WO2010114095A1 - Cigarette and method for processing cigarette materials - Google Patents

Cigarette and method for processing cigarette materials Download PDF

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Publication number
WO2010114095A1
WO2010114095A1 PCT/JP2010/056020 JP2010056020W WO2010114095A1 WO 2010114095 A1 WO2010114095 A1 WO 2010114095A1 JP 2010056020 W JP2010056020 W JP 2010056020W WO 2010114095 A1 WO2010114095 A1 WO 2010114095A1
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Prior art keywords
acid
transition metal
tobacco
cigarette
organic acid
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PCT/JP2010/056020
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French (fr)
Japanese (ja)
Inventor
菅井　一紀
康信 井上
清弘 笹川
近藤　満
阪井　敦
貞子 今井
文子 村田
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日本たばこ産業株式会社
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Application filed by 日本たばこ産業株式会社 filed Critical 日本たばこ産業株式会社
Priority to JP2011507290A priority Critical patent/JP5250694B2/en
Priority to ES10758866.7T priority patent/ES2593112T3/en
Priority to EP10758866.7A priority patent/EP2415362B1/en
Publication of WO2010114095A1 publication Critical patent/WO2010114095A1/en
Priority to US13/250,117 priority patent/US20120024303A1/en

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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/281—Treatment of tobacco products or tobacco substitutes by chemical substances the action of the chemical substances being delayed
    • A24B15/282—Treatment of tobacco products or tobacco substitutes by chemical substances the action of the chemical substances being delayed by indirect addition of the chemical substances, e.g. in the wrapper, in the case
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D1/00—Cigars; Cigarettes
    • A24D1/02—Cigars; Cigarettes with special covers

Definitions

  • the present invention relates to a method for treating cigarettes and cigarette materials.
  • Patent Document 1 describes that a catalyst made of Fe 2 O 3 nanoparticles is added to a tobacco cut filler.
  • a complicated process is required to prepare fine metal oxide nanoparticles.
  • Patent Document 2 describes that high surface area carrier particles supporting nanoscale metal particles or metal oxide particles are added to a tobacco cut filler.
  • a more complicated process such as derivation of the high surface area carrier particles from the colloidal solution is required.
  • Patent Document 3 describes that a metal oxyhydroxide is added to a wrapping paper, a tobacco cut filler, a filter, and the like. Patent Document 3 shows in Table 1 that the CO reduction rate when a metal oxyhydroxide is added is 29%. This CO reduction rate is lower than the 33% CO reduction rate shown in Table 1 when the metal oxide and calcium carbonate are added from the beginning.
  • An object of the present invention is to provide a cigarette and a method for treating a cigarette material in which carbon monoxide in mainstream smoke is further reduced.
  • a cigarette comprising a tobacco cut rod and a wrapping paper surrounding an outer peripheral surface of the tobacco cut rod, wherein the tobacco cut and / or the wrapping paper contains a transition metal salt of an organic acid.
  • a method for treating a cigarette material including treating tobacco cuts and / or wrapping paper with a transition metal salt of an organic acid.
  • carbon monoxide in cigarette mainstream smoke can be significantly reduced.
  • FIG. 1 is a configuration diagram of an apparatus for analyzing carbon monoxide reduction ability using a model gas.
  • FIG. 2 is a graph showing the heating temperature of the reaction tube filled with the organic acid transition metal salt and the concentration of carbon monoxide in the gas passing through the reaction tube.
  • the cigarette of the present invention includes a rod of tobacco and a wrapping paper that wraps around the outer peripheral surface of the rod.
  • the tobacco cut is a cut or crushed tobacco material and can contain suitable additives.
  • the tobacco material can be burley tobacco, yellow tobacco, orient tobacco tobacco leaf or leaf tobacco bone, fermented tobacco, dark cured tobacco or reconstituted tobacco material, or mixtures thereof.
  • additives include natural or synthetic flavors, polyhydric alcohols such as glycerin and propylene glycol, sugar alcohols such as erythritol, xylitol, and sorbitol, hyaluronic acid, and the like.
  • the wrapping paper itself that wraps the rod of tobacco is a wrapping paper used for ordinary cigarettes.
  • agricultural by-product fibers such as bagasse, non-wood fibers such as bamboo, and the like can be used as the raw material for the wrapping paper.
  • Wrapping paper also contains white ashing agents and combustion modifiers such as aluminum hydroxide, aluminum sulfate, aluminum oxide, magnesium oxide, talc, titanium dioxide, and carbonic acid, formic acid, acetic acid, malic acid, citric acid, tartaric acid, lactic acid. And any one or more of sodium, potassium, calcium and magnesium salts of nitrate.
  • the tobacco cut and / or the wrapping paper contains a transition metal salt of an organic acid.
  • the organic acid include fumaric acid, citric acid, oxalic acid, formic acid, benzoic acid, lactic acid, and stearic acid. Of these, organic acids having 2 to 7 carbons in total are preferred, fumaric acid, citric acid and oxalic acid are more preferred, and fumaric acid is particularly preferred.
  • the transition metal is at least one selected from the group consisting of Ti, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ce, Ir, Pt, and Au. These metals can be used. Fe, Cu, and Mn are preferable, and Fe is particularly preferable.
