RU111989U1 - CIGAR FILTER SEGMENT - Google Patents

Abstract

1. A segment of a cigarette filter containing a porous gas-permeable base, with an applied layer of polymer nanofibers with an average fiber diameter of 100 to 200 nm, a layer surface density of 0.02 to 0.2 g / m2, and an air flow resistance of no more than 20 Pa at air flow speed 0.2 ± 0.03 m / s. ! 2. The segment of the cigarette filter according to claim 1, characterized in that the layer of polymer nanofibers is applied by electrospinning from solutions of polymers selected from the range: cellulose, cellulose acetate, polyamide, polyvinyl chloride, polyvinyl alcohol, polyethylene oxide, styrene-butadiene-styrene copolymer, polylactide, polyethylene terephthalate, copolymer of tetrafluoroethylene with vinylidene fluoride. ! 3. The segment of the cigarette filter according to claim 1, characterized in that filter paper or nonwoven fabric of the spunbond type is used as the porous gas-permeable base.

Description

The inventive utility model relates to filters, and in particular to a segment of a cigarette filter intended for use in cigarettes to filter tobacco smoke from harmful components.

A traditional cigarette filter is a device made of a porous material (e.g. paper, cotton, cork) attached to the end of a cigar or cigarette to absorb moisture, tar, nicotine and various impurities. The filter may also be a special holder in which a cigar or cigarette (mouthpiece) is inserted.

The most popular in the tobacco industry is a cellulose acetate cigarette filter containing 5-10% glycerol triacetate as a plasticizer. Filters based on it slightly reduce the intake of suspended smoke particles into the smoker's body. Acrolein, phenols and highly carcinogenic nitrosamines are selectively removed by such filters. Their effectiveness can be increased by reducing the diameter of the filaments (fibers), increasing the length of the filter, or adding certain substances to the fibers, for example, activated carbon, which is widely known for its ability to remove some components of the gas phase from smoke. Activated carbon cellulose acetate filters can remove up to 40% of carbon and nitrogen oxides, 80% of hydrogen cyanide and 70% of acrolein and benzene from cigarette smoke. However, such filters retain suspended particles worse than pure acetate filters. This leads to the fact that in most cases almost as many tar and nicotine enter the body of a smoked filter cigarette as he would get from cigarettes without a filter.

Currently, the development of new cigarette filters continues, through the use of polymer fibers and various additives.

A tobacco filter has been developed (RF patent 94024343, IPC A24D 3/14, 1996 (publ.)), Which consists of at least two sections in series along the course of the tobacco smoke: the outer one, located on the side of the smoker and made of cellulose-containing or acetate fiber, and the middle, located on the side of the tobacco, filled with an adsorbing agent (14-28 mg) of porous carbon fibers (may have a tissue structure) with an amount of carbon of at least 95% and a specific surface area of 700 to 1500 m ² / g, which increases absorption capacity s filter relative to nicotine, tar, carbon monoxide.

A product filter is known, which is made of several alternating layers, the first of which limiting the length of the tobacco composition is made of a porous sorbent of tobacco soot, the second layer is made of a microporous sorbent of volatile fractions and phases containing carbon black residues with the inclusion of a nicotine vapor-gas part (phase) and the third layer, limiting the length of the tobacco product, is made of a material including nanofibers, nanotubes and nanoclusters, and is designed to sorb fine and ultrafine fractions of the soot and nicot phases ina.

In this product, the part and the entire filter are made in the form of separate three tablets, forming the indicated three filter layers, while the surfaces of the tablets along the generatrix and at the ends are made microrough for a denser and stronger fit between themselves and when interacting with the product shell.

In this product, the first layer of the sorbent contains cured sublimation products of 20 Ca, 14 Si, and 12 C, the second contains the same materials with the addition of 20-32 C and 60 C, and the third is made of nanofibers, nanotubes, and nanoclusters of these materials and with a size particles from 50-300 nm to 50-100 μm with a porosity between particles of 40-60% in the form of micro-nanopores of stachostatic nature (the location of micro-nanoparticles and pores between them). (RU utility model patent No. 66662, 2007113223/22, 04/09/2007)

The disadvantage of the above filter is the presence of nanotubes and nanoclusters with a size of less than 100 nm. It is considered an established fact that the ingress of such objects into the human body can lead to health problems. At least, the question of the effect of nanotubes and nanoclusters on human health is being actively studied at the present time and, therefore, the use of products containing these nano-objects requires additional testing. Another disadvantage of the above filter can be considered a high resistance to gas flow, i.e. puff resistance. Although this value is not specified in patent No. 66662, nevertheless, based on the filter porosity indicated therein, one can expect a significant pressure drop created by this filter during smoking.

