U.S. patent number 3,924,642 [Application Number 05/306,655] was granted by the patent office on 1975-12-09 for tobacco and tobacco substitute material including metal chelate compounds.
This patent grant is currently assigned to Haarmann & Reimer GmbH. Invention is credited to Theo Eicher, Klaus-Werner Krebs, Friedemann Muller.
United States Patent |
3,924,642 |
Eicher , et al. |
December 9, 1975 |
Tobacco and tobacco substitute material including metal chelate
compounds
Abstract
In a smokable product comprising a cellulose-based combustible
material, the improvement which comprises incorporating therein at
least one chelate compound of the stoichiometric formula. K.sub.z
[Me.sub.x R.sub.y ].sub.w In which K is an alkaline earth metal or
divalent manganese, Me is trivalent iron or aluminum, R is the
radical of a chelate-forming organic carboxylic acid, and w, x, y,
and z are integers up to about 5, The chelate compound being
incorporated in an amount ranging from about 0.5 to 70% by weight
of the combustible material. Preferably R is the radical of an
organic dicarboxylic acid containing 2 to 8 carbon atoms or a
hydroxy- or keto-substituted carboxylic acid. The product may also
contain fillers, compounds which split off ammonia, oxidizing
agents, ammonium salts of polymeric acids, low sulfur-content
proteins and/or tobacco extracts. The product may be used as such
or in blends with tobacco as cigarettes, cigars or pipe
tobacco.
Inventors: |
Eicher; Theo (Dormagen,
DT), Muller; Friedemann (Dormagen, DT),
Krebs; Klaus-Werner (Dormagen, DT) |
Assignee: |
Haarmann & Reimer GmbH
(Holzminden, DT)
|
Family
ID: |
25762035 |
Appl.
No.: |
05/306,655 |
Filed: |
November 15, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Nov 19, 1971 [DT] |
|
|
2157370 |
Mar 29, 1972 [DT] |
|
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2215412 |
|
Current U.S.
Class: |
131/359 |
Current CPC
Class: |
A24B
15/16 (20130101) |
Current International
Class: |
A24B
15/00 (20060101); A24B 15/16 (20060101); A24B
015/00 (); A24B 015/02 () |
Field of
Search: |
;131/2,15,17,200,201,10-10.9,140-144,261,262,264,265,266,267 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
The Chemistry and Technology of Tobacco (Text), by A. A. Shmuk,
published by Pishchepromizat, Moscow, 1953 and by the The National
Science Foundation, 1961, pp. 588, 590, 602 and 603 cited. .
"Dangerous Properties of Industrial Materials," (Text) by N. Irving
Sax, p. 888 cited pub. by the Reinhold Book Corp., N.Y.
(1968)..
|
Primary Examiner: Rein; Melvin D.
Attorney, Agent or Firm: Burgess, Dinklage & Sprung
Claims
What is claimed is:
1. In a smokable product comprising a cellulose-based combustible
material, the improvement which comprises incorporating therein at
least one chelate compound of the stoichiometric formula.
K.sub.z [Me.sub.x R.sub.y ].sub.w
in which
K is an alkaline earth metal or divalent manganese,
Me is trivalent iron or aluminum,
R is the radical of a chelate-forming organic carboxylic acid,
and
w, x, y and z are integers up to about 5,
the chelate compound being incorporated in an amount ranging from
about 0.5 to 70% by weight of the combustible material.
2. A smokable product according to claim 1, wherein K is
magnesium.
3. A smokable product according to claim 1, wherein the organic
carboxylic acid has from 2 to 8 carbon atoms and is substituted
with at least one hydroxy or keto group or has at least two
carboxylic acid groups.
4. A smokable product according to claim 3, wherein the organic
carboxylic acid is a material selected from the group consisting of
oxalic, glyceric, glycolic, malic, tartaric, citric, galactaric and
saccharic acids.
5. A smokable product according to claim 1, wherein x is 1 or 2 and
y is from 1 to 4.
6. A smokable product according to claim 1, wherein the chelate
compound is incorporated in an amount ranging from about 5 to 50%
by weight of the combustible material.
7. A smokable product according to claim 1, wherein the chelate
compound is a material selected from the group consisting of
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 and manganese-aluminum
saccharate.
8. A smokable product according to claim 1, containing about 1 to
70% by weight of at least one filler selected from the group
consisting of minerals and salts which are inert under conditions
of smoking, and hydroxides and hydrated oxides which split off
water under conditions of smoking.
9. A smokable product according to claim 8, wherein the filler is
at least one material selected from the group consisting of
hydrated oxides of aluminum and silicic acid.
10. A smokable product according to claim 1, containing at least
one compound which splits off ammonia under conditions of smoking
and which is present in an amount such that the smoke has a pH of
about 5 to 8.
11. A smokable product according to claim 10, wherein the compound
which splits off ammonia is at least one material selected from the
group consisting of ammonium salts of inorganic acids, ammonium
salts of organic acids, salts of amino acids and acid amides.
12. A smokable product according to claim 10, wherein the compound
which splits off ammonia is at least one material selected from the
group consisting of acid or neutral ammonium carbonate, nitrate or
phosphate, ammonium citrate, ammonium tartrate, ammonium or
magnesium glutamate, urea, ammonium-iron (III) glycolate,
ammonium-iron (III) oxalate, ammonium-iron (III) citrate,
ammonium-iron (III) tartrate, ammonium-iron-(III) galactarate,
ammonium-iron (III) saccharate, ammonium-aluminum glycolate,
ammonium-aluminum oxalate, ammonium-aluminum citrate,
ammonium-aluminum tartrate, ammonium-aluminum galactarate and
ammonium-aluminum saccharate.
13. A smokable product according to claim 1, containing about 0.01
to 7% by weight of at least one oxidizing agent selected from the
group consisting of alkali metal or alkaline earth metal nitrates
and alkali metal permanganates.
14. A smokable product according to claim 1, containing about 0.01
to 10% by weight of the ammonium salt of at least one polymeric
acid selected from the group consisting of pectin, alginic acid,
gum arabic or carboxymethylcellulose.
15. A smokable product according to claim 1, containing about 0.01
to 5% by weight of at least one low sulfur-content protein selected
from the group consisting of zein, hordein and gliadin.
16. A smokable product according to claim 1, containing about 0.1
to 50% by weight of a tobacco extract.
17. A smokable product according to claim 7, wherein x is 1 or 2
and y is from 1 to 4 and the chelate compound is incorporated in an
amount ranging from about 5 to 50% by weight of the product; said
product optionally containing about 1 to 70% by weight of at least
one material selected from the group consisting of hydrated oxides
of aluminum and silicic acid; at least one compound which splits
off ammonia under conditions of smoking and which is present in an
amount such that the smoke has a pH of about 5 to 8, said compound
being selected from the group consisting of acid or neutral
ammonium carbonate, nitrate and phosphate, ammonium citrate,
ammonium tartrate, ammonium or magnesium glutamate, urea,
ammonium-iron (III) glycolate, ammonium-iron (III) oxalate,
ammonium-iron (III) citrate, ammonium-iron (III) tartrate,
ammonium-iron-(III) galactarate, ammonium-iron (III) saccharate,
ammonium-aluminum glycolate, ammonium-aluminum oxalate,
ammonium-aluminum citrate, ammonium-aluminum tartrate,
ammonium-aluminum galactarate and ammonium-aluminum saccharate;
about 1 to 5% by weight of at least one oxidizing agent selected
from the group consisting of alkali metal or alkaline earth metal
nitrates and alkali metal permanganates; about 0.01 to 10% by
weight of the ammonium salt of at least one polymeric acid selected
from the group consisting of pectin, alginic acid, gum arabic or
carboxymethylcellulose; about 0.01 to 5% by weight of at least one
low sulfur-content protein selected from the group consisting of
zein, hordein and gliadin; and about 0.1 to 50% by weight of a
tobacco extract; said cellulose-based combustible material being in
the form of a paper-like web of about 10 to 120 .mu. in thickness
and weighing about 10 to 250 grams per square meter.
18. A smokable product according to claim 17, blended with
tobacco.
19. A smokable product according to claim 1, in the form of a
cigarette or cigar.
