JPWO2006082748A1 - Tobacco filter material and tobacco filter - Google Patents

Abstract

Provided is a tobacco filter material useful for selectively and efficiently removing formaldehyde while retaining taste components such as nicotine and tar. A carrier such as cellulose acetate fiber is subjected to an adhesion treatment with a dispersion liquid composed of a granular amino group-containing polysaccharide (such as chitosan) and a dispersion medium to obtain a tobacco filter material. The dispersion medium may be a polar solvent (water, alcohols, etc.), a plasticizer for the carrier, or the like. A cigarette filter made of such a cigarette filter material can efficiently and selectively remove formaldehyde. For example, while maintaining nicotine and tar at a retention rate of 75% or more, the retention rate of formaldehyde is 65% or less. Can do.

Description

  The present invention provides a cigarette filter material useful for selectively removing aldehydes (particularly formaldehyde) efficiently while retaining taste components such as nicotine and tar, a method for producing the same, and a cigarette filter material. It is related with the tobacco filter comprised and the tobacco provided with this tobacco filter.

  Various components have been proposed as adsorbents for filtering components in tobacco smoke. As such a component, many have been reported in which a basic component such as an amine component is added for the purpose of adsorption of an acidic component, adsorption of formaldehyde, and the like. For example, JP-A-59-88078 (Patent Document 1), JP-A-59-1519882 (Patent Document 2), and JP-A-60-54669 (Patent Document 3) disclose activated carbon. Tobacco smoke filter adsorbents impregnated with polyethyleneimine or an aliphatic amine having a low vapor pressure are disclosed, and disclosed in JP-T-2002-528105 (Patent Document 4) and JP-A-2002-528106 (Patent Document 5). Discloses a cigarette filter in which 3-aminopropylsilyl and related atomic groups are covalently bonded, and JP 2003-505618 A (Patent Document 6) discloses a filler containing an ammonium salt. Japanese Patent No. 71388 (Patent Document 7) discloses that an amino acid is added to improve the flavor of tobacco.

  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. In addition, although the basic component can suppress volatilization by making the liquid property at the time of attachment acidic, it may be liberated for some reason, for example, contact with other basic substances or hydrolysis. There is. In many cases, amino acids and the like are crystallized and have low volatility. However, in such a crystalline state, the activity for adsorption is low and a sufficient effect cannot be expected. In this way, adsorbents using ordinary basic components are considered to be effective to some extent for removal of acidic substances and aldehydes, but have problems in safety and effectiveness, and are practically used as adsorbents for cigarette filters. It was not right.

  On the other hand, among such basic substances, chitosan derivatives such as chitin and chitosan do not cause crystallization and volatilization, are safe for the human body, and are known to have antibacterial properties. Yes. For example, Japanese Patent Application Laid-Open No. 11-100713 (Patent Document 8) 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.

  In addition, tobacco filters using such chitin and chitosan derivatives have been proposed. For example, JP-A-53-142600 (Patent Document 9) discloses a tobacco filter containing chitin or a chitin derivative in a proportion of 3% by weight 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 bundle 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. 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.

In JP-A-60-168373 (Patent Document 10), chitin or a derivative thereof (chitosan obtained by deacetylating part or all of the acetylamino group of chitin, its OH group or CH ₂ OH group is etherified, Tobacco filters using fibers made of esterified, hydroxyethylated or O-methylated compounds) 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 wet-spun 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 adhesion capacity 1.5 to 2 times that of conventional filters. is doing.

  JP-A-62-211679 (Patent Document 11) discloses polysaccharide ion exchangers and powdered polysaccharides (cellulose, agarose, amylose, chitin, Cigarette filter materials containing chitosan and the like are disclosed. This document describes that polysaccharide ion exchangers and powdered polysaccharides can be used as a filter of a cigarette body, and in a form of being dispersed or sandwiched in the space of an acetate filter.

  JP-A-7-31452 (Patent Document 12) discloses a tobacco filter having 5 to 100% by weight of chitin or chitosan. This document describes that chitin / chitosan may be used alone or in admixture with silica, alumina, aluminosilicate, zirconia, rayon, cellulose, protein, synthetic resin powder or fiber. ing. This document also describes chitin / chitosan solutions such as silica, alumina, aluminosilicate, zirconia, activated carbon or 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 / chitosan powder, in Example 3, 80 mg of powdered chitin / chitosan was filled into 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.

  Traditionally, nicotine and tar are considered to be the main harmful components in cigarette smoke, and there is interest in delivery of nicotine and tar, and in many countries, labeling of nicotine and tar is imposed. 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, 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.

  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.

  In addition, chitosan and the like are hard and brittle objects themselves, and in a filter made of chitosan fibers, the chitosan fibers that have fallen from the filter may be sucked into the human body and damage the respiratory organs (for example, bronchial flagella). . Further, as described in Patent Document 12, 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 respirators (eg, May hurt bronchial flagella).

Therefore, there has been a demand for a cigarette smoke filter that maintains a selective adsorption property of formaldehyde and has a small amount of adsorption of tar and nicotine.
JP 59-88078 A (Claims) JP 59-1519882 A (Claims) JP-A-60-54669 (Claims) Japanese translation of PCT publication No. 2002-528105 (Claims) JP-T-2002-528106 Publication (Claims) Japanese translation of PCT publication No. 2003-505618 (Claims) JP-A-57-71388 (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-62-111679 (Claims, page 2, upper left column, lines 1 to 17) JP-A-7-31452 (Claims, paragraph numbers [0004] [0006], Examples)

  Therefore, an object of the present invention is to provide a tobacco filter material that can efficiently remove (or reduce) aldehydes (particularly formaldehyde) while maintaining a high level of taste (or flavor) components such as tar and nicotine. There is to do.

  Another object of the present invention is to provide a material for a tobacco filter which is odorless and safe even when taken orally and is useful for selectively removing aldehydes (particularly formaldehyde).

  Still another object of the present invention is to provide a method for easily and efficiently producing a tobacco filter material capable of selectively removing aldehydes (particularly formaldehyde).

  Another object of the present invention is to provide a cigarette filter capable of selectively removing aldehydes (particularly formaldehyde) without impairing the taste, and a cigarette equipped with the cigarette filter.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that a carrier (such as a tow structure (filter rod structure) carrier), a polysaccharide having a granular amino group (such as chitosan) and a dispersion medium (for example, In a cigarette filter material that has been subjected to adhesion treatment with a dispersion composed of a hydroxyl group solvent such as water or alcohol, a plasticizer for a carrier such as triacetin, etc., this is due to the amino group of the polysaccharide having the amino group. The present inventors completed the present invention by discovering that aldehydes (particularly formaldehyde) can be selectively adsorbed to taste components such as tar and nicotine, probably because the chemical adsorption performance which is supposed to be exhibited.

That is, the tobacco filter material (cigarette smoke filter material) of the present invention is a tobacco filter material in which a polysaccharide having an amino group is attached to a carrier, and the carrier has a polysaccharide having a granular amino group ( Adhesion treatment is performed with a dispersion liquid composed of a polysaccharide particle having an amino group) and a dispersion medium (specifically, a dispersion medium for the polysaccharide). The carrier may be a carrier having a tow structure (filter rod structure) (or a tow structure carrier, for example, a tow structure filter) (or the filter material may have a tow structure, Specifically, the filter material may be composed of a filament and may have a tow structure), and the polysaccharide having an amino group may be chitosan. The tow structure is a structure (filter structure) formed by aligning monofilament fibers in a predetermined bundle (for example, a bundle of about 3000 to 100,000) in the main smoke flow direction. In the dispersion, the average particle diameter of the granular amino group-containing polysaccharide may be about 0.1 to 100 μm (for example, 0.5 to 50 μm). May be at least one selected from a polar solvent (particularly a solvent having a hydroxyl group) and a plasticizer for the carrier (for example, triacetin may be simply referred to as a plasticizer). The solvent having a hydroxyl group may be a solvent having at least one hydroxyl group selected from water and alcohols, and the plasticizer is a lower fatty acid of a polyol (eg, glycerol, polyglycerol, etc.). (For example, C _1-4 alkanecarboxylic acid such as acetic acid) ester may be used. The dispersion medium may contain a moisturizing component that remains or can adhere to the carrier even after the adhesion treatment. For example, the dispersion medium may be a polyol as a moisturizing component [for example, C _2-6 alkanediol, Di- to tetra-C _2-4 alkylene glycol, and C _3-10 alkanetriol (such as glycerin) may be included].