The objective of this utility model is to reduce the resistance of the filter element to gas flow while maintaining or increasing its filtering ability with respect to tar and nicotine, as well as increasing the safety for consumer health by eliminating the possibility of nanotubes and nanoclusters entering the consumer's body.

The problem is solved by a cigarette filter segment containing a porous gas-permeable base, with a layer of polymer nanofibers with an average fiber diameter of 100 to 200 nm, a surface density of the layer from 0.02 to 0.2 g / m ² , and air flow resistance of not more than 20 Pa at an air flow rate of 0.2 ± 0.03 m / s.

Preferably, the layer of polymer nanofibers was deposited by electroforming from solutions of polymers selected from the range: cellulose, cellulose acetate, polyamide, polyvinyl chloride, polyvinyl alcohol, polyethylene oxide, styrene-butadiene-styrene copolymer, polylactide, polyethylene terephthylene fluoride and copolymer.

Preferably, filter paper or non-woven spunbond type material is used as the porous gas permeable base.

The base material should create as little additional resistance to the air flow, but at the same time it must have a mechanical strength sufficient for its use in tape drive systems.

In the following, the description of the utility model is illustrated by examples of specific implementation.

The electroforming of the polymer nanofiber layer was carried out at the industrial installation NS-1600 and the laboratory installation NS-200 M manufactured by Elmarco (Czech Republic). These installations allow the use of rolled base materials with a width of up to 1600 mm and up to 450 mm, respectively. The parameters of the electroforming process for both plants were identical. The standard parameters of the electroforming process were as follows: electrical voltage 60-95 kV, the distance between the electrodes 16-20 cm

The diameter of polymer nanofibers was determined using a NeoScope JCM 5000 scanning electron microscope manufactured by Jeol using the Image Scope program. Preliminarily, the nanofiber material was coated with a platinum layer on a JFC-1600 installation manufactured by Jeol.

The surface density of the layer of polymer nanofibers was determined by increasing the weight per unit area of the substrate material after applying a layer of nanofibers. For weighing we used Ohaus Explorer Pro scales with an accuracy of 0.0001 g.

As the base material onto which the layer of polymer nanofibers was deposited, we used filter paper for air filtration of the BFV-105P brand (GOST 20358-78), paper for air filtration of the VFB-550AB and VFB-750AB brands produced by NPP Filtration Materials CJSC, as well as spanbonds of the Polispan Medi brand of the SS-50 and SS-80 brands manufactured by POLIMATIZ CJSC (STO 96891647-002-2009). The main properties of these materials are shown in table 1.

Table 1. Physico-mechanical properties of filter paper and spunbond used as a base material. BFV-105P VFB-550AB VFB-750AB SS-50 SS-80 Surface density, g / cm ² 140 ± 10 120 ± 5 110 ± 5 50 ± 3 80 ± 5 Breathability, l / m ² s > 800 550 ± 50 750 ± 60 1700 ± 200 700 ± 100 Resistance to air flow, Pa <2.5 3.5 ± 0.3 2.6 ± 0.3 1.3 ± 0.2 2.7 ± 0.4 Destructive Force, N > 12 > 90 > 75 > 55 > 85

After a layer of polymer nanofibers was deposited onto the base, filter segments in the form of disks were cut out from the obtained two-layer material.

For testing, the segment was connected to a Java Original cigarette in two ways. The first way - the segment is located inside the cigarette filter:

1) removed the original standard cigarette filter from the "Original Java" cigarettes;

2) cut off from it a part 4 mm long;

3) put the rest of the filter length back into the cigarette;

4) the filter segment described in the utility model was placed so that the layer of nanofibers was facing the fragment of the original filter already placed in the cigarette;

5) covered with the remaining fragment of the initial filter with a length of 4 mm

The length of cut filter fragments with a length of 4 mm was selected solely on the basis of ease of handling and reliability of fixation of all elements.

The second way - the segment is located outside the cigarette filter:

1) the segment described in the utility model was applied to the cigarette filter with the side on which the layer of nanofibers is located;

2) the segment was fixed together with the cigarette using a paper tube 15 mm long, which was tightly mounted on the cigarette filter and on one side of which there was an inner edge that pressed the segment to the cigarette filter when putting the tube on the cigarette filter.

Subsequent tests showed that the filtering ability of the modified filter did not depend on the method of connecting the inventive segment with an exemplary filter of original Java cigarettes.

