JP4366267B2 - Cigarette filter with excellent selective removal of formaldehyde - Google Patents

Description

The present invention relates to a tobacco element that can reduce the inflow amount of a specific smoke component into the smoker's mouth and adjust the taste according to the smoker's preference, and a method for manufacturing the same.

In recent years, so-called light cigarettes tend to be preferred and health effects are taken into account, especially in developed countries, to reduce the amount of smoke components flowing into the mouth (delivery amount) during smoking. Various studies have been made. One important way to do this is to improve the filter.
The current filter for tobacco smoke uses a large amount of crimped fiber tow of cellulose diacetate. To increase the filtration efficiency, a tow having a small single fiber fineness is used, or the fiber filling amount is increased. However, in these methods, the ventilation resistance is increased, and thus there is a limit to the improvement of the filtration efficiency within the practical range of the ventilation resistance.
Further, when the filtration efficiency is increased by these methods, it is difficult to selectively remove only a specific component in the smoke component, that is, to greatly change the filtration ratio of the smoke component.

Until now, nicotine and tar have been considered the main harmful components in tobacco smoke, interest in nicotine and tar delivery has been imposed, and many countries have imposed nicotine and tar labeling obligations. However, nicotine itself is a favorite component of tobacco and is thought to be directly involved in smoking satisfaction. Further, regarding tar, it is not preferable to remove the tar component in the tobacco smoke component at a relatively high level because the flavor is impaired.
That is, if smoke components with low volatility including tar and nicotine are indiscriminately removed, the taste becomes light and satisfaction cannot be obtained. Therefore, it is required to selectively remove only a specific component in the smoke component while keeping the amount of tar and nicotine in the tobacco smoke component at a relatively high level.
One such group of substances is aldehydes. Aldehydes, especially formaldehyde, not only have an irritating odor, but also are unfavorable for health as they have recently attracted attention as one of the causative agents of allergies.

Conventionally, various filter constituents and additives to the filter constituents have been proposed as adsorbents for filtering harmful components in tobacco smoke.
JP-A-59-088078 (Patent Document 1), JP-A-59-151882 (Patent Document 2) and JP-A-60-054669 (Patent Document 3) are intended for adsorption of formaldehyde and the like. However, all of these are adsorbents for cigarette smoke filters in which polyethyleneimine or an aliphatic amine having a low vapor pressure is added to activated carbon.
Japanese Laid-Open Patent Publication No. 09-168736 (Patent Document 4) discloses fibrous activated carbon impregnated with polyethyleneimine or p-aminoacetanilide.
Japanese translations of PCT publication No. 2002-528105 (Patent Document 5) and Japanese Patent Publication No. 2002-528106 (Patent Document 6) disclose a filter formed by covalently bonding 3-aminopropylsilyl and related atomic groups.
Japanese Patent Publication No. 2003-505618 (Patent Document 7) proposes a filler containing an ammonium salt.
However, the amine substances used in the above filters are characterized by the ability to simultaneously remove tar and nicotine, and selectively remove only aldehydes while maintaining a relatively low removal rate of tar and nicotine. It was not a thing.
Moreover, these amines are synthetic high molecular amines and exhibit a characteristic amine odor due to residual low molecular weight components and decomposition. In addition, amine-based substances themselves or volatile substances contained in them are often toxic to the living body, and may cause unexpected problems when added to a tobacco smoke filter that is directly consumed by humans. . Even if it does not volatilize at all, it may cause liberation of the amine compound for some reason, for example, contact with a basic substance or hydrolysis.

JP-A-57-71388 (Patent Document 8) discloses that an amino acid is added to improve the flavor of tobacco. When such amino acids are used, they often become crystals and have low volatility, but this state is inert to adsorption and selectively removes only the expected aldehydes. Does not perform the function. It can be read from the obtained results that tars are reduced.
As described above, the addition of amine compounds is thought to be effective in removing acidic substances and aldehydes, but there are problems in terms of odor, safety and effectiveness when actually used as a tobacco filter or additive. There was nothing practical.
U.S. Pat. No. 2968306 discloses the use of certain amino acids such as glycine to remove aldehydes in tobacco smoke. Although glycine can reduce formaldehyde levels in tobacco smoke, it has been discovered that it is not stable in the cigarette filter manufacturing process. Furthermore, it is unsuitable for use in tobacco because it emits an ammonia odor during storage of the filter.

