U.S. patent number 3,640,285 [Application Number 04/784,472] was granted by the patent office on 1972-02-08 for cigarette paper and method for preparation.
This patent grant is currently assigned to Sutton Research Corporation. Invention is credited to Theodore Briskin, Geoffrey R. Ward.
United States Patent |
3,640,285 |
Briskin , et al. |
February 8, 1972 |
CIGARETTE PAPER AND METHOD FOR PREPARATION
Abstract
Cigarette paper having improved taste and aroma during pyrolysis
wherein the paper is loaded with an agent comprising up to 45
percent by weight calcium oxalate preferably formed in situ
internally in the paper fibers and/or conversion of the cellulosic
fibers by selective oxidation to convert preferably 40 to 60
percent of the methylol groups on the C.sub.6 position to
carboxylic acid groups and further treatments. This is a
continuation-in-part of our copending application, Ser. No.
745,372, filed July 17, 1968 and titled "Cigarette Paper and Method
for Preparation," now abandoned which in turn is a
continuation-in-part of the copending application, Ser. No.
595,622, filed Nov. 21, 1966, and titled "Smoking Products," now
Pat. No. 3,447,539 and Ser. No. 674,994, filed Oct. 12, 1967, and
titled "Smoking Products and Process for Making Such Products" now
abandoned.
Inventors: |
Briskin; Theodore (Beverly
Hills, CA), Ward; Geoffrey R. (Beverly Hills, CA) |
Assignee: |
Sutton Research Corporation
(Los Angeles, CA)
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Family
ID: |
25132539 |
Appl.
No.: |
04/784,472 |
Filed: |
December 17, 1968 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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745372 |
Jul 17, 1968 |
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595622 |
Nov 21, 1966 |
3447539 |
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674994 |
Oct 12, 1967 |
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Current U.S.
Class: |
131/365; 162/139;
162/179; 162/157.6; 536/56 |
Current CPC
Class: |
A24D
1/02 (20130101); D21H 5/16 (20130101); A24B
15/16 (20130101) |
Current International
Class: |
A24B
15/16 (20060101); A24B 15/00 (20060101); A24b
015/00 (); A24f 003/00 (); D21f 011/00 () |
Field of
Search: |
;162/139,157C,179
;131/2,15 ;260/212 |
References Cited
[Referenced By]
U.S. Patent Documents
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3447539 |
June 1969 |
Briskin et al. |
3478751 |
November 1969 |
Briskin et al. |
3478752 |
November 1969 |
Briskin et al. |
3491766 |
January 1970 |
Briskin et al. |
|
Foreign Patent Documents
Primary Examiner: Caine; Howard R.
Claims
We claim:
1. In the method of producing a cellulosic wrapper for smokable
material in the fabrication of cigarettes and cigars, the steps of
providing a paper of cellulosic fiber for wrapping smokable
material in the fabrication of cigarettes and cigars, uniformly
distributing throughout the cellulosic fibers of the paper 5 to 45
percent by weight of an ashing ingredient in the form of a salt
having a cation in the form of an alkaline earth metal and an anion
selected from the group consisting of oxalic acid, tannic acid,
pivalic acid, glycolic acid, diglycolic acid and lactic acid,
sheeting the paper before or after treatment to wrapper form, and
packaging the smokable material within the treated wrapper to
produce the cigarette or cigar.
2. The method as claimed in claim 1 in which the cation is selected
from the group consisting of calcium, magnesium, strontium, and
barium.
3. The method as claimed in claim 1 in which the ashing ingredient
comprises a mixture of calcium oxalate and magnesium oxalate
present in the ratio of one part by weight magnesium oxalate to one
to four parts by weight calcium oxalate.
4. The method as claimed in claim 1 in which the ashing ingredient
is introduced by the steps of wetting the cellulosic material with
the salt while in a solubilized state in aqueous medium and aging
the treated fibers to precipitate the salt in situ within the
cellulosic fibrous structure.
5. The method as claimed in claim 4 comprising the steps of
providing one aqueous solution containing the cation and a second
aqueous solution containing the anion and substantially
simultaneously wetting the cellulosic material with the
solutions.
6. The method as claimed in claim 5 in which the solutions are
admixed immediately prior to wetting the cellulosic material.
7. The method as claimed in claim 5 in which the solutions are
separately applied substantially simultaneously onto the cellulosic
material.
8. The method as claimed in claim 1 in which the ashing ingredient
is introduced into the cellulosic fibers prior to paper formation
and which includes the step of forming the cellulosic fibers into a
thin paper wrapper and rinsing the formed paper with water to
remove water solubles and then drying the paper.
9. The method as claimed in claim 8 which includes the step of
introducing an acid into the treated paper in an amount up to 0.5
percent by weight of the paper in which the acid is selected from
the group consisting of oxalic acid, tannic acid, pivalic acid,
glycolic acid, diglycolic acid, and lactic acid.
10. The method as claimed in claim 8 in which the acid is oxalic
acid.
11. The method as claimed in claim 1 in which the salt is present
in an amount of at least 5 percent by weight of the cellulosic
fibers and the remainder making up the ashing component is a filler
selected from the group consisting of perlite, talc, alumina,
silica, and calcium carbonate.
12. The method as claimed in claim 1 which includes the additional
step of oxidizing the cellulosic material with nitrogen dioxide
selectively to oxidize methylol groups on the C.sub.6 position of
the cellulosic molecule by an amount within the range of 15 to 60
percent.
13. The method as claimed in claim 12 in which the nitrogen dioxide
oxidizing medium is liquid nitrogen dioxide and which includes the
step of separating the liquid oxidizing medium from the oxidized
cellulosic fiber upon completion of the oxidation reaction.
14. The method as claimed in claim 12 in which the cellulosic
material is oxidized by an amount insufficient to destroy the
fibrous characteristics of the cellulosic material.
15. The method as claimed in claim 12 in which the cellulosic
material is oxidized by an amount within the range of 40 to 60
percent.
