DE1517318A1 - Additive-releasing filter and method for releasing additives to tobacco smoke - Google Patents

Description

Patent Attorneys DI.-ING. WALTER ABITZ -., - _{r> rn ,, K1} " _1Q

MCncSen

September 28, 1964

582-440

PHILIP MORRIS IHCQRPORATED 100 Park Avenue, New York 17, N, Y., V ₃ St-A

Toeate-releasing filter and process for the release of additives to tobacco raw

The present invention relates to an accessory-releasing filter for tobacco smoke and a method for releasing additives to tobacco smoke. Specifically, the present invention relates to a Zueata-freigebandes filter 't ÜR; Tobacco smoke and a process for releasing additives to tobacco smoke, whereby the additives can be maintained and preserved during storage of the tobacco soap containing them and are released in controlled quantities when raw tobacco passes through the filter, \

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One of the additives that can be delivered to tobacco smoke in accordance with the present invention is nicotine. In the The tobacco industry has long been known to achieve this a satisfactory smoking enjoyment helps maintain the nicotine content of the tobacco product a uniform value is desirable. However, this result is difficult to achieve because the nicotine content of tobacco varies widely depending on the type of tobacco and the conditions under which the tobacco is planted varies.

Factors which influence the nicotine content of any tobacco variety include the conditions prevailing during the growth of the tobacco, for example the conditions of humidity, soil type, fertilizers used, the number of tobacco plants per unit area and the care given to the plants during this Growth is used. The fiikotingehalt also varies widely AuemaS ie after the type of tobacco · Many of the newer varieties of tobacco plants yield nikotinaraen tobacco. On the other hand, the working methods for the preparation of fabakeraugniesen often remove the nicotine naturally present in tobacco partly or wholly * Parts, for example the stalk, have a low ricotine content.

Β4 " ^{BAD orig |} nal

It is apparent that the maintenance of nicotine to the desired physiological activity and the desired taste and flavor desired supply at a sufficiently high level * au, which gives this material the smoke, without increasing the nicotine content to an undesirably high value, is a major problem in the tobacco industry. The addition of nicotine su tobacco in such a way that it remains inert and stable in the tobacco product and yet is released in a controlled amount into the smoke aerosol when the tobacco is pyrolyzed would be a very desirable result.

Previous attempts to adjust the amount of nicotine in tobacco were unsuccessful. It is not practical to add nicotine as such to tobacco products. Ba it duroh Intact skin can be absorbed is nicotine difficult and dangerous to handle the processing operations » to have. In addition, free nicotine is an unstable material and it has been found that it is easily displaced under ambient conditions. Therefore, when nicotine is simply called if free material were added to tobacco, it would probably during the storage of the tabker product decomposed, which would lead to the formation of unwanted replacement products and a decrease in nicotine · Although the nicotine content of tobacco products

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Addition of nicotine under conditions which require considerable effort, initially uniform could be made, the decomposition accompanying the storage of the product would not result in smoke with a uniform content of nicotine.

In U.S. patent application serial no. 149 5 ¹ K) of November 2, 1961, a solution to this problem was given by introducing nicotine-containing ion exchange resins [hereinafter called nicotine ion exchange resins] into the tobacco. The present invention represents a significant improvement over the above invention in that no ion exchange degradation products are introduced into the smoke.

The present invention provides a solution to this longstanding problem and provides precise control of the amount of nicotine that is released into tobacco smoke. By employing the procedures and compositions of the present invention it is possible eliminate the dangers of nicotine handling, and Introduce precise amounts of nicotine into a tobacco composition that will remain constant over long periods of time and ultimately result in a smoke that is a controlled one Contains amount of nicotine. In addition, the present process does not result in any degradation products from the ion exchanger in the Smoke a.

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Another type of additive that can be delivered to tobacco smoke in accordance with the present invention is a Flavoring agent. Often a flavor or flavor that is introduced into tobacco goes while during the subsequent processing stages or during storage is lost or is or are changed. Except- ' it is difficult to control the amount of flavor released during smoking of a tobacco product control to ensure a consistent tobacco aroma throughout smoking.

