JP4739875B2 - Tobacco filter manufacturing method - Google Patents

Description

  The present invention relates to a treatment liquid for treating a carrier (for example, cellulose ester fiber), which is useful for imparting aldehydes (particularly formaldehyde) removal performance to the carrier.

  Various components have been proposed for imparting a function as an adsorbent for removing components in air and smoke to a carrier such as fiber. For example, in tobacco smoke, many adsorbents to which basic components such as amine components are added have been reported for the purpose of adsorbing acidic components and formaldehyde. Japanese Patent Application Laid-Open No. 59-88078 (Patent Document 1) discloses an adsorbent for a tobacco smoke filter in which activated carbon is impregnated with polyethyleneimine or an aliphatic amine having a low vapor pressure.

  However, many of the basic components as described above, especially synthetic high molecular amines, often exhibit a characteristic amine odor due to decomposition and the remaining low molecular weight components. In addition, the basic component itself or a volatile substance contained therein often volatilizes and exhibits toxicity to the human body. Examples of basic substances in which such problems are not recognized include chitosan derivatives such as chitin and chitosan. Chitosan derivatives are known not to cause crystallization or volatilization, are safe for the human body, and have antibacterial properties. For example, Japanese Patent Application Laid-Open No. 11-100713 (Patent Document 2) discloses chitosan-containing cellulose acetate fiber containing chitosan and having a sterilization rate of 26% or more. In this document, a method of adding or mixing a dispersion obtained by pulverizing and dispersing chitosan in a cellulose acetate solvent to a predetermined size or less (maximum particle size of 3 μm or less), adding or mixing chitosan directly, and a predetermined dispersion It is described that chitosan is dispersed and contained in a spinning dope by a method of adjusting the size of chitosan depending on conditions. However, in dry spinning, in which spinning is performed using a solution in which such a polymer substance is dissolved in an organic solvent, a granular solid clogs the spinneret or accumulates in the spinneret, which may cause the spun yarn to break. There is a problem that the spinning productivity is remarkably lowered.

  In addition, a tobacco filter obtained by adding such chitin and chitosan derivatives to a tobacco filter material has also been proposed. For example, JP-A-53-142600 (Patent Document 3) discloses a tobacco filter containing chitin or a chitin derivative at a ratio of 3 wt% or more with respect to the tobacco filter material. In this document, chitin is poly-N-acetyl D-glucosamine, and as a method of containing this chitin, powder obtained from chitin may be directly blended into a tobacco filter material, or isopropyl ether after dissolving chitin in a polar solvent. It is described that a fiber or a film obtained by extrusion into a coagulating liquid such as fiber or film may be blended. For example, in Example 1 of this document, after the cellulose acetate fiber bundle is sufficiently opened with air and 6% by weight of triacetin is sprayed uniformly, the fiber surface is adhered while the filament surface is sticky. It is described that chitin powder was blended at a ratio of 3 to 70% by weight with respect to the bundle. In this document, chitin and chitin derivatives possess an acetyl group in their structure, and therefore, when blended in an acetate filter, give a unique light flavor to tobacco by a synergistic effect with the acetyl group of acetate. Specifically, in the examples, the tar removal rate is 34 to 41% and the nicotine removal rate is 28 to 29%, which is equivalent to or higher than that of the conventional product. ing. However, although the method of this document is sufficiently opened with air, the fiber bundle naturally has an overlap or entanglement between the fibers. Therefore, when triacetin is sprayed on such a fiber bundle and then chitosan powder is blended, the chitosan powder is plasticized by triacetin and not only the filament surface having adhesiveness but also triacetin. Because it adheres to the unplasticized filament surface, the chitosan particles are likely to fall off the tobacco filter material.

On the other hand, JP-A-60-168373 (Patent Document 4) discloses chitin or a derivative thereof (chitosan obtained by deacetylating part or all of the acetylamino group of chitin, and its OH group or CH ₂ OH group is an ether. Cigarette filters made from fibers made of a compound comprising a compound formed of, for example, an esterified, esterified, hydroxyethylated or O-methylated compound are disclosed. This document describes that as a method for producing the fiber, a method in which chitin or a derivative thereof is dissolved in a solvent to form a dope, and the dope is subjected to wet spinning to form a fiber is preferably used. The cigarette filter of this document is easier to adsorb tar and nicotine during use than filters made of triacetylcellulose or rayon, and has an adsorption capacity 1.5 to 2 times that of conventional filters. ing. However, since the mechanical strength of chitosan or the like is not high, when chitosan or the like is used as a fiber, the fiber is broken or easily removed from the tobacco filter.

  JP-A-7-31452 (Patent Document 5) discloses a tobacco filter having 5 to 100% by weight of chitin or chitosan. This document describes that chitin or chitosan may be used alone or in combination with silica, alumina, aluminosilicate, zirconia, rayon, cellulose, protein, synthetic resin powder or fiber. ing. This document also describes chitin or chitosan solutions such as silica, alumina, aluminosilicate, zirconia, activated carbon, cellulose such as rayon, cotton, and wood pulp, proteins such as starch, gelatin, and casein, or cellulose acetate. In other words, it may be used after being impregnated into a base made of powder or fiber of synthetic resin such as polyethylene, polyester and nylon. The filter described in this document can effectively adsorb and collect harmful components such as nicotine tar and aldehydes in tobacco smoke. As a specific method of using the chitin or chitosan powder, in Example 3, 80 mg of powdered chitin / chitosan was filled in a paper tube, and both sides of the paper tube were covered with 10 mg of cotton nonwoven fabric, A filter chip was formed, and a commercially available highlight cigarette portion was connected to the filter chip to form a filter chip. A filter having a nicotine collection rate of 70%, a tar collection rate of 75%, and an acrolein collection rate of 96% was obtained. It is described. However, in the method of this document, it is necessary to dissolve chitosan which is difficult to dissolve, and the viscosity of the prepared solution is very high, and it is difficult to impregnate a powder or fiber carrier with an appropriate amount.

  And it is difficult to sufficiently remove aldehydes (particularly formaldehyde) by any of the methods described in any of the above documents. That is, in the methods described in these documents, chitosan and the like are easily removed (or detached), and it is difficult to stably remove aldehydes.

  Traditionally, in the tobacco sector, nicotine and tar are considered to be the main harmful ingredients in tobacco smoke, and interest in delivery of nicotine and tar has been imposed, and many countries have been obligated to label nicotine and tar. . 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. On the other hand, aldehydes, in particular formaldehyde, not only have an irritating odor, but are recently unfavorable for health as they are attracting attention as one of the causative agents of allergies, and are preferably removed as much as possible.

  Therefore, in the tobacco field, it is required to selectively remove only the aldehyde component (especially formaldehyde) in the smoke component while keeping the amount of tar and nicotine in the tobacco smoke component at a relatively high level. Yes.

  However, cigarette filters using chitin and chitosan derivatives as described above are relatively safe for the human body, but they remove not only aldehydes such as formaldehyde but also substances such as nicotine and tar. , Impair the taste (or savory taste).

  Specifically, when particles and fibers such as chitin and chitosan derivatives are used as they are in a cigarette filter, selective adsorptivity to formaldehyde is not obtained, and not only formaldehyde but also tar and nicotine are adsorbed similarly to activated carbon. Resulting in. As a result, tar and nicotine are reduced, the taste is unsatisfactory for the smoker, and the smoker inhales deeply before the smoker intends, and the frequency of inhaling smoke during smoking increases.