16. The method as claimed in claim 13 which includes the step of
bubbling an oxygen containing gas through the liquid nitrogen
dioxide during the oxidation reaction.
17. The method as claimed in claim 12 in which the liquid oxidizing
medium contains up to 8 percent by weight water.
18. The method as claimed in claim 17 in which the amount of water
is within the range of 0.5 to 5 percent in the oxidizing
medium.
19. The method as claimed in claim 13 in which the oxidation is
carried out at a temperature within the range of 15.degree. to
65.degree. C.
20. The method as claimed in claim 13 which includes the step of
rinsing the oxidized fibers with anhydrous liquid nitrogen dioxide
after separating the liquid oxidizing medium from the oxidized
cellulose fibers.
21. The method as claimed in claim 12 which includes the step of
subjecting the oxidized cellulosic material to a mild reduction
reaction.
22. The method as claimed in claim 21 in which the reduction
reaction is carried out with a reducing agent selected from the
group consisting of freshly prepared hydrogen and a
borohydrate.
23. The method as claimed in claim 12 which includes the step of
adding an acid to the dried oxidized cellulosic material in an
amount up to 5 percent by weight and in which the acid is selected
from the group consisting of oxalic acid, tannic acid, pivalic
acid, glycolic acid, diglycolic acid, and lactic acid.
24. The method as claimed in claim 23 in which the applied acid is
oxalic acid.
Description
In the aforementioned copending applications, description is made
of the preparation of a smoking product suitable for cigarettes,
cigars, or pipes, in which relatively pure cellulosic material is
subjected to selective oxidation with liquid nitrogen dioxide to
convert more than 90 percent of the free hydroxyl groups on the
cellulosic molecule to carboxyl groups to yield a product which can
be referred to as an oxycellulose. The oxidation reaction product
is further processed by removal of the liquid nitrogen dioxide by
vaporization and washing of the oxidized product with water and/or
alcohol for removal of solubilized foreign materials and/or
treatment with solvents, such as acetone for removal of oils,
waxes, lattices and the like which contribute undesirably to the
taste and odor when the product is used as a smoking product.
As further described in the aforementioned copending applications,
the oxidized and cleansed cellulosic derivative is further
processed by a reduction reaction with a hydride or borohydride of
an alkali or alkaline earth metal, such as sodium, or lithium
borohydride, for reducing groupings which otherwise have a tendency
to evoke unpleasant odors or taste as the product is pyrolized. The
product before or after being processed by the described reduction
reaction can be subjected to oxidation with peroxide solutions as a
means for eliminating further components which contribute
undesirable aroma or taste to the product during pyrolysis.
The resulting oxidized and reduced cellulosic material is then
formulated with mineralizing agents to the form of oxalates
lactates, pivalates or tannates of such metals as calcium,
magnesium, lithium, potassium, barium or strontium, preferably
introduced internally, preferably within the cellulosic derivative
for purposes of providing desirable ashing characteristics,
although beneficial ashing characteristics of limited utility can
be achieved by external application of such mineralizing agents to
coat the fibers or for admixture with the fibers. As described, the
desired internal application of the mineralizing agents can be
achieved by first wetting the fibers with a solution of the desired
metal ion for absorption into the cellulosic derivative, followed
by exposure to a solution of the desired anion whereby the
corresponding metal salt forms in situ with the cellulosic
material.
Maintenance of glow and burning rate, characteristic of tobacco, is
achieved by formulation to include a potassium salt, such as
potassium oxalate, or by the addition of rubidium or cesium
compounds in amounts within the range of 1 percent to 10 percent by
weight but preferably less than 1 percent by weight, as described
in the copending application Ser. No. 623,528, filed Mar. 16, 1967,
and titled "Smoking Products and Process for Their Manufacture" now
abandoned. Smoke generators can be added to increase the visual
effect of the smoking product when burned.
The resulting product is suitable for use as a smoking product
alone or in admixture with tobacco to produce a smoking product
having better taste and less undesirable ingredients in the
smoke.
The concept of this invention resides in the improvement of the
paper or sheet material in which the tobacco or the smoking product
is rolled in the fabrication of cigarettes, cigars, or the like
smoking products.
To the present, use is made of cigarette paper formed of purified
cellulose pulp loaded with about 20 percent to 30 percent by weight
calcium carbonate with small amounts of other possible modifiers.
Pyrolysis of this paper gives a most undesirable irritant odor
which, though diluted with the smoke from the tobacco, undesirably
affects the odor and taste of the smoking product. Many of the
attributes obtained from the improved smoking product prepared of
cellulosic materials, as described in the aforementioned copending
applications, are upset in part by the use of conventional
cigarette paper or wrappers.
Thus, it is an object of this invention to produce and to provide a
method for producing a paper or wrapper of cellulosic material
which is characterized by having improved odor, taste, and aroma
during pyrolysis whereby cigars and cigarettes currently produced
with tobacco can materially be improved, at least from the
standpoint of taste and aroma, and wherein the balance of good
taste and aroma of cigars and cigarettes produced in cellulosic
materials in the manner described in the aforementioned
applications are not materially upset by the wrapper or paper in
which the smoking material is incorporated.
It is a further object of this invention to provide a number of
methods and means which individually operate to provide a more
desirable paper or wrapper from the standpoint of taste and aroma
and which, in various combinations, offer still greater improvement
when utilized as a part of a smoking product.
The invention will be described with reference to paper formed of
purified cellulose or woodpulp, such as alpha-cellulose, but it
will be understood that the term cellulose is intended to include
other cellulosic fibers and materials of the type used in the
making of paper and the like wrapping material.
First, with reference to cigarette paper as it is now prepared from
purified cellulose loaded with 20 percent to 30 percent by weight
calcium carbonate, considerable improvement is derived by the
treatment of cigarette paper with a dilute solution of oxalic acid
containing from 1 percent to 10 percent by weight oxalic acid in a
dissolved state in an aqueous medium at a temperature within the
range of room temperature to 80.degree. C.
