1296506 九、發明說明： 【發明所屬之技術領域】 本發明有關香煙用過濾器及具備該過濾器之香煙，特 別是有關主流煙中的氮氧化物（NOx)去除效率優異之香煙 用過滤、裔及具備該過遽器之香煙。 【先前技術】 目刖，對香煙有種種要求。其中之一係要求降低香煙 的主/瓜煙中的NOx量（日本專利特開2〇〇2_11927〇號公 2002-119270 過慮器之長絲（filament)中含有原花青素（pr〇cyanidin)類之 香煙過濾器。 然而，已知先前的於草過渡器，並不能以令人滿意的 程度從主流煙去除NOx。 【發明内容】 因而，本發明之目的在於提供一種能從菸草主流煙中 •有效去除氮氧化物之香煙用過濾器、以及具備該過滤器之 香煙。 依據本發明，可提供含有添加2_苯基_4,4,5,5_四甲基 咪唑啉-3-氧化物小氧基之香煙用過濾器素材之香煙用二 濾器。 再者，依據本發明，亦可提供具備本發明的香煙用過 濾器之香煙。 【實施方式】 [發明之最佳實施形態] 317279 5 1296506 . 以下’就本發明加以詳細說明。 本發明的香煙用過濾器，係於香煙用過濾器素材中添 =2-笨基乂4,5>四甲基咪唑啉_3_氧化物_ ι _氧基（打犯) 、、於本發明的香煙過濾器中，屬於去除氮氧化物的有效 成刀之PTIO，其本身係一種既知的化合物（例如，參考曰 本專利特開平9-43153號公報）。 本發明的香煙用過濾器中之過濾器素材，可使用乙酸 "f維素酯之纖維束（tow)、濾紙（filtering paper)、活性碳等 •多孔質粒狀載體。使用乙酸纖維酯纖維束作為素材時，對 纖雉束噴霧PTIO,即可使其添加。如使用濾紙時，可使濾 紙中含浸PTIO。如此所得之過濾器素材，可依通常方法使 用包裝材料（Wrapper)捲取後，連接於香煙的一端。 使用活性碳等的多孔質粒狀載體作為過濾器素材時， 在夕孔貝載體粒子添加pTI〇後，進行所得之ρτι〇載持粒 鲁子之所謂孔腔填充（cavity filling)，或添加於 纖維束。關於 孔腔填充之方法，具體上可於過濾器捲取紙管的兩端部設 置平布過濾器（plain filter)，並於此等平布㉟滤器之間的孔 腔中填充PTIO載持粒子。另一方面，關於纖維束添加之 方法，係依與市售香煙的活性碳過濾器（charcoal filter)同 枚的手法，使PTIO載持粒子分散於乙酸酯過濾器的纖维 之間。 ΡΤΙ〇Θ相對於過濾器素材每100重量份，較佳為添加3 至10重里伤、特佳為添加5至7重量份。ρτι〇在相當於1296506 IX. The invention relates to a filter for cigarettes and a cigarette provided with the same, and particularly relates to a filter for cigarettes having excellent nitrogen oxide (NOx) removal efficiency in mainstream smoke. And a cigarette with the filter. [Prior Art] It is seen that there are various requirements for cigarettes. One of them is to reduce the amount of NOx in the main/smoke of cigarettes. (Japanese Patent Laid-Open No. 2〇〇2_11927 No. 2002-119270 The filament of the filter contains pr〇cyanidin cigarettes. However, it is known that previous grass transitioners do not remove NOx from mainstream smoke to a satisfactory extent. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an effective removal of tobacco mainstream smoke. a filter for cigarettes of nitrogen oxides, and a cigarette provided with the filter. According to the present invention, it is possible to provide a small oxygen containing 2_phenyl-4,4,5,5-tetramethylimidazolinium-3-oxide Further, according to the present invention, a cigarette including the filter for cigarettes of the present invention can be provided. [Embodiment] [Best Embodiment of the Invention] 317279 5 1296506 . The present invention will be described in detail below. The filter for cigarettes of the present invention is added to the filter material for cigarettes by adding 2-2-stirth 4,5>tetramethylimidazoline_3_oxide_ ι _ oxygen Base (offence), in the present invention In the cigarette filter, the PTIO which is an effective knives for removing nitrogen oxides is a known compound (for example, refer to Japanese Laid-Open Patent Publication No. Hei 9-43153). For the material, a porous plasmid-like carrier such as tow, filter paper, activated carbon, etc. of acetic acid "f-dimensional ester ester. When using cellulose acetate fiber bundle as a material, spray PTIO on the fiber bundle beam. If it is used, the filter paper can be impregnated with PTIO. The filter material thus obtained can be wound up by a