DE2543087C3 - Granular composition for tobacco filters - Google Patents

Description

a) 40-80% by weight of a granulate of 5-70% by weight whey protein from cow's milk Protein and 30-95% by weight excipients and

b) 20-60% by weight of activated carbon granules

with a bulk density of 0.5-0.7 g / ml and a grain size of 0.29-1.65 mm.

The invention relates to a granular composition for use in tobacco filters or pipes, the for the selective and highly effective removal of carcinogenic and harmful components in tobacco smoke is suitable and contains a mixture of protein granules with excipients and activated charcoal granules.

The development of compositions for removing carcinogenic components from tobacco smoke without associated deterioration in smoke taste is an urgent social problem. Around To bring this problem closer to a solution, cigarettes with cellulose or acetyl cellulose filters or brought onto the market with filters made of coal granules, which are known to be tar, nicotine or others Remove pollutants in tobacco smoke by adsorption. The rating of tobacco filters should however due to the ratio of adsorptive removal of 3,4-benzopyrene, volatile phenol and tar in the Tobacco smoke happens because the latter two components are the most important carcinogenic and cocarcinogenic, respectively Substances in tobacco smoke represent, and tar beyond that, the extensive unfavorable effects or causes side effects. A filter material that is resistant to both non-polar molecules such as 3.4-Benzopyrene as well as polar molecules such as phenol is effective, however, has not yet been specified been.

From US-PS 36 70 740 a cigarette filter material is known that by kneading a mixture of gluten, i.e. a vegetable protein, and wheat flour with water, heating the mixture and grinding. The effect of this filter material is not with regard to the tar substances selective, since gluten has only a low adsorptive capacity for 3.4-benzopyrene, which is the is the most important carcinogen in tobacco smoke.

From US-PS 32 34 948 a filter material is also known, which consists essentially of hard cheese particles with a fat content of more than 20% and possibly activated charcoal granules, i.e. animal protein contains. In this publication it is pointed out that the activated carbon per se is a relatively bad one Is adsorbent for the tar present in the smoke and therefore mainly for adsorption of the Fats separated from the cheese component to prevent them from going rancid and to promote them the passage of smoke through the filter.

In CH-PS 3 29 353 filters for tobacco smoke are also described in which an animal, native protein is combined with an excipient such as polysaccharides or diatomaceous earth

The invention is based on the finding that proteins from cow's milk whey and egg white are preferred associate with the carcinogenic hydrocarbons

ίο (see JP-OS 19 800/73 and 93 600/74); that there The specified process relates to the manufacture of tobacco filters for the selective removal of carcinogens Hydrocarbons through adhesion of protein from cow's milk whey, egg white or a mixture these two proteins in powder form on a fiber filter in an amount of 3% by weight fibrous substrate.

The use of such protein powders in tobacco filters made removal more carcinogenic Hydrocarbons obtained from tobacco smoke, but at the same time caused a strong pressure loss when smoking, because the fine protein powder reduced the empty spaces between the filter fibers and as a result, the smoke taste balance deteriorated. This problem shone through Use of filters with a solvable granulate made exclusively from this protein. Attempts to produce these granules from the protein alone on an industrial scale have been found

jo, however, when using conventional devices for granulation due to the extraordinary stickiness of the protein when mixed with water or being exceptionally difficult when compressing to produce granules. The pure protein granulate, which was difficult to prepare manually in small amounts showed a lower separation ratio Pollutants from tobacco smoke.

The reason for this is that the granules made from the pure protein have a smoother surface exhibited and the unspecific physical interaction between the grain and the smoke components was inhibited. The removal of smoke components by such protein granules is also only depends on their specific chemical interaction with the protein.

The invention is based on the object of a granular composition for removing pollutants from tobacco smoke, which is capable of removing carcinogenic, harmful components

so and at the same time refined the smoke taste, so a allows safer smoking in terms of pollutants.

The problem is solved according to the claims.