The oxalic acid solution operates to convert calcium carbonate to
insoluble calcium oxalate. The latter is sufficiently stable
thermally to remain while the cellulosic material is pyrolyzed
during the smoking of the cigarette so that the effect of calcium
on the odor is minimized and a cleaner tasting cigarette is
obtained. During the final stages of the pyrolysis, the calcium
oxalate breaks down to calcium oxide and calcium carbonate which
remain as ash and carbon dioxide and/or carbon monoxide gas which
goes off with the smoke and is substantially odorless and
tasteless.
Treatment with oxalic acid does not interfere with the desirable
characteristics of the paper for its intended use as a wrapper.
Treatment with oxalic acid can be effected by passing the preformed
paper web through an aqueous solution of oxalic acid at a rate to
provide a residence time sufficient to achieve the desired
transformation (about 2 to 10 minutes), after which the web is
washed with water to remove excess oxalic acid or other solubles
present in the processed paper.
Improvement in the smoking characteristics of the paper wrapper in
cigarettes is achieved, in accordance with the practice of this
invention when the calcium oxalate and/or magnesium oxalate or
corresponding mineralizing agent, as described herein, is present
in the paper in an amount greater than 5 percent by weight but it
is undesirable to make use of an amount greater than 45 percent by
weight and it is preferred to make use of a cigarette paper
containing 10-40 percent by weight of such mineralizing agent.
It will be understood, of course, that the desired construction can
be obtained by the substitution of calcium oxalate and/or magnesium
oxalate for calcium carbonate in the finish or slurry of cellulosic
pulp used in the original formation of the paper web.
Instead of oxalic acid, use can be made of pivalic acid or tannic
acid to form the corresponding pivalate or tannate. Instead of
calcium, use can be made of magnesium, barium, or strontium to
provide the corresponding magnesium, barium, or strontium oxalate,
pivalate, or tannate in the cigarette paper and it is preferred to
make use of the combination of a major proportion of calcium and a
minor proportion of magnesium as the cation of which the filler is
formed.
By way of modification of this initial concept, it has been found
that still further improvement in the smoking characteristics of
the paper can be obtained when a small amount of free pivalic,
tannic and preferably oxalic acid is reintroduced or otherwise
provided in the cigarette paper. The function of the free acid
returned to the treater paper is to ensure that small amounts of
ions of heavy metals, such as calcium, barium, strontium,
magnesium, copper, cobalt, iron, and aluminum remaining in the
paper or subsequently released are taken up to form the
corresponding insoluble heat-stable oxalate, tannate or pivalate,
as the case may be. For this purpose, it is undesirable to provide
for more than 0.5 percent by weight acid since excessive amounts of
oxalic or the like acids are objectionable from the standpoint of
the taste and aroma which additional amounts thereof contribute to
the product when it is smoked. When employed, it is preferred to
introduce the oxalic or like acid in an amount within the range of
0.1 percent to 0.25 percent by weight. Reintroduction can be made
by dissolving the calculated amount of acid in an aqueous medium to
provide a solution containing 0.1 percent to 1 percent by weight of
the acid and then spraying the solution onto the web or by passing
the web through a solution followed by drying, or by mixing the
solution with the pulp fiber slurry during the paper making.
The foregoing concepts will now be illustrated by way of the
following examples.
EXAMPLE 1
Cigarette paper, already formed, is passed through a bath heated to
30.degree. C. and formed of an aqueous solution containing 5
percent by weight oxalic acid. Passage is made at a rate to provide
a residence time of about 5 minutes.
Upon emergence from the bath, the treated web is subjected to two
or three washings with water to remove excess oxalic acid or other
water solubles. A controlled excess of oxalic acid is then applied
by spraying the treated and washed and semidried paper with an
aqueous solution containing 0.2 percent by weight oxalic acid in an
amount to provide about 0.1 percent by weight free acid in the
paper. The paper is finally dried to about 40 percent relative
humidity.
Tannic acid can be substituted, in whole or in part, for the oxalic
acid in equivalent amounts in Example 1.
EXAMPLE 2
Purified cellulose pulp is slurried with a mixture of calcium
oxalate and magnesium oxalate in the ratio of about four parts by
weight calcium oxalate to one part by weight magnesium oxalate with
the total oxalate present in an amount to make up about 20 percent
to 40 percent by weight of the solids of the fibrous slurry.
The slurry is used as a furnish in a conventional papermaking
machine to produce a cigarette paper fabricated of cellulosic
fibers containing 20 percent to 40 percent by weight of calcium and
magnesium oxalate.
For the embodiment wherein calcium and/or magnesium oxalate is
embodied in the paper, or in the fibrous materials with which the
paper is formed, it is preferred to take advantage of the lapse of
time between the admixture of the calcium cation and the oxalic
acid anion to the precipitation of an insoluble calcium oxalate to
achieve fuller penetration or impregnation of the cellulosic
system. It appears that calcium oxalate remains in the dissolved
state in a highly hydrated form for a length of time sufficient to
enhance penetration of impregnation of the cellulosic system. It
appears that calcium oxalate remains in the dissolved state in a
highly hydrated form for a length of time sufficient to enhance
penetration or impregnation of the cellulosic system, before
precipitation of calcium oxalate in response to separation to water
of hydration. This same effect is experienced with the combination
of magnesium and oxalic acid, only at a slower rate.
In practicing this phase of the invention for introduction of
calcium and/or magnesium oxalate, separate aqueous solutions are
prepared containing the calcium cation in one solution in an amount
within the range of 1-15 percent by weight and preferably 3-7
percent by weight, while the other aqueous solution contains the
oxalic acid anion in equivalent amounts. The two solutions are
admixed immediately prior to application with the cellulosic
material or the separate solutions are applied substantially
simultaneously to the cellulosic material or paper web, followed by
drying.
