TW386867B - Cigarette wrapping paper having a flavorant which improves sidestream smoke smell, and a cigarette - Google Patents

Description

[Background of the Invention] The present invention relates to cigarette paper and cigarettes with sidestream smoke odor improving flavor. (The so-called sidestream smoke refers to the smoke emitted when the cigarette is placed without being smoked after being lit.) "In tobacco products such as cigarettes, various flavors are often added to improve the taste and aroma of the cigarette. Recently, in order to improve smoking, The odor of cigarette sidestream smoke (hereinafter referred to as "sidestream smoke") emitted to the surrounding area is suggested to add flavor to the cigarette paper to cover the unpleasant odor. However, tobacco products such as perfume added to the cigarette paper Most of the flavors used are highly volatile at normal temperature, so the flavors will evaporate due to evaporation or sublimation. During the manufacture of cigarette products, the aroma emitted by the flavors will be mixed into the cigarette manufacturing site, and even the shadow of the cigarette products. Physical properties, such as fragrant flavor, may become the cause of the deterioration of the quality of cigarette products during storage. In particular, the flavor added in the roll paper may be transferred to the packaging material of tobacco cigarette products, which affects the flavor and taste of cigarettes. Here, it is recommended It can inhibit the volatilization of flavors when non-smoking, and is stable under the conditions of manufacture and storage of cigarette products, non-volatile, decomposes by heat under smoking conditions, or A modified fragrance or fragrance releasing agent that emits fragrance separately. For example, disclosed in Japanese Patent Publication No. 2_501 075 or U.S. Patent No. 4,804 '002, a fragrance in which a fragrance is blended with barium. The cyclodextrins disclosed in Japanese Patent Application Laid-Open No. 5_146285 or U.S. Patent No. 5, Η4 964 and Japanese Patent Application No. 7_5〇4〇80 or U.S. Patent No. 5, 479, 94 No. 9 Technology of fragrance inclusion. However, in the above-mentioned conventional technology, in order to suppress non-absorption

V. Description of the invention (2) ---- Additive, carbohydrate sugar ridges or cyclodextrin of vulcanizing agent added to the volatilization of fragrant materials, spices will produce thermal decomposition products when smoking, and the products will be mixed into cigarettes It may hinder the flavor and taste of cigarettes. Furthermore, there are problems such as high manufacturing costs. [Summary of the Invention] Therefore, the object of the present invention is to provide a simpler structure, which does not emit aroma under non-smoking conditions, can cover the unpleasant odor of sidestream smoke when smoking, and contains an improved sidestream smoke odor Cigarette paper and cigarettes with sidestream smoke and odor improving agent. In order to achieve the above objective, the present inventors and others continued to make in-depth research on the sidestream smoke odor improving agent attached to the cigarette paper, and as a result, unexpectedly discovered that the lactone can slightly release the aroma when smoking, but the non-smokers In a free state without actually releasing the aroma, it can be maintained in a state of being stably attached to the cigarette paper. That is, based on the above-mentioned conclusion (the first feature), the present invention provides a cigarette paper roll with a sidestream smoke odor improving agent including a lactone in a free state. The lactone in the present invention is preferably a ring member having 5 or more members. The preferred lactone can be selected from γ-butyrolactone, r-valerolactone, 7 * -heptanolactone, γ-caprolactone, 7 " -caprolactone, 7-nononactone, 71-decyl Lactone, 7-undecal lactoparalysis, sotlon, apohexon, caprolactone, 5-nononolactone, caprolactone, -rolactone, ω- Group of fifteen burning inner mills and the lactone mixture mentioned above. The lactone is particularly suitable as the lactone or < 5-lactone. In the present invention, the lactone is dissolved in an aqueous solvent

V. Explanation of the invention (3) The solution is used in the form of a cigarette paper to obtain a dry form. Further, according to the above-mentioned first side stream ', the present invention provides a cigarette, the cigarette is rolled with a cigarette paper, and the twig paper contains a side stream smoke odor improving agent including a lactone. In this case, the roll paper is internally ground with a water-based adhesive, so that the roll paper can be contained in the adhesive to be contained in the roll paper. Based on this, the inventors studied the above lactone more deeply, and had the second feature, that is, adding the endogenous ring in the aqueous solvent of the internal gambling test to obtain the base of the base acid. The base itself has no The aroma is also odorless. When the paper is burned (smoke), it will be closed to form an internal brew. It will emit the same aroma as when it is freely seen. That is, based on the above-mentioned second feature, the present invention also provides a cigarette roll paper with a sidestream smoke odor improving agent corresponding to the lactone hydroxy acid halide. In the present invention, the rhenium hydroxy acid is preferably an alkali metal rhenium or an alkaline earth metal rhenium. In addition, the light acid hydrazone is preferably an acid hydrazone corresponding to a lactone having a 5-membered ring or more. The preferred hydroxy acid hydrazone can be selected from the group consisting of T-butyrolactone, 7-valerolactone, captolactone, T-caprolactone, 7-caprylide, 7-caprylide, γ-decalactone, 7 * -pyridine-hexyllactone, sotalone, apraxon, 5-caprylide, Groups of 5-nodonate, 5-decanone, burned internal grinding, omega-pentadecyllactone, and mixtures of the above lactones. In addition, the hydroxy acid is particularly suitable as r-lactone or < 5-lactone. In the present invention, hydroxyamidine is dissolved in an aqueous solvent and used as a solution in a cigarette paper to obtain a dried form. Also, based on the feature of the second item, the present invention provides a cigarette,