  Furthermore, chitosan and the like are hard and brittle themselves, and in a filter made of chitosan fibers, the chitosan fibers dropped from the filter may be sucked into the human body and damage the bronchial flagella. In addition, as described in Patent Document 5, even when chitosan particles are added to a cellulose acetate filter that is commonly used as a smoke filter for cigarettes, the particles fall off and bronchial flagella similar to the above can be obtained. There is a possibility of hurting.

For this reason, there has been a demand for a treatment liquid for simply attaching a polysaccharide having an amino group such as chitosan to a carrier such as a fiber. In particular, in the tobacco field and the like, there has been a demand for a treatment liquid for obtaining an adsorbent capable of selectively removing aldehydes such as formaldehyde without increasing the removal rate of nicotine and tar. These treatment liquids are required to fix polysaccharides having amino groups uniformly and firmly, and to exert adhesion strength such that the polysaccharides having amino groups are not easily detached from the carrier. It was.
JP 59-88078 A (Claims) Japanese Patent Laid-Open No. 11-100713 (claims, paragraph number [0012]) JP-A-53-142600 (claims, page 2, upper left column, line 1 to upper right column, line 2, example) JP-A-60-168373 (Claims, page 1, right column, line 16 to page 2, upper right column, line 15) JP-A-7-31452 (Claims, paragraph numbers [0004] [0006], Examples)

  Accordingly, an object of the present invention is to provide a treatment liquid capable of imparting a removal performance of aldehydes (particularly formaldehyde) at a high level to a carrier (for example, a carrier composed of cellulose ester or the like).

  Another object of the present invention is to provide a treatment liquid capable of selectively removing aldehydes (particularly formaldehyde).

  Still another object of the present invention is to provide a treatment solution capable of efficiently removing aldehydes (especially formaldehyde) while suppressing dropping (or elimination) of polysaccharides having amino groups (such as chitosan) from a carrier at a high level. Is to provide.

  Another object of the present invention is to treat the tobacco filter material (or tobacco filter carrier) to maintain a high level of taste (or flavor) components such as tar and nicotine, while maintaining aldehydes (particularly, It is an object of the present invention to provide a treatment liquid capable of efficiently and selectively removing (formaldehyde).

  Still another object of the present invention is to provide a treatment solution useful for obtaining a carrier that is odorless and safe even when taken orally and can selectively remove aldehydes (particularly formaldehyde).

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that a carrier (for example, a tow-structured carrier), a polysaccharide having a granular amino group (such as chitosan) and a plasticizer for the carrier (for example, This is because, when treated (attachment treatment) with a treatment liquid (usually a dispersion liquid) composed of triacetin, etc., the chemical adsorption performance that seems to be caused by the amino groups of the polysaccharide having amino groups is exhibited. Aldehydes (especially formaldehyde) can be selectively removed at a high level, and since the polysaccharide is adhered while plasticizing the carrier with a plasticizer, it is possible to suppress dropping of the polysaccharide from the carrier. That the polysaccharide particles having amino groups (chitosan, etc.) are dispersed in the plasticizer for Firmly it found that hardly fall off adhering to the carrier, to complete the present invention.

That is, the treatment liquid of the present invention is a treatment liquid for attaching (or containing) an amino group-containing polysaccharide to a carrier, and a plasticizer for the amino group-containing polysaccharide and the carrier (plasticizing the carrier). Plasticizer for). The polysaccharide having an amino group may be chitosan. In the treatment liquid, the polysaccharide having an amino group is usually dispersed in a powdery form. For example, the treatment liquid may be a dispersion liquid in which a plasticizer is a liquid plasticizer at room temperature and a polysaccharide having a granular amino group is dispersed in the plasticizer. In such a dispersion, the polysaccharide having an amino group may be dispersed in the plasticizer in the form of particles having an average particle size of about 0.5 to 50 μm. The plasticizer can be suitably selected according to the type of carrier. For example, the carrier may be composed of a cellulose ester, and the plasticizer may be a lower fatty acid ester of polyols. The ratio of the polysaccharide having an amino group may be, for example, about 10 to 150 parts by weight with respect to 100 parts by weight of the plasticizer. The representative treatment liquid is a treatment liquid for attaching a polysaccharide having an amino group to a carrier whose carrier is composed of cellulose acetate, and the polysaccharide having an amino group has an average particle diameter of 1 to 20 μm. Chitosan having an average deacetylation degree of 70% or more (for example, chitosan having an average particle diameter of 1 to 20 μm), and the plasticizer is composed of C _3-6 alkanetriol-di or tri C _1-4 acylate And a treatment liquid (dispersion) in which the ratio of the polysaccharide having an amino group is about 20 to 100 parts by weight with respect to 100 parts by weight of the plasticizer.

  The plasticizer may in particular consist of diacetin and triacetin.

The treatment liquid may further contain a moisturizing component in order to further improve the performance of removing aldehydes. Such a moisturizing component is, for example, a compound having a plurality of hydroxyl groups (for example, at least one selected from C _2-6 alkanediol, di to tetra C _2-4 alkylene glycol, and C _3-10 alkanetriol). ). The ratio of the moisturizing component may be about 3 to 50 parts by weight with respect to 100 parts by weight of the polysaccharide having an amino group.

  By treating the carrier with the treatment liquid of the present invention, the removal performance of aldehydes can be imparted to the carrier. Therefore, the treatment liquid of the present invention can be used as a treatment liquid for imparting aldehydes (particularly formaldehyde) removal performance to the carrier. In particular, since the treatment liquid of the present invention can selectively remove aldehydes while maintaining taste components such as nicotine and tar at a high level, it can be suitably used for treating a tobacco filter material.

In the present specification, “chitosan” means heating chitin [β-1,4-poly-N-acetyl-D-glucosamine, (C ₈ H ₁₃ NO ₅ ) _n ] with a concentrated alkaline solution, and the like. Is a compound having at least a polymer structure of β-1,4-poly-D-glucosamine.

  Since the treatment liquid of the present invention is a combination of a granular amino group-containing polysaccharide and a plasticizer, the carrier can be provided with a high level of aldehydes (particularly formaldehyde) removal performance. Further, the treatment liquid of the present invention can selectively remove aldehydes (particularly formaldehyde) derived from amino groups. Furthermore, since it contains a plasticizer for the carrier, the polysaccharide can be attached while plasticizing the carrier, and the polysaccharide (such as chitosan) having a granular amino group is removed (or detached) from the carrier. Aldehydes (especially formaldehyde) can be removed efficiently while suppressing the above-mentioned at a high level. In particular, since the treatment liquid of the present invention can selectively remove formaldehyde, processing a tobacco filter material (or a tobacco filter carrier) can increase the level of taste (or flavor) components such as tar and nicotine. Aldehydes (especially formaldehyde) can be selectively and efficiently removed. In addition, since the treatment liquid of the present invention can be composed of a polysaccharide having a granular amino group, it is odorless after drying, and even if taken orally by dropping or the like (and further taken into the trachea) It is useful to obtain a carrier that is safe and capable of selectively removing aldehydes (particularly formaldehyde).

  The treatment liquid of the present invention is composed of a polysaccharide having an amino group and a plasticizer for the carrier. And this processing liquid can be used as a processing liquid (or processing agent) for attaching or containing the polysaccharide which has an amino group to the said support | carrier. In general, when a polysaccharide having an amino group (such as chitosan) is contained in a plasticizer by dissolution or dispersion, the surface of the polysaccharide is covered with the plasticizer, and the activity of the polysaccharide is lost. It was thought. However, in the present invention, by combining a polysaccharide having an amino group and a plasticizer for a carrier, further using a specific plasticizer, or adding a moisturizing component in the plasticizer, the polysaccharide In addition, the selective removal of aldehydes (particularly formaldehyde) can be remarkably improved.

