JPH10201831A - Deodorant composition for cigarette - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant compsn. useful for removal of the malodors of cigarettes. SOLUTION: This deodorant component for cigarettes is constituted by incorporating >=1 kinds among a phosphate compd. formed by intercalating an amine compd. in laminar phosphate, >=1 kinds of the oxide of zinc or magnesium and aluminum dihydrogentripolyphosphate respectively at >=5wt.%, in the compsn. consisting of the three components described above. The laminar phosphate is preferably α-zirconium phosphate, aluminum dihydrogentripolyphosphate, etc. The amine compd. is preferably the polyamine expressed by the formula H2 NC2 H4 (NHC2 H4 )x-1 NH2 [where, (x) is an integer from 1 to 5] and the polyamine expressed by the formula H2 NC3 H6 (NHC3 H6 )y-1 NH2 [where, (y) is an integer from 1 to 3]. The oxide of the zinc or magnesium is preferably zinc oxide and magnesium oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant composition useful for removing malodor such as smoke from cigarettes (hereinafter referred to as "tobacco").

[0002]

2. Description of the Related Art Odor components in smoke generated when smoking cigarettes are as shown in Table 1 below, for example.
Above all, acetaldehyde, ammonia, lower amines, hydrogen sulfide and the like are often smelled and hated.

[0003] Therefore, various proposals have been made in the past to remove the smell of tobacco and indoor odors in offices, homes, automobiles and the like.

For example, for aldehydes, an adsorbent in which aniline is added to activated carbon is proposed in JP-A-56-53744, and in JP-A-59-88078, a polyalkylimine is added to activated carbon. Adsorbents have been proposed and are disclosed in JP-A-60-48138 and JP-A-60-54.
669, JP-A-60-202735 and the like each propose an adsorbent in which amino alcohol is added to activated carbon. Furthermore, Japanese Patent Publication No. 60-54095 proposes an adsorbent in which aniline is added to activated carbon.

[0005] Japanese Patent Application Laid-Open No. 2-52043 discloses that
It has been reported that an activated carbon / inorganic acid aniline salt (inorganic acid: phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid) composition has an excellent adsorption effect on aldehydes, ammonia, amines and the like.

JP-A-2-119933 proposes an adsorbent in which aniline and aniline phosphate are added to activated carbon, and JP-A-5-23588 discloses an aromatic aminocarboxylic acid / inorganic acid. An adsorbent in which an organic acid / iodine / iodide composite adsorbent is supported on a porous carrier has been proposed.

Further, Japanese Patent Application Laid-Open No. 5-49922 discloses that
An air purifier comprising aniline and an organic acid impregnated on activated carbon fiber has been proposed and reported to be suitable for adsorption of aldehydes and ammonia. JP-A-5-161842 proposes an air purifying agent in which activated carbon is impregnated with an amine, an alkaline earth metal salt or hydroxide and / or an alkali metal salt or hydroxide.

JP-A-5-317703 proposes an adsorbent in which an organic carboxylic acid and an organic amine are impregnated on a porous substance (crushed coal, granulated coal, alumina, silica gel) and has a heat resistance of 150 ° C. It is reported that it has excellent acetaldehyde adsorption ability.

Furthermore, Japanese Patent Application Laid-Open No. 7-251066 proposes an adsorbent obtained by calcining sulfuric acid-impregnated activated carbon, which is superior in the ability to adsorb aldehyde and ammonia as compared with the conventional amine-impregnated activated carbon-based adsorbent, and has an amine-impregnated activated carbon. It is reported that the disadvantage that the amine of the system adsorbent is easily oxidized and unstable is avoided.

[0010]

However, although the above-mentioned adsorbents have excellent points,
It has many issues to be solved, such as:

[0011] The amines impregnated on the activated carbon are easily oxidized, and the adsorption ability decreases with time. -Amines impregnated on activated carbon cannot remove animal odors mainly composed of ammonias. -The aniline impregnated on activated carbon is a toxic substance, and there is a problem in using it as an adsorbent or deodorant in ordinary households. -Amine does not have sufficient heat resistance, desorbs and does not maintain its effect, and emits a strong odor. -When activated carbon is used, it becomes blackish and has a poor clean appearance.