The granular composition of the invention

■ 55 for the removal of pollutants from tobacco smoke contains a protein and an excipient, has a grain size of> 0.246 mm and is marked by

bo a) 40-80% by weight of a granule made of 5-70% by weight of whey protein from cow's milk as protein and 30-95% by weight of excipients and
b) 20-60% by weight activated carbon granules

b'i with a bulk density of 0.5-0.7 g / ml and a grain size of 0.29-1.65 mm each. It has the property of being selective and highly effective carcinogens and to remove other pollutants from tobacco smoke.

The granulate consists of whey protein from cow's milk and one or more powdered whey Cellulose, starch, glucose or lactose selected excipients mixed with activated charcoal granules.

The invention is based on the finding that the mechanical production of protein granules in even with conventional granulating devices succeeds in a satisfactory manner if the aforementioned Protein powder is mixed with suitable excipients; it was also found that the resulting Composition is able to selectively remove carcinogenic and neuter components from tobacco smoke, without a disruptive loss of pressure or a deterioration in the smoke taste.

(1) Preparation of the protein granules and the compositions

Table I.

Properties of the protein granules Example I Example 2

Shape pellet

Bulk weight (g / ml) 0.57

Mean diameter 1.36

knife (mm)

Moisture content

6.1

spherical

0.58

1.12

5.8

Qualitative
stability

no coloration during storage for 2 months at 30 ° C. and 85% relative humidity, none Odor formation or agglomeration

The protein powder used to prepare the composition according to the invention is commercially available, Unchanged powdered whey protein from cow's milk, free of foreign odors.

The excipient used in the compositions of the invention is also an unchanged one or a single material that is unadulterated and free of foreign odors or a mixture of more than two corresponding materials, among the commercially available powdered cellulose, starch, glucose and lactose are selected.

The activated charcoal granules used in the compositions according to the invention are also commercially available available product and free of extraneous odors.

The protein powder and the excipient are mixed in a ratio of 5-70% protein powder to 30-95% excipient and mixed with water, an aqueous solution of methanol or glycerol with a concentration below 20% or an aqueous solution of ethylene glycol with a concentration below 5% . The mixture is then granulated using conventional extruding or granulating devices with openings of 0.8-2.0 mm in diameter. The grains are then dried ^{at 70 °} C. to achieve a moisture content below 10%; those grains which fall in the size range of 0.29-1.65 mm are screened out to produce the protein granules. The protein granules obtained in this way with a bulk density of 0.5-0.7 g / ml are used for the compositions.

The protein granules can also be obtained by applying the protein to the surface of previously prepared, Excipient grains of 0.25-0.83 mm grain size serving as cores are produced. That by a such coating process produced protein granules with the grain size specified above and the above bulk density is suitable for use according to the invention.

The protein granules are mixed with activated charcoal granules with a grain size of 0.29-1.65 mm and a bulk weight of 0.5-0.7 g / ml mixed in a ratio of 40-80% protein granules and 20-60% activated charcoal granules.

Typical properties of protein granules according to those described in Examples 1 and 2 Procedures made are listed in Table I.

(2) Effect of the protein granules

(Experiment 1) Proof of removal
of pollutants from cigarette smoke

Protein granules with contents of whey protein adjusted to 3, 5, 20, 50, 70 and 90%, in which the Excipiensköaier made from corn starch alone were prepared by following the procedure of Example 2, with the whey protein being through Isolate by adjusting the pH of skimmed milk to 4.6, followed by centrifugation to separate the Casein precipitate, dialyzing the supernatant and spray drying. the Preparation consisted of practically pure whey protein without fat, lactose and ash content. the Production of a protein granulate with an increased protein content of 70 and 90% proved difficult since The addition of water caused extreme stickiness of the matrix; the preparation was therefore done manually by using 30-50% ethanol instead of water.

100 mg of the protein granules described above and the above excipient granules were in the middle layer of a conventional triple filter for cigarettes as in FIG. 1 provided.

Fig. 1

_r , O _n ° OO

⁰ O ⁰ OO
ov-, 000
ο ooo

A and B represent acetyl cellulose and the protein granules, respectively. The numbers mean the Layer lengths in mm.

