WO1987002869A1

WO1987002869A1 - Adsorbent for mutagenic substance contained in tobacco smoke and use thereof

Info

Publication number: WO1987002869A1
Application number: PCT/JP1986/000571
Authority: WO
Inventors: Shinichiro Kusunoki; Takuto Nishikawa; Michiko Yagi; Midori Kobayashi
Original assignee: Kabushiki Kaisya Advance
Priority date: 1985-11-12
Filing date: 1986-11-11
Publication date: 1987-05-21
Also published as: EP0246330A1; EP0246330A4

Abstract

An adsorbent for a mutagenic substance contained in tobacco smoke comprises a polysaccharide (e.g., cellulose) or its modified product (e.g., ion-exchanged polysaccharide).

Description

Ming Adsorbent for mutagens in tobacco smoke, its use Technical field

The present invention relates to an adsorbent for a mutagen present in tobacco smoke during smoking, a method of using the adsorbent, and a tobacco filter containing the adsorbent. Landscape technology

Various studies have shown that smoking increases the incidence of diseases such as lung cancer. Also, tobacco smoke contains a wide variety of carcinogens, such as polycyclic aromatic hydrocarbons such as benzo (a) pyrene and benzo (a) antracene. It has been confirmed that it is contained.

In light of the above, a variety of tobaccos with low tar values or low nicotine values have recently been marketed. However, when the mutagenicity of a limited amount of tobacco smoke concentrate (CSC) was tested by A mes test, low tar tar or low nicotine brand tobacco generally showed high levels. Follow the trend. In other words, it is considered that the amount of CSC and the risk of carcinogenesis correlate slightly. At this point, low tar tobacco is not necessarily considered to be low risk, and facts have become known. Therefore, it is considered necessary to evaluate the risk of carcinogenesis for tobacco using the total mutagenic activity per cigarette as an index. Therefore, an object of the present invention is to provide an adsorbent for a mutagenic substance which can significantly reduce the total mutagenic activity in tobacco smoke without lowering the original flavor of tobacco.

Another object of the present invention is to provide a method for removing mutagenic substances present in tobacco smoke using the adsorbent, and a filter for tobacco having the adsorbent. Disclosure of the invention

That is, the present invention relates to an adsorbent for a mutagenic substance present in tobacco smoke, comprising a polysaccharide or a modified product thereof.

The present invention also relates to a method for removing the mutagenic substance from tobacco smoke by adsorbing the mutagenic substance present in the tobacco smoke to a polysaccharide or a modified product thereof. '

Furthermore, the present invention relates to a filter for tobacco, particularly a filter for cigarettes, comprising a polysaccharide or a modified product thereof. BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between tar content and specific mutagenic activity in various cigarettes.

FIG. 2 is an explanatory view showing the structure of the filter of the present invention and a state in which the filter is mounted on a cigarette body.

FIG. 3 is a graph showing the relationship between the amounts of various adsorbents of the present invention and the total mutagenic activity.

FIG. 4 is a graph showing the relationship between the amount of the adsorbent having various particle diameters of the present invention and the mutagen removal rate. BEST MODE FOR CARRYING OUT THE INVENTION

As used herein, the term "polysaccharide" refers to a high molecular compound in which about 7 or more monosaccharide molecules are condensed, and includes not only monopolysaccharides composed of the same disaccharide molecule but also various monosaccharides. Saccharides include complex polysaccharides composed of derivatives thereof. Representative polysaccharides according to the present invention include cellulose, agarose, amirose, chitin, chitosan and derivatives thereof. Preferably, the polysaccharide is cellulose.

In the present invention, the above polysaccharide can be used as an adsorbent in any shape such as powder, granular material, porous rosemary fiber-like material, etc., but is used in the form of powder. I prefer to do it. The size of the powder is not particularly critical, but generally the average particle size is between 0.1 and 200'm, preferably between 0.1 and 40'm. Preferably, a powder of 1 to 10'm is used.

