U.S. patent number 3,608,564 [Application Number 04/825,069] was granted by the patent office on 1971-09-28 for cigarette filter.
This patent grant is currently assigned to Mitsubishi Acetate Co., Ltd., Mitsubishi Rayon Co., Ltd.. Invention is credited to Katsumi Hayashi, Shigeya Hayashi, Takashi Kaneko, Kazuo Kuwahara, Kenji Okano, Atsushi Saito, Hiroji Takahashi.
United States Patent |
3,608,564 |
Takahashi , et al. |
September 28, 1971 |
CIGARETTE FILTER
Abstract
Cigarette filters comprising one graft polymer selected from the
group consisting of polyvinyl alcohol grafted with at least one
monoethylenically unsaturated vinyl monomer and partially
saponified polyvinyl alcohol grafted with at least one
monoethylenically unsaturated vinyl monomer. A plug comprising a
bundle of opened fibers to fit a cigarette carries said
polymer.
Inventors: |
Takahashi; Hiroji (Hiroshima,
JA), Saito; Atsushi (Toyama, JA), Kuwahara;
Kazuo (Yamaguchi, JA), Hayashi; Katsumi (Tokyo,
JA), Kaneko; Takashi (Hiroshima, JA),
Hayashi; Shigeya (Tokyo, JA), Okano; Kenji
(Hiroshima, JA) |
Assignee: |
Mitsubishi Rayon Co., Ltd.
(Chuo-ku, Tokyo, JA)
Mitsubishi Acetate Co., Ltd. (Chuo-ku, Tokyo,
JA)
|
Family
ID: |
12366888 |
Appl.
No.: |
04/825,069 |
Filed: |
May 15, 1969 |
Foreign Application Priority Data
|
|
|
|
|
May 15, 1968 [JA] |
|
|
43/32728 |
|
Current U.S.
Class: |
131/342;
131/332 |
Current CPC
Class: |
A24D
3/08 (20130101) |
Current International
Class: |
A24D
3/08 (20060101); A24D 3/00 (20060101); A24b
015/02 (); A24d 001/06 () |
Field of
Search: |
;131/266,269,267
;260/885 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
irwin, T. Hydron New Miracle Plastic With Myriad of Uses Popular
Science. Vol. 194, No. 2, February, 1969 p. 92-95. Pages 93 &
95 cited..
|
Primary Examiner: Koren; Samuel
Assistant Examiner: Yahwak; George M.
Claims
We claim:
1. In a cigarette filter comprising a plug made from a bundle of
opened fibers, the improvement which comprises said fibers having
dispersed thereon a porous, finely divided, substantially
hydrophobic graft polymer selected from the group consisting of
polyvinyl alcohol grafted with at least one monoethylenically
unsaturated vinyl monomer and partially saponified polyvinyl
alcohol grafted with at least one monoethylenically unsaturated
vinyl monomer.
2. Cigarette filters of claim 1 wherein said partially saponified
polyvinyl alcohol has a saponification value ranging from about 60
to about 92 percent.
3. Cigarette filters of claim 1 wherein said grafted polymer has a
polymerization degree of from 300 to 10,000.
4. Cigarette filters of claim 1 wherein at least one of said vinyl
monomers is a compound selected from the group consisting of lower
alkyl esters of acrylic acid and lower alkyl esters of methacrylic
acid.
5. Cigarette filters of claim 4 wherein said lower alkyl ester of
acrylic acid is a compound selected from the group consisting of
methyl acrylate, ethyl acrylate and butyl acrylate.
6. Cigarette filters of claim 4 wherein said lower alkyl ester of
methacrylic acid is methyl methacrylate.
7. Cigarette filters of claim 1 wherein the grafting ratio ranges
from about 10 to about 310 percent by weight of the polymer to be
grafted.
8. Cigarette filters of claim 1 wherein said grafted polymer is a
finely divided powder having a particle size ranging from about 10
to about 300 mesh.
9. Cigarette filters of claim 8 wherein said grafted polymer is a
finely divided powder having a particle size of from about 60 to
about 80 mesh.
10. Cigarette filters of claim 8 wherein said finely divided powder
has a surface area of from about 15 to about 200 m..sup.2 /g.