[Carrier]
The carrier is not particularly limited as long as it is a base material for attaching (or containing) a polysaccharide having an amino group, and is composed of, for example, a resin (synthetic resin, semi-synthetic resin, natural resin, etc.). Can do.

  Synthetic resins constituting the carrier include, for example, condensation polymerization resins (for example, polyester resins, polyurethane resins, polyamide resins, etc.), addition polymerization resins (for example, olefin resins (polyethylene, polypropylene, etc.), styrene) Resin (polystyrene, etc.), acrylic resin (polyacrylonitrile, etc.), vinyl alcohol resin, halogen-containing vinyl resin [eg, vinyl chloride resin (polyvinyl chloride, etc.), vinylidene chloride resin, etc.], etc. A thermoplastic resin can be illustrated.

  Examples of the semi-synthetic resin and natural resin include cellulose derivatives (eg, cellulose esters), regenerated cellulose (viscose rayon, copper ammonia rayon, nitrated human silk, etc.), natural resins such as cellulose, and derivatives thereof. It is done. These resins may be used alone or in combination of two or more to form a carrier.

  The carrier can be appropriately selected depending on the application. For example, if it is used for wallpaper, it may be a woven fabric such as a blend of cellulose ester fibers and other fibers or a blend of fibers.

  In particular, when the carrier is a tobacco filter material, the resin may be preferably composed of cellulose ester and / or cellulose (particularly cellulose ester and cellulose). Examples of the cellulose ester include organic acid esters such as cellulose acetate, cellulose propionate, cellulose butyrate, mixed fatty acid ester (cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, etc.); cellulose nitrate, cellulose sulfate Inorganic acid esters such as cellulose phosphate; mixed acid esters such as cellulose nitrate acetate; and cellulose ester derivatives such as polycaprolactone-grafted cellulose acetate. These cellulose esters may be used alone or in combination of two or more. Among these, preferable cellulose esters include organic acid esters (for example, esters with organic acids having about 2 to 4 carbon atoms) such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose. Acetate butyrate and the like are included, and cellulose acetate (particularly cellulose diacetate) is particularly preferable. When the carrier is composed of such a cellulose ester, acetins (such as triacetin and diacetin) can be used as a plasticizer.

  In addition, the viscosity average polymerization degree of a cellulose ester may be about 10-1000 (for example, 50-1000) normally, Preferably it is 50-900 (for example, 100-800), More preferably, about 200-800 may be sufficient. Moreover, the average substitution degree of cellulose ester (especially cellulose acetate) can be selected from the range of about 1-3 (for example, 1-2.9), for example, Preferably it is 1.5-2.7, More preferably, it is 1. It may be about 7 to 2.6.

  The shape (or structure) of the carrier may be a shape (one-dimensional or two-dimensional shape) such as a fibrous shape, a hair shape, or a granular shape (or granular shape), and these shapes are further processed (molded). Shapes [for example, woven fabric, nonwoven fabric, tow structure (or tow shape, for example, crimped fiber tow structure), paper shape (or paper shape or paper structure), sheet shape, granulated product shape ( Three-dimensional shape), etc.]. The carrier may have a shape that can be used as it is as a molded product (for example, a flat air filter). The tow structure (that is, the monofilament focusing structure) is made of filaments having an infinite length and can be formed by spinning (dry, melting, or wet spinning) a conventional fiber. The paper structure carrier can be obtained, for example, by cutting fibers and forming them into staple sheets as a staple by a dry and wet nonwoven fabric manufacturing method, or by making a slurry containing the staples. Moreover, a planar sheet | seat (planar sheet-like support | carrier) can be obtained using the well-known manufacturing method of a porous membrane, for example.

  In particular, when used as a carrier for a cigarette filter material, the carrier has a tow shape (or tow structure) formed of fibers [or is a tow structure filter (filter carrier) formed of fibers]. Is preferred.

  The cross-sectional shape of the fibers constituting the carrier is not particularly limited, and may be any of irregular shapes (for example, a Y shape, an X shape) and a hollow shape. In particular, in a toe-structured carrier, a polygonal irregular fiber cross section is preferable.

  Moreover, the average fiber diameter and the average fiber length of the fiber which comprises a support | carrier can be selected according to the kind and use of a fiber. For example, the average fiber length of the fibers constituting the carrier (for example, cellulose ester fibers) can be selected from the range of about 0.05 to 50 mm (for example, 0.1 mm to 5 mm) for tobacco filter applications. It may be about 5 to 30 mm (for example, 1 to 25 mm), preferably 2 to 20 mm, and more preferably about 3 to 15 mm (for example, 5 to 10 mm). In many cases, the average fiber length of the fibers constituting the tow structure carrier is selected from the range of about 50 μm to 5 cm, preferably about 100 μm to 3 cm. In particular, in the case of a filter-like carrier, it is a fiber having an average fiber length of a length (about 3 to 30 mm, for example, 10 mm, 14 mm, etc.) corresponding to the length of the filter or a part constituting the filter. Preferably there is.

  Moreover, the average fiber diameter of the fiber which comprises a support | carrier is a tobacco filter use, for example, 0.01-100 micrometers, Preferably it is 0.5-80 micrometers, More preferably, about 1-50 micrometers may be sufficient. In particular, the average fiber diameter of the fibers constituting the tow structure carrier may be, for example, about 0.01 to 100 μm, preferably about 0.1 to 50 μm.

  The fineness (average fineness) of the fibers (such as cellulose ester fibers) constituting the carrier can be selected from a range of, for example, 1 to 16 deniers, preferably about 1 to 10 deniers.

  The fibers constituting the carrier (for example, cellulose ester fibers) may be crimped fibers or non-crimped fibers, and particularly may be crimped fibers.

  The tow-structure carrier is, for example, 3,000 to 1,000,000 fibers (for example, 3,000 to 100,000 fibers), preferably about 5,000 to 100,000 fibers (particularly cellulose ester). It may be a tow (fiber bundle) formed by bundling (focusing) single fibers (filaments).

  In the granular carrier (or granular substance), the average particle diameter may be, for example, 0.1 to 2000 μm, preferably 10 to 1500 μm, and more preferably about 100 to 1000 μm.

[Treatment solution]
(Polysaccharides having amino groups)
The polysaccharide having an amino group is not particularly limited as long as it is a glucan derivative and has an amino group as a substituent, and a representative example thereof is chitosan.

  As described above, chitosan only needs to have at least the acetyl group of chitin deacetylated, and the average degree of deacetylation of chitosan is, for example, 20% or more (for example, about 30 to 100%), preferably 40 % Or more (for example, about 50 to 99%), more preferably 60% or more (for example, about 65 to 98%).

In particular, in order to improve selective removal of aldehyde, the average deacetylation degree of chitosan is, for example, 60% or more (for example, about 65 to 100%), preferably 70% or more (for example, about 75 to 99%). More preferably, it may be 80% or more (for example, about 85 to 98%). In the chitosan, the “degree of deacetylation” is represented by the following formula when the chitosan acetyl group is A1 mol and the chitosan deacetyl group (ie, amino group) is A2 mol. Such a degree of deacetylation can be analyzed by, for example, ¹ H-NMR, ¹³ C-NMR or the like.