wrapper according to the usual method and attached to one end of the cigarette. When the porous plasmid-like carrier is used as a filter material, after the pTI〇 is added to the sulphate carrier particles, the obtained ρτι〇 carries the so-called cavity filling of the granules, or is added to the fiber bundle. The method of filling the cavity, in particular, a plain filter can be arranged at both ends of the filter take-up paper tube, and filled in the cavity between the flat cloth 35 filters PTIO carries particles. On the other hand, the method of adding fiber bundles is based on the same method as the activated carbon filter of a commercially available cigarette, and the PTIO-supporting particles are dispersed in the fiber of the acetate filter. Between the dimensions, ΡΤΙ〇Θ is preferably added in an amount of 3 to 10 parts by weight, and particularly preferably 5 to 7 parts by weight, per 100 parts by weight of the filter material.
^MllQ 6 .1296506 實際抽煙狀態之濕潤狀態下，仍能顯著降低香煙主流煙中 的NO及NOx。 以下，藉由實施例說明本發明，惟本發明並不因此等 實施例而有所限定。 實施例1 〈添加PTIO之活性碳的調製〉 將PTIO(和光純藥工業（股）製，CAS : 18390-00-6) 10mg、30mg、50mg以及100mg，分別完全溶解於乙醇 鲁2490mg、2470mg、2450mg以及2400mg中，分別調製濃 度為0.4重量％、1.2重量％、2重量％以及4重量％的PTIO 乙醇溶液。各乙醇溶液中，添加預先在200°C下真空加熱 乾燥之椰子殼活性碳（日本環境化學品公司製；比表面積： 約1200m2/g) lg，使用試管混合機攪拌60秒鐘。然後，於 50°C的水浴中一面喷入氮氣一面去除溶劑乙醇，在120°C 下真空加熱乾燥後製得添加PTIO之活性碳。測定結果為 #用PTIO濃度0.4重量％的乙醇溶液所得之添加PTIO之 活性碳，係添加相當於活性碳重量的1 %之PTIO(添加PTIO 之活性碳I)，使用PTIO濃度1.2重量％的乙醇溶液所得之 添加PTIO之活性碳，係添加相當於活性碳重量的3%之 PTIO(沃加PTIO之活性碳II)，使用PTIO濃度2重量％的 乙醇溶液所得之添加PTIO活性碳，係添加相當於活性碳 重量的5%之PTIO(添加PTIO之活性碳III)，使用PTIO濃 度4重量％的乙醇溶液所得之添加PTIO之活性碳，係添加 相當於活性碳重量的10%之PTIO(添加PTIO之活性碳 7 ^11ΊΊ0 .1296506 ιν) 〇 <香煙試樣的製作> 作為香煙支（tabaco rod)，採用市售的美國牌香煙支。 於此香煙支的一端，裝上由上述所得之添加PTIO之活性 碳填充而成之過濾器塞頭（filter plug)。過濾器塞頭係於兩 端裝上5mm長的平布過濾器（plain filter)(由乙酸纖維酯纖 維束構成），對該等平布過濾器之間的孔腔以最緊密方式填 充添加PTIO之活性碳粒子Omg、50mg、100mg以及 • 200mg，惟並未設置通氣孔（ventilation hole)。 <NO及NOx量的測定〉 於抽煙器（候克瓦特（Borgwaldt)公司製RM26)上裝上 製得之香煙試樣，並依下述條件使其燃燒。 吸煙容量 喷煙時間 噴煙間隔 喷煙次數 17.5ml/噴煙（puff) 2秒鐘/喷煙 58秒鐘 7次 就7次噴煙（有抽煙）及空喷煙（燃燒終了後1次）的各種 情形，將通過法蘭絨濾布（Cambridge filter)後的煙稀釋20 倍（捕集於預先灌注有17.5mLx 19=332.5mL氮氣之鋁袋 中），依化學發光法（chemiluminescene)測定NO及NOx的 濃度。從所得濃度計算NO及NOx的重量，將全喷煙和空 喷煙時的計算重量值合計，作為一支香煙的輸出（delivery) 量。為比較起見，使用未添加PTIO之活性碳製作同樣香 煙試樣，依同樣方式求出一支香煙的輸出量。NO及N〇x ΊλΙΊΙΟ 1296506 煙Γ未連接有過濾器之兩頭裁切紙煙同樣求得 之一支香煙的N〇u〇x輪出量作為基準加二 NO的降低率(%)表示於第i圖 二：加？异。將 用添加PTI0之活性碳j的 圖中，、線a表示使 之活…的結果;線。表二用=使用添力，。 的妹罢·妗rl主- 〜、、加PTIO之活性碳ΠΙ 則、Γ — #、用/不使用添加PTI0之活性碳的結果；而線e 貝j衣不使用無添加PTI0之活性碳的結果。 - 從=圖所示結果可知，含有添加m〇之活性碳粒 之過濾斋’ * No f較不含ρτι 火" 減少。牲則β ^ ^ 舌丨生奴拉子者顯著 1 NO的Ρ夂Γ， #有3至1〇重量％的PTI0之活性碳， ，助的降低效果顯著較高。临的降低率，转示 述NO的降低率同樣傾向。 、/、 實施例」^ ^ 實^ !所調製之添加ρτι〇之活性碳π，在溫 ^ 相1濕度60%之下實施吸濕處理至達成平 止，製得經吸濕且添加ΡΤΙΟ之、、卜 u◦之活性石反111。除使用該經吸 =且添加mo之活性碳m以外，其餘則依照實施例】同 樣=式製作香煙，以求出主流煙中的N〇降低率。其結果 士第2圖所不。第2圖中，、線a表示使用經吸濕且添加阳〇 之活性碳m的結果、線b表示使用除了未添加ρτι〇之 外，同樣實施吸濕處理之活性碳的結果。從第2圖所示結 果可知，貫施吸濕處理時，Ν0降低率會較經乾燥且添加 有ΡΉΟ之活性碳ΠΙ時（實施例】）稍微降低，惟能較活性 ^17979 9 1296506 . 碳單獨者顯著降低N 〇量，可知即使假設在實際抽煙（相當 於50%過濾器通氣（filter ventilation))時，ΡΤΙΟ能充分發揮 減少NO量之效果。N0x的降低率亦顯示與上述n〇的降 低率同樣傾向。 實施例3 除了將實施例1所製作之香煙試樣之抽煙容量作成 35mL/喷煙以外’其餘則按與實施例i同樣條件下使其燃 燒。對於使用未添加PTIO之活性碳之香煙試樣，亦按抽 煙容量35mL/喷煙使其燃燒，以計算主流煙中的n〇降低 率。