Many attempts have been made to use 'flavorings in Introducing tobacco smoke, but a completely satisfactory procedure has not been found. For example, aromatizing acids were found in tobacco in Fora from introduced stable esters, which are broken down into acids during pyrolysis. However, such a mode of operation is only applicable to certain types of flavoring agents useful and also leads to the inclusion of other breakdown products of the pyrolysis of the esters in the stomach.

The present invention overcomes the above mentioned Disadvantage. The present invention permits the release of desired flavoring agents in controlled amounts into the tobacco smoke Bowit also when desired the release of nicotine in controlled amounts in the

Tobacco smoke.

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According to the invention, the desired additive is incorporated into a tobacco-containing product in such a way that it is not released before the time in which the tobacco product is smoked. The expression "Tobacco ¹¹ , as used here, means any composition that is intended for human consumption through smoking, regardless of whether it consists of tobacco plant parts or substitute materials or of both "

The present invention comprises introducing a material containing as an additive a Ionenaustauscberharz [hereinafter called Zuaatz ion exchange resin (additive-ion exchange resin)] denotes ¹ * may, in a filter for tobacco smoke. This additive ion exchange resin can be a flavoring ion exchange resin or a Kikotin ion exchange resin.

In the case of nicotine, deflagration ion exchange resin can be used be a nicotine cation ion exchange resin (hereinafter referred to as a nicotine cation exchange resin for convenience). The obtained · composition is inert and stable uad can be put in a filter for Cigarettes, pipes, cigars or in other tobacco products. The nicotine-cationic dew resin does not decompose under normal storage · » conditions and does not give the tobacco or dtm filter any

• Olli IΛ 8 ft

unwanted odors. However, when the tobacco is smoked and the smoke goes through the filter «becomes nicotine from that Nicotine cation exchange resin is released and goes in the puff. The «long nicotine that is desirable in smoke 1st »can, within desired limits, by appropriately controlling the length of nicotine cation dew hars that initially introduced into the filter, “Inge B te lit.

The nicotine ion exchange resin, which is used in the following Also known as nicotine resin, it can be made by bringing a cation exchange resin into contact with the nicotine either by working continuously or in batches. When contacting batchwise, the reaction components are placed in a reaction flask with a volume of Resin moves, which can make up, for example, 20-50 wt .- ^ of the reaction component. The amount of ax materials the operating temperature and riding depend τοη the involved reaction bicomponents. The mixture is through Shake or stir agitated. The use of a finely divided resin sets any phyeikaliftohe Vereohleohteruat of the resin, which is called out by a stirrer » could, come down to a minimum. Particles in the range corresponding to 100-200 mesh (US sieve size) are avoided. As At the end of the reaction time, the solution can be decanted and the suspended hair can be recovered by filtration. Dae

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ΠΛΟ

Resin can then be rinsed and air dried and is then ready to use. The solvent is preferably water, but the others can also be inert Liquids in which the nicotine is soluble can be used.

Continuous column operation can be performed by adding pretreated resin to a column Suitable size is introduced and the reaction components are continuously passed through the column.

Preferably the contacting is continuous carried out. This can be done by adding a pillar to the Ion exchange resin is packed in particulate form, for example in the form of beads, and an aqueous solution of nicotine is passed through the column. the The procedure used can be the same as that used in chromatography columns. As in the case of the Batch-wise contacts can be brought into contact with other inert ones Liquids are used instead of water.

Both in batches and in continuous operations, the resin came after the desired one Amount of nicotine absorbed by the resin, from the contact tube removed and used directly in accordance with the present invention.

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The exact amount of nicotine incorporated into the resin can be determined by methods known per se. For example, the canoe from R.B. Griffith in Tobacco Science ", Vol. 1 ('.95?), Pp. 130-137, specified procedure can be applied. Another way of working is that in "Official and Tentative Methods of Analysis of the Association of Official Agricultural Chemists ", 4th edition, 1935, described method of operation.

The proportion of nicotine in the resin is not critical, as long as the amount of nicotine is known. However, it is advantageous to use a hicotine resin in which a considerable amount of nicotine is converted, since the amount of nicotine resin that is needed to introduce any- special amount of nicotine that is desired in a filter is, obviously decreases as the proportion of nicotine in the resin increases.