The representative dispersion is composed of, for example, chitosan having an average degree of deacetylation of 70% or more and an average particle size of 1 to 20 μm, and C _3-6 alkanetriol (particularly glycerin). Dispersions etc. are included. Such a dispersion may contain water, alkanols, the plasticizer, and the like.

  In the tobacco filter material of the present invention, at least the polysaccharide having an amino group is attached to or contained in the carrier. In such a cigarette filter material of the present invention, the amount of the polysaccharide having an amino group may be, for example, about 1 to 100 parts by weight with respect to 100 parts by weight of the carrier.

  In the tobacco filter material of the present invention, a dispersion medium may remain on the carrier, and the remaining dispersion medium may be a part or all of the dispersion medium in the dispersion. Good. When the carrier (or tobacco filter material) contains or remains a dispersion medium, the selective removal of aldehydes (particularly formaldehyde) can be further improved. The content of such a dispersion medium may be, for example, about 0.5 to 100 parts by weight with respect to 100 parts by weight of the carrier. Moreover, the adhesion amount of the polysaccharide having an amino group is about 1 to 80 parts by weight with respect to 100 parts by weight of the carrier, and the residual amount of the dispersion medium is 5 to 100 parts by weight with respect to 100 parts by weight of the polysaccharide having amino groups. It may be about 400 parts by weight. In particular, when the moisturizing component is used as a dispersion medium, the dispersion medium can efficiently remain, contain, or adhere to the carrier even after the adhesion treatment. For example, in the tobacco filter material, the remaining dispersion medium Further, it is composed of at least a polyol as a moisturizing component, and the residual amount of the polyol may be about 3 to 200 parts by weight with respect to 100 parts by weight of the polysaccharide having an amino group.

  In the tobacco filter material of the present invention, as described above, the carrier is subjected to an adhesion treatment with a dispersion composed of a polysaccharide having a granular amino group and a dispersion medium (a dispersion medium for dispersing the polysaccharide). Can be manufactured.

  In addition, the present invention includes a tobacco filter composed of the tobacco filter material. Since such a cigarette filter can selectively remove (or reduce) aldehydes (especially formaldehyde) efficiently, the present invention further comprises the cigarette filter by using the cigarette filter material. Also included is a method of reducing aldehydes (particularly formaldehyde) in cigarette smoke that passes (or circulates) (specifically, cigarette smoke or mainstream smoke that passes (or circulates) the cigarette filter). In such a method, taste components such as nicotine and tar can be maintained at a high level. For example, while maintaining nicotine and tar at 75% or more, the formaldehyde retention can be 65% or less.

  The present invention also includes a cigarette provided with the cigarette filter.

In this specification, “chitosan” refers to 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.

  In the present invention, a polysaccharide having a granular amino group and a dispersion medium are combined and a carrier (such as a cellulose ester fiber tow structure carrier) is attached and treated in the form of a dispersion, so that tar, nicotine, etc. Aldehydes (particularly formaldehyde) can be efficiently removed while maintaining the taste (or flavor) component at a high level. In addition, since the tobacco filter material of the present invention uses a polysaccharide having an amino group such as chitosan, it is odorless and safe even when ingested, and selectively removes aldehydes (particularly formaldehyde). Useful. Therefore, the cigarette filter constituted by the cigarette filter of the present invention can selectively remove aldehydes (particularly formaldehyde) without deteriorating the taste.

Detailed Description of the Invention

  The material for tobacco filter of the present invention (hereinafter sometimes simply referred to as filter material, material, etc.) is a polysaccharide whose carrier is a granular amino group and a dispersion medium (specifically, a dispersion medium for this polysaccharide). A material for a tobacco filter that has been subjected to an adhesion treatment with a dispersion liquid comprising: a polysaccharide having at least an amino group (and a dispersion medium) adhered to the carrier.

  That is, polysaccharides having an amino group (such as chitosan) usually have weak basicity or nucleophilicity because the amino group that is largely involved in the removal of aldehydes (particularly formaldehyde) forms hydrogen bonds. Even if it is used as a tobacco filter material or a tobacco filter as it is, it cannot sufficiently exhibit the adsorption performance of aldehydes (particularly formaldehyde).

  Therefore, in the present invention, the removal performance (selective removal property) of the aldehydes of the polysaccharide is improved by combining the polysaccharide having a granular amino group and the dispersion medium. The reason why the selective removal (or reduction) of such aldehydes is improved is not clear, but in the tobacco filter material of the present invention, a carrier containing such a polysaccharide and a dispersion medium is used. For example, (a) a polysaccharide having an amino group can be efficiently attached to the carrier while maintaining the granular form, (b) the dispersion medium (and the dispersion remaining on the carrier after the attachment treatment) (C) having an amino group attached to the carrier, which can effectively suppress or alleviate the hydrogen bond of the amino group of the polysaccharide by the action of the medium) and effectively act on the selective removal of aldehydes. The surface area of the polysaccharide can be increased, (d) the adhesive force of the polysaccharide having an amino group attached to the carrier can be increased, (e) these (a) to (d) act complementarily or synergistically, etc. Effective It is selectively removed with respect to polysaccharide aldehydes having the amino group is considered to be effectively exhibited.

[Carrier]
The carrier is only required to be treated with a dispersion containing a polysaccharide having an amino group and a dispersion medium. Depending on the shape (or structure) of the carrier, for example, natural or synthetic fibers {for example, cellulose ester fibers (cellulose acetate fibers, etc.) , Cellulose fibers [wood fibers (such as wood pulp fibers such as conifers and hardwoods), seed hair fibers (such as cotton such as linter), gin leather fibers, leaf fibers (such as Manila hemp and New Zealand hemp)], regenerated cellulose Fibers (or fibrous materials) such as fibers (viscose rayon, copper ammonia rayon, nitrate silk, etc.), polyester fibers, polyurethane fibers, polyamide fibers, polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), etc. (For example, activated carbon, diatomaceous earth, silica gel, alumina, oxidation Tan, zirconia, inorganic particles such as zeolites, wood chips, etc. particles composed of other natural or synthetic polymers) can be constituted by a protein (gelatin, casein, etc.). These carrier components may be used alone or in combination of two or more.

  Among these, examples of preferable constituent components of the carrier include fibers (fibrous substances) such as cellulose ester fibers. In the cellulose ester fiber, 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.); Inorganic acid esters such as cellulose nitrate, cellulose sulfate, and 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.

  The polymerization degree (viscosity average polymerization degree) of the cellulose ester is usually 10 to 1000 (for example, 50 to 1000), preferably 50 to 900 (for example, 100 to 800), and more preferably about 200 to 800.

  Moreover, the substitution degree (average substitution degree) of cellulose ester (especially cellulose acetate) can be selected from the range of about 1 to 3 (for example, 1 to 2.9), preferably 1.5 to 2.7, More preferably, it may be about 1.7 to 2.6.

  In the fibers (for example, cellulose ester fibers) constituting the carrier, the average fiber length can be selected from a range of about 0.1 mm to 5 cm, for example, 0.5 to 30 mm (for example, 1 to 25 mm), preferably 2 to 2 mm. It may be about 20 mm, more preferably about 3 to 15 mm (for example, 5 to 10 mm). The average fiber diameter of the fibers may be, for example, about 0.01 to 100 μm, preferably about 0.5 to 80 μm, and more preferably about 1 to 50 μm.

  The fibers such as cellulose ester fibers (for example, filaments or fibers constituting the filter tow) may be crimped fibers or non-crimped fibers.

  Moreover, in a granular material (or granular material), an average particle diameter may be about 0.1-2000 micrometers, for example, Preferably it is 10-1500 micrometers, More preferably, about 100-1000 micrometers may be sufficient.

  The shape (or structure) of the carrier can be appropriately selected according to its constituent components (fibers, particles, etc.), and may be the shape of the constituent components themselves such as fibrous or granular (or granular), or hairy Woven fabric, non-woven fabric, tow structure (or tow shape or filter rod structure, for example, crimped fiber tow structure), paper-like shape (or paper-like or paper-making structure), sheet shape, granulated material, etc. It may be a shape. In addition, the paper-making structure carrier is cut into the above-mentioned staples and then made into a sheet by a dry and wet nonwoven fabric manufacturing method, or made into a slurry in which the above staple and beaten pulp are confused before making paper. Is obtained.