  • transition metal salts of organic acids added to tobacco cuts and / or wrapping paper are decomposed and converted to transition metal oxides during tobacco combustion, and its catalytic action reduces carbon monoxide in mainstream smoke.
  • a catalyst is automatically generated by the combustion heat of tobacco.
  • the transition metal salt of an organic acid functions as a precursor of a carbon monoxide reduction catalyst, and generates a catalyst by burning cigarettes.
  • the above-mentioned transition metal salt of an organic acid is preferably contained in an amount of 1 to 50% by weight with respect to tobacco. If it is less than 1% by weight, the carbon monoxide reducing ability tends not to be exhibited sufficiently. On the other hand, if it exceeds 50% by weight, it is not preferable because it becomes difficult to process tobacco.
  • the transition metal salt of organic acid is preferably contained in the wrapping paper at a rate of 0.1 to 50 g / m 2 . If the amount is less than 0.1 g / m 2 , the carbon monoxide reducing ability tends not to be fully exhibited. An amount exceeding 50 g / m 2 can make the paper wrapper difficult to process.
  • the transition metal salt of an organic acid When included in a wrapping paper, it preferably has a particle size of 0.05 to 5 ⁇ m from the viewpoint of smoothness of the wrapping paper and retention in the wrapping paper.
  • the present invention also relates to a method for treating a cigarette material including treating tobacco cuts and / or wrapping paper with the above-mentioned transition metal salt of an organic acid.
  • a solution obtained by dispersing the transition metal salt of the organic acid in an organic solvent (not dissolving the transition metal salt of the organic acid) is distributed on tobacco and / or wrapping paper.
  • Any organic solvent may be used as the organic solvent, and examples thereof include alcohols such as ethanol.
  • the aqueous solvent it becomes difficult for the aqueous solvent to distribute more than the amount absorbed by the wrapping paper.
  • the transition metal salt of an organic acid is dispersed in an organic solvent, it is more preferable to add an emulsifier and use it in a slurry state.
  • the emulsifier may be any known one used as a food additive, such as lecithin.
  • the emulsifier can be used in an amount of 1% to 50% by weight of the transition metal salt of the organic acid. If it is less than 1%, the dispersion effect is not sufficiently exhibited, and if it exceeds 50%, the decomposition of the transition metal salt of the organic acid is hindered.
  • transition metal salt of an organic acid can be kneaded into tobacco, or can be applied to a wrapping paper. Furthermore, the transition metal salt of an organic acid can also be blended into a paper furnish when making a paper wrapper.
  • the method for treating a cigarette material of the present invention is a very simple method in which a cigarette material (tobacco carved and / or cigarette wrapping paper) is treated with a transition metal salt of an organic acid.
  • a cigarette material tobacco carved and / or cigarette wrapping paper
  • a transition metal salt of an organic acid As will be described later, carbon monoxide in mainstream smoke can be further reduced by such a simple method as compared with iron oxide nanopowder that has been considered to be excellent.
  • Example 1 Using model gas, the carbon monoxide reducing ability of transition metal salts of various organic acids added to the cigarette of the present invention was examined.
  • iron was used as the transition metal.
  • organic acid iron salt iron citrate was manufactured by Nacalai Tesque, and other organic acid iron salts were manufactured by Wako Pure Chemical.
  • an iron salt of an organic acid particles that passed through a sieve diameter of 75 ⁇ m were used.
  • FIG. 1 shows an apparatus for analyzing the ability to reduce carbon monoxide of an organic acid transition metal salt.
  • the organic acid iron of Example 1 containing the amount of iron shown in Table 1 below was charged into the reaction tube 9 installed in the heating furnace 8.
  • Carbon monoxide (CO) gas and carbon dioxide (CO 2 ) are supplied from gas cylinders 3 and 5 via mass flow meters 4 and 6, respectively, and water is measured with electronic balance 1, and from metering pump 2 Supplied. Together with the CO gas and CO 2 gas, the water was passed through the evaporator 7 (200 ° C.). Water evaporates into water vapor.
  • a model gas (CO concentration: 4 mol%, CO 2 concentration: 8 mol%, H 2 O concentration: 10 mol%, nitrogen balance) was prepared in the evaporator 7.
  • the flow rate of this model gas was set so that the space velocity (SV) was 500,000 h ⁇ 1 , and the model gas was circulated through the organic acid iron salt layer filled in the reaction tube 9. While raising the temperature of the organic acid iron layer in the reaction tube 9 from 200 ° C. to 900 ° C., the model gas was circulated for 3.5 hours.
  • PG is a pressure gauge
  • TIC is a thermometer that measures the temperature of the tube wall of the reaction tube 9
  • TI is a thermometer that measures the temperature of the packed bed. The temperature measured by the thermometer TIC is used as a monitor temperature for control when heating by the heating furnace 8.
  • Table 1 shows the results of carbon monoxide oxidation amount of each organic acid iron, carbon monoxide oxidation amount per mol of iron element, and carbon monoxide removal rate. What is shown as “additive” in the table is iron organic acid.
  • Comparative Example 1 The carbon monoxide removal rate and the like were measured under the same conditions as in Example 1 except that iron oxide (iron tetroxide) powder (manufactured by Sigma-Aldrich) was added instead of the organic acid iron salt. The results are also shown in Table 1.