Page 8 V. Description of the invention (4) The cigarette is rolled from a cigarette paper, and the paper contains a sidestream smoke odor improving agent including lactone hydroxy acid. In this case, the roll paper is adhered with a water-based adhesive, and the hydroxy acid may be contained in the adhesive to be attached to the roll paper. [Simplified description of the circle surface] The first circle is an oblique circle of a partially expanded example of the cigarette of the present invention, the second circle is a NMR spectrum circle of τ-undecanolactone, and the third figure is 7 * -undecane The NMR spectrum of the europium hydroxy acid obtained after the ester was treated with alkali. [Detailed Description of the Invention] Hereinafter, the present invention will be described in detail. The lactone used in the present invention is a fragrance that can release a strong aroma only when it is slightly soluble in water. It is known that the entrails are used in cigarettes with its aqueous solution, and the amount carried when dry can emit a sufficient aroma when smoking, and the aroma hardly emits when smoking, that is, it has practically no odor. The lactone used in the present invention is not particularly limited, but a ring of 5 or more is preferred. Examples of the preferred lactone include butyrolactone: slightly fragrant), valerolactone (fragrance: stable light hay and vanilla fragrance), r-heptanolactone (fragrant: coconut-like, Micro-caramel), lactone (fragrance: light scent like strong vanilla), 7_ cinnamo, 7 c ester (fragrance: like coconut fruit), r-capecene (fragrance: Peach fruit-like) 7, Yishu internal brew (fragrant: peach-like), sotalone (4, 5_diylfuranone (fragrant: curry-like spicy), Ap black item (43 Methyl-5-ethyl-3-hydroxy-2 (5H) -furanidine), octyl-octyl'nminth-nononactone mnnr 9 i ~ '' V. Description of the invention (5) (Aromatic: Coconut-like), 5-decenolide (fragrant: coconut-like), Chamundecane (fragrant: peach-like), omega-pentadecanone (fragrant: pale Musk), and mixtures of the above-mentioned lactones. The lactone used in the present invention is particularly suitable as r-lactone or 5-lactone. The cigarette sidestream smoke odor improving agent of the present invention contains free lactone. The Free state means that it is stored in cigarette paper in the state of lactone molecules, or The components of the cigarette paper, such as cellulose, and calcium carbonate, are maintained by physical absorption or chemical action. Therefore, in the present invention, the internal milling and other types of chemicals are chemically related to other ingredients in advance. The state of combination (such as the state of forming a sugar skull) or the state of being physically combined with other ingredients in advance (such as the state of forming an inclusion body) is different from those added to cigarette paper. The sidestream smoke and odor of the present invention The improving agent is preferably one made of the lactone described above. The lactone-containing sidestream smoke odor improving agent of the present invention is applied to a cigarette paper as a solution dissolved in an aqueous solvent, and can be appropriately dried after drying. It is included in cigarette paper. Water-based solvents can be water or organic solvents (especially ethanol), especially water. At this time, 'lactone is dissolved in the above-mentioned water-based solvent to prepare a lactone solution =, application The internal solution is applied to cigarette paper. The method of applying the lactone solution to cigarettes can be a method of immersing the cigarette paper in the lactone solution, a coating method such as a maker, a rotary printer, or the like. Available on Cigarette Roll ^ The glued part of the cigarette paper is coated with a lactone solution. This: roll η: coated on the entire cigarette paper, or partially flavored. Furthermore, when manufacturing cigarette paper, add lactone to Completely ΗΗΊΗΗ Page 10 V. Description of the invention (6) In the paper stock, the complete paper can also be used to make paper to produce cigarette rolls with lactones in the state. "The cigarette rolls in the present invention can be used for ordinary cigarettes. Roll paper, cigarette paper containing cigarette powder, low sidestream cigarette paper, etc. Any kind of cigarette paper for cigarettes. Especially low sidestream cigarette paper, in addition to the small amount of sidestream smoke, it is also free of odor. The improvement effect according to the present invention is remarkable. Particularly good low sidestream cigarette paper is below the unit of air permeability of 25 Coris Star (coistar) units, and the reference director is in the range of 15 to 80g / m2 ', and it can reduce the sidestream smoke effect. Cigarette rolls of compounds. In addition, the compound exhibiting the effect of reducing sidestream smoke is a compound selected from the group consisting of metal or earth metal oxides, organic or inorganic acids, metal or earth metal gadolinium, or added per square meter of rolled paper. The surface area of acid breaking Ma Da is more than 80 square meters. In the present invention, the lactone loading capacity is preferably 100 mg per square meter of cigarette paper, and more preferably 0.5 to 100 mg. Such a lactone flavor affixed to the cigarette paper is maintained in the cigarette roll in a stable manner at normal temperature, and practically does not emit aroma, nor does it transfer during storage. In addition, the lactone attached to the cigarette paper is accompanied by selective combustion aromas emitted to the sidestream smoke during smoking, thereby covering the unpleasant odor of the sidestream smoke and improving the sidestream smoke odor. Next, in the present invention, the above-mentioned lactone solution in which a lactone ring is opened by adding a base to generate a few bases of acid (via acid) may be used instead of the above-mentioned free lactone and attached to cigarette paper. This kind of cigarette paper with rhenium hydroxy acid on it has low volatility and no odor, so it is used in the manufacture or storage of cigarettes.