  Further, the carrier may be a preformed filter (for example, a filter having a tow structure of a cellulose ester crimped fiber such as cellulose acetate). When such a preformed filter (or filter-shaped) carrier is used, it can be used as it is as a tobacco filter after the adhesion treatment (and drying).

  Preferred carriers include a tow-like (or tow structure or filter rod structure) carrier formed of fibers [or a tow-structured filter formed of fibers (filter carrier)]. That is, a large amount of airborne particulates such as nicotine and tar are present in cigarette smoke, especially mainstream smoke. Such suspended fine particles are likely to be captured at the fibril portion when fibers having a fibril structure are contained in the carrier. Therefore, in the carrier having a fibril structure, the transmittance of nicotine and tar decreases, and there is a possibility that the carrier does not meet the object of the present invention. However, the tow structure (tow structure filter) described later has a monofilament (multifilament having a substantially infinite continuous length) structure defined by polymer engineering in a broad sense, and is a fibril. Therefore, it does not trap airborne particles and excels in nicotine and tar permeability.

  Therefore, from this point of view, a sheet structure carrier made of natural fibers such as cotton linters and absorbent cotton (Example 3 of JP-A-7-31452) or natural fibers having a fibril structure such as beating pulp ( (Or rod) is preferably a carrier (or rod) composed of fiber bundles having a tow structure (tow structure filter-like) formed from monofilaments.

(Tow structure carrier or tow structure filter carrier)
As described above, the most preferable carrier in the present invention is a tow structure carrier (particularly, a tow structure filter carrier). The tow structure (tow structure filter) is made of filaments having an infinite length, and can be formed by spinning (dry, melting or wet spinning) a conventional filter material (fiber). Examples of fibers constituting the carrier of the tow structure (that is, monofilament bundling structure) include the above-described fibers such as cellulose fibers, regenerated cellulose fibers (viscose rayon fibers, copper ammonia rayon fibers, etc.), cellulose derivative fibers (cellulose). Ester fibers, etc.), polyester fibers, polyurethane fibers, polyamide fibers, and synthetic fibers such as polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.). These fibers can be used alone or in combination of two or more.

  Preferred fibers include cellulose fibers, cellulose ester fibers, and the like, and fibers made of at least cellulose ester fibers are particularly preferable. Examples of the cellulose ester fiber include fibers similar to those described above, for example, organic acid ester (for example, organic acid ester having about 2 to 4 carbon atoms) fiber such as cellulose acetate fiber, cellulose propionate fiber, and cellulose butyrate fiber; cellulose Examples include mixed fatty acid ester fibers such as acetate propionate fiber and cellulose acetate butyrate fiber; and cellulose ester derivatives such as polycaprolactone-grafted cellulose ester fiber. Preferred cellulose ester fibers include, for example, cellulose acetate fiber, cellulose propionate fiber, cellulose butyrate fiber, cellulose acetate propionate fiber, cellulose acetate butyrate fiber, and the like, and cellulose acetate fiber is particularly preferable. These cellulose ester fibers can also be used alone or in combination of two or more.

  In the tow structure (tow structure carrier), the degree of polymerization (average polymerization degree, viscosity average polymerization degree) of the cellulose ester may be, for example, in the range of about 50 to 900, preferably about 200 to 800. Moreover, the substitution degree (average substitution degree) of a cellulose ester can be selected from the range of about 1.5-3.0, for example.

  The cross-sectional shape of the filament (or fiber) is not particularly limited, and is, for example, circular, elliptical, irregular (for example, Y-shaped, X-shaped, I-shaped, R-shaped, H-shaped, etc.) or hollow. However, a polygonal deformed fiber cross section such as a Y shape, an X shape, an I shape, an R shape, or an H shape is preferable. The average fiber diameter and the average fiber length can be selected according to the type of fiber, and may be, for example, an average fiber diameter of 0.01 to 100 μm, preferably about 0.1 to 50 μm, and an average fiber length of 50 μm to 5 cm. Preferably, it is often selected from the range of about 100 μm to 3 cm. In particular, in the case of a filter-like carrier, it is preferable to have an average fiber length of a length (about 3 to 30 mm, for example, 10 mm, 25 mm, etc.) corresponding to the length of the filter or a part constituting a part of the filter. .

  The fineness of the fibers (such as cellulose ester fibers) can be selected from a range of, for example, about 1 to 16 denier, preferably about 1 to 10 denier. The fibers such as cellulose ester fibers may be non-crimped fibers or crimped fibers, but monofilaments having a crimped structure (crimped fibers) are more preferable.

  The tow structure carrier (filter carrier) has, for example, 3,000 to 1,000,000 (for example, 3,000 to 100,000), preferably about 5,000 to 100,000. It is the form of the tow | toe (fiber bundle) formed by bundling the single fiber (filament) of this fiber (especially cellulose ester fiber).

  In the case of a carrier (or filter) having a tow structure, a carrier (or filter) may be formed by mixing and converging filaments treated with a polysaccharide containing amino groups (for example, chitosan) and untreated filaments. it can. If cellulose ester (preferably cellulose acetate) is used as the material of such untreated filament, it is advantageous in terms of taste, and it is possible to adjust the reduction rate of formaldehyde and the residual rate of tar and nicotine. .

[Dispersion]
(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 typical example 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%).

  The chitosan used in the present invention usually has a relatively high degree of deacetylation (ie, has many amino groups) in order to increase the selective removal rate of aldehydes (particularly formaldehyde). There are many cases. That is, chitosan having a high degree of deacetylation has more amino groups than chitin and the like, and is excellent in the selective removal effect of aldehydes (particularly formaldehyde).

Therefore, the degree of deacetylation (average degree of deacetylation) of chitosan is, for example, 60% or more (for example, about 65 to 100%), preferably 70% or more (for example, about 75 to 99%), and 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 and 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 a derivatized 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 degree of polymerization (average degree of polymerization, viscosity average degree of polymerization) of polysaccharides having amino groups (particularly chitosan) can be selected from the range of about 10 to 5000 (for example, 50 to 4000), for example, 20 to 3000, preferably May be about 300 to 2000, more preferably about 50 to 1000 (for example, 100 to 500).

  The polysaccharide having an amino group is dispersed in the form of powder (or powder) in the dispersion. The polysaccharide having an amino group may be in the form of powder (particulate, particulate, pellet, etc.), and may be spherical, ellipsoidal, columnar (such as prismatic), or amorphous.

  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. In the dispersion, the polysaccharide having an amino group in a granular form may be a primary particle or a secondary particle depending on the type of the dispersion medium. By adjusting the particle size of the polysaccharide in the dispersion, selective removal of aldehydes (particularly formaldehyde) can be enhanced.

  In the dispersion, the content (dispersion amount) of the polysaccharide having an amino group is 0.01 to 200 weights with respect to 100 parts by weight of the dispersion medium (total amount of dispersion medium), although it depends on the type of dispersion medium. Part range, for example, 0.05 to 150 parts by weight (for example, 0.1 to 100 parts by weight), preferably 0.2 to 100 parts by weight (for example, 0.5 to 90 parts by weight), More preferably, it may be about 1 to 80 parts by weight (for example, 1 to 70 parts by weight).

(Dispersion medium)
The dispersion medium is not particularly limited as long as it is a solvent (or a poor solvent for the polysaccharide) that can disperse the granular amino group-containing polysaccharide, and such a dispersion medium is an amino group-containing polysaccharide. A dispersion medium (solvent) that can be selected according to the type (degree of polymerization, degree of deacetylation, etc.), can be a conventional solvent (polar solvent, nonpolar solvent), and can dissolve (or plasticize) the carrier. It may be. The dispersion medium also includes a solid moisturizing component and the like, as will be described later. The dispersion medium may be used alone or in combination of two or more.

  Examples of the solvent include nonpolar or nonpolar solvents [for example, hydrocarbons (aliphatic or alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc.), chain carboxylic acid esters (for example, A solvent having a relatively low dielectric constant or non-dielectric constant (for example, a dielectric constant of less than 15) such as ethyl acetate and butyl acetate), but usually at least a polar solvent (or a polar liquid) ). The polar solvent usually does not dissolve the carrier in many cases.

  Examples of polar solvents include water, alcohols, ketones (dialkyl ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone), ethers [cyclic ethers (such as tetrahydrofuran), dialkylene glycol alkyl ethers (diethylene glycol dimethyl ether). Etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.) and the like.