  • Examples 2 to 3 Carbon monoxide reducing ability was examined under the same conditions as in Example 1 except that organic acid copper and organic acid manganese were used instead of the organic acid iron salt. The results are shown in Tables 2 and 3. In these examples, the transition metal salt of the organic acid was made by Wako Pure Chemical.
  • a preferred particle size is 0.05 to 5 ⁇ m.
  • a slurry was prepared by dispersing iron fumarate in 30 mL of the above ethanol / lecithin mixed solution. It was found that iron fumarate can be added to the tobacco cut by spraying the slurry using a sprayer so that the iron fumarate is 10% by weight with respect to the tobacco cut weight.
  • Example 5 In this example, the action mechanism of a transition metal salt of an organic acid will be considered.
  • a tobacco tube (2R4F) 100 mg and iron fumarate 10 mg were mixed and packed in a sample tube.
  • This sample tube was set in a catalyst analyzer (BELCAT, manufactured by Nippon Bell Co., Ltd.).
  • a model gas (CO: 3.39 mol%, O 2 : 2.19 mol%, He: remainder) was circulated through the sample tube, and the temperature was raised at 40 ° C./min, and the temperature was raised from 200 ° C. to 800 ° C. The CO concentration was measured.
  • the results are shown in FIG.
  • the cigarette was oxidized and burned at around 600 ° C., and after the carbon monoxide temporarily increased, the carbon monoxide tended to decrease. From this, it can be presumed that the iron fumarate was heat-treated at around 600 ° C., so that the iron fumarate was decomposed into iron oxide and functioned as a catalyst.

Abstract

Disclosed is a cigarette equipped with a rod of tobacco cut filler and wrapping paper that is wrapped around the outer periphery of the aforementioned rod of tobacco cut filler. A transition metal salt of an organic acid is included within the tobacco cut filler and/or the wrapping paper.

Description

シガレットおよびシガレット材料の処理方法Cigarette and cigarette material processing method
　本発明は、シガレットおよびシガレット材料の処理方法に関する。 The present invention relates to a method for treating cigarettes and cigarette materials.
　これまで、シガレット主流煙中に存在する一酸化炭素を除去するために、タバコ刻、巻紙またはフィルタに、貴金属触媒や遷移金属酸化物触媒を添加することによって、一酸化炭素を酸化して二酸化炭素に変換することが提案されている。 Until now, in order to remove carbon monoxide present in cigarette mainstream smoke, carbon monoxide is oxidized to carbon dioxide by adding a noble metal catalyst or transition metal oxide catalyst to cigarettes, wrapping paper or filters. It has been proposed to convert to
　例えば、特許文献１には、タバコカット充填材にＦｅ2Ｏ3のナノ粒子からなる触媒を添加することが記載されている。しかし、微細な金属酸化物のナノ粒子を調製するには煩雑な工程が必要になる。特許文献２には、タバコカット充填材に、ナノスケールの金属粒子または金属酸化物粒子を担持させた高表面積担体粒子を添加することが記載されている。しかし、ナノスケールの金属粒子または金属酸化物粒子を高表面積担体粒子に担持させるには、高表面積担体粒子をコロイド溶液から誘導するなど、さらに煩雑な工程が必要になる。 For example, Patent Document 1 describes that a catalyst made of Fe 2 O 3 nanoparticles is added to a tobacco cut filler. However, a complicated process is required to prepare fine metal oxide nanoparticles. Patent Document 2 describes that high surface area carrier particles supporting nanoscale metal particles or metal oxide particles are added to a tobacco cut filler. However, in order to support the nanoscale metal particles or metal oxide particles on the high surface area carrier particles, a more complicated process such as derivation of the high surface area carrier particles from the colloidal solution is required.
　特許文献３には、金属オキシ水酸化物を巻紙、タバコカットフィラーおよびフィルタ等に添加することが記載されている。特許文献３は、その表１に、金属オキシ水酸化物を添加した場合のＣＯ低減率は２９％であることを示している。このＣＯ低減率は、同表１に示された、当初から金属酸化物と炭酸カルシウムを添加した場合のＣＯ低減率３３％よりも低い。 Patent Document 3 describes that a metal oxyhydroxide is added to a wrapping paper, a tobacco cut filler, a filter, and the like. Patent Document 3 shows in Table 1 that the CO reduction rate when a metal oxyhydroxide is added is 29%. This CO reduction rate is lower than the 33% CO reduction rate shown in Table 1 when the metal oxide and calcium carbonate are added from the beginning.
特表２００５－５２２２０６号公報JP 2005-522206 A 特表２００７－５２７６９８号公報Special table 2007-527698 米国特許出願公開第２００５／０１５５６１６号明細書US Patent Application Publication No. 2005/0155616
　本発明は、主流煙中の一酸化炭素がより一層低減したシガレットおよびシガレット材料の処理方法を提供することを目的とする。 An object of the present invention is to provide a cigarette and a method for treating a cigarette material in which carbon monoxide in mainstream smoke is further reduced.