20. The process for making a smoking product according to claim 17
which comprises applying to a paper-like web of said
cellulose-based combustible material of about 10 to 120 .mu. in
thickness an aqueous solution containing said chelate compound,
said filler, said compound which splits off ammonia, said oxidizing
agent, said ammonium salt of polymeric acid, said protein and said
tobacco extract, and drying, application being effected by spraying
or painting said solution onto said web or by immersing said web in
said solution, the impregnated web on a solvent-free basis weighing
about 10 to 250 grams per square meter.
21. The process for making a smoking product according to claim 17,
which comprises forming a solution containing said cellulose-based
combustible material, said chelate compound, said filler, said
compound which splits off ammonia, said oxidizing agent, said
ammonium salt of polymeric acid, said protein and said tobacco
extract, casting said solution to form a sheet having a
solvent-free weight of about 10 to 250 grams per square meter, and
drying said sheet to remove the solvent and leave the sheet with a
thickness of about 10 to 120 .mu..
22. A smokable product according to claim 1, wherein the
combustible material is selected from the group consisting of
tobacco, tobacco waste products, hay, straw, lupins, fern,
cellulose, wood pulp, carboxymethyl cellulose, hydroxyethyl
cellulose and methyl cellulose.
Description
This invention relates to smoking products which contain
combustible materials based on cellulose together with other
constituents, in particular metal chelates, and to a process for
producing them.
It is known how to produce a smokable material, which is not
natural tobacco, from tobacco waste products or mixtures thereof
with other plant materials, as well as from natural or synthetic
non-tobacco products, which are made up into paper-like webs or
foils or fibres. According to DOS No. 1,900,491, for example,
smoking materials can be produced from cellulose, cellulose
derivatives or starch using certain inorganic fillers which keep
the material glowing. According to U.S. Pat. No. 3,461,879,
hydrated magnesium citrate and calcium tartrate may be added to
certain cellulose derivatives to assist the combustion process.
The non-tobacco smokable products produced by the previously known
processes do not have satisfactory organoleptic properties but on
the contrary organoleptic properties which are unpleasant to a
greater or lesser degree, e.g. sharpness and poor aroma in the main
and side streams. For example, even tobacco substitute products
with only a low sulphur content, e.g. in the form of sulfates, are
found to produce a smoke with an unpleasant sulfidic flavor.
Tobacco substitute products with a high cellulose content which
contain the alkali metal, alkaline earth metal and iron salts
normally present in smokable products give rise, when allowed to
glow, to a sharp and biting smoke with a cellulosic flavor and
leave behind a persisting astringent effect in the mouth. Moreover,
the known non-tobacco smoking products generally manifest an
organoleptic incompatibility with numerous sorts of tobacco when
blended with them.
For example, the addition of substances such as magnesium citrate
or calcium tartrate which, according to the prior art, may be added
to a smoking material to improve its glowing properties, results in
smoking products which are completely unsatisfactory in their
organoleptic properties. The sharpness of the smoking products is
not sufficiently reduced. A particularly disturbing feature of such
a product is that the burning of the cellulosic material in it
gives rise to an unpleasant flavor (cellulosic flavor) and to a
smell of burnt paper, which are practically the same as the smell
and flavor of burning pure cellulose. These products are therefore
not economically utilizable as smokable products or as additions to
smokable products.
Other disadvantages of the known non-tobacco smokable products are
their low bulk volume, their generally insufficient wet strength
and their low mechanical strength, which leads to an excessive
production of dust in processing.
It is accordingly an object of the present invention to provide a
smokable product which has desirable organoleptic properties and a
relatively low content of undesired condensible materials in its
smoke and which is free of the disadvantages noted hereinabove.
These and other objects and advantages are realized in accordance
with the present invention pursuant to which there is provided a
cellulose-based combustible material having incorporated therein
trivalent metal chelate compounds of alkaline earth metals and/or
of manganese, the trivalent metal chelate compounds being complex
anions which contain trivalent iron or aluminum as the central atom
and the anions of chelate-forming organic carboxylic acids as
ligands.
A smokable product comprising a combustible material based on
cellulose has now been found characterised in that the smokable
product contains metal (III) chelate of alkaline earth metals
and/or of manganese (II), the "metal (III) chelate compounds" being
complex anions which contain trivalent iron or aluminium as the
central atom and the anions of chelate-forming organic carboxylic
acids as ligands.
The alkaline earth metal-metal (III)-chelate compounds used in the
products according to the invention may be, for example, the
calcium or magnesium compounds.
The chelate compounds used in the products according to the
invention will hereinafter be referred to simply as "chelates."
The term chelate is therefore used to denote complex salts with a
chelate structure which contain alkaline earth metal ions or
manganese (II) ions as the cation, and as the anion, a chelate
complex consisting of iron (III) ions or aluminium ions as the
central atom and chelate-forming organic carboxylic acids as
ligands (see, e.g., A. E. Martell, M. Calvin, Die Chemie der
Metall-Chelat-Verbindungen, page 204, Verlag Chemie, Weinheim
(1958)).
Smokable products according to the invention may preferably contain
at least one chelate compound of the stoichiometric formula I
K.sub.z [Me.sub.x R.sub.y ].sub.w (I)
in which:
K is an alkaline earth metal or divalent manganese,
Me is trivalent iron or aluminum,
R is the radical of a chelate-forming organic carboxylic acid,
and
w, x, y and z are integers up to about 5,
In general, x denotes 1 or 2 and y denotes integers of from 1 to 4,
and z resp. w denote the number of divalent cations K resp. anions
and depend on the number of free negative valencies remaining in
the anion complex.
The cations of the chelates contained in the products according to
the invention may be calcium, magnesium or manganese (II),
preferably magnesium or manganese (II).
In some cases, it has been found advantageous partly to replace the
cations of the chelates by hydrogen so that the corresponding acid
salts are formed. Acid chelates which contain one hydrogen ion are
preferred.
Chelate-forming organic carboxylic acids, hereinafter referred to
as "Chelate formers" (see A. E. Martell, M. Calvin, Die Chemie der
Metallchelatverbindungen (pages 462-517) Verlag Chemie, Weinheim
(1958), are, for example, organic carboxylic acids which contain 2
to 8 carbon atoms and in addition to the carboxylic group contain
at least one hydroxyl group, keto group or additional carboxyl
group.
Chelate formers may therefore for example be dicarboxylic acids.
The following are mentioned as examples of dicarboxylic acids:
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. Hydroxy acids such as hydroxymonocarboxylic acids,
hydroxydicarboxylic acids and hydroxytricarboxylic acids may also
be chelate formers. Examples of such hydroxymonocarboxylic acids
are: lactic acid, glycolic acid, .beta.-hydroxypropionic acid,
glyceric acid and hydroxypivalic acid. Glycolic acid and glyceric
acid are particularly preferred hydroxymonocarboxylic acids. The
following are mentioned as examples of hydroxydicarboxylic acids
and hydroxytricarboxylic acids: hydroxymalonic acid, malic acid,
tartaric acid, 2-hydroxglutaric acid, 3-hydroxyglutaric acid,
3-methylmalic acid, 2,5-dihydroxyadipic acid, 2,4-dihydroxyadipic
acid and citric acid, among which malic acid, tartaric acid and
citric acid are preferred.
Mono- and dicarboxylic acids derived from pentoses and hexoses, for
example, may also be chelate formers. Examples of these chelate
formers are the isomeric monocarboxylic acids known as uronic
acids, for example, glucuronic acid, galacturonic acid and
mannuronic acid, the compounds known as saccharic acids, e.g.
saccharic acid itself, manosaccharic acid and idosaccharic acid, as
well as the isomeric mucic acids (galactaric acids). The pentaric
acids derived from pentoses, ribotrihydroxyglutaric acid and
xylotrihydroxyglutaric acid may also be mentioned as examples.
Ketocarboxylic acids containing 3 to 8 carbon atoms may be used as
chelate formers which contain a keto group. Examples of keto
carboxylic acids are: pyroracemic acid, acetoacetic acid.
laevulinic acid and mesoxalic acid.
The preferred chelate formers used are dicarboxylic acids and
hydroxycarboxylic acids, in particular oxalic acid, glyceric acid,
glycolic acid, malic acid, tartaric acid, galactaric acid,
saccharic acid and citric acid.
It has been found particularly advantageous, for example, to use
chelates of the general formula (I) which have 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.
The chelates used in the smokable products according to the
invention may, for example, have the composition indicated in Table
(I). The compounds shown in Table (I) correspond to the general
formula (I) (K.sub.z [Me.sub.x R.sub.y ].sub.w), in which K
represents magnesium, calcium or manganese (II), Me represents iron
(III) or aluminum and R represents the chelate-forming carboxylic
acid. The values indicated for x, y, w and z are substituted in the
general formula (I) in each case to give the summation formula of
the given example of chelate.