For polysaccharide powders, for example, mechanically process animal and plant raw materials (eg, crushing, cutting). Use what has been prepared. Typical examples of such powders include cellulose powder, such as cotton powder, pulp powder, hemp powder, or cellulose-based regenerated textile powder. Furthermore, crystalline cellulose powder obtained by subjecting pulp to hydrolysis or cellulose treatment is used. It is preferable to use fine particles having an average particle size of 0.1 to 200 m, particularly 1 to 10 m, as the crystalline cellulose powder. The use of fine particles with an average particle size of 1 to 10 m can maximize the mutagenic substance adsorption effect without changing the tobacco smoke suction resistance. It is preferable to separate the particles into an average particle size ^ m by centrifugation. Furthermore, agarose powder (eg, manufactured by Wako Pure Chemical Industries KK), amyloose powder (eg, manufactured by Hanoi Chemicals), chitin powder (eg, manufactured by Hanoi Chemicals KK), chitosan powder A body (eg, the chitin powder obtained by subjecting the chitin powder to an alkaline treatment) and the like can also be used.

In the present specification, “modified polysaccharide” means a material obtained by chemically modifying the above polysaccharide, particularly polysaccharide powder, and for example, ion exchange polysaccharide or hemipolysaccharide. And dyed polysaccharides.

The ion-exchanged polysaccharide is obtained by introducing various dissociable substituents into the polysaccharide, especially the powder thereof, to give an ion-exchange resin-like property. A typical example thereof is amino. Ethyl (AE) — Cellulose, Jethylaminocetyl (DEAE) — Senorelose, Triethylaminotechnyl (TE.4 £) — Cellulose, etc. — Cell-based anion exchanger , Carboxysimethyl (CM) — senorose, phosphate (P) — cellulose, snorejotyl (SE) — cell π — cell, etc. Paruru can cite the agarose-ion exchanger.

Hemin-stained polysaccharides are obtained by subjecting polysaccharides, especially powders, to ripening in an aqueous solution of 2-chloro-piethylamine and NaOH, followed by dyeing with hemin. In this case, for example, hemi-dyed cellulose powder is installed.

Since the mutagenic substance present in tobacco smoke is adsorbed to the adsorbent simply by bringing the adsorbent of the present invention into contact with tobacco smoke, the adsorbent of the present invention can be used in various modes. .

For example, the adsorbent of the present invention is combined with a cigarette filter. Can be used. In this case, the adsorbent of the present invention is blended into a foaming polymer such as, for example, polyvinyl alcohol (PVA) or polyvinyl formal (PVF), and then foamed. The adsorbent can be dispersed throughout the filter. The average particle size of the adsorbent compounded during the filter molding is preferably from 0.1 to 200 m, particularly preferably from 1 to 10 <um. Further, it can be used in such a form that it is dispersed between cellulose acetate fibers for a filter or that an adsorbent aggregate unit is inserted into the space between cellulose acetates. In this case, the average particle size of the adsorbent powder is preferably 50 to 200 <um. Further, it can be used by dispersing it in tobacco leaves. Furthermore, it can be effectively used as a component of a mutagen-removing layer in a pipe to be attached to a cigarette when smoking. '

The amount of the adsorbent of the present invention can be appropriately selected according to the conditions of use.However, when the adsorbent is used in one type, 1 to 500 pieces of tobacco is used. Use 100 g to 100 rag and 1 to 1 g per cigarette. Example

Hereinafter, the present invention will be described more specifically with reference to examples. Mutagenic activity assay

In the following Examples, mutagenic activity was measured by the following method. T / JP86 / 00571

The cigarette smoke particle phase is collected by an automatic suction device onto a ottoman glass filter GFZC (^ 37 «), and the filter is eluted with dimethyl sulfoxide (DMS0). (CSC) and used in the experiment in the form of a DMS0 solution. Suction was performed once every 20 seconds at a speed of 650 m / min for 2 seconds, and the suction was repeated 12 times with one cigarette. The mutagenicity of the obtained CSC (300 μg / plate) was determined by the method of Ames et al. [BNAmes et al., Utant Res. 3i, 347 (1975): Improved and improved Yahagi's pre-incubation method [ Takae Yahagi, Protein, Nucleus II, Enzyme, 1178 (1975). As the strain, a cell in the middle logarithmic phase of Sal 98 el la typhimurimn TA98 was used. When rat liver microgross fraction (S9) was added to CSC, strong mutagenicity was observed. Therefore, S9 (30 mg protein m 9) 100, and TA 9 8 strains (L 10 ⁸ ) 100 び CSC (0.3) D S0 solution 100 ΰ. S 9 mixed solution 500 ′ was used. For S9, an SD-based rat weighing about IC'Og was treated with polychlorinated biphenyl (PCB) to prepare an enzyme-induced liver. The amount of CSC was determined by measuring the absorbance at 260 nm with a spectrophotometer, calculating the weight per cigarette (), and measuring it with a precision electronic balance (! Let ler AE 163). .