　本発明の第１の側面によれば、タバコ刻のロッド、および前記タバコ刻ロッドの外周面を包む巻紙を備え、前記タバコ刻および／または巻紙に有機酸の遷移金属塩が含まれているシガレットが提供される。 According to a first aspect of the present invention, a cigarette comprising a tobacco cut rod and a wrapping paper surrounding an outer peripheral surface of the tobacco cut rod, wherein the tobacco cut and / or the wrapping paper contains a transition metal salt of an organic acid. Is provided.
　本発明の第２の側面によれば、有機酸の遷移金属塩により、タバコ刻および／または巻紙を処理することを包含するシガレット材料の処理方法が提供される。 According to a second aspect of the present invention, there is provided a method for treating a cigarette material including treating tobacco cuts and / or wrapping paper with a transition metal salt of an organic acid.
　本発明によれば、シガレットの主流煙中の一酸化炭素を有意に低減することができる。 According to the present invention, carbon monoxide in cigarette mainstream smoke can be significantly reduced.
図１は、モデルガスを用いて一酸化炭素低減能を分析するための装置の構成図である。FIG. 1 is a configuration diagram of an apparatus for analyzing carbon monoxide reduction ability using a model gas. 図２は、有機酸遷移金属塩を充填した反応管の加熱温度と反応管を通過したガス中の一酸化炭素濃度を示すグラフである。FIG. 2 is a graph showing the heating temperature of the reaction tube filled with the organic acid transition metal salt and the concentration of carbon monoxide in the gas passing through the reaction tube.
　以下、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail.
　本発明のシガレットは、タバコ刻のロッドおよびこのロッドの外周面を包む巻紙を備える。 The cigarette of the present invention includes a rod of tobacco and a wrapping paper that wraps around the outer peripheral surface of the rod.
　タバコ刻は、タバコ材料を切断あるいは粉砕したものであり、適切な添加物を含むことができる。タバコ材料としては、バーレータバコ、黄色タバコ、オリエントタバコのタバコ葉もしくは葉タバコ中骨、発酵タバコ、ダークキュアタバコもしくは再構成タバコ材料、またはそれらの混合物を用いることができる。添加物としては、天然または合成の香味料、グリセリン、プロピレングリコール等の多価アルコール、エリスリトール、キシリトール、ソルビトール等の糖アルコール、ヒアルロン酸等を例示することができる。 The tobacco cut is a cut or crushed tobacco material and can contain suitable additives. The tobacco material can be burley tobacco, yellow tobacco, orient tobacco tobacco leaf or leaf tobacco bone, fermented tobacco, dark cured tobacco or reconstituted tobacco material, or mixtures thereof. Examples of additives include natural or synthetic flavors, polyhydric alcohols such as glycerin and propylene glycol, sugar alcohols such as erythritol, xylitol, and sorbitol, hyaluronic acid, and the like.
　タバコ刻のロッドを包む巻紙自体は、通常のシガレットに用いられる巻紙である。巻紙の原料として、亜麻、木材のほか、バガス等の農業副産物繊維、竹等の非木材繊維等を用いることができる。また、巻紙には、白色灰化剤および燃焼調整剤として、水酸化アルミニウム、硫酸アルミニウム、酸化アルミニウム、酸化マグネシウム、タルク、二酸化チタン、並びに炭酸、ギ酸、酢酸、リンゴ酸、クエン酸、酒石酸、乳酸および硝酸のナトリウム、カリウム、カルシウムおよびマグネシウムの塩のいずれか１種またはそれ以上が含まれ得る。 The wrapping paper itself that wraps the rod of tobacco is a wrapping paper used for ordinary cigarettes. In addition to flax and wood, agricultural by-product fibers such as bagasse, non-wood fibers such as bamboo, and the like can be used as the raw material for the wrapping paper. Wrapping paper also contains white ashing agents and combustion modifiers such as aluminum hydroxide, aluminum sulfate, aluminum oxide, magnesium oxide, talc, titanium dioxide, and carbonic acid, formic acid, acetic acid, malic acid, citric acid, tartaric acid, lactic acid. And any one or more of sodium, potassium, calcium and magnesium salts of nitrate.
　本発明において、タバコ刻および／または巻紙には、有機酸の遷移金属塩が含まれている。有機酸としては、例えばフマル酸、クエン酸、シュウ酸、ギ酸、安息香酸、乳酸およびステアリン酸を挙げることができる。中でも炭素を合計で２～７個有する有機酸が好ましく、フマル酸、クエン酸、シュウ酸がより好ましく、フマル酸が特に好ましい。 In the present invention, the tobacco cut and / or the wrapping paper contains a transition metal salt of an organic acid. Examples of the organic acid include fumaric acid, citric acid, oxalic acid, formic acid, benzoic acid, lactic acid, and stearic acid. Of these, organic acids having 2 to 7 carbons in total are preferred, fumaric acid, citric acid and oxalic acid are more preferred, and fumaric acid is particularly preferred.
　遷移金属としては、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｅ、Ｉｒ、ＰｔおよびＡｕから成る群から選択される少なくとも１種の金属を用いることができる。Ｆｅ、Ｃｕ、Ｍｎが好ましく、Ｆｅが特に好ましい。 The transition metal is at least one selected from the group consisting of Ti, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ce, Ir, Pt, and Au. These metals can be used. Fe, Cu, and Mn are preferable, and Fe is particularly preferable.