Accordingly, an object of the present invention is to solve the problems in the prior art as described above and to provide a deodorant composition useful for removing malodor such as cigarette smoke.

[0013]

According to the present invention, there is provided a phosphate compound obtained by intercalating an amine compound into a layered phosphate, one or more oxides of zinc or magnesium,
Aluminum dihydrogen tripolyphosphate was added to each of the above 3
The above object has been achieved by constituting a deodorant composition for tobacco by including at least 5% by weight of the composition comprising the components.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In describing the deodorant composition for tobacco of the present invention in detail, first, typical examples of components contained in tobacco smoke will be shown. is there.

[0015]

[Table 1]

At present, it is not always clear which component of the malodor of tobacco each component of the deodorant composition for tobacco of the present invention effectively works, but each component will be described in detail below. We will talk about those functions as we go along.

First, a layered phosphate serving as a base material of a phosphate compound obtained by intercalating an amine compound with a layered phosphate is a layered phosphate which is hardly soluble or insoluble in water. Examples of the layered phosphate include Al
Aluminum phosphate, such as HP ₃ O ₁₀ .2H ₂ O, Z
r (HPO ₄ ) ₂ .H ₂ O or Zr (HPO ₄ ) ₂ .2H
Zirconium phosphate, such as ₂ O, Ti (HPO ₄ ) ₂
· H ₂ O and Ti (PO ₄₎ titanium phosphate such as _{(H 2 PO 4) · 2H} 2 O, Ce (HPO 4) 2 · 1.33H
Cerium phosphate, such as ₂ O, may be used. These layered phosphates exhibit excellent affinity for basic substances such as nicotine, ammonia, pyridine and other amines.

Examples of the amine compound to be intercalated into the layered phosphate include aliphatic amines such as methylamine and ethylamine, aromatic amines such as aniline, ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine. Chemical formula of min, pentaethylenehexamine, etc .: H ₂ NC
₂ H ₄ (NHC ₂ H ₄ ) _x-1 NH ₂ [where x is 1 to
A chemical formula of polyamine, propylenediamine, dipropylenetriamine, tripropylenetetramine, etc. represented by the formula: H ₂ NC ₃ H ₆ (NHC ₃ H ₆ )
_and polyamines represented by _y-1 NH ₂ [where y is an integer of 1 to 3].

The phosphate compound obtained by intercalating an amine compound with the layered phosphate does not oxidize or release the amine even after a long period of time, and releases the amine even at a high temperature. Less likely to be. Therefore, the material has excellent adsorption ability to acetic acid, aldehyde, hydrogen sulfide and the like under various environments.

For example, the degree of elimination of aniline at 50 ° C. between a phosphate compound in which aniline is intercalated in aluminum dihydrogen tripolyphosphate (AlHP ₃ O ₁₀ .2H ₂ O) and activated carbon in which aniline is adsorbed is determined. Table 2 shows a comparison.

[0021]

[Table 2]

The aniline release test shown in Table 2 above was conducted by placing 0.5 g of each sample in a 3-liter odor bag, further injecting nitrogen gas to fill the odor bag, and then drying in a dryer. The heating was performed by measuring the aniline gas generated after 0 minutes (that is, at the start of heating) and after 120 minutes with a detector tube.

In Table 2, ATP indicates aluminum dihydrogen tripolyphosphate, and D added in parentheses after aniline indicates that the following dry treatment was performed. "Using a small mixer (Matsushita Electric Industrial Co., Ltd., MX-X60 type)
The aniline is dry-mixed with aluminum dihydrogen tripolyphosphate or activated carbon and left in a dryer at 60 ° C. for 12 hours. "

In addition, W added in parentheses after aniline in Table 2 indicates that the following wet processing was performed.
"75 g of aluminum dihydrogen tripolyphosphate and 225 g of water are put into a beaker having an inner volume of 500 ml to form a 25% by weight slurry, and a predetermined amount of aniline is gradually added to the slurry. In the case of / 1, the amount is 21.9 g, and in the case where the treatment amount (equivalent ratio) is 4/1, the amount is 11 g.
After stirring for 2 hours, the mixture is filtered, left in a dryer for 12 hours, and then crushed. "

The treatment amount (equivalent ratio) is ATP [aluminum dihydrogen tripolyphosphate (AlH ₂ P ₃ O ₁₀ .2H)
₂ O) and a molecular weight of 318] are calculated as 2 equivalents, and 1 mol of aniline (C ₆ H ₅ NH ₂ , molecular weight 93) is calculated as 1 equivalent. Therefore, the processing amount 2/1 is AT
P / aniline = 318 g / 93 g.