Table I ______________________________________ R x y free negative
z w valences ______________________________________ citrate 1 2 3 3
2 citrate 1 2 6 3 1 citrate 1 3 6 3 1 citrate 2 3 6 3 1 tartrate 1
1 1 1 2 tartrate 1 2 3 3 2 tartrate 1 3 3 3 2 tartrate 2 3 4 2 1
oxalate 1 2 1 1 2 oxalate 1 3 3 3 2 oxalate 1 4 4 2 1 glycolate 1 2
1 1 2 glycolate 1 3 3 3 2 galactarate 1 1 1 1 2 galactarate 1 1 2 1
1 galactarate 1 2 3 3 2 galactarate 1 3 3 3 2
______________________________________
Particularly preferred chelate formers are tartaric acid, citric
acid and galactaric acid.
Particularly preferred chelates are magnesium-iron-(III)-tartrate,
magnesium-iron-(III) citrate, magnesium-aluminium tartrate,
magnesium-aluminum citrate, manganese-iron-(III)-galactarate and
manganese-iron-(III)-citrate.
The chelates contained in the smokable products according to the
invention may be prepared in known manner in aqueous solution, e.g.
by reacting the iron or aluminum salts of the desired
chelate-forming carboxylic acids with calcium magnesium or
manganese salts, which may be added as hydroxides, carbonates or
salts of the corresponding chelate-forming carboxylic acids (see
DRP 514,504; Hanus and Quadrate Z Anorg. Chem. 63, page 314 (1909)
and W. Franke, Liebig Ann. Chem. 486, page 248 (1931)).
Examples of combustible materials based on cellulose are:
cellulose-containing plant materials, particularly tobacco, tobacco
waste products, e.g. stalks, ribs or fragments, decomposed
cellulose-containing plant material such as for example hay, straw,
lupins or fern, as well as cellulose or wood pulp or cellulose
derivatives, alone or as mixtures. The cellulose derivatives used
may be, for example, carboxymethyl cellulose, hydroxyethylcellulose
or methyl cellulose.
The combustible materials used may also be polymerlike lower
molecular weight fragments of cellulose obtained by thermal
degradation of cellulose, or they may be cellulose derivatives
prepared by chemical processes, particularly by alkaline or acid
oxidation.
Particularly satisfactory results are obtained by the use of
tobacco or of paper-like webs composed of tobacco waste products or
of cellulose or wood pulp.
The smokable products according to the invention generally contain
about 0.5 to 70% by weight of chelate, based on the total weight of
combustible material used in the products. It has been found
advantageous to adjust the quantity of chelate according to the
cellulose content of the combustible material used. If, for
example, the cellulose content of the combustible material is about
10% by weight, then the quantity of chelate used is preferably
about 1 to 15% by weight, based on the total weight, and in
particular about 5 to 10% by weight. If the cellulose content of
the combustible material is higher than 70% by weight, the quantity
of chelate used, based on the total weight, is about 10 to 70% by
weight, preferably 25 to 50% by weight.
According to a preferred embodiment of the invention, the smokable
products contain a filler. By fillers are meant minerals, inorganic
salts and oxides which have no effect on the flavor under smoking
conditions, for example silica, silicates, mica, alumina, dolomite,
magnesite and chalk or carbonates, phosphates and oxides of
aluminum iron, magnesium and calcium. Inert fillers which split off
water under smoking conditions may also be used. This elimination
of water may be due to the presence of a large quantity of water of
crystallization in the filler or it may be due to chemical
decomposition, e.g. from metal hydroxides. Fillers which have been
found to be particularly advantageous are the hydroxides and
hydrated oxides of aluminum and iron, natural silicates such as
vermiculite and kaolin, precipitated silicates such as silicic
acid, silica gel, silica sol and alkaline earth metal and alkali
metal silicates, the hydrated oxides of aluminum and/or silicic
acid being preferred. It is generally suitable to use about 1 to
70% by weight of fillers, based on the total quantity of smokable
product. The quantity used is preferably about 15 to 50% by
weight.
It has been found particularly advantageous to use the fillers in
ratios within the range of about 9:1 to 1:9, inclusive, based on
the quantity of chelate used.
According to another preferred embodiment of this invention, the
smokable products contain compounds which split off ammonia under
smoking conditions, in particular, ammonium salts of inorganic
acids and organic carboxylic acids, salts of amino acids and acid
amides.
The preferred compounds which split off ammonia under smoking
conditions are the acid and neutral ammonium salts of inorganic
acids such as carbonic acid, nitric acid and phosphoric acid,
particularly the ammonium salts of phosphoric acid.
Good results are also obtained with the acid and neutral ammonium
salts of organic carboxylic acids which have a carbon to oxygen
ratio in the overall formula within the range of about 2:1 to 1:2,
inclusive, preferably about 1:1 to 1:2, inclusive. Suitable
ammonium salts are therefore, for example the ammonium of
monocarboxylic acids such as formic acid and acetic acid, ammonium
salts of dicarboxylic acids such as oxalic acid, malonic acid and
succinic acid, ammonium salts of hydroxymono-, hydroxydi- and
hydroxytricarboxylic acids such as glycolic acid, lactic acid,
.beta.-hydroxypropionic acid, glyceric acid, malic acid, tartaric
acid and citric acid, and the ammonium salts of mono- and
di-carboxylic acids derived from pentoses and hexoses, such as
glucuronic acid, galacturonic acid and mannuronic acid, saccharic
acid and the isomeric mucic acids. Ammonium tartrate and ammonium
citrate are preferred.
The ammonium salts corresponding to the chelates according to the
invention ("K" representing ammonium in the general formula (I) are
also very advantageous to use as compounds which split off ammonia.
The following ammonium chelate compounds are preferably used:
ammonium-iron-(III)-glycolate, ammonium-iron-(III)-oxalate,
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.
Ammonium-iron-(III)-citrate, ammonium-iron-(III)-tartrate,
ammonium-iron-(III)-galactarate, ammonium-aluminium citrate and
ammonium-aluminum tartrate are particularly preferred.
It has also been found advantageous to use acid amides as compounds
which split off ammonia, for example acetamide, propionamide,
succinic acid monoamide and diamide and particularly urea.
Ammonium, magnesium or manganese (II) salts of aminoacids may also
be used as compounds which split off ammonia, the aminoacids being
preferably glycine, serine, lysine, arginine, leucine, proline,
valine, aspartic acid or glutamic acid. Magnesium glutamate and
manganese glutamate are particularly preferred as compounds which
split off ammonia.
The compounds which split off ammonia are used, for example, in
quantities of about 1 to 25% by weight, based on the smokable
product, preferably about 5 to 15% by weight.
It has been found suitable to adjust the quantity of compounds
which split off ammonia under smoking conditions so that the acids
which are formed in the smoke when the smokable product smolders
are neutralized. This can easily be controlled by pH measurements
in the main stream smoke. The compounds which split off ammonia are
advantageously added in such quantities that the pH of the main
stream smoke is adjusted to about 5 to 8, preferably 6 to 7.5.
According to another special embodiment of the invention, the
smokable products contain about 0.01 to 7% by weight, preferably
about 1 to 5% by weight based on the total weight of the smoking
product, of an oxidizing agent. By oxidizing agent is meant a
substance which improves the glowing of the smoking product.
The oxidizing agents used may be, for example, salts of nitric
acid, particularly alkali metal or alkaline earth metal nitrates.
The nitrates preferably used are potassium nitrate and/or sodium
nitrate.
Oxidizing agents which have been found to be particularly
advantageous in the smokable products according to the invention
are compounds of manganese (VII), in particular alkali metal
permanganates, e.g. potassium permanganate.
According to another preferred embodiment of the invention, the
smokable products contain about 0.01 to 10% by weight, preferably
about 0.1 to 5% by weight, based on the smokable product, of
ammonium salts of polygalacturonic acids such as pectin, alginic
acid or gum arabic and/or ammonium salts of carboxymethyl
cellulose.