A2 / (A1 + A2) × 100 (%)
Also, the basic dissociation constant pK _b of chitosan, for example, at 25 ° C., 5.5 or higher (e.g., about 6 to 12), preferably 6 or more (e.g., about 6.3 to 10), more preferably 6. It may be 5 or more (for example, about 6.8 to 9). In order to obtain a higher aldehyde (particularly formaldehyde) removal rate, usually 7 or more (for example, about 7.3 to 11), Preferably, it may be 7.5 or more (for example, about 7.8 to 10), more preferably 8 or more (for example, about 8.5 to 9.5).

The chitosan may be derivatized chitosan (chitosan derivative). Examples of such chitosan derivatives include chitosan salts (for example, carboxylates such as pyrrolidone carboxylate, lactate and alginate), hydroxylated chitosan [hydroxyalkyl groups such as hydroxypropyl chitosan (hydroxyethyl group, hydroxy And the like, and cationized chitosan and the like, which are protected (or substituted) by a propyl group or the like] and glycerylated chitosan. In the chitosan derivative, an OH group or a CH ₂ OH group constituting the skeleton of chitosan is a protective group (or substituent), for example, an alkyl group (C _1-4 alkyl group such as a methyl group), an ester group, etc. Also included is chitosan protected or substituted with (or an acyl group such as an acetyl group).

  The viscosity average polymerization degree of the polysaccharide having an amino group (particularly chitosan) can be selected from the range of about 10 to 5000 (for example, 50 to 4000), for example, 20 to 3000, preferably 300 to 2000, and more preferably. About 50-1000 (for example, 100-500) may be sufficient.

  The polysaccharide having an amino group may be usually suspended or dispersed in the treatment liquid. In particular, the treatment liquid is often a dispersion in which the polysaccharide having an amino group is dispersed in a plasticizer. In such a dispersion, the form of the polysaccharide having an amino group is not particularly limited, but may usually be in the form of powder (or powder). In processing liquids (dispersions), polysaccharides having amino groups in the form of particles (including particles, particles, pellets, etc.) are spherical, ellipsoidal, columnar (such as prismatic), amorphous, etc. There may be.

  The average particle size of the polysaccharide having a granular amino group can be selected from the range of 0.05 to 500 μm (for example, 0.08 to 300 μm), for example, 0.1 to 100 μm, preferably 0.5 to 50 μm. More preferably, it may be about 1 to 20 μm. Moreover, in the said process liquid, the polysaccharide which has a granular amino group may be a primary particle, or a secondary particle according to the kind of plasticizer. By adjusting the particle size of the polysaccharide in the treatment liquid, selective removal of aldehydes (particularly formaldehyde) can be enhanced.

(Plasticizer)
In this invention, the removal performance of aldehydes (especially formaldehyde) can be efficiently improved by combining the said polysaccharide and a plasticizer.

  Conventionally, when the surface of the polysaccharide is covered with some substance, the activity of the polysaccharide (chitosan, etc.) is lowered, and as a result, the removal performance of aldehydes (particularly formaldehyde) is thought to be lowered. . However, it has been found that the selective removal performance of aldehydes of the polysaccharide can be improved by combining the polysaccharide and a plasticizer for the carrier.

  That is, polysaccharides having amino groups (such as chitosan) are usually dense and hard substances, and the amino groups that are largely involved in the removal of aldehydes (particularly formaldehyde) form hydrogen bonds. Since the basic or nucleophilicity is weak, even if the carrier (cigarette filter material, etc.) is treated with the polysaccharide as it is, the adsorption performance of aldehydes (particularly formaldehyde) cannot be sufficiently exhibited. When the support is treated together with the material to be coated, the adsorption performance of aldehydes is further reduced.

  Therefore, in the present invention, the removal performance (and selective removal property) of the aldehydes of the polysaccharide is improved by combining a polysaccharide having an amino group and a plasticizer for the carrier to be treated. The reason why such selective removal of aldehydes is improved is not clear, but, for example, (a) by adhering a carrier and a polysaccharide with a plasticizer, the adhesion amount of the polysaccharide to the carrier can be increased. , (B) The action of the plasticizer (and the plasticizer remaining on the treated carrier) suppresses or relaxes the hydrogen bond of the amino group of the polysaccharide, and effectively acts to selectively remove the aldehyde. (C) The plasticizer can relax the influence of the three-dimensional structure of the polysaccharide attached to the carrier, thereby increasing the substantial surface area of the polysaccharide that acts on the selective removal of aldehydes. It is considered that (d) the effect of acting complementarily or synergistically is obtained, and the selective removal of the amino group-containing polysaccharide with respect to aldehydes is effectively exhibited. . Moreover, by combining the polysaccharide and a plasticizer, the polysaccharide can be attached with high adhesion without dropping off the polysaccharide.

  The plasticizer may be any component having the property (or ability) to adhere the polysaccharide to the carrier. For example, (i) a component having a function of sticking the carrier (for example, dissolving, softening and softening the carrier) A component having a function of swelling and sticking), or (ii) a component having a sticking function (or stickiness) and capable of effectively attaching the polysaccharide to a carrier, (iii) ) It may be a component having these characteristics. In general, the term “plasticizer” means the above component (i), but “plasticizer” in the present specification refers to any of the above components (i) to (iii). May also be used to mean

  The plasticizer may be a solid plasticizer (solid at room temperature or normal temperature) as long as it has the above characteristics and can hold the treatment liquid in a liquid state. The plasticizers may be used alone or in combination of two or more. The plasticizer may be a component that remains (or remains) on the surface of the polysaccharide having an amino group after the treatment, or may be a component that volatilizes (or evaporates) with time after the treatment. . Note that the plasticizer having adhesiveness often remains on the carrier without volatilization or drying after the carrier is treated.

The specific plasticizer can be appropriately selected according to the type of the carrier. For example, when the carrier is composed of cellulose ester (cellulose acetate or the like) or other cellulose ester derivatives, the plasticizer may be polyol or polyhydric alcohols {e.g., a diol [for example, alkane diols (ethylene glycol, propylene glycol, trimethylene glycol, C _2-6 alkanediol such as 1,4-butanediol), polyalkylene glycols (diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene such di- to tetra C _2-4 alkylene glycols such as glycol), etc.], a polyol having 3 or more hydroxyl groups (e.g., glycerin, trimethylolpropane, pentaerythritol And tri-hexaalkanols such as sorbitol, etc.), polyol oligomers (eg, dimers, ditrimethylolpropane, dipentaerythritol, triglycerins and other alkanetri-hexaol multimers (eg, 2 to 4 mers, Fatty acid esters, ester oligomers (such as caprolactone oligomers) and the like.

Representative polyol fatty acid esters include polyol lower fatty acid (eg, C _1-4 alkanecarboxylic acid such as acetic acid) ester [eg, alkanetriol mono- to triacylate (eg, monoacetin, diacetin, triacetin etc. C _{3− 6} alkanetriol-mono to tri-C _1-4 acylate, preferably glycerin mono- to tri-C _2-3 acylate) and the like, and lower oligomers of polyol oligomers [for example, alkanetriol dimers of mono- to tetra acylate (e.g., di-C _3-6 alkanetriol such as diglycerin tetraacetate - such as mono- to tetra C _1-4 acylate) such as dimers or lower fatty acid ester of trimer polyols, etc.] and the like That. These polyol fatty acid esters may be used alone or in combination of two or more.