As shown in Table 2 above, when aniline is adsorbed on activated carbon (in Table 2, "activated carbon / aniline (D)"), 5 ppm after heating at 50 ° C. for 120 minutes.
Of aniline was removed.

On the other hand, phosphate compounds obtained by intercalating aniline with aluminum dihydrogen tripolyphosphate [Table 2 shows that ATP / aniline (D), ATP
/ Aniline (W) etc.] did not release aniline at all.

Examples of zinc or magnesium oxides include zinc oxide and magnesium oxide, and these components have excellent ability to adsorb acidic gases such as acetic acid and hydrogen sulfide in malodor of tobacco. This zinc or magnesium oxide is an amphoteric oxide,
Further, not only the exemplified oxides but also hydrated oxides may be used.

Aluminum dihydrogen tripolyphosphate belongs to a layered phosphate, and this aluminum dihydrogen tripolyphosphate has an excellent ability to adsorb nicotine, ammonia, pyridine and other basic substances contained in malodor of tobacco. .

In the deodorant composition for tobacco of the present invention,
A phosphate compound obtained by intercalating an amine compound with a layered phosphate, an oxide of zinc or magnesium, and aluminum dihydrogen tripolyphosphate are each contained in an amount of 5% or more of the composition composed of the above three components on a weight basis. And it is preferable that the content is 10% or more. That is, in the deodorant composition for tobacco of the present invention, a phosphate compound obtained by intercalating an amine compound with a layered phosphate is 5 to 90% by weight, and zinc or magnesium oxide is 5 to 90% by weight. It is necessary to contain 5-90% by weight of aluminum dihydrogen tripolyphosphate, particularly 10-80% by weight of a phosphate compound obtained by intercalating an amine compound with a layered phosphate;
10 to 80% by weight of zinc or magnesium oxide;
10 to 80% by weight of aluminum dihydrogen tripolyphosphate
It is preferred to contain.

The content of any one of the phosphate compound obtained by intercalating an amine compound with the layered phosphate, zinc or magnesium oxide, and aluminum dihydrogen triphosphate is less than 5% by weight. If it does, the bad smell of cigarettes cannot be sufficiently deodorized.

The deodorant composition for tobacco of the present invention mainly comprises three components: a phosphate compound obtained by intercalating an amine compound with the above-mentioned layered phosphate, an oxide of zinc or magnesium, and aluminum dihydrogen tripolyphosphate. Although it is constituted as a component, in addition to these three components, a common deodorant such as activated carbon, zeolite, activated silica gel, silica gel, and silica alumina gel may be contained in a range that does not impair the features of the present invention. .

As described above, the deodorant composition for tobacco of the present invention includes a phosphate compound obtained by intercalating an amine compound with a layered phosphate, an oxide of zinc or magnesium, aluminum dihydrogen tripolyphosphate. May contain other than the three components described above, but when such other components are contained, the content of the above three components is determined by a phosphate compound obtained by intercalating an amine compound into a layered phosphate. , A phosphate compound obtained by intercalating an amine compound with a layered phosphate in a composition composed of only three components, oxides of zinc or magnesium and aluminum dihydrogen triphosphate, oxides of zinc or magnesium And aluminum dihydrogen tripolyphosphate may be at least 5% by weight.

The deodorant composition for tobacco of the present invention comprises powder,
It can be used as it is as a granulated product, or it can be used in building materials, containers, clothing, paints, filters, etc. by putting them in fibers, plastics, papers and the like.

[0035]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.

Example 1 First, a phosphate compound obtained by intercalating an amine compound with the layered phosphate used in Example 1 (hereinafter referred to as a phosphate compound).
Preparation of the deodorizer composition, preparation of gas having odor of tobacco, and evaluation of deodorization performance will be described first. Will be described in this order.