其結果如第3圖所示。第3圖中，線&表示使用添加 ptI0之活性碳m的結果、線b表示使用未添加ρτι〇之 活性碳的結果。從第3圖所示結果可知，如增加抽煙容量， 即與貫施例1的情形比較，雖然Ν〇降低率會下降，惟使 用：加卿之活性碳m之試樣，係顯示較使用未添加 ^τιο之活性碳之香煙試樣顯著較高的购降低率之事實。 ΝΟχ降低率亦顯示與^^〇降低率同樣傾向。 貝 實施例4 將與實施例2同樣的香煙試樣（使用經吸濕之 照貫施例3同樣條件使其燃燒，以計算_降） ^添加ΡΤΙ〇之活性碳之香煙試樣，亦算出NO降低^ …结果如第4圖所示。第4圖中，線a表示使用添加阳〇 之活性碳的結杲、、線b表示使用未添加m〇之活性石炭的 ]〇^MllQ 6 .1296506 Under the wet state of the actual smoking state, it can still significantly reduce NO and NOx in cigarette mainstream smoke. The invention is illustrated by the following examples, but the invention is not limited thereto. Example 1 Preparation of Activated Carbon with PTIO Addition PTIO (manufactured by Wako Pure Chemical Industries, Ltd., CAS: 18390-00-6) 10 mg, 30 mg, 50 mg, and 100 mg, respectively, completely dissolved in ethanol 2490 mg, 2470 mg, In 2450 mg and 2400 mg, PTIO ethanol solutions having a concentration of 0.4% by weight, 1.2% by weight, 2% by weight, and 4% by weight, respectively, were prepared. To each of the ethanol solutions, coconut shell activated carbon (manufactured by Nippon Environment Chemical Co., Ltd.; specific surface area: about 1200 m 2 /g) lg, which was previously dried under vacuum at 200 ° C, was added, and stirred for 60 seconds using a test tube mixer. Then, the solvent ethanol was removed while spraying nitrogen gas in a water bath at 50 ° C, and dried under vacuum at 120 ° C to obtain activated carbon to which PTIO was added. The measurement result was # PTIO-added activated carbon obtained by using a PTIO concentration of 0.4% by weight in an ethanol solution, and 1% of PTIO (activated carbon I added with PTIO) corresponding to the weight of activated carbon was added, and PTIO concentration of 1.2% by weight of ethanol was used. The PTIO-added activated carbon obtained by the solution was added with PTIO (Wojia PTIO activated carbon II) equivalent to 3% by weight of activated carbon, and PTIO activated carbon was added by using PTIO concentration of 2% by weight in ethanol solution. PTIO (activated carbon III added with PTIO) at 5% by weight of activated carbon, PTIO-added activated carbon obtained by using a PTIO concentration of 4% by weight in ethanol solution, adding PTIO equivalent to 10% by weight of activated carbon (adding PTIO) Activated carbon 7^11ΊΊ0 .1296506 ιν) 〇<Production of cigarette sample> As a cigarette branch, a commercially available American cigarette branch was used. At one end of the cigarette holder, a filter plug filled with the PTIO-added activated carbon obtained as described above was attached. The filter plug is fitted with a 5 mm long plain filter (consisting of cellulose acetate fiber bundles) at both ends, and the pores between the flat cloth filters are filled in the tightest manner to add PTIO. Activated carbon particles Omg, 50 mg, 100 mg, and • 200 mg, but no ventilation holes were provided. <Measurement of NO and NOx Amount] A cigarette sample prepared was attached to a smoker (RM26, manufactured by Borgwaldt Co., Ltd.), and burned under the following conditions. Smoking capacity, smoke