Among these plasticizers, as a plasticizer combined with a carrier composed of a cellulose ester (particularly cellulose acetate), acetins (for example, glycerin diesters such as diacetin and triacetin) are excellent in terms of their ability to swell and dissolve in the carrier. Or a lower fatty acid ester of a polyol such as triacetate) is preferably used. In particular, among the lower fatty acid esters of polyols, polyol di- or tri-C _1-4 acylates (especially C _3-6 alkanes such as diacetin) are also excellent in the function of improving the adsorption performance of the aldehydes of polysaccharides containing amino groups. Triol-di or tri-C _1-4 acylate) can be most preferably used. Therefore, a plasticizer (particularly acetins) composed of at least polyol di or triacylate (particularly diacetin, triacetin, etc.) may be suitably used as the plasticizer combined with the carrier composed of the cellulose ester.

In particular, the plasticizer may comprise at least polyol diacylate (particularly diacetin C _3-6 alkanetriol-diC _1-4 acylate), for example, diacetin and triacetin.

Note that diacetin and monoacetin may be included depending on the triacetin used, and industrial triacetin usually contains diacetin and monoacetin as impurities. Polyol di C _1-4 acylate (particularly, diacetin) at least containing a plasticizer, polyol di C _1-4 acylate (particularly, diacetin) content of the plasticizer (particularly acetin acids) total 1 wt% or more ( For example, it may be about 2 to 100% by weight), preferably 3 to 80% by weight or more, and more preferably about 5 to 60% by weight (for example, 8 to 40% by weight). In addition, the adsorptivity of aldehydes can be efficiently improved by constituting the plasticizer with diacetin as a main component (for example, diacetin alone, a mixture of diacetin and triacetin containing diacetin as main components). Further, by combining diacetin and other acetins (particularly triacetin), the viscosity of the dispersion can be appropriately increased while enhancing the adsorption performance of aldehydes. Such lower fatty acid esters of polyols (especially diacetin, triacetin, and mixtures thereof) not only have excellent plasticizing ability of cellulose esters, but also have the ability to alleviate hydrogen bonding of amino groups of the polysaccharides. Therefore, selective removal of aldehydes (especially formaldehyde) can be enhanced, safety is high, and even when used for applications related to the human body such as a cigarette filter, it can be suitably used.

  The plasticizers may be used alone or in combination of two or more.

  The plasticizer may be usually in a liquid form (liquid form at room temperature). Further, the boiling point of the plasticizer varies depending on the form, but can be selected from a range of 100 ° C. or higher (for example, about 130 to 550 ° C.) as long as it is a component remaining in the carrier, for example, 150 to 500 ° C., preferably 200 In many cases, it is about -450 degreeC, More preferably, it is about 220-400 degreeC (for example, 250-380 degreeC). Moreover, as long as it is a component which does not remain on the carrier, a plasticizer having a relatively low boiling point (for example, a boiling point of less than 100 ° C.) can be used.

  In the treatment liquid, the content (dispersion amount) of the polysaccharide having an amino group is from about 0.1 to 300 parts by weight with respect to 100 parts by weight of the plasticizer, although it depends on the type of plasticizer. For example, 1 to 250 parts by weight (for example, 5 to 200 parts by weight), preferably 10 to 150 parts by weight (for example, 15 to 120 parts by weight), and more preferably 20 to 100 parts by weight (for example, 30 to 30 parts by weight). 80 parts by weight).

(Moisturizing ingredient)
The treatment liquid of the present invention may further contain a moisturizing component (or humectant). Such a moisturizing component remains or adheres to the carrier even after treatment (and drying), and acts as a moisturizing component (or moisturizing agent). Specifically, such a moisturizing component remains in the treated carrier and is excellent in the ability to relax the hydrogen bond of the amino group of the polysaccharide, which is useful for improving the selective removal of aldehydes. It is. Moreover, since such a moisturizing component remains in the carrier, the selective removal of aldehydes can be stably maintained over a long period of time.

The moisturizing component may be a liquid or solid component at room temperature (or room temperature) as long as the treatment liquid can be held in a liquid state. Examples of the moisturizing component include polyols {diols [eg, alkanediol (ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, C _2-10 alkane diols such as xylene glycol, preferably C _2-8 alkane diols, more preferably C _2-6 alkane diols, especially C _2-4 alkane diols), polyalkylene glycols (diethylene glycol, dipropylene glycol, triethylene glycol, di- to tetra C _2-4 alkylene glycols such as tripropylene glycol, polyethylene glycol, polypropylene glycol), etc.], triols [alkane triol (glycerin, trimethylolpropane Hexanetriol C _3-10 alkane triols such as triol, preferably C _3-6 alkane triol, more preferably C _3-4 alkane triol), etc.], tetrafunctional or higher polyols [tetraol (erythritol, Pentaerythritol, etc.) and multimers of tri- or higher functional polyols (eg, alkanetriol) (eg, diglycerin, ditrimethylolpropane, dipentaerythritol, triglycerin, polyglycerin, etc.)], alkylene oxides (ethylene oxide, C _2-4 alkylene oxide such as propylene oxide, especially ethylene oxide) adducts (or adducts)}, saccharides or derivatives thereof [eg monosaccharides (eg glucose), polysaccharides (eg cellobiose, trehalose, etc.) Disaccharide , Starch, etc.), sugar alcohol (eg, pentitol such as xylitol, hexitol such as sorbitol, mannitol, galactitol, etc.)], amino acid or protein (eg, collagen, gelatin, etc.), cellulose derivative (hydroxyethylcellulose, hydroxypropyl, etc.) Hydroxyalkyl celluloses such as cellulose, cellulose derivatives having hydroxyl groups such as alkyl-hydroxyalkyl celluloses such as ethyl hydroxyethyl cellulose, carboxyalkyl celluloses such as carboxymethyl cellulose, cellulose ethers such as alkyl celluloses such as ethyl cellulose), hydroxyl groups Synthetic polymer [for example, vinyl alcohol polymer (for example, polyvinyl alcohol Le etc.) and water-soluble synthetic polymers such as] the like. These moisturizing components may be used alone or in combination of two or more.

Preferred moisturizing components include compounds having a plurality of hydroxyl groups (for example, polyols, saccharides or derivatives thereof, synthetic polymers having hydroxyl groups, etc.) in that they are particularly excellent in the ability to relax hydrogen bonds of amino groups. Can be mentioned. Among these compounds having a plurality of hydroxyl groups, polyols that are liquid at room temperature (for example, C _2-6 alkanediol, di to tetra C _2-4 alkylene glycol, C _3-10 alkanetriol, etc.) are preferable.

  The boiling point of the liquid moisturizing component is, for example, 150 ° C. or higher (for example, about 180 to 500 ° C.), preferably 200 ° C. or higher (for example, about 210 to 400 ° C.), more preferably 220 ° C. or higher (for example, 230 to 350 ° C.), particularly 250 ° C. or higher (for example, about 260 to 320 ° C.).

  In the treatment liquid containing the moisturizing component, the content (dispersion amount) of the moisturizing component can be selected from a range of about 0.5 to 150 parts by weight with respect to 100 parts by weight of the polysaccharide having an amino group. It may be about -100 parts by weight (for example, 2 to 80 parts by weight), preferably 3 to 50 parts by weight, and more preferably about 5 to 40 parts by weight (for example, 10 to 35 parts by weight).

  Further, the content (dispersion amount) of the moisturizing component is, for example, 0.5 to 80 parts by weight, preferably 1 to 50 parts by weight (for example, 2 to 40 parts by weight) with respect to 100 parts by weight of the plasticizer, More preferably, it may be about 3 to 30 parts by weight (for example, 5 to 25 parts by weight).