V. Description of the invention (7)-And the 'acid attached to the cigarette paper corresponds to the acidic acid of the internal series, and when the cigarette is smoked (the cigarette paper is burned), a closed-loop lactone is formed, and the case of using the free lactone: the same, It emits a sufficient aroma and covers the unpleasant odor of the sidestream smoke, and has the effect of improving the sidestream smoke. Among them, the formation of lactone and the corresponding hydrazone is based on the equilibrium reaction. An aqueous solution containing the appropriate test and lactone at the same time is exactly the same as that in the case of using a free end, and is applied to the cigarette paper or at the same time as the manufacture of the cigarette paper, the lactone and test are added to the complete paper at the same time. The superacid hydrazone corresponding to lactone is maintained in cigarette paper by papermaking. In addition, the hydroxy acid corresponding to the lactone generated in the aqueous solution was added in the alkali-added solution. Due to its high solubility in water, the concentration in the aqueous solution should be increased compared to the situation in the free solution. Is maintained in cigarette paper. Since the lactone generated by the acid ring closed due to combustion, the internal friction in the above-mentioned free state is the same. Therefore, the preferred hydroxy acid fluorene is a hydroxy acid fluorene corresponding to a lactone having more than 5 members. The preferred ones can be listed as r- Butyrolactone, r-valerolactone, r-heptanolactone, r-caprolactone, γ-capryrolactone, nonolactone, τ-decanolactone, r-undecanolactone, sotalone, Alzheimer's, caprylide, di-nononolactone, caprolactone, undecanolactone, omega pentadecane lactone, and the acid mash of a mixture of the above lactones. In addition, 7-lactone or <?-Lactone hydroxyacid is particularly suitable as the acid. In order to open the lactone ring so that the corresponding hydroxy acid europium is used, the test used is not particularly limited, and it is preferable to use europium carbonate, europium bicarbonate, argon oxide, etc. of more than one type of alkali metal or alkaline earth metal. Therefore, the preferred hydroxy acid rhenium is metal rhenium and alkaline earth metal rhenium. In addition, considering normal acid

Page 12 V. Description of the invention (8) The pH value of the alkaline solution is preferably 10 or more, but it can produce light acid hydrazone when it is 8 or more, and the time required to generate hydroxy acid hydrazone at high temperature is shortened. . Further, in an alkaline aqueous solution containing lactone and a corresponding hydroxy acid sulfonium, when the test concentration is increased, when the aqueous solution is applied to cigarette paper, the cigarette paper may turn yellow. To avoid this phenomenon, it is expected that the concentration of alkali will be maintained at, for example, less than 1% of sodium oxide and less than 4% of sodium carbonate. In addition, if the lactone concentration increases under alkaline conditions, a foaming phenomenon (examination) may occur, and the lactone may not be stably attached to the cigarette paper. To avoid this foaming phenomenon ', it is preferable that the sodium argon oxide is 1¾ and the lactone concentration is 5% or less. In the present invention, the amount of hydrazone attached is converted to the weight of the corresponding lactone. It is preferably 0.1 to 1,000 mg per square meter of cigarette paper, and more preferably 0.5 to 100 mg. To make a cigarette of the present invention, a cigarette roll paper prepared with a lactone in a free state or a cigarette roll paper loaded with a hydroxy acid peptone can be rolled into a cigarette according to a conventional method. When rolled into a cigarette with such a roll paper containing a cigarette sidestream smoke odor improving agent, the roll paper is water-based adhesive (for example, carboxymethyl cellulose-based adhesive, hexenyl acetate-based adhesive) The so-called sticky paste. Or 'roll into a cigarette that has not been previously loaded with the cigarette sidestream smoke odor improving agent of the present invention, and on the other hand, add the sidestream smoke odor of the present invention to improve the paste]' and use the sticky paste to stick the cigarette roll Paper can also be used to make cigarettes of the present invention. Of course, the cigarette of the present invention may be provided with a filter. That is, the cigarette of the present invention has the same structure as a normal cigarette except that the paper is made of the paper of the present invention.

