JP5635782B2 - Granular composition carrying chitosan and cigarette filter containing the same - Google Patents

Description

  The present invention relates to a granular composition useful for selectively and efficiently removing aldehydes (particularly formaldehyde) while retaining taste components such as nicotine and tar, a method for producing the same, and a tobacco filter containing the granular composition The present invention relates to a cigarette provided with the cigarette filter.

  Traditionally, nicotine and tar are considered to be the main harmful components in tobacco smoke, and there has been interest in nicotine and tar delivery, and many countries have imposed nicotine and tar labeling obligations. However, nicotine itself is a favorite component of tobacco and is thought to be directly involved in smoking satisfaction. Further, regarding tar, it is not preferable to remove the tar component in the tobacco smoke component at a relatively high level because the flavor is impaired. That is, if smoke components with low volatility including tar and nicotine are indiscriminately removed, the taste becomes light and satisfaction cannot be obtained.

  Aldehydes, in particular formaldehyde, not only have an irritating odor, but are recently unfavorable for health, and are preferably removed as much as possible, as they are recently attracting attention as one of the causative agents of allergies. Therefore, there has been a demand for a tobacco filter that maintains the selective adsorption property of formaldehyde and has a small amount of adsorption of tar and nicotine.

  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. However, many of the basic components, particularly synthetic polymeric 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 this way, adsorbents using ordinary basic components are considered to be effective to some extent for removal of acidic substances and aldehydes, but there are problems with safety and effectiveness, and practical use as adsorbents for cigarette filters. It was not right.

  Among basic substances, chitosan derivatives such as chitin and chitosan are known not to cause crystallization or volatilization, are safe for the human body, and have antibacterial properties.

  Japanese Patent Application Laid-Open No. 11-100713 (Patent Document 1) 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.

  Tobacco filters using chitin and chitosan derivatives have also been proposed. JP-A-53-142600 (Patent Document 2) discloses a tobacco filter containing chitin or a chitin derivative in a proportion of 3 wt% or more with respect to the tobacco filter material. This document states that chitin and chitin derivatives possess an acetyl group in their structure, and thus give a unique light flavor to tobacco due to a synergistic effect with the acetyl group of acetate, especially when formulated in acetate filters. 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.

In JP-A-60-168373 (Patent Document 3), 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 described in this document is easier to adsorb tar and nicotine during use than filters made of triacetyl cellulose or rayon, and has an adsorbing ability 1.5 to 2 times that of conventional filters. doing.

  JP-A-62-211679 (Patent Document 4) 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, or in a form of being dispersed or sandwiched in the space of an acetate filter.

  JP-A-7-31452 (Patent Document 5) discloses a tobacco filter having 5 to 100% by weight of chitin or chitosan. As a specific method of using a chitin / chitosan solution, in Example 5, 80 mg of absorbent cotton was immersed in a 1% aqueous solution of chitin / chitosan (deacetylation degree 50%) and then vacuum-dried to obtain 20 mg of chitin / chitosan. It is described that 100 mg of impregnated absorbent cotton is filled into a paper tube to form a filter chip, and a filter having a nicotine collection rate of 48%, a tar collection rate of 45% and an acrolein collection rate of 72% is obtained.

  However, cigarette filters using chitin and chitosan derivatives as described above are relatively safe for the human body, but remove not only aldehydes such as formaldehyde but also nicotine and tar. Therefore, the taste (or savory taste) is impaired. Furthermore, chitosan and the like are hard and brittle themselves, and in the case of a filter made of chitosan fibers, the chitosan fibers dropped from the filter may be sucked into the human body and damage the bronchial flagella. In addition, as described in Patent Document 5, even when chitosan particles are added to a cellulose acetate filter commonly used as a smoke filter for cigarettes, the particles fall off, and bronchial flagella can be removed in the same manner as described above. There is a possibility of hurting.

  Japanese Patent Application Laid-Open No. 2007-319041 (Patent Document 6) discloses a tobacco filter in which an amino acid solution is attached to a fiber of cellulose acetate generally used in a tobacco filter. In this invention, a carrier (such as a carrier having a tow structure of cellulose ester fiber) is treated in the form of a solution with an amino acid or a salt thereof (and an acidic component such as a hydroxy acid if necessary). It describes that aldehydes (particularly formaldehyde) can be efficiently removed while maintaining the taste (or flavor) component at a high level. Further, it is described that since the granular material is not included in the filter material, the influence on the ventilation resistance is small and the taste can be maintained. This cigarette filter is described as being useful for selectively and efficiently removing formaldehyde while retaining taste components such as nicotine and tar. It is described that such a tobacco filter can efficiently and selectively remove formaldehyde, and can maintain a nicotine and tar in the smoke passing through the tobacco filter at a retention rate of 80% or more and a formaldehyde removal rate of 60% or more. ing. However, amino acids are expensive and raise the price of the filter material.