　タバコ刻および／または巻紙に添加された有機酸の遷移金属塩は、タバコ燃焼時に分解して遷移金属酸化物に転換され、その触媒作用により主流煙中の一酸化炭素が低減するものと考えられる。つまり、本発明によれば、タバコの燃焼熱により自動的に触媒が生成する。有機酸の遷移金属塩は、一酸化炭素低減触媒の前駆体として機能し、シガレットを燃焼させることにより、触媒を生成する。 It is considered that transition metal salts of organic acids added to tobacco cuts and / or wrapping paper are decomposed and converted to transition metal oxides during tobacco combustion, and its catalytic action reduces carbon monoxide in mainstream smoke. . That is, according to the present invention, a catalyst is automatically generated by the combustion heat of tobacco. The transition metal salt of an organic acid functions as a precursor of a carbon monoxide reduction catalyst, and generates a catalyst by burning cigarettes.
　上記の有機酸の遷移金属塩は、タバコ刻に対して、好ましくは１～５０重量％含まれている。１重量％未満であると、十分に一酸化炭素低減能を発揮することができない傾向にある。また５０重量％を超えるとタバコ刻の処理が困難となり好ましくない。 The above-mentioned transition metal salt of an organic acid is preferably contained in an amount of 1 to 50% by weight with respect to tobacco. If it is less than 1% by weight, the carbon monoxide reducing ability tends not to be exhibited sufficiently. On the other hand, if it exceeds 50% by weight, it is not preferable because it becomes difficult to process tobacco.
　上記の有機酸の遷移金属塩が巻紙に含まれる場合には、有機酸の遷移金属塩は、好ましくは０．１～５０ｇ／ｍ2の割合で巻紙中に含まれる。０．１ｇ／ｍ2未満の量は、一酸化炭素低減能を十分に発揮させ得ない傾向にある。５０ｇ／ｍ2を超える量は、巻紙の処理が困難とさせ得る。 When the above-mentioned transition metal salt of organic acid is contained in the wrapping paper, the transition metal salt of organic acid is preferably contained in the wrapping paper at a rate of 0.1 to 50 g / m 2 . If the amount is less than 0.1 g / m 2 , the carbon monoxide reducing ability tends not to be fully exhibited. An amount exceeding 50 g / m 2 can make the paper wrapper difficult to process.
　有機酸の遷移金属塩は、巻紙に含める場合、巻紙の平滑度および巻紙中での被保持性の観点から、０．０５～５μｍの粒径を有することが好ましい。 When the transition metal salt of an organic acid is included in a wrapping paper, it preferably has a particle size of 0.05 to 5 μm from the viewpoint of smoothness of the wrapping paper and retention in the wrapping paper.
　また、本発明は、上記有機酸の遷移金属塩により、タバコ刻および／または巻紙を処理することを包含するシガレット材料の処理方法に関する。 The present invention also relates to a method for treating a cigarette material including treating tobacco cuts and / or wrapping paper with the above-mentioned transition metal salt of an organic acid.
　本発明のシガレット材料の処理方法は、例えば、上記有機酸の遷移金属塩を有機溶媒（有機酸の遷移金属塩を溶解しない）に分散させた溶液を、タバコ刻および／または巻紙に撒布することにより行なうことができる。有機溶媒としてはいずれの有機溶媒を用いてもよく、例えばエタノールのようなアルコール等を挙げることができる。水系溶媒は上記有機酸の遷移金属塩が溶解する結果、巻紙に吸収される量以上を撒布することが困難となる。有機酸の遷移金属塩を有機溶媒に分散させる場合には、乳化剤をさらに加えてスラリーの状態で使用することがより好ましい。乳化剤は、食品添加物として用いられている既知のものであればよく、例えばレシチン等である。乳化剤は、有機酸の遷移金属塩の重量の１％～５０％の量で用いることができる。１％を下回ると、分散効果が十分に発現されず、５０％を上回ると、有機酸の遷移金属塩の分解に支障をきたす。 In the method for treating a cigarette material of the present invention, for example, a solution obtained by dispersing the transition metal salt of the organic acid in an organic solvent (not dissolving the transition metal salt of the organic acid) is distributed on tobacco and / or wrapping paper. Can be performed. Any organic solvent may be used as the organic solvent, and examples thereof include alcohols such as ethanol. As a result of the dissolution of the transition metal salt of the organic acid, it becomes difficult for the aqueous solvent to distribute more than the amount absorbed by the wrapping paper. When the transition metal salt of an organic acid is dispersed in an organic solvent, it is more preferable to add an emulsifier and use it in a slurry state. The emulsifier may be any known one used as a food additive, such as lecithin. The emulsifier can be used in an amount of 1% to 50% by weight of the transition metal salt of the organic acid. If it is less than 1%, the dispersion effect is not sufficiently exhibited, and if it exceeds 50%, the decomposition of the transition metal salt of the organic acid is hindered.
　さらに、有機酸の遷移金属塩は、タバコ刻に練り込むことができるし、あるいは巻紙に塗布することもできる。さらに、有機酸の遷移金属塩は、巻紙を抄紙する際の完成紙料に配合することもできる。 Furthermore, the transition metal salt of an organic acid can be kneaded into tobacco, or can be applied to a wrapping paper. Furthermore, the transition metal salt of an organic acid can also be blended into a paper furnish when making a paper wrapper.