V. Description of the invention (9) The first circle is an example of a partially expanded perspective view of the cigarette of the present invention. Β The cigarette shown in the first circle is a system containing the cigarette sidestream smoke odor improvement system (not shown) of the present invention. The roll paper 12 is rolled up, and a cigarette portion 10 is formed by a generally cylindrical smoke column 11. The smoke column 11 is made of cut tobacco. The roll paper 12 is followed by a paste 13. One end of the cigarette portion 10 is packaged with thin wrapping paper 22, for example, a filter portion 20 constituted by a filter element main component 21 made of a weaving acetate fiber bundle. The cigarette portion 10 and the filter portion 20 are connected to each other in a so-called wood chip paper 30 roll. The wood chip paper can be designed with a plurality of puncture holes 31 a to 3 1 π punctured in the circumferential direction of the cigarette. »In the first figure, two such puncture hole rows are formed. When the cigarette of the present invention is smoking, the aroma emitted by the sidestream smoke odor improver of the present invention can cover the unpleasant odor of the sidestream smoke, and the aroma emitted by the sidestream smoke odor improver when smoking is actually not in the mainstream Emitted in the smoke, only in the sidestream smoke, so it does not affect the taste of the cigarette. (The so-called mainstream smoke is smoke that enters the mouth of a smoker when smoking.) As mentioned above, since the present invention contains a free lactone or a sidestream smoke odor improving agent of hydroxy acid, it is suitable for use in an aqueous solvent. The solution, especially in the form of an aqueous solution, is applied to the cigarette paper, so it is also applicable to the free state from the viewpoint of workability and safety. Hereinafter, the present invention will be further described by examples. (Example 1) "Preparation of lactone-containing rolled paper" A commercially available low-sidestream cigarette paper was coated with an aqueous solution of? -Undecanolactone (r-pinenolactone concentration / 7.5 to 100 mg / L). Followed by the volume

Page 14 V. Description of the invention (10) The paper was heated under vacuum at 300 ° C for 1 hour, and the generated r-undecanolactone vapor was captured with liquid nitrogen, and its amount was determined by gas chromatography (will be Quantitative method of heating paper to decompose and measure the amount of lactones hereinafter referred to as &quot; Thermal Decomposition Method, Table 1 below shows the T-undecyl lactone degree (rag / L) of the aqueous solution, and the volume per square meter The attached amount of r-undecanolactone attached to the paper (mg / m2) (&quot; Initial Amount &quot;). <The distribution change of the attached amount of lactone> Next, to review the attached amount of r-undecanolactone The amount of time-varying changes was subjected to the following accelerated test as a storage test. That is, the above-mentioned various lactone-containing rolled paper samples were loaded into an adsorption container with a gas vessel inlet and a gas outlet, and the gas skull The introduction port supplies nitrogen at a temperature of 37 * t and a relative humidity of 60¾ until the nitrogen gas reaches a state of equilibrium (steady state) with the roll paper sample (more than 48 hours). When the equilibrium state is reached, r-undecanolactone of the roll paper sample The attached document is based on the above-mentioned thermal decomposition legal directors. The results are based on the balance after the accelerated test. The attached Dong's are also shown in Table 1. Aqueous solution __ Selective paper T • Undecyl ester attached amount r-undecanolactone concentration (mg / L) Surface (ma / m2, Accelerated fiber) Equilibrium amount img / m2) 7.5 0.4 0.4 3.0 0.9 0.9 60 1.4 1.3 100 1.6 1.3 From the results shown in Table 1, it can also be seen that '7-undecanolactone is attached to the roll paper, and the amount and initial stage after the accelerated test The loading capacity is almost the same, which shows that the loading capacity of r-undecanolactone in the roll paper is stored at room temperature.

P.15 5. Description of the invention (11) A certain value can be maintained. Furthermore, various rolled papers with 7 · -undecanolactone were loaded at 30. (: Temperature, Lily under 10-2Pa under vacuum drying for 2 days, the loading capacity of τ-undecanolactone is also almost unchanged. (Example 2) On a commercially available low sidestream cigarette paper, 11 is burned The internally brewed aqueous solution (the concentration of the enzyme in T-11 unburned mg / L) is applied to the pressure-sensitive part of the papermaking hemp (width 205m × length 2700m). Use side detector gc-MS (SIM) to thermally decompose It was determined by the method (condition 300 C, 0.1 point). From the results, it can be seen that the average amount of r_undecanolactone is 15 mg / m2, and the standard deviation is 0.17 mg / m2. Ester loading was almost uniform. Using the various lactone-loaded roll paper obtained in Example 1, rolled into cigarettes in accordance with the usual method. At a temperature of 22 (:, relative humidity of 60%, the various cigarettes were stored for 4 days After 100 days and 100 days, each cigarette was taken out of the roll paper, and the r-undecanolactone by-products were measured by a thermal decomposition method (temperature 300 t, 1 hour). The results are shown in Table 2. Table 2 Roll paper Medium γ-eleven roasted Nessy with the initial childhood load (mg / m2) after 40 days of postharvest (mg / m1, 100 days of postharvest (mg / m2) 0.4 0.3 0.3 0.9 1.0 0.7 1.4 1.1 1.2 1 . 6 1.4 1.4 From the results shown in Table 2, it can be seen that the amount of r-undecanolactone in the roll paper actually maintained a certain value.

