JP6673564B2 - Composition - Google Patents

Description

  The present invention relates to compositions, and in particular, to compositions for, for example, tobacco products.

There is a great need to reduce the sidestream smoke odor of cigarettes, and the fragrances used to achieve this are being actively researched. In order to further enhance the low odor function of cigarettes and to expand product variations according to the tastes of customers, technical knowledge on the types and combinations of compounds constituting fragrances is always required.
On the other hand, a method of reducing the odor by treating tobacco leaves is also conceivable, but there are few studies. In the case of improving the flavor and taste of mainstream smoke, in order to enhance the technology (Patent Document 1) of esterifying and nitrite-treating a part of the tobacco content component, and to enhance the ester flavor component or the component contributing to the flavor taste. A method of ripening tobacco cuts under sealed conditions in an air atmosphere (Patent Document 2) is known.

Japanese Patent Publication No. 45-32917 International Publication No. WO 2013/098920

Shimizu, Takei, Journal of the Japanese Society of Agricultural Chemistry, 23, 286, (1949)

The technique described in Patent Document 1 requires a plurality of steps, and the steps are complicated. Further, in this technique, the components contained in the tobacco to be subjected to the esterification reaction are components distributed to the hexane phase, so that the amount and type of the generated ester are limited.
In the technique described in Patent Document 2, a long time (1 week to 3 months) is required for the reaction (aging).
In addition, the techniques described in any of the above-mentioned patent documents focus on changes in the flavor and taste of mainstream smoke, and are not aimed at reducing sidestream smoke odor. Furthermore, since the amount and type of the generated ester are limited, it is hard to say that the above method can effectively reduce the sidestream smoke odor. In addition, in the technology described in any of the above patent documents, through the treatment of tobacco leaves without adding a fragrance, a means of causing a change in the aroma of the tobacco itself has been studied, but this is the mainstream. The present invention focuses on the change in the taste of smoke and is not intended to reduce the sidestream smoke odor.
From the above, the present invention provides a composition capable of efficiently reducing sidestream smoke odor when added to tobacco leaves, a tobacco raw material containing the composition and tobacco leaves, and a method for producing the same. Make it an issue.

  As a result of intensive studies by the present inventors, it has been found that a composition containing diethyl malate and at least one of ethyl levulinate, ethyl palmitate and triethyl citrate can solve the above-mentioned problems, and has reached the present invention.

That is, the present invention is as follows.
[1] A composition comprising diethyl malate and at least one selected from ethyl levulinate, ethyl palmitate and triethyl citrate.
[2] The composition according to [1], which is for tobacco products.
[3] The composition according to [1] or [2], wherein the amount of diethyl malate is 5 to 95% by weight based on the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate.
[4] The composition according to any one of [1] to [3], wherein the amount of diethyl malate is 20 to 60% by weight based on the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate. Stuff.
[5] A tobacco raw material comprising tobacco leaves and the composition according to any one of [1] to [4].
[6] diethyl malate and levulinic acid, comprising: an extraction step of obtaining an extract of tobacco leaves using ethanol; and an esterification reaction step of adding a catalyst to the extract obtained in the extraction step to perform an esterification reaction. A method for producing a composition comprising at least one of ethyl, ethyl palmitate and triethyl citrate.
[7] The method according to [6], wherein the catalyst is a solid acid, and the method includes a step of removing the catalyst of the added solid acid before the esterification reaction.
[8] a step of obtaining an extract of tobacco leaves using water or a solvent comprising water and ethanol, and a step of the following (1) or (2),
(1) Step of concentrating the extract obtained in the extraction step to obtain a concentrate, and adding ethanol to the concentrate (2) Step of adding ethanol to the extract obtained in the extraction step i) After adding a catalyst to any one of (iv) to (iv), the method includes an esterification reaction step of performing an esterification reaction, wherein diethyl malate and one or more of ethyl levulinate, ethyl palmitate, and triethyl citrate are used. A method for producing a composition comprising:
(I) Extract obtained in the extraction step (ii) Concentrate obtained in the step (1) (iii) Solution obtained through the step of (1) (iv) Obtained through the step of (2) [9] The production method according to [8], wherein the catalyst is a solid acid, and the method further comprises a step of removing the added solid acid catalyst before the esterification reaction.
[10]
Tobacco leaves, including a step of esterification reaction of a material obtained by mixing ethanol and a catalyst, including diethyl malate, and ethyl levulinate, ethyl palmitate, and at least one of triethyl citrate Manufacturing method for tobacco raw materials.
[11] The production method according to [10], wherein the catalyst is a solid acid, and the method includes a step of removing the catalyst of the solid acid before the esterification reaction.
[12] The production method according to any one of [6] to [11], wherein the step of the esterification reaction is performed at a temperature of 60 to 150 ° C for 5 to 500 minutes.
[13] The production method according to any one of [6] to [11], wherein the catalyst is a solid acid having an elimination amount at an elimination peak at less than 500 ° C. of 10 μmol / g or more in an ammonia TPD method. .
[14] The production method according to any one of [6], [8], [10], and [12], wherein the catalyst is a liquid acid.

  When the composition of the present invention is added to tobacco leaves, or when a tobacco raw material containing the composition and tobacco leaves is used, the sidestream smoke odor can be efficiently reduced.