11. Cigarette filters of claim 8 wherein said finely divided powder
is porous and has a specific gravity of from about 0.2 to about
1.1.
12. Cigarette filters of claim 8 wherein said plug is a fiber
tow.
13. Cigarette filters of claim 8 wherein the weight of said finely
divided powder ranges from about 5 to about 80 percent based on the
weight of said plug.
14. Cigarette filters of claim 1 wherein said plug comprises a
crimped fiber bundle having a monofilament size ranging from about
1.6 to about 15 denier and from about 30,000 to about 90,000 total
filament denier.
15. Cigarette filters of claim 14 wherein said fibers have crimps
of from about 5 to 30/inch.
16. Cigarette filters of claim 14 wherein said fibers are cellulose
diacetate fibers.
17. Cigarette filters of claim 14 wherein said fibers are
polypropylene fibers.
18. Cigarette filters of claim 14 wherein said fibers are viscose
fibers.
19. Cigarette filters of claim 1 wherein said plug comprises fibers
treated with an adhesive consisting of a solution or dispersion
containing more than 20 percent by weight of a plasticizer.
20. Cigarette filters of claim 19 wherein said fibers are sprayed
with said adhesive in an amount of from 5 to 18 percent by weight
of said fibers.
21. Cigarette filters of claim 19 wherein said plasticizer is a
compound selected from the group consisting of triacetin, ethylene
glycol acetate, polyethylene glycol acetate, methyl ethyl ether,
and vinyl acetate.
22. Cigarette filters of claim 14 wherein the monofilament size of
the fiber bundle ranges from 1.6-8.0 denier.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a cigarette filter which effectively
removes tar and nicotine, and to a method of making the same.
2. Description of the Prior Art
Hitherto, many species of fibrous materials have been used as the
raw material for cigarette filters. As an excellent filter produced
commercially, there is one comprising a bundle of crimped cellulose
acetate fibers as described in U.S. Pat. No. 2,794,239. This filter
has a certain degree of filtration capacity for injurious
materials, it is easy to form it continuously and quickly in a rod
shape and it is possible to use nonvolatile plasticizers such as
triacetin, etc. However, it is still necessary to develop a filter
having a high filtration ratio, since injurious materials are not
completely removed from smoke of the cigarette by the above filter,
and the ratio of tar and nicotine removal is not high.
Other methods comprise varying the surface and section of the
filter fibers, and using starch or derivatives thereof, cellulose
derivatives such as cellulose, methyl cellulose, oxycellulose and
partially hydrolyzed cellulose, vinyl polymers such as polymethyl
methacrylate, polyvinyl acetate and polyvinyl butyral, activated
alumina, silica gel, ion exchange resins and activated carbon as
the adsorbent. These have a fault of impairing the flavor of
tobacco, though the nicotine removal thereof is excellent.
This invention has been completed as the result of many studies
about methods for producing a cigarette filter having good tar and
nicotine removal which does not injure the flavor of the cigarette
at smoking.
SUMMARY OF THE INVENTION
The present invention involves the discovery of an improved
cigarette filter formed from at least one graft copolymer selected
from the group consisting of polyvinyl alcohol grafted with at
least one monoethylenically unsaturated vinyl monomer and partially
saponified polyvinyl acetate grafted with at least one
monoethylenically unsaturated vinyl monomer.
It is an object of the present invention to provide an improved
cigarette filter.
It is a further object of the present invention to provide
materials for use in a cigarette filter which provide excellent tar
and nicotine removal, and also provide an excellent flavor during
smoking.
It is a further object of the present invention to provide a
cigarette filter which is capable of yielding a valuable tar and
nicotine removal ratio.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention relates to a cigarette filter which is characterized
by comprising a graft copolymer composed of polyvinyl alcohol
grafted with a copolymerizable vinyl compound and partially
saponified polyvinyl acetate grafted with copolymerizable vinyl
compound.
The most preferable filter in this invention is one comprising a
porous finely divided powder of said graft copolymer having a
surface area of 15 to 200 m..sup.2 /g. and a 10 to 300 mesh
particle size dispersed in a bundle of mechanically crimped
cellulose diacetate fibers having a 1.6 to 15 denier monofilament
size and from 30,000 to 90,000 total filaments denier.