The triple filter was fitted with a grain addition device equipped double-shaft complex filter machine. Fiber as well as total denier the acetyl cellulose in this triple filter was 4 I- w. 43,000. The filters were as follows indicated, numbered according to the protein content of the protein granules contained therein.

Filter number

Protein content in%

(Acetylcellulosc single layer)

0 (only corn starch as excipient)

20th 40 70 90

Cigarettes were provided with the triple filters listed above and a mechanically simulated one Smoke test with a smoke throughput of 17.5 ml / s, a "draw" period of 2 s, a smoke frequency of l / m: n and a silent length of 30 mm, with the smoke condensate on Cambridge filters CM-113 of 44 mm in diameter was collected. The determination of tar, volatile phenol or 3.4-benzopyrene on the filter was carried out with peeling off the determined by the Karl Fischer method Water content (K. Fischer, Angewandte Chemie 48,394 [1935]) on the weight of the smoke condensate using the 4-aminoantipyrine reagent (Y. Kaburagi et al., Scientific Papers of the Central Research Institute, Japan Tobacco and Sa! *. Public Corporation, No. 107, 181 [1965]) and according to the Davis method (Davis, H. J. et al., Analytical Chemistry 38, 1752 [1966]).

The ratio of the separation of pollutants in smoke was calculated using the following equation:

Separation ratio =

100 (%);

A and B denote the amounts of smoke constituents obtained from cigarettes without a filter or from cigarettes provided with the corresponding filters. The results are given in Table 2.

Table 2

Filter no. Bulk weight separation ratio (%)

(g / ml)

3.4-BP *) Π. Phenol **) tar

0.34
0.34
0.37
0.42
0.62
0.74
0.76

9
15th
19th
41
42
42
41
41

65 34 42 67 70 71 66 62

38 34 36 39 42 41 39 32

Removal of 3.4-Benzopyrene is five times higher than the corresponding filter with a single layer Acetyl cellulose. The separation ratio for volatile phenol was remarkably increased when the protein ") content in the granulate was over 5%. The separation ratio for tar was, however, reduced when the Protein content was over 70%.

The protein content in the protein granules should therefore be between 5 and 70%, around one

in satisfactory separation of the pollutants Enable tobacco smoke.

Filter cigarettes, the filter of which is granulated activated carbon or a mixture of granulated activated carbon and hydrated Magnesium silicate granules are included

π commercially available; such conventional granules The same tests for removing tobacco smoke components were carried out in the manner indicated above subjected. With them a separation of 33 and 40% tar, 51 and 54% volatile was achieved

2 (i phenol and 32 and 24% 3,4-benzopyrene in cigarette smoke determined. The protein granulate is accordingly able to separate 1.4 times more volatile phenol, than is the case with conventional granules when they are in a triple filter. the

-'i capacity for the separation of 3,4-benzopyrene by the Protein granules also exceeded the capacities of conventional granules by a factor of 1.4-1.8 in remarkable degree.

As a result, the protein granules have the un-

JO waited property of a double affinity for both to polar (phenol) and non-polar (3,4-benzopyrene) components in tobacco smoke, while Acetyl cellulose and carbon preferably only bind only one component each.

It therefore initially seemed contradictory that the filter with the protein granules, which was made from the unchanged Protein (protein content 90%) and had a "smoother" surface, a lower separation ratio showed as a granulate in which the protein

4 (i was mixed with the excipient.

The protein granulate produced from the mixture of protein and excipient in the quantity range described above has a fairly rough outer surface, which creates both a physical and chemical adsorption of the smoke constituents is made possible, which when introduced into the filter to a higher separation ratio leads.

*) 3,4-benzopyrene.
**) I-Powerful Phenol.

It can be seen from the results that the capacity of the triple fish containing the protein granules for (Experiment 2) grain size of the protein granules

It became protein granules according to the procedure

of Example 1, which was screen fractionated to give material in the grain size range from

less than 0.29 mm,

0.29-0.54 mm,

0.54 - 1.65 mm as well
over 1.65 mm

to win. In each case 100 mg of these corresponding protein granules were as in experiment 1 in triple filters brought in. The pressure drop was determined under standard "pull" conditions as in Experiment 1, to determine the significant size range for the protein granules (see Table 3).