Japanese Unexamined Patent Publication No. H07-31452 (Patent Document 9) discloses a tobacco filter containing 5 to 100% by weight of chitin or chitosan for the purpose of adsorbing aldehydes. However, in these chitin and chitosan, nicotine and tar were also collected together with aldehydes, and it was not possible to selectively remove only aldehydes.

JP 59-088078 A JP 59-151882 A JP-A-60-054669 Japanese Patent Laid-Open No. 09-168736 Special Table 2002-528105 Japanese translation of PCT publication No. 2002-528106 Special table 2003-505618 gazette JP 57-71388 A JP H07-31452 A U.S. Pat. No. 2968306

The problem to be solved is that a filter for cigarette smoke that can selectively remove only aldehydes with a relatively low removal rate of tar and nicotine and that is highly safe even when ingested orally. There is no point. In addition, there is no method for incorporating a substance to be selectively removed into the cigarette smoke filter so that the ventilation resistance does not increase.

The present invention has found that a substance suitable for selective removal of aldehydes is a basic polypeptide, and a tobacco smoke filter characterized by containing a basic polypeptide has a relative removal rate of nicotine and tar. It has been found that it is suitable for selectively removing only formaldehyde while keeping it low. The basic polypeptide of the present invention is a substance that is not easily crystallized because it is a polymer, and also has high water solubility.

For this reason, after dissolving the basic polypeptide of the present invention in water, it is supported on the crimped fiber tow fiber of cellulose diacetate, which is usually used as a filter for tobacco smoke, by a method such as spraying, coating, or dipping. In this case, it is easy to form a thin film. As another embodiment, a large surface area can be provided by, for example, supporting on a porous carrier such as activated carbon added to the tobacco smoke filter by the same method.
Of these basic polypeptides, polylysine and white protein (protamine) are most preferred. These polylysine and protamine are extremely low in toxicity to the human body even when taken orally.

  The tobacco filter to which the basic polypeptide of the present invention is added is tasteless and odorless, and has the advantage of selectively removing aldehydes without adversely affecting the taste of tobacco.

  Further, in the tobacco filter to which the basic polypeptide of the present invention is added, there is an advantage that aldehydes are further selectively removed by making the isoelectric point of the basic polypeptide basic.

  Further, a tobacco smoke filter in which a basic polypeptide or polyamino acid or a compound containing them is supported or attached to the fiber surface has a remarkable effect of removing formaldehyde, but hardly removes nicotine and tar. There is an advantage that the ventilation resistance is hardly changed.

  Further, the basic polypeptide used in the present invention is dissolved in water so that it can be easily attached (carried) to the tobacco filter fiber by a method such as spreading, spraying, coating, or dipping. It is easy to introduce these attaching steps into the existing manufacturing apparatus, and there is an advantage that a uniform thin film can be formed, which is less likely to drop out than the method of adding powder.

(Basic polypeptide)
The basic polypeptide in the present invention can be used even if it is a synthesized polypeptide, but it is a high molecular weight polyamine produced by a living organism or obtained by adding some chemical treatment to a living organism. Can be suitably used. Specific examples include, but are not limited to, and so-called basic proteins and basic peptides fall under this category. And what dissolves in water is used as a basic polypeptide.
The basic polypeptide in the present invention is more preferably a protein, polypeptide, or the like that contains many primary amino groups (including guanidine and amino groups in amidine).

(Polylysine)
Polylysine is a basic polypeptide obtained by aerobic culture of Streptomyces Albulus, a kind of actinomycetes. Usually, it is a basic polypeptide produced by adsorption, separation, and production on an ion exchange resin.
In addition, although what is presently available as polylysine used for this invention is said substance, this is only an example of polylysine to the last. Whether the origin of the polylysine is biological or chemical (such as ring-opening polymerization of a mixed cyclic anhydride of amino acid and carbon dioxide, or polymerization of an amino acid derivative using a carbodiimide derivative or the like as a dehydrating agent) As long as it contains 30 mol% or more of lysine, it is functionally equivalent, and “polypeptide containing lysine as a main component” can be suitably used for the purpose of the present application.
When the polylysine is obtained synthetically, it is desirable that the lysine contained in the polylysine is a pure L-form from the viewpoint of safety when entering the digestive tract. However, this is not a necessary condition for the function.

