U.S. patent number 3,618,619 [Application Number 05/016,209] was granted by the patent office on 1971-11-09 for tobacco smoke filters.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to J OHN E. Kiefer.
United States Patent |
3,618,619 |
Kiefer |
November 9, 1971 |
TOBACCO SMOKE FILTERS
Abstract
Crimped celluclose acetate filter tow having dispersed therein
at least one metal oxide selected from zinc oxide, ferric oxide and
cuprous oxide, the tow being adapted to be activated by the
application thereto of an organic activating agent to alter the
characteristics of the individual filaments of the tow to make
accessible the oxide dispersed in the two to hydrogen cyanide for
removal thereof from the vapor phase of tobacco smoke.
Representative of the organic activating agents are triethylene
glycol, triacetin, polyethylene glycol, triethylene glycol
diacetate, triethyl citrate, propylene glycol, and dimethoxyethyl
phthalate. Also disclosed are tobacco smoke filters made from the
tow.
Inventors: |
Kiefer; J OHN E. (Kingsport,
TN) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
21775949 |
Appl.
No.: |
05/016,209 |
Filed: |
March 3, 1970 |
Current U.S.
Class: |
131/342;
131/343 |
Current CPC
Class: |
A24D
3/14 (20130101); A24D 3/16 (20130101) |
Current International
Class: |
A24D
3/14 (20060101); A24D 3/16 (20060101); A24D
3/00 (20060101); A24f 013/06 () |
Field of
Search: |
;161/174
;131/10,10.3,10.5,10.7,10.9,261,264-269 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rein; Melvin D.
Claims
I claim:
1. Crimped cellulose acetate tow adapted to be cut up into filter
plugs, said tow being made up of a multitude of continuous
filaments, the tow being characterized in that the individual
filaments thereof are spun from a cellulose acetate solution having
dispersed therein about 4 percent or more, by weight of the tow, of
discrete particles of a metal oxide selected from zinc oxide,
ferric oxide and cuprous oxide, the metal oxide particles ranging
in size up to about 1 micron, said tow activated by the application
thereto of an organic activating agent solvent selected from the
group consisting of triethylene glycol, triacetin, polyethylene
glycol, triethylene glycol diacetate, triethyl citrate, propylene
glycol and dimethoxyethyl phthalate to alter characteristics of the
individual filaments in such manner that they are permeable to
hydrogen cyanide and the action of the exposed metal oxides in
removing this gas from the vapor phase of the tobacco smoke is
facilitated.
2. Crimped cellulose acetate filter tow of claim 1 in which the
denier/filament ranges from 1.5 to 16 and the crimps per inch range
from 7 to 20.
3. Tobacco smoke filter comprising a filter plug of crimped
cellulose acetate filaments, said filaments being spun from a
solution of cellulose acetate having dispersed therein about 4
percent or more, by weight of discrete particles, of a compound
selected from zinc oxide, ferric oxide or cuprous oxide, said
filaments having been activated with an organic activating agent
selected from the group consisting of triethylene glycol, triactin,
polyethylene glycol, triethylene glycol diacrtate triethyl citrate,
propylene glycol and dimethoxyethyl phthalate to alter
characteristics of said acetate cellulose acetate filaments in such
manner that the permeability to hydrogen cyanide of the filaments
is increased and the removal of this gas from the vapor phase of
the tobacco smoke by exposure to the contained metal oxide, is
facilitated. said tow being made up of a multitude of continuous
filaments, the tow being characterized in that the individual
filaments thereof are spun from a cellulose acetate solution having
dispersed therein about 4 percent or more, by weight of the tow, of
discrete particles of a metal oxide selected from zinc oxide,
ferric oxide and cuprous oxide, the metal oxide particles ranging
in size up to about 1 micron, said tow activated by the application
thereto of an organic activating agent solvent selected from the
group consisting of triethylene glycol, triacetin, polyethylene
glycol, triethylene glycol diacetate, triethl citrate, propylene
glycol and dimethoxyethyl phthalate to alter characteristics of the
individual filaments in such manner that they are permeable to
hydrogen cyanide and the action of the exposed metal oxides in
removing this gas from the vapor phase of the tobacco smoke is
facilitated.