Satisfactory organoleptic properties are also obtained when using
about 0.01 to 5% by weight, preferably about 0.1 to 3% by weight,
based on the smokable product, of proteins which have a low sulfur
content, e.g. zein, hordein or gliadin, as well as the alcoholic
extracts of these proteins, e.g. the ethanol extracts. Apart from
liberating ammonia in the smokable products, these compounds impart
a pleasant plant flavor with a tobacco-like note. The smokable
products obtained by this method are completely compatible in their
aroma with any tobacco with which they may be blended.
According to another preferred embodiment, the smokable products
contain about 0.1 to 50% by weight, based on the total weight of
smokable product, of tobacco constituents. Tobacco constituents are
substances or groups of substances which can be obtained from
tobacco by known processes, e.g. by pressing, distillation or
extraction. It is preferred to use tobacco constituents which have
been obtained by extraction carried out, for example, with water or
organic solvents.
The combustible material which forms the basis of the smokable
products according to the invention may be in the form of a
paper-like-web, a fleece, a foil or a thread or strand, cut or
uncut. The paper-like webs, fleeces or the like may be produced by
known technical processes (see Ullmanns Enzyklopadie der techn.
Chemie, 3rd Edition, Volume 13, pages 122-130 (1962) and ibid.
Volume 17, pages 288 to 296 (1966)).
It has been found particularly advantageous to produce the product
according to the invention in the form of paper-like webs with a
surface weight of about 10 to 250g/m.sup.2, preferably about 15 to
60 g/m.sup.2 and thicknesses generally in the region of about 10 to
120 .mu., preferably about 20 to 60 .mu., and particularly about 30
to 45 .mu..
The smokable products according to the invention may be produced,
for example, by applying the chelates used according to the
invention in the form of a solution, preferably an aqueous
solution, to the combustible material based on cellulose which is
in the form of a paper-like web, a fleece, a foil or a thread or
strand, cut or uncut. Application of the chelate solution may be
carried out, for example, by immersing the combustible material in
a bath of the solution of chelate compounds and then drying it,
advantageously at temperatures of about 50.degree. to 120.degree.C.
Alternatively, the material may be sprayed or painted with the
solution of chelates. Furthermore, the chelates may be introduced
directly into the starting mixture from which the combustible
material is produced, e.g. in the form of paper-like webs, fleeces,
foils, threads or strands.
The chelates may, for example, be introduced directly into a
casting solution containing the combustible material. These casting
solutions may advantageously contain about 0.1 to 20% by weight of
a binder, in addition to optional fillers compounds which split off
ammonia, oxidizing agents and tobacco constituents. The binders may
be for example polysaccharides or their derivatives, gum arabic,
starch, carboxymethylcellulose with a low alkaline content and/or
ammonium-carboxymethylcellulose. If the binder comprises a
combustible material based on cellulose, it may, of course, take
over the function of combustible material in the products according
to the invention. The products according to the invention may be
produced, for example, by pouring the casting solution on to an
endless band and by drying at 50.degree.C to 120.degree.C.
The smokable products according to the invention are preferably
produced using paper-like webs or fleeces.
The amount of chelates taken up by the foil or fleece may be
controlled not only by the various operating conditions but also by
the structure of the foil and the viscosity and concentration of
the chelate solution. Adjustment of the viscosity can be achieved
for example by varying the concentration of the solution of
chelates or by adding thickeners such as a carboxymethylcellulose
which has a low alkaline content, a hydroxyethyl, cellulose,
pectins, gum arabic, alginates, galactomanan, starch and
derivatives thereof. A high uptake of salts into the smokable
product is possible, for example, by using concentrated, highly
viscous solutions.
The fillers which may be used according to a preferred embodiment
of the invention may be incorporated into the combustible material
at the same time as the chelates. Alternatively, they may be
incorporated partly or completely in a separate stage of the
process before or after the treatment with chelates. Incorporation
of the fillers may be carried out by known technical methods
employed for producing paper-like webs, fleeces or foils which
contain fillers.
The compounds which split off ammonia, which may also be used
according to a preferred embodiment of the invention, may be
introduced into the combustible material either together with the
chelates or in a separate stage of the process before or after
incorporation of the chelates. Introduction of the compounds which
split off ammonia is carried out e.g. by spraying or painting the
combustible material with aqueous solutions of the compounds which
split off ammonia, or by immersing the material in such solutions,
and then drying the material.
The oxidizing agents used according to a preferred embodiment of
the invention may be introduced into the combustible material at
the same time as the chelates or before or after their
incorporation into the material.
Introduction of the oxidizing agents is carried out e.g. by
spraying or painting the combustible material with an aqueous,
alcoholic or acetonic solution of the oxidizing agent or by
immersing the material in such a solution.
The ammonium salts of polygalacturonic acids used according to
another preferred embodiment of the invention, as well as the
proteins with a low sulfur content and their alcoholic extracts,
and the tobacco constituents which are used according to a further
embodiment of the invention, may be introduced together with the
chelates or before or after the latter are incorporated into the
combustible material. They are preferably incorporated into the
combustible material together with or after the chelates.
In all the embodiments, the usual additives employed in tobacco
processing, e.g. moisturizing agents, "flavor" and nicotine, may be
introduced in the same or separate process steps.
The preferred embodiments of the process for producing the smokable
products according to the invention may, of course, be applied in
any combination.
When the products according to the invention are compared with
smokable products produced from the same combustible material to
which the combustion modifying substances of the prior art have
been added, it is found that when smoked, the products of the
invention are organoleptically less acrid, they have a pleasant,
mild flavor without any astringent effect the aroma is improved.
For example, when the smokable products according to the invention
are added to tobaccos which have a cellulosic sharpness or when
such tobaccos are treated by the process according to the
invention, then not only is the sharpness reduced but the aroma of
these tobaccos is greatly enhanced. The smokable products according
to the invention are not only distinguished by their exceptionally
low condensate value but also have excellent glowing properties.
The smokable products according to the invention are particularly
distinctive in producing a smoke which has no cellulose flavor and
therefore no organoleptically irritating components.
Smoke analyses of smokable products according to the invention show
in part a considerable reduction in physiologically harmful
substances as compared with those found in tobacco. Thus, a
cigarette containing the products according to the invention is
found to have a substantially lower phenol content and hydrocyanic
acid content as well as substantially lower condensate values than
a cigarette comprising tobacco. For example, when comparing
cigarettes produced from cellulose foils containing a filler and
treated with chelates with cigarettes produced from tobacco, the
phenol content in each cigarette was found to be reduced by more
than 90%, the hydrocyanic acid content by about 40% and benzpyrene
content by about 25%. The quantity of dry condensate could be
reduced by about 80 to 90% compared with that in tobacco.
The addition of the smokable products according to the invention to
tobacco can have an advantageous influence on the burning
properties of tobacco, especially in that the amount of
physiologically harmful substances in the smoke is substantially
reduced, as was to be expected from the individual components of
these mixtures.
The aroma and flavor of the smokable products can be varied and if
desired, for example, the flavor can be neutralized, by varying the
chelates used as well as the other components which are added
according to various preferred embodiments of the invention, e.g.
by adjusting the ratios of the quantity of chelate compounds to the
quantity of compounds which split off ammonia under smoking
conditions. By means of the process according to the invention
therefore, the characteristics of the smokable products can easily
be adjusted to those of various synthetic aromatic components or
aromatic components obtained by extraction from tobacco as well as
to those of various kinds of tobacco such as Burley, Virginia or
Oriental with which the smokable products may be blended. A
harmonious blend of tobacco aromas and flavors can therefore be
obtained in every case and constantly reproduced. Application of
the chelates contained in the products according to the invention
is found to be particularly advantageous because these compounds
are generally readily soluble in water. Homogeneous distribution of
the chelates in the smokable products can therefore easily be
achieved in one step. Due to their low tendency to crystallization
and their hygroscopic properties, the products obtained by the
process according to the invention are smooth and elastic and
therefore particularly easy to work with.
They have a tobacco-like texture and in their processing
properties, such as the ease with which they can be cut and mixed,
they are comparable with natural tobacco. The bulk volume can be
increased to a value higher than that of an equal quantity of
tobacco by adjusting the surface weight of the support, for example
to a value of about 15 to 60 g/m.sup.2, so that, by blending
tobacco with such smokable products, the individual smokable
article, such as a cigarette, cigar or pipeful of tobacco, is
reduced in weight, and consequently the total quantity of substance
smoked, and hence the quantity of condensate produced, is still
further reduced.
The smokable products according to the invention may be used alone
or as components of blends of cigarette tobacco, cigar tobacco and
pipe tobacco. They are also suitable for use as cigar wrappers or
binders or as cigarette paper.