Preferable polar solvents include solvents having hydroxyl groups such as water and alcohols from the viewpoint of efficiently relieving hydrogen bonds of amino groups of the polysaccharide. Examples of alcohols include monools [alkanols (C _1-10 alkanols such as methanol, ethanol, 1-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, etc., preferably C _1-8 alkanols, Preferably, C _1-6 alkanol, especially C _1-4 alkanol, etc., cycloalkanol (C _4-10 cycloalkanol, such as cyclohexanol), alkylene glycol monoalkyl ether (methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl) Ethers), dialkylene glycol monoalkyl ethers (methyl carbitol, ethyl carbitol, etc.), (poly) alkylene glycol monoacylates (ethylene group) Coal monoacetate and the like], polyols {diols [eg, alkanediols (ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, C _2-10 alkane diols such as hexylene 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, and di or tetra _{C 2-4} alkylene glycols such as tripropylene glycol), etc.], triols [alkane triol (glycerol, 1,2,6-hexane _C, such as triol _{3- 10} alkanetriols, preferably C _3-6 alkanetriols, more preferably C _3-4 alkanetriols)], tetrafunctional or higher polyols [multifunctional polymers of trifunctional or higher polyols (such as alkanetriols) Glycerin, polyglycerin such as triglycerin) and the like].

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

  In particular, the polar solvent may be composed of at least a polar solvent as a moisturizing component (a polar solvent that acts as a moisturizing component, hereinafter sometimes referred to as a moisturizing polar solvent). Examples of such polar solvents include dialkylene glycol monoalkyl ethers, (poly) alkylene glycol monoacylates, polyols [for example, alkanediols, alkanetriols (such as glycerin)] among the polar solvents exemplified above. Can be mentioned. Particularly preferred moisturizing polar solvents include polyols in that they have a plurality of hydroxyl groups and are excellent in the ability to relax the hydrogen bonds of the amino groups of the polysaccharide.

  That is, since the polyols and the like have a relatively high boiling point, they remain or adhere to the tobacco filter material even after the adhesion treatment (and drying) and act as a moisturizing component (or humectant). Specifically, such a moisturizing polar solvent (polyols or the like) as a moisturizing component does not evaporate from the carrier after the adhesion treatment and remains on the tobacco filter material (or carrier), and the amino acid of the polysaccharide. It has an excellent ability to relax the hydrogen bond of the group, and is useful for improving the selective removal of aldehydes. In addition, since such a moisturizing component remains in the tobacco filter material or carrier, the selective removal of aldehydes can be stably maintained over a long period of time. In addition, the moisturizing polar solvent as the moisturizing component seems to have a function of suppressing volatilization of water, monools (alkanol, etc.) after the adhesion treatment, and such a polar solvent is used as a carrier. It can be made to remain and the hydrogen bond of the amino group of the said polysaccharide can be relieved effectively.

The moisturizing polar solvent as the moisturizing component may be used alone or in combination of two or more. Also, a volatile dispersion medium [particularly at least one selected from volatile polar solvents or non-moisturizing polar solvents such as water and monools (for example, alkanols such as C _1-4 alkanol). Solvent etc.] and a moisturizing polar solvent may be combined.

  The boiling point of the moisturizing polar solvent (especially polyols) 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, it may be 230 to 350 ° C., particularly 250 ° C. or more (for example, about 260 to 320 ° C.).

  The boiling point of the volatile dispersion medium (water, volatile polar solvent such as alkanols) is, for example, less than 150 ° C. (for example, 35 to 145 ° C.), preferably 40 to 130 ° C., more preferably 50 to 120. It may be about ° C.

The dispersion medium capable of plasticizing the carrier includes a conventional plasticizer for the carrier. A dispersion medium capable of plasticizing such a carrier can efficiently enhance the adhesion to the carrier by plasticizing the carrier. Examples of the plasticizer include phosphate esters {aliphatic phosphate esters (eg, tri-C _1-12 alkyl esters such as triethyl phosphate), aromatic phosphate esters (phosphorus such as octyldiphenyl phosphate). Acid C _1-20 alkyl-diC _6-15 aryl ester, phosphoric acid tri-C _6-15 aryl ester such as tricresyl phosphate), condensed phosphoric acid ester [for example, dihydroxy arenes such as resorcinol bis (diphenyl phosphate)- Bis (diaryl phosphate), etc.], carboxylic acid ester {eg, aromatic carboxylic acid ester [eg, aromatic dicarboxylic acid ester (dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, etc.] of phthalate _{C 1 12} alkyl esters, and aromatic polycarboxylic esters, such as phthalic acid esters) such as phthalic acid C _1-6 alkoxy C _1-12 alkyl esters such as phthalic acid dimethoxyethyl], aliphatic carboxylic acid esters [e.g., fats Dicarboxylic acid esters (for example, adipic acid esters such as dibutyl adipate, dioctyl adipate, dibutoxyethoxyethyl adipate, and C _6-12 dicarboxylic acids such as azelaic acid ester and sebacic acid ester corresponding to these adipic acid esters) C _1-12 alkyl ester), citrate ester (acetyl tributyl citrate, etc.), unsaturated fatty acid ester (butyl oleate, methyl acetyl ricinoleate, etc.) and C _8-30 alkene carboxylic acid-C _1-12 alkyl ester Etc.), polyols or polyhydric alcohols (fatty acid esters of the above-exemplified polyols such as tri to hexaalkanols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.), ester oligomers (such as caprolactone oligomers), etc. Can be mentioned.

Examples of the fatty acid ester of the polyol include lower fatty acid polyol (eg, C _1-4 alkanecarboxylic acid such as acetic acid) ester [eg, alkanetriol mono to triacylate (eg, C _3-6 alkane such as monoacetin, diacetin, triacetin, etc.) Triol-mono to tri-C _1-4 acylate, preferably glycerin mono- to tri-C _2-3 acylate)], polyol oligomer lower fatty acid ester [for example, alkanetriol dimer mono- to tetraacylate (for example, diglycerin) A dimer of a polyol such as di-C _3-6 alkanetriol-mono to tetra-C _1-4 acylate such as tetraacetate) or the like, and the like.

Among these plasticizers, as a plasticizer to be combined with a carrier composed of cellulose ester (particularly cellulose acetate), acetins (for example, glycerin di to triacetate such as diacetin, triacetin, etc.) are excellent in terms of swelling ability with respect to the carrier. A lower fatty acid ester of a polyol such as) 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 (especially C _3-6 alkanetriol-diC _1-4 acylate such as diacetin), 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, by combining diacetin and other acetins (particularly triacetin), the viscosity of the dispersion can be increased appropriately 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, the selective removal property of aldehydes (particularly formaldehyde) can be enhanced, and the safety is high and it can be suitably used.

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

  The dispersion medium capable of plasticizing the carrier may be usually liquid (liquid at room temperature). The dispersion medium capable of plasticizing the carrier usually has a relatively high boiling point [for example, boiling point of 150 to 500 ° C, preferably 200 to 450 ° C, more preferably 220 to 400 ° C (for example, 250 to 380 ° C). In many cases, it remains on the carrier or the tobacco filter material after the adhesion treatment without volatilization or drying. Therefore, normally, the dispersion medium capable of plasticizing the carrier may be non-volatile.

The dispersion medium capable of plasticizing a preferred carrier depends on the kind of the carrier, but from the viewpoint of oral safety to the human body, a lower fatty acid ester of a polyol (for example, glycerol tri-C _2-3 acylate such as triacetin) Etc. are included. The dispersion medium capable of plasticizing the carrier may be used alone or in combination of two or more.

  In the present specification, the dispersion medium includes a solid (solid at room temperature) dispersion medium as long as it can be dissolved in a liquid dispersion medium (the polar solvent, the plasticizer, or the like). That is, the dispersion medium may be composed of a solid dispersion medium and a dispersion medium that can dissolve the dispersion medium. Such a solid dispersion medium can act as a moisturizing component in the same manner as the moisturizing polar solvent and the like by remaining on the carrier even after the adhesion treatment (and drying).

  Examples of solid dispersion media include synthetic polymers having a hydroxyl group or an ether bond (ether group) [polyvinyl alcohol, polyalkylene glycol (polyethylene oxide, polypropylene oxide, polyethylene oxide-polypropylene oxide, etc.)], natural polymers, and the like. (Gelatin, dextrin, starch, etc.), cellulose derivatives (hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl 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 cellulose such as ethyl cellulose), Hydrates (or saccharides) [eg, monosaccharides (eg, xylose, glucose, etc.), disaccharides (cellobiose, trehalose, etc.), sugar alcohols (eg, inositols, such as inositol, borneositol, etc.), etc. Can be mentioned. The solid dispersion medium may be used alone or in combination of two or more.