[Preparation of Zirconium Phosphate (ZrP) / Diethylenetriamine (2E3A) Intercalation Compound] α-Zirconium phosphate [Zr (HP
O ₄ ) ₂ .H ₂ O] 75 g (0.25 mol) and water 225
25.7 g (0.25 mol) of diethylenetriamine was added to the slurry consisting of
For 1 hour. After filtration, the powder was washed with water and dried, and the carbon content in the powder was measured by a CHN elemental analyzer (PE-2400, manufactured by PerkinElmer) to find that it was 8.5% by weight. This is converted to α-zirconium phosphate (ZrP)
When expressed in terms of the amount of intercalate of diethylenetriamine (2E3A) with respect to that of ZrP: 2E3A
= 1.0: 0.69.

[Preparation of Deodorant Composition] A zirconium phosphate / diethylenetriamine-based intercalation compound prepared as described above was used as a phosphate compound in which an amine compound was intercalated into a layered phosphate, and zinc or zinc was used. As the magnesium oxide, zinc oxide (fine zinc white (special name) manufactured by Honjo Chemical Co., Ltd.) was used, and as aluminum trihydrogenphosphate, K-Fresh 100P (trade name) manufactured by Teika Co., Ltd.
And these components were weighed in a polybeaker so that the amounts shown in Table 3 were obtained. Small mixer (MX-X60, manufactured by Matsushita Electric Industrial Co., Ltd.)
), And the weighed powder obtained in step (1) was crushed for 3 minutes to obtain a uniform powder mixture.

In indicating the above components in Table 3,
The zirconium phosphate / diethylenetriamine-based intercalation compound is represented by ZrP / 2E3A for simplification, zinc oxide is represented by ZnO for simplification, and aluminum dihydrogen tripolyphosphate is represented by ATP for simplification. These are the same in the following tables.

[Preparation of gas having tobacco odor] 100 ml of cigarette smoke (0.2 ordinary cigarettes) was inhaled into a syringe having an inner volume of 100 ml, and the resulting mixture was inflated with an inner volume of 2 cigarettes.
By injecting it into a 0-liter large odor bag and then injecting nitrogen gas to fill the large odor bag,
A gas with tobacco odor was prepared.

[Evaluation of deodorizing performance] N of the composition shown in Table 3
o. 4 g of each of the samples 1 to 4 was placed in an odor bag having an internal volume of 3 liters, and the gas having the odor of the cigarette was injected to fill the odor bag. One hour and 24 hours after that point, the odor in the odor bag was evaluated by a sensory test using four non-smokers as panelists. At the time of evaluation, evaluation was made by scoring according to the following criteria, and the results are shown in Table 3 for each panelist (A, B, C and D). The criteria for scoring are as follows, and the blank to be compared in the criteria refers to the case where the test was performed without putting the deodorant composition in the odor bag, and the higher the score in this standard, Indicates that the deodorizing performance is excellent.

3: Almost no odor 2: Better than blank 1: Better than blank but unpleasant odor 0: Same level as blank Overall rating: Average score of four panelists after 24 hours Show

[0043]

[Table 3]

As shown in Table 3, the sample No. 1-4 are
In each case, the evaluation score was high, and it was clarified that the cigarette had an excellent effect on deodorization of offensive odor.

Example 2 First, the intercalation compound used in Example 2 was prepared as follows.

[Aluminum dihydrogen tripolyphosphate (A
Preparation of TP) / diethylenetriamine (2E3A) -based intercalation compound] A mixture of 75 g (0.24 mol) of aluminum dihydrogen triphosphate and 225 g of water was added to a slurry of diethylenetriamine 2 while stirring.
4.3 g (0.24 mol) was added and heated at 80 ° C. for 1 hour. After filtration, washing with water and drying, the carbon content in the powder obtained was analyzed using a CHN elemental analyzer (PE-PerkinElmer).
2400) and found to be 9.4% by weight. This is called aluminum dihydrogen tripolyphosphate (AT
In terms of the amount of intercalate of diethylenetriamine (2E3A) with respect to P), the molar ratio of ATP: 2E
3A = 1.0: 0.78.