Therefore, the total mutagenic activity of one cigarette is

S X C S C

T =

0.3

Is required. Where T is the total mutagenic activity of one cigarette

5 o 5

S is the number of restored colonies per plate (excluding the number of spontaneously restored colonies), and C S C is the number of cigarettes per cigarette.

C S C Weight ()

The mutagenic activity of CSC increases linearly from 400 to 500 βg / plate, regardless of the type of cigarette and the presence or absence of the filter. Therefore, the number of recovered colonies of 300 g / P1ate The total mutagenic activity was determined based on the above, and the specific mutagenic activity (Specific mutagenicity) was also shown under the same conditions.

Reference example: Comparison of specific mutagenic activity by cigarette brand

0 This reference example shows that the amount of cigarette tar and the mutagenic activity are correlated.

Calculated relative mutagenic activity based on the mutagenic activity measurement method for 9 brand cigarettes and imported cigarettes manufactured by Japan Tobacco Inc. In comparison, two to three times the difference was found for each issue. Next, since the amount of tar per I bottle differs depending on the brand, the ratio of the amount of tar and the variation of CSC ^ activity were compared. The amount of tar per hit and the specific mutagenic activity were inversely correlated, which revealed that the risk of carcinogenesis of low tar cigarettes was not necessarily low.

Fig. 1 compares the amount of tar in cigarettes and the specific mutagenic activity, and the specific mutagenic activity was calculated according to the method described above, using several hundreds of recovered colonies of CSC 300 μg / plate. Then, the number of return colonies per rag of CSC was shown (the average value of 20 cigarettes each). The amount of tarl per cigarette () is Japan I cited a cigarette industry brochure. The cigarettes whose results are shown in Figure 1 are Mild Seven (1), Seven Star (2), Cabin '85 Mild (3), Highlight (4), Mild Dossier light (5), Hope (6), Eco (7), Piece (8) びマセ以上以上以上以上 (1) The cigarettes (1) to (9) are made by Japan Tobacco Industry Co., Ltd.), furthermore, LQM (Rigid Manger) (10), Lark (Rigid) Majors (U), Norament 100's [Filip Morris: (12), Lark Mold 100's [Rejected Mars] ( 13), Lark 100's (Rejected Magic) (14), Serum Lite (L'J 'Reynolds) (15), Larks -No, 'One Lite [ Rigid Marsers (16), Rack Streamer (Brown-and-Dark Realm Sons) (17), Nuclear Gentlemen Console: Philip Morris) (18), Mor: Earl 'Jay Reynolds' (19), Jumpy MFD. DLRH' I.C. : Shows the result of (20). In Fig. 1, white circles indicate American cigarettes, and black circles indicate Japanese cigarettes.

Example 1: Comparison of mutagen removal rates due to differences in adsorbents

Various mutagen adsorbents were filled in the filter body (1) shown in Fig. 2 and the following experiment was performed. The filter body (1) in Fig. 2 consists of a cellulose acetate filter part (2) and a centrally located mutagen adsorbent filling space (3) located in the center of the filter part (2). (4) is connected to the cigarette body (5).

BAD ORKS '"L Acoco

Lively binn

Mutagenic ability of cellulose and cellulosic ion exchangers

Efficiency ^ 1 To compare Lulur, cellulose powder, Avicel (made by Asahi Kasei Corporation), and cellulose-based anion exchanger, DEAE-Cellulose (DE52; して) CM-Cellulose (CM52; manufactured by Petman) as a cellulosic anion exchanger, 25 each in the space of a cigarette filter (1) [Length 6 mm] was used for the experiment. Cigarettes were made by Rigid Mars (U.S.A.). The results are summarized in Table 1.