  Typical dispersion media include (1) a dispersion medium composed of water and / or monols (such as alkanols including the polyols) (which may include the solid moisturizing component). (2) A dispersion medium composed of the plasticizer (such as a lower fatty acid ester of polyol) (which may contain the solid moisturizing component) is included.

  As a preferable dispersion medium, a dispersion medium containing the moisturizing polar solvent, for example, (1a) a dispersion medium composed of water and / or monols and the moisturizing polar solvent (for example, polyols such as glycerin). And (2a) a dispersion medium composed of the plasticizer and the moisturizing polar solvent.

  In the dispersion medium containing the moisturizing polar solvent, the ratio of the moisturizing polar solvent (polar solvent as the moisturizing component) is relative to the entire dispersion medium (or the dispersion medium in the dispersion) constituting the dispersion. , 0.01 to 100% by weight (for example, 0.05 to 50% by weight), for example, 0.1 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably 0. It may be about 5 to 15% by weight (for example, 1 to 10% by weight).

  In particular, in the dispersion liquid of the above aspect (1a), the ratio of the moisturizing polar solvent is, for example, 0.05 to 30 parts by weight (for example, 0.1% with respect to 100 parts by weight of water and / or monools). ˜20 parts by weight), preferably 0.3 to 15 parts by weight, more preferably about 0.5 to 10 parts by weight (for example, 1 to 8 parts by weight).

Depending on the type of dispersion medium used and its combination, various characteristics may be imparted to the resulting tobacco filter material. For example, when a dispersion medium containing a polar solvent such as alkanols (C _1-4 alkanol, etc.) is used, swelling or aggregation of the polysaccharide can be efficiently suppressed or prevented in the dispersion medium. It seems that the surface area of saccharides can be increased efficiently. In addition, when a dispersion medium containing a polar solvent such as water or polyols is used, aggregation and swelling of the polysaccharide in the dispersion medium occur, and the surface area of the polysaccharide attached to the carrier tends to be small. There exists a tendency which can reduce the influence of the hydrogen bond of the hydroxyl group of the said polysaccharide, and can improve the selective removal property of formaldehyde.

[Material for cigarette filters]
In the tobacco filter material of the present invention, polysaccharides having amino groups are attached to the carrier. The shape of the polysaccharide attached to the carrier usually corresponds to the shape of the polysaccharide in the dispersion and is often in the form of a powder. Moreover, the adhering powdery polysaccharide may be aggregated.

  In the cigarette filter material of the present invention, the adhesion amount (or content or attachment amount) of the polysaccharide having an amino group is 100 parts by weight or less with respect to 100 parts by weight of the carrier, although it depends on the type of dispersion medium. (For example, about 1 to 100 parts by weight), for example, 1 to 80 parts by weight, preferably 60 parts by weight or less (for example, about 2 to 60 parts by weight), preferably 40 parts by weight or less (for example, 3 to 40 parts by weight), particularly 30 parts by weight or less (for example, about 4 to 30 parts by weight), and usually 20 parts by weight or less (for example, about 5 to 20 parts by weight). If the content of the polysaccharide having an amino group is too large, the adsorption amount of tar and nicotine may be increased.

In the tobacco filter material, the surface area (specific surface area) of the polysaccharide having amino groups attached to the carrier is 1 g of the polysaccharide having amino groups depending on the type of dispersion medium, the particle size of the polysaccharide, and the like. per, for example, 50 m ² or less (e.g., 0.01～40M ^2), preferably 0.1～30M ^2, more preferably it may be about ² 0.5 to 20 m.

In particular, when the alkanols or the plasticizers are used as the dispersion medium, the surface area (specific surface area) of the polysaccharide having amino groups attached to the carrier is relatively large, per 1 g of the polysaccharide having amino groups. , for example, 1 to 50 m ^2, preferably 3～30M ^2, more preferably 5 to 20 m ² (e.g., 6~15m ²⁾ may be about.

  As described above, the surface area of the polysaccharide having an amino group varies depending on the type of the dispersion medium, and when the conditions such as the type of the dispersion medium and the particle size of the polysaccharide are the same, In many cases, the larger the surface area of the attached polysaccharide, the higher the selective removal of aldehydes (particularly formaldehyde). On the other hand, when a dispersion medium containing water or polyols is used, the surface area (specific surface area) of the polysaccharide having an amino group tends to be relatively small as described above. Is excellent in the ability to relax hydrogen bonds of the amino group, and can be used as a dispersion medium, and further remain on the carrier, thereby allowing selective removal of aldehydes even if the specific surface area is small. Can be increased.

  In the cigarette filter material, the dispersion medium may be completely removed by drying (including volatilization and natural drying), or a part or all of the dispersion medium may remain on the carrier. Good. In particular, a dispersion medium such as a moisturizing polar solvent such as polyol, the plasticizer, and the solid dispersion medium usually remains as it is in the tobacco filter material or carrier even after drying. The volatile dispersion medium (water, alkanols, etc.) can be left on the carrier or the tobacco filter material by appropriately adjusting the drying conditions. For example, in a fiber having a relatively large fiber surface area such as a fiber composed of cellulose acetate filaments, adsorbed water or the like can be retained after a normal manufacturing process. However, such a moisture content is about several milligrams (for example, 1 to 3 mg) at most per 100 mg of the carrier, and is usually in an absolutely dry state (almost 0) particularly when vacuum drying is performed. Become.

  In the tobacco filter material, the remaining amount (attachment amount, content) of the dispersion medium can be selected from the range of 0 to 100 parts by weight with respect to 100 parts by weight of the carrier, although it depends on the amount and concentration of the dispersion. For example, 0.5 to 100 parts by weight (for example, 0.8 to 90 parts by weight), preferably 1 to 80 parts by weight (for example, 1.5 to 80 parts by weight), more preferably 2 to 70 parts by weight ( For example, it may be about 3 to 60 parts by weight), particularly 4 to 50 parts by weight (for example, 5 to 30 parts by weight), and usually about 5 to 20 parts by weight (for example, 5 to 15 parts by weight).

In particular, when a dispersion medium containing the moisturizing polar solvent is used, the remaining dispersion medium is composed of a moisturizing polar solvent (particularly, polyols as a moisturizing component). In particular, the residual amount (adhesion amount, content) of polyols can be selected from the range of 0.1 to 100 parts by weight, for example, 1 to 100 parts by weight, preferably 2 to 100 parts by weight of the carrier. It may be about 60 parts by weight, more preferably 3 to 40 parts by weight, and particularly about 5 to 20 parts by weight (for example, 5 to 15 parts by weight). The remaining ratio (attachment ratio, content ratio) of at least one selected from water, monools (for example, C _1-4 alkanols) and the plasticizer and the moisturizing polar solvent is the former / the latter. (Weight ratio) = 99/1 to 0/100, preferably 95/5 to 5/95, more preferably about 90/10 to 10/90 (for example, 85/15 to 15/85). .

  Further, the residual amount (attachment amount, content) of the dispersion medium is 0 to 500 parts by weight, preferably 5 to 400 parts by weight, and more preferably 10 to 300 parts by weight with respect to 100 parts by weight of the polysaccharide having amino groups. Part (for example, 20 to 200 parts by weight). Furthermore, when a dispersion medium containing a moisturizing polar solvent is used, the remaining dispersion medium is composed of a moisturizing polar solvent (particularly, polyols as a moisturizing component), and a moisturizing polar solvent (particularly, The residual amount (adhesion amount, content) of the polyols as a moisturizing component is, for example, 1 to 300 parts by weight, preferably 3 to 200 parts by weight, more preferably 100 parts by weight of the polysaccharide having an amino group. May be 5 to 180 parts by weight (for example, 8 to 150 parts by weight), particularly about 10 to 120 parts by weight.

  In particular, when a dispersion medium containing a polar solvent having a hydroxyl group [water, alcohols (monools, polyols, etc.)] is used, the residual amount (attachment amount, content) of the dispersion medium is an amino group. 0.1 mol or more (for example, 0.3 to 0.3 mol) in terms of hydroxyl group of the dispersion medium (or the total amount of hydroxyl groups in the entire dispersion medium) with respect to 1 mol of the glycosyl (or monosaccharide) unit of the polysaccharide having About 500 mol), for example, 0.5 mol or more (for example, about 0.8 to 300 mol), preferably 1 mol or more (for example, about 1.2 to 150 mol), more preferably 1.5 mol or more ( For example, it may be about 1.6 to 100 mol), particularly 1.8 to 80 mol (for example, 2 to 50 mol).