Using the obtained intercalation compound and the same zinc oxide and aluminum dihydrogen tripolyphosphate as in Example 1, the same operation as in Example 1 was carried out, and the deodorant composition having the composition shown in Table 4 (Sample No. 4) was used. 5 to 8) were prepared, and a gas having a odor of tobacco was prepared in the same manner as in Example 1 to evaluate the deodorizing performance. Table 4 shows the results. In the display in Table 4, the aluminum dihydrogen tripolyphosphate / diethylene triamine-based intercalation compound is simply represented by ATP / 2E3A. This is the same in the following tables.

[0048]

[Table 4]

As shown in Table 4, the sample No. 5-8
In each case, the evaluation score was high, and it was clarified that the cigarette had an excellent effect on deodorization of offensive odor.

Example 3 In Example 3, the preparation of the deodorant composition, the preparation of the odorous sample gas, and the evaluation of the adsorption performance will be described in this order.

[Preparation of Deodorant Composition] Aluminum dihydrogen tripolyphosphate / diethylenetriamine intercalation compound prepared in Example 2 as a phosphate compound obtained by intercalating an amine compound with a layered phosphate (in the table) Is displayed as "ATP / 2E3A").
This and the same zinc oxide as in Example 1 (“ZnO” in the table)
) And aluminum dihydrogen tripolyphosphate (represented by “ATP” in the table), and in the same manner as in Example 1, a deodorant composition having the composition shown in Table 5 (sample No. 1).
9-No. 19) was prepared. For comparison, aluminum dihydrogen tripolyphosphate / diethylene triamine-based intercalation compound, zinc oxide, and aluminum dihydrogen tripolyphosphate were used alone as deodorants (samples Nos. 20 to 22).

[0052]

[Table 5]

[Preparation of odorous sample gas] Using ammonia, trimethylamine, hydrogen sulfide and methyl mercaptan,
Sample gases were prepared individually using each of them as an odor source.

The above-mentioned ammonia, trimethylamine, hydrogen sulfide, and methyl mercaptan all use standard gases manufactured by Sumitomo Seika Co., and their concentrations are adjusted with nitrogen gas. About 25ppm initial concentration
The initial concentration of hydrogen sulfide was 94.6 ppm, and the initial concentration of methyl mercaptan was 50.3 ppm.
ppm.

The preparation of such a malodorous sample gas and the evaluation of the adsorption performance thereof as described below are performed in order to evaluate the deodorization of the malodor of tobacco by the sensory test as shown in Examples 1 and 2 above. Since it cannot be relied on and cannot be evaluated by actual measurement, a sample gas containing a substance that is considered to constitute a malodor of tobacco is prepared, and a malodorous substance in the sample gas is adsorbed by the deodorant composition. By grasping the degree of adsorption from the measurement result of the residual concentration, it is possible to estimate how much the substance constituting the malodor of tobacco is adsorbed and removed by the deodorant composition and how much the malodor is deodorized.

[Evaluation of Adsorption Performance]
ATP / 2E3A-ZnO-ATP-based deodorant compositions of Sample Nos. 9 to 19 and Sample Nos. 0.5 g of each of the 20 to 23 deodorizers was placed in a 3 liter odor bag, and the malodor sample gas prepared as described above was individually injected to fill the odor bag. At 0 minute, 5 minutes, 30 minutes, and 24 hours after that point, the residual concentration of each offensive odor substances was measured using a detector tube. The results are shown in Tables 6, 7, 8, and 9 in the order of ammonia, trimethylamine, hydrogen sulfide, and methyl mercaptan. In the table, 0 minutes after the residual concentration measurement was 0 minutes, and 5 minutes after the residual concentration measurement was 5 minutes.
30 minutes after 30 minutes, 24 hours after 24 hours
Indicated by hrs. The simplified display of the time is the same in the following tables.

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

[Table 8]

[0060]

[Table 9]

As shown in Tables 6 to 9, the residual concentrations of ammonia, trimethylamine, hydrogen sulfide, and methyl mercaptan varied with time, though varying in degree. 9-19 ATP / 2
It is clear that any of the E3A-ZnO-ATP-based deodorant compositions adsorbs and removes substances that become odor sources.