  WO2006 / 070662 (Patent Document 7) discloses a material for a tobacco filter in which a carrier is coated with a polysaccharide having an amino group and a polar solvent. In this invention, the carrier is a tow structure carrier, (i) chitosan having an average degree of deacetylation of 70% or more is 3 to 15 parts by weight with respect to 100 parts by weight of the carrier, and (ii) a solvent having a hydroxyl group. 9 mol or more in terms of hydroxyl group with respect to 1 mol of the glycose unit of the chitosan, and (iii) monohydroxy C2-6 alkane monocarboxylic acid is 0 in terms of carboxyl group with respect to 1 mol of the glycose unit of the chitosan. The tobacco filter material according to claim 7, which contains 0.5 to 2 mol. In this invention, it is described that a moisturizing component may be further contained. As a specific moisturizing component, polyglycerin (diglycerin, triglycerin, etc.) is disclosed. In the examples, 123 mg of water was added as a polar solvent in Example 1 containing no humectant, and the removal rate of formaldehyde was 66%. In Example 6, 6 mg of water and 28 mg of glycerin as a humectant were added. It is described to show a removal rate of 57% formaldehydes. Thus, an invention of a material for a tobacco filter useful for selectively removing formaldehyde selectively while retaining taste components such as nicotine and tar has been disclosed.

  Japanese Patent Application Laid-Open No. 2008-48650 (Patent Document 8) discloses a tobacco filter material composed of a polysaccharide containing an amino group and silica gel, and a tobacco filter using the same. In this invention, the tobacco filter is composed of a tobacco filter material composed of a polysaccharide having at least one amino group selected from amino acids and aminosulfonic acids and silica gel having an average pore diameter of 20 nm or more. Is described. In the tobacco filter material of the present invention, (i) the polysaccharide having an amino group is chitosan, and (ii) silica gel has an average water content of 0.10 to 0.10 at an average pore diameter of 25 nm or more, a temperature of 22 ° C. and 60% RH. It is described that it is 1.00% silica gel, and (iii) the ratio of the polysaccharide having an amino group may be 0.05 to 10 parts by weight with respect to 100 parts by weight of silica gel. Further, it is described that a humectant may be included, and it is described that such a humectant may be composed of polyols (for example, glycerin and the like). And it is described that such a moisturizing agent is useful for efficiently improving the selective adsorption property of aldehydes by the tobacco filter material.

  As described in Patent Document 7 and Patent Document 8 above, when chitosan is used, it is described that the moisturizing agent is effective in improving the selective adsorptivity of formaldehydes and contains the moisturizing agent. The purpose of this is to retain water in the filter material, and the technique of Patent Document 7 and Patent Document 8 described above loses the effect of reducing formaldehyde when water is lost.

Japanese Patent Application Laid-Open No. 11-100713 JP 53-142600 A JP 60-168373 A JP-A-62-111679 Japanese Unexamined Patent Publication No. 7-31452 JP 2007-319041 A WO2006 / 077062 JP 2008-48650 A

  An object of the present invention is to provide a granular composition suitable for a tobacco filter capable of efficiently removing aldehydes (particularly formaldehyde) and a method for producing the same.

  Another object of the present invention is to provide a cigarette filter using the above granular composition and a cigarette using the cigarette filter.

This invention provides the granular composition containing the composite_body | complex by which chitosan salt was carry | supported to the cellulose acetate particle | grains satisfy | filling requirements (a)-(d) as a solution means of a subject.
(A) Particle size of cellulose acetate particles: 1.7 to 0.1 mm
(B) Specific surface area of cellulose acetate particles is 0.1 to 1000 m ² / g
(C) The bulk specific gravity of the cellulose acetate particles is 0.1 to 0.6.
(D) The limonene absorption amount of cellulose acetate particles is 1 to 60%.

The present invention provides a solution to other problems.
It is a manufacturing method of the granular composition of Claim 1 or 2, Comprising:
Dissolving chitosan salt in water to obtain an aqueous chitosan salt solution,
Step of immersing cellulose acetate particles in chitosan salt aqueous solution or spraying chitosan salt aqueous solution onto cellulose acetate particles,
After taking out cellulose acetate, the manufacturing method of a granular composition which has the process of drying under reduced pressure and obtaining a composite_body | complex is provided.