In each of the examples described below, 40 segments of a cigarette filter were made and, accordingly, 40 samples of modified cigarette filters containing new filter segments were tested. In each example, 10 samples were made in accordance with the first method of connecting a new segment of the cigarette filter with a sample filter, and 30 samples were made in accordance with the second method of connection. There were no differences in the filtering ability of the samples from the connection method. Table 2 shows the data averaged over 40 samples for each example.

After the segment was connected to a cigarette, these cigarettes were tested on a Borgwaldt rm20 / cs 20-position rotary smoking automatic machine under the following conditions:

tightening volume 35 ml, air flow rate 0.20 ± 0.03 m / s, tightening time 2 s,

pause time 1 s, environmental parameters (pressure, temperature and humidity) - in accordance with GOST R ISO 3402-2002.

Control sample, i.e. a sample of the original Java cigarette without an additional segment, had the following characteristics:

length: cigarettes - 79.0 mm, filter - 18.0 mm, smoking part - 61.0 mm (determined in accordance with GOST 3935-2000);

the diameter of the cigarette is 7.82 mm (determined in accordance with GOST R 51974-2002);

weight: cigarettes - 0.860 g, tobacco tow - 0.729 g, net tobacco - 0.685 g, filter - 0.131 g (determined in accordance with GOST R 51974-2002);

puff resistance: cigarettes - 101 mm. water Art., filter - 76 mm. water Art. (determined in accordance with GOST R ISO 6565-2002);

content in tobacco smoke: nicotine - 0.430 mg / sig (determined in accordance with GOST R 51974-2002); resins - 6,570 mg / sig (determined in accordance with GOST R 51976-2002); carbon monoxide - 6.06 mg / sig (determined in accordance with GOST R 51358-2008).

Example 1. A segment of a cigarette filter with cellulose acetate nanofibres.

Electroforming was carried out at the Elmarco NS-1600 continuous industrial plant. The molding solution is a solution of cellulose acetate (15 ± 1% wt.) In a mixture of acetic acid and water (70/30). Substrate material - filter paper VFB-750AB in rolls 1000 mm wide. The voltage at the electrodes is 90-95 kV for forming nanofibers with an average diameter of 70 nm, 80-90 kV for forming nanofibers with an average diameter of 100 nm, 70-85 kV for forming nanofibers with an average diameter of 150 nm, 65-80 kV - for forming nanofibers with an average diameter of 60-75 kV - for forming nanofibres with an average diameter of 250 nm. The distance between the electrodes: 20 cm - for forming nanofibers with an average diameter of 150 nm and 16 cm - for forming nanofibres with an average diameter of 250 nm. The substrate drawing speed was set in accordance with the technical regulations for the NS-1600 installation to obtain the required surface density of nanofibers of the corresponding diameter. To remove solvent residues after the deposition of nanofibers, the rolls of coated nanofibers were dried at 90 ° C. In all the examples described below, the drying temperature was about 0.7 T _bales (° C) of the boiling point T _bales (° C) of the solvent used. After that, the parameters of the layer of nanofibers were measured: their average diameter and surface density were determined. If the values of these parameters deviated from the required values by more than the value of the standard error of the measurements, the parameters of the electroforming process were adjusted. In particular, the concentration of the molding solution was corrected (in this case, the concentration range is indicated), the voltage between the electrodes (the interval in which the variation was carried out), as well as the broaching speed of the substrate material, are indicated. After obtaining a layer of nanofibers with the required properties, 40 filter segments in the form of disks with a diameter of 7.78 mm were cut out of the obtained filter material. Further, the filter segments were connected to the filters of 40 “Original Java” cigarettes according to one of the methods described above and cigarettes with a modified filter were tested on a Borgwaldt rm20 / cs automatic smoking machine. The obtained data on the filtering ability of filters containing the claimed filter segments are shown in table 2.