A typical equation for the healing involved in the manufacture of the nicotine catalyst resin is schematize}! then reproduced:

H ^- H ⁺ + Knuckle

nicotine

Nicotine resin

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The above equation represents the implementation when the cation exchange resin is in the hydrogen form, as described below, will. A corresponding response can result with a cation exchange hara. In which the hydrogen ion is replaced by another ion such as Sodium ion, potassium ion or other ions. However, the hydrogen ion type is preferred, since it is more easily replaced by nicotine, and at that In contact eringen the nicotine absorbs more easily.

Cation exchange resins made according to the present invention Resins of atark cationic type, medium cationic type or weakly cationic can be used Type, and they can be, for example, any of the commercially available cation exchange resins.

Too satisfactorily stronger. Include cation exchange resins those of the sulfonic acid type such as, for example Kar2e made by crosslinking polystyrene with divinylbenzene and suifing of the crosslinked product are formed. Such resins are believed to have the following structural formula explained:

SAD ORlGiNAL - 10 -

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SO, H 5

SO ₅ H

• GH— CH ^ - CH-OHg— GH — CH -

SO ₃ H-YY

SO, H

- CH ₂ -CE ₂ -GH • -CH ₂ - CH-GH ₂ -CH

SO ₅ H

SO ₅ H

-CH- CH ~ —GH — CH «-

C.

SO ₅ H

There are numerous commercial cation builders of this type, including Amberlite XR ⁺

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Amberlite IR 120-H ⁺ , (both manufactured by Rohm and Haas Co.), Dowex 50 W-X8 (manufactured by Dow Chemical Co.), and the like.

Satisfactory intermediate cation exchange resins include those of the phosphonic acid type, such as resins formed by crosslinking polystyrene with divinylbenzene and reacting the crosslinked product with phosphonic acid to introduce a difunctional phosphonic acid group into the styrene-divinylbenzene skeleton. Such resins can be represented by the following structural formula;

CH-CH ₂ -CH-CH ₂ -CH PO ₃ H ₂

PO ₅ H ₂

- CH-

-CH-CH ₂ - CH-CH ₂ --CH -

PO ₅ H ₂

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»5 * 2

Typical for an im. Commercially available resin of this type is Bio-Rex 63 (manufactured by Bio-Rad Laboratories).

Satisfactory weak cation exchange resins include those of the carboxylic acid type such as "for example Resins obtained by copolymerizing methacrylic acid with a crosslinking agent, for example divinylbene sol, are formed. Such resins can be represented by the following structural formula:

GH,

ι -

—C-COOH

OH,

OH,

> - C - GH «- GH - CH _O - 0 - CH ₀ - • ι 2 t 2 j 2

COOH

- C - GH ₂ - C _{- CH 2} - CH - CH ₂ -

GOOH GOOH

Typical of a commercially available resin of this type is Amberlite CG 5Q Type 1 (manufactured by Rohm and Haas Co.), which is described as a synthetic, weakly acidic, carboxylic acid-type, water-like resin.

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Another type of weak cation exchange resin comprises resins with an -OH group as an ion functional group = These resins are formed by reacting polyhydric phenols with formaldehyde. Selche resins can be represented by the following structural formula:

OH

CH ₂ -IJ-- GH ₂ -

OH

Such resins may further by the introduction of one or more other functional groups to be modified. For example, the above phenol-formaldehyde resins can be sulfonated to introduce sulfonic acid groups, resulting in a resin that contains both SO, H and OH groups, as represented by the following structural formula:

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OH

OH

GH ₂ Pi — CH ₂ -y-0H ₂ —Pj CH _{2 -}

OH

SO ₃ H

Other types of cationic exchange resins can also be used. Suitable resins include, for example carbonaceous cation exchange resins from the sulfonated Type of coal, either in the hydrogen or the Nätribimfογει, d. 3i. in which the ion, which is caused by the Nicotine is replaced by either hydrogen or sodium is. Such resins are commercially available, such as Zeo-Karb-H & rse. Another type of resin. That is suitable is j is the natural or synthetic zeolite type. These are hydrated alkali aluminum silicates .

The nicotine resin can be applied to the filter in a variety of ways. For example, it can be direct

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can be used as it is removed from reaction vessel after its manufacture, or it can be used for formation first smaller particles are ground. The size of the resin particles can vary widely. The nicotine resin particles can be coated with a binder such as a Mix shark syrup solution, honey, molasses or other similar materials and then spray on, mix with the components of the filter, or otherwise onto the Filters are applied.