Table i Adsorbent Specific mutagenic activity Total mutagenic activity Peni-number / 300 β g of CSC) (co π ::-number / 1)

903-5 38 300 ± 2900 888 = 43 35 200 ± 1380 776 = 70 24 600 2760

D E A Ε— Cellulose 774 = 69 26000: 3620

2D

C ― Cellulose 738-102 19800-4410

2 D Numerical value 1 Average of Q examples ± standard error

Example 2: Comparison of mutagen removal rates according to the amount used

The same cellulose powder, DEAE-cellulose powder, and CM—cellulose powder used in Example 1 as 5, 10, 20, 25, and 30 rags, respectively, were added to the lacquer filter. Filling the space of 6 κπ »length located in the center of the ruta section, the total mutagenic activity per cigarette was compared. The results are summarized in FIG. To the graph in Fig. 3 o5 On the other hand, the total mutagenic activity index (%) on the vertical axis is expressed as a ratio with the total mutagenic activity obtained when the activated carbon was removed from the gap of the lark filter as 100%. In Fig. 3, X indicates the I mutagenic activity index in the presence of activated carbon 80, X (O) indicates cellulose powder, and Υ (Δ) indicates D-E- Cellulose powder,

Z (marked with D) shows the results when CM-cell α powder was used as a mutagen adsorbent.

Example 3: Panel test

A panel test was performed using the five types of filters used in Example 1. Evaluation is 7 levels compared to Filter No. 5 (very;; 3, 3; 2, 3; +1, equivalent; 0, ゃ bad; -1, bad; — 2, very bad;-3), the results of 17 people (12 males, 5 females) are summarized in Table 2. This shows that the filter of the present invention It shows that the characteristics are almost the same. In addition, the adsorbents shown in the filter shown in Table 2 are listed below.

Filter I. 1 = Activated carbon 80 rag (normal Lark filter) Filter o. 2 = Ahi 'cell 25 mg

Finale o. 3 = C M Cellulose 2 5

Ί-o-ruta o. 4 = secrerose 2 5 m &

Filter-5 = Activated carbon 0 mg (cell α-acetate filter only)

BAD OR '(3 / w, Table 2

1!

Filter No. J \ '

V 1 Taste <Sesshikiru Mild feeling 1

1! -2.6: -2.3; -2.4 + 1.09!

. ¹ 9: - 1.3; 0.9 '1.9 2.0 2.3:

; 3 - 0. 8; - 0 , 6; 1. - 1. 0 ÷ 1. 3;

! 4: -0.8: -0.4: 0.1.4.0.8;

0: 0 0 0 0

⁰ Example 4: Comparison of the effect of removing total mutagen due to the difference in particle size of crystalline cellulose _ powder

A pulp obtained by treating pulp obtained from Sanyo Kokusaku Parve with dilute sulfuric acid with an average particle size of 0.4 μm. 4 m4 0-. The powder ^ is mixed with foaming foam / vinyl alcohol (ΡVA) foam 11 and the resulting material is molded into a cylindrical shape with a diameter of 7 mm and a length of 10 mm.へへへへへ装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着装着The O It mutagenic activity was calculated per unit, and the mutagen removal rate of each UJ filter is shown in Fig. 4.

In Fig. 4, A (mark), B (mark), C (mark), and D (mark) each have a crystal of 0.4'm4m40'm100m. The relationship between the weight (g) of the crystalline cellulose powder contained in the foaming polymer (PVA) 1Φ made of cellulose powder and the removal rate of the mutagen was shown.

BAD -1

5 12 Example 5: Reduction of specific mutational activity of CSC in crystalline cellulose powder filter

An expandable polymer PVA containing 35 g / of crystalline cellulose powder having an average particle diameter of 4 m (manufactured by Asahi Kasei Corporation; Avicel SF) was prepared, and the diameter of the polymer was adjusted in the same manner as in Example 4. It is molded into a cylindrical filter with a length of 10, and the crystalline cellulose powder is placed together with the PVA filter. A smoking experiment was performed according to the method described above.

Japan Tobacco Sangyo Paper Cigarette Mail Seven, Longpi

10 cabins' 8 5 Mild Jet Reject Majors

The specific mutagenic activity of CSC was examined according to the method described above using 10 Lark FSKs (US). As shown in 袠, even cigarettes with misalignment have crystalline cellulose powder. 有し V Mutagenic activity was significantly reduced only when a ΑV filter was used. It was confirmed that a selective adsorption effect depending on the agent was used. The value is shown in the form of the mean = standard error, index 9 ₀ when the numbers in in Table 3 () with a full I filter no 100

20 Table 3 Specific mutagenic activity

(Return command-number / CSC 300, "g)

Mild Piping Cabin '85! . La chromatography click cell blanking down ¹ peak one scan Ma I le de FSK 1 full Note1 No 461 ± 33; 330 ± 22 624 = 82 '863 - 28!