Example 2. Installation of electroforming NS-1600; polymer - polyamide-6 (9 ± 1% weight); solvent - a mixture of formic and acetic acids (1/2); substrate material - a roll of filter paper VFB-750AB 1000 mm wide. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 3. Installation of electroforming NS-1600; polymer - a copolymer of tetrafluoroethylene with vinylidene fluoride (fluoroplast-42) (7 ± 1% weight); solvent - DMF; the substrate material is a roll of filter paper VFB-550 with a width of 1000 mm. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 4. Installation of electroforming NS-1600; polymer - polyethylene terephthalate (7 ± 1% weight); the solvent is cyclohexanone; substrate material - spunbond rolls SS-50 and SS-80 manufactured by ZAO POLIMATIZ 1600 mm wide. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 5. Installation of electroforming NS-1600; polymer - polyvinyl chloride (6 ± 1% weight); solvent - DMF; substrate material - spunbond rolls SS-50 and SS-80 manufactured by ZAO POLIMATIZ 1600 mm wide. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 6. Installation of electroforming NS-1600; polymer - polyethylene oxide (7 ± 1% weight); solvent - a mixture of ethyl alcohol and water (90/10); substrate material - rolls of filter paper VFB-750AB and VFB-550AB width of 1000 mm, respectively. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 7. Installation electroforming NS-200 M; polymer - polyvinyl alcohol (9 ± 1% weight); solvent - a mixture of ethyl alcohol and water (90/10); the substrate material is a roll of filter paper BFV-105P and VFB-750AB width of 430 and 450 mm, respectively. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 8. Installation electroforming NS-200 M; polymer - polylactide (7 ± 1% weight); the solvent is tetrahydrofuran; substrate material - SS-50 spunbond rolls manufactured by POLIMATIZ 400 mm wide. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 9. Installation electroforming NS-200 M; polymer - cellulose (surgical cotton wool) (2.5 ± 0.5% weight); the solvent is N, N-dimethylacetamide / LiCl (92/8); substrate material - SS-50 spunbond rolls manufactured by POLIMATIZ 400 mm wide. The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Example 10. Installation electroforming NS-200 M; polymer - styrene-butadiene-styrene triblock polymer (9 ± 1% weight); the solvent is a mixture of tetrahydrofuran and dimethylformamide (75/25); substrate material - SS-80 spunbond rolls manufactured by POLIMATIZ 400 mm wide.

The remaining parameters are the same as in example 1. The data obtained are shown in table 2.

Table 2. Data on the filtering ability of cigarette filter segments containing nanofibres of various polymers having different diameters and different surface densities. All measurements were carried out at environmental parameters corresponding to GOST R ISO 3402-2002. Data averaged over 40 samples for each example. Example Polymer Solvent Backing material The average fiber diameter, nm Surface density, g / cm ² Nicotine content, mg / sig. The resin content, mg / sig. The content of CO, mg / sig. one Cellulose Acetate (15% wt.) Acetic acid + water (70/30) VFB-750AB 70 0.10 0.133 2,016 2.43 one hundred 0.10 0.139 2,100 3.39 150 0.02 0.295 4,125 5.55 150 0.10 0.147 2,201 4.21 150 0.20 0.003 0.248 3.18 200 0.10 0.263 3,419 5.01 250 0.10 0.370 4,437 5.72 2 Poly-amide-6 (nylon-6) (9% wt.) Formic + Acetic Acid (1/2) VFB-750AB 70 0.10 0.138 2,021 2.64 one hundred 0.10 0.143 2,113 3.56 150 0.02 0,306 4,183 5.70 150 0.10 0.151 2,217 4.49 150 0.20 0,000 0.260 3.37 200 0.10 0.267 3,430 5.19

250 0.10 0.384 4,443 5.83 3 A copolymer of tetrafluoroethylene with vinylidene fluoride (fluoroplast - 42) (7% wt.) DMF VFB-550 70 0.10 0.144 2,033 2.69 one hundred 0.10 0.149 2,133 3.61 150 0.02 0.326 4,201 5.81 150 0.10 0.158 2,227 4,54 150 0.20 0.009 0.285 3.44 200 0.10 0.270 3,436 5.27 250 0.10 0.391 4,501 5.94 four Polyethylene-terephthal at (7% wt.) Cyclohexanone SS-50 150 0.02 0.323 4,482 5.95 SS-80 150 0.10 0.165 2,609 4.63 SS-50 150 0.20 0.017 0.371 3.52 5 Polyvinyl chloride (6% wt.) DMF SS-50 150 0.02 0,309 4,191 5.78 SS-80 150 0.10 0.156 2,223 4,53 SS-50 150 0.20 0.008 0.266 3.41 6 Polyethylene Oxide (7% wt.) Ethyl alcohol + water (90/10) VFB-750AB 150 0.02 0.281 4,022 5.42 VFB-550AB 150 0.10 0.140 2,130 4.17 VFB-750AB 150 0.20 0,000 0.211 3.15 7 Polyvinyl alcohol Ethyl alcohol + water BFV-105P 150 0.02 0.275 4,032 5.31 VFB-750AB 150 0.10 0.138 2,120 4.12

