DE2527234A1 - CIGARETTE FILTER - Google Patents

Description

PAT Z N TA N VV Λ LT Ξ.

A. GRÜNECKER

DIPL.-INQ.

H. KINKELDEY

DR.-INQ.

W. STOCKMAIR

DR.-ING. AoH (CALTeCH)

K. SCHUMANN

DR. RER. NAT. · DIPL.-PHYS.

P. H. JAKOB

DIPL.-ING.

G. BEZOLD

DR. RER. NAT. · DIPL.-CHEM.

MUNICH

MUNICH 22

MAXIMILIANSTRASSE 43

P 9331

June 19, 1975

Eiichi Arakawa

1-26-16, Senzoku, Meguro-ku, Tokyo, Japan

Cigarette filters

The invention relates to a new cigarette filter which consists mainly or exclusively of cyclodextrin; it relates in particular to a cigarette filter which, using cyclodextrin with a cyclic structure, which consists of 6 to 8 glucose units, as an adsorbent Component has been manufactured.

Cyclodextrin is obtained when starch is treated with an enzyme which, for example, is produced by Bacillus macerans will. It can be obtained in a wide variety of forms, for example in the form of powders, granules or fibers

509882/0749

TELEPHONE (OBQ) SQ 28 62

TELEX Ο5-29 38Ο

TELEGRAMS MONAPTH

Molds or can be processed into a filter by filling into a container. You get an excellent one Cigarette filters, which remove the harmful chemical components of cigarette smoke, such as nicotine and Tars, adsorbed and removed therefrom in an efficient and selective manner.

Various cigarette filters have been proposed and / or used commercially, made from bundles of linear natural fibers, chemical fibers or synthetic resins, formed into fibers, as well as filters made from such fibers in the form of non-woven fabrics Fabrics have been made, and filters made from crepe papers that have been activated with carbon, aluminum oxide and the like are. From the standpoint of economy (cost) and the effectiveness of eliminating the harmful components from the point of view of cigarette smoke, however, the usefulness of such materials is either alone or in the form of limited to various combinations or mixtures thereof. In particular, their effectiveness in terms of removal of the harmful components of cigarette smoke, such as nicotine and especially of tars, are insufficient. As in the ones below Examples and comparative examples described, conventional cigarette filters have the disadvantage that they Alkaloids, such as nicotine, are less effective from cigarette smoke remove than tars. The reason for this is believed to be that the volatile constituents in the smoke, such as nicotine, are after once they have been adsorbed on the conventional filter material, they are desorbed again in the course of further smoking be, ^ ies is a serious disadvantage. It will believed to be due to chemical and physical affinity or bond strength between the filter material and the alkaloids, such as nicotine, is insufficient in the smoke.

509882/0749

In view of these circumstances, there has long been a search for a better filter material in which this Phenomenon does not occur, i.e. after a filter material that adds the alkaloids once adsorbed by the filter the high temperature and the gas flow rate, as occur when smoking, is not desorbed again.

Recently, there has been an increasing demand for filter cigarettes. One requirement made on filter cigarettes is that nicotine and tars be eliminated from their smoke or are to be selectively reduced with regard to their quantity, while at the same time the odor of the cigarette, Taste and that their own aroma should remain unchanged.

The aim of the invention is therefore to provide an improved cigarette filter indicate that satisfies the conditions specified above and the disadvantages of the previously known cigarette filters does not have.

It has now been found that cyclodextrin specifically and selectively adsorbed and that the harmful components, once adsorbed thereon, upon continued smoking cannot be desorbed again.

The invention relates to a new cigarette filter, which is characterized in that it is mainly or exclusively consists of cyclodextrin.

That of the present invention as an effective cigarette smoke filtering material Cyclodextrin used has a cyclic structure consisting of 6 to 8 glucose units and it can be through Treating starch with an enzyme produced by Bacillus macerans as indicated above, prepared.

509882/0749

Cyclodextrin has a chemical structure that can be represented by the following formula:

where η is a number from 4 to 6.

It is known that cyclodextrin is mainly present in the a, ß- and V-shapes. According to the invention, any of these three forms and mixtures thereof can be used as the filter material will. They are simultaneously with the action of the enzyme formed by the said microorganism on starch obtain. The fermentation product consists mainly of a mixture of α- and ß-cyclodextrins and this mixture is available at a low price. According to the invention, this mixture can be used as a filter material.