It is a figure which shows the kind of ester obtained through esterification about the ethanol extract of a Japanese yellow variety, and its relative amount. Esterification conditions: 120 ° C., 1 h, amount of catalyst: 50% by weight per wet weight of tobacco It is a figure which shows the measurement conditions of ammonia TPD. FIG. 4 is a view showing the ester content of the treatment liquids of Example 2 and Comparative Example 1. Esterification conditions: 120 ° C., 3 h, catalyst addition amount: 50% by weight per tobacco wet weight It is a figure which shows the tobacco odor sensory evaluation result before and after the process of Example 1 using Japanese yellow seed. It is a figure which shows the tobacco odor sensory evaluation result at the time of using the processing liquid of Example 2 using a yellow seed medium bone. It is a figure which shows the tobacco odor sensory evaluation result obtained using the commercial cigarette which added the processing liquid of Example 1 and the comparative example 1 using the Japanese yellow seed. It is a figure which shows the evaluation result of the influence which the kind and addition amount of an ester give to a cigarette odor. It is a figure which shows the result of having investigated the tobacco odor reduction effect of the mixture of ethyl palmitate and diethyl malate. It is a figure which shows the result of having investigated the tobacco odor reduction effect of the mixture of triethyl citrate and diethyl malate. It is a figure which shows the result of having investigated the influence which diethyl malate gives to a cigarette odor. It is a figure which shows the production amount of the ethyl ester in Examples 3-5. Tobacco leaves: Japanese yellow 14 is a chromatogram obtained by analyzing the processed product of Example 6.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail by showing embodiments and examples, but the present invention is not limited to the following embodiments and examples, etc. Can be changed and implemented.

The composition of the present invention contains diethyl malate and one or more selected from ethyl levulinate, ethyl palmitate and triethyl citrate.
That is, the composition of the present invention contains not only diethyl malate but also a combination thereof with any one or more selected from ethyl levulinate, ethyl palmitate and triethyl citrate.
Not only diethyl malate, but also a composition comprising a combination of any one or more selected from ethyl levulinate, ethyl palmitate and triethyl citrate, when this composition is added to tobacco leaves, When a tobacco raw material including a product and tobacco leaves is used, the effect of reducing tobacco odor is increased.

The composition of the present invention containing any one or more selected from diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate may be prepared by mixing these compounds isolated in advance. Then, as in the method for producing the composition of the present invention described below, malic acid, levulinic acid, palmitic acid, citric acid previously contained in tobacco leaves, and a step of esterifying by reacting with ethanol are obtained. The composition may be prepared by separating and purifying malic acid, levulinic acid, palmitic acid, and citric acid from the treated solution.
As a method for separation and purification at that time, known chromatography can be used, for example, ion-exchange chromatography or reversed-phase high-performance liquid chromatography can be used. Known conditions can be used for these chromatography conditions.

Preferably, the compositions of the present invention are for tobacco products.
“For tobacco products” means that it can be used by adding to tobacco leaves used for producing tobacco products, or can be used as a tobacco raw material for producing tobacco products.

The content of diethyl malate in the composition of the present invention may be 5% by weight or more based on the total content of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate contained in the composition. The content is preferably 10% by weight or more, more preferably 20% by weight or more. On the other hand, the content of diethyl malate is preferably 95% by weight or less, and more preferably 80% by weight or less based on the total content of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate. More preferably, it is still more preferably 60% by weight or less.
The total content of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate with respect to the total amount of the composition of the present invention can be in the range of 5 to 95% by weight, and is in the range of 10 to 80% by weight. , And more preferably 20 to 60% by weight.

The content of each of ethyl levulinate, ethyl palmitate and triethyl citrate in the composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired. An embodiment that satisfies the relationship ethyl ethyl> ethyl palmitate> triethyl citrate may be mentioned.
These ethyl esters may be combined with diethyl malate alone, or a plurality of these may be combined with diethyl malate.
Ethyl palmitate is preferably used in combination with diethyl malate. One or both of ethyl levulinate and triethyl citrate may be combined with this combination.

  When the composition is added to tobacco leaves, the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate in the composition is 0.01% by weight or more based on the wet weight of the raw material of the tobacco leaves. An embodiment can be given, and the content is preferably 0.05% by weight or more, more preferably 0.1% by weight or more. On the other hand, as for this weight, an embodiment in which the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate in the composition is 10% by weight or less based on the wet weight of the raw material of the tobacco leaf can be mentioned.

In the case of using the composition and the tobacco raw material including the tobacco leaf (including the tobacco leaf and its notch), the tobacco raw material may be, for example, diethyl malate, ethyl levulinate, ethyl palmitate with respect to the wet weight of the tobacco leaf raw material. And the total amount of triethyl citrate is 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more.
On the other hand, with respect to this weight, there can be mentioned an embodiment in which the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate is 10% by weight or less.

When the composition of the present invention is used by adding it to tobacco leaves, the respective compounds of the above-mentioned isolated ethyl esters may be mixed to form a composition. As the isolated diethyl malate, ethyl levulinate, ethyl palmitate, and triethyl citrate, commercially available ones can be used, and the respective ethyl esters obtained by synthesis are fractionated to adjust their concentrations. You may get it.
In addition, as described later, a solution containing malic acid, levulinic acid, palmitic acid, citric acid and carbohydrates (precursor of levulinic acid) contained in tobacco leaves is obtained by previously extracting from a tobacco leaf. Alternatively, the composition may be prepared by mixing and reacting the obtained extract with a solution containing ethanol, causing the mixture to react and esterify, and separating and purifying a treatment solution containing ethyl ester.
In addition, as a method of separation and purification at that time, a known vacuum distillation method and chromatography can be used, and for example, adsorption chromatography using a rotary evaporator or silica gel can be used. Known conditions can be used for these separation and purification methods.
The tobacco leaves that can be used at that time include, in addition to those described below, uncut, tobacco leaves that have been cut into a predetermined shape, tobacco powder having a predetermined particle size, or uncut lamina. You may.
The tobacco leaves to be subjected to the extraction treatment may contain water.