As the base polymer, polyvinyl alcohol and partially saponified
polyvinyl acetate is employed. The degree of polymerization of
these polymers are preferably from 300 to 10,000.
The monoethylenically unsaturated vinyl monomers grafted to these
polymers, which are not restricted, include acrylic acid,
methacrylic acid and alkyl esters of these acids, for example,
methyl methacrylate, methyl acrylate, ethyl acrylate and butyl
acrylate, which have a carbon number from 2 to 18, acrylamide,
acrylonitrile, vinyl chloride, vinylidene chloride, vinyl acetate,
ethylene, propylene and styrene. These monomers are used alone or
by mixing two or more thereof. Ester-type monomers are most
preferred among these monomers, and graft polymers produced
therefrom have high affinity for tar and nicotine. Consequently,
good filters are obtainable.
The amount of the vinyl monomer grafted to the base polymer is from
10 to 310 weight percent to the polymer. If it is less than 10
weight percent, effective results are not obtained in the resulting
graft polymer, and if it is over 310 weight percent, the flavor of
the smoke decreases. Further, it is not preferred to graft in an
amount of over 310 weight percent because of difficulty in
processing. The amount of the branching polymer is preferably from
10 to 310 weight percent to the base polymer.
Since graft polymers in this range have excellent affinity for tar
and nicotine and give excellent flavor at smoking, it is possible
to produce excellent cigarette filters using said polymers.
As the method of graft polymerization used in this invention, any
method may be adopted according to the kinds of vinyl monomers,
such as a method using a persulfate, a peroxide, a cerium salt or
an azobisisobutylonitrile as the catalyst, or methods utilizing
radioactive rays, etc. Further, the polymerization may be carried
out either in a homogenous system or in a heterogeneous system. In
other words, the polymerization process per se is not critical.
These polymers have good absorbing capacity for the ingredients
which afford a bitter taste and a stimulative smell in the smoke of
tobacco, such as phenols and aldehydes, but have a suitable degree
of adsorbing capacity with respect to ingredients which lend good
flavor, such as water and organic acids. Accordingly, cigarettes
using the filter of this invention do not have a stimulative smell,
a bitter taste or a lack of flavor, because these fibers decrease
tar and nicotine in cigarette smoke to give a pleasant taste to the
smoke. Furthermore, it is possible to vary the ratio of removal of
tar and nicotine by changing the species and the ratio of vinyl
monomers. Accordingly, it is possible to produce cigarette filters
corresponding to the kind of tobacco and the kind of taste
desired.
Though there are many shapes of the graft polymers which can be
used in the cigarette filter, a finely divided powder is most
preferable.
The finely divided powder has a 10 to 300 mesh, preferably from 60
to 80 mesh, particle size, and most preferably a 15 to 200 m..sup.2
/g. surface area. It becomes a porous finely divided powder. In
this case, the specific gravity thereof is from 1.1 to 0.2.
The finely divided powder can be produced by the following methods.
(1) A polymer slurry which is prepared as a solution or dispersion
of graft polymer gelatinized in poor solvent, water or by salting
out gradually, is separated by precipitation, dried, powdered and
screened to arrange the particle size within the range described
above. (2) A solution or dispersion containing the graft polymer is
frozen at less than -20.degree. C., and then solvent is removed
under a reduced pressure of from 18 mm. Hg to
1.2.times.10.sup.-.sup.3 mm.Hg. After drying, the polymer is
powdered. (3) A solution or dispersion containing the graft polymer
is dried by spraying into a dry heating stream at
60.degree.-130.degree. C. or by spraying at from 40.degree. to
110.degree. C. under from 260 to 58 mm. Hg., and then the polymer
is powdered.
The resulting porous finely divided powder is dispersed in a raw
material of the filter, for example, an opened fiber bundle, and
then the fiber bundle is formed into a rod shape and finally into
the filter tip shape. The method for producing the filter by adding
the powder into the fiber bundle is not restricted. The easiest
method comprises uniformly dispersing the powder in an opened tow
by a disperser as used in the step of making common filter plugs,
such as by rolling up a paper to a 7.9 mm. diameter with a
cigarette paper rolling machine to produce a filter plug, and
cutting such a plug to a 17 mm. length to make filter tips.