Table 3

Grain size

Length of
Middle class

(mm)

Pressure drop

(mm H ₂ O)

> 1.65 mm
0.54-1.65 mm
0.29-0.54 mm
<0.29mm
Acetyl cellulose *)

5.2 5.2 5.2 5.0

37
46
46
56
45

*) Acetylcellulose single tube diameter of 17 mm.

Conventional acetyl cellulose filters currently introduced and accepted by consumers showed a pressure loss of 45 mm H2O, which is why the size of the protein granules should be 0.29-1.65 mm.

(Experiment 3) Bulk weight of the granules

Various types of protein granules, the bulk weights of which varied in the range of 0.3-0.8 g / ml , were prepared according to the method of Example 2, using 20% ethanol instead of water as the granulating agent in an amount of 20-200% of the mixture of protein and excipients was used. In this way , granules with a bulk density in the range from 0.3-0.8 g / ml were obtained. The protein granules were then mixed with an equal amount of commercially available carbon granules for cigarette filters with a grain size of 0.29-1.65 mm and then subjected to 200 inserts in test tubes. The appearance of a single homogeneous layer after use was seen as an examination criterion; those areas of the bulk density of the protein granules in which two separate layers appeared were discarded. It was found that protein granules with a bulk density of 03-0.7 g / ml were in accordance with the above criterion and that the bulk weight of the protein granules should be accordingly within this range.

(3) Properties of the
compositions according to the invention

(Experiment 4) Evidence of removal
of pollutants from cigarette smoke

Triple filters were produced according to the procedure described in Experiment 1; the eight numbers given in the table below correspond to the compositions that were introduced into the middle layer of the triple filters. The compositions were prepared according to the method described in Example 3, the protein granules being the same as those obtained by the method of Examples 1 and 3 before mixing with the charcoal granules. The Kohiegranuiat used in this experiment was identical to that of Experiment 3.

Filter no. Composition of the triple filter

1 none (middle class empty)

2 100 mg protein granules from Example 1

3 100 mg of the composition of Example 2

4 100 mg protein granules from Example 1

5 100 mg of the composition of Example 2

6 100mg activated carbon granulate (0.29-l, 65mm)

7 50 mg protein granules from Example 1

8 50 mg granulated activated carbon (0.29-1.65 mm)

The above triple filters were then attached to cigarettes and subjected to the mechanically simulated smoke test described in Experiment 1. The determination of tar, moisture and volatile phenol was carried out according to that described in Experiment 1 Procedure. The total alkaloid content in the tar was determined using a method by Willits (C O. Willits et al, Analytical Chemistry 22,430 [1950]) determines 1 ml of the Gas phase of the fourth puff underwent gas chromatographic analysis of isoprene, acetaldehyde, and acetone subjected (see K. Maeda et aL, Scientific Papiers of the Central Research Institute, Japan Tobacco and Salt Public Corporation No. 115,33 [1973]). The separation ratio was as described in Experiment 1 Equation determined; the results are in the given in Table 4 below.

Table 4 Filter no.
1 2 5 3 5 4th 5 5 5 6th 5 7th 2.5 8th 2.5 0 50 50 100 100 0 50 0 Length of middle class
(mm) 0 50 50 0 0 100 0 50 Weight of protein
granules (mg) 0 44 47 44 46 46 37 39 Weight of coal
granules (mg) 32 Pressure loss (mm H ₂ O) 40 42 36 36 36 34 31 Separation (%) 28 30th 34 32 30th 30th 24 26th tar 23 68 61 68 60 54 59 50 Alkaloids 48 58 60 0 0 79 0 50 fl. phenol 0 51 49 0 0 75 0 48 Isoprene 0 72 73 8th 6th 82 3 60 acetaldehyde 4th acetone