  The following procedure can be mentioned as a specific method for preparing the composition when the above-mentioned ethyl ester compound is obtained by the reaction.

Water, ethanol, or a mixture thereof is added to the tobacco leaf, and the mixture is subjected to an extraction treatment at a temperature from room temperature to about 70 ° C. to separate an extract and an extraction residue.
As the solvent used for the extraction, water or ethanol can be used alone or in combination.
When extraction is performed using water or a mixture of water and ethanol as a solvent, more compounds (including organic acids, sugars, and carbohydrates) subjected to the esterification reaction can be extracted. However, since water becomes an inhibitory substance during the esterification reaction, the extract is concentrated to obtain a concentrate, and then ethanol is added to the concentrate or the concentration of the water is reduced to a sufficiently low level. It is desirable to adjust the amount of water in the reaction solution by, for example, adding ethanol to the extract. A known method can be used as the concentration method.
The temperature and time conditions for the extraction may be the same as those in the case of using an extraction solvent containing ethanol as a main component.
When using ethanol or a mixed solution of ethanol and water as the extraction solvent, if the extraction solvent is ethanol, the extraction liquid is used as it is, and if the extraction solvent contains water, at least until the reaction proceeds, After reducing the amount of water, it can be subjected to the following reaction.
As a method of reducing the amount of water, a method of concentrating the extract can be mentioned.
As the amount of water at that time, an embodiment in which the amount of water in the esterification reaction is performed is less than 90% by weight, an embodiment in which the amount is less than 50% by weight is preferable, and an embodiment in which the amount is less than 10% by weight is more preferable. .
When the extraction solvent is ethanol, a step of removing water from the extract may not be included.

The obtained extract is concentrated, and an esterification reaction is caused to occur together with the catalyst under conditions such that the pressure is equal to or lower than a predetermined value. Therefore, the reaction is preferably performed using a pressure-resistant container or the like. The catalyst that can be used will be described later.
The pressure during the reaction may be from normal pressure to 1 MPa.
The reaction time may be 5 to 500 minutes, preferably 10 to 300 minutes, more preferably 10 to 180 minutes.
The temperature during the reaction may be, for example, 60 to 150 ° C, preferably 80 to 120 ° C, and more preferably 100 to 120 ° C. In order to secure such a temperature, the reaction is preferably performed under heating.
When the solid acid is used, for example, the amount of the catalyst can be 5 to 400% by weight, preferably 10 to 300% by weight, and preferably 20 to 200% by weight based on the wet weight of the tobacco leaf. More preferably, it is% by weight.
When using a liquid acid, the wet weight of the tobacco leaf can be 0.001 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.1 to 5% by weight. More preferably, there is.

  The esterification reaction may be carried out with the catalyst contained in the solution to be reacted, or, when the catalyst is a solid acid, removed from the solution to be reacted before the esterification reaction is carried out. Is also good. In the case of using the solid acid exemplified above, the esterification reaction proceeds if the catalyst is brought into contact with the solution in which the reaction is performed to perform proton exchange. Specifically, when heating is performed, the esterification reaction proceeds even if the solid acid does not exist in the solution.

The solution obtained by performing the esterification reaction on the extract contains diethyl malate and at least one selected from ethyl levulinate, ethyl palmitate and triethyl citrate. A treatment liquid containing the composition of the present invention can be obtained by removing unnecessary substances such as the above.
The treatment liquid containing the composition of the present invention obtained through this operation may be returned to the tobacco leaf extraction residue. When added to other materials used for tobacco products such as tobacco cuts, the treatment liquid is separated and purified to adjust the composition, and then added to the materials used for tobacco products.
As conditions for the separation and purification at that time, a known vacuum distillation method and chromatography can be used.

Without performing the extraction treatment, malic acid contained in tobacco leaves, and a composition containing the above ethyl ester compound obtained by reacting at least one selected from levulinic acid, palmitic acid and citric acid with ethanol and tobacco leaves Examples of a method for producing a tobacco raw material including the above include a method in which a catalyst and ethanol are added to tobacco leaves to cause an ethyl esterification reaction.
According to this production method, a tobacco raw material including tobacco leaves and diethyl malate, one or more compositions selected from ethyl levulinate, ethyl palmitate, and triethyl citrate can be produced. In this case, it can be used as a tobacco raw material containing the obtained composition and tobacco leaves. The tobacco raw material containing the composition and the tobacco leaves prepared by this method can be used by mixing with other materials used in tobacco products such as tobacco leaves.
As the conditions for the esterification at that time, the same conditions as those for the esterification of the above-mentioned extract can be used.

Examples of the catalyst used when synthesizing the ethyl ester compound include a liquid acid and a solid acid.
The liquid acid preferably has an acid dissociation constant of 6 or less, and more preferably has an acid dissociation constant of less than 3.
Specific examples of liquid acids include sulfuric acid, sulfurous acid, hydrochloric acid, hypochlorous acid, benzoic acid, formic acid, citric acid, malic acid, tartaric acid, valeric acid, isovaleric acid, butyric acid, malonic acid, glutamic acid, succinic acid, Lactic acid, acetic acid, salicylic acid, oxalic acid, phosphoric acid and the like can be mentioned.