Reapplication can be made a number of times until the desired
concentration of ashing ingredients is inserted within the
cellulosic system.
As in the preceding case, the calcium and magnesium can be
substituted with barium or strontium and the oxalic acid can be
substituted with tannic, pivalic, glycolic, diglycolic, or lactic
acid.
The following example will illustrate the practice of this phase of
the invention.
EXAMPLE 3
Purified cellulose pulp is slurried with 25 times its weight of a
freshly prepared mixture of equal parts of 5 percent solution of
calcium acetate and a 5 percent solution of oxalic acid. The slurry
is cast on a screen in the usual manner for the formation of
cigarette paper. The calcium acetate and oxalic acid do not
immediately react to form an insoluble calcium oxalate, especially
when the slurry is maintained at ambient temperature or below. As a
result, the components are capable of soaking into the cellulose
fibers before the calcium oxalate is precipitated to provide
internal loading in situ in the fibers with the mineralizing agent.
This pulp is then dried, the process repeated a number of times
until the desired ash level is achieved. The calcium oxalate can be
added as an insoluble compound for suspension with the pulp to
provide a concentration within the range of 10 to 45 percent, best
results are secured, especially from the standpoint of the
characteristics of the ash, when the oxalate and the like
mineralizing agent is formed internally within the pulp fibers. The
formed paper is washed with water to remove water solubles
including acetic acid formed upon replacement by oxalic acid and
any excess oxalic acid or calcium acetate, as the case may be. Free
oxalic acid can be reintroduced as in Example 1 or the free acid
can be omitted.
When, instead of conventional cigarette paper, use is made of paper
prepared as in Examples 1 to 3, a cigarette is produced having
better aroma and taste when burned. When used in the preparation of
a cigarette or cigar with a smoking product prepared of cellulosic
material, as described in the aforementioned copending
applications, the taste and aroma of the smoking product are upset
less by the paper wrapper prepared in accordance with Examples 1 to
3 as compared with conventional cigarette paper.
This is an improvement which is important to the current field of
smoking products since it provides for better taste and odor to
current tobacco products as well as to synthesized smoking products
of any type.
A second concept of this invention resides in the practice wherein
the prepared cigarette paper, and preferably the purified cellulose
pulp of which the cigarette paper is formed, is treated to effect
selective oxidation of the methylol groups on the C.sub.6 position
of the cellulose molecule with permissible oxidation at the C.sub.2
and/or C.sub.3 position to produce a preferably partially oxidized
cellulose hereinafter referred to as oxycellulose in which the
oxidation reaction product may be comprised of polyuronic acids and
their derivatives.
In the practice of this modification of the invention, the amount
of oxidation of the cellulosic material should be limited to within
the range of 15 to 95 percent calculated on the conversion of the
methylol group on the C.sub.6 position of the cellulose molecule.
It is preferred to provide for an oxycellulose in which the level
of oxidation has been limited to within the range of 40 to 60
percent. Below the level of 15 percent oxidation the improvement of
odor and taste during pyrolysis of the paper is not significant.
Above an oxidation level of 60 percent, the oxycellulose tends to
lose some of its fibrous characteristics such that the oxycellulose
pulp becomes less capable of being interfelted and therefore less
suitable for use in the preparation of a paper of sufficient
strength and integrity for use as a cigarette wrapper. Previously
formed paper oxidized to a level beyond 60 percent similarly
becomes less suitable for use. When the oxycellulose is
characterized by more than 60 percent oxidation, the oxycellulose
can be blended with conventional pulp for use in the fabrication of
cigarette paper but it is important to have a blend in which at
least 15 percent of the total methylol groups have been oxidized in
order to achieve significant improvements. Within the preferred
range of 40 to 60 percent oxidation, the oxycellulose retains
sufficient of its fibrous characteristics to enable use of the
already formed cigarette paper or to enable use of the oxycellulose
pulp in the preparation of cigarette paper by conventional
paper-forming machines.
In effecting the desired level of selective oxidation, it is
preferred to make use of nitrogen dioxide as the oxidizing medium.
Since the preferred level of oxidation is substantially less than
that for complete oxidation, it is possible to make use of gaseous
nitrogen dioxide as the oxidizing medium. However, from the
standpoints of oxidation rate, uniformity of oxidation and process
control, it is preferred to make use of liquid nitrogen dioxide,
especially in the treatment of previously formed cigarette paper.
The oxidation reaction will hereinafter be described with reference
to the use of liquid nitrogen dioxide as the oxidizing medium but
it will be understood that corresponding results can be achieved by
the use of gaseous nitrogen dioxide.
Liquid nitrogen dioxide offers a number of advantages over gaseous
nitrogen dioxide or other oxidizing agents in that liquid nitrogen
dioxide gives the desired selectivity in oxidation of methylol on
the C.sub.6 position of the cellulose molecule. Liquid nitrogen
dioxide operates immediately and completely to wet the cellulosic
fibers so that all of the cellulosic material is subject to
immediate and uniform oxidation. Further, liquid nitrogen dioxide
is available to quench hot spots whereby heat generated by the
exothermic oxidation reaction is immediately dissipated thereby to
avoid the creation of hot spots which might otherwise lead to
combustion.
Still further, it is possible to effect modifications in the use of
liquid nitrogen dioxide whereby the reaction rate can be increased
to levels suitable for continuous processing. When use is made of
liquid nitrogen dioxide as the oxidizing medium, treatment can be
made with an amount of liquid nitrogen dioxide, one to one thousand
times the cellulosic material and preferably 25 to 50 times the
cellulosic material on a weight basis. The oxidation reaction
should be carried out with the materials at a temperature within
the range of 15.degree. to 65.degree. C. and under autogenous
pressure. Reaction at temperatures below 15.degree. C. is too slow
for commercial practice and reaction at temperatures in excess of
65.degree. often leads to undesirable side reactions and the
production of an unstable product under the conditions of use.