The invention will be further described with reference to the
following examples wherein all parts are by weight unless otherwise
expressed.
EXAMPLES
The smokable products produced according to the Examples were made
up into filter cigarettes with cellulose acetate filters. The
filter cigarettes had a length of 82 mm, a diameter of 8 mm and a
butt length of 15 mm. They were smoked down to an average butt
length of 23 mm.
The density of packing of the cigarettes was measured in terms of
the draft resistance. The draft resistance was determined for
individual cigarettes by using a draft resistance measuring
instrument supplied by Filtrona, London, which indicated the
pressure drop in "mm H.sub.2 O."
The filter cigarettes produced from the smokable products generally
had draft resistances of from 100 to 125 mm H.sub.2 O.
The quantities of condensate given in the examples were quantities
of dry condensate in mg/cig.. They were determined in accordance
with Coresta Standard No. 10. The test cigarettes were smoked with
a puff volume of 35 ml a puff time of 2 seconds and a puff
frequence of 60 seconds. The condensate formed was deposited on a
Cambridge filter and weighed. The water content was determined by
titration using the Karl-Fischer method and was subtracted from the
total condensate.
The smokable products obtained in the examples were assessed for
their organoleptic properties which were graded as follows:
a. Sharpness:
(++) usual sharpness of cellulose
(+) light sharpness, especially when lighting up the cigarette
(-) hardly any sharpness, similar to that of tobacco material
(--) completely free from sharpness
b. Smoking flavor:
(++) usual pronounced taste of cellulose, burning paper, strongly
astringent
(+) light taste of cellulose, not astringent
(-) no taste of cellulose, slight impairment of flavor
(--) mild, no impairment of flavor.
Example 1a
100 g of a paper-like foil of bleached sulfate cellulose having a
surface weight of 58 g/m.sup.2, a thickness of 60 .mu. and an ash
content of 0.06% were sprayed with a 25% aqueous solution of
magnesium-aluminum citrate, Mg.sub.3 [Al.sub.2 (citrate).sub.3 ]
and dried so that the resulting dry foil contained 20% by weight of
the chelate. The foil was cut up into strips of various lengths
about 0.9 mm in width (fine cigarette cut), and made up into
cigarettes with an average draft resistance of 113 mm H.sub.2 O
using ordinary commercial cigarette paper tubes with cellulose
acetate filters.
When smoked, the cigarettes glowed uniformly without ignition of
the smoking product,, and the ash was gray white and
self-supporting.
Organoleptic assessment:
Sharpness (+)
Smoking flavor: (-)
Condensate; 7.3 mg
Example 1b
100 g of a paper-like foil of bleached sulfate cellulose with a
surface weight of 25 g/m.sup.2, a thickness of 32 .mu. and an ash
content of 0.08% were sprayed with a 25% aqueous solution of
magnesium-aluminum citrate Mg.sub.3 [Al.sub.2 (citrate).sub.3 ],
and dried so that the resulting dry foil contained 20% by weight of
the chelate. The treated foil was cut up into strips of various
lengths about 0.9 mm in width (fine cigarette cut) and made up into
cigarettes with an average draft resistance of 102 mm H.sub.2 O
using ordinary commercial cigarette paper tubes with cellulose
acetate filters.
When smoked, the cigarettes glowed uniformly without ignition of
the smoking product. The ash was self-supporting.
Organoleptic assessment:
Sharpness (+)
Smoking flavor (-)
Condensate: 5.0 mg.
Example 1c
100 g of a paper-like foil produced in known manner on a
Fourdrinier machine from about 60% by weight of ground tobacco
ribs, 30% by weight of tobacco leaf waste (fragments and dust) and
10% by weight of unground sulfate cellulose and having a surface
weight of 70 g/m.sup.2 and a thickness of 60 .mu., were sprayed
with a 25% solution of magnesium-aluminum citrate, Mg.sub.3
[Al.sub.2 (citrate).sub.3 ], and dried so that the impregnated foil
contained 5% by weight of the chelate. The resulting product was
cut up and made into filter cigarettes as in Example 1a. The
cigarettes had an average draft resistance of 109 mm H.sub.2 O.
The cigarettes glowed uniformly. The main stream smoke and
subsidiary stream smoke were assessed as being distinctly
aromatic.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor (-)
Condensate: 6.2 mg
Example 2
A product was produced as described in Example 1a but with the
addition of magnesium citrate instead of magnesium-aluminium
citrate. This was obtained as follows:
100 g of a paper-like foil as described in Example 1a consisting of
bleached sulfate cellulose, having a surface weight of 58 g/m.sup.2
and a thickness of 60 .mu. and containing 11.3% by weight of
magnesium carbonate as a filler, were immersed in a 10% aqueous
citric acid solution at 30.degree.C. so that the product contained
magnesium citrate produced in situ. When the excess citric acid had
been washed out and the foil dried, the weight increase of the foil
was found to be 19 g, which corresponds to a magnesium citrate
content of 22% by weight. The resulting product was cut up and made
into filter cigarettes as in Example 1a. The cigarettes had an
average draft resistance of 102 mm H.sub.2 O.
Organoleptic assessment:
Sharpness: (++)
Smoking flavor: (++)
Condensate: 9.3 mg/Cig.
Example 3a
100 g of a paper-like foil according to Example 1b were sprayed
with a 25% aqueous solution of magnesium-iron-(III)-citrate,
Mg.sub.3 [Fe(citrate).sub.2 ].sub.2, and dried so that the dried
foil contained 20% by weight of chelate. The resulting product was
cut up into strips of various lengths about 0.9 mm in width and
made up into cigarettes with a draft resistance of 115 mm H.sub.2 O
by the method described in Example 1a.
When smoked, the cigarettes glowed like tobacco without ignition of
the smoking product. The ash was brownish gray and
self-supporting.
Organoleptic assessment:
Sharpness: (+)
Smoking flavor (+)
Condensate: 4.5 mg
EXAMPLE 3b
300 g of dried, cut stalks of shield fern (Dryopteris filix-mas)
were heated to 105.degree.C. with 6 litres of a 5percent aluminum
sulfate solution for 4 hours in a 10 1 pressure vessel. The
decomposed plant material was then filtered and washed free from
sulphate with water. It was then pulped up in a Hollander and made
up into a web with a surface weight of 68 g/m.sup.2 and a thickness
of 60 .mu. on a Fourdrinier machine. 90 g of the resulting foil
were sprayed with a 10percent magnesium-iron citrate solution and
dried so that the foil contained 10percent by weight of chelate.
The resulting product was then cut up and made into filter
cigarettes as in Example 1a. The cigarettes had an average draft
resistance of 120 mm H.sub.2 O. They were mild in the main stream
smoke and had a pleasant, plant-like flavor.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor (-)
Condensate: 5.2 mg/Cig
EXAMPLE 3c
100 g of a paper-like foil produced in known manner on a
Fourdrinier machine from about 60percent by weight of ground
tobacco ribs, 30percent by weight of tobacco waste (fragments and
dust) and 10percent by weight of unground sulfate cellulose, and
having a surface weight of 70 g/m.sup.2 and a thickness of 60 .mu.,
were sprayed with a 5% aqueous solution of
magnesium-iron-(III)-citrate, Mg.sub.3 [Fe(citrate).sub.2 ].sub.2,
and dried so that the weight increase after drying was 5percent,
i.e. the chelate content was 5percent by weight. The cigarettes
produced in accordance with Example 1a, which had a draft
resistance of 115 mm H.sub.2 O, glowed uniformly. The ash was
brownish red and self-supporting.
When smoked, the product had a light, aromatic flavor without
cellulosic sharpness.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (--)
Condensate: 4.4 mg/Cig.
Example 4
A paper-like foil similar to that described in Example 1b was
repeatedly dipped alternately into a saturated calcium hydroxide
solution and then into a 10percent tartaric acid solution and then
washed and dried until the weight increase was 25.3percent by
weight, i.e. the foil contained about 20percent by weight of
calcium tartrate. The product produced in this way was cut up as in
Example 1 (fine cigarette cut), and made up into filter cigarettes
with a draft resistance of 117 mm H.sub.2 O.
The cigarettes had a dull, musty after-taste and very pronounced
cellulosic sharpness.
Organoleptic assessment:
Sharpness: (++)
Smoking flavor: (++)
Condensate: 8.4 mg/Cig.