The present invention provides a solution to other problems.
It is a manufacturing method of the granular composition of Claim 1 or 2, Comprising:
Dissolving chitosan salt in water to obtain an aqueous chitosan salt solution,
A step of adding an alkali to the aqueous chitosan salt solution as necessary,
Step of immersing cellulose acetate particles in chitosan salt aqueous solution or spraying chitosan salt aqueous solution onto cellulose acetate particles,
After taking out cellulose acetate, the manufacturing method of a granular composition which has the process of heat-drying and obtaining a composite_body | complex is provided.

  The present invention provides a cigarette filter containing the above particulate composition and a cigarette provided with the cigarette filter.

  The granular composition of the present invention is excellent in selective adsorption with respect to aldehydes, particularly formaldehyde.

2 is an SEM photograph of a cross section of the granular composition of Example 1. FIG. The figure which shows the relationship between the amount of limonene absorption using the granular composition of Examples 10-13, and formaldehyde retention.

<Granular composition>
The granular composition of the present invention contains a composite in which chitosan salt is supported on cellulose acetate particles that satisfy the following requirements (a) to (d).

Requirement (a)
The particle size (measured by the method described in Examples) of the cellulose acetate particles is 1.7 to 0.1 mm, preferably 1.0 to 0.18 mm, and more preferably 0.85 to 0.25 mm.

  As for the particle size of requirement (a), the amount of 90% by mass or more passes through a sieve having a mesh opening (JIS Z 8801-1 2006) of 1.7 to 0.1 mm (however, a sieve having a mesh opening of 1.7 mm) 0.1 mm sieve does not pass through). Therefore, it means that the sieves of the upper limit values in the above ranges pass, but do not pass the sieves of the lower limit values.

By setting it as such a particle size, there is almost no influence on the ventilation resistance calculated | required by the tobacco filter raw material. In the case of a normal porous granular material, the particle size and the specific surface area have a correlation, and when the particle size is as in the present invention, the specific surface area decreases. However, cellulose acetate is characterized by its production method.

That is, cellulose acetate is acetylated by reacting cellulose with acetic anhydride in the presence of an acetic acid solvent to obtain cellulose acetate (primary cellulose acetate) almost completely substituted with an acetyl group. Subsequently, this primary cellulose acetate is adjusted to a desired degree of acetylation by adding water in a dissolved state of an acetic acid solution to obtain cellulose acetate. The obtained cellulose acetate having the desired degree of substitution becomes a concentrated solution (dope) dissolved in an acetic acid solvent. By adding water to the dope, the cellulose acetate is precipitated from the diluted cellulose acetate solution to obtain a solid cellulose acetate.

  Cellulose acetate, as its solids are called flakes, is the first step in the precipitation process described above, when the high-viscosity polymer comes into contact with a non-compatible solvent, so Solidification occurs. At this stage, since the concentration of acetic acid in the polymer solution is high, the polymer exists in a polymer solution state dissolved in a solvent, but gradually solidifies as a dilute acetic acid solution enters the domain. In the solidification stage, the volume of the cellulose acetate polymer solution and the volume of the solid cellulose acetate are naturally different, so that they are precipitated as a porous body that is connected or disconnected.

By such a process for producing cellulose acetate, it is possible to obtain a granular material having a specific specific surface area and a limonene absorption amount while maintaining the specific particle size. For this reason, even if the particle size is large as described above, an appropriate specific surface area can be obtained. In addition, the cellulose acetate particle used by this invention can be manufactured by passing through the precipitation process in manufacture of said general cellulose acetate, and does not require special processing. As will be described later, it is obtained by selecting the particle size from commercially available cellulose acetate.

  In addition, since the chitosan salt is carried in the surface and pores of the cellulose acetate particle, the influence on the particle size is small, and the particle size of the cellulose acetate particle and the particle size of the composite may be considered to be substantially the same. .

Requirement (b)
The specific surface area of cellulose acetate particles (exemplary measured by the method of Example described) is 0.1~1000m ² / g, preferably 1~200m ² / g, more preferably 2~50m ² / g, better Preferably it is 2-20 m < ² > / g. As described above, in the case of cellulose acetate particles, it is unlikely that the chitosan salt is preferentially coated on the particle surface, and the chitosan salt is supported so as to be coated on the surface and pores of the cellulose acetate particle. This is probably because the specific surface area of the cellulose acetate particles and the composite hardly changes.