　上記した通り本発明のシガレット材料の処理方法は、シガレット材料（タバコ刻および／またはシガレット巻紙）を有機酸の遷移金属塩により処理するという非常に簡便な方法である。後述するように、このように簡便な方法をもって、従来優れているとされていた酸化鉄ナノパウダーよりも、主流煙中の一酸化炭素をさらに低減することができる。 As described above, the method for treating a cigarette material of the present invention is a very simple method in which a cigarette material (tobacco carved and / or cigarette wrapping paper) is treated with a transition metal salt of an organic acid. As will be described later, carbon monoxide in mainstream smoke can be further reduced by such a simple method as compared with iron oxide nanopowder that has been considered to be excellent.
　実施例１
　モデルガスを用いて、本発明のシガレットに添加される各種有機酸の遷移金属塩の一酸化炭素低減能を調べた。実施例１では遷移金属として鉄を用いた。 Example 1
Using model gas, the carbon monoxide reducing ability of transition metal salts of various organic acids added to the cigarette of the present invention was examined. In Example 1, iron was used as the transition metal.
　有機酸鉄塩として、クエン酸鉄はナカライテスク株式会社製のものを、その他の有機酸鉄塩は和光純薬製のものを用いた。なお、有機酸の鉄塩として、７５μｍのふるい径を通過した粒子を使用した。 As the organic acid iron salt, iron citrate was manufactured by Nacalai Tesque, and other organic acid iron salts were manufactured by Wako Pure Chemical. In addition, as an iron salt of an organic acid, particles that passed through a sieve diameter of 75 μm were used.
　図１は、有機酸遷移金属塩の一酸化炭素低減能を分析するための装置を示す。下記表１に示される量の鉄を含む実施例１の有機酸鉄を加熱炉８内に設置された反応管９に充填した。一酸化炭素（ＣＯ）ガスおよび二酸化炭素（ＣＯ2）を、それぞれガスボンベ３および５から、質量流量計４、６を経由して供給し、水を電子天秤１で測量して、定量ポンプ２から供給した。ＣＯガスおよびＣＯ2ガスとともに、上記水を蒸発器７（２００℃）に通した。水は、蒸発して水蒸気となる。こうして、蒸発器７内で、モデルガス（ＣＯ濃度；４モル％、ＣＯ2濃度；８モル％、Ｈ2Ｏ濃度１０モル％、窒素残部）が調製された。このモデルガスを、５００，０００ｈ-1の空間速度（ＳＶ）となるようにその流量を設定し、反応管９中に充填した有機酸鉄塩の層に流通させた。反応管９中の有機酸鉄の層の温度を２００℃から９００℃までに昇温させながら、モデルガスを３．５時間流通させた。図１中、ＰＧは、圧力計であり、ＴＩＣは反応管９の管壁の温度を測定する温度計であり、ＴＩは充填層の温度を測定する温度計である。温度計ＴＩＣで測定された温度は、加熱炉８により加熱する際の制御用モニター温度として使用される。反応管９から流出したガスを冷却トラップ１０に通した後、株式会社堀場製作所製赤外ガス分析計（ＶＩＡ－５１０；非分散形赤外線吸収法による）１１により、一酸化炭素量を定量した。 FIG. 1 shows an apparatus for analyzing the ability to reduce carbon monoxide of an organic acid transition metal salt. The organic acid iron of Example 1 containing the amount of iron shown in Table 1 below was charged into the reaction tube 9 installed in the heating furnace 8. Carbon monoxide (CO) gas and carbon dioxide (CO 2 ) are supplied from gas cylinders 3 and 5 via mass flow meters 4 and 6, respectively, and water is measured with electronic balance 1, and from metering pump 2 Supplied. Together with the CO gas and CO 2 gas, the water was passed through the evaporator 7 (200 ° C.). Water evaporates into water vapor. Thus, a model gas (CO concentration: 4 mol%, CO 2 concentration: 8 mol%, H 2 O concentration: 10 mol%, nitrogen balance) was prepared in the evaporator 7. The flow rate of this model gas was set so that the space velocity (SV) was 500,000 h −1 , and the model gas was circulated through the organic acid iron salt layer filled in the reaction tube 9. While raising the temperature of the organic acid iron layer in the reaction tube 9 from 200 ° C. to 900 ° C., the model gas was circulated for 3.5 hours. In FIG. 1, PG is a pressure gauge, TIC is a thermometer that measures the temperature of the tube wall of the reaction tube 9, and TI is a thermometer that measures the temperature of the packed bed. The temperature measured by the thermometer TIC is used as a monitor temperature for control when heating by the heating furnace 8. After the gas flowing out from the reaction tube 9 was passed through the cooling trap 10, the amount of carbon monoxide was quantified with an infrared gas analyzer (VIA-510; by non-dispersive infrared absorption method) 11 manufactured by Horiba, Ltd.
　各有機酸鉄の一酸化炭素酸化量、鉄元素１モル当たりの一酸化炭素酸化量、および一酸化炭素除去率の結果を表１に示す。表中、「添加剤」として示すものが有機酸鉄である。 Table 1 shows the results of carbon monoxide oxidation amount of each organic acid iron, carbon monoxide oxidation amount per mol of iron element, and carbon monoxide removal rate. What is shown as “additive” in the table is iron organic acid.
