 g 10 g 60 - - sen (III) citrate 50 g magnesium Al (OH) 3 rubber glutamate arabi- cum 9 C 100 g magnesium aluminum 200 g ammonium - - 24 - - minium citrate citrate 10 C 100 g magnesium aluminum 200 g ammonium 250 g 8 g 40 - - aluminum citrate citrate Al (OH) 3 rubber arabic cum 11 C 120 g magnesium egg 50 g urea - - 19.5 - - sen (III) cutrate 10 g magnesium glutamate 12 D 60 g magnesium aluminum 100 g ammonium - - - 6 - + minium citrate tartrate * Increase in% by weight after drying, based on the film used. Example 14: A 30% by weight blend of the film from Example 6 resulted in a slightly weakened aroma impression of the tobacco mixture with little residual sharpness (-). There was the same effect as in Example 10 on the reaction.

Example 15: A 30% by weight blend of the film from Example 8 becomes weaker organoleptically in terms of aroma, but perfect in terms of spiciness judged indirrerently. A cellulosic aftertaste was neither in the main stream found in sidestream smoke. The response was opposite to the examples 13 and 14 weakened even further.

Films treated with tobacco extracts (Examples 16-22) The films of Examples 7, 9 and 10 were in a solution of aqueous tobacco extract, which approximately Contains 30% by weight of soluble tobacco ingredients, dipped or sprayed with this solution, The dry absorption was up to 50% by weight. Drying was carried out with warm air at 6o to 100 ° C., Example 16: The one with a water-methanol extract from a commercial tobacco mixture with 20 wt. Ingredients acted upon film of the Example 7 gave a dry pick-up of 30% by weight.

The product obtained shows a filter cigarette in the main flow aromatic overall impression without any sharpness and without cellulosic Secondary taste and a fully aromatic side stream with clearly noticeable Reaction.

Example 17: The film of Example 9 takes from the same above The immersion bath described in the example contains 29% by weight of dry tobacco ingredients. you Taste impression is judged to be poor in aroma and indifferent, with only a low sharpness is found when smoking. The sidestream roughness is aromatic and mild.

Example 18: The film of Example 10 shows dry absorption at 25% total compared to that of example 17 a fuller taste impression with good reaction, no sharpness or a cellulosic aftertaste was found even when smoked will. The sidestream smoke is pleasantly aromatic.

Example 19: The film of Example 10 was made with a water-soluble Virginia extract sprayed such that the weight gain was 31%. At the smoke a filter cigarette made from this material will have an unadulterated, typical Virginia taste found whose flavor is not affected by the film.

Example 20: The film of example 12 was made with a water-methanol-burley extract sprayed so that the weight gain was 20 7%.

The taste impression corresponds to that of a good, characteristic Burley with a sweet note. The smoke product shows less heat than that for extraction used Burley tobacco itself. The films of Examples 16-20 are in each Mixing ratio with the aroma of the tobacco places Virglnla, Burley and Orient as well their mixtures compatible.

Example 211 The starting film C was passed through an immersion bath, the 160 g ammonium citrate, 80 g magnesium aluminum citrate and 280 g water soluble Contained tobacco ingredients and was adjusted to pH 7 with ammonia. The dry pickup was 50% by weight. The film alone shows a slight, aromatic, aftertaste and sharpness-free smoke impression and is in every proportion with the usual types of Tibak compatible.

Example 22: A 5% aqueous casting solution of sodium carboxymethyl cellulose / ammonium carboxymethyl cellulose 3: 1 are added 15 parts of ground pure linters, 15 parts of aluminum hydroxide 5 parts magnesium aluminum citrate 5 parts magnesium iron citrate The solution is made up an endless Teflon-coated metal band is cast by means of a die caster and dried at 130 ° C.

The cast film has a weight of 15 A 30 wt.% Mixing this film with a Virginia-Burley mixture 3: 1 shows opposite. the original a slight weakening of the aroma but no adulteration of the aroma and no sharpness Example 23t A commercially available cigarette paper was used with a 6 Weight

own solution of magnesium aluminum citrate and ammonium aluminum citrate sprayed in a ratio of 2: 1 and dried at 90 ° C. The salt intake was 9% by weight. The taste and smell of the cigarettes made with it came on the opposite side A comparison is easier to print out because the paper treated with the complex salts had no sharpness and no more annoying cellulosic aftertaste.