EXAMPLE 5
A paper-like foil according to Example 1a was treated in an aqueous
immersion bath containing 12.6percent by weight of
magnesium-aluminum tartrate Mg.sub.3 [A1(tartrate).sub.3 ].sub.2,
squeezed off between steel rollers and dried so that the
impregnated web showed a weight increase of 24.8percent, which
corresponded to a chelate content of 20percent by weight. The
resulting product was cut up as in Example 1a and made up into
filter cigarettes which had an average draft resistance of 115 mm
H.sub.2 O. The cigarettes glowed slowly and constantly and formed a
pale, self-supporting ash.
Organoleptic assessment:
Sharpness: (+)
Smoking flavor: (-)
Condensate: 6.8 mg/Cig.
Example 6
100 g of a paper-like foil according to Example 1a were sprayed
with a 25percent manganese-iron-(III) oxalate solution, Mn.sub.3
[Fe(oxalate).sub.3 ].sub.2, and dried so that the treated foil
contained 20percent by weight of the chelate. The resulting product
was cut up and made up into filter cigarettes in a manner analogous
to Example 1a. Draft resistance: 123 mm H.sub.2 O. The cigarettes
glowed very uniformly and formed a brown, self-supporting ash.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (+)
Condensate: 4.2 mg/Cig.
EXAMPLE 7
100 g of a paper-like foil according to Example 1a were sprayed
several times with a total of 250 m1 of a 10percent
magnesium-aluminum glycolate solution, Mg.sub.3
[A1(glycolate).sub.3].sub.2, and dried so that the chelate content
was 20percent by weight.
The resulting product was made up into filter cigarettes as in
Example 1a. The cigarettes had a draft resistance of 122 mm H.sub.2
O. They glowed uniformly and formed a light white ash.
Organoleptic assessment:
Sharpness: (+)
Smoking flavor: (+)
Condensate: 7.0 mg/Cig.
EXAMPLE 8
100 g of a paper-like foil according to Example 1bwere sprayed with
a 12percent solution of manganese-iron galactarate, Mn.sub.3
[Fe(galactarate).sub.3 ].sub.2, and dried. The foil contained
19.5percent by weight of the chelate.
The material cut up as in Example 1a and made up into filter
cigarettes having a draft resistance of 121 mm H.sub.2 O glowed
uniformly and formed a brownish gray ash.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (+)
Condensate: 4.9 mg/Cig.
EXAMPLE 9
A mixture of 30percent weight of the impregnated foil from Example
1a, and 70percent by weight of an American Virginia tobacco having
a condensate of 28 mg/Cig. was made up into filter cigarettes with
a draft resistance of 126 mm H.sub.2 O. The aromatic substances and
the characteristic sweetness of Virginia tobacco were found to be
completely preserved when the mixture was smoked. The nicotine
reaction on the respiratory tract was considerably attenuated;
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (--)
Condensate: 15 mg/Cig.
EXAMPLE 10
A mixture of 30percent by weight of the foil from Example 3aand
70percent by weight of an Italian Burley tobacco having a
condensate of 22 mg/Cig. was made up into filter cigarettes with an
average draft resistance of 121 mm H.sub.2 O. The cigarettes were
found when smoked to have the complete characteristic cigar-like
flavour of Burley tobacco.
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (--)
Condensate: 12 mg/Cig.
EXAMPLE 11
A mixture of 30percent by weight of the foil from Example 6 and
70percent by weight of a commercial tobacco mixture with a light
note (American blend type flavor ) having a condensate of 15
mg/Cig. was made up into filter cigarettes. The cigarettes were
found when smoked to have a pleasant, mild flavor. The smoke
appeared much thinner than that produced by the tobacco mixture
alone. The glowing process was similar to that of natural tobacco
in its uniformity and rate. Draft resistance: 118 mm H.sub.2 O
Organoleptic assessment:
Sharpness: (-)
Smoking flavor: (-)
Condensate: 9.3 mg / Cig.
EXAMPLE 12
The combustible material used as a tobacco which was characterized
as rough Burley with a strong cigar note. This tobacco was sprayed
with a solution of ammonium-iron (III) citrate, (NH.sub.4).sub.3
[Fe(citrate).sub.2 ], and acid magnesium-aluminum tartarate, Mg H
[A1 (tart).sub.3 ], in a ratio by weight of 1:1, so that the amount
of dry substance taken up was 2.5percent by weight, i.e. the amount
of each compound present in the treated tobacco material is
1.25percent by weight.
Compared with this material, the Burley tobacco which has been
treated by the process according to the invention was less sharp
when smoked but with an overall spicy aromatic flavor. The Burley
note was completely preserved.
Assessment:
Sharpness: (--)
Smoking flavor: (--)
Example 13
The combusticle material used was a paper-like foil produced from a
1:1 mixture of ground tobacco ribs and sulfate cellulose and having
a surface weight of 45 g/m.sup.2 and a thickness of 55 .mu.. This
material was treated in an immersion bath containing 15 parts by
weight of magnesium-aluminum citrate, Mg.sub.3 [Al (citrate).sub.2
].sub.2, 6 parts of ammonium aluminum citrate, (NH.sub.4).sub.3 [Al
(citrate).sub.2 ], 4 parts of aluminum hydroxide, 4 parts of
silicic acid, 11 parts of tobacco extract and 60 parts of water.
The treated foil was squeezed off and dried in a stream of air at
95.degree.C. A weight increase of 55% by weight was obtained. The
components dissolved in the immersion bath were incorporated in the
foil at the same concentration ratio, i.e. the foil contained 13.6%
by weight of Mg.sub.3 [Al (citrate).sub.2 ].sub.2 and 5% by weight
of (NH.sub.4).sub.3 [Al (citrate).sub.2 ].
Compared with a product obtained without the addition of chelate,
the smokable product obtained had no astringent effect, was free
from sharpness and produced a light, aromatic smell. It was found
to be completely compatible with commercial cigarette tobaccos with
which it was blended.
Assessment:
Sharpness: (--)
Smoking flavor: (-)
Examples 14-22
Chelate complexes on Cellulose webs
Paper-like foils or webs with and without fillers were produced on
a paper-machine to be used as starting materials for the smoking
products. A description of the foils obtained is summarized in
Table II.
Table II ______________________________________ Foil Surface Thick-
Constituents Filler % Ash weight ness after (g/m.sup.2) (.mu.)
glowing ______________________________________ A 45 38 bleached --
0.07 sulfate cellulose B 16 20 do. -- 0.09 C 50 52 do. Al(OH).sub.3
29 D 68 60 do. Vermic- 34 ulite
______________________________________
Foils A to D were prepared in an immersion bath consisting of the
aqueous solution of the chelate together with the compound which
splits off ammonia when smoked. In Examples 15, 17, 18 and 19, the
immersion bath contains in addition a filler and a binder. The
immersed foil was squeezed off in its passage through rollers and
dried on an endless band in an air stream at 95.degree.C.
Table III summarizes for Examples 14 to 22 the nature of the foil
used as combustible material, the composition of the immersion
bath, the increase in dry weight of the treated foil (total weight
increase and increase due to chelate content) and the assessment of
the organoleptic properties of the resulting smokable products as
well as the condensate values. The quantity of solids taken up by
the foil (compounds which split off ammonia, fillers) is obtained
from the weight increase, the individual constituents being taken
up into the foil in the same ratio by weight as that found in the
immersion bath. The quantity of chelates taken up is indicated
separately.