Requirement (c)
The bulk specific gravity (measured by the method described in Examples) of the cellulose acetate particles is 0.1 to 0.6, preferably 0.2 to 0.6, and more preferably 0.3 to 0.5. .

Requirement (d)
The limonene absorption amount (measured by the method described in the examples) of the cellulose acetate particles is 1 to 60%, preferably 10 to 50%, more preferably 20 to 40%, particularly preferably 20 to 30%, and better. Preferably it is 20 to 25%.

  The degree of acetylation of the cellulose acetate particles may be in the range of 43 to 62%, but is preferably 50 to 58%.

The content of cellulose acetate particles in the composite is preferably 80 to 99.5% by mass, more preferably 85 to 98% by mass, and still more preferably 90 to 95% by mass. Chitosan salt (in terms of chitosan amount) ) Is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, still more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 2.0% by mass. Yes and contains water.
When the content ratio of the chitosan salt is increased, the formaldehyde reduction rate tends to decrease because the pores of cellulose acetate are blocked. Conversely, when the content ratio of the chitosan salt decreases, the amount of chitosan salt having a formaldehyde reducing effect decreases, and the chitosan salt does not reach all the pores, so the formaldehyde reduction rate is also lowered.

  The mercury intrusion method cumulative pore volume is also closely related to the formaldehyde reduction rate. If the mercury intrusion method cumulative pore volume is larger than 0.3 ml / g, the formaldehyde reduction effect is large, and the preferred range is as follows. 0.3 to 0.7 ml / g.

  The composite contains water as described above, and the content of water is 2 to 10% by mass, preferably 3 to 9% by mass, particularly preferably 4 to 7% by mass, and more preferably 4 to 6%. % By mass. When the water content is increased, the water may be affected by microorganisms such as soot in the air and an odor may be generated. Moreover, when decreasing, the load of a drying process will become great.

  The granular composition can contain other components added to, for example, a tobacco filter, but does not contain a humectant such as glycerin. In the present invention, formaldehydes are efficiently absorbed by supporting chitosan on cellulose acetate particles having a specific specific surface area and a limonene absorption amount without containing a humectant. Examples of other components include various known fragrances described in Japanese Patent No. 2770977, Japanese Patent No. 311468, and Japanese Patent Application Laid-Open No. 11-178562.

<The manufacturing method of a granular composition>
(1) 1st manufacturing method Each process in the following may be implemented as a separate process, and may implement two or more processes as one process.

In the first step, chitosan is dissolved in an aqueous solution of the corresponding acid (eg, lactic acid) to obtain an aqueous chitosan salt solution. The chitosan salt is salted to make it water-soluble because chitosan itself is insoluble in water.
For example, chitosan Xg is added to purified water Yg, dispersed by stirring, 50 mass% lactic acid aqueous solution Xg is added dropwise thereto and stirred to dissolve chitosan, and Z mass% of chitosan lactate (Z mass% = {1.5X / (2X + Y)} × 100) aqueous solution is obtained. Furthermore, it is also a preferred method to add water to the prepared chitosan lactate Z mass% aqueous solution and adjust the concentration as necessary.

The chitosan used in the present invention preferably satisfies the following requirements.
Those having a degree of deacetylation of 70% or more, more preferably those having a degree of deacetylation of 80% or more.
When the aqueous solution viscosity of an acetic acid 1 mass% aqueous solution at 20 ° C. is measured with a B-type viscometer (rotation speed 30 r / m, rotor No. 1), the value is 3 to 100 mPa · s.

  The acid used in the present invention is preferably an organic acid listed in a food additive official standard, but lactic acid is preferred because it does not smell.

  The concentration of the chitosan salt aqueous solution is preferably 0.5 to 15% by mass. When dipping or spraying in the next step, it is preferable to adjust the concentration of the aqueous solution so that the cellulose acetate particles to be added can be completely immersed or sprayed.

  In the next step, cellulose acetate particles are immersed in an aqueous chitosan salt solution. Note that two steps can be combined into one by simultaneously adding chitosan and cellulose acetate particles to the acid aqueous solution.

  In this step, the amounts of both components are adjusted so that the cellulose acetate particles and the chitosan salt (in terms of the amount of chitosan) have the above-mentioned content ratio.

Immersion can be left for 1 to 60 minutes at room temperature (20 to 30 ° C.) in a state where cellulose acetate particles are completely immersed in an aqueous chitosan salt solution, or can be stirred as necessary. At that time, vacuum degassing may be performed.
The spraying may be performed so that the aqueous chitosan salt solution and the cellulose acetate particles can sufficiently come into contact with each other, and the spraying can be directly transferred to the next drying step after the spraying.