Examples of solid acids include natural minerals, cation exchange resins, supported acids, metal oxides / composite metal oxides, calcined metal sulfates, and the like.
As a specific example of the solid acid, it is preferable to use one having an ammonia desorption amount of 10 μmol / g or more at a desorption peak in a temperature range of less than 500 ° C. measured by an ammonia TPD method described later.
Further, the amount of ammonia desorbed at the desorption peak in the temperature range of less than 400 ° C., measured by the ammonia TPD method, of the solid acid that can be used in the production method of the present invention is 500 μmol / g or more. Is more preferred.
When such a catalyst is used, an ethyl ester compound is efficiently produced.
Examples of the solid acid having the above properties include those in which an acidic functional group is supported on an organic substance such as a resin having an acidic exchange group (for example, a styrene resin) or an inorganic substance such as silica gel. Examples of the acidic exchange group or acidic functional group include a sulfonic acid group.
Specific solid acids include those described in the following table.

In the ammonia TPD method, after water adsorbed on a solid acid is removed by pretreatment, ammonia is adsorbed and the temperature is raised to desorb ammonia. When the amount of desorption with respect to the temperature at the time of temperature rise desorption is drawn, the amount of acid can be inferred from the amount of desorption, and the strength of the acid can be inferred from the desorption temperature.
The measurement conditions are shown below:
Measuring device: Full-automatic thermal desorption spectrometer TPD-1-ATw Nippon Bell Co., Ltd. Sample amount: about 0.05 g
Thermal desorption measurement: The target gas component is detected by a quadrupole mass spectrometer.
Measurement range: 80 to 800 ° C
Measurement atmosphere: He 50 mL / min
Detection fragment: m / z = 16
FIG. 2 shows details of the heating conditions and the like.

To summarize the above, the following embodiments (A) to (C) can be mentioned as a method for producing a composition of the present invention and a tobacco raw material containing the composition and tobacco leaves. In the following embodiments, the conditions for the extraction and the esterification reaction are as described above.
(A) A production method comprising an extraction step of obtaining an extract of tobacco leaves using ethanol, and an esterification reaction step of adding a catalyst to the extract obtained in the extraction step and subjecting the extract to an esterification reaction.
(B) a step of obtaining an extract of tobacco leaves using water or a solvent consisting of water and ethanol, and the following (1) or (2):
(1) Step of concentrating the extract obtained in the extraction step to obtain a concentrate, and adding ethanol to the concentrate (2) Step of adding ethanol to the extract obtained in the extraction step A production method comprising an esterification reaction step in which a catalyst is added to any of i) to (iv), followed by an esterification reaction.
(I) The extract obtained in the extraction step (ii) The concentrate obtained in the step (1) (iii) The solution obtained through the step (1) (iv) The solution obtained through the step (2) A method for producing the solution (C), comprising the step of esterifying a material obtained by mixing tobacco leaves, ethanol and a catalyst.
The embodiment (A) is a method in which an extract is obtained from tobacco leaves using ethanol as an extraction solvent, the above catalyst is added to the extract, and an esterification reaction is performed.
In the embodiment (B), an extract is obtained from tobacco leaves using water or water and ethanol as extraction solvents, and the extract is once concentrated to obtain a concentrate, and then ethanol is added to the concentrate ( Ethanol is added to the extract (step (1)) or without concentration (step (2)), and the above catalyst is added to the solution or concentrate obtained in any of these steps to obtain an ester. This is a method for performing a chemical reaction.
The embodiment (C) differs from the embodiments (A) and (B) in that the extraction operation is not performed on tobacco leaves, and the esterification reaction is performed by adding ethanol and the above catalyst.
In any of the above embodiments (A) to (C), when the above solid acid is used as the catalyst, the catalyst may be removed from the solution by an operation such as filtration before the esterification reaction is performed. . This is because, as described above, once proton exchange is performed by contacting with a solid acid, the reaction proceeds even if the catalyst is not present in the reaction solution. When the solid acid is removed, the catalyst can be reused.

Examples of tobacco leaves that can be used for producing the composition of the present invention or tobacco raw materials containing the composition include tobacco cuts used for cigarettes (hereinafter also referred to as leaf tobacco cuts).
When using tobacco cut as tobacco leaves, any varieties can be used.For example, yellowed, burley, oriented bolled leaves and bones, and regenerated sheets composed of these materials can be used. Can be used. By tobacco cut means generally ready for the manufacture of tobacco products. As for the size of the cut pieces of the tobacco cut, known ones can be used without limitation.
In the present invention, the same tobacco leaves as those described above can be used for extracting malic acid, levulinic acid, palmitic acid and citric acid.

  If the tobacco product is a cigarette, a known size can be adopted for the size of the tobacco-cut leaves constituting the cigarette. The configuration of the cigarette as a tobacco product is not particularly limited, and may include known embodiments.

  Other additives may be added to the composition of the present invention as long as the effects of the present invention are not impaired. Such additives include, for example, fragrances and humectants.