Description
This invention relates to a new and improved tow useful in the
manufacture of tobacco smoke filters and filters made
therefrom.
More particularly the invention concerns crimped cellulose acetate
filter tow having dispersed therein at least one metal oxide
selected from zinc oxide, ferric oxide and cuprous oxide, the tow
when activated by the application thereto of an organic activating
agent is rendered reactive with hydrogen cyanide in the vapor phase
of tobacco smoke.
The presence of ciliatoxic agents in tobacco and especially
cigarette smoke has been demonstrated by numerous investigators
whose test specimens ranged from protozoan to human cilia, the
latter serving to clear the broncial tree of inhaled foreign
matter. In every case, in vitro or in vivo, cigarette smoke was
found to be toxic to the cilia. Kensler and Battista have reported
that the vapor phase of cigarette smoke is responsible for the
ciliatoxic properties of smoke. Walker and Kiefer found, in their
study of smoke gases, that hydrogen cyanide was the most active
ciliatoxic agent in cigarette smoke gases. Numerous other studies
are reported in the literature concerning the toxicity of hydrogen
cyanide. Consequently, much effort has been applied to the
development of filters which would selectively remove this
undesirable component from cigarette smoke.
In U.S. Pat. No. 3,251,365, Keith discloses a cigarette filter
containing adsorbent granules impregnated with certain zinc and
iron oxides which removes about 50 percent of the hydrogen cyanide
in the smoke from cigarettes equipped with these filters. The
adsorbent granules are essential in the operation of his invention
since he states that the smooth and nonporous nature of the
commonly used fibrous filtering materials, while effective in
capturing tobacco smoke droplets, does not present a sufficient
surface area to effectively adsorb gaseous molecules.
More recently, Horsewell and Tolman (U.S. Pat. No. 3,403,690)
disclosed a cigarette filter containing an organozinc salt compound
that is claimed to remove a substantial portion of the hydrogen
cyanide from cigarette smoke. The organozinc salts are added as
aqueous solutions. Application of a water solution to a
conventional cellulose acetate filter tow destroys the crimp of the
tow and therefore its effectiveness as a filter for tar and
nicotine is decreased. Furthermore, since the salts are on the
surface of the fibers within the filter, they may be transferred to
the smoker's mouth or lungs via the smoke aerosol.
In considering the prior art I have found that U.S. Pat. No.
2,136,201 discloses cellulose ester textile yarns which have been
delustered by means of incorporating therein certain pigments. Some
of these pigments are titanium dioxide, zinc oxide, antimony oxide,
barium sulfate, etc. However, there is no suggestion that any of
the textile yarns disclosed in the patent would be useful in
cigarette filters and particularly there is simply no suggestion by
the inventors thereof that the additives did any more than deluster
the yarn. U.S. Pat. No. 2,057,712 discloses that oxides, hydroxides
or hydrated oxides of titanium, aluminum, zinc and tin which are
precipitated from aqueous media in a gelatinous or flocculent form
are useful to deluster cellulose acetate yarn and have the
advantage of not unduly cutting or wearing away of guides on
processing equipment.
I have discovered an improved cellulose acetate tow particularly
adapted for making tobacco smoke filters that effectively adsorb
hydrogen cyanide from tobacco smoke. The tow of this invention
offers the advantage of making available the metal oxides to effect
the removal of hydrogen cyanide from tobacco smoke without the risk
of the oxides sifting out of the filter and into a smoker's mouth
and lungs. Likewise, the use of the tow of this invention does not
require that additive be sprayed, dusted, etc., on the tow by the
plug manufacturer. In fact, no additional process steps are
demanded of the plug maker and yet a superior filter is produced.
The tow of this invention provides a simple and economical way to
produce a tobacco smoke filter having the desirable property of
removing hydrogen cyanide from tobacco smoke. The fabrication of
the filter requires no extra labor or equipment since the metal
oxides are present in the filaments of the tow as spun by the tow
manufacturer.