time, smoke interval, smoke spray interval, 17.5ml, puff, 2 seconds, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke, smoke The tobacco after the flange filter was diluted 20 times (trapped in an aluminum bag pre-filled with 17.5 mL x 19 = 332.5 mL of nitrogen), and the NO and NOx were measured by chemiluminescene. concentration. The weights of NO and NOx were calculated from the obtained concentrations, and the calculated weight values at the time of full-spraying and empty-spraying were totaled as the amount of delivery of a cigarette. For the sake of comparison, the same cigarette sample was prepared using activated carbon without PTIO, and the output of one cigarette was obtained in the same manner. NO and N〇x ΊλΙΊΙΟ 1296506 Two cuts of cigarettes without a filter attached to the soot are also obtained. The reduction rate (%) of the N〇u〇x round of one cigarette is taken as the reference plus the second NO. Figure 2: Plus? different. In the figure in which the activated carbon j of PTI0 is added, the line a indicates the result of making it live; Table 2 uses = add force. The sister 妗 主 rl main ~ ~, plus PTIO activated carbon ΠΙ, Γ - #, with / without the use of PTI0 added activated carbon results; result. - From the results shown in the graph, it is known that the filter containing the activated carbon particles added with m〇 is less than the ρτι fire " Sacrifice is β ^ ^ tongue scorpion born slaves significantly 1 NO Ρ夂Γ, # 3 to 1 〇 wt% of PTI0 activated carbon, the help of the reduction effect is significantly higher. The rate of reduction of the initial rate is similar to that of the rate of reduction of NO. / /, Example "^ ^ Real ^! The added activated carbon π of ρτι〇 is prepared, and the moisture absorption treatment is carried out under the humidity of 60 °% of the temperature to achieve the flattening, and the moisture absorption and the addition of hydrazine are obtained. ,, Bu, the active stone counter 111. Except that the activated carbon m was used and the mo was added, the cigarettes were produced in the same manner as in the examples to determine the N〇 reduction rate in the mainstream smoke. The result is not shown in Figure 2. In Fig. 2, the line a shows the result of using the activated carbon m which is hygroscopic and added with impotence, and the line b shows the result of using the activated carbon which was subjected to the moisture absorption treatment in addition to the addition of ρτι〇. From the results shown in Fig. 2, it can be seen that when the hygroscopic treatment is applied, the Ν0 reduction rate is slightly lower than that of the dried and activated cerium-incorporated activated carbon ruthenium (Example), but it is more active than 17979 9 1296506. Separately, the amount of N 〇 was significantly reduced, and it was found that even if it is assumed to be actually smoking (corresponding to 50% filter ventilation), the effect of reducing the amount of NO can be sufficiently exerted. The reduction rate of N0x also shows the same tendency as the above-described