(100) (100) (100) (100) ''

'PVA filter 508 ± 41; 348 ± 30 609 ± 40! 847 Sat 42:

(100), (105) (98); (98);

Microcrystalline cellulose 369-28; 271 ± 28 485 ± 16: 690-27:

: PVA containing powder (80); (82) (78)! (80); Fisoreta

! i! 1 Example 6: Total mutagen using hemi-stained cell alpha-powder powder

Substance removal effect and reduced specific mutation activity of CSC

Triethylaminocetinoreser ore obtained by reacting crystalline cellulose powder (Asahi Kasei Co., Ltd .; Ahicell SF) having an average particle size of 6 m with 2-chloroacetylamine. Cellulose was stained with hemin, and then unadsorbed hemin was sufficiently removed to obtain a hemi-stained cell mouth powder. An adsorbent was obtained by mixing 2% by weight of hemine-stained powder with α-crystalline powder that had been dyed. The total mutagen removal rate and specific mutagenic activity were measured in the same manner as in Examples 4 and 5.

The total mutagen removal rate is 45% when unfiltered cellulosic adsorbent alone is 0% when no filter is used, whereas hemi-stained cellulosic The value was 55 for the adsorbent containing 2% by weight of powder.

For specific mutagenic activity, cellulo-acetate-tofu When the filter was used at 0%, the non-stained cellulose adsorbent reduced by 15%, while the adsorbent containing 2% by weight of hemi-stained cellulose powder reduced by 30%. Was.

Thus, it was confirmed that by hemin-staining the crystalline cellulose powder, the total mutagen removal rate and the reduction rate of the specific mutagenic activity could be further increased.

Example 7: Panel test ''

A panel test was performed using the four filters of the present invention used in Example 4. Evaluation was performed on a five-point scale (very good; ÷ 2, good ぃ; +1; normal; 0, bad; -1; very bad; _2); 34 (34 males, Table 4 summarizes the results for 10 women). This indicates that the filter of the present invention has almost the same flavor characteristics.

A panel test was performed by mounting the filter on the holder part of the Mimphthalo finoleta made by Fance. For cigarettes, Mild Seven (Japan Tobacco Inc.) was used.

The adsorbent contained in the filter α 1 No. 6 is as follows.

Filter o. ΊController; no filter

Filter o.2 control; PVA filter

Filter 3 Average particle size 0.4 β m containing crystalline cellulose powder

PVA (35 g /) filter

Filter, o.4 Contains 4 μm average particle size crystalline cellulose powder

PVA (35 g / ί) Filter Να 5 Average particle size 40 β m Crystalline cellulose powder PVA (35 g /) filter

Filter α 6 Average particle size 100 m Contains crystalline cellulose powder

PVA (35 s / £) Filter

Table 4

Industrial applicability

The adsorbent of the present invention can effectively and selectively adsorb and remove mutagens in tobacco without lowering the original flavor of tobacco, and can be used for diseases such as lung cancer caused by smoking. It greatly contributes to lowering the appearance rate of

Claims

Scope of Claim West

1. An adsorbent for mutagens present in tobacco smoke, consisting of polysaccharides or denatured forms thereof.

2. The adsorbent according to claim I, wherein the polysaccharide or a modified product thereof is a powder.

3. The adsorbent according to claim 2, wherein the powder has an average particle size of 0.1 to 200 'm.

i 1

4. The adsorbent according to claim 1, wherein the polysaccharide is cellulose.

5. The adsorbent according to claim 4, wherein the cellulose is crystalline cellulose.

6. The adsorbent according to claim 1, wherein the denatured product is an ion exchange polysaccharide or a hemi-stained polysaccharide.

7. A method for removing the mutagen from tobacco smoke by adsorbing the mutagen present in the tobacco to the polysaccharide or its variant.

8. Tobacco filters containing polysaccharides or modified forms thereof

9. The filter according to claim S, wherein the tobacco is a cigarette.