Within the defined range of reaction conditions, oxidation is
continued until the desired level of oxidation is achieved, as
measured by titration to determine the amount of conversion of
methylol to carboxyl groups. At 20.degree. C., the desired level
will be obtained in about 4 days for 90 to 95 percent oxidation and
in about 1 day for 40 to 60 percent oxidation. At higher reaction
temperatures of 40.degree. to 45.degree. C., the reaction time will
be reduced to the matter of an hour or less for 40 to 60 percent
oxidation and about 1 day for 90 to 95 percent oxidation.
It is possible to modify the liquid nitrogen dioxide system to
include water in the reaction medium provided that the temperature
of the reaction is maintained at a level sufficiently high to
counteract excessive ionization in the medium, as measured by its
electrical conductivity. It is believed that when the medium is
conductive, the water in the nitrogen dioxide is in the form of
nitric (and nitrous) acid which is capable of attacking and/or
degrading the fibrous cellulosic material. Thus it is desirable to
avoid formation of nitric or nitrous acids in the oxidizing medium.
We have found that the electrical conductivity of a liquid nitrogen
dioxide solution containing as little as 1 percent by weight water
is very high at 0.degree. but that the solution becomes
substantially nonconductive at 20.degree. C. The conversation range
from conductivity to nonconductivity rises in temperature with
increased concentration of water in the reaction medium. However,
when oxidizing to a level of 95 percent, it is undesirable to make
use of more than 8 percent by weight water in the liquid nitrogen
dioxide system and when oxidizing to a level within the preferred
range of 40 to 60 percent, an upper limit of about 10 percent by
weight water in the oxidizing medium is established before the
oxycellulose tends to be taken into solution.
On the other hand, the presence of water in the liquid oxidizing
medium, which is rendered relatively nonconductive by going to
elevated temperature, is effective to accelerate the rate of
oxidation so that the combination of water and elevated temperature
permits the desired level of oxidation to be achieved in a fraction
of the time required for the liquid nitrogen dioxide alone. Thus
means are provided to reduce the residence time of the fibrous
cellulosic materials to achieve the desired level of oxidation.
In the preferred practice of this concept, it is desirable to make
use of an oxidizing medium of liquid nitrogen dioxide containing
0.5 to 5 percent by weight water and preferably 1.5 to 3.5 percent
by weight water. At a temperature of 40.degree. to 45.degree. C.,
an oxidation level of 40 to 60 percent can be reached in a matter
of minutes to hours thereby to permit oxidation as a continuous
operation by passage of the paper continuously through the
oxidizing medium under autogenous pressure.
By way of still further modification, dependent upon the use of
liquid oxidizing medium, such as liquid nitrogen dioxide, with or
without water, the rate and uniformity of oxidation can still
further be improved by means of introduction into the reaction
medium of gaseous oxygen or a molecular oxygen-containing gas, such
as air or oxygen-enriched air, but in which any gas in which the
oxygen is included is an inert gas. The oxygen not only serves as a
means to agitate or stir the ingredients, but, more importantly, it
provides an oxidizing function of its own in the presence of
nitrogen dioxide thereby to contribute to the oxidation and the
rate of oxidation of the cellulosic fibers. It operates further in
the system to oxidize formed nitric oxide to nitrogen dioxide
thereby to maintain the level of oxidizing medium in the system.
When used, the amount of oxygen used should range from
equimolecular proportions with the cellulosic segments making up
the cellulosic material (such as glucose or hexose) to about twenty
times the theoretical amount, as described in our copending
application Ser. No. 745,134, filed July 16, 1968, titled
"Cellulosic Smoking Product and Method in the Preparation of Same,"
now U.S. Pat. No. 3,478,752.
The presence of calcium oxalate or other corresponding mineralizing
agent heretofore described does not interfere with the reaction of
oxidation of the cellulosic fibers, whether in the form of paper or
pulp. As a result, the described oxidation reaction can be carried
out with pulp or paper embodying calcium oxalate or other
mineralizing agent or it can be carried out with paper or pulp in
the absence of such mineralizing agent.
Having generally described the basic concepts of the modification
for providing a pulp for the manufacture of paper or a paper of
oxycellulose, examples will now be given by way of illustration,
but not by way of limitation, of the practice of this concept of
the invention.
EXAMPLE 4
Cigarette paper, previously formed of purified woodpulp, is
immersed in 100 times its weight of liquid nitrogen dioxide and
maintained at a temperature of 20.degree. C. until 50 percent of
the C.sub.6 methylol groups have been oxidized to carboxyl groups
(about 2 days). During this period, air is bubbled through the
reaction vessel at a rate of 5 to 50 parts by weight per part by
weight of cellulosic material, spread over the reaction time. The
oxidized cellulosic material still retains its fibrous
characteristics such that the paper still has strength and
integrity and can be passed through two to three water washes
wherein deionized water is flushed through the oxidized paper. The
paper is dried to about 40 to 50 percent relative humidity and
calendered for subsequent use in the conventional manner as
cigarette paper.
EXAMPLE 5
Purified woodpulp is introduced into a pressure vessel with 50
times its weight of liquid nitrogen dioxide containing 1.5 percent
by weight water. The mixture is maintained under a constant state
of agitation by recirculating a small stream of the liquid
oxidizing medium from the bottom to the top of the reaction vessel.
The reactants are maintained at a temperature of about 35.degree.
to 40.degree. C. and the autogenous pressure and reaction is
continued until 40 to 60 percent of the methylol groups on the
C.sub.6 position have been oxidized (about 2 hours). When reaction
is completed, the liquid oxidizing medium is drawn off and the
oxycellulose is washed several times with water.
The oxycellulose can be suspended in aqueous medium to form a
slurry which can be employed in the conventional manner to form
cigarette paper since the oxycellulose still retains sufficient of
its fibrous characteristics for interfelting by the paper forming
machine to produce a cigarette paper which can be processed and
used in the conventional manner.