An embodiment in which the composition of the present invention is used by adding to a tobacco leaf used for producing a tobacco product, or using the composition and the tobacco raw material containing the tobacco leaf as it is, can be preferably mentioned.
Particularly preferred tobacco products include smoking articles. That is, as the use of the composition of the present invention and the tobacco raw material containing the composition and tobacco leaves, it is particularly preferable to use for smoking articles among tobacco products.
The composition of the present invention and tobacco raw materials containing the composition and tobacco leaves may also be used for oral tobacco products and electronic tobacco.
Examples of the smoking article include cigarettes, cigars, and cigarillos.

When the composition of the present invention is added to a tobacco leaf used for making a tobacco product, the composition of the present invention is added to a tobacco leaf used for preparing a tobacco product.
When the tobacco raw material containing the composition of the present invention and tobacco leaves is used as it is, the tobacco leaves used in the above-mentioned tobacco product are used in the stage of preparing the composition of the tobacco raw material. In this case, the tobacco raw material including the composition of the present invention and tobacco leaves can be used as it is as a tobacco material for tobacco products.
When the composition itself is used as a tobacco raw material, there may be mentioned an embodiment in which the material derived from tobacco leaves such as tobacco cuts contained in the composition is 80 to 99.99% by weight based on the total weight of the composition. it can.

When the composition of the present invention is added to tobacco leaves, the amount of addition is not particularly limited, but is included in the material for tobacco products composed of tobacco leaves after addition, diethyl malate, ethyl levulinate, palmitin. There may be mentioned an embodiment in which diethyl malate is added in an amount of 5 to 95% by weight based on the total weight of ethyl acid and triethyl citrate.
In this embodiment, the content of diethyl malate is more preferably 20 to 60% by weight based on the total weight of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate.
When the composition of the present invention is added to the tobacco leaf in the above-described amount, the effect of reducing the sidestream smoke odor can be favorably obtained.
Further, the composition of the present invention is added so that the content of diethyl malate with respect to the wet weight of the tobacco product material composed of the tobacco leaves after the addition is 0.0005 to 1% by weight. Is preferred.

On the other hand, even when the tobacco raw material including the composition of the present invention and tobacco leaves is used, diethyl malate is 5% based on the total weight of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate in the tobacco raw material. To 95% by weight.
In this embodiment, the content of diethyl malate is more preferably 20 to 60% by weight based on the total weight of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate.
In this embodiment, the content of diethyl malate with respect to the wet weight of the tobacco leaf is preferably 0.0005 to 1% by weight.
When diethyl malate is contained in the composition or tobacco raw material of the present invention at the above content, the effect of reducing the sidestream smoke odor can be favorably obtained.

  In any of the above embodiments, the amount of diethyl malate is 5 to 95% by weight based on the total amount of diethyl malate, ethyl levulinate, ethyl palmitate and triethyl citrate in the composition or tobacco raw material of the present invention. Is more preferably 20 to 60% by weight.

  The present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

<Example 1> Ethyl esterification reaction using tobacco extract using solid acid as a catalyst As a catalyst for the esterification reaction, a liquid acid such as sulfuric acid or a solid acid having an acidic functional group supported on a resin or the like is used. It is common to use. Particularly, when the reactant / product is liquid, a solid acid which can be easily separated is useful. Therefore, an ethyl ester compound of an ethanol extract of tobacco leaves was synthesized using the solid acid.

・ Effect of catalyst species on the reaction Add 1g-wet tobacco: 10ml of ethanol to the domestic yellow varieties, shake and extract in a 60 ° C water bath for 1 hour, and extract and extract with nonwoven fabric The residue was separated. After the extract was concentrated to a predetermined concentration, it was heated together with the catalyst at 120 ° C. for 1 hour in a pressure vessel. The five catalysts shown in Table 2 were used. From the state at the time of purchase of the catalyst, the catalyst was used without any pretreatment, and the addition amount was 50% by weight based on the wet weight of the tobacco.

-Analysis of treatment solution As a preliminary test, qualitative analysis was performed by GC-MS using Agilent's DB-WAX (J & W 122-7032) as a column. As a result, the component produced in the treatment solution of Example 1 in large amount was ethyl levulinate. , Diethyl malate, ethyl palmitate and triethyl citrate. In this test system, GC-FID analysis was performed on the above four ethyl ester compounds using the same column, and quantification was performed from the peak area by the internal standard method. The result is shown in FIG.

＊表中の比表面積及び平均細孔径はカタログ値を示す。市販品固体酸ｂについては、比表面積と平均細孔径のカタログ値なし。

* The specific surface area and average pore diameter in the table indicate catalog values. For the commercially available solid acid b, there is no catalog value of specific surface area and average pore diameter.

  From FIG. 1, the progress of the reaction with a commercially available solid acid could be confirmed. This result is merely an example, and suitable reaction and pretreatment conditions can be selected depending on the desired amount, composition, and equipment used of the ethyl ester.

-Characterization of used catalyst For the catalyst used in Example 1, the acid strength and acid amount were estimated by the ammonia TPD method. This method is one method for examining the amount and strength of acid sites. After removing adsorbed water by pretreatment, ammonia is adsorbed, and the temperature is increased to be desorbed. When the amount of desorption with respect to the temperature at the time of temperature rise desorption is drawn, the amount of acid can be inferred from the magnitude of the amount of desorption, and the strength of the acid can be estimated from the desorption temperature.
The measurement conditions are shown below (the temperature rise conditions and the like are also shown in FIG. 2);
Measuring device: Full-automatic thermal desorption spectrometer TPD-1-ATw Nippon Bell Co., Ltd. Sample amount: about 0.05 g
Thermal desorption measurement: The target gas component was detected by a quadrupole mass spectrometer.
Measurement range: 80 to 800 ° C
Measurement atmosphere: He 50 mL / min
Detection fragment: m / z = 16

Table 3 shows the measurement results. From the results in Table 3, the catalyst whose progress of the esterification reaction was confirmed by the method of Example 1 had a desorption amount of 10 μmol / g or more at the desorption peak in the temperature range of 500 ° C. or less in the ammonia TPD method. Was.