  In addition, the said process liquid may contain the usual solvent as needed. As the solvent, for example, water and alcohols (for example, alkanols such as methanol and ethanol) can be suitably used, and ethers (chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, etc.) , Esters (acetates such as methyl acetate and ethyl acetate), ketones (acetone, ethyl methyl ketone, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, butoxycarb Tall acetate), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (carbitol, etc.), hydrocarbons (hexane, heptane, etc. aliphatic Alicyclic hydrocarbons, toluene, and aromatic hydrocarbons such as xylene), and also like.

  The solvent may be a conventional solvent (organic solvent) that can swell (and dissolve) the carrier. When a solvent capable of swelling the carrier is used, the adhesion force of the polysaccharide to the carrier can be increased more efficiently. For example, when the carrier is a carrier composed of a synthetic resin (the synthetic resin exemplified above, such as an olefin resin), the solvent is an aliphatic or alicyclic hydrocarbon such as hexane or heptane. Hydrocarbons, aromatic hydrocarbons such as toluene and xylene), ethers (chain ethers such as diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran), esters (such as methyl acetate and ethyl acetate) Acetic acid esters), ketones (for example, dialkyl ketones such as acetone and ethyl methyl ketone), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, butoxycarbitol acetate, etc.), SE Cellosolve such (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), may be constituted by an organic solvent such as carbitol (such as carbitol). Such an organic solvent can be appropriately selected according to the type of the synthetic resin. For example, in a carrier composed of an olefin resin, an olefin resin such as hydrocarbons (for example, aromatic hydrocarbons such as toluene) is used. An organic solvent capable of swelling (and dissolving) can be used.

  When using a solvent (for example, a solvent capable of swelling the carrier), the ratio of the plasticizer to the solvent is the former / the latter (weight ratio) = 95/5 to 5/95, preferably 90/10 to 10/90. More preferably, it may be about 80/20 to 20/80.

  The solvents may be used alone or in combination of two or more.

  The treatment liquid may contain the constituent components of the carrier (the synthetic resin, semi-synthetic resin, natural resin, etc.). Since the component of the carrier (for example, cellulose ester) often dissolves (and swells) the plasticizer, when used as a component of the treatment liquid, it can impart an appropriate viscosity to the treatment liquid and adhere to the carrier ( (Or adhesion force) can be increased. For example, the carrier may be composed of a cellulose ester, and the treatment liquid may be composed of the polysaccharide, a cellulose ester plasticizer (for example, the acetins), and a cellulose ester.

  The proportion of the constituent components of the carrier may be, for example, 5 to 300 parts by weight, preferably 10 to 200 parts by weight, and more preferably about 20 to 100 parts by weight with respect to 100 parts by weight of the plasticizer.

  Further, the treatment liquid may contain a conventional additive as required.

(Process liquid manufacturing method)
The treatment liquid of the present invention can be produced (or prepared) by mixing the constituents of the treatment liquid [for example, the polysaccharide and the plasticizer (and a moisturizing component if necessary)].

  As described above, the treatment liquid of the present invention may be in the form of a dispersion in which the polysaccharide (particularly a polysaccharide having a granular amino group) is dispersed in a plasticizer (liquid plasticizer). Many. Such a treatment liquid (dispersion) can be prepared by performing a dispersion treatment (and a pulverization treatment or a pulverization treatment) on the polysaccharide in the presence of a dispersion medium. For example, the dispersion includes (i) a method in which the polysaccharide is dispersed in the plasticizer in a granular form, and (ii) a liquid in which the polysaccharide is dispersed or suspended (or dissolved) in the solvent or the like (usually , A dispersion or suspension) and the plasticizer (and a moisturizing component as required) may be prepared.

  The dispersion medium may be composed of a plasticizer. For example, the dispersion medium may be composed of a plasticizer (liquid plasticizer) alone, may be composed of a plasticizer and a moisturizing component, or a plasticizer and a solvent ( You may comprise with the solvent of the said illustration etc.).

  The polysaccharide may be in a granular form in the final dispersion, and may be in a granular form at an appropriate stage of preparation of the dispersion. For example, the dispersion may be (i) a dispersion process in a granular form having a desired particle size in advance, (ii) a dispersion process that can be dispersed and pulverized (or crushed) (for example, a wet pulverization process). To disperse and pulverize a mixture containing the polysaccharide coarse particles (or preliminarily pulverized particles) and the dispersion medium, for example, by a dispersion treatment while pulverizing to a desired particle size And the like.] (Iii) Dispersion treatment with pulverization, etc.], (iii) Dispersion treatment followed by pulverization treatment, (iv) Combination of these, etc.

  In particular, in order to efficiently suppress or alleviate the influence of hydrogen bonding due to the amino group of the polysaccharide, a method for preparing a treatment liquid by mixing the constituent components includes a dispersion medium [for example, a plasticizer and / or an organic solvent ( In particular, it preferably includes at least a step of wet crushing the polysaccharide in the presence of a hydrophilic organic solvent such as the alcohol.

  In addition, the said polysaccharide and / or a plasticizer may be mixed (and disperse | distributing) at once, and may be mixed in multiple times. Further, when the moisturizing component is used, the moisturizing component may be mixed at an appropriate stage in the preparation process of the dispersion, for example, may be previously contained in the dispersion medium or may be mixed in the dispersion treatment.

  A commercially available product may be used as the polysaccharide used for the dispersion treatment, or a prepared product may be used. In addition, the polysaccharide used for the dispersion treatment may be in the form of a dispersion containing a solvent. In addition, when preparing the polysaccharide used for a dispersion | distribution process, the method etc. which are described in Unexamined-Japanese-Patent No. 9-143205 can also be referred, for example. Usually, the polysaccharide is often subjected to a dispersion treatment in the form of at least particles [for example, preliminarily pulverized particles (preliminarily pulverized particles, coarse particles), powder]. Therefore, although the average particle diameter of the polysaccharide used for the dispersion treatment depends on the desired particle diameter in the treatment liquid, it is, for example, 800 μm or less (for example, about 1 to 600 μm), preferably 500 μm or less (for example, about 10 to 400 μm). ), More preferably 300 μm or less (for example, about 20 to 200 μm).

  A conventional disperser or dispersion medium may be used for the dispersion (and pulverization) treatment. Also, the dispersion treatment conditions (temperature, pressure, time, etc.) can be adjusted as appropriate according to the type and particle size of the polysaccharide.

[Usage and use of treatment liquid]
The treatment liquid of the present invention can be used as a treatment liquid for attaching or containing the polysaccharide to a carrier by treating (attaching treatment) the carrier. The method for treating the carrier is not particularly limited as long as the carrier and the treatment liquid can be brought into contact with each other. According to the form or shape of the carrier, for example, a method of applying the treatment liquid to the carrier, the treatment liquid is applied to the carrier. Examples thereof include a method of spraying (spraying, spreading, spraying) and a method of immersing (or impregnating, dipping) the treatment liquid in a carrier. The treatment of the carrier may be performed by a conventional coating method alone or in combination of two or more.

  The treatment liquid (particularly dispersion liquid) of the present invention can be suitably used as a treatment liquid for imparting aldehydes (particularly formaldehyde) removal performance to a carrier, and can be used for various applications depending on the type of carrier. . For example, since the treatment liquid of the present invention is excellent in the performance of removing aldehydes (particularly formaldehyde), it is suitably used for filter applications (or applications having a filter function) such as filters, cigarette filters, and masks of air cleaners. be able to. In addition, in order to remove aldehydes contained in building materials (for example, plywood for building), sheet-like materials (for example, wallpaper, closet sheets) for contacting or laying near building materials , Closet laying paper, etc.).