The amount of nicotine resin added to the filter varies depending on the original nicotine content in the tobacco and according to the nicotine content desired in the tobacco. In general, the nicotine content of the filter will be on a level brought about 0.1 - 3.0 mg of nicotine in the smoke per cigarette.

A method of determining how much of a particulate nicotine resin is added to a particular filter is to analyze the smoke for nicotine eu, which is done by usual methods, for example as in Journal of the Association of Official Agricultural Chemists, (Vol. 42, Nov. 2, 1959), pp. 424-429. According to this method, an aqueous solution of smoke particle phase under suitable conditions

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breastfeeds. This is followed by the spectrophotometric analysis of the distillate obtained in the ultraviolet Spectral range to »

The rules for the details of this mode of operation include the following information:

The smoke particle phase from 10 consecutive cigarettes using a standard robot smoking process (35 ml puff volume, taken over a period of 2 seconds, once per minute) is placed on a glass wool plug or equivalent collection medium capable of separating 0.1 µ particles and larger particles from a gas particle phase mixture suitable, collected. The nicotine alkaloids are stripped from the collecting medium with four 10 ml portions of 0.0ϊ> η HGl. The separated eluates are combined and diluted to exactly 50 λΙ with 0.05 η HCl. A 10 ml aliquot of this solution is transferred into the inlet opening of the distillation unit. Then about 100 ml are distilled and discarded. The sample in the unit is made alkaline by adding one NaCl capsule, size 00, and one NaOH capsule, size - 00, in the order given. The distillation is repeated and a second 100 ml portion is made as follows collected: About 98 ml are distilled in a 1oC ml Mtißkolben in which previously 5 ml 3 η ^ HgSO were segeben. The distillate becomes, to be precise, the mark with distilled

BATH ORIGINAL

Water made up, well mixed, and spectrographically between 250 and 300 mja examined »The absorption of the unknown Solution is corrected at about 260 mu by a baseline chosen based on the curve. From the A line is drawn at the lowest point on either side of the maximum absorption. The difference between the baseline and the peak at the wavelength of the peak is taken as the absorbance of the sample. This corrected absorption is compared to the absorption of the standard nicotine solution corrected in the same way, and the Nicotine content of the sample is taken directly from this comparison using standard spectrophotometric procedures calculated.

mg nicotine alkaloid ■ (Α / Α ¹ ) χ (mg known per ml χ dilution factor / number of cigarettes in the sample): where A is the corrected absorption of the unknown sample and A ^{1 is} the corrected absorption of the known sample. The nicotine resin content for the filter. can then be adjusted to bring the nicotine in the puff into the desired range.

In the case of a flavoring agent, the additive ion exchange resin a flavoring anion exchange resin, a flavoring agent inter-ion exchange resin or a flavoring cation exchange resin be"

- Ίβ -

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Flavoring agents that can be used in accordance with the present invention include both acidic and basic flavoring materials which can volatilize and be released from the ion exchange resin to be carried into smoke when the tobacco containing the flavoring ion exchange resin is burned . Basic flavor materials that can be used include aromatic alkaloids, amines, myosmin, or quinine derivatives. For example, the basic flavoring agents can be the following: alkaloids, such as, for example, nornicotine, cotine, myosmin, nicotelline, nicotyrine, anabasine, anatabine and metanicotine; heterocyclic bases, such as, for example, pyridine, pyrrolidine, 2,3-dipyridyl, 2-picoline, 3-K-coline ,. 4-picoline, α-collidine, ß-collidine, γ-collidine, 2,4-LxItIdIn ₁ 3,4-lutidine, 2,6-lutidine, 3-pyridyl ethy ketone, 3-pyriclyl methyl ketone, methyl nicotinate, ilethyl isonicotinate _t 6- Methylquinoline and 6-isopropylquinoline; aliphatic compounds, such as, for example, ammonia, triethylamine, benzylamine, octylamine; aromatic amines, such as 3-I'henyl "2-p3Open-1-ylanthranilat, _{Met'ayl-S-methyl-aminobenzoate%} üthyl-o ~ aminobenzoate, methyl anthranilate (methyl o aminobenzoate) 'and o-phenylethyl-aminobenzoati ship' see bases such as methyl N-3,7-dimethyl-7-hydroxyoctylidene anthranilate and methyl N- (p-tert-butyl-α-methylhydrocinnamylidene) anthranilate; and amino acids, like both