(9% weight.) (90/10) BFV-105P 150 0.20 0,000 0.209 3.11 8 Polylactide (7% wt.) Tetrahydrofuran (THF) SS-50 150 0.02 0.291 4,079 5.49 150 0.10 0.143 2,141 4.22 150 0.20 0.003 0.242 3.17 9 Cellulose (surgical cotton wool) (3% wt.) N, N-dimethylacetamide + LiCl (92/8) SS-50 150 0.02 0.285 4,113 5.47 150 0.10 0.141 2,151 4.13 150 0.20 0,000 0.245 3.14 10 Styrene-butadiene styrene
triblock polymer (9% wt.) THF + DMF (75/25) SS-80 150 0.02 0,307 4,203 5.91 150 0.10 0.161 2,230 4,59 150 0.20 0.011 0.269 3.43

The data in Table 2 were obtained for a disk-shaped cigarette segment with a diameter equal to the diameter of the cigarette filter to which it was connected. It should be noted that the cigarette filter segment may have other shapes, in particular, a disk with a hole in the middle, which can be used to connect the segment to a cigarette. Also, the segment may be in the form of a square or an equilateral triangle, which fit into a circle with a diameter equal to the diameter of the filter of the cigarette with which it is connected. This form of the segment allows to reduce the waste of materials due to the rational cutting down of segments from sheet blanks. In all these cases, the data shown in table 2 are adjusted in the direction of decreasing the filtering ability in proportion to the decrease in the area of the filtering surface of the cigarette filter segment.

It should be noted that the increase in drag resistance did not depend on the type of polymer material, but correlated with the surface density of the nanofiber layer and was approximately 10 Pa at a surface density of 0.20 g / cm ² , 5 Pa - at a surface density of 0.10 g / cm ² and less than 1 Pa - at a surface density of 0.02 g / cm ² .

The data presented in table 2 indicate that the filtering ability of the cigarette filter segments containing a layer of nanofibers does not depend on the substrate material, little depends on the material of the nanofibers, but is determined by their diameter and surface density. It should be noted that the electroforming of nanofibers with a diameter of less than 100 nm is a technologically more complex process, because the range of all technological parameters of the electroforming process (voltage, viscosity and conductivity of the molding solution, atmospheric humidity, etc.) is greatly narrowed. Therefore, the optimal lower value of the diameter of the nanofibers can be considered 100 nm. The filtering ability with respect to resin and nicotine is worse for nanofiber filter segments with an average diameter of 250 nm than for segments with 150 nm diameter fibers at the same surface density. This result is observed on nanofibers made of three different types of polymers (examples 1-3 in table 2), which suggests that it is not associated with the type of polymer, but is apparently associated with an increase in the porosity of the layer of nanofibers. Thus, the optimal average fiber diameter corresponds to an interval of 100-200 nm. For this reason, in the examples from number 4 to number 10, the average fiber diameter is fixed at 150 nm, i.e. in the middle of the optimal range of diameters, the surface density varied, since it is more technologically advanced (the surface density varies due to the speed of drawing the substrate tape). It should be noted that samples with an average nanofiber diameter of 150 nm are representative for the entire range of diameters of 100-200 nm, taking into account the observed dispersion of fiber diameters of 30-35%.

A layer of nanofibers with an average diameter of 150 nm and a surface density of 0.02 g / cm ² retards nicotine by an average of 30% and resin by 35%. This significantly reduces the content of substances harmful to humans, therefore, to reduce the surface density of less than 0.02 g / cm ² impractical. A layer of nanofibers with an average diameter of 150 nm and a surface density of 0.2 g / cm ² almost completely inhibits nicotine, which leads to a decrease in consumer properties of cigarettes. Thus, the optimal surface density of the layer of polymer nanofibers is from 0.02 g / cm ² to 0.2 g / cm ² .

Claims (3)

1. A segment of a cigarette filter containing a porous gas-permeable base, with a deposited layer of polymer nanofibers with an average fiber diameter of 100 to 200 nm, a surface density of the layer from 0.02 to 0.2 g / m ² , and resistance to air flow not more than 20 Pa at an air flow rate of 0.2 ± 0.03 m / s. 2. The cigarette filter segment according to claim 1, characterized in that the layer of polymer nanofibers is deposited by electroforming from polymer solutions selected from the series: cellulose, cellulose acetate, polyamide, polyvinyl chloride, polyvinyl alcohol, polyethylene oxide, styrene-butadiene-styrene copolymer, polylactide, polyethylene terephthalate, a copolymer of tetrafluoroethylene with vinylidene fluoride. 3. The cigarette filter segment according to claim 1, characterized in that filter paper or non-woven material such as spunbond are used as the porous gas-permeable base.