Page 16 V. Description of the invention (12) Determination of 7-undecanolactone in mainstream smoke for the above-mentioned various cigarettes Dong. The smoking conditions were based on the conditions of IS03308 (35mL, sucking every 2 seconds for 1 minute). The number of cigarettes smoked was 20 cigarettes of each kind, and the amount of r-undecanolactone in the tar captured in cambridgef i Iter was measured. From this result, it can be seen that in all the cigarettes mentioned above, the lactones in mainstream cigarettes are below the detection limit of GC-MS (mass spectrometry circle) (; each cigarette is below 100 叩). From this result, it is also known that 7-undecanolactone in the cigarette of the present invention is hardly transferred to mainstream smoke. (Example 3) Using three types of lactones shown in Table 3 below, the same method as in Example 1 was used to prepare a rolled paper with a lactone, and the initial load and the equilibrium load after the accelerated test were measured. The results are shown in Table 3. Table 3 Concentration of lactones in lactone k solution (mg / L) Attached loading of lactones in rolled paper (mg / m2) W Decolactone 400 12.5 10.8 Lactone 800 13.5 11.4 Lactone 800 22.4 18.0 From the results shown in Table 3, after the accelerated test, the amount of lactones other than taudecyl lactone was maintained at 80% or more of the initial value, which was a stable load. (Embodiment 4) <Confirm generation of hydrazone corresponding to inner box> In order to confirm that lactone will generate its hydroxy acid hydrazone in the presence of hydrazone, γ-undecanolactone aqueous solution (r_undecane internal gull was obtained Nmr quality μM with a concentration of 200jng / L) Page 17

V. Explanation of the invention (13) Spectrum circle The NMR spectrum circle contains an aqueous solution of potassium hydroxide concentration of 0.1% by weight and r-undecane internal domain 800mg / L. The second circle is the mass spectrum circle of the r-Eleven Ridge solution. The third circle is the mass spectrum circle of the r-eleven solution in the presence of potassium hydroxide. From the second and third laps, it can be confirmed that the gaseous hydrazone but the water under the r-undecanolactone will ring open to generate the corresponding hydrazone hydroxy acid. Presence (the production rate of tritium hydroxyacid in the presence of various bases) 7-Eleven gauge &lt; inner vinegar was added to sodium argon, sodium hydroxide, magnesium hydroxide, sodium carbonate (1 crystal water), potassium carbonate ( 1.5 crystal water), 0.1 wt.% Aqueous solution of sodium argon carbonate at a concentration of 1001/8/1 ^ or Table 4 Production rate (%) of lutetium hydroxy acid in aqueous solution 7j &lt;solution; ^ pri 1 0.1% NaOH 100 100 12.4 0.1% KOH 100 100 12.2 0.1% NajCO3 after 5 small bribes 9.0 hoursH20 86 91 11.0 0.1% ^ 〇〇1, 1.5HjO 83 88 11.0 0.1% Iwfe (OH) 5 49 91 10.4 0.1% CaCO3 3 26 9.71 0.1% NaHCO3 8 9 8.65, and continuously stirred at room temperature (25 ° C) for 9 hours. In the meantime, the residual rate of r-undecanolactone in the aqueous solution after 5 hours of i was removed and the residual rate of r-undecanolactone in the aqueous solution after stirring for 9 hours were measured to determine the yield of the lutetium hydroxy acid. The results are shown in Table 4. From this result, it can be seen that the lactones in the test solution will form the corresponding acid sulfonium acid's hydroxyacid hydrazone. The rate of formation is faster when a strong base is added than when a weak base is added. ~ In addition, the magnesium hydroxide aqueous solution with a slower generation rate of europium hydroxy acid

Page 18 V. Description of the invention (14) Experiment of the formation of tritium hydroxy acid at high temperature. That is, the aqueous solution was stirred at a temperature of 80 ° C to determine the generation rate of the hydroxy acid hydrazone. At this time, the generation rate of the hydroxy acid hydrazone was approximately 10 times that at 25 ° C, which violated 0.04mM / min. The generation speed. From this result, it can be seen that, taking into account the generation time of europium hydroxyacid at normal temperature, the pH of the alkaline solution is preferably 10 or more, and can also be formed at 8 or more, and the time required to generate europium hydroxyacid under high temperature conditions may be shortened. <Confirmation of lactone formation from acid sulfonate> Each of the hydroxy acid hydroxy acid aqueous solution produced above was dissolved in 3,000. (: After heat treatment at a temperature of 1 minute, the generation of T-undecanolactone in each solution was confirmed by thermal decomposition GC-MS. <Preparing the roll paper with osmium hydroxy acid supported> T-undecanolactone was prepared The alkali is dissolved in water to the concentration shown in Table 5 below to obtain an odorless aqueous solution. The aqueous solution is smeared on a commercially available low emission cigarette paper and dried at 100 ° C for 2 hours. The paper does not produce the unique aroma of r-undecanolactone. The "chitosan" attached to the rolled paper with uric acid hydrazone is used as 7 *-^-the amount of burning lactone is quantified by thermal decomposition method. The results are shown in Table 5. In addition, 7-undecanolactone was dissolved in an 80% by weight aqueous solution of ethanol, and the solution was applied to the roll paper. The roll paper obtained by drying was also thermally decomposed. Quantitative loading of τ-undecalactone. The results are shown in the table together