<Example 2> Reaction of ethanol extract A 10 g solid-liquid ratio of ethanol was added to leaf tobacco, and the mixture was shaken and extracted in a water bath at 60 ° C for 1 hour. separated. After the extract was concentrated to a predetermined concentration, it was placed in a pressure-resistant container, and 50% by weight of the tobacco wet weight was added to a commercially available solid acid c, which was heated at 120 ° C. for 3 hours.

Comparative Example 1: Comparison with Patent Document 1 Reaction of Hydrophobic Fraction in Methanol Extract Solution 1g-wet tobacco: 5 ml amount of methanol was added to leaf tobacco cut, and the mixture was shaken in a 50 ° C water bath for 1 hour. Then, the mixture was separated into an extract and an extraction residue with a nonwoven fabric. The methanol was devolatilized from the extract, and equal amounts of hexane and water were added and shaken vigorously. Only this organic phase was recovered, hexane was devolatilized and then dissolved in ethanol. This solution was subjected to a reaction under the same conditions as in Example 1.

-Composition of treatment solution The ethyl ester content in the treatment solutions of Example 2 and Comparative Example 1 is shown in Fig. 3. In Example 2, the amounts of diethyl malate and ethyl levulinate not produced in Comparative Example 1 are particularly large, and the amount of ethyl palmitate commonly produced in Example 1 and Comparative Example 1 is almost the same. It was shown that.
Regarding this difference, it is considered that in Comparative Example 1, the extracted highly polar organic acids such as malic acid and citric acid were not generated because they were distributed to the aqueous phase by the hexane / water separation operation and did not participate in the reaction. . The levulinic acid ester confirmed in Example 1 is produced by a reaction between a carbohydrate such as sugar or starch and an alcohol (Non-Patent Document 1). Therefore, it is considered that the extracted carbohydrate was not generated in Comparative Example 1 because the extracted carbohydrate was distributed to the aqueous phase by the liquid separation operation and did not participate in the reaction. Since the reactions of Example 1 and Comparative Example 1 were performed under the same conditions, it can be said that the qualitative / quantitative difference between the products was caused by a method of preparing a reaction solution to be subjected to the reaction of extraction and separation. .

-Sensory evaluation using treatment liquid The sensory evaluation of the sidestream smoke odor was performed by causing cigarettes to naturally burn in a room and comparing and evaluating the odor in the room after a predetermined time. The evaluation was performed by one pair comparison, and the number of panels per pair of evaluation was about 30 persons. The panel replied alternatively which room felt tobacco smell.

Sensory evaluation result 1: Changes before and after treatment according to Example 2. Treated tobacco: Japanese yellow seed Material: Paper tube used for commercial cigarette products-After treatment: Harmonized and cut using domestic yellow seed After performing the treatment of Example 1 (120 ° C., 3 hours, catalyst addition amount: 50% by weight based on wet weight of tobacco) to obtain a treatment liquid (composition), the treatment liquid is returned to the original extraction residue. Cigarettes made using paper tubes of commercial cigarette products.
-Unprocessed: Cigarettes made from harmonized and engraved domestic yellow varieties and paper tubes of commercial cigarette products.
FIG. 4 shows the results of the evaluation panel in which the person who felt the cigarette odor was strongly selected. According to FIG. 4, the number of persons who answered that the cigarette after treatment had a smaller tobacco odor was significantly larger. Therefore, the odor reduction effect of the tobacco sidestream smoke was confirmed.

Sensory evaluation result 2: Effect of addition of treated product of Example 2 Treated tobacco: Yellow seed medium bone material: Commercially available cigarette product paper tube / test sample: Harmonized and cut foreign yellow seed bone A composition containing an ester compound was separated from the treatment solution prepared by the treatment of Example 1 (120 ° C., 3 hours, catalyst addition amount: 50% by weight per wet weight of tobacco) by distillation under reduced pressure and solid phase extraction, and then a commercially available cigarette Cigarette fragranced to the time (time A) where the product was opened and the fragrance was volatilized. The composition was added such that the total amount of ester was 0.14 to 0.95% by weight based on the amount of chopped A.
-Control article: Cigarette made in time A.
FIG. 5 shows the result of alternatively selecting the person who felt the tobacco odor strongly in the evaluation panel. The numerical value on the vertical axis in FIG. 5 indicates the weight ratio of the total ester amount to the step A amount in each sample. Significantly more people reported that the cigarette odor of the test product was smaller. Therefore, it was confirmed that the composition of the present invention exerted the effect of reducing the odor of tobacco sidestream smoke by adding fragrance to other portions.