  In the next step, the cellulose acetate carrying the chitosan salt is taken out and then dried under reduced pressure to obtain a composite.

  The drying under reduced pressure is performed at a pressure of −40 kPa or less, preferably −80 kPa or less until the water content in the composite is 10% by mass or less, preferably 5% by mass or less. The temperature during drying is preferably from room temperature to 80 ° C, and more preferably from 40 to 60 ° C.

  The reason for drying under reduced pressure as described above is to avoid drying at high temperature. In the method for producing a composite of the present invention, when hot air drying is performed at a high temperature, the formaldehyde reduction rate is lowered because the properties of the chitosan salt change. This reduction is particularly noticeable when performed at temperatures that greatly exceed the boiling point of water. Since water has a large latent heat, it is dried by applying heat energy exceeding the latent heat to the material at an industrially high temperature for drying. For this reason, although depending on the temperature of the heat medium, industrial drying is often performed at a temperature of about 150 ° C.

  When dried at such a high temperature, the object of the present invention is not achieved. However, when dried with hot air at a temperature close to the boiling point of water (105 ° C.), the composite is not effective due to the latent heat of water. Since the temperature is less than 100 ° C., the object of the present invention may be achieved. However, when hot-air drying is performed at such a temperature, the formaldehyde adsorptivity is inferior to that obtained by the above-described reduced-pressure drying.

(2) Second Production Method In the second production method, the step of obtaining chitosan salt aqueous solution by dissolving chitosan in the corresponding acid aqueous solution is the same as the first production method.

  In the second production method, either a method of adding an alkali to the chitosan salt aqueous solution or a method of not adding an alkali can be selected. When no alkali is added, it is the same as the first production method except for the drying method.

  When adding an alkali to chitosan salt aqueous solution, a well-known alkali is used and there is no limitation in particular, Sodium hydroxide, sodium carbonate, and sodium hydrogencarbonate are preferable. The pH after addition of alkali is preferably 4 to 9, and more preferably 7.5 to 8.5. When alkali is added and heat-dried, productivity can be improved without impairing the selective adsorption performance of formaldehyde of the granular composition, which is preferable.

  In the next step, cellulose acetate particles are immersed in an alkali-added chitosan salt aqueous solution or an alkali-free chitosan salt aqueous solution. In the step of adding an alkali to the chitosan salt aqueous solution, cellulose acetate particles may be immersed in the chitosan salt aqueous solution in advance, and the pH may be adjusted by adding alkali thereto. These steps are immersed in the same manner as in the first manufacturing method. Moreover, it can also spray like the 1st manufacturing method.

In the next step, the cellulose acetate carrying the chitosan salt is taken out and then dried by heating to obtain a composite.
The heat drying is performed at a temperature of 40 to 150 ° C., preferably 60 to 120 ° C., until the water content in the composite is 10% by mass or less, preferably 5% by mass or less. For drying, a method of blowing hot air at normal pressure, a method of leaving in a predetermined temperature atmosphere, or the like can be applied.

  The composite obtained by applying the first production method or the second production method described above has a chitosan salt supported on the surface of cellulose acetate particles serving as a carrier and mainly in the pores thereof. It is.

  The granular composition of the present invention may consist only of a composite obtained by applying the first production method or the second production method, or may further contain other components such as a fragrance. Good. When it contains a fragrance | flavor, you may make it contain in the manufacture of a composite_body | complex, However, It is preferable to make it contain after a drying process.

  The granular composition of the present invention can selectively adsorb aldehydes, particularly formaldehyde. This adsorptive action decreases when it contains a humectant such as glycerin.

<Tobacco filter and tobacco>
The tobacco filter of the present invention includes the above granular composition, and the particulate composition may be dispersed in the filter tow, and a layer made of the granular composition is formed on a part of the tobacco filter. It may be a thing. In addition, in order to solve the subject of this invention, a tobacco filter does not need to contain moisturizing agents, such as glycerol.
The cigarette of the present invention is provided with the above-described cigarette filter, and is excellent in selective adsorption with respect to aldehydes, particularly formaldehyde.

  The measuring method of each item shown in Table 1 is as follows.

(A) Particle size of 90% by mass or more The particle size was measured using an electromagnetic vibration sieving separator MS-200 manufactured by Ito Manufacturing Co., Ltd. with an amplitude of 2 mm and a time of 2 minutes.

(B) Specific surface area Determined by the BET method (using nitrogen gas).