  In the cigarette filter material of the present invention, the amount of polysaccharides having amino groups, dispersion media, and the like may be adjusted according to the length of the material or filter. For example, when the filter length is short, the permeability of nicotine and tar increases, so the amount of polysaccharide having amino groups may be increased, and the amount of the dispersion medium may be increased accordingly. .

  In addition, the tobacco filter material is composed of other components such as inorganic fine powder (kaolin, talc, diatomaceous earth, quartz, calcium carbonate, barium sulfate, titanium oxide, alumina, etc.), heat stabilizer (alkali or alkaline earth). Metal salts, etc.), colorants, whiteness improvers, oils, yield improvers, sizing agents, adsorbents (such as activated carbon), biodegradation or photodegradation accelerators (such as anatase-type titanium oxide), natural polymers or Derivatives thereof (such as cellulose powder) may be included. Other components can be used alone or in combination of two or more.

  The shape of the material for a tobacco filter of the present invention is not particularly limited, and may be, for example, a fiber shape, a hair shape, a woven fabric shape, a non-woven fabric shape, a tow shape, a sheet shape, a particulate shape (or a powdery shape). Or any other shape. The shape of the tobacco filter material may be a filter shape (filter rod shape). Note that these shapes may be preliminarily provided in the carrier (that is, the carrier before the adhesion treatment), and the adhesion-treated carrier (for example, a fibrous carrier, a particulate carrier, etc.) is converted into a conventional method ( For example, it may be formed or shaped by papermaking. In particular, the tobacco filter material preferably has a tow shape (or a tow structure, particularly a fiber tow shape) as described above.

[Production method of tobacco filter material]
The material for tobacco filter of the present invention can be obtained by subjecting the carrier to the dispersion (dispersed liquid composed of a granular amino group-containing polysaccharide and a dispersion medium for the polysaccharide). That is, the cigarette filter material of the present invention is usually prepared by attaching a carrier with the above-mentioned dispersion and at least a polysaccharide having an amino group [and optionally a dispersion medium (such as the moisturizing polar solvent)]. It can be obtained by adhering (or containing).

  The adhesion treatment method (treatment method) can be appropriately selected according to the shape (fibrous shape, filter shape, etc.) and type of the carrier, and is not particularly limited as long as the carrier can be brought into contact with the dispersion. , (I) a method of immersing (or impregnating, dipping) the carrier in the dispersion, (ii) a method of spraying or spraying (or spreading) the dispersion onto the carrier, and (iii) applying the dispersion to the carrier. The method etc. are mentioned. These processing methods may be used alone or in combination of two or more.

  Such a treatment method of the present invention may be introduced into an existing production apparatus for tobacco filters, particularly an apparatus for producing a tobacco filter having a tow structure using cellulose acetate filaments. For example, the dispersion liquid is spun into a filter tow. In the step, the polysaccharide (and the dispersion medium) may be attached to the carrier by contacting with the above method (spraying, coating, dipping, etc.). Furthermore, the polysaccharide (and dispersion) is dispersed on the carrier by a method such as spraying, coating, and dipping in the process of winding the tow band from the filter tow band integrated packing material (veil) and forming it into a filter rod (winding process). Medium) may be attached. Further, the polysaccharide (and dispersion medium) 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 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 carrier having a tow structure), the polysaccharide (and the dispersion medium) having an amino group with respect to the carrier (or the immersed portion of the carrier) can be easily used. And can be contained efficiently.

  The treatment with the dispersion may be performed on a part or all of the carrier. In particular, in the case of a tow structure carrier, the plasticizer (triacetin) is used in the filter plug forming process (winding step) of the tow structure filter. The dispersion liquid can be disposed or installed as a part of a plasticizer adding device for a filter tow commonly used to attach to the filter tow. In this case, it is not necessary that all of the tow has been treated with the dispersion. In the dipping method (i), at least the entire surface of the support (or the immersed portion of the support) (preferably, the entire surface of the immersed portion and the inside of the support) may be subjected to adhesion treatment.

  In the dipping method (i), the dipping time (or treatment time) can be selected according to the content and content of the polysaccharide having an amino group, and is, for example, 0.001 second or more (for example, 0.001). Seconds to 24 hours), preferably 0.005 seconds to 1 hour, more preferably about 0.01 seconds to 30 minutes, and industrially, for example, 0.001 seconds or more (for example, 0.002 seconds). 003 seconds or more), preferably 0.003 to 30 seconds, and more preferably about 0.005 to 15 seconds.

  The carrier that has been subjected to the adhesion treatment with the dispersion medium is usually dried. By such drying, volatile components such as volatile dispersion media (water, alkanols, etc.) may be completely removed, or a part or all of them may remain. By appropriately adjusting such drying conditions, the content of the dispersion medium (volatile dispersion medium) remaining on the carrier can be adjusted.

  Drying can be selected according to the type of dispersion medium (volatile polar solvent, moisturizing polar solvent, etc.) and the amount of the remaining dispersion medium, and may be natural drying or air drying. In many cases, the drying is performed using a dryer (such as a vacuum dryer) or a hot air dryer.

  The drying may be performed at room temperature (for example, about 15 to 25 ° C.) or under heating (for example, 40 to 200 ° C., preferably 45 to 180 ° C., more preferably about 50 to 150 ° C.). Also good. Moreover, you may perform drying under a normal pressure or pressure reduction. The drying time depends on the drying temperature, drying pressure, type of dispersion medium, and the like, but is, for example, 1 minute or more (for example, 3 minutes to 24 hours), preferably 5 minutes to 18 hours (for example, 10 minutes to 12 hours). ), More preferably about 20 minutes to 10 hours (for example, 30 minutes to 8 hours).

[Tobacco filters and tobacco]
The tobacco filter material of the present invention is useful for constituting a tobacco filter. The cigarette filter may be composed of the cigarette filter material of the present invention singly or in combination of two or more according to the form of the cigarette filter material, and the cigarette filter material of the present invention and other cigarette filter You may comprise by the raw material [For example, the powdery tobacco filter material by which the coating process was carried out, and the said fibrous material (such as the fibrous material which is not the coating process etc.)]. For example, the cigarette filter of the present invention constitutes at least one divided part of a cigarette filter having a structure divided into a plurality of parts (two parts (dual (dual), three parts (triple), etc.)) (for example, 2 One part of the divided filter, both ends of the divided filter, etc.) and the other divided part (for example, the other part of the divided filter, the middle part of the divided filter, etc.) Filter material [For example, a filter material filled with particulate matter such as activated carbon (part containing particulate matter such as activated carbon (dalmatian part) and other part not containing particulate matter (natural)) Etc.) may be configured.

  The tobacco filter can be formed by a conventional method depending on the structure of the carrier or the filter. For example, a tow structure filter (filter having a filter rod) is a plug hoist that opens the cigarette filter material, attaches a conventional plasticizer such as triacetin, converges it to a predetermined diameter, and fixes it with a wrapping paper You may shape | mold by the method of using 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 tobacco filter of the present invention is composed of the tobacco filter material, it can efficiently remove aldehydes such as formaldehyde while maintaining taste components such as nicotine and tar at a high level. Therefore, the present invention provides a method for reducing aldehydes (particularly formaldehyde) in tobacco smoke passing through the tobacco filter (or tobacco) by constituting the tobacco filter (or tobacco) with the tobacco filter material. [Specifically, a method of reducing aldehydes (particularly formaldehyde) while retaining nicotine and tar in tobacco smoke passing through the tobacco filter] is also included.

  For example, the formaldehyde retention rate (weight conversion) of the tobacco filter can be selected from a range of 90% or less (for example, 0 to 88%), for example, 85% or less (for example, 3 to 80%), preferably 70%. It is below (for example, 5 to 65%), more preferably about 65% or less (for example, 10 to 60%), particularly about 50% or less (for example, 15 to 45%), and formaldehyde can be removed at a high level.

  Further, the nicotine retention rate (weight conversion) and tar retention rate (weight conversion) of the tobacco filter can be selected from the range of 50% or more (for example, 55 to 100%), for example, 60% or more (for example, 65 to 100%), preferably 70% or more (for example, 75 to 99%), more preferably 75% or more (for example, 80 to 98%), particularly about 80% or more (for example, 85 to 97%). .