The unexpected result obtained by this invention is not fully
understood. Although the metal oxides are dispersed within the
fiber, the fiber can be activated by certain organic activating
agents. One possible explanation is that the activating agent
increases the permeability of the cellulose acetate matrix for
hydrogen cyanide, thus the hydrogen cyanide molecules can penetrate
the surface of the fiber and make contact with the metal oxide. I
have found that about 4 percent of the oxide based on the weight of
the tow is necessary to result in appreciable adsorption of
hydrogen cyanide and that more than about 15 percent does not add
any appreciable adsorption characteristic to the activated tow.
Further, greater amounts tend to create problems in the spinning of
the tow.
Generally, the tow of this invention is made by incorporating into
a spinning solution a finely ground zinc oxide, ferric oxide or
cuprous oxide ranging in size up to about one micron and in the
amount of about 4 percent or more, by weight of the tow, the
spinning solution comprising cellulose acetate and a solvent such
as acetone. Methods for dispersing particles such as these oxides
in spinning solutions are well known. The spinning solution is
forced through a spinneret and pulled into a fiber by the
conventional techniques for manufacturing cellulose acetate fibers.
The denier per filament may range from about 1.5 denier per
filament to about 16 denier per filament and the crimps per inch
may range from about 7 to about 20. The fibers are bundled together
and crimped in a manner similar to that described in U.S. Pat. No.
2,747,233. The tows have physical properties and appearances
similar to those of conventional cellulose acetate tows used in the
manufacture of cigarette filters. The surface of the fibers are
virtually identical in appearance to convention cellulose acetate
fibers.
As a preferred embodiment of this invention I provide crimped
cellulose acetate filter tow made up of a multitude of continuous
filaments, the tow being characterized in that the individual
filaments thereof have dispersed therein about 4 percent or more,
by weight of the tow, of discrete particles of a metal oxide
selected from zinc oxide, ferric oxide and cuprous oxide, the metal
oxide ranging in size up to about 1 micron, said tow being adapted
to be activated by the application thereto of an organic activating
agent to alter characteristics of the individual filaments of said
tow to make accessible said metal oxides to hydrogen cyanide for
removal thereof from the vapor phase of tobacco smoke. The tow
ranges from 1.5 to 16 denier per filament and is provided with 7 to
20 crimps per inch. Representative of organic activating agents
which are useful as activators in this invention are triethylene
glycol, triacetin, polyethylene glycol, triethylene glycol
diacetate, diethyl citrate, propylene glycol and di(methoxyethyl)
phthalate.
I provide a process for producing cellulose acetate filter tow
having improved characteristics comprising opening cellulose
acetate tow which has dispersed in the filter tow about 4 percent
or more by weight of the tow, of discrete particles of at least one
metal oxide selected from zinc oxide, ferric oxide and cuprous
oxide, the particles ranging in size up to about 1 micron; and
applying an organic activating agent to said tow to activate said
tow by altering characteristics of the individual filaments to make
accessable said metal oxides to hydrogen cyanide for removal
thereof from the vapor phase of tobacco smoke.
A process for producing tobacco smoke filters of this invention
having improved affinity for hydrogen cyanide in tobacco smoke,
comprises opening cellulose acetate tow which has dispersed in the
filaments thereof about 4 percent or more, by weight of the tow, of
discrete particles of at least one metal oxide selected from zinc
oxide, ferric oxide and cuprous oxide, the particles ranging in
size up to about 1 micron, applying an organic activating agent to
said tow to activate said tow by altering characteristics of the
individual filaments to make accessable said metal oxides to
hydrogen cyanide for removal thereof from the vapor phase of
tobacco smoke, and forming said filaments into a filter plug.
A further embodiment of this invention is a tobacco smoke filter
comprising a filter plug of crimped cellulose acetate filament,
said filaments having dispersed therein about 4 percent or more by
weight of the tow of discrete particles of a compound selected from
zinc oxide, ferric oxide or cuprous oxide, said filaments having
been activated with an organic activating agent to alter the
characteristics of said cellulose acetate filaments to make
accessable the metal oxides to hydrogen cyanide for removal thereof
from the vapor phase of tobacco smoke.