(C) Bulk specific gravity Bulk specific gravity (ρ) is measured on a rubber sheet with a thickness of 1 mm, which is packed in a 300 ml graduated cylinder with about 150 ml of a sample whose mass (Wg) has been measured in advance, and laid horizontally on an experimental table. Put. Next, with the bottom of the graduated cylinder kept as horizontal as possible, it was dropped approximately 10 times vertically from a height of about 10 mm, and the exact volume (Vml) was measured with the memory of the graduated cylinder. Calculated by the formula.
ρ = W / V

(D) Limonene absorption (mass%)
When 10 g of granular cellulose acetate is placed in an Erlenmeyer flask and D-limonene (Wako Pure Chemical Reagent grade 1) is added to the Erlenmeyer flask, the granular cellulose acetate is not completely absorbed until the flask begins to get wet with D-limonene. The addition amount (xg) was measured (measured at a room temperature of 22 ° C.) and obtained by x / (10 + x) × 100.

(Degree of acetylation)
The acetylation degree was measured according to the measurement method of the acetylation degree of ASTM: D-817-91 (testing method for cellulose acetate and the like).
First, 1.9 g of dried cellulose acetate was precisely weighed and dissolved in 150 ml of a mixed solvent of acetone and dimethyl sulfoxide (volume ratio 4: 1), 30 ml of 1N sodium hydroxide aqueous solution was added, and 2% at 25 ° C. Saponify time. Next, after adding a phenolphthalein solution as an indicator and titrating excess sodium hydroxide with 1N-sulfuric acid, the acetylation degree is calculated according to the following formula. In addition, a blank test is performed by the same method.
Degree of acetylation (%) = [6.005 × (BA) × F] / W
(In the formula, A is the number of ml of 1N-sulfuric acid required for the titration of the sample, B is the number of ml of 1N-sulfuric acid required for the titration of the blank test, F is the concentration factor of 1N-sulfuric acid, and W is the weight of the sample. ).

(Production of tobacco samples)
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 (length: 20 mm, inner diameter: 8 mm) on the filter part on the long piece (ie, tobacco leaf filling piece) side, and a length (11 mm) corresponding to the remaining filter length of the long piece (to the end of tobacco leaf filling) ) Inserted and bound with sealing tape.

  100 mg of the granular composition to be evaluated was filled into the space of the glass tube having a length of 9 mm protruding by the insertion of the glass tube. Next, the open end of the glass tube was plugged using the previously cut short piece (that is, the filter part having a length of 14 mm). And the sealing tape was wound around the connection part of this glass tube and a filter, and it sealed, and the tobacco sample for a smoking test was obtained. Therefore, the filter length of the cellulose diacetate crimped fiber tow is 25 mm. Also, the extended portion between the filters is filled with 100 mg of granular composition per cigarette.

  Moreover, the tobacco sample used as a control | contrast was obtained like preparation of the said tobacco sample except not filling a granular composition.

  Smoking experiments were conducted on these tobacco samples to evaluate formaldehyde retention, nicotine retention and tar retention.

(Nicotine retention rate, tar retention rate)
Smoking using a tobacco sample with a piston-type constant-volume automatic smoker (RM20 / CS manufactured by Borgwald) at a flow rate of 17.5 ml / second and a smoking time of 2 seconds / time and a smoking frequency of 1 time / minute. It was. Nicotine and tar in the smoke that passed through the tobacco sample 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.

Retention rate of nicotine and tar according to the following equation, where Tn and Tt are the amounts of nicotine and tar adhering to the Cambridge filter of the control cigarette sample, and Cn and Ct are the amounts of nicotine and tar adhering to the Cambridge filter in the comparative examples and examples. Was calculated.
Nicotine retention rate (%) = 100 × Cn / Tn
Tar retention (%) = 100 × Ct / Tt

(Formaldehyde retention)
Smoking using a tobacco sample with a piston-type constant-volume automatic smoker (RM20 / CS manufactured by Borgwald) at a flow rate of 17.5 ml / second and a smoking time of 2 seconds / time and a smoking frequency of 1 time / minute. It was. The formaldehyde in the smoke that passed through the tobacco sample was 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 retention rate was calculated by the following formula, using the amount of formaldehyde collected by the control cigarette as Tf and the amount of formaldehyde collected in the following Comparative Examples and Examples as Cf. The smaller the formaldehyde retention rate, the better the adsorption performance of formaldehyde.
Formaldehyde retention (%) = 100 × Cf / Tf

Production Example 1 (Production of cellulose acetate particles)
Cellulose acetate L-40 manufactured by Daicel Chemical Industries, Ltd. is classified using 1.0 mm and 0.425 mm sieves (JIS Z 8801-1 2006), and the particle size is in the range of 1.0 to 0.425 mm ( However, cellulose acetate particles A having a mesh size of 1.0 mm but not passing through a 0.425 mm sieve were obtained.