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for example glycine, alanine, (^ .utamine, lysine, valine, leucine, isoleucine, proline, ornithine, arginine and serine. The preferred basic flavoring agents are the following: nornicotine, myosmin, 3-pyridyl methyl ketone, methyl nicotinate, ethyl-o-aminobenzoate, Methyl anthranilate (methyl o-aminobenzoate), glycine, and alanine. Acid flavor materials that can be used include organic carboxylic acids of 3 to 8 carbon atoms, inclusive. Typical acids are the saturated aliphatic fatty acids such as propionic acid, n-butyric acid, and isobutyric acid, 4 -Methylvaleric acid, 3-methylvaleric acid, 2,2-dimethylbutyric acid, 2-methylisovaleric acid, straight-chain or branched-chain caprylic acids; the unsaturated fatty acids, such as acrylic acid, crotonic acid, vinylacetic acid, 4-methyl-4-henenic acid (4-methyl-4-heneoio acid ) and 5-methylaorbinic acid; the cycloalkanoic or cycloalkenaliphatic acids, such as, for example, cyclopentanecarboxylic acid, cyolohexanoa rbonic acid, cyclopentane acetic acid or cyclohexaneaeiga acid or the corresponding unsaturated cycloalkenes; the aromatic carboxylic acids, such as benzoic acid or toluic acids, and phenylacetic acid. In addition, the volatile derivatives of the above acids such as hydroxy acids or keto acids can be used. The flavoring acid is preferably an aliphatic or alicyclic saturated monocarboxylic acid of the fatty acid series having 4, 5 or 6 carbon atoms.

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Although many of the materials mentioned above are suitable for sieve, either are odorless or have an unpleasant odor »if you smell them in certain concentrations, increase Improve the aroma of tobacco smoke when used in low concentrations by changing the acid-base ratio in the smoke. The acids also tend to produce the "mild" effect.

The chemical exchange resins with the flavoring agents can be used in accordance with the present invention can, can be strong, weak or intermediate cation exchange resins of the same type as si © described above in relation to the mcotinic cation exchange resins became.

Anion exchange resins which can be used in accordance with the present invention can be strongly basic harae, such as, for example, the polystyrene-quaternary ammonium resins. Satisfactory commercial resins of this type are Amberlite IRA 400, Amberlite IRA 401, Amberlite IRA 410, Dowex I, and Dowex 2 and can be represented by the following formulaί

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-CH '■ · CHp ■■' ■ CH ——— CHp ——— CH ——— CHp-

⁺ C1 "CH ₂ N (CH ₅ ) J ⁺ Cl"

CH ₉ N (CH ₅ ) ₅ ⁺ Cl "

Resin obtained by treatment with trimethylamine, illustrates strongly "basic anion exchange resins.

Satisfactory weak base anion exchange resins include the primary, secondary, and tertiary amines, and are replaced by such commercially available tertiary amines as Amberlite IH 45, Dowex 5, Amberlite IR 4B, Duolite A2, Duolite A4, Duolite A6, and Duolite A? explained.

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Duolite A 114 ·, which is typical for the weakly basic anion exchange resins, can be represented by the following "formula:

Resin that is adhered to by treatment with dimethylamine.

The flavoring ion exchange resin, i.e., the resinate, can be prepared by contacting the hare with the flavoring material under either continuous or batch conditions. The amount of materials, the temperature and the operating time depend on the reaction components involved. Generally, however, the time will be between about one second and about 30 minutes and the temperature between about

10 and about 54 ° C (about 50 to about 150 *). Ion exchange particles with a size corresponding to 20 to 40 lakes (US mesh size) are preferred. At the end of the reaction time, the solution and the suspended resinate can be decanted can be removed by filtration. The resinate is then rinsed and be air-dried

Typical equations for the reactions involved in the production of the aromatizing agent-ion exchanger share are shown below schematically:

R "H ⁺

Cations from Basic Flavoring Agent

exchanger resin aromatizing ion exchange resin

middle

R ⁺ OH "+ R ¹ OOOH >» H ⁺ 8 ¹ OOOJ

Anions from- sour flavoring agent-

dipping resin flavoring ion exchange resin

• middle

The filter base can contain any filter material that is an adsorbent and / or absorbent material, including commercially available filter materials. For example, it can be paper, cellulose acetate, cellulose paper or a synthetic polymer such as polyethylene. The filter can also contain additives such as carbon, molecular sieves, crystalline

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line cellulose, aluminum oxide, puller earth, hot starch, Cellulose powder or diatomaceous earth.