A still further embodiment of this invention is a shaped article
comprising cellulose acetate fiber having dispersed therein a
compound selected from zinc oxide, ferric oxide or cuprous oxide,
the article having been activated by subjecting it to plasticizing
action of an organic activating agent to impart thereto an affinity
for hydrogen cyanide found in the vapor phase of tobacco smoke.
Another process for manufacturing cellulose acetate tow for tobacco
smoke filter comprises dispersing in cellulose acetate dope about b
4 percent or more, by weight of the tow, of a compound selected
from zinc oxide, ferric oxide or cuprous oxide, spinning filaments
from said cellulose acetate dope, forming said filaments into a
tow, and treating said filaments with an organic activating agent
to activate the filaments to render them capable of adsorbing
hydrogen cyanide from tobacco smoke.
The tow can be boxed, baled, or packaged by any of the methods now
used for conventional cellulose acetate filter tow. When
nonactivated textile tows made by this method are formed into
cigarette filters they exhibit the same properties as filters made
from conventional cellulose acetate tow in that they remove a
substantial portion of the tars and nicotine from cigarette smoke,
by are not effective for adsorbing gases such as hydrogen cyanide.
However, after the tow is treated with an activating solvent, it
adsorbs hydrogen cyanide readily.
This invention will be further illustrated by the following
examples of preferred embodiments, although it will be understood
that these examples are included merely for purposes of
illustration and are not intended to limit the scope of the
invention.
EXAMPLE 1
Twelve parts of zinc oxide particles (Horse Head Kadox-15) were
dispersed in a spinning solution consisting of 88 parts of
cellulose acetate and 400 parts of acetone. The dispersion was spun
into fibers using a conventional spinning cabinet. The fibers were
3.3 denier per filament and had an average tensile strength of 1.14
grams per denier. The fibers were white and had the appearance of
conventional cellulose acetate fibers. Examination of the fibers
with a light microscope and with a scanning electron microscope did
not reveal the presence of any particles on the surface of the
fibers. Fifteen thousand fibers were bundled together and passed
through a filter tow crimper. The fibers in the crimped tow were
separated by combing, then pulled together into a plastic cylinder
which has an internal circumference of 22 mm. The cylinder was cut
into 20-mm. segments or filters and divided into two equal samples
of five filters each. One sample was designated control filters and
the other set was designated activated filters. Diethylether, as a
carrier, containing 15 mg. of triethylene glycol and 15 mg. of
triacetin was added to each filter designated activated. The
diethylether was removed by evaporation, then both types of filters
were attached to 85-mm. cigarettes. A 20-mm. segment of tobacco was
removed from each of the cigarettes so that their total length was
85 mm. The cigarettes were smoked with an automatic smoking device
and the amount of hydrogen cyanide delivered by each cigarette was
determined spectrophotometrically. The results were as follows:
Hydrogen Cyanide Type Filter Cigarette Found, .mu.g./Cigarette
__________________________________________________________________________
Cigarette without filter 227 Cigarette with unactivated filter 204
Cigarette with activated filter 106
__________________________________________________________________________
EXAMPLE 2
Eight parts of zinc oxide particles (Horse Head Kadox-15) were
dispersed in a spinning solution consisting of 92 parts of
cellulose acetate and 400 parts of acetone. The dispersion was spun
into fibers using a conventional spinning cabinet. The fibers were
3.3 denier per filament and had an average tensile strength 1.16
grams per denier. Fifteen thousand fibers were bundled together and
passed through a filter tow crimper. The tow was spread to a band
width of 12 inches and sprayed with a solution of 1:1
triacetin:triethyleneglycol until the tow contained 21 percent of
the solution. It was then pulled into a plastic tube and cured
overnight. The plastic tube was cut into 20-mm. lengths. Control
filters were made by the same procedure except that no zinc oxide
was added to the spinning solution. Both sets of filters were
attached to cigarettes and tested as in example 1. The cigarettes
containing the control filters delivered 161 .mu.g. of hydrogen
cyanide per cigarette compared to only 89 .mu.g. of hydrogen
cyanide for the cigarettes with the zinc oxide filters. Cigarettes
without filters delivered 200 .mu.g. of hydrogen cyanide.