  In addition, cellulose acetate L-40, LT-55, LM-80, and LL-10 manufactured by Daicel Chemical Industries, Ltd. are classified using sieves of 1.0 mm and 0.18 mm openings (JIS Z 8801-1 2006). Then, cellulose acetate particles B, C, D and E having a particle size in the range of 1.0 to 0.18 mm (however, passing through a sieve having an aperture of 1.0 mm but not passing through a sieve having a mesh size of 0.18 mm) are obtained. It was.

Production Example 2
(Preparation of lactate aqueous solution of chitosan)
10 g of chitosan (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Daichitosan VL deacetylation degree 83%, viscosity 7 mPa · s ) was added to 80 g of purified water, and the mixture was stirred and dispersed. Thereto, 10 g of 50% by mass lactic acid aqueous solution (manufactured by Musashino Chemical Laboratory Co., Ltd.) was added dropwise and stirred to dissolve chitosan to obtain 100 g of chitosan lactate (15%) aqueous solution.
Based on the aqueous solutions prepared above, aqueous solutions having various concentrations of chitosan lactate used in Examples 1 to 13 and Comparative Examples 1 to 4 were prepared.

Examples 1-5, Comparative Examples 1-3
In 50 ml of a lactate aqueous solution of chitosan having a concentration shown in Table 1, 5 g of cellulose acetate particles A having (a) to (d) and an acetylation degree shown in Table 1 were immersed at room temperature (20 to 25 ° C.). In Comparative Examples 1 to 3, glycerin was added to a chitosan lactate aqueous solution before immersion of the cellulose acetate particles.

  Then, after leaving it in that state for 5 minutes, cellulose acetate particles carrying chitosan lactate were taken out.

Then, it dried for 240 minutes in the reduced pressure atmosphere of -84 kPa at 60 degreeC, and obtained the composite_body | complex (granular composition) of this invention. Table 1 shows the formaldehyde retention test results.

  1 is an SEM photograph of the composite obtained in Example 1. FIG. It can be confirmed that there are many pores of about 0.1 μm to several μm. Moreover, since chitosan salt particles are not recognized, it is considered that the chitosan salt is supported on the surface and pores of the cellulose acetate particles in a state where a film is formed.

  In the SEM photograph, the granular composition was cut with a razor to obtain a cross-section, and platinum deposition was performed for SEM observation. A typical cross section was observed at a magnification of 10000, and cracks found in the cross section were observed at a magnification of 5000, each at two locations. In the 10000x photo, the black part corresponds to the hole. Since no particulate matter was observed on the surface of the pores, it was estimated that chitosan lactate formed a film.

Example 6 and Comparative Example 4
5 g of cellulose acetate particles A having the degree of acetylation (a) to (d) shown in Table 2 were immersed in 50 ml of a 3.0 mass% aqueous solution of chitosan lactate at room temperature (20 to 25 ° C.). In Comparative Example 4, glycerin was added to the chitosan lactate aqueous solution before the immersion of the cellulose acetate particles.

  Then, after leaving it in that state for 5 minutes, cellulose acetate particles carrying chitosan lactate were taken out.

  Thereafter, it was dried with hot air at 105 ° C. for 100 minutes to obtain a composite (granular composition) of the present invention. Table 2 shows the test results of the formaldehyde retention rate.

Examples 7-9
In Example 7, a composite was produced in the same manner as in Example 6. In Example 8, a complex was produced in the same manner as in Example 6, except that the pH of the lactate aqueous solution of chitosan was adjusted. Further, Example 9 is a step of adding alkali to the chitosan salt aqueous solution, and in the same manner as in Example 6 except that cellulose acetate particles were previously immersed in the chitosan salt aqueous solution and pH was adjusted by adding alkali thereto. The composite was manufactured. For comparison, together with the composites of Examples 1 and 6, the test results of formaldehyde retention are shown in Table 3.

Examples 10-13
In 50 ml of a lactate aqueous solution of chitosan having a concentration shown in Table 4, 5 g of each of cellulose acetate particles B, C, D and E having the degree of acetylation shown in Table 4 was added at room temperature (20 to 20). (25 ° C.). Then, after leaving it in that state for 5 minutes, cellulose acetate particles carrying chitosan lactate were taken out.