Example 4 In Example 4, the preparation of the deodorant composition, the preparation of the odorous sample gas, and the evaluation of the adsorption performance will be described in this order.

[Preparation of Deodorant Composition] A zirconium phosphate / diethylenetriamine-based intercalation compound prepared in Example 1 as a phosphate compound obtained by intercalating an amine compound with a layered phosphate (in the table, "ZrP / 2E3A") and this and Example 1
And zinc dihydrogen tripolyphosphate ("AT" in the table)
P "), the ZrP / 2E3A-ZnO-ATP-based deodorant compositions (Sample Nos. 23 to 26) having the compositions shown in Table 10 were prepared in the same manner as in Example 1. For comparison, a zirconium phosphate / diethylene triamine-based intercalation compound, zinc oxide, and aluminum dihydrogen tripolyphosphate were used as deodorizers (Sample Nos. 27 to 29).

[0064]

[Table 10]

[Preparation of Offensive Odor Sample Gases] Ammonia, hydrogen sulfide, acetaldehyde, acetic acid, and pyridine were used, and sample gases using each of them as an odor source were individually prepared.

As the ammonia and hydrogen sulfide, standard gases manufactured by Sumitomo Seika Co., Ltd. are used, and their concentrations are adjusted with nitrogen gas.
ppm, and the initial concentration of hydrogen sulfide is 85 ppm.
And

Acetaldehyde, acetic acid, and pyridine were prepared using a gas generator Permical Permeator (PD-1B manufactured by Gastech). The initial concentration of acetaldehyde was 20 ppm, and the initial concentration of acetic acid was 20 ppm. Was set to 20 ppm, and the initial concentration of pyridine was set to 10 ppm. Note that nitrogen gas was used as a diluent gas for concentration adjustment.

[Evaluation of Adsorption Performance] Sample N shown in Table 10
o. Sample No. 23 to ZrP / 2E3A-ZnO-ATP-based deodorant composition and Sample Nos. 0.5 g of each of the 27-29 deodorizers was placed in an odor bag having an internal volume of 3 liters, and the malodor sample gas prepared as described above was individually injected to fill the odor bag. Five minutes, 30 minutes, and 24 hours after that time, the residual concentration of each offensive odor substances was measured using a detector tube. The results are shown in Table 11 for ammonia and hydrogen sulfide, in Table 12 for acetaldehyde and acetic acid, and in Table 13 for pyridine.

[0069]

[Table 11]

[0070]

[Table 12]

[0071]

[Table 13]

As shown in Tables 11 to 13, the residual concentrations of ammonia, acetaldehyde, acetic acid, and pyridine varied with time, though varying in degree. ZrP / 2E3A of 23-26
It is clear that each of the -ZnO-ATP-based deodorant compositions adsorbs and removes substances that are sources of offensive odors.

As is apparent from the results of Examples 3 and 4, the deodorant composition of the present invention has excellent adsorption performance to various substances that are sources of malodor of tobacco. From this, it can be estimated that the deodorant composition of the present invention exerts an excellent deodorizing effect on the malodor of tobacco.

[0074]

As described above, according to the present invention, a deodorant composition useful for removing malodor of tobacco can be provided.

Claims (4)

[Claims] 1. A composition comprising a phosphate compound obtained by intercalating an amine compound with a layered phosphate, one or more oxides of zinc or magnesium, and aluminum dihydrogen triphosphate in each of the above three components. 5% by weight or more of a deodorant composition for cigarettes. 2. The deodorant composition for tobacco according to claim 1, wherein the layered phosphate is α-zirconium phosphate. 3. The deodorant composition for tobacco according to claim 1, wherein the content of each component is 10% by weight or more in the composition. 4. An amine compound having the chemical formula: H ₂ NC ₂ H
₄ (NHC ₂ H ₄ ) _x-1 NH ₂ [where x is an integer of 1 to 5] or a chemical formula: H _{2
NC 3 H 6 (NHC 3 H} 6) y-1 NH 2 [however, y is a is an integer of 1 to 3] according to claim 1 tobacco deodorant composition wherein the polyamine represented by.