(Protamine)
What is collectively called protamine contained in the sperm nucleus of a male animal is preferably used. Protamine is industrially extracted as “Shirako protein”, which is extracted from salmon milk.
Shirako protein (protamine), like polylysine, has an excess of amino groups and is effective in removing acidic substances and aldehydes. However, the resource is not limited to the white larvae, but protamines are extracted from the white larvae of various male animals and given unique names.
These protamines are characterized by an arginine content of 50 mol% or more.

(Other basic polypeptides)
Any basic polypeptide can be used in the present invention. Histone, which is said to form a complex with DNA in the eukaryotic nucleus of most animals, is also a representative of the basic protein of the present invention. Those having a high lysine content and those having a high arginine content are known.
In addition, lysozyme used as an anti-inflammatory agent is one of basic proteins.
The basic polypeptide that can be used for the purpose of the present invention preferably has a high content of basic amino acids, and more preferably 30 mol% or more of all constituent amino acids.

(Isoelectric point of basic polypeptide)
In the present invention, the isoelectric point of the basic polypeptide used is also important. That is, chitosan disclosed in JP-A-H07-031452 is common in that it has a large number of reactive amino groups in the molecule, although the basic structure is different from polysaccharides in terms of chemical structure. . However, when the basic polypeptide of the present invention is compared with chitosan, the selective removability differs greatly. That is, when chitosan is used, as described in JP-A-H07-031452, the removal rate of aldehydes is about the same as that of nicotine and tar, and the selective removability is poor. Probably due to nuclear nature.
Considering the difference between the effects of the addition of the basic polypeptide of the present invention and chitosan, it is preferable that it is basic and the acid dissociation constant is as large as possible, that is, it is preferably strongly basic. Therefore, it is a basic polypeptide. The isoelectric point is preferably 7 or more, preferably 8 or more, more preferably 10 or more, and most preferably 10 to 12.
In addition, the isoelectric point of the basic polypeptide in the present invention refers to the hydrogen ion exponent pH in a state where the algebraic sum of the effective charges of the entire particle is zero, and specifically, hydrogen at which the electrophoresis speed is zero. It can be measured as ion index pH.

(Method for producing tobacco filter containing basic polypeptide)
The method of bringing the basic polypeptide of the present invention into contact with tobacco smoke may be any method, but the method of adding or carrying it on a conventional tobacco filter is most preferred. As a method of adding to a conventional tobacco filter, a method of adding to a filter tow in a liquid state can be taken by utilizing the fact that the basic polypeptide of the present invention is water-soluble. Further, a method of pulverizing a basic polypeptide solid and adding it to a filter tow can also be used.

(Addition in solution)
The basic polypeptide of the present invention can be dissolved in water. For this reason, the aqueous solution can be applied by being applied, sprayed and impregnated onto cellulose acetate fiber, cellulose fiber, polypropylene fiber, a nonwoven fabric or a paper-like sheet containing these as a main component. Among these fibers, a filter for tobacco smoke is often used with a crimped fiber tow of cellulose diacetate, and the crimped fiber tow of cellulose diacetate is excellent in the taste of cigarettes. It is most suitable as a carrier for carrying a peptide.
Since the basic polypeptide of the present invention can be dissolved in water, it is sprayed in the form of a mist on the crimped fiber tow of cellulose diacetate, or the filter of the crimped fiber tow of cellulose diacetate is used in the present invention. It can be added by immersing in an aqueous solution of a basic polypeptide.
In this way, since the added material can form a homogeneous thin film, the specific surface area with respect to the added amount can be increased, and the selective removal performance can be improved as compared with the addition in granular form. .