The additional ion exchange resin (resinate) can also be used Filter base material can be dispensed in different ways. For example, the resinate can be placed between two parts of a double filter type of oilulose acetate filter will; a finely divided hesinate can be divided into Löäi2D £ 3mittel dispersed and on a cellulose acetate cable Sprayed, then dried and put on a filter is manufactured; the resinate can be ground and added as dust to the cellulose acetate, after which the cellulose acetate ι or the resinate is made on a filter köii'.ien in situ in ion exchange paper or in certain Geliuloses are prepared with ion exchange activity, and the materials are then processed into filters,

The range of contents for the application of the hesinates is 3 at about 0.01 - 50 mg / cigarette for all additive ion exchange resins on the filter base material. The preferred range is that which is 0.10-0.50 mg / cigarette Flavoring agent in the smoke results.

The flavoring ion exchange resin decomposes does not under normal storage conditions and does not give the tobacco product any undesirable odors.

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When filter that the flavoring ion exchange resin contained, attached to cigar liners and smoked, the flavoring agent will be good in the smoke convicted.

The following examples illustrate the invention without restricting it:

example 1

A sulfonated polystyrene cation exchange resin (Rohm and Haas Amberlite IR 112) is converted into the H ⁺ ~ form and mixed with an aqueous solution of nicotine. After the rapid absorption of nicotine has ended, the resin is filtered off and air-dried. Analysis of the dried resin shows that it contains 33 GeWe - '/ ύ nicotine. It has no noticeable smell of nicotine. The percentage of nicotine in the resinate does not change noticeably after one year of storage.

The resin is ground to a particle size corresponding to 60-80 mesh (US sieve size) and placed in the filter of Double filter type cigarettes inserted by inserting it between the carbon filter and the cellulose acetate filter will. The amount used is 20 mg of resin per cigarette. A smoking committee that subjects cigarettes

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tive, reports that these cigarettes have the characteristic effect of nicotine, that is, they increase the effect on the throat and increase the overall aroma and the "smoke ^{feeling" 11} in comparison with control cigarettes of the same kind which, however, contain no resin Nicotine in the smoke according to the procedure described earlier [Journal of the Association of Official Agricultural Chemists (Vol. 42, Nov. 2, 1959) pp. 424-429] shows that the cigarettes containing the resin in the filter are 0.98 mg per cigarette give compared to 0.83 0 * 8 for the control cigarettes.

Example 2

Lin cation exchange resin of the phosphonic acid type (Bio-Rex 63) in the H ⁺ form is treated as in Example 1 with nicotine. After drying, the resin contains 30% by weight of nicotine. Bs has no nicotine smell. The resin is introduced into the filter of filter cigarettes of the double filter type according to the procedure used in Example 1. The increased nicotine effect in the smoke compared with that of the control is subjectively observed. The analyzes show: resin cigarette; 0.96 mg per cigarette, control: 0.83 mg per cigarette nicotine in the smoke.

Example 3

The IR-112 resin, which contains 33% nicotine, (Example 1),

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is ground to a particle size such that it will pass through a 200 mesh screen (US sieve size) and then cut into Ethanol dispersed. The ethanol suspension of the resin is sprayed onto cellulose acetate filter tow. The cable will after spraying processed into filter sticks, which are cut into lengths of 15 mm and attached to 57 mm sections of Tobacco insert can be added to form cigarettes. The amount of hair introduced into the filter is 18 mg per cigarette. These cigarettes have one when smoked noticeable "nicotine effect" in comparison with control filter cigarettes, which are made in the same way but do not contain resin.