Because of its "cyclic structure, its properties, its reactivity and its reaction mechanisms" is cyclodextrin has long been the subject of scientific research. Although many researchers have made it clear that cyclodextrin forms inclusion compounds with various other compounds, there is as yet no theory about the formation such inclusion compounds. Cyclodextrin has not yet been used for technical purposes and it has been Also not heretofore known that cyclodextrin has excellent properties as a cigarette filter material.

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The mechanism of adsorption of harmful components of cigarette smoke by that used in the invention Cyclodextrin is believed to be the same as described below, although the mechanism has not yet been fully elucidated. One molecule of an alkaloid, such as nicotine, contained in cigarette smoke is included in one molecule of cyclodextrin. In this way, adsorption occurs through the formation of this simple molecular compound (i.e., an inclusion compound of cyclodextrin and nicotine). The affinity between both is very strong and therefore the alkaloid adsorbed in this way can hardly be used with continued smoking be desorbed again.

It has also been found that the molecular compound formed from nicotine and cyclodextrin is isolated in the form of crystals can be. This supports the view that the invention New cigarette filter materials used have a high affinity for alkaloids, such as nicotine, found in cigarette smoke are contained, so that the alkaloids are no longer easily desorbed with continued smoking. By Use of the cyclodextrin cigarette filter according to the invention can irritate or inflame the mouth and throat of smokers as a result of the lower amount of nicotine and tars can be significantly reduced.

When using cyclodextrin for the preparation of the invention Cigarette filters can contain fibrous cyclodextrin similar to the fibrous cigarette filters previously suggested or have been used commercially, formed into a bundle; the fibrous cyclodextrin can also deformed into non-woven fabrics; Cyclodextrin, that is in the form of a powder, can be combined with other filter materials; and cyclodextrin, which is in the form in the form of granules or flakes, can be formed into the desired shape or poured loosely into a container.

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Of course, other effective cigarette smoke filter substances can also be incorporated or combined with them, such as special types of activated charcoal for the further removal of some special components of the cigarette smoke, menthol or other taste-forming substances to change the taste and smell of the smoke as well as other harmless filling materials that are only used to to increase the volume of the filter. Such additive materials can be filled into the cavities in the cyclodextrin filter or they can be incorporated into partitioned chambers in the filter. In the practice of the invention, the GycIodextrinmaterial which has been brought by deformation in the proper form or filled in a container can be used directly v / ground by passing it ei η into a cigarette _holder> or the cyclodextrin can be in the form of one usable filter mouthpieces or in the form of filter mouthpieces which can be exchanged after smoking a large number of cigarettes, or in the form of filter mouthpieces which form a unit with the cigarettes, as in conventional filter cigarettes.

The cyclodextrin material can also be used for a filter mouthpiece that attaches to a commercially available cigarette is. The filter mouthpiece is divided into two parts. The contents of the one part that is adjacent to the tobacco, is removed, leaving the cylindrical paper sleeve. The cavity filled by the cylindrical paper sleeve becomes filled with β-cyclodextrin granules. Instead of the ß-cyclodextrin granules can also be a material such as chemical fibers, natural fibers, a non-woven fabric and crepe paper, can be used that ~ effectively with β-cyclodextrin or the grains thereof has been added. In addition, common adsorbents, such as carbon, can be found in β-cyclodextrin be incorporated. When the filter mouthpiece is in

SO9882 / 0749

divided into three parts, came the one next to the tobacco The cavity can be filled with conventional chemical fibers and the central cavity with ß-cyclodextrin.

In the case of a separate cigarette mouthpiece that can be placed on a commercially available cigarette the ß-CycIodextrin also in the above Way to be used. The cigarette filter according to the invention can also be used for a cartridge-type cigarette holder in the manner described above. Otherwise the cartridge of a holder can be completely filled with ß-cyclodextrin. In the case of a water filter type cigarette holder There is a filter housing with water and β-cyclodextrin or a combination of fibers, β-cyclodextrin and. Filled with water.

It has already been pointed out above that the inventive Filter has the effect of removing alkaloids such as e-nicotine, contained in the cigarette smoke to remove therefrom. The filter also has the effect of removing other harmful components, such as tars, from the Eauch in an effective manner.

The excellent, usable cigarette filter forming the subject of the invention has the property that it forms special molecular compounds with the undesirable components of cigarette smoke. The filter is made (mainly or exclusively), from cyclodextrin, which is manufactured on an industrial scale from starch can and is free from toxic effects. Harmful components, such as nicotine and tars, can be found in cigarette smoke can be removed therefrom in a very effective manner by having these components adsorbed thereon so firmly that they are during further smoking will no longer be desorbed.