Sensory evaluation result 3: Comparative treatment with prior art document (Patent Document 1) Tobacco: Japanese yellow seed material: Commercially available cigarette product paper tube-Example 1: Method A of the present invention at time A A composition obtained by separating the ester compound from the treatment liquid (the treatment raw material is a domestic yellow variety, the reaction condition is 120 ° C., 3 hours, and the catalyst addition amount is 50% by weight based on the wet weight of the tobacco) by vacuum distillation and solid phase extraction. Cigarettes created. The weight ratio of the tobacco used for preparing the treatment liquid: the time A to which the treatment liquid was flavored was 1: 2.
Comparative Example 1: A cigarette prepared in the same manner as above except that the additive was a processed product prepared by the method of Comparative Example 1.
As shown in FIG. 6, the number of persons who evaluated the cigarette produced by the method (Comparative Example 1) shown in the prior art document (Patent Document 1) as having a cigarette smell was significantly larger. Therefore, the superiority of the tobacco odor reduction effect of the composition of the present invention could be confirmed.

Sensory Evaluation Result 4: Contribution for Each Component Concerning the ester compound produced by the method of the present invention, the reagent of each compound was attached to tobacco cut and the contribution of the odor reduction effect was examined.
Ingredients: Commercially available cigarette paper tubes and test specimens: Test reagents dissolved in ethanol, sprayed to 0.1% or 1% with respect to wet weight of cigarette A, conditioned and dried Is a cigarette made using a commercially available paper tube.
-Control product: A cigarette made with a chopping A sprayed with the same amount of ethanol as the test product.
From FIG. 7, at 1% perfume, the effect of reducing tobacco odor was observed in triethyl citrate, ethyl palmitate, and ethyl levulinate. On the other hand, in cigarettes flavored with diethyl malate, the selectivity of tobacco odor increased. At 0.1% scent, the result was obtained that all the components reduced tobacco odor or did not substantially change.

Sensory evaluation result 5: Mixing of components Ethyl palmitate, triethyl citrate and diethyl malate obtained through the above-mentioned treatment were focused on, and the added amount and the effect of mixing were confirmed.
Material: Paper tube used for commercial cigarette products. Test product: Test in which each reagent was dissolved in ethanol so that the amount of addition was as shown in Table 4, sprayed on the wet weight of cigarette A, and harmoniously dried. Cigarettes created by time.
-Control product: A cigarette made with a chopping A sprayed with the same amount of ethanol as the test product.

As shown in FIG. 8-1 and FIG. 8-2, ethyl palmitate and triethyl citrate are stronger when cigarette sidestream smoke is used when mixed with diethyl malate than when each is added alone. It was suggested that odor reduction effect was exhibited.
Focusing on the abundance ratio of each component from FIGS. 8A and 8B, the above-described embodiment is extracted and reprinted. The numbers on the vertical axis in the figure correspond to the sample numbers in Table 4 above. The test article selection rate in the table is the number of persons / participants who selected the test article to have a stronger odor.

FIG. 9 shows the ratio of diethyl malate to the total ester content in Table 5 and the alternative cigarette odor selectivity. When the vertical axis of FIG. 9 was smaller than 0.5, the test article (the product with the addition of the ethyl ester compound) felt that the odor due to the tobacco sidestream smoke was smaller than the control product (the product without the addition of the ethyl ester compound). Indicates that the proportion of people is large.
Therefore, by mixing diethyl malate at a specific ratio, a low odor effect is more strongly exhibited. Further, even if this malate obtained from malic acid contained in tobacco is used as a single reagent. It was inferred that the separated one had the same effect.

Hereinafter, a method for producing more of the above-mentioned ester compound and a method for more easily producing the ester compound will be described.
<Process including water extraction>
In Examples 1 and 2, the organic acid contained in the tobacco leaves was transferred to the liquid phase by extraction with ethanol, and the extract was heated under acidic conditions to cause an esterification reaction. Ethanol here is an extraction solvent for organic acids and is itself subjected to the esterification reaction.
In order to further increase the yield of the generated ethyl ester compound, it was considered that the yield can be improved by extracting with a solvent having a higher solubility of the organic acid and subjecting it to the reaction. Also devised. Furthermore, from the viewpoints of ease of regeneration of the catalyst and reduction of the process energy, which are important in the production, a process in which the catalyst itself is not heated and a process in which the water is subjected to the reaction without completely devolatilizing the water were also devised.

<Example 3> Water extraction step 1
To the leaf tobacco was added 10 g of water in a solid-liquid ratio of 1 g-wet tobacco, and the mixture was shaken and extracted in a 60 ° C. water bath for 1 hour, and separated into an extract and an extraction residue with a nonwoven fabric. The water of the extract was devolatilized under reduced pressure and then transferred to ethanol to prepare an ethanol solution of the tobacco-water extract at a predetermined concentration. The reaction conditions were the same as in Example 1; the temperature was set at 120 ° C. for 3 hours;

<Example 4> Water extraction step 2
To the leaf tobacco was added 10 g of water in a solid-liquid ratio of 1 g-wet tobacco, and the mixture was shaken and extracted in a 60 ° C. water bath for 1 hour, and separated into an extract and an extraction residue with a nonwoven fabric. A catalyst was added to the water extract at 166% by weight per wet weight of tobacco and shaken to perform proton exchange. After separating and removing the catalyst by filtration, water was devolatilized under reduced pressure to obtain a tobacco-water extract to which protons had been supplied. This was dissolved in ethanol so as to have a predetermined concentration, and heated at 120 ° C. for 3 hours in a pressure vessel to allow the esterification reaction to proceed.