decrease rate of n〇. (Example 3) The smoking capacity of the cigarette sample produced in Example 1 was changed to 35 mL/spraying, and the others were burned under the same conditions as in Example i. For cigarette samples using activated carbon to which no PTIO was added, a smoke volume of 35 mL/smoke was also burned to calculate the rate of decrease in n〇 in mainstream smoke. The result is shown in Fig. 3. In Fig. 3, the line & indicates the result of using the activated carbon m to which ptI0 is added, and the line b indicates the result of using the activated carbon to which no ρτι is added. From the results shown in Fig. 3, if the smoking capacity is increased, that is, compared with the case of the first embodiment, although the rate of reduction of hydrazine will decrease, the use of the sample of the activated carbon m of Jiaqing is displayed. The fact that the cigarette sample of activated carbon of ^τιο was significantly higher was reduced. The reduction rate of ΝΟχ also shows the same tendency as the reduction rate of ^^〇. Example 4 A cigarette sample similar to that of Example 2 (combustion was carried out under the same conditions as in the case of moisture absorption to calculate _ drop) ^ A cigarette sample of activated carbon added with hydrazine was also calculated. NO decreases ^ ... The result is shown in Figure 4. In Fig. 4, the line a indicates the use of the crucible in which the activated carbon of the impotence is added, and the line b indicates the use of the activated charcoal to which the m crucible is not added.
^17?7Q 1296506 結杲。從第4圖所示結杲可知，如增加抽煙容量，盘實施 =的情形比較，雖然N〇降低率會下降，惟使用添加、ρτι〇 /舌性碳之香煙試樣，能顯示較使用未添加ΡΤΙΟ之活性 =香煙試樣顯著較高的Ν0降低率之事實。降低率 亦…員示與NO降低率同樣傾向。 如上所述，本發明的香煙用過濾器，可怂夭4 煙中有效去除氮氧化物。了攸香煙之主流 【圖式簡單說明】 Μ第1圖係表示實施例1及比較例所製作之香煙之主冷 煙中的NO降低率之曲線圖。 之主抓 第2圖係表示實施例2及比較例所製 煙中的NO降低岸之曲線圖。 日煙之主抓 击第3圖係表*實施例3及崎例所製作 主 煙中的NO降低率之曲線圖。 煙之主肌 第4圖係表示實施例4及比較例制 f中的NO降低率之曲線目。 衣日煙之主流^17?7Q 1296506 Scarred. As can be seen from the cruscation shown in Figure 4, if the smoking capacity is increased, the disc implementation is compared, although the N〇 reduction rate will decrease, but the cigarette sample added with ρτι〇/tongue carbon can be displayed. Addition of sputum activity = the fact that the cigarette sample has a significantly higher Ν0 reduction rate. The rate of reduction is also the same as that of the NO reduction rate. As described above, the filter for cigarettes of the present invention can effectively remove nitrogen oxides in the smoke. The mainstream of sputum cigarettes [Simplified description of the drawings] Fig. 1 is a graph showing the NO reduction rate in the main cold smoke of cigarettes produced in Example 1 and Comparative Example. Fig. 2 is a graph showing the NO reduction shore in the smoke produced in Example 2 and Comparative Example. The main smoker of Japan is the graph of the reduction rate of NO in the main smoke produced by the third embodiment. The main muscle of the smoke Fig. 4 shows the curve of the NO reduction rate in Example 4 and Comparative Example f. Mainstream of clothing