The use of the invention can be restricted by statutory provisions, in particular by the food law.

Claims (19)

Patent claims: 1. Rauqhbaren products with cellulosic components, consisting from consumable cellulose-containing plant material, cellulose or cellulose derivatives and / or mixtures thereof with improved smell and taste character, thereby characterized in that they are 0.5-70% by weight, based on the consumable product of a Ammonium or alkaline earth metal chelates of carboxylic acids with iron or aluminum contained as a central atom, 2. Smokable products according to claim 1, characterized in that that as a metal chelate complex a magnesium or ammonium aluminum citrate and / or Magnesium or ammonium iron citrate is used. 3. Smokable products according to claim 1, characterized in that as metal chel atkomple x an ammonium aluminum tartrate and / or ammonium iron tartrate is used. 4. Smokable products with cellulosic components, consisting of from consumable cellulose-containing plant material, cellulose or cellulose derivatives and / or mixtures thereof without cellulosic sharpness and without astringent Effect, characterized in that it is 0.5-70% by weight, based on the consumable Product of a mixture of metal chelates of carboxylic acids and under smoking conditions ammonia-releasing compounds in a ratio of 9 t 1 to 3 t 7. 5. Smokable products according to claim 4, characterized in that ammonium nitrate and / or tartrate can be used as the ammonia-releasing compound. 6. Usable products according to claim 4, characterized in that urea is used as the ammonia-releasing compound. 7. Smokable products according to claim 4, characterized in that Magnesium glutamate is used as the ammonium-releasing compound. 8. Smokable products with cellulosic components, consisting of from consumable cellulose-containing plant material, cellulose or cellulose derivatives and / or mixtures thereof with improved smell and taste character, thereby characterized in that they, 5 - 70 wt.%, Based on the consumable product, a Combination of metal chelates of carboxylic acids with those that release ammonia at smoking temperature Compounds in the ratio 9 t 1 to 3 t 7 and tasteless inorganic Fillers that release water under smoking conditions in relation to the salt combination ton 9 t 1 to 1 z 9 included. 9. Smokable products according to claim 8, characterized in that aluminum hydroxide is used as the water-releasing inorganic filler. 10. Smokable products according to claim 8, characterized in that As water-releasing inorganic fillers, precipitated silica and / or vermiculite is used. 11. Smokable paper-like webs, fleeces, foils or threads h6 «h claims 1, 4 and 8, characterized in that it contains 95 to 30% by weight of cellulose, Cellulose derivatives, tobacco waste products, digested plant material alone or contained in mixtures. 12. Smokable products according to claim ll, characterized in that they contain 5 - 50% by weight of low-alkali soluble tobacco ingredients 13. Procedure for the production of smokable products, characterized in that cellulose, Cellulose derivatives, tobacco waste products, digested plant material alone or in mixtures in the form of paper-like webs, fleeces or threads with a aqueous solution of a metal chelate complex of carboxylic acids and one at smoking temperature Treated ammonia-releasing compound, the solution optionally one at smoke temperature contains dehydrating filler in dispersed form, and at Temperaturn dries between 60 and 120 0C. 14. A method for making a paper-like web according to claim 13, characterized in that a paper web with 40% aluminum hydroxide for coating is used. 15. A method for making a paper-like web according to claim 13, characterized in that the paper web used for coating consists of unprecipitated cellulose fibers with 30 ffi aluminum hydroxide. 16. A method for producing smokable films according to claim 8, characterized in that the components in a casting solution of low alkali Carboxymethyl cellulose and / or ammonium carboxymethyl cellulose or gum arabic dissolves or disperses, pours onto an endless steel belt and at 90 - 120 0C dries. 17. A method for producing smokable films according to claim 16, characterized in that tobacco ingredients are added to the casting solution. 18. Use of the smokable products according to claims 1-12 as mixture components in cigarette, cigar and pipe tobacco. 19. Use of the smokable products according to claims 1-12 as cigarette paper or cigar wrapper.