In addition, a plastic component can be mixed with the basic polypeptide of the present invention. For example, glycerin, diglycerol, polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyacrylamide, organic acid, phosphoric acid and the like can be exemplified, and the content with respect to the basic polypeptide is 10% or more and 1000% or less. It is desirable. However, since these plastic components can affect the taste, they must be carefully selected. Preferred plastic components are glycerins such as glycerin, diglycerol, polyethylene glycol and polypropylene glycol.
In addition, a crimped fiber tow filter of cellulose diacetate is usually added with a binder (ie, a component that is commonly referred to as a plasticizer) to partially dissolve and bond the binder, in order to impart hardness. For example, as the most commonly used plasticizer addition method, triacetin is sprayed in the form of a mist. An addition method in which the basic polypeptide of the present invention is dissolved or dispersed and suspended as fine particles in this binder or plasticizer can also be employed.

(Addition as powder)
The basic polypeptide of the present invention can be contained alone or as a powder of a complex with an auxiliary agent. Further, the basic polypeptide of the present invention can be granulated and contained in an appropriate size. As a method of adding the basic polypeptide of the present invention as a powder, a more effective aspect is that it is added as a complex with other components, or added after being supported on a carrier, rather than being added alone. That is.
As the carrier here, a carrier which gives an appropriate dispersion state and an appropriate resistance against tobacco smoke and does not impair the function of the basic polypeptide can be used.
Specifically, a cellulose acetate fiber, a cellulose fiber, a polypropylene fiber, a non-woven fabric or a paper-like sheet containing these as a main component, and a method of supporting in a powder state can be considered.
In addition, it is possible to adopt a method of supporting the particles on activated carbon, diatomaceous earth, silica gel, alumina, titanium oxide, zirconia, zeolite, or the like. Furthermore, these granular materials and basic polypeptide fine particles can be mixed and diluted. Furthermore, it is also possible to use a method in which a basic polypeptide is supported on a part of the above fine particles and then mixed with unsupported fine particles and then added to cellulose acetate fiber or the like.
The support may be an inorganic component, and fine particles made of wood chips, synthetic or natural polymers can also be used. Further, an inert diluent powder can be mixed.
The inert diluent powder mixed with the carrier or basic polypeptide may be, for example, starch, dextran or cellulose powder, but is preferably at least apparently homogeneously mixed with the basic polypeptide. It is a substance.

In the following measurements, all five cigarettes were measured, and the average value was obtained.
Using the following methods, air resistance, nicotine, tar amount, and formaldehyde amount were measured using a commercial cigarette piece light box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.).

[Ventilation resistance]
The pressure loss (mmWG) when passing through the cigarette smoke filter sample at an air flow rate of 17.5 ml / second was measured using an automatic ventilation resistance measuring device (FTS 300, manufactured by Filtrona).

[Nicotine and tar content]
Using the sample-type tobacco obtained above with a piston-type constant-volume automatic smoker (RM20 / CS, manufactured by Borgwald), the flow rate is 17.5 ml / second, the smoking time is 2 seconds / time, and the smoking frequency is 1 time / minute. Smoking at. Nicotine and tar in the smoke that passed through the filter were collected by a glass fiber filter (Cambridge filter), and the amount of nicotine was measured using a gas chromatograph (G-3000 manufactured by Hitachi, Ltd.).
The amount of tar was measured by a gravimetric method.
The amount of nicotine and tar adhering to the target Cambridge filter is Tn, Tt, and the amount of nicotine and tar adhering to the Cambridge filter in the following comparative examples and examples is Cn, Ct. Calculated.
Nicotine removal rate (%) = 100 × Cn / Tn
Tar removal rate (%) = 100 × Ct / Tt

[Formaldehyde removal rate]
Using the sample-type tobacco obtained above with a piston-type constant-volume automatic smoker (RM20 / CS, manufactured by Borgwald), the flow rate is 17.5 ml / second, the smoking time is 2 seconds / time, and the smoking frequency is 1 time / minute. Smoking at. Formaldehyde in the smoke that has passed through the filter is collected with a DNPH (dinitrophenylhydrazine) solution, derivatized with DNPH, and then subjected to UV using a high-performance liquid chromatograph gas chromatograph (G-3000 manufactured by Hitachi, Ltd.). The absorbance was measured.
The removal rate of nicotine and tar was calculated according to the following formula using the amount of formaldehyde collected by the target product as Tf and the amount of formaldehyde collected in the following Comparative Examples and Examples as Cf.
Formaldehyde removal rate (%) = 100 × Cf / Tf