509882/0749

The formation of a molecular compound from cyclodextrin and nicotine is explained in more detail in the following preparation example. It should be noted that this molecular compound is new and not previously known in the literature.

Manufacturing example

Production of the ß-Cy £ lodje ^ rin / Nik £ tm-M2ljekülverbi.ndung _> _

g ß-cyclodextrin and 0.482 g nicotine were dissolved in 10 times the amount of water at 60 to 65 ° C. After the solution was left to stand, colorless, platelet-shaped crystals were precipitated and collected by filtration, washed thoroughly with cold water and dried in a desiccator under vacuum at tree temperature over potassium hydroxide, whereby 0.858 g of a ß-cyclodextrin / nicotine molecular compound, F. 311 to 312 ° C (dec.) _{V were} obtained.

By immersing this molecular compound with heating in an organic solvent such as ethanol, ethyl acetate or chloroform, it was practically quantitatively separated into β-cyclodextrin and nicotine. The β-cyclodextrin isolated in this way had a melting point which was identical to that of the standard compound (decomposition in both cases at 293 to ⁰ ).

The nicotine isolated in the process was converted into the picrate salt and identified by the mixed melting point with a standard nicotine picrate. The melting point was identical to that the standard compound (melting point of the standard picrate 219.5 to 220 ° C, melting point of the picrate isolated after the test 220 ° C, mixed melting point 220 ° C). By Immersion of the compound in the solution obtained under heating organic solvent gave the same spots (Dragendorff reagent) and the same peaks in the

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Thin-layer chromatography and gas cliromatography like standard nicotine.

The structure of the inclusion compound obtained from nicotine and β-cyclodextrin was also determined with the aid of the IR absorption spectrum. The compound was examined in the form of a KBr tablet and found to have absorptions different from those of nicotine and β-cyclodextrin, namely at 2760, 1600, 1580, 1460 and 1370 cm " ¹ .

The results of the elemental analysis of the ß-cyclodextrin / nicotine molecular compound were the following: Molecular formula

qO ^. 5HpO

calc .: C 45.02 H 6.83 N 2.02 found: 44.68 6.73 2.29

The results of the above experiment show that β-cyclodextrin together with nicotine forms a molecular compound which is believed to be an inclusion compound consists of 1 molecule of ß-cyclodextrin and 1 molecule of nicotine.

The invention is explained in more detail by the following examples with reference to the accompanying drawings, without, however to be limited to it. In the accompanying drawing show:

1 shows a schematic representation of a commercially available cartridge filter as used in Example 2; and

Fig. 2 is a schematic drawing of the filter "Lark" r < Cigarette as used in Example 3.

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example 1

In this example, as comparative materials, Seven Stars (trade oak) cigarettes commercially available in Japan are used.

The filter mouthpiece of a "Seven Stars" cigarette was through Cutting the cigarette separated from the tobacco precisely at the junction between the mouthpiece and the tobacco. The contents of the filter mouthpiece, consisting of activated carbon, were taken out, leaving the cylindrical paper envelope. 200 mg of ß-cyclodextrin granules (particle size 0.25 mm (60 mesh JIS)). The whole thing got cautious into the mouthpiece of a commercially available cylindrical cigarette holder from which the cigarette holder cut off had been taken out. After that, the remainder of the cigarette was attached to the junction as indicated above had been separated (i.e. the cigarette without the mouthpiece) inserted so that it was attached to the cyclodextrin-containing element so that there was no space between them. In this way the filter was inserted into the mouthpiece of the cigarette holder used in close contact with one end of the cigarette. Then the cigarette was smoked in the usual way to 1.0 cm the cigarette was left. The smoke test was predetermined by the same people by inhaling deeply in beforehand Periodic intervals carried out for a predetermined period of time to ensure practically uniform smoking conditions maintain. After smoking, the remaining cigarette (length 1 cm) was taken out with tweezers. the Cyclodextrin granules on which components of the smoke were adsorbed were completely taken out with a spatula. If the same filter was used to smoke two cigarettes, the first cigarette was used after the full one Smoking the same and then the

S09882 / 07A9

next cigarette (from which the filter was removed) used and smoked in the same way.

The cyclodextrin filter material removed as described above was immersed in 5 ml of acetone overnight without heating, and the above liquid was removed by decantation removed to obtain a liquid sample containing the nicotine adsorbed on the filter material and the contained tars adsorbed thereon. Separately, 100 mg of nicotine were dissolved in 100 ml of acetone and 100 mg of phenanthrene were dissolved in 100 ml of acetone.