Page 19 V. Description of the invention (15) Table 5 Aqueous solution of r-tenyl lactone (n ^ / m2) solution lion r Pinanelactone concentration ime / U 80% acetic acid 100 3.5 0.1% KOH 100 4.0 1 % ΚΟΗ 100 4.5 From the results shown in Table 5, it can be seen that potassium hydroxide was added to transform the lactone into an acidic aqueous solution and applied to the roll paper. The p-fibrillated internal load was directly added to γ- Undecanolactone is approximately the same. Therefore, a lactone-test solution can be used to convert a lactone into a hydroxy acid beforehand and add it to the paper or material used in the manufacture of cigarettes. (Example 5) r-undecanolactone was added to an aqueous solution of 0.1% by weight of sodium argonate, acid-breaker (1.5 crystallization water), sodium carbonate, argon oxidation ball, or argon oxide solution. After stirring at room temperature (25 ° C) for 23 hours, the low sidestream cigarette paper was immersed in each solution and 'dried at 10G ° C for 2 hours to obtain the various roll papers required. In addition, the added concentration of r-undecanolactone is 5 times higher than that in Example 4, reaching 500 mg / L. Also, an aqueous solution of acetic acid containing 30% by weight of 7-undecanolactone is coated on a roll of paper as In contrast, the same was dried to obtain a rolled paper carrying lactone. GC-MS (SIM) was used to measure the amount of undecanolactone on the roll paper by a thermal decomposition method (thermal decomposition conditions: 300 t, 0.1 minute). The results are shown in Table 6.

笫 Page 20 V. Description of the invention (16) Table 6 Loading capacity of the lion's l-undecane (mg / m1) KaOH 26.5 KaCOj. 1.5H20 30.7 NaaCO, 25.3 Μβί〇Η &gt;, 24.8 Ca (OH &gt; 32.0 Comparison Γ 4.1 From the results shown in Table 6, it can be seen that τ- 所得 -alkanolactone can be produced from the roll paper obtained under various conditions. Furthermore, the concentration of 7-H-alkanolactone reaches the control (4.1 mg / m2) 6 to 7 times, and when it is confirmed that an alkaline solution is used, it can be efficiently loaded on the roll paper and thermally decomposed to generate lactones. (Example 6) Use a general roll paper containing calcium carbonate and organic acid hydrazone. 3 kinds of commercially available low sidestream cigarette paper and cigarette paper containing cigarette powder. 250, 500, 1000 mg / L r-undecanolactone / 0.1% sodium argon oxide aqueous solution was stirred at room temperature until r_ Until the undecanolactone aroma disappeared, the above-mentioned roll paper was impregnated with each solution, and then dried at 100 ° C for 2 hours. The amount of γ-undecanolactone carried in the obtained roll paper was measured by a thermal decomposition method. The volume of 7-undecane internal domain per unit weight of each roll of paper is approximately constant, and the constituents of the roll of paper have nothing to do with it. The ratio, when the 1000 mg / L solution is loaded, the loading amount of each roll of paper is about (13.4 to 41.2 mg / m2). Therefore, it is known that this technology can be applied to a variety of rolls of paper. (Example 7) For research rolls To what extent can τ-undecanolactone be carried in paper

Page 21 V. Description of Invention (17) The following experiments were performed. That is, '5% (v / v) of γ-undecylate was added to a 1¾ sodium argon aqueous solution, and after being placed in a water bath at 80 ° C for 4 hours, the paper was immersed in each of the above solutions. As a result of measuring the obtained rolled paper by thermal decomposition method, the loading amount of 7-undecanolactone is about 18,000 mg / m2. (Example 8) The improvement effect of r-undecanolactone on sidestream smoke odor attached to cigarette paper was evaluated by a functional test method. The evaluation method uses cigarettes rolled with no added lactone roll paper (control sample) and cigarettes with rolled lactone or its corresponding acidic rolled paper rolled to smell the sidestream smoke generated. And compare-contrast method, the degree of difference between samples is recorded according to the evaluation standard table described in the Sheffe method. In addition, in order to eliminate the sequence effect caused by the obscenity order of the samples, the combination order was reversely sniffed and evaluated. The effect is judged based on whether the standard deviation between the samples obtained from each evaluation item is statistically significant. Two sets of adjacent sidestream smoke generating devices generate sidestream smoke as the smelly smell 'field of sniffing mouth: Severe sores form the purple smoke that surrounds the nose, and do it at about 2 sticks / m3 ^ Tasteful condition ° The odor evaluation panel is based on the olfactory method, which is from 20 to 3 with excellent health. Old men and women are. To 15. In addition, the specifications of the smoke samples are exactly the same. Table 7 shows the evaluation samples, and Table 8 shows the evaluation results.