Table III
__________________________________________________________________________
Ex. Composition of the immersion bath Solids Assessment taken up*
(Foil) Chelate Compound which Filler Binder Total Chelate Sharp-
Cellulose Condensate (g/l) splits off (g/l) (g/l) ness flavor
ammonia (g/l)
__________________________________________________________________________
14 200 g of magnes- 100 g of -- -- 29.6 20.0 (-) (+) 9.7 (A)
ium-aluminum ammonium citrate tartrate Mg.sub.3 [Al.sub.2
(citrate).sub.3 ] 15 100 g of magnes- 100 g of 250 g 10 g 25 5.7
(-) (-) 8.3 (A) ium-aluminum ammonium Al(OH).sub.3 of gum citrate
tartrate arabic Mg.sub.3 [Al(citrate).sub.2 ].sub.2 16 200 g of
magnes- 50 g of -- -- 36.4 29.1 (-) (-) 9.6 (A) ium-aluminum urea
citrate Mg.sub.3 [Al(citrate.sub.2 ].sub.2 17 190 g of acid 30 g of
urea 200 g 30 g 56 20.0 (--) (-) 6.3 (B) magnesium-alum- 84 g of
ammonium- of of inum tartrate aluminum Al(OH).sub.3 corn
MgH[Al(tar- tartrate starch trate).sub.2 ] NH.sub.4 [Al(tartrate)]
18 100 g of magnesium 50 g of urea 200 g 10 g 60 15 (--) (--) 4.8
(B) iron (III) citrate 50 g of magnesium Al(OH).sub.3 gum Mg.sub.3
[Fe(citrate).sub.2 ].sub.2 glutamate arabic 19 100 g of magnesium
200 g of ammon- -- -- 24 8.1 (-) (-) 8.5 (C) aluminum citrate ium
citrate Mg.sub.3 [Al(citrate).sub.2 ].sub.2 20 100 g of magnesium
200 g of ammonium 250 g 8 g 40 7.3 (-) (--) 7.8 (C) aluminum
citrate citrate Al(OH).sub.3 of gum Mg.sub.3 [Al(citrate).sub.2
].sub.2 arabic 21 120 g of magnesium 50 g of urea -- -- 19.5 13.1
(-) (--) 5.5 (C) iron-(III) citrate 10 g of magnes- Mg.sub.3
[Fe(citrate).sub.2 ].sub.2 ium glutamate 22 60 g of magnesium 100 g
of -- -- 16 6.0 (-) (+) 7.3 (D) aluminum citrate ammonium Mg.sub.3
[Al.sub.2 (citrate).sub.3 ] tartrate
__________________________________________________________________________
*Increase in % by weight after drying, based on the original
foil.
Examples 23-25
Tobacco mixtures
The cut foils from Examples 15, 16 and 18 were mixed with a
commercial cigarette tobacco with a light note and made up into
filter cigarettes.
Example 23
A 30% mixture of the foil from Example 15 and a commercial
cigarette tobacco with a light note resalted in a round, soft aroma
without any cellulosic sharpness. The only effect of the low
nicotine content in the total mixture was an attenuation of the
reaction to inhalation of the main stream smoke.
Assessment:
Sharpness: (--)
Smoking flavor: (-)
Condensate: 13.6 mg
Example 24
A 30% mixture of the foil from Example 16 resulted in a slightly
attenuated aromatic impression in the tobacco mixture with a low
residual sharpness (-). The nicotine reaction on inhalation of the
main stream smoke was the same as in Example 13.
Assessment:
Sharpness: (-)
Smoking flavor: (-)
Condensate: 14.1 mg
Example 25
A 30% by weight mixture of foil from Example 18 was assessed to be
organoleptically weaker as regards its aroma but to be completely
inert as regards its sharpness. No cellulose after-taste was found
either in the main stream smoke or in the side-stream smoke. The
nicotine reaction on inhalation of the main stream smoke was even
weaker than in Examples 23 and 24.
Assessment:
Sharpness: (--)
Smoking flavor: (--)
Condensate: 15.0 mg
Examples 26-31 Foils from Examples 14-22 were immersed in
accordance with the following Examples 26-31 in a solution of
aqueous tobacco extract containing about 30% by weight of soluble
tobacco constituents or sprayed with this solution so that the dry
weight increase was up to 50% by weight. Drying was carried out
using hot air at 60.degree.C. to 100.degree.C.
Example 26
20% of the constituents of commercial tobacco mixture with an
"American Blend" type flavor were extracted using a cold
methanol/water solution (70 vol/30 vol). This aqueous-methanolic
extract was sprayed on the smoking product produced according to
Example 17 so that the dry weight increase was 30% by weight. The
resulting product was made up into filter cigarettes which gave an
aromatic overall impression without sharpness in the main stream
(assessment (--)) and no cellulosic after-taste (assessment: (-) )
on inhalation, with a distinctly perceptible nicotine reaction and
a fully aromatic side stream. The resulting smokable product was
compatible when mixed in any proportion with Virginia, Burley and
Orient type tobaccos and mixtures of such tobaccos (Condensate: 9.8
mg).
Example 27
The foil obtained according to Example 19 was treated with the same
extract of tobacco constituents as in Example 26 to result in a dry
weight increase of 29% by weight. The flavor of the product made up
into filter cigarettes was assessed as inert with little aroma and
with only a slight sharpness (assessment: (-) ) when the cigarette
was lit up. The side stream smoke was aromatic and mild (assessment
of smoking flavor: (-), condensate: 10.7 mg).
Example 28
The foil obtained according to Example 20 was treated with the same
extract of tobacco constituents as in Example 26 so that the
increase in dry weight was about 25% by weight. Compared with
Example 27, a fuller flavor was obtained with a good reaction, and
even when lighting up the cigarette no sharpness (assessment: (-))
and no cellulosic after-taste (assessment: (--) ) were experienced.
The side stream smoke was pleasantly aromatic. (Condensate: 9.0
mg).
Example 29
The constituents of American Virginia tobacco were completely
extracted with hot water. The aqueous extract was sprayed onto the
smokable product produced according to Example 20 so that the
increase in dry weight was 31%. When this cigarette was smoked, it
was found to have an unmistakable, typical Virginia flavor the
spiciness of which was not impaired by the foil.
Assessment:
Sharpness: (--)
Smoking flavor: (--)
Condensate: 11.0 mg
Example 30
The soluble constituents were completely extracted from Italian
Burley tobacco by means of a cold methanol/water solution (60
vol/40 vol). The extract was sprayed onto the smokable product
obtained according to Example 22 so that the weight increase was
20%. The flavor was that of a good quality, characteristic Burley
tobacco with a sweetish note. The smokable product was less sharp
than the Burley tobacco used for extraction. The smokable product
obtained was compatible in any proportions with Virginia, Burley
and Orient type tobaccos and mixtures thereof.
Assessment:
Sharpness: (-)
Smoking flavor: (--)
Condensate: 11.3 mg
Example 31
Foil C indicated in Table II was treated in an immersion bath which
contained 160 g of ammonium citrate, 80 g of magnesium-aluminum
citrate, Mg.sub.3 [Al.sub. 2 (citrate).sub.3 ], and 280 g of the
tobacco constituents obtained by extraction with water in
accordance with Example 19 and which had been adjusted to pH 7 with
ammonia. The increase in dry weight of the foil was 50% and the
resulting smokable product contained 5.1% by weight of chelate.
When smoked, the product was light, aromatic and practically free
from any after-taste or sharpness. It was compatible with all the
usual sorts of tobacco in any proportions.
Assessment:
Sharpness: (-)
Smoking flavor: (-)
Condensate: 9.9 mg
Example 32
15 parts of ground, pure linters (99.8% .alpha.-cellulose), 15
parts of aluminum hydroxide, 5 parts of magnesium-aluminum citrate,
Mg.sub.3 [Al (citrate).sub.2 ].sub.2, and 5 parts of magnesium-iron
citrate, Mg.sub.3 [Fe(citrate).sub.2 ].sub.2, were added to a 5%
aqueous casting solution of sodium carboxymethylcellulose/ammonium
carboxymethylcellulose (3:1).
The solution was cast onto a polytetrafluorethylene-coated band
using a pressure casting tool and dried at 130.degree.C. The cast
foil weighed 15 g/m.sup.2. A 30% by weight mixture of this product
with a Virginia-Burley mixture (proportion by weight: 3:1) had a
slightly weaker aroma than the Virginia Burley mixture without the
product but there was no adulteration of the aroma and no sharpness
(--). (Condensate: 12.4 mg).
Example 33
A commercial cigarette paper was sprayed with a 6% by weight
solution of 2 parts of magnesium-aluminum citrate, Mg.sub.3
[Al.sub. 2 (citrate).sub.3 ], and 1 part of ammonium-aluminum
citrate, (NH.sub.4).sub.3 [Al (citrate).sub.2 ]and dried at
90.degree.C. The amount of salt taken up was 9% by weight.
Cigarettes produced using this paper were improved in flavor and
aroma compared with cigarettes produced with untreated paper
because the treated paper was free from sharpness and had no
unpleasant cellulosic after-taste.
Examples 34-49
The combustible materials used were paper webs of bleached sulfate
cellulose with different filler contents and surface weights. The
compositions of the foils used as combustible starting material are
shown in Table IV.
Table V shows examples of the preparation of smokable products by
the process according to the invention and quantities of condensate
formed by these products.