　比較例１
　有機酸鉄塩の代わりに、酸化鉄（四酸化鉄）パウダー（シグマアルドリッチ社製）を添加したこと以外は、実施例１と同様の条件で、一酸化炭素除去率等を測定した。結果を表１に併記する。
Figure JPOXMLDOC01-appb-T000001
 Comparative Example 1
The carbon monoxide removal rate and the like were measured under the same conditions as in Example 1 except that iron oxide (iron tetroxide) powder (manufactured by Sigma-Aldrich) was added instead of the organic acid iron salt. The results are also shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
　実施例２～３
　有機酸鉄塩の代わりに、有機酸銅および有機酸マンガンを用いたこと以外は実施例１と同様の条件下で、一酸化炭素低減能を調べた。結果を表２および３に示す。これら実施例では、有機酸の遷移金属塩は、和光純薬製のものを用いた。
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
 Examples 2 to 3
Carbon monoxide reducing ability was examined under the same conditions as in Example 1 except that organic acid copper and organic acid manganese were used instead of the organic acid iron salt. The results are shown in Tables 2 and 3. In these examples, the transition metal salt of the organic acid was made by Wako Pure Chemical.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
　表１～３から明らかな通り、一酸化炭素は酸化されていることがわかった。実施例１～３の結果から、遷移金属として鉄を用いた場合に優れた一酸化炭素低減能を示すことがわかった。実施例１において添加剤中に含有されている鉄元素のモル数が、比較例１の従来の酸化鉄触媒中の鉄元素のモル数よりも少ないにも拘わらず、鉄元素１モル当たりのＣＯ酸化量は比較例１と同等若しくはそれ以上であった。中でも、フマル酸鉄を用いた場合には、比較例１よりも、一酸化炭素酸化量、鉄１モル当たりの一酸化炭素酸化量および一酸化炭素除去率の全てにおいて優れていることがわかった。またステアリン酸鉄を用いると一酸化炭素除去率等が大きく低減するため、有機酸として、合計炭素数が２～７個程度のものを用いることが好ましいことがわかった。 As is clear from Tables 1 to 3, it was found that carbon monoxide was oxidized. From the results of Examples 1 to 3, it was found that excellent carbon monoxide reduction ability was exhibited when iron was used as the transition metal. Although the number of moles of iron element contained in the additive in Example 1 is smaller than the number of moles of iron element in the conventional iron oxide catalyst of Comparative Example 1, CO per mole of iron element is present. The amount of oxidation was equal to or greater than that of Comparative Example 1. In particular, when iron fumarate was used, it was found that the carbon monoxide oxidation amount, the carbon monoxide oxidation amount per mol of iron, and the carbon monoxide removal rate were all superior to those of Comparative Example 1. . In addition, when iron stearate is used, the carbon monoxide removal rate and the like are greatly reduced, and it has been found preferable to use an organic acid having a total carbon number of about 2 to 7.
　実施例４
　有機酸の遷移金属塩としてのフマル酸鉄１４５ｇと、亜麻パルプ（リンセル社製）１５ｇを、２０００ｇのエタノール／レシチン混合液（エタノール：レシチン重量比＝９０：０．５）に分散させたスラリーを調製した。このスラリーをシート状にキャスティングするか、または１６メッシュと２００メッシュのステンレス金網を重ねた手漉き紙作製用具上に流して、坪量が５０ｇ／ｍ2のタバコ巻紙を作製した。 Example 4
A slurry in which 145 g of iron fumarate as a transition metal salt of an organic acid and 15 g of flax pulp (manufactured by Rinsel) are dispersed in 2000 g of an ethanol / lecithin mixed solution (ethanol: lecithin weight ratio = 90: 0.5). Prepared. The slurry was cast into a sheet shape or poured onto a handmade paper making tool in which a 16 mesh and 200 mesh stainless wire mesh was stacked to produce a tobacco wrapping paper having a basis weight of 50 g / m 2 .
　ここで、フマル酸鉄の粒径が大きすぎると巻紙の平滑度が低下し、また均一に分散しない。粒径が小さすぎると、手漉き試作用具を抜け落ちて巻紙上に担持できないことがわかった。好ましい粒径は０．０５～５μｍである。 Here, if the particle size of the iron fumarate is too large, the smoothness of the wrapping paper is lowered and it is not uniformly dispersed. It was found that if the particle size was too small, the hand-made prototype tool fell off and could not be carried on the wrapping paper. A preferred particle size is 0.05 to 5 μm.
　また、フマル酸鉄を上記エタノール／レシチン混合液３０ｍＬに分散させてスラリーを調製した。タバコ刻重量に対してフマル酸鉄が１０重量％となるように、噴霧器を用いて上記スラリーを噴霧することにより、タバコ刻にフマル酸鉄を添加できることがわかった。 Further, a slurry was prepared by dispersing iron fumarate in 30 mL of the above ethanol / lecithin mixed solution. It was found that iron fumarate can be added to the tobacco cut by spraying the slurry using a sprayer so that the iron fumarate is 10% by weight with respect to the tobacco cut weight.