The most preferred filter in this invention is that comprising from
5 to 80 percent of a porous finely divided powder (consisting of
the graft polymer as described above based on the weight of fibers)
dispersed in a fiber bundle of mechanically crimped cellulose
diacetate having a 1.6 to 8 denier monofilament size, a 30,000 to
90,000 total filament denier, and with crimps of from 5 to
30/inch.
The finely divided powder of the graft polymer prepared by grafting
the monoethylenically unsaturated vinyl monomers to the polyvinyl
alcohol and the partially saponified polyvinyl acetate does not
have a large adsorbing capacity for water, and is comparatively
hard before smoking. Further, it does not become sodden by moisture
in the mouth or the tobacco and have the adsorption resistance
increase by dissolution of polyvinyl alcohol by the moisture.
Furthermore, since the finely divided powder has a suitable
hydrophobic property, it has the characteristic that the smoke of
the tobacco does not dry excessively. Moreover, since the removal
of perfume, often added during preparation of the tobacco, is small
when compared with the removal upon the use of polyvinyl alcohol,
the smoking taste of the tobacco is not injured.
In producing the fiber as described above, an adhesive consisting
of a solution or dispersion containing more than 20 weight percent
of a plasticizer such as triacetin, the acetate of ethyleneglycol,
the acetate of polyethylene glycol and methylethyl ether, etc., or
vinyl acetate, may be sprayed in an amount of from 5 to 18 weight
percent (to the fiber tow) in order to bind the fibers to
themselves, as well as to bind the finely divided powder and
fibers. If desired, other additives or adsorbents for injurious
materials may be used together therewith.
Thought it is most preferable to use cellulose diacetate as the
fiber (as described above), any fiber, for example polypropylene
fiber or viscose fiber, which is known as suitable for cigarette
filter fibers, may be used.
Besides the filter described above, a filter which is produced by
spraying a solution or dispersion of the graft polymer onto the
filter tow to cause the graft polymer to adhere to the surface of
fibers, removing solvent and forming said tow by rolling it up with
a paper is included in this invention.
Further, filters in which a finely divided powder is contained as
associated matter are included in this invention. For example,
there are filter tips in which a finely divided powder is contained
therein as capsules, and filter tips in which said powder is
sandwiched between fiber filters.
A polymer prepared by grafting methyl methacrylate to polyvinyl
alcohol and partially saponified polyvinyl acetate is quite soluble
in acetone, dimethylsulfoxide (DMSO) and dimethylformamide
(DMF).
However, from the viewpoint of its toxic character and the ease of
removal of the solvent, DMSO and DMF are not suitable as the
solvent of the graft polymer, and acetone is preferably used.
Solvents for polymers grafted by vinyl monomers besides methyl
methacrylate are as follows.
---------------------------------------------------------------------------
Methyl acrylate: Ethyl acetate, DMSO and DMF. Ethyl acrylate:
Toluene, DMSO and DMF. Butyl acrylate: Toluene, DMSO and DMF.
Acrylamide: DMF. Acrylonitrile: DMSO and DMF.
__________________________________________________________________________
however, employable solvents are restricted by the above-mentioned
reasons, i.e., toxicity and ease of removal.
When a suitable solvent is not present, the graft polymer is
dispersed in a nonsolvent together with a surface active agent to
produce a homogeneous emulsion, which is then sprayed onto the
fiber bundle.
Before turning to the examples, the various methods used therein
will be explained.
---------------------------------------------------------------------------
Gas permeation resistance Flux 17.5ml./sec. Conditions Smoking
device: definite flux type of smoking Smoking time: 2 sec./round
Smoking interval: 58 sec Smoking flux: 17.5 ml/sec Smoking round: 8
/cigarette
Method for Cambridge Filter CM-113 collecting smoke: (10% aqueous
sodium hydroxide solution for phenolic compounds) Number of
cigarettes smoked 20
Smoked length 50 mm Method for analyzing tar Gravimetric Method for
analyzing nicotine Alkali steam (whose alkaloid) distillation and
ultraviolet ray absorption
Method for analyzing phenolic compounds Spectrometric method with
nitrosophenol
Filtration ratio = [A/(A+B)] .times. 100 A: Amount removed in
filter tip B: Amount removed in Cambridge filter (amount removed in
10% sodium hydroxide solution, in compounds)
__________________________________________________________________________
The "standard" tobacco described in this specification was a
side-cut (both sides) cigarette made by the Nippon Monopoly
Corporation, from which the acetate filter tips had been removed.