Table VI shows the production of smokable products according to
Table V which in addition contain potassium permanganate as an
oxidizing agent and the quantities of condensate formed by these
products.
Table IV ______________________________________ Foil Cellulose
Fillers Surface Thickness material weight .mu. g/m.sup.2
______________________________________ A bleached 43.5% by weight
42 55 sulfate Al (OH).sub.3 cellulose 10.2% by weight SiO.sub.2 B
do. 44.6% by weight 50 62 Al (OH).sub.3 C do. 40.2% by weight 54 70
Al (OH).sub.3 10.0% by weight SiO.sub.2 D do. 31.1% by weight 38 45
Al (OH).sub.3 12.4% by weight SiO.sub.2 E do. 16.1% by weight 32 40
Al (OH).sub.3 F do. 18% by weight 25 35 Al (OH).sub.3
______________________________________
Table V
__________________________________________________________________________
Example Foil from Composition of immersion bath (g/l) Solids taken
Condensate Table III up* Total/Chelate
__________________________________________________________________________
34 A 80 Magnesium-iron citrate Mg.sub.3 [Fe(citrate).sub.2 ].sub.2
20.2 10.6 3.8 30 amminium-iron citrate (NH.sub.4).sub.3
[Fe(citrate).sub.2 ] 20 urea 20 ammonium citrate 35 B as in Example
34 16.8 8.9 3.7 36 C as in Example 34 17.4 9.3 4.1 37 D as in
Example 34 26.6 14.0 4.3 38 E 120 Magnesium-iron citrate Mg.sub.3
[Fe(citrate).sub.2 ].sub.2 27.5 18.7 6.6 50 urea 10 magnesium
glutamate 39 F 160 Magnesium-iron citrate Mg.sub.3
[Fe(citrate).sub.2 [.sub.2 44.0 23.0 4.8 30 ammonium-iron citrate
(NH.sub.4).sub.3 [Fe(citrate).sub.2 ] 20 urea 20 ammonium citrate
75 water-soluble tobacco constituents**
__________________________________________________________________________
*Increase in % by weight after drying, based on the foil used as
startin material **Obtained by complete extraction of Burley
tobacco with hot water
Table VI
__________________________________________________________________________
Example Production Application of potassium permanganate Potassium
Condensate of the foil permanganate as in Example content of foil
(% by weight)
__________________________________________________________________________
40 34 Addition of 10 g/l into the immersion bath 2.8 1.2 41 35
after drying, the foil treated with complex 3.0 1.9 salts is passed
through an aqueous-acetonic bath of KMnO.sub.4 42 36 after drying
of the complex salt solution, 2.6 1.8 the foil is passed through an
aqueous KMnO.sub.4 bath 43 36 sprayed from solution in acetone 3.0
1.7 44 37 foil was treated with aqueous KMnO.sub.4 solution 3.0 3.0
before application of the complex salts and dried 45 38 before
application of the complex salts, the 2.9 2.7 foil was treated with
aqueous KMnO.sub.4 solution and dried 46 39 as in Example 44 2.1
2.6 46a 39 as in Example 45 2.1 2.6
__________________________________________________________________________
Example 47a
A 1% solution of citrus pectin in the form of the ammonium salt was
sprayed onto the product produced according to Example 34 so that
the dry weight of citrus pectin taken up by the product was 1.3% by
weight.
The material made up into cigarettes and smoked was found when
compared with the product according to Example 34 to have an
improved, pleasantly fresh and slightly plant-like flavor and the
same condensate value.
Example 47b
A mixture of 30% by weight of the product according to Example 47a
and 70% by weight of a commercial fine cut tobacco mixture with the
type of flavor of an American blend was made up into cigarettes.
The flavor produced by the pectin in the main stream smoke was
completely compatible with the tobacco aroma and rounded off the
aroma bouquet.
Example 48
A 2% solution of zein in ethanol was sprayed onto the product
produced according to Example 35 so that the weight increase due to
the zein was 1.7% after drying.
The product made up into cigarettes was found when smoked to
produce an improved aroma in the main stream and subsidiary stream
smoke compared with the product according to Example 35 and had the
same condensate value.
Example 49
A 2% ethanolic solution of zein was sprayed onto the product made
according to Example 39 so that the weight increase due to the zein
was 1.5% by weight after drying.
The product made up into cigarettes had a much more intense tobacco
aroma and a rounder flavor than the product according to Example 39
and the same condensate value.
Example 50
Mixtures were prepared as indicated in Table VII from the smoking
products according to Example 39 and 46 and a commercial tobacco
mixture which had a nicotine content of 0.86 mg and a condensate of
14.8 mg/filter cigarette. Table VII shows the expected and found
condensate contents and nicotine contents for various mixtures.
When calculating the expected values, the bulk volumes of the
various mixtures were taken into consideration.
Table VII
__________________________________________________________________________
Smokable product Tobacco Calculated condensate Condensate Nicotine
Nicotine from Example 29 (% by content (tobacco content found
calculated found (% by weight) weight) + smokable product (mg/Cig.)
(mg/Cig) content)
__________________________________________________________________________
20 80 10.7 + 1.3 = 12.0 9.9 0.62 0.45 40 60 6.7 + 2.1 = 8.8 7.4
0.39 0.28 60 40 3.5 + 2.4 = 5.9 4.4 0.22 0.17 Smokable product from
Example 36 (% by weight) 20 80 10.5 + 0.7 = 11.2 10.0 0.61 0.39 40
60 7.6 + 1.3 = 8.9 6.7 0.44 0.26 60 40 3.9 + 1.5 = 5.4 3.8 0.22
0.14
__________________________________________________________________________
EXAMPLE 51
The foil produced according to Example 36 was sprayed with an
aqueous alcoholic solution of potassium nitrate and dried, the
increase in dry weight being 1%. Condensate: 3.1 mg/Cig.
Example 52
The foil produced according to Example 36 was sprayed with an
aqueous potassium nitrate solution and dried, the increase in dry
weight being 2%. Condensate: 2.5 mg/Cig.
Example 53
A foil produced according to Example 38 was sprayed with an aqueous
potassium nitrate solution and dried, the increase in dry weight
being 2%. Condensate: 3.2 mg/Cig.
Example 54
A combustible material in the form of a paper web of bleached
sulfate cellulose containing 45% by weight of aluminum hydroxide as
a filler and having a surface weight of 50 g/m.sup.2 and a
thickness of 38 .mu. was treated in an immersion bath
containing:
10 parts of manganese-iron citrate, Mn.sub.3 [Fe(citrate).sub.2
].sub.2
6 parts of ammonium-iron citrate, (NH.sub.4).sub.3
[Fe(citrate).sub.2 ]
5 parts of urea
12 parts of tobacco constituents obtained buy complete extraction
of Burley tobacco with hot water
100 parts of water,
so that, after drying at temperatures constantly increasing from
55.degree.C to 95.degree.C, the increase in dry weight was 34%. The
resulting smokable product contained 7.6% by weight of the chelate.
It was made up into filter cigarettes. The product was assessed
organoleptically as neutral in flavor with a marked impression of
tobacco. Condensate: 3.1 mg/Cig.
Example 55
A combustible material as in Example 54 consisting of a foil of
bleached sulfate cellulose which contained 45% by weight of
aluminum hydroxide as a filler and which had been pretreated with a
2% aqueous potassium permanganate solution was treated in an
immersion bath which consisted of:
8 parts of manganese-iron galactarate, Mn.sub.3
[Fe(galactarate).sub.3 ].sub.2
8 parts of magnesium-aluminum citrate, Mg.sub.3 [Al (citrate.sub.2
].sub.2
6 parts of ammonium iron galactarate, NH.sub.4
[Fe(galactarate)]
6 parts of urea
12 parts of tobacco constituents (which had been obtained according
to Example 29)
100 parts of water
so that, after drying at 55.degree.C. to 95.degree.C with
constantly increasing temperature, the increase in dry weight was
41%. The resulting smokable product contained 11.4% by weight of
the chelate. It was made up into filter cigarettes. The product was
assessed organoleptically as exceptionally mild and tobacco-like.
Condensate: 2.8 mg/Cig.
The product obtained by this Example was exceptionally compatible
with a commercial tobacco mixture which had a light note.
It will be appreciated that the instant specification and examples
are set forth by way of illustration and not limitation and that
various modifications and changes may be made without departing
from the spirit and scope of the present invention.
* * * * *