The separation ratio for the granules in the middle layer is obtained by subtracting the value of filter # 1 is obtained from the values of filters 2-8. The separation ratio of tar by 50 mg Protein granules (No. 7) and 50 mg of carbon granules (No. 8) were 6 (ie 34 minus 28) and 3 (ie 31 minus 28)%, respectively, while the values for 100 mg of composite granules (No. 2 and 3) 12 (i.e. 40 minus 28) to 14 (i.e. 42 minus 28)%. These values are significantly higher than a simple sum of the separation ratios through the protein granules (No. 7) and the activated charcoal granules (No. 8). That with The separation ratio achieved with the compositions was consequently synergistically increased to values that were higher than the values obtained by simple addition for each granulate contained alone. This synergistic effect in the separation ratio of the compositions according to the invention was shown in just as evidently also observed with the alkaloids, with isoprene and acetone. The separation ratio of tar and volatile phenol with 100 mg composite granules was also significant higher than the ratios obtained with equal amounts of the individual granules contained.

From the results cited it is clear that the compositions according to the invention a Separation of pollutants from cigarette smoke with a higher separation ratio than it is possible by mere addition of the separation ratios of each of the individual granules contained therein alone or for conventional tobacco filter materials.

(Experiment 5) Reduction of cell toxicity

of tobacco smoke by filtering
by the compositions according to the invention

The toxicity of tobacco smoke to mammalian cell cultures and its reduction through the triple filter with the composite granulate were tested. MEM medium (cf. H. Eagle, Science, 130, 432 [1959]) with 1% calf serum, which was placed in Petri dishes 3 cm in diameter, to a cell density of 5 × 10 ⁵ per dish for 7 days at 37 ° C The culture medium was discarded and the cell layer was rinsed with isotonic saline solution (see L. R. Dulbecco et al. Journal of Experimental Medicine 99, 1967 [1954]) (hereinafter referred to as PBS). The triple filters, which contained the granules or compositions of numbers 3.5 and 6 from Experiment 4, as well as conventional acetyl cellulose single-layer filters were attached to cigarettes. These were then connected to the smoking machine, which had been irradiated with UV light to avoid bacterial contamination , and subjected to a simulated mechanical smoke test in a sterile chamber. The tobacco smoke from 10 smoking cycles was introduced into 18 ml MEM medium with 0.05% dimethyl sulfoxide. Then 2 ml serum was added, whereupon 2 ml portions of the "smoked" medium were added to the cell layer obtained above. The cells were exposed to the smoked medium at 37 ° C. for 4 hours. The medium was then discarded and the cells were rinsed repeatedly with PBS . 2 ml of MEM serum medhim were then added and the cells were incubated for 7 days at 37 ° C. The cell density was determined The relative cell density after incubation in the smoked medium was given in%, based on the comparison cell density of 100% for control purposes after incubation in the medium without exposure to smoke.

Table 5 Smoke exposure Relative
Cell density 10
Filter no.
(Vers. 4) *) not exposed (100) **) 2 exposed 1.0 ¹⁵ filterless exposed 16.8 Acetyl cellulose
Single layer exposed 89.2 3 exposed 65.2 20 5 exposed 70.3 6th

*) The filter numbers are identical to those of experiment 4.
**) 1.28 XlO ⁶ per dish.

The surviving fraction of cells after exposure to by the invention The composition of the tobacco smoke passed through was 4 times higher than in the case of the acetylcellulose monolayer. The effectiveness of the filter with the composition to reduce cell toxicity of tobacco smoke was also a factor of 5 and 1.2 higher than that of acetyl cellulose and charcoal. The inventive Composition, as a result, reduces the toxicity of tobacco smoke to the organs of Smokers. The effectiveness of the composition in reducing the cellular toxicity of tobacco smoke remained comparable to that of the activated charcoal granulate in this biological experiment. This is because the harmful gas components in tobacco smoke dominate cell lethality in this experimental system are responsible, thereby reducing the cell toxicity caused by the carbon granules experienced an apparent increase in that this preferably removes gaseous constituents. It is clear, however, that the significance in the removal of carcinogenic or cocarcinogenic Substances in tobacco smoke tar for the composition is greater than for the granulated activated carbon alone, such as is apparent from the results of the chemical analysis described in Experiment 1

(Experiment 6) Quantity ratio of protein and
Activated carbon granules in the composition

Compositions were prepared according to the method of Example 1 in which the amount of protein granules (protein content 5%) ranged from 10-90% , with 10 or 20% steps as shown in Table 6. These compositions became as in experiment 5 with regard to reducing the cell toxicity of tobacco smoke. specified.