Cigarettes having a 78.+-.2 mm.H.sub.2 O gas permeation resistance
were selected for use.
The method for measuring the surface area of the porous, finely
divided powder used in this invention was the B.E.T. method.
Namely, an inert gas is adsorbed in a finely divided powder at near
its boiling point. From a graph in which adsorbed amounts of gas
are plotted, the amount of the gas necessary to form a
monomolecular layer on the surface of the solid is determined, and
the relative surface area is determined. This method is explained
in detail in the following references.
S. brunauer, P. H. Emmet, and E. Teller: J. Am. Chem. Soc. 60, p.
309. (1938), and F. M. Nelsen and F. T. Eggertsen: Anal. Chem. 30,
p. 1387, (1958).
The tobacco used for determination was conditioned at 25.degree.
C., and 60 percent RH for over 48 hours.
EXAMPLE 1
100 parts of partially saponified polyvinyl alcohol having an 8,000
average degree of polymerization and a 92 percent saponification
value was dissolved completely in 1,600 parts of boiled distilled
water at 85.degree. C. in a nitrogen stream, and then 2.5 parts of
the cerium salt of ammonium sulfate, 230 parts of methyl
methacrylate, and 2.0 parts of conc. nitric acid (concentration
60-62 percent) were added thereto. The graft polymerization took
place at 60.degree. C. for 4 hours (degree of grafting was 135
weight percent). After the reaction was over, the polymerization
solution was gradually poured into about a 10-fold amount of
methanol with vigorous stirring. The resulting precipitate was
washed, filtered and dried, and then powdered to give a finely
divided powder having a 60-80 mesh particle size. This powder had a
14.2 m..sup.2 /g. surface area average.
A tow of cellulose diacetate filaments mechanically crimped having
a 4 denier monofilament size and a 55,000 total filament denier was
opened. After spraying triacetin in an amount of 6.7 weight percent
to the tow, the finely divided powder described above (consisting
of polyvinyl alcohol grafted with methyl methacrylate) was
dispersed in an amount of 29.8 weight percent to the tow by a
disperser together with a gas stream at from 28 to 30 cm./sec.
flux. The tow was then rolled up to a 7.9 mm. diameter using a
paper by means of a cigarette plug making machine to produce a
filter plug.
The plug was cut to a 17 mm. length to produce tips. A tip was then
put onto an end of the standard cigarette by a cellophane tape
having a 12 mm. width so as to keep it in close contact with the
cutting surface. The properties of the resulting filter are shown
in table 1, in comparison with those of a filter which does not
contain a finely divided graft polymer powder.
The filter of this invention not only provides good removal of tar
and nicotine in tobacco smoke, but good removal of phenolic
compounds (stimulative ingredient) and gives an excellent smoking
flavor to smokers. ##SPC1##
EXAMPLE 2
One hundred parts of partially saponified polyvinyl alcohol having
an 87 percent saponification value, 35 parts of acrylamide, 180
parts of purified styrene and 2,500 parts of water were mixed under
a nitrogen stream. By adding 3.8 parts of persulfate, emulsion
polymerization was carried out. The ratio of grafting was 180
percent. After 5 hours, the reaction product was frozen with dry
ice and dried under reduced pressure at 1.3 .times.10.sup.-.sup.1
mm. Hg The resulting porous material was powdered, and particles
having a 80 to 110 mesh size were selected therefrom. The resulting
graft copolymer had an approximately 63 m..sup.2 /g. surface area,
measured by the B.E.T. method.
A tow of cellulose diacetate filaments mechanically crimped having
4 denier monofilaments and a 55,000 total filaments denier was
opened. After spraying triacetin in an amount of 6.7 percent based
on the weight of the tow, the finely divided powder described above
was dispersed in the amount of 32.5 weight percent onto the tow by
an electromagnetic vibrator. The tow was then rolled upon a
cigarette plug making machine and sufficiently dried. After being
plasticized, a plug having a 7.9 mm. diameter was obtained.