  Then, it dried for 240 minutes in the reduced pressure atmosphere of -84 kPa at 60 degreeC, and obtained the composite_body | complex (granular composition) of this invention. Table 4 shows the test results of formaldehyde retention rate, nicotine retention rate and tar retention rate.

Moreover, about the granular composition of Examples 10-13, the cumulative pore volume measured by the following mercury intrusion method is also shown in Table 4.
(Measurement of pore size distribution by mercury intrusion method)
Measuring device: Fully automatic pore distribution measuring device
PoreMaster 60-GT (QuantaChromeCo.)
Sample pretreatment: None Sample amount: About 0.3 to 0.5 g
Sample cell: Small cell (10Φ × 30mm, 0.5sec)
Measurement range: High range Measurement range: Pore diameter 0.0036 μm to 10 μm
Calculation range: Pore diameter 0.0036 μm to 10 μm
Mercury contact angle: 140deg
Mercury surface tension: 480 dyn / cm
Measurement cell volume: 0.5 sec

  This result shows that these granular compositions can reduce formaldehyde while maintaining the nicotine retention rate and tar retention rate in cigarette mainstream smoke at 90% or more.

  FIG. 2 shows the relationship between the oil absorption amount (limonene absorption amount) of cellulose acetate particles used as the raw material of the granular composition obtained in Examples 10 to 13 and the reduction rate of formaldehyde (100-formaldehyde retention rate). It is a graph. It was confirmed that the reduction effect of formaldehyde was increased by increasing the amount of limonene absorbed.

Example 14
Further, a test was conducted in the same manner as in Example 3 using chitosan having a high degree of deacetylation. 2 g of chitosan (manufactured by Dainichi Seika Kogyo Co., Ltd .: trade name: Daichitosan 100D, degree of deacetylation 98%, viscosity 50 mPa · s ) was added to 96 g of purified water and dispersed by stirring. Thereto, 2 g of 50% by mass lactic acid aqueous solution (Musashino Chemical Laboratory Co., Ltd.) was added dropwise and stirred to dissolve chitosan to obtain 100 g of chitosan lactate (3%) aqueous solution. Based on the obtained aqueous chitosan solution, a formaldehyde retention test was conducted in the same manner as in Example 3. As a result, it was 60%.

Claims (4)

A method for producing a granular composition comprising a composite in which a chitosan salt is supported on cellulose acetate particles, which satisfies the following requirements (a) to (d):
Dissolving chitosan salt in water to obtain an aqueous chitosan salt solution,
Adding an alkali to the chitosan salt aqueous solution,
Step of immersing cellulose acetate particles in chitosan salt aqueous solution or spraying chitosan salt aqueous solution onto cellulose acetate particles,
The manufacturing method of a granular composition which has the process of taking out cellulose acetate and heat-drying and obtaining a composite_body | complex.
(A) Particle size of cellulose acetate particles: 1.0 to 0.18 mm
(B) Specific surface area of cellulose acetate particles is 1 to 200 m ² / g
(C) The bulk specific gravity of cellulose acetate particles is 0.2 to 0.6.
(D) The limonene absorption amount of cellulose acetate particles is 5 to 50%.   The method for producing a granular composition according to claim 1, wherein the heat drying step is a step of drying at a temperature of 60 to 150 ° C until the water content becomes 10% by mass or less. A method for producing a granular composition comprising a composite in which a chitosan salt is supported on cellulose acetate particles, which satisfies the following requirements (a) to (d):
Dissolving chitosan salt in water to obtain an aqueous chitosan salt solution,
Adding an alkali to the chitosan salt aqueous solution,
Step of immersing cellulose acetate particles in chitosan salt aqueous solution or spraying chitosan salt aqueous solution onto cellulose acetate particles,
The manufacturing method of a granular composition which has the process of taking out cellulose acetate and drying under reduced pressure and obtaining a composite_body | complex.
(A) Particle size of cellulose acetate particles: 1.0 to 0.18 mm
(B) Specific surface area of cellulose acetate particles is 1 to 200 m ² / g
(C) The bulk specific gravity of cellulose acetate particles is 0.2 to 0.6.
(D) The limonene absorption amount of cellulose acetate particles is 5 to 50%.   The composite according to any one of claims 1 to 3, wherein the composite contains cellulose acetate particles 80 to 99.5 mass%, chitosan salt (in terms of chitosan amount) 0.1 to 20 mass%, and water. The manufacturing method of the granular composition of 1 item | term.