  In particular, the nicotine retention rate (weight conversion) of the tobacco filter can be selected from the range of 60% or more (for example, 65 to 100%), for example, 70% or more (for example, 75 to 99%), preferably 80%. It is more than the above (for example, 82 to 98%), more preferably about 85% or more (for example, 88 to 97%). The tar retention (weight conversion) of the cigarette filter can be selected from a range of 50% or more (for example, 55 to 100%), for example, 55% or more (for example, 60 to 100%), preferably 65%. It is more than 70% (for example, 70 to 99.9%), more preferably 70% or more (for example, 75 to 99.5%), especially 75% or more (for example, 80 to 99%).

  The retention rate (formaldehyde retention rate, nicotine retention rate, tar retention rate) is the amount of formaldehyde (or nicotine amount or tar) in the tobacco smoke that passes through the tobacco filter made of the tobacco filter material before the coating treatment. Amount) can be measured as a reference. That is, the “retention ratio” is a predetermined condition (flow rate, time, number of times, etc.) of the tobacco filter composed of the tobacco filter material that has not been coated (or the tobacco filter material before the coating treatment). The amount of formaldehyde (or nicotine or tar) in the cigarette smoke that passes through is X, and the cigarette smoke that passes under the same conditions (flow rate, time, number of times, etc.) as this formaldehyde (or nicotine or tar) X When the amount of formaldehyde (or the amount of nicotine or tar) is Y, it is represented by the following formula.

          Retention rate (%) = (Y / X) × 100.

  In the present invention, since the carrier treated with the dispersion containing the polysaccharide having an amino group and the dispersion medium is used, it can be incorporated into the tobacco filter without increasing the ventilation resistance of the tobacco filter. Therefore, the cigarette filter of the present invention has air permeability suitable for cigarette smoke, and the cigarette filter has an airflow resistance of 120 mm in length and 24.5 ± 0.2 mm in circumference with a flow rate of 17 mm. When measured by pressure loss when passing air at 5 ml / second, it can be selected from the range of 150 to 600 mmWG (water gauge), for example, 180 to 500 mmWG, preferably 200 to 450 mmWG (for example, 220 to 400 mmWG) More preferably, it may be about 250 to 350 mmWG.

  Moreover, the tobacco of this invention is equipped with the said tobacco filter (or tobacco filter material). The location of the cigarette filter is not particularly limited, but in cigarettes that are formed into a rod shape by wrapping paper, the cigarette filter is often arranged at the mouth portion or between the mouth and the cigarette. In addition, the cross-sectional outer periphery of tobacco often corresponds to the cross-sectional outer periphery of the filter, and may be generally 15 to 30 mm, preferably about 17 to 27 mm.

  The material for a tobacco filter of the present invention is useful for constituting a tobacco filter (and a tobacco). In such a cigarette filter (and a cigarette) of the present invention, it is possible to maintain a suitable ventilation resistance while maintaining the taste components such as nicotine and tar at the time of smoking. Aldehydes such as formaldehyde that are harmful to the human body can be selectively removed without impairing the feeling.

  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 commercially available 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 defined as Tn and Tt, respectively, and the amount of nicotine and tar adhering to the Cambridge filter in Comparative Examples and Examples is defined as Cn and Ct, respectively. Was calculated.

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 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)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, the 14 mm filter part, was diluted 3 times with chitosan aqueous dispersion (Daichi Seika Kogyo Co., Ltd., “Daichitosan FP slurry”) containing 2% by weight of chitosan having a deacetylation degree of 95%. 1) for 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 8 hours 30 minutes under the conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 13 mg and water 0 mg, and the specific surface area of chitosan adhering to the carrier was less than 1 m ² per 1 g of chitosan (lower measurement limit of 0.92 m ² or less). It was.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 98%, a tar retention rate of 100%, a formaldehyde removal rate of 19% (that is, a retention rate of 81%), and a ventilation resistance of 162 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 the cut 14 mm filter piece was used without any treatment.

(Example 2)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, the 14 mm filter part, was diluted 3 times with chitosan aqueous dispersion (Daichi Seika Kogyo Co., Ltd., “Daichitosan FP slurry”) containing 2% by weight of chitosan having a deacetylation degree of 95%. 1) for 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 5 hours under conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 13 mg and water 71 mg, and the specific surface area of chitosan adhering to the carrier was less than 1 m ² per 1 g of chitosan (lower measurement limit of 0.92 m ² or less). It was.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 83%, a tar retention rate of 100%, a formaldehyde removal rate of 45% (that is, a retention rate of 55%), and a ventilation resistance of 179 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 the cut 14 mm filter piece was used without any treatment.

(Example 3)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, the 14 mm filter part, was diluted 3 times with chitosan aqueous dispersion (Daichi Seika Kogyo Co., Ltd., “Daichitosan FP slurry”) containing 2% by weight of chitosan having a deacetylation degree of 95%. 1) for 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 6 hours and 15 minutes under the conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 13 mg and 19 mg of water, and the specific surface area of chitosan adhering to the carrier was less than 1 m ² per 1 g of chitosan (lower measurement limit of 0.92 m ² or less). It was.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 89%, a tar retention rate of 97%, a formaldehyde removal rate of 64% (that is, a retention rate of 36%), and a ventilation resistance of 168 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 the cut 14 mm filter piece was used without any treatment.

Example 4
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, the 14 mm filter part, was diluted 3 times with chitosan aqueous dispersion (Daichi Seika Kogyo Co., Ltd., “Daichitosan FP slurry”) containing 2% by weight of chitosan having a deacetylation degree of 95%. 1), and further immersed in a dispersion with 1% by weight of glycerin added for 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 8 hours and 30 minutes under the conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 13 mg and glycerol 7 mg, and the specific surface area of chitosan adhering to the carrier was less than 1 m ² per 1 g of chitosan (lower measurement limit of 0.92 m ² or less). It was.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 99%, a tar retention rate of 86%, a formaldehyde removal rate of 51% (that is, a retention rate of 49%), and a ventilation resistance of 158 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 the cut 14 mm filter piece was used without any treatment.

(Example 5)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, the 14 mm filter part, was diluted 3 times with chitosan aqueous dispersion (Daichi Seika Kogyo Co., Ltd., “Daichitosan FP slurry”) containing 2% by weight of chitosan having a deacetylation degree of 95%. 1) was further immersed for 10 minutes in a dispersion containing 4% by weight of glycerin. The filter part after immersion was put into a vacuum dryer and dried for 8 hours and 30 minutes under the conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 14 mg and 27 mg of glycerin, and the specific surface area of chitosan adhering to the carrier was less than 1 m ² per 1 g of chitosan (lower measurement limit of 0.92 m ² or less). It was.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 94%, a tar retention rate of 93%, a formaldehyde removal rate of 72% (ie, a retention rate of 28%), and a ventilation resistance of 162 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 the cut 14 mm filter piece was used without any treatment.

(Example 6)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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 cut short piece, that is, a 14 mm filter part was immersed in an ethanol dispersion of chitosan containing 6% by weight of chitosan having a deacetylation degree of 90% (manufactured by Dainichi Seika Kogyo Co., Ltd.) for 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 5 hours under conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. The chitosan adhering to the filter part obtained after drying was 30 mg, and the specific surface area of chitosan adhering to the carrier was 9.8 m ² per 1 g of chitosan.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 96%, a tar retention rate of 87%, a formaldehyde removal rate of 66% (that is, a retention rate of 34%), and a ventilation resistance of 186 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 the cut 14 mm filter piece was used without any treatment.

(Example 7)
In the same manner as in Comparative Example 1, a 14 mm portion from the end of the filter body (25 mm) of the cellulose diacetate crimped fiber tow was cut with a razor. A glass tube with a length of 20 mm and an inner diameter of 8 mm was inserted into the filter piece 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.

Dispersed solution in which 3% by weight of glycerin is further added to an ethanol dispersion of chitosan containing 6% by weight of chitosan having a deacetylation degree of 90% (manufactured by Dainichi Seika Kogyo Co., Ltd.). For 10 minutes. The filter part after immersion was put into a vacuum dryer and dried for 5 hours under conditions of a temperature of 22 ° C. and an atmospheric pressure of 80 mmHg. Chitosan adhering to the filter part obtained after drying was 30 mg, glycerin was 15 mg, and the specific surface area of chitosan adhering to the carrier was 7.5 m ² per 1 g of chitosan.