The resulting plug was cut into a 17 mm. length to produce tips. By
selecting a tip having a definite gas-permeation resistance, the
characteristics of the filter were determined. The results are
shown in table 2. ##SPC2##
EXAMPLE 3
One hundred parts of partially saponified polyvinyl alcohol having
a 6,300 average degree of polymerization and a 64 percent
saponification value, 35 parts of acrylamide and 84 parts of methyl
methacrylate were mixed with 1,200 parts of distilled water. By the
addition of 4.2 parts of persulfate, emulsion polymerization was
carried out. The grafting ratio was 63 percent.
The reaction product was force-sprayed into a heating stream at
128.degree. C. to form a finely divided powder. From this finely
divided powder, particles of a 60 to 90 mesh size were selected.
The surface area of the resulting finely divided powder was
approximately 28 m..sup.2 /g., measured by the B.E.T. method.
A tow of mechanically crimped polypropylene filaments having a 9.5
denier monofilament and an 82,000 denier total filament size was
sufficiently opened. After spraying the tow with a 5 percent
toluene solution of 4.2 weight percent of ethylene-vinyl acetate
copolymer (72:28) to the tow, the finely divided powder of the
graft copolymer described above was dispersed in the amount of 28
weight percent, to the tow.
The tow containing the finely divided powder was treated by a
cigarette plug making machine to produce a filter plug having a 7.9
mm. diameter, which was then cut to 102.+-.0.2 mm. By further
cutting, filter tips having a 17 mm. length were obtained.
The properties of the resulting filter are shown in table 3,
together with a filter composed of the plain prior art
polypropylene fibers. ##SPC3##
EXAMPLE 4
A graft polymer was produced by mixing 100 parts of partially
saponified polyvinyl alcohol which had a 1,750 average degree of
polymerization and an 85 percent saponification value, 30 parts of
methyl methacrylate and 150 parts of methacrylonitrile in water,
and then carrying out emulsion polymerization. Into the system
containing the polymer solution was added 95 parts of activated
clay. The mixture was frozen at - 63.degree. C. and dried under 1
mm. Hg.
The graft polymer obtained was powdered into 60 to 80 mesh size by
a mill. The finely divided powder had a 92 m..sup.2 /g. surface
area.
A tow consisting of mechanically crimped polypropylene filaments
having a 9.5 denier monofilament size and an 80,000 total filament
size was opened by compressed air. Then a toluene solution of 4.2
weight percent (to the tow) of ethylene-vinyl acetate copolymer
(72:28) was sprayed onto the tow. Then the finely divided powder
described above was added to the tow in an amount of 31.1 weight
percent by a disperser. The tow containing the finely divided
powder was treated by a cigarette plug making machine to produce a
filter plug having a 7.9 mm. diameter, which was then cut to
102.+-.0.2 mm. By further cutting, filter tips having a 17 mm.
length were obtained.
The properties of this filter tip are shown in table 4, in
comparison with those of a filter which does not contain the finely
divided powder of this invention. ##SPC4##
EXAMPLE 5
One hundred parts of partially saponified polyvinyl alcohol having
a 500 degree of polymerization, a 60 percent saponification value
and 100 parts of acrylamide were mixed in water. Graft
polymerization was carried out by adding ceric ammonium nitrate at
70.degree. C. for 3 hours. The grafting ratio of the resulting
polymer was 34 weight percent.
The graft polymer was dissolved in toluene to produce a solution
having a 2 weight percent concentration. Mechanically crimped
cellulose diacetate filaments having a 4 denier monofilament size
and a 55,000 denier total filament size were sufficiently opened,
and then the toluene solution containing the graft polymer was
sprayed thereon by a centrifugal device for adding a plasticizer.
The graft polymer was contained in the tow at an amount of 10
weight percent. Triacetin was then sprayed (6 weight percent) onto
the tow by a centrifugal plasticizer applicator. The tow was
treated by a cigarette plug making machine to produce a plug having
a 7.8 mm. diameter, which was then cut to 102.+-.0.2 mm. After
further cutting to 17 mm., filter tips were obtained.
The properties of the filter tip are shown in the table 5, in
comparison with those of a filter produced by the same procedure
but without adding a toluene solution of the graft polymer of this
invention. ##SPC5##
* * * * *