EXAMPLE 6
The process of Example 5 is repeated with the cellulosic pulp of
Example 3 containing 10 to 45 percent by weight of internally
formed calcium oxalate.
EXAMPLE 7
Purified cellulose pulp is introduced into a pressure vessel with
30 times its weight of liquid nitrogen dioxide containing 2 percent
by weight water. The reaction is carried out under 30 p.s.i. with
the materials maintained at a temperature of 35.degree. C. until
more than 90 percent of the methylol groups on C.sub.6 have been
oxidized (about 4 to 5 hours). When oxidation has been completed,
the liquid oxidizing medium is drawn from the vessel and the
oxycellulose is washed first with anhydrous nitrogen dioxide to
remove moist nitrogen dioxide and soluble impurities such as gums,
waxes, lignins, natural resins, and the like. After evaporation of
the anhydrous nitrogen dioxide, the material is then washed with
water to wash out nitric acid and water-soluble components. Unlike
Examples 4 to 6 wherein the oxycellulose retains fibrous
characteristics sufficient to enable interfelting to form cigarette
paper, the cellulosic material oxidized to better than 90 percent
no longer retains sufficient of its fibrous characteristics to
enable fabrication into a paper of sufficient strength or integrity
for use as cigarette paper.
The oxycellulose of Example 7 is admixed in the ratio of one part
by weight oxycellulose to 0.5 to l part by weight of unmodified,
purified papermaking wood pulp and the materials are slurried in
aqueous medium having a pH below 7 and preferably within the range
of 4 to 6 to prevent solution of the oxycellulose. Powdered calcium
oxalate is included in the slurry in amount sufficient to give an
ash of 23 percent in the finished paper. The slurry is processed in
the conventional manner for paper making by casting on a
Fourdrinier screen for interfelting of the oxycellulose and pulp
fibers in uniform distribution for paper formation. The paper after
being dried and calendered can be used as cigarette paper in the
preparation of cigarettes, cigars and the like.
The papers of Examples 1 to 7 can be used in the conventional
manner as cigarette paper or cigarette wrappers with smoking
products of the type produced in accordance with the aforementioned
copending application or with tobacco or with mixtures thereof, or
with other materials capable of use as a filler for smoking in
cigarettes and cigars.
A remarkable difference will be observed from the standpoint of a
markedly improved and milder odor, aroma and taste when cigarette
paper of Examples 4 to 7 is employed instead of conventional
cigarette paper in cigarettes, cigars, and the like. This vast
difference can be detected when conventional cigarette paper is
pyrolyzed alone in a closed vessel to seal in the odor for
comparison with the pyrolysis of cigarette paper produced in
accordance with Examples 4 to 7, representative of the practice of
this invention.
Further modification, additionally to improve the taste and aroma
of cigarette paper and smoking products formed thereof, can be
achieved by subsequent treatments of the oxycellulose produced in
accordance with the practice of this invention, as by subjecting
the cellulosic material selectively oxidized with nitrogen dioxide
to a reduction reaction with a borohydride or nascent hydrogen, as
described in our copending application filed concurrently herewith
and titled "Method for Preparation of Smoking Products with
Selective Reduction Following Selective Oxidation."
For this purpose, the cellulosic fibers, which have previously been
oxidized with nitrogen dioxide (gaseous or liquid) are reacted in a
dilute aqueous solution of a borohydride under conditions which
operate to effect a reduction reaction. As the borohydride, use can
be made of alkali metal and ammonium borohydride or alkaline earth
metal borohydrides, but it is preferred to make use of an alkali
metal borohydride such as the borohydride of sodium, potassium or
lithium. Beneficial results are secured with solutions containing
the borohydride dissolved in aqueous medium in an amount within the
range of 0.5 to 5 percent by weight and preferably within the range
of 0.1 to 1 percent by weight. With such solutions, it is desirable
to carry out the reaction with materials present in the ratio of
one part by weight of the oxidized cellulosic derivative to 10 to
1,000 parts by weight of the solution and preferably 20 to 100
parts by weight of the solution. The time of exposure for reaction
is not critical since beneficial results can be secured with a
residence time of 1 minute or more but it is preferred to make use
of a reaction time within the range of 5 to 60 minutes.
Solution of the borohydride in aqueous medium usually results in an
alkaline solution having a pH above 7. When use is made of a
borohydride solution having an alkaline pH, there is a tendency for
the oxidized cellulosic material to be taken into solution.
We have found that the desired reduction reaction with a minimum of
degradation or dissolution can be achieved by adjustment of the
solution of the borohydride to a pH of 7 or below but not below 3
and preferably within the range of 6 to 7. At a pH below 3, the
borohydride becomes too unstable. The pH adjustment to the desired
level can be achieved with an organic acid, such as oxalic acid,
acetic acid or glucuronic acid, oxidized cellulose or the like
water soluble organic acid or by the use of an inorganic acid such
as hydrochloric acid and the like. It is preferred to make use of
an organic acid such as oxalic acid, otherwise subsequent treatment
would be required for removal of undesirable ions, such as the
chloride ions and the like materials introduced by the acid. In the
preferred use of oxalic acid, any of the latter which remains as a
residue need not be removed since beneficial use can be made of
oxalic acid to produce oxalates for mineralizing the smoking
product and to neutralize heavy metal ions which might otherwise be
present.
Under the conditions described, the reaction can be carried out at
a temperature within the range of 0.degree. to 30.degree. C. and
preferably within the range of 0.degree.to 25.degree. C.
This concept will now be illustrated by way of example.
EXAMPLE 8
Cellulosic paper fibers previously oxidized, as in Examples 4 to 7,
are immersed in a 0.2 percent water solution of sodium borohydride
in which the pH has been adjusted with oxalic acid to within the
range of 6.5 to 7. Exposure in the ratio of about one part by
weight oxycellulose to 100 parts by weight of solution is continued
for from 1 to 10 minutes. Thereafter, the solution is drained from
the oxidized cellulosic material and the treated fibers are rinsed
with one or more increments of deionized water.