  Among these uses, in particular, the treatment liquid of the present invention attaches the polysaccharide (such as chitosan) firmly to a filter (or filter carrier) with a plasticizer, and has high taste components such as nicotine and tar. Since formaldehyde can be selectively removed while being held, it is useful for treating a tobacco filter material as a carrier.

  Below, the processing method of the raw material for tobacco filter (or tobacco filter) is explained in full detail.

  The shape of the tobacco filter material to be processed may be a filter shape. In addition, the carrier before processing with the treatment liquid may have these shapes in advance, and the treated carrier (for example, a fibrous carrier, a particulate carrier, etc.) can be used by a conventional method (for example, paper making) ) May be molded or shaped. In particular, the tobacco filter material is preferably in the form of a fiber bundle [for example, tow shape (or tow structure, especially fiber tow shape, etc.)].

  A specific treatment method can be appropriately selected according to the shape (fiber bundle shape, filter shape, etc.) and type of the carrier. For example, (i) a method of immersing (or impregnating, dipping) the carrier in the dispersion. And (ii) a method of spraying or spreading (or spreading) the dispersion on a carrier, and (iii) a method of applying the dispersion on a carrier. These processing methods may be used alone or in combination of two or more.

  Such a treatment method may be introduced into an existing production apparatus for cigarette filters, particularly a production apparatus for a cigarette filter having a tow structure using cellulose acetate filaments. For example, the treatment liquid (dispersion) is added to the filter tow. In the spinning step, the polysaccharide may be attached to the carrier by contacting with the method. As the contact method (attachment method), spraying, coating, and the like are preferable, but when the polysaccharide is a dispersion containing a plasticizer at a sufficiently low concentration, it may be brought into contact with the carrier by dipping. Furthermore, the polysaccharide (and plasticizer) is adhered to the carrier by spraying, coating, or the like in the process of unwinding the tow band from a filter tow band packing material (bale) and forming it into a filter rod (winding process). May be. Further, the polysaccharide (and the plasticizer) may be adhered to the carrier by a method such as dipping in the produced tow bundling body (plug).

  Of these methods, the method (ii) in which the treatment liquid (dispersion) is sprayed or dispersed on a carrier is preferable. In such a method, in particular, when the carrier is a fibrous substance (for example, a tow-structure carrier), a polysaccharide (and a plasticizer) having an amino group with respect to the carrier is conveniently and efficiently contained (or Can be attached).

  The treatment with the dispersion may be performed on a part or the whole of the carrier. In particular, in the case of a tow structure carrier, the plasticizer (triacetin) in the filter plug molding process (winding step) of the tow structure filter. The processing liquid (dispersion) can be placed or installed as part of a plasticizer addition device for filter tow, such as, and attached to the filter tow.

  The tobacco filter material thus obtained is useful for constructing a tobacco filter. Depending on the form of the tobacco filter material, the tobacco filter may be composed of the tobacco filter material singly or in combination of two or more types, and the tobacco filter material and other tobacco filter materials [eg, processing The powdered tobacco filter material and the fibrous material (such as untreated fibrous material)] may be used. For example, the material for the tobacco filter constitutes at least one divided portion of the tobacco filter having a structure divided into a plurality of parts (two divisions, three divisions, etc.) (for example, one part of the two-divided filter, three divisions) And other divided parts (for example, the other part of the two-divided filter, the middle part of the three-divided filter, etc.) and other tobacco filter materials (for example, activated carbon or other particulate matter) Or a filter material filled with s.

  The tobacco filter can be formed by a conventional method depending on the structure of the carrier or the filter. For example, a filter having a tow structure uses a plug hoisting machine in which the tobacco filter material or carrier is treated with the treatment liquid, the plasticizer and the polysaccharide are attached, converged to a predetermined diameter, and fixed with a wrapping paper. You may shape | mold by the method of setting it as a filter plug. In addition, the non-towed filter can be obtained by a conventional method, for example, (a) a method of filling a filter rod molding die as it is with a filter material such as a fiber or powder into a filter plug, and (b) You may manufacture by the method of filling the said filter raw material in the space of the shape | molded filter plug.

  Since the treatment liquid of the present invention is excellent in removal performance (adsorption performance) of aldehydes (particularly formaldehyde), for example, filters (filters for air cleaners, masks, tobacco filters), building materials (wall materials, etc.) It is useful as a treatment liquid (coating agent) for treating a carrier such as In particular, when smoking, while maintaining the taste components such as nicotine and tar, moderate ventilation resistance can be maintained, taste (flavor), and formaldehyde that is harmful to the human body without impairing smoking satisfaction The aldehydes can be selectively removed, which is useful for treating tobacco filter materials.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, each characteristic (ventilation resistance, nicotine amount, tar amount, formaldehyde amount) is a commercial tobacco [Peace Light Box (registered trademark No. 21222839) (manufactured by Japan Tobacco Inc.). )] Was measured by the following method.

[Ventilation resistance]
The ventilation resistance of the above-mentioned tobacco [Peace Light Box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.)] was directly measured using a filter sample for tobacco smoke including a tobacco leaf portion. In this sample, the length of the filter portion was 25 mm and the circumference was about 25 mm. The airflow resistance was measured by using an automatic airflow resistance measuring instrument (Filtona Corp., FTS300) for the pressure loss (mmWG) when air was passed through the cigarette smoke filter sample at a flow rate of 17.5 ml / sec. .

[Amount of nicotine, amount of tar]
Using a cigarette smoke filter sample, with a piston-type constant-volume automatic smoker (RM20 / CS manufactured by Borgwald) at a flow rate of 17.5 ml / second, with a smoking time of 2 seconds / time and a smoking frequency of 1 time / minute. Smoking was done. 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 control Cambridge filter is Tn and Tt, and the amount of nicotine and tar adhering to the Cambridge filter in Comparative Examples and Examples is Cn and Ct. did.

Nicotine removal rate (%) = 100 × (1−Cn / Tn)
Tar removal rate (%) = 100 × (1−Ct / Tt).

[Formaldehyde removal rate]
Using a cigarette smoke filter sample, with a piston-type constant-volume automatic smoker (RM20 / CS manufactured by Borgwald) at a flow rate of 17.5 ml / second, with a smoking time of 2 seconds / time and a smoking frequency of 1 time / minute. Smoking was done. 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 (ultraviolet) using a gas chromatograph (G-3000 manufactured by Hitachi, Ltd.). The absorbance was measured.

  The formaldehyde removal rate was calculated according to the following equation using the amount of formaldehyde collected in the control product as Tf and the amount of formaldehyde collected in the following Comparative Examples and Examples as Cf.

  Formaldehyde removal rate (%) = 100 × (1−Cf / Tf).

(Comparative Example 1)
In Comparative Example 1, chitosan particles were used. Chitosan particles were prepared by pulverizing “Daichitosan M” manufactured by Dainichi Seikagaku Corporation 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 cellulose diacetate crimped fiber tow of commercially available tobacco [Peace 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 cut long piece, that is, a tobacco leaf-filled piece by a length (11 mm) corresponding to the remaining filter length, and these were bound with a sealing tape.

  The 9 mm space produced by this glass tube was filled with 20 mg of the chitosan powder. Next, the glass tube was plugged using a short piece cut first, that is, a 14 mm filter part (110 mg). 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 smoke filter sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. And the obtained nicotine, tar, and formaldehyde removal rate (reduction rate) were computed by the said formula. The results are shown in Table 1.