For the measurement, five standard solutions were prepared from each of the two solutions using the multiple dilution method, so that each of the five solutions is 50 mg, 25 mg, 12.5 mg, 6.25 mg and 3.125 mg, each based on 100 ml of acetone, nicotine "or Contained phenanthrene. 5 ml of each of the five solutions thus contained 2.5 mg, 1.25 mg, 0.625 mg, 0.315 mg, 0.15625 mg and 0.078125 mg nicotine or phenanthrene. 2 microliters of the solutions were introduced into the measuring device so that the nicotine and tar amounts in the extracts were determined by gas chromatography using a Shimadzu GC-4-B (DF) apparatus of Shimadzu Co. by calculating the sizes of the areas of the compared the respective maximum values (peaks) with those of the maximum values of the standard solutions. Since the gas chromatographic Graphs of the sample solutions indicated many maximum values in the area of the tarry material, the total amount became the tars was regarded as that represented by the size of the area of the maximum value, which is very close where phenanthrene was lying. The calibration curve obtained from the standard solution of phenanthrene was used as an aid for the determination the tar amounts used. The amounts of the components of the sample were calculated by comparing the respective ones integrated areas (intensities) and calibration curves of the standard as in the case of nicotine.

509882/0749

The "comparative material (Seven Stars) with filter was on Smoked the same way as above until 1 cm of cigarette remained. The activated carbon was removed from the filter section and in the same way as when using the cyclodextrin filter, the nicotine and tar quantities determined. The measurement results are given in Table I below. In the table, N gives the the respective filters amount of nicotine adsorbed and T the amount of tar adsorbed.

Table I.

Sample N T

SS Comparative- Usual Seven Stars- 0.72 mg 0.054 mg material cigarette (a cigarette)

SS ^ j filled with Seven Stars without mouth-

200 mg cyclops (used for 2.30 mg 0.120 mg iodextrin in a cigarette)

filled with seven stars without mouth

200 mg cyclops (used for 3.67 mg 0.135 mg

lodextrin two cigarettes)

Example 2

In this example, commercially available materials were used as comparative materials Cartridge filter (sleeve filter) used.

The commercially available cartridge filters shown in FIG. 1 were used as comparison materials. It was made in Japan commercially available Peace (Trade Mark) cigarettes without mouthpieces.

In Fig. 1, numeral 1 designates a fibrous eliminierendes _t tar material and the numeral 2 designates a plastic cartridge (plastic sleeve). The comparison group

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Heit regular commercial cartridges (cases) that your usual fibrous filter materials without any treatment contained. In another group of samples, the fibrous filter materials were of the same cartridge type (Sleeve type) and then 400 mg of the β-cyclodextrin granules (particle size 0.25 mm (60 mesh)) instead of the standard filter. Each of the cartridges was then placed in a holder. The cartridges were used for smoking that on the the same manner as in Example 1 was carried out. The filters became without mouthpieces after smoking 1, 2 or 3 cigarettes ("Peace") subjected to a gas chromatographic analysis in the same way as in Example to determine those of the to determine the amount of nicotine and tar adsorbed by the respective filter. The measurement results are shown in Table II below specified.

Table II

Sample N T

Ty, comparative material; commercial filler; "Peace", 1 cigarette 1.10 mg 0.030 mg smoked

Pp comparison material; more commercially available

Filler; "Peace", smoked 2 cigarettes 2.50 0.150

P, comparative material; commercial -> filler; "Peace", smoked 3 cigarettes 2.60 0.155

PS. Cyclodextrin 4-00 mg; "Peace" 1 cigarette smoked

₂ cyclodextrin 400 mg; "Peace"

Smoked 2 cigarettes

PS, cyclodextrin 400 mg; "Peace"

Smoked 3 cigarettes

5, 00 0 , 200 10, 00 0 , 300 14, 80 0 , 820

509882/0743

Example 3

In this example, Lark (trademark) cigarettes were used as comparative materials. It became "Lark" cigarettes used with a filter as shown in FIG.

In Fig. 2 ", the numerals 1 'and 3' denote porous Plugs (stoppers) made of fibrous materials for the removal of nicotine and tars and the numeral 2 'denotes granular activated carbon.