Others of the alkali metal and ammonimum hydrides or borohydrides
can be substituted, in whole or in part, for the sodium borohydride
of Example 8 in solution in concentrations within the range of 0.1
to 1 percent by weight.
Instead of borohydride reduction, a beneficial reduction reaction
can be achieved by the use of hydrogen freshly released from the
negative pole of an electrolytic cell in which the oxidized
cellulosic material is immersed, as illustrated by the following
example. This example finds best use in the treatment in a
continuous operation of an endless web of cigarette paper
previously oxidized as in the manner of Example 4.
EXAMPLE 9
The oxidized cellulosic cigarette paper is passed between
horizontally disposed, vertically spaced-apart poles of an
electrolytic cell with the negative pole lowermost in the form of a
metal gauze or metal screen. A plastic screen such as porous
polyethylene is positioned to separate the oxidized cellulosic
paper from the positive pole. Use is made of an electrolyte
formulated of oxalic acid dissolved in aqueous medium in an amount
within the range of 0.1 to 4 percent by weight and a current having
a density of 5 to 50 a./cm..sup.2 of screen area is passed between
the poles while the electrolyte is maintained at ambient
temperature.
Hydrogen gas bubbles up from the negative pole through the web of
oxidized cellulosic material as it is advanced continuously through
the cell. The freshly formed nascent hydrogen is effective to
reduce at least some of the nitro, quinone, keto or aldehyde groups
and unsaturates in the oxidized cellulosic paper fibers. Upon
issuance from the electrolyte, the treated web is rinsed with one
or more increments of water and dried.
The reduction treatment described is not essential to the
preparation of an improved cigarette or cigar wrapper but it will
be found that such reduction still further improves the taste and
aroma upon pyrolysis of the paper, whereby an improved smoking
product can be secured.
By way of a still further modification, instead of introducing the
mineralizing or ashing ingredients prior to oxidation, some
advantage can be derived from the introduction of the ashing
components after oxidation has been carried out whereby, with or
without reduction, calcium and/or magnesium oxalate or the like
ashing ingredients can be embodied as an internal component formed
in situ within the cellulosic system, although limited benefits are
derived when the ashing ingredients are applied externally onto the
oxidized cellulosic fibers. It appears, at present, that the use of
calcium or magnesium oxalate is perferable since such oxalates,
when incorporated within the fibers of the oxidized cellulosic
material, are effective ash-producing agents. Moreover, the
oxalates do not have the side effects of producing undesirable
odors or of affecting the combustion rate of the material. It is
believed that the oxalate anion is sufficiently refractory to
maintain the calcium or magnesium as an oxalate while the oxidized
cellulose is undergoing pyrolysis. This prevents the immediate
formation of calcium or magnesium polyuronate and the corresponding
pyrolytic odor effects, reminiscent of ketones as produced by the
pyrolysis of organic calcium salts.
The aforesaid oxalates are insoluble and therefore the problem is
to provide means whereby such normally insoluble ash-forming
materials may be incorporated into the fibers of the oxidized
cellulose. We have discovered a number of ways in which such
mineralizing materials can be introduced into the fibers of the
oxidized cellulosic material.
For example, if oxidized cellulose is the starting product,
incorporation of the oxalate into the fibers can be achieved by
first soaking the oxidized cellulose in a soluble mineral salt
solution such as a dilute solution of calcium acetate. The cation
readily incorporates itself into the oxidized cellulosic material
to form the calcium salt of the oxidized cellulose which can be
described as a calcium polyuronate. This treatment is followed by a
soaking in a solution of oxalic acid whereby the calcium
polyuronate reacts with the oxalic acid which regenerates the
polyuronic acid and produces insoluble calcium oxalate as an
internal component inside the oxidized cellulosic fibers. Acetic
acid which is formed during the replacement reaction and any excess
oxalic acid is removed from the treated cellulosic material by
means of a water wash.
The calcium can be introduced in the dissolved state in an aqueous
medium in which the oxidized cellulosic material is suspended and
wherein the calcium ion is made available for reaction to form
insoluble calcium polyuronate. For this purpose, the calcium may be
introduced as a water soluble salt such as calcium acetate, calcium
chloride, calcium glucuronate, calcium bicarbonate, or the like,
but it is preferred to make the calcium available for reaction with
the oxidized cellulosic material by means of dissolving chalk or
lime (slaked lime or preferably quicklime) in an acidic aqueous
medium into which the oxidized cellulosic material is introduced to
take up calcium to form insoluble calcium polyuronate. Thereafter
oxalic acid is added whereby the oxalic acid which diffuses into
the fiber is taken up by the calcium to form the calcium oxalate in
situ within the cellulosic fiber, and thus to regenerate the
oxidized cellulosic material in its original acidic condition.
When use is made of lime as the source of calcium, the acidic
aqueous medium to which the calcium is added can be formulated from
an organic or inorganic acid, such as acetic acid, nitric acid,
hydrochloric acid, glucuronic acid and the like, with the acid
present in an amount to provide an acidic solution having a pH less
than 7 and preferably a pH within the range of 4 to 5. With
hydrochloric acid or with acetic acid, the desired level can be
obtained with the acid present in the aqueous medium in an amount
within the range of 0.1 to 2 percent by weight. The pH of the
solution into which the oxidized cellulose is introduced should not
exceed 6.5, otherwise the oxidized cellulosic material will tend to
dissolve therein. As a result, lime should not be added in an
amount which will operate to raise the pH above 6.5 and it is
preferred to add lime in an amount to raise the pH of the acidic
aqueous medium to within the range of 4 to 6, and preferably about
5. For this purpose, lime can be added in an amount within the
range of 0.01 to 4 percent by weight and preferably in an amount
within the range of 0.01 to 1 percent by weight and still more
preferably in an amount within the range of 0.02 to 0.05 percent by
weight. Calcium oxide readily dissolves in the acidic aqueous
medium to form the corresponding calcium salt. The addition of lime
will operate to raise the pH of the solution. To avoid localized
effects, it is preferred to conduct the calcium replenishment in a
portion of the liquid separate from the portion containing the
oxidized cellulose.