  In addition, as a control product for evaluating the removal rate of nicotine, tar and formaldehyde, a product produced in the same manner as described above was used except that chitosan particles were not filled.

(Comparative Example 2)
In Comparative Example 2, activated carbon that is often used for cigarette smoke filters is usually 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. And the obtained nicotine, tar, and formaldehyde removal rate were computed by the said formula. The results are shown in Table 1.

  In addition, as a reference product for evaluating the removal rate of nicotine, tar and formaldehyde, a product produced in the same manner as the above method was used except that the activated carbon was not filled.

(Example 1)
Chitosan having an average degree of deacetylation of 90% is wet-pulverized in triacetin (triacetin containing 0.10% by weight of diacetin and 0.02% by weight of monoacetin as impurities) using a disperser, and 40% by weight of chitosan is obtained. % Triacetin dispersion was obtained. Then, the obtained dispersion was attached to a cellulose diacetate crimped fiber tow (filament denier 2.2, total denier 40,000, manufactured by Daicel Chemical Industries, Ltd.) and focused. A tobacco filter rod having a thickness of 100 mm and an outer diameter of 8 mm was produced, and this was cut into four equal parts in the length direction to obtain a filter chip having a length of 25 mm. Chitosan adhering to the filter chip having a length of 25 mm was 16 mg and triacetin was 23.8 mg. The specific surface area of chitosan adhering to the carrier was 6.8 m ² per 1 g of chitosan.

  The filter body (25 mm) portion of the cellulose diacetate crimped fiber tow of commercially available tobacco [Peace Light Box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.)] was cut with a razor. Only 11 mm of a glass tube having an inner diameter of 8 mm and a length of 20 mm was inserted into the cut long piece, that is, a tobacco leaf filling piece part, and these were bound with a sealing tape. Using the filter chip prepared using a chitosan triacetin dispersion as a plasticizer, a 9 mm space created by the glass tube was plugged. 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 cigarette smoke filter sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The sample obtained had a nicotine removal rate of 7%, a tar removal rate of 3%, a formaldehyde removal rate of 38%, and a ventilation resistance of 164 mmWG.

  In addition, as a control product for evaluating the removal rate of nicotine, tar and formaldehyde, a product prepared in the same manner as described above was used except that triacetin was used as a plasticizer.

(Example 2)
10 parts by weight of glycerin was added to 100 parts by weight of the triacetin dispersion of chitosan obtained in Example 1 to obtain a dispersion. Then, the obtained dispersion was attached to a cellulose diacetate crimped fiber tow (filament denier 2.2, total denier 40,000, manufactured by Daicel Chemical Industries, Ltd.) and focused. A tobacco filter rod having a thickness of 100 mm and an outer diameter of 8 mm was produced, and this was cut into four equal parts in the length direction to obtain a filter chip having a length of 25 mm. The chitosan adhering to the filter chip having a length of 25 mm was 15 mg, triacetin was 22.5 mg, and glycerin was 2 mg. The specific surface area of chitosan adhering to the carrier was 3.4 m ² per 1 g of chitosan. .

  The filter body (25 mm) portion of the cellulose diacetate crimped fiber tow of commercially available tobacco [Peace Light Box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.)] was cut with a razor. Only 11 mm of a glass tube having an inner diameter of 8 mm and a length of 20 mm was inserted into the cut long piece, that is, a tobacco leaf filling piece part, and these were bound with a sealing tape. Using the filter chip prepared using a chitosan triacetin dispersion as a plasticizer, a 9 mm space created by the glass tube was plugged. 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 cigarette smoke filter sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The sample obtained had a nicotine removal rate of 10%, a tar removal rate of 9%, a formaldehyde removal rate of 52%, and a ventilation resistance of 168 mmWG.

  In addition, as a control product for evaluating the removal rate of nicotine, tar, and formaldehyde, those prepared in the same manner as described above were used except that triacetin and glycerin were used as plasticizers.

(Example 3)
To 100 parts by weight of the chitosan triacetin dispersion obtained in Example 1, 10 parts by weight of diacetin (diacetin containing less than 0.01% by weight of monoacetin and triacetin as impurities) was added to obtain a dispersion. Then, the obtained dispersion was attached to a cellulose diacetate crimped fiber tow (filament denier 2.2, total denier 40,000, manufactured by Daicel Chemical Industries, Ltd.) and focused. A tobacco filter rod having a thickness of 100 mm and an outer diameter of 8 mm was produced, and this was cut into four equal parts in the length direction to obtain a filter chip having a length of 25 mm. Chitosan adhering to this 25 mm long filter chip is 15.5 mg, triacetin is 23.3 mg, and diacetin is 2.1 mg. The specific surface area of chitosan adhering to the carrier is 3.2 m per 1 g of chitosan. ² .

  The filter body (25 mm) portion of the cellulose diacetate crimped fiber tow of commercially available tobacco [Peace Light Box (registered trademark No. 2122839) (manufactured by Japan Tobacco Inc.)] was cut with a razor. Only 11 mm of a glass tube having an inner diameter of 8 mm and a length of 20 mm was inserted into the cut long piece, that is, a tobacco leaf filling piece part, and these were bound with a sealing tape. Using the filter chip prepared using a chitosan triacetin dispersion as a plasticizer, a 9 mm space created by the glass tube was plugged. 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 cigarette smoke filter sample was measured for the ventilation resistance, nicotine, tar amount, and formaldehyde amount. The sample obtained had a nicotine removal rate of 5%, a tar removal rate of 2%, a formaldehyde removal rate of 68%, and a ventilation resistance of 172 mmWG.

  In addition, as a reference product for evaluating the removal rate of nicotine, tar and formaldehyde, those prepared in the same manner as described above were used except that triacetin and diacetin were used as plasticizers.

  The results are shown in Table 1.

Claims (7)

A method for producing a tobacco filter by treating a tobacco filter material as a carrier with a treatment liquid and attaching chitosan in the treatment liquid, wherein the chitosan having an average particle size of 0.05 to 500 μm is The method comprises a step of treating a cigarette filter material with a treatment liquid dispersed in a plasticizer for the carrier, and attaching chitosan to the carrier in a particulate form , wherein the plasticizer is C _3-6 alkanetriol-mono to A method for producing a cigarette filter , comprising Tri C _1-4 acylate .   The production method according to claim 1, wherein the plasticizer is a liquid plasticizer at normal temperature, and a chitosan having an average particle size of 0.5 to 50 µm is dispersed in the plasticizer. The carrier is a carrier composed of cellulose acetate, chitosan is chitosan having an average deacetylation degree of 70% or more, and the plasticizer is composed of at least C _3-6 alkanetriol-di or tri-C _1-4 acylate. The method according to claim 1 or 2, wherein the ratio of chitosan is 20 to 100 parts by weight with respect to 100 parts by weight of the plasticizer.   The production method according to any one of claims 1 to 3, wherein the plasticizer is composed of diacetin and triacetin. Furthermore, as the _{humectant, C 2-6} alkane diols, a manufacturing method of claim 1 further comprising at least one member selected from di- to tetra _{C 2-4} alkylene glycols and _{C 3-10} alkane triol.   The production method according to any one of claims 1 to 5, wherein the carrier is a tow structure carrier of cellulose acetate fibers, and a treatment liquid in a form in which chitosan having an average particle diameter of 1 to 20 µm is dispersed in a plasticizer is used.   A tobacco filter obtained by the method according to claim 1.