V. Description of the invention (18) Table 7 Secreted lactone coating method Roll paper load (mg / m2) 1 r-~ f lactone water-soluble surface cloth low side flow paper 1.3 2 τ-undecanolactone water-soluble Yubu low-column leg 4.1 3 ri monolactone soluble face cloth usually rolled paper 10.0 4 r-nononactone water-soluble cloth low-liquid cigarette paper 13.5 5 5-decanolactone water-soluble cloth low-liquid cigarette paper 12.5 6 Sodium lactone water-soluble cloth low-coated paper roll 22.4 Table 8 Functional IW ancient project secret number 1 2 3 4 5 6 Nothing but 雠 △ ◎ △ Δ △ Δ Smoke scale 雠 ◎ ◎ ◎ ◎ ◎ Coke Odor of odor ◎ ◎ △ ◎ — tar odor ◎ 〇A 〇Δ reduction of irritation △ ◎ —— — — smoke smell of dirt — ◎ △ — — Λ discovery of spice odor ◎ ◎ ◎ ◎ Λ surface Note of odor intensity) ◎ "1% significant difference highly improved 〇 ~ 5% significant difference improved △ ... has improvement tendency-... has not improved sample number 1, sample number 2 The sidestream smoke has a fruity aroma and reduces Cigarette odor represented by tar or tar odor. Within sample number 3 on page 23 Note (19) When applying the test solution of the mill, confirm that the same improvement effect is carried. The sidestream smoke of sample No. 2 has an improvement effect on the irritation of the original item or the so-called smoke particles, and it has a reduction effect. The unpleasantness has a strong improvement effect. The sidestream smoke of sample No. 4 and sample No. 5 has coconut milk-like aroma to reduce cigarette odor. Sample No. 6 has curry spice-like aroma to cover cigarette odor. As mentioned above, Depending on the type and amount of the lactone, the sidestream smoke odor of the cigarette rolled with a roll of paper carrying a sidestream smoke odor improving agent is covered by the lactone aroma and significantly improved. (Example 9) This example studies the hardening situation when the sidestream smoke odor improver of the present invention is added to the paste. A vinyl acetate copolymer-based paste or a carboxymethyl oryzanol-based paste is used for each paste. 1000 mg / L of 7 * -undecanolactone was added to the paper and coated on a commercially available low sidestream cigarette paper. Coating was also performed on the paper with an r-undecanolactone aqueous solution and then dried. The experiment is used as a control. The paper was heated at 1000 ° C. for 2 hours, the accelerated test of Example 1 was performed, and the amount of 7-undecanolactone in the roll paper was measured by a thermal decomposition method. The results are shown in Table 9. Table 9 Sticky paste Addition of lactone (mg) Loading capacity of lactone after accelerated test (mg) Aroma (%) Vinyl acetate copolymer 0.49 0.39 80 Chemimethylandrosin 0.67 0.08 12 Control (addition of aqueous solution) 0.33 0.08 24 by As can be seen from the results shown in Table 9, the 7-h-hyun internal mill was added to the paste

Page 24 Five-Case number 87117470 Description of the invention (20)

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Medium 'τ-Η • —Alkanolactone can still be stably attached to the roll of paper》 Also, it is recognized that when r-undecanolactone is added to the paste, the aroma of r-undecanolactone is weakened ° Particularly When using vinyl acetate copolymer based paste, there is almost no + angstrom odor. As described above, according to the present invention, a simpler structure can be provided, which does not emit aroma under non-smoking conditions, and can cover the unpleasant odor of sidestream smoke when smoking, and can be provided with an improved sidestream smoke odor. Cigarette paper and cigarettes with sidestream smoke odor improver. [Simplified description of 囷 式 式] 10 Cigarette part 11 Smoke column 12 Roll paper 13 Sticky paste 20 Filter part 21 Filter element main ingredients 22 Thin packaging paper 30 Wood chip paper 3 1 a to 3 1 η Piercing hole

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Claims (1)