　実施例５
　本実施例において、有機酸の遷移金属塩の作用機構について考察する。 Example 5
In this example, the action mechanism of a transition metal salt of an organic acid will be considered.
　タバコ刻（２Ｒ４Ｆ）１００ｍｇとフマル酸鉄１０ｍｇを混合し、サンプル管に詰めた。このサンプル管を触媒分析装置（日本ベル社製：ＢＥＬＣＡＴ）にセットした。サンプル管に、モデルガス（ＣＯ：３．３９モル％、Ｏ2：２．１９モル％、Ｈｅ：残部）を流通させ、４０℃／分で昇温させ、２００℃から８００℃まで昇温したときのＣＯ濃度を測定した。結果を図２に示す。図２から明らかな通り、６００℃付近でタバコ刻が酸化燃焼して、一酸化炭素が一時的に増加した後、一酸化炭素が低減する傾向が見られた。このことにより、６００℃付近でフマル酸鉄を加熱処理したことによりフマル酸鉄が分解して酸化鉄になり、触媒として機能したものと推測できる。 A tobacco tube (2R4F) 100 mg and iron fumarate 10 mg were mixed and packed in a sample tube. This sample tube was set in a catalyst analyzer (BELCAT, manufactured by Nippon Bell Co., Ltd.). A model gas (CO: 3.39 mol%, O 2 : 2.19 mol%, He: remainder) was circulated through the sample tube, and the temperature was raised at 40 ° C./min, and the temperature was raised from 200 ° C. to 800 ° C. The CO concentration was measured. The results are shown in FIG. As apparent from FIG. 2, the cigarette was oxidized and burned at around 600 ° C., and after the carbon monoxide temporarily increased, the carbon monoxide tended to decrease. From this, it can be presumed that the iron fumarate was heat-treated at around 600 ° C., so that the iron fumarate was decomposed into iron oxide and functioned as a catalyst.

Claims (10)

  1. 　タバコ刻のロッド、および前記タバコ刻ロッドの外周面を包む巻紙を備え、前記タバコ刻および／または巻紙に有機酸の遷移金属塩が含まれているシガレット。 A cigarette comprising a tobacco carved rod and a wrapping paper surrounding an outer peripheral surface of the tobacco carved rod, wherein the tobacco carved and / or wrapping paper contains a transition metal salt of an organic acid.
  2. 　前記有機酸がフマル酸、クエン酸、シュウ酸、ギ酸、安息香酸、または乳酸である請求項１に記載のシガレット。 The cigarette according to claim 1, wherein the organic acid is fumaric acid, citric acid, oxalic acid, formic acid, benzoic acid, or lactic acid.
  3. 　前記遷移金属が、Ｔｉ，Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｅ、Ｉｒ、ＰｔおよびＡｕから成る群から選択される少なくとも１種の金属である請求項１に記載のシガレット。 The transition metal is at least one selected from the group consisting of Ti, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ce, Ir, Pt, and Au. The cigarette according to claim 1, wherein the cigarette is a metal.
  4. 　前記有機酸の遷移金属塩が、前記タバコ刻に対して１～５０重量％の量で含まれている請求項１に記載のシガレット。 The cigarette according to claim 1, wherein the transition metal salt of the organic acid is contained in an amount of 1 to 50% by weight with respect to the tobacco.
  5. 　前記有機酸の遷移金属塩が、前記巻紙に０．１～５０ｇ／ｍ2の量で含まれていることを特徴とする請求項１に記載のシガレット。 The cigarette according to claim 1, wherein the transition metal salt of the organic acid is contained in the wrapping paper in an amount of 0.1 to 50 g / m 2 .
  6. 　有機酸の遷移金属塩により、タバコ刻および／または巻紙を処理することを包含するシガレット材料の処理方法。 A method for treating a cigarette material comprising treating tobacco cuts and / or wrapping paper with a transition metal salt of an organic acid.
  7. 　前記有機酸が、フマル酸、クエン酸、シュウ酸、ギ酸、安息香酸、または乳酸である請求項６に記載の処理方法。 The processing method according to claim 6, wherein the organic acid is fumaric acid, citric acid, oxalic acid, formic acid, benzoic acid, or lactic acid.
  8. 　前記遷移金属が、Ｔｉ，Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｙ、Ｚｒ、Ｎｂ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｅ、Ｉｒ、ＰｔおよびＡｕから成る群から選択される少なくとも１種の金属である請求項６に記載の処理方法。 The transition metal is at least one selected from the group consisting of Ti, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Ce, Ir, Pt, and Au. The processing method according to claim 6, wherein the metal is a metal.
  9. 　前記有機酸の遷移金属塩を有機溶媒に分散させた溶液を、タバコ刻および／または巻紙に撒布することを特徴とする請求項６に記載の処理方法。 The processing method according to claim 6, wherein a solution in which the transition metal salt of the organic acid is dispersed in an organic solvent is distributed on tobacco and / or wrapping paper.
  10. 　前記溶液がさらに乳化剤を含むことを特徴とする請求項９に記載の処理方法。 The processing method according to claim 9, wherein the solution further contains an emulsifier.
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EP2415362B1 (en) 2016-09-14
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EP2415362A1 (en) 2012-02-08
JP5250694B2 (en) 2013-07-31
JPWO2010114095A1 (en) 2012-10-11
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