Example 4-

A strongly basic anion exchange resin of the quaternary ammonium type (Rohm and Haas IRA 400) is converted into the OH ~ form transferred and stirred with an aqueous solution of glycolic acid. After the acid has been absorbed, the resin becomes air-dried and ground to a particle size corresponding to 60-80 mesh (US sieve size). The resin will by displacing the adsorbed glycolic acid in solution with tetramethylammonium hydroxide and determining the displaced Glycolic acid analyzed by gas chromatography. This analysis shows that the Hara 0.183 g of glycolic acid de g of resin.

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The resin containing glycolic acid is used in cigarettes vcm Double filter type as in Example 1 introduced. Be ee 50 mg of resin applied per cigarette. These cigarettes will mechanically smoked, and all particulate matter, that is collected on FTC filters becomes on glycolic acid analyzed by a gas chromatographic procedure. The results are as follows: Cigarettes with glycolic acid resin in the filter: 375 jig glycolic acid Per cigarette.

Control cigarettes with no resin in the filter: less than that "detectable limit of 100 μg glycolic acid per cigarette.

Example 5

A weakly basic anion exchange resin of the tert-amine type (Rohm and Haas IRC 4-S) is converted into the OH-form and handled with an aqueous solution of acetic acid. After the acid has been absorbed by the hair, the resin is dried and ground to a particle size corresponding to 60-80 mesh (US sieve size). Anal the resin by the same procedure as was used in Example ¹ V, ieigt that this resin contains 16.4 wt .-% acetic acid.

This Hars is introduced into cigarettes of the double filter type according to the procedure used in üeiepiel 1 in an amount of 50 ng per cigarette. The pH of the Rauohe · la main stream of the cigarettes is 5.4, while

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the pH value of the control cigarettes, which do not contain any resin in the filter, is 5 | 9 in the main flow of the abdomen. The analysis of the acetic acid in the smoke of these cigarettes gives the following results:

Cigarettes that contain acetic acid resin in the filter: 720 jug of acetic acid per cigarette.
Control cigarettes without resin: 460 µg acetic acid per cigarette,

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Claims (16)

Claims 1. Filters for tobacco products, characterized by a Filtergruidiaat trial and an additional ion exchange resin, the resin being deα additive after contact with tobacco smoke can share. 2. Filters for cigarettes, characterized by a filter base material and an additive ion exchange resin, the resin releasing the additive nacti contact with tobacco smoke 3 ο Additional-releasing filter for cigarettes, characterized by a filter base material and an additional ion exchange resin. 4 ₀ nicotine releasing filter for ¹ tobacco products, ( gekemizeichnet through a filter base material and a nicotine ion exchange resin. 5 ο Nicotine-releasing filter for cigarettes, characterized by a filter base material and a nicotine ion exchange resin. - 31 909839 / 05U 'bad original 6. Flavoring agent-releasing filter for tobacco products, characterized by a filter base material and a flavoring ion exchange resin. 7. Flavoring agent-releasing filter for cigarettes, characterized by a filter base material and a flavoring ion exchange resin. 8. Nicotine-releasing filter for cigarettes, characterized by a filter base material and a nicotine cation exchange resin . 9. Filter for cigarettes that releases flavoring agents, characterized by a filter base material and an 8 acidic flavoring anion exchange resin. 10. Flavoring agent-releasing filter for cigarettes, characterized by a filter base material and a basic-flavoring agentX-ionic thawing oherhars 11. method for introducing an additive in tobacco smoke, characterized in that the smoke is passed through a filter containing an additive ion exchange resin. . 12.Methods of introducing nicotine into tobacco smoke, characterized in that the smoke is passed through a filter containing a nicotine ion exchange resin. - 32 909839/0544 13 · Method of incorporating a flavoring agent in tobacco smoke, characterized in that the smoke is passed through a filter containing a flavoring ion exchange resin contains. 14. A method for introducing nicotine into tobacco smoke, characterized in that the smoke is passed through a filter which is a nicotine cation exchange resin contains. Ä 15. Method for introducing a basic flavoring agent in tobacco smoke, characterized in that the smoke is passed through a filter containing a basic Contains flavoring cation exchange resin. 16. Method for introducing an anionic aromatic agent in tobacco smoke, characterized in that the smoke is passed through a filter that contains an acidic * Contains flavoring anion exchange resin. 909839/0544