The received
listed.

Table 6

Results are in Table 6

% Protein granules
in the composition

Smoke exposure

Relative
Cell density

exposed
exposed
exposed
exposed
exposed
exposed
exposed
exposed
not exposed

69
76
76
91
90
91
79
72
(100) *)

1.28 XlO ⁶ per cup.

The results in Table 6 convincingly show that the cell toxicity of Tobacco smoke was reduced when the smoke was filtered through compositions in which the Protein granules were present in a proportion of 40-80%.

(Experiment 7) Improvement of the smoke taste
by the composition

The triple filters designated with the numbers 3, 5 and 6 of Experiment 4 were each used on cigarettes appropriate and with regard to the smoke taste of an organoleptic examination by 18 test persons subjected. Performing the test twice was required; the taste impression had to be assessed using a rating scale ranging from 1 (preferred), 2 (medium) and 3 (not preferred). The evaluation results of the three filters are shown in Table 7 below

Table 7

Filter no. in verse 4 No. 3 Number of tests No. 6 No. 5 (C) (A) (B) 2 (O) 1 3 1 5 2 3 2 16 J i 1 9 3 2 6th

valuation
82

84

(36)

The rating was calculated by taking the sum of the respective values A χ D, B D and C χ D in the vertical columns. The ratings for the carbon and protein granules were almost comparable, while the composite granules remarkably improved the smoke taste

The above results show the excellent effectiveness of the compositions according to the invention for the removal of pollutants from tobacco smoke.

In Trials 1-7, lactose and corn starch were used as excipients. The separation ratio of volatile phenol in tobacco smoke was determined with other excipients besides that the results obtained are shown in Table 8

κι are. The production of the excipient granules and the Protein granules with 20% protein and the determination were carried out as in experiment 1.

Table 8
¹ 'separation ratio of volatile phenol (%)

Excipiens

Excipiensgranulat protein granules

Acetyl cellulose 53
Glucose 33

75
68

The results show that protein granules in which powdered acetyl cellulose and glucose were used as excipient constituents, very similar properties to the granules of experiment 1 exhibit.

example 1

10 kg commercial lactose (lactose content 94%, ash 0.5%, moisture 5%) and 3 kg whey protein from cow's milk (protein content 51%, lactose 41%, ash 2%, fat 3%, moisture 3%) were initially in mixed in a screw mixer, adding 2 kg of tap water while mixing. That Mixture was extruded from nozzles 1.5 mm in diameter with an extrusion pelleter and then The granules thus obtained were passed through a rotary mill with openings of 2 mm in diameter was then dried for 48 h at 60 ° C and then sieved, whereupon about 10 kg of protein granules of A grain size of 0.29 to 1.4 mm and a bulk density of 0.57 g / ml were obtained.

Example 2

100 kg of corn starch were mixed with 20 kg of whey protein from cow's milk (protein content 53%, lactose 31%, ash 3%, fat 2%, moisture 2%), whereupon the mixture was mixed with a fluidized bed granulator while introducing 15 kg of water at an air flow of 1.2mVmin was granulated. The grains were ^{dried at 60 °} C. for 24 hours and then sieved, whereupon about 70 kg of protein granules with a grain size of 0.29 to 1.65 mm, a moisture content of 7% and a bulk density of 0.58 g / ml were obtained.

60 kg of the protein granules were with an equal amount of granulated activated carbon with a grain size of 0.29 to 1.65 mm and 0.5 g / ml bulk density with a V-mixer mixed whereupon about 120 kg of composition with a grain size of 0.29 to 1.65 mm and a bulk density of 0.54 g / ml were obtained.

A polyethylene cylinder 102 now in length and 24 mm in circumference was filled with 2 g of the composition filled, whereupon 17 mm sections in tobacco pipes were introduced.

Claims (1)

Claim: Granular composition for the removal of pollutants from tobacco smoke with a protein and an excipient and a grain size of> 0.246 mm,
marked by