Case No. 87117470 Sect. 6, Application for patent scope 8 &amp; 9. 0 8 Supplement 1. A cigarette paper, the stick is a cigarette sidestream smoke odor improver with% lactones in free state 5 2. If you please Cigarette roll paper in item 1 of the patent scope, in which the lactone is a ring carrying 5 or more members. 3. As described in the cigarette wrap paper in item 1 of the patent scope, in which the lactone is r-lactone or δ -Lactones 0 4. Cigarette roll paper of item 1 of the patent scope, where the content is selected from the group consisting of 7-butyrolactone, T-valerolactone, T-heptanolactone, 7 * -caprolactone Vinegar, caprolactone, 7 &quot; -nonolactone, T-caprolactone, γ-Η-lactone, sotholactone, apraxon, 5-octanolactone, &lt; 5-nononactone, 5-Decanolactone, (5-undecanolactone, omega-pentadecanolactone, and a mixture of the above-mentioned lactones. 5. In the case of cigarette paper, It is applied to cigarette paper in the form of lactone aqueous solution and then dried. 6. A cigarette paper roll, characterized in that it contains a cigarette sidestream smoke odor improving agent containing a corresponding hydroxyamidine containing lactone. 7. For example, the cigarette paper roll of claim 6, wherein the hydroxy acid is塩 is a metal test 碱 or alkaline earth metal 塩 tester. 8. For example, the cigarette roll paper of item 6 of the patent application scope, in which the hydroxy acid 塩 is a hydroxy acid 对应 corresponding to 5 or more lactones. 9. If applied Cigarette roll paper of item 6 of the patent, wherein the hydroxy acid is the hydroxy acid corresponding to lactone or (5-lactone. 10. For example, the cigarette roll paper of the application of the scope of the patent, the hydroxy acid is塩 is corresponding to the group selected from 7-butyrolactone, 7-valerolactone, T-heptanolactone, caprolactone 61, 7 &quot; -caprylic vinegar, 7 &quot; -nononyl vinegar, 7-caprylide, 7 —H C: \ Program Files ^) atent \ 310167.ptc Page 1 1999.09.06. 026 Case No. 87117470 Muji 6, Application Patent Scope 8 &amp; 9. 0 8 Supplement 1. A cigarette roll paper, the sticks of which contain% Cigarette sidestream smoke odor improving agent containing free lactones 5 2. If the cigarette roll paper of item 1 of the patent scope is requested, the lactone is a ring with more than 5 members 0 3. If the patent is requested Cigarette roll paper of scope item 1, wherein the lactone is r-lactone or δ-lactone. 0. For example, please refer to the cigarette roll paper of scope item 1 of patent, where the content is selected from 7-D Lactone, T-valerolactone, T-heptanolactone, 7 * -caprolactone, caprylic vinegar, 7 &quot; -nononolactone, T-caprolactone, γ-Η-nolide, sotalone , Alprahsson, 5-octanolactone, &lt; 5-nonolactone, 5-decanolactone, (5-undecanolactone, omega-pentadenolactone, and mixtures of the above-mentioned lactones' The group of people. 5. For example, the cigarette paper of the scope of patent application No. 1 in which the lactone is water-soluble The liquid form is applied to a cigarette rolled paper and then dried. 6. A cigarette rolled paper characterized by containing a cigarette sidestream smoke odor improving agent containing a corresponding hydroxyamidine containing lactone. 7. If applied Cigarette roll paper in item 6 of the patent, in which the hydroxy acid 塩 is metal test 碱 or alkaline earth metal 塩. 8. For the cigarette roll paper in the application in the scope of patent item 6, the hydroxy acid 其中 is corresponding to more than 5 members The hydroxy acid of the cyclic lactone. 9. For example, the cigarette paper of item 6 of the patent application scope, wherein the hydroxy acid of the hydroxy acid is corresponding to the lactone or (5-lactone of the hydroxy acid.) 10. If applied Cigarette roll paper of item 6 of the patent, in which the hydroxy acid is corresponding to the selected from the group consisting of 7- butyrolactone, 7-valerolactone, T-heptanolactone, caprolactone 61, 7 &quot; -caprylide, 7 &quot; -nonone vinegar, 7 decanal vinegar, 7 —h C: \ Program Files ^) atent \ 310167.ptc Page 1 1999.09.06. 026 A domestic lactone, sotalone, apraxon, 5-octyl lactone, nonolactone, 5-decanolactone, sultone, omega_five stilbene lactone, 11 and a mixture of the above lactones Groups of hydroxy acids. • If the cigarette paper is covered by item 6 of the patent application, which is applied in the form of a 12-aqueous solution through a basic acid solution, and then applied to the cigarette paper, and then dried into a cigarette • A cigarette, which is a cigarette wrapped with a cigarette paper, The rolled paper is loaded with a cigarette sidestream smoke odor improving agent containing a lactone in a free state. 13. If the cigarette within the scope of patent application No. 12 is a 5-member ring. 14. If a cigarette is applied for item 12 of the patent scope, where the lactone is η or octa-lactone "15. If a cigarette is applied for item 12 of the patent scope, wherein the lactone is selected from butyrolactone, r- Valerolactone, r-heptanolactone, τ * -caprolactone, 7-octanolactone, r''nonolactone, r-decanolactone, --- alkanolactone, Sotalum interior wall, Apheson Group consisting of 5-octyl lactone, 5-nononolactone, decanolactone, octa-undecanolactone, omega-pentadenolactone, and mixtures of the above-mentioned lactones "16 · 如Cigarettes with a scope of patent application No. 12 in which the lactone is applied to the cigarette paper in the form of an aqueous solution and then dried. 17. The cigarette according to item 12 of the patent application, wherein the paper roll is adhered with an aqueous adhesive, and the lactone is contained in the adhesive so as to be attached to the paper roll. 18. A cigarette comprising a cigarette rolled paper &apos; The cigarette rolled paper is provided with a cigarette sidestream smoke odor improving agent containing a lactone hydroxy acid peptone. * _Case No. 87117470_Year_Month__ VI. Patent application scope 19. For example, for a cigarette in the scope of patent application No. 18, the hydroxy acid 塩 is alkali metal 碱 or alkaline earth metal 塩. 20. For example, the cigarette in the scope of patent application No. 18, in which the hydroxy acid is a hydroxy acid corresponding to a lactone of more than 5 members. 21. For a cigarette in the scope of patent application No. 18 or 19, the hydroxy acid 塩 is corresponding to the hydroxy acid T corresponding to T-lactone or 5-lactone. 2 2. The cigarette according to item 18 of the scope of patent application, wherein the hydroxy acid fluorene is corresponding to the selected from the group consisting of T-butyrolactone, T-valerolactone, enantolactone, γ-caprolactone, and T-octanolactone. , 7 * -nonone_, 7 &quot; -caprolactone, T-^-lactone, sotalone, aprasiden, 5-octyllactone, &lt; 5-nononactone, 5-decyl Lactone, &lt; 5-undecanolactone, omega-pentadecanolactone, and the hydroxy acid group formed by a mixture of the above lactones. 23. For example, the cigarette in the scope of the patent application No. 18, in which the hydroxy acid is applied to the cigarette paper in the form of an aqueous solution, and then dried. 24. For example, the cigarette in the scope of patent application No. 18, in which the roll paper is adhered with a water-based rhenium adhesive, and the hydroxy acid rhenium is contained in the adhesive so as to be attached to the roll paper. C: \ Program Files ^) atent \ 310167.ptc Page 3 1999. 09. 06. 028