  Using the 14 mm filter part after drying, the 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 obtained sample had a nicotine retention rate of 88%, a tar retention rate of 76%, a formaldehyde removal rate of 77% (that is, a retention rate of 23%), and a ventilation resistance of 182 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 the cut 14 mm filter piece was used without any treatment.

(Example 8)
Triacetin of chitosan containing 40% by weight of chitosan having a deacetylation degree of 90% as a plasticizer in a cellulose diacetate crimped fiber tow (manufactured by Daicel Chemical Industries) with a filament denier of 2.2 and a total denier of 40,000 A dispersion liquid (manufactured by Dainichi Seika Kogyo Co., Ltd.) is attached and focused, and a cigarette filter rod having a length of 100 mm and an outer diameter of 8 mm is produced by an automatic winder, and this is cut into four equal parts in the length direction Thus, a filter chip having a length of 25 mm was obtained. Chitosan adhering to the filter chip having a length of 25 mm was 16 mg and triacetin was 23.8 mg, and the specific surface area of chitosan adhering to the carrier was 6.8 m ² per 1 g of chitosan.

  A filter body (25 mm) portion of a cellulose diacetate crimped fiber tow of a 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 obtained sample had a nicotine retention rate of 93%, a tar retention rate of 97%, a formaldehyde removal rate of 38% (that is, a retention rate of 62%), 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 produced in the same manner as the above method was used except that triacetin was used as a plasticizer.

Example 9
Triacetin of chitosan containing 40% by weight of chitosan having a deacetylation degree of 90% as a plasticizer in a cellulose diacetate crimped fiber tow (manufactured by Daicel Chemical Industries) with a filament denier of 2.2 and a total denier of 40,000 A dispersion filter (manufactured by Dainichi Seika Kogyo Co., Ltd.) with 100 parts by weight of 10 parts by weight of glycerin added is attached and focused, and a cigarette filter rod having a length of 100 mm and an outer diameter of 8 mm is produced by an automatic winder. 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 this 25 mm long filter chip was 15 mg, triacetin was 22.5 mg, glycerin was 2 mg, and the specific surface area of chitosan adhering to the carrier was 3.4 m ² per 1 g of chitosan. .

  A filter body (25 mm) portion of a cellulose diacetate crimped fiber tow of a 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 obtained sample had a nicotine retention rate of 93%, a tar retention rate of 97%, a formaldehyde removal rate of 38% (that is, a retention rate of 62%), and a ventilation resistance of 168 mmWG.

  In addition, as a control 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 triacetin was used as a plasticizer.

(Example 10)
Triacetin of chitosan containing 40% by weight of chitosan having a deacetylation degree of 90% as a plasticizer in a cellulose diacetate crimped fiber tow (manufactured by Daicel Chemical Industries) with a filament denier of 2.2 and a total denier of 40,000 A mixture of 10 parts by weight of diacetin added to 100 parts by weight of a dispersion (Daiichi Seika Kogyo Co., Ltd.) and focused, and a cigarette filter rod having a length of 100 mm and an outer diameter of 8 mm was obtained by an automatic winder. 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 .

  A filter body (25 mm) portion of a cellulose diacetate crimped fiber tow of a 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.

Various components have been proposed as adsorbents for filtering components in tobacco smoke. As such a component, many have been reported in which a basic component such as an amine component is added for the purpose of adsorption of an acidic component, adsorption of formaldehyde, and the like. For example, JP-A-59-88078 (Patent Document 1), JP-A-59-151882 (Patent Document 2), and JP-A-60-54669 (Patent Document 3) disclose activated carbon. Tobacco smoke filter adsorbents impregnated with polyethyleneimine or an aliphatic amine having a low vapor pressure are disclosed, and disclosed in JP-T-2002-528105 (Patent Document 4) and JP-A-2002-528106 (Patent Document 5). Discloses a cigarette filter in which 3-aminopropylsilyl and related atomic groups are covalently bonded, and JP 2003-505618 A (Patent Document 6) discloses a filler containing an ammonium salt. Japanese Patent No. 71388 (Patent Document 7) discloses that an amino acid is added to improve the flavor of tobacco.

Therefore, there has been a demand for a cigarette smoke filter that maintains a selective adsorption property of formaldehyde and has a small amount of adsorption of tar and nicotine.
Patent Document 1: Japanese Patent Application Laid-Open No. 59-88078 (Claims)
Patent Document 2: JP-A-59-151882 (Claims)
Patent Document 3: Japanese Patent Application Laid-Open No. 60-54669 (Claims)
Patent document 4: Japanese translations of PCT publication No. 2002-528105 (Claims)
Patent document 5: Japanese translations of PCT publication No. 2002-528106 (Claims)
Patent document 6: Japanese translations of PCT publication No. 2003-505618 (Claims)
Patent Document 7: Japanese Patent Laid-Open No. 57-71388 (Claims)
Patent Document 8: Japanese Patent Application Laid-Open No. 11-1000071 (claims, paragraph number [0012])
Patent Document 9: JP-A-53-142600 (Claims, page 2, upper left column, line 1 to upper right column, line 2, example)
Patent Document 10: JP-A-60-168373 (Claims, page 1, right column, line 16 to page 2, upper right column, line 15)
Patent Document 11: Japanese Patent Application Laid-Open No. 62-111679 (Claims, upper left column, page 1 to line 17)
Patent Document 12: Japanese Patent Laid-Open No. 7-31452 (claims, paragraph numbers [0004] [0006], Examples)

Claims (16)

  Tobacco filter material in which a polysaccharide having an amino group is attached to a carrier, wherein the carrier is attached and treated with a dispersion comprising a polysaccharide having a granular amino group and a dispersion medium .   The tobacco filter material according to claim 1, wherein the carrier is a carrier having a tow structure, and the polysaccharide having an amino group is chitosan.   In the dispersion, the average particle size of the polysaccharide having an amino group in a granular form is 0.5 to 50 μm, and the dispersion medium is at least one selected from a solvent having a hydroxyl group and a plasticizer for the carrier. Item 3. A tobacco filter material according to item 1 or 2.   The tobacco filter material according to claim 3, wherein the solvent having a hydroxyl group is at least one selected from water and alcohols, and the plasticizer for the carrier is a lower fatty acid ester of polyols.   The tobacco filter material according to any one of claims 1 to 4, wherein the dispersion medium contains polyols as a moisturizing component. The tobacco filter material according to claim 5, wherein the polyol is composed of at least one selected from C _2-6 alkanediol, di to tetra C _2-4 alkylene glycol, and C _3-10 alkanetriol. The tobacco according to any one of claims 1 to 6, wherein the dispersion is composed at least of chitosan having an average degree of deacetylation of 70% or more and an average particle size of 1 to 20 µm and C _3-6 alkanetriol. Filter material.   The material for a tobacco filter according to any one of claims 1 to 7, wherein the amount of the polysaccharide having an amino group is 1 to 100 parts by weight with respect to 100 parts by weight of the carrier.   The tobacco filter material according to any one of claims 1 to 8, wherein the dispersion medium remains on the carrier.   The tobacco filter material according to claim 9, wherein the residual amount of the dispersion medium is 0.5 to 100 parts by weight with respect to 100 parts by weight of the carrier.   The amount of the polysaccharide having an amino group is 1 to 80 parts by weight with respect to 100 parts by weight of the carrier, and the residual amount of the dispersion medium is 5 to 400 parts by weight with respect to 100 parts by weight of the polysaccharide having an amino group. The tobacco filter material according to claim 9.   The remaining dispersion medium is composed of at least a polyol as a moisturizing component, and the content of the polyol is 3 to 200 parts by weight with respect to 100 parts by weight of the polysaccharide having an amino group. Item 9. A tobacco filter material according to Item 9.   The method for producing a material for a tobacco filter according to claim 1, wherein the carrier is attached and treated with a dispersion composed of a polysaccharide having a granular amino group and a dispersion medium.   A tobacco filter composed of the tobacco filter material according to claim 1.   A method for reducing formaldehyde in tobacco smoke by constituting a tobacco filter with the tobacco filter material according to claim 1, wherein the retention rate of formaldehyde is maintained while maintaining nicotine and tar at a retention rate of 75% or more, respectively. Method to make it 65% or less.   A tobacco comprising the tobacco filter according to claim 14.