The oxidized cellulosic material, after taking up a suitable
quantity of calcium ion, is then reacted with at least a
stoichiometric amount of oxalic acid in solution in aqueous medium
at a pH within the range of 2 to 7 and preferably within the range
of 3 to 5. Calcium is taken from the calcium polyuronate to form
the corresponding calcium oxalate in situ in the oxidized
cellulosic fibers. Calcium oxalate is comparatively stable by
comparison with the oxidized cellulosic material so that it will
remain while the cellulosic material is being pyrolyzed during
smoking of the smoking product.
The reaction to form the calcium oxalate is not critically
dependent upon temperature. However, it is preferred to carry out
the described reaction at a temperature within the range of
0.degree. to 40.degree. C. with a reaction time of 5 to 10 minutes.
Longer times can be used but will be unnecessary.
Instead, the mineralizing agents can be introduced into the
oxidized cellulosic material in the manner previously described by
introduction into the paper or cellulosic fiber and as illustrated
in Examples 1 to 3, but with the oxidized cellulosic material
substituted for the cellulosic paper or pulp.
The foregoing concepts of mineralizing the cellulosic material
after oxidation reaction are illustrated by the following
examples.
EXAMPLE 10
Oxidized cellulose, prepared in accordance with Examples 4 to 7, or
oxidized cellulose which has been reduced in accordance with
Examples 9 and 10 is introduced into a reaction vessel with
sufficient water to provide mobility of the slurry upon stirring.
Acetic acid is added to provide a concentration of 2 percent by
weight and the lime is added in an amount to provide an ash level
of about 5 percent when completely absorbed by the oxidized
cellulosic material. The pH of the solution will rise from 4 to
about 5 and as the calcium cation is taken up by the oxidized
cellulose, the pH of the solution will fall back to about 4. After
about 5 minutes at ambient temperature, oxalic acid is added in a
stoichiometric amount with a drop in pH to about 3. As the oxalic
acid is absorbed into the fibers by reaction with calcium to form
calcium oxalate, the pH of the system will rise again to about
4.
The foregoing cycle may be repeated a number of times to produce an
oxidized cellulosic material containing calcium oxalate internally
dispersed with the fibrous system in an amount corresponding to 5
to 45 percent by weight calculated on calcium carbonate ash
level.
After the final cycle, the treated oxidized cellulosic material is
thoroughly washed with deionized water to remove excess oxalic acid
and the resulting cellulosic material is dried.
The cellulosic pulp which has been oxidized and ashed can be
suspended in aqueous medium to form a funish used in the
preparation of paper.
EXAMPLE 11
The process of Example 10 is repeated except that the paper that is
formed and dried is subsequently wet with an aqueous solution
containing 0.25 percent by weight oxalic acid to reintroduce oxalic
acid into the formed paper.
EXAMPLE 12
The process of Example 10 is repeated but instead of treating the
oxidized cellulosic material with lime dissolved in acetic acid,
the oxidized cellulosic material is treated directly with an
aqueous solution containing about 0.1 percent by weight calcium
acetate followed by the introduction of the solution of oxalic
acid.
EXAMPLE 13
The procedure of Examples 10, 11, and 12 is followed except that
magnesium, strontium or barium oxide or acetate are substituted in
equivalent amounts for the calcium oxide and instead of making use
of oxalic acid, tannic acid is substituted to form the
corresponding tannate.
EXAMPLE 14
A 5 percent solution of calcium acetate is provided in one
container and a 6 percent solution of oxalic acid is provided in
another and the two solutions are mixed one with the other and
immediately applied by spraying onto the oxidized cellulosic
material. Application is made while the materials are maintained at
a temperature within the range of 0.degree. to 10.degree. C. to
provide the oxidized cellulosic material with calcium oxalate which
remains soluble for a period of time to enable penetration into the
oxidized cellulosic system and which thereafter precipitates out
upon loss of water of hydration. After aging the material for 10 to
30 minutes to allow precipitation to be completed, the oxidized
cellulosic material is washed with water to remove soluble salts
and the resulting product is dried. The application can be made a
number of times to provide the desired ash level. The foregoing
applications may be made with the oxidized cellulose in the form of
pulp or in the form of paper to incorporated the desired ashing
ingredients. When in the final form, the dried paper of ashed and
oxidized cellulosic material may be treated with a 0.1 to 0.5
percent by weight solution of oxalic acid in deionized water to
incorporate up to 5 percent by weight of oxalic acid into the
fibrous system.
The cellulosic materials and paper formed thereof in accordance
with the foregoing description may be further processed in the
manners described in the aforementioned copending applications to
incorporate various agents such as agents for controlling the
burning rate by the addition of potassium, rubidium or cesium
salts, or the addition of agents to provide neutralization of the
smoke, such as by the addition of ammonia, or amine salts or
nicotine, or by the introduction of agents for generation of
increased amounts of smoke as by the introduction of fatty acids,
esters and ethers, and the introduction of coloring agents, all as
described in the aforementioned copending parent applications.
It will be apparent from the foregoing that we have provided a
cigarette paper and method and means for producing same wherein the
taste and aroma of the cigarette paper during pyrolization and
during the burning of the smoking product wrapped therein are
markedly improved. Such papers or wrappers, produced in accordance
with the practice of this invention, find beneficial use with
current smoking products or smoking products of the type fabricated
of cellulosic materials or other synthesized smoking products.
It will be understood that changes may be made in the details of
formulation and operation without departing from the spirit of the
invention, especially as defined in the following claims.
* * * * *