Comparative Example 1
In this comparative example, chitosan was used. As chitosan, Daichitosan M manufactured by Dainichi Seika Kogyo Co., Ltd. was pulverized using a pulverizer. The chitosan particles were sieved to collect particles that passed 28 mesh and not 60 mesh.
A portion of 14 mm from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow of a commercial tobacco piece light box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.) was cut with a razor. A glass tube having a length of 20 mm and an inner diameter of 8 mm was inserted into the filter portion of the cut long piece, that is, a tobacco leaf filling piece, for a length (11 mm) corresponding to the remaining filter length, and these were bound with a sealing tape.
The 9 mm space created by this glass tube was filled with 20 mg of the chitosan powder. Next, the glass tube was plugged using a previously cut short piece, that is, a 14 mm filter.
And the sealing tape was wound around the connection part of this glass tube and a filter, and it sealed. Accordingly, the filter length of the cellulose diacetate crimped fiber tow is 25 mm. The extended 9 mm portion between the filters was filled with chitosan particles. The filling amount of chitosan particles was 20 mg per cigarette.
The cigarette sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The obtained nicotine, tar and formaldehyde reduction rate was calculated by the above formula. The results are listed in Table 1.

Comparative Example 2
In this comparative example, activated carbon often used for a normal cigarette smoke filter was used. As activated carbon, crushed coal CW350SZ manufactured by Nimura Chemical Co., Ltd. was used. The crushed charcoal was sieved to collect particles that passed 30 mesh and not 50 mesh. In the same manner as in Comparative Example 1, activated carbon was filled between the filters. The filling amount of activated carbon was 20 mg per cigarette.
The cigarette sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The obtained nicotine, tar and formaldehyde reduction rate was calculated by the above formula. The results are listed in Table 1.

Example 1
A portion of 14 mm from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow of a commercial tobacco piece light box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.) was cut with a razor. The cut short piece, that is, a 14 mm filter part was immersed in the aqueous poly-L-lysine solution. This was dried with a vacuum dryer.
In the same way as in Comparative Example 1, a 14 mm filter part soaked in a filter piece of a commercial tobacco cut, that is, a tobacco leaf filling piece, is connected with a glass tube, and sealing is also applied to the connection part of the glass tube and the filter. Tape was wrapped and sealed. In this case, no space was created between the long and short pieces of the cut filter.
The amount of poly-L-lysine added was 30 mg per cigarette, calculated from before and after immersing the cut short piece, that is, the 14 mm filter part in the poly-L-lysine aqueous solution. The cigarette sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The obtained nicotine, tar and formaldehyde reduction rate was calculated by the above formula. The results are listed in Table 1.

  As is apparent from Table 1, the tobacco smoke filter to which the basic polypeptide of the present invention is added is excellent in the selective removal performance of formaldehyde and reduces formaldehyde by 15%, while tar and nicotine are almost reduced. I won't let you. Further, the ventilation resistance is not increased even for a cigarette smoke filter that is commonly used. On the other hand, when the powder of Comparative Example 1 or Comparative Example 2 is used, the ventilation resistance is increased. Moreover, since nicotine is removed more than the removal rate of formaldehyde, the satisfaction of smoking is impaired.

Claims (4)

A tobacco smoke filter in which a water-soluble basic polypeptide is supported on or attached to the surface of a fiber constituting the tobacco smoke filter. The tobacco smoke filter according to claim 1, wherein the basic polypeptide has an isoelectric point of 10 to 12. The tobacco smoke filter according to claim 2, wherein the basic polypeptide is polylysine obtained by aerobic culture of Streptomyces Albulus, a kind of actinomycetes. After the basic polypeptide is dissolved in water, the basic polypeptide is supported on or attached to the surface of the fiber constituting the tobacco smoke filter by spraying, spraying, coating, or dipping on the surface of the fiber constituting the tobacco smoke filter. The method for producing a tobacco smoke filter according to claim 1.