The middle section of the filter mouthpieces of the "Lark" cigarettes was cut off precisely and the filter (granular activated carbon) was taken out, and then 150 mg of β-cyclodextrin granules became (! Particle size 0.25 mm (60 mesh)) as used in Example 1 was filled in place of the activated carbon. The ends of the paper cut off as above were sealed with a piece of paper. Usual "Lark" cigarettes without any treatment and "Lark" cigarettes modified as indicated above were smoked and then measurements were made on the filters in the same manner as above to determine the nicotine and Determine tar amounts. The measurement results are given in Table III below. *

Table III

Sample N T

L comparison material; usual

Lark cigarette (I50 mg activated charcoal) 0 0.002 mg

LS modified "Lark" cigarette, filled with 150 mg cyclodextrin 0.90 mg 0.030 mg

509882/0749

Example 4-

In this example, a commercially available filter mouthpiece and animal charcoal (charcoal) were used as comparison materials. used «, a cigarette connected to a device for continuously inhaling the smoke of the cigarette was "lit" and it vairde a stream of air a predetermined flow rate generated. The harmful ingredients, particularly nicotine, were also removed by these removing agents, such as a filter mouthpiece attached to a commercially available cigarette, animal charcoal (charcoal) or ß-cyclodextrin conducted » The device had the following structure:

a commercial cigarette, Hilight (trade name), became separated from its mouthpiece and inserted into a holder. The cigarette was 62 mm long. The keeper was on the other End connected to a plastic tube with an inner diameter of S mm and a length of 28 mm. The plastic pipe was closed at the respective end with half of the Hilight mouthpiece with a length of 8.5 am. aside from that the cavity formed by the two mouthpieces and the cylindrical tube with agents to remove the filled with harmful ingredients. The tube was connected to a glass tube by means of a rubber hose. The device was also equipped with a cleaning trap, a three-way valve, a flow meter and a suction device, which were arranged one behind the other in the specified order. Then the three-way valve was operated and the aspirator was actuated to operate at a flow rate of 5 ml per second. Then the tobacco was continuously burned over the length of 45 mm, while the smoke with the aspirator was inhaled. Immediately after the test, the increase in weight of the cylindrical tube was determined. Of the

509882/0749

The contents of the tube, which, in addition to the smoke condensate and the removal means, contained the filter mouthpiece seals and wash water, were collected and steam distilled according to the method described by RB Griffith and RN Jeffrey in "Anal.Chem.", 20 , 307 (1948) . In the distillate obtained, which contained nicotine, the nicotine was after that of CO. Willits et al. UV absorption spectrum method described in "Anal. Chem.", 22, -4-30 (1950).

At this point additional nicotine aqueous solutions were prepared separately and used to prepare a standard graph. As a result, the nicotine removal efficiency was found to be nearly 100 % . As agents for removing harmful components, β-cyclodextrin granules having a diameter of 0.25 m (60 mesh) and those having a diameter of 0.4-25 to 0.25 mm (4-0 to 60 mesh) and finely divided ones have been used Animal charcoal (charcoal) used as a reference material. In addition, no agent was used to test the blank, in which case the smoke only passed through two pieces of Hilight mouthpieces. The measurement results are given in Table XV below.

Table IV

Sample number Amount of the with the amount of the with the b / a χ 100 d.Ver- pipe (a) entrapped pipe (b) in% look for smoke condensate nicotine in

sate in mg mg

Blind 2 38.1 (+9.3) 0.5 (± 0.1) 1.2 (+ O, 3)

sample ~

Animal charcoal 5 111.2 (± 20.2) 0.9 (+0.5) 0.9 (± 0.6)

7) 2.3 (± O, *>

small size
0.25 mm
(60 mesh)

ß-cyclodex

trin, part- 3 118.5 (± 10.8) 2.9 (+0.6) 2.4 - (+ 0.3)

small size "~

0.425 to

0.25 mm

(40-60 mesh) 5G9882 / 0749

The invention has been described above with reference to preferred embodiments explained in more detail, however, it is it goes without saying for the person skilled in the art that it is by no means restricted to this, but that it is in many respects can be changed and modified without departing from the scope of the present invention will.

Patent claims:

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Claims (2)

Claims 1. Cigarette filter, characterized in that it consists mainly or exclusively of cyclodextrin ". 2. cigarette filter according to claim 1, characterized in that that it is in the form of a cigarette holder with a mouthpiece and a cigarette holder, wherein the cyclodextrin is located within the cigarette holder and filters the smoke coming from a cigarette is sucked into the receiving device. 3 · Cigarette with an integral filter mouthpiece, characterized in that it is the main effective filter material Contains cyclodextrin. 509882/0749