<Example 5> Water extraction step 3
Water was added to the leaf tobacco at a solid-liquid ratio of 1 g-wet tobacco: 10 ml, and the mixture was shaken and extracted in a water bath at 60 ° C. for 1 hour. A catalyst was added to the water extract at 166% by weight per wet weight of tobacco and shaken to perform proton exchange. After separating and removing the catalyst by filtration, the water was concentrated to a predetermined concentration to obtain a tobacco-water extract. An equal amount of ethanol was added to the water extract and on a volume basis, and the mixture was heated in a pressure vessel at 120 ° C. for 3 hours to allow the esterification reaction to proceed.
The results of Examples 3 to 5 are shown in Table 6 and FIG. As shown in FIG. 10, it was suggested that the same reaction as the result of the above-described ethanol extraction was progressing even in the solution extracted with water. In particular, in Example 4, about eight times or more of diethyl malate was produced as compared with Example 2, and the yield was able to be improved. In Example 3, it was considered that the influence of the decrease in the reaction rate due to the increase in the impurities was more strongly reflected than the increase in the amount of the organic acid extracted due to the extraction with water. In Example 5, although the yield was reduced due to the inhibition of the water reaction, diethyl malate and ethyl palmitate could be produced even when the amount of ethanol was reduced to half.

<Example 6> One-step process using a small amount of solvent As described above, it was confirmed whether or not the reaction proceeds only by mixing tobacco leaves, a small amount of ethanol and a catalyst and heating without going through the extraction separation step. .
About 10 ml of a 0.05 g / ml citric acid-ethanol solution was added to 5 g of the wet weight of the tobacco, and the mixture was heated in a pressure-resistant vessel for reaction. The heating condition was 120 ° C. for 3 hours.
The solution containing the tobacco leaf after the reaction was dispersed in a predetermined amount of ethanol, and the solution filtered through a 0.45 μm filter was subjected to GC-MS analysis under the above-mentioned conditions to obtain qualitative information of the product.
The GC chart of the processed product of Example 6 is shown in the upper part of FIG. 11, and the GC chart of the standard reagent is shown in the lower part. From FIG. 11, it was confirmed that diethyl malate and ethyl palmitate were produced under these conditions. Ethyl levulinate and triethyl citrate were traces. Since the amount of citric acid ethyl ester was very small, it was inferred that the added citric acid mainly functions as a catalyst.
The first dissociation constant of citric acid is 3.09, which is classified as a weak acid. In the method of the present invention, it was suggested that the reaction proceeded sufficiently even with a small amount of weak acid.

  When the composition of the present invention is added to a material used for a tobacco product such as tobacco chopping, or when the composition and the tobacco leaf are used per se, the tobacco sidestream smoke when smoking the tobacco product is used. Has the effect of reducing odor. The present invention also provides a method for conveniently preparing such a composition.

Claims (11)

Diethyl malate;
And a any one or more selected from Pas palmitic acid ethyl and triethyl citrate, tobacco products composition. Diethyl malate, relative to the total amount of Pas palmitic ethyl and triethyl citrate, the amount of malic acid diethyl is 5 to 95 wt%, tobacco products composition according to claim 1. Diethyl malate, relative to the total amount of Pas palmitic ethyl and triethyl citrate, the amount of malic acid diethyl is 20 to 60 wt%, according to claim 1 or tobacco products composition according to 2.   A tobacco raw material comprising tobacco leaves and the composition for a tobacco product according to any one of claims 1 to 3. Including an extraction step of obtaining an extract of tobacco leaves using ethanol, and an esterification reaction step of adding a catalyst to the extract obtained in the extraction step to perform an esterification reaction, diethyl malate, ethyl levulinate, palmitin Ethyl acid, a method for producing a composition comprising at least one of triethyl citrate ,
The method according to the above-mentioned method, wherein the catalyst is a solid acid having a desorption amount at a desorption peak lower than 500 ° C. of 10 μmol / g or more in an ammonia TPD method . Prior to an ester reaction, comprising the step of removing the catalyst of the solid acid was added, The method of claim 5. A step of obtaining an extract of tobacco leaves using water or a solvent consisting of water and ethanol, and the following step (1) or (2),
(1) Step of concentrating the extract obtained in the extraction step to obtain a concentrate, and adding ethanol to the concentrate (2) Step of adding ethanol to the extract obtained in the extraction step i) After adding a catalyst to any one of (iv) to (iv), the method includes an esterification reaction step of performing an esterification reaction, wherein diethyl malate and one or more of ethyl levulinate, ethyl palmitate, and triethyl citrate are used. The method according to claim 1, wherein the catalyst is a solid acid having a desorption amount at a desorption peak of less than 500 ° C. in an ammonia TPD method of 10 μmol / g or more.
(I) Extract obtained in the extraction step (ii) Concentrate obtained in the step (1) (iii) Solution obtained through the step of (1) (iv) Obtained through the step of (2) Solution The added pressure catalyst of the solid acid, comprising the step of removing prior to esterification process according to claim 7. Including a step of an esterification reaction in which a material obtained by mixing tobacco leaves, ethanol and a catalyst is subjected to an esterification reaction, including diethyl malate, and ethyl levulinate, ethyl palmitate, and at least one of triethyl citrate A method for producing a tobacco raw material ,
The method according to the above-mentioned method, wherein the catalyst is a solid acid having a desorption amount at a desorption peak lower than 500 ° C. of 10 μmol / g or more in an ammonia TPD method . Prior to an ester reaction, comprising the step of removing the catalyst of the solid acid, the production method according to claim 9.   The method according to any one of claims 5 to 10, wherein the step of the esterification reaction is performed at a temperature of 60 to 150 ° C for 5 to 500 minutes.

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