EXAMPLE 3
Ten parts of ferric oxide particles were dispersed in a spinning
solution consisting of 90 parts of cellulose acetate and 400 parts
of acetone. The dispersion was spun into fibers of 5 denier per
filament. Nine thousand fibers are bundled together and crimped by
conventional techniques. The crimped tow was bonded, treated with
11 percent triethylene glycol diacetate, and recompacted into a
cord and drawn through a device that seals it with a thin paper
wrapper into the form of a continuous rod having a circumference of
24.8 mm. As the rod exited from the machine it was cut into 120 mm.
lengths. After curing for 2 hours the rods were cut into six equal
segments which were attached to 85-mm. cigarettes; 20-mm. segments
of tobacco were removed from each of the cigarettes so that the
total length of each cigarette was 85 mm. The cigarettes containing
the filter deliver 81 .mu.g. of hydrogen cyanide compared to 231
.mu.g. for 85-mm. nonfilter cigarettes.
EXAMPLE 4
Twelve parts of cuprous oxide particles were dispersed in a
spinning solution consisting of 88 parts of cellulose acetate and
400 parts of acetone. The dispersion was spun into fibers of 3
denier per filament. Fifteen thousand fibers are bundled together
and crimped by conventional techniques. The crimped tow was treated
with 15 percent of a mixture of 1:1 triethyl citrate:tetraethylene
glycol then made into cigarette filters by the procedure outline in
example 3. Cigarettes equipped with these filters deliver 72 .mu.g.
of hydrogen cyanide compared to 231 .mu.g. for 85-mm. nonfilter
cigarettes.
EXAMPLE 5
Four parts of zinc oxide particles (Horse Head Kadox-15) were
dispersed in a spinning solution consisting of 96 parts of
cellulose acetate and 400 parts of acetone. The dispersion was spun
into fibers using a conventional spinning cabinet. The fibers were
3.3 denier per filament and had an average tensile strength of 1.16
grams per denier. Fifteen thousand fibers were bundled together and
passed through a filter tow crimper. The tow was spread to a band
width of 12 inches and sprayed with a solution of 1:1
triacetin:triethyleneglycol until the tow contained 21 percent of
the solution. It was then pulled into a plastic tube and cured
overnight. The plastic tube was cut into 20-mm lengths. Control
filters were made by the same procedure except that no zinc oxide
was added to the spinning solution. Both sets of filters were
attached to cigarettes and tested as in example 1. The cigarettes
containing the control filters delivered 161 .mu.g. of hydrogen
cyanide per cigarette compared to only 116 .parallel.g. of hydrogen
cyanide for the cigarettes with the zinc oxide filters. Cigarettes
without filters delivered 200 .mu.g. of hydrogen cyanide.
EXAMPLE 6
Filters were prepared as in example 1 except that the activating
solution contained 10 mg. of propylene glycol and 20 mg. of
triacetin. Cigarettes equipped with these filters deliver 110
.mu.g. of hydrogen cyanide.
EXAMPLE 7
Filters were prepared as in example 1 except that the activating
solution contained 15 mg. of polyethylene glycol (molecular weight
of 600) and 15 mg. of triacetin. Cigarettes equipped with these
filters deliver 95 .mu.g. of hydrogen cyanide.
EXAMPLE 8
Filters were prepared as in example 1 except that the activating
solution contained 20 mg. of dimethoxyethyle phthalate and 10 mg.
of triethylene glycol. Cigarettes equipped with these filters
deliver 98 .mu.g. of hydrogen cyanide.
EXAMPLE 9
Filters were prepared as in example 1 except that the activating
solution contained 15 mg. of triacetin. Cigarettes equipped with
these filters deliver 118 .mu.g. of hydrogen cyanide.
The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *