JPH07815A - Deodorant and its production - Google Patents

Abstract

PURPOSE:To provide a deodorant with outstanding stability with the lapse of time and gas adsorptive properties and a method of producing the deodorant. CONSTITUTION:The subject deodorant comprises a first carrier 1 which carries an acidic gas adsorbent 10 on a carrier 5 and a second carrier 2 which carries a basic gas adsorbent 20 on the carrier 5, both being mixed, and at the same time, amphoteric compound 3 is present between both the carriers 1, 2. The acidic gas adsorbent 10 is preferably an organic matter containing an amino group, while the basic gas adsorbent 20 is preferably an organic matter containing a carboxylic group. The carrier 5 is activated carbon or the like. In producing the deodorant, for example, the first and the second carriers 1, 2 are prepared in advance, then both are mixed in a solution containing the amphoteric compound 3, and the mixture is molded and finally dried.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant used for a filter for an air purifier, a deodorizing sheet, a decorative material for deodorizing, etc., and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, activated carbon has been used to remove a bad odor.
It is effectively used in air purifier filters, deodorant sheets, deodorant decorations, etc. For example, a deodorant (Japanese Examined Patent Publication No. 3-41187) prepared by mixing activated carbon with malic acid impregnated with activated carbon with iron salt is strongly adsorbed to lower fatty acid aldehydes, and is a petroleum stove. It is suitable for removing the odor immediately after digestion. In addition, a deodorant obtained by mixing activated carbon impregnated with aniline phosphate and activated carbon impregnated with phosphoric acid (JP-A-2-160).
No. 042) can adsorb various odorous components.

[0003]

[Problems to be Solved] However, all of the above deodorants have insufficient stability over time. for that reason,
When used for a long period of time, the ability to adsorb odorous components tends to decrease. In view of such conventional problems, the present invention aims to provide a deodorant having excellent stability over time and a method for producing the same.

[0004]

According to the present invention, a first carrier having an acidic gas adsorbent supported on a carrier and a second carrier having a basic gas adsorbent supported on a carrier are mixed, and both carriers are supported. It is a deodorant characterized in that an amphoteric compound is present in between. What is most noticeable in the present invention is that the amphoteric compound is present between the first carrier carrying the acidic gas adsorbent and the second carrier carrying the basic gas adsorbent. .

The amphoteric compound has an amino group and a carboxyl group in one molecule. As an amphoteric compound, β-
Alanine, azaserine, L-asparagine, L-α-aminobutyric acid, γ-aminobutyric acid, L-alanine, L-arginine, L-alothreonine, ergotineine, L-ornithine, L-canavarin, L-kynurenine, glycine,
L-glutamine, creatine, L-cysteine, L-citrulline, L-serine, L-tryptophan, L-threonine, norvaline, L-propyne, L-lanthionine and the like are used. In addition, amphoteric compounds can be selected over a wide range regardless of the size of the molecule. This is because the amphoteric compound is hydrophilic and thus it is difficult for it to enter the inside of the hydrophobic carrier.

As the above-mentioned acid gas adsorbent, 3-aminopropyltrihydrosilane (hereinafter referred to as AS),
γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, dimethyltrimethylsilylamine, N- (β-aminoethyl) -γ- Examples include amino group-containing organic substances such as aminopropyl-trimethoxysilane.

As the basic gas adsorbent, a substance having an extremely small ionization constant such as a carboxyl group-containing organic substance is used. Examples of the carboxyl group-containing organic matter include L-tartaric acid, succinic acid, maleic acid, citric acid, gluconic acid,
Malic acid, fumaric acid, glutamic acid, glital acid, m-
Examples include hydroxybenzoic acid, pimelic acid, picolinic acid, itaconic acid, adipic acid, salicylic acid, glyceric acid, and gallic acid.

Examples of the carrier include activated carbon, activated carbon fiber, powdered activated carbon, granular activated carbon, porous materials such as zeolite and silica gel, or ultrafine particles of titanium oxide, aluminum oxide, silicon dioxide obtained by a gas phase method. It is possible to use ultrafine particles of An acidic gas adsorbent or a basic gas adsorbent is carried on the surface and pores of the carrier.

As a method for producing the above deodorant, a first carrier carrying an acidic gas adsorbent on a carrier and a second carrier carrying a basic gas adsorbent on a carrier are prepared respectively, and then There is a method for producing a deodorant characterized by mixing the first carrier and the second carrier in a solution containing an amphoteric compound, and then molding and drying.

When the first carrier and the second carrier are mixed, it is preferable to mix the reinforcing fiber and the binder. This facilitates molding into a plate-shaped body, a rod-shaped body, a granular body, or the like, and can reinforce the manufactured deodorant.
Examples of the reinforcing fibers include polyester, nylon, pulp, linter pulp, and Manila hemp.

Examples of the binder include vinylon, acrylic emulsion, vinyl chloride, acrylic styrene copolymer, ether-ester polyurethane resin, polyester urethane, urethane resin, polyvinyl alcohol, water-soluble polymer such as acrylic, and the like. .

When the first carrier and the second carrier are mixed and molded in a solution containing the amphoteric compound, the both carriers are submerged in water, using a round net, a flat net, or the like. Wet papermaking can be performed by scooping up to form a thin sheet. This makes it possible to produce a paper-like thin deodorant.

[0013]

FUNCTION AND EFFECT In the deodorant of the present invention, the functional groups of the acidic gas adsorbent and the basic gas adsorbent are independently present in the active state on the surface of the pores of the carrier. Therefore, the basic gas such as ammonia which is the adsorbed gas is due to the functional group of the basic gas adsorbent, while the acidic gas such as hydrogen sulfide and acetaldehyde which is the adsorbed gas is due to the functional group of the acidic gas adsorbent.
Each is chemically adsorbed by the neutralization reaction.

Further, since an appropriate amount of gas adsorbent is carried on the surface of the pores of the carrier, an appropriate space is secured in the pores. Therefore, the neutral gas such as toluene, which is the adsorbed gas, is physically trapped in this space. Therefore, the deodorant of the present invention can exhibit a multi-type high adsorption capacity suitable for adsorption of all acidic, basic and neutral gases.

The carrier is then hydrophobic, while the amphoteric compound is hydrophilic. Therefore, the amphoteric compound is difficult to be adsorbed in the pores of the carrier. Therefore, it is possible to secure an adsorption space for gas components. Further, since the amphoteric compound inhibits the reaction between the acidic gas adsorbent supported in the pores and the basic gas adsorbent, the excellent gas adsorption ability of both gas adsorbents can be maintained for a long period of time. . That is, since the amphoteric compound exists between the first carrier and the second carrier,
It is possible to keep the gas adsorbing ability of both carriers stable, and to keep the excellent gas adsorbing ability stable for a long period of time. Therefore, it has excellent stability over time.

Next, in the above method for producing a deodorant,
When mixing and molding the deodorant, the electrolytic amphoteric compound
The functional groups of the acidic gas adsorbent and basic gas adsorbent, and the released components of both gas adsorbents released from the carrier are neutralized (Fig. 1
reference). Therefore, the functional groups of both gas adsorbents can be prevented from causing a neutralization reaction, and the functional groups of both gas adsorbents can be maintained in the active state. Therefore, the destructive decrease in adsorption capacity can be suppressed.

Further, since the functional groups of both gas adsorbents carried on the surface of the carrier form an ionic bond with the functional groups of the amphoteric compound, both gas adsorbents are not attracted to each other. Therefore, the elution of both gas adsorbents can be prevented. Therefore, as described above, a deodorant having excellent adsorption performance can be produced. As described above, according to the present invention, it is possible to provide a deodorant excellent in stability over time and gas adsorption, and a method for producing the deodorant.

[0018]

【Example】

Example 1 The deodorant of the present invention will be described with reference to FIGS. As shown in FIG. 1, the deodorant of this example comprises a first carrier 1 having a carrier 5 carrying an acidic gas adsorbent 10 and a second carrier 2 having a carrier 5 carrying a basic gas adsorbent 20. It is mixed. An amphoteric compound 3 is present between the two carriers 1, 2 as shown in FIGS.

AS acid gas adsorbent 10 is AS
(3-aminopropyltrihydrosilane) was used.
As the basic gas adsorbent 20, L-tartaric acid was used. As the amphoteric compound 3, β-alanine was used. As the carrier 5, as shown in FIG. 3, activated carbon fiber having a large number of pores 50 and a specific surface area of 800 to 1500 m ² / g was used. An acidic gas adsorbent 10 or a basic gas adsorbent 20 is carried on the surface of the carrier 5 and in the pores 50.

Next, a method for producing the above deodorant will be described with reference to FIG.
Will be explained. First, in the step A of the supporting step,
A 0.01-0.1 mol / liter AS aqueous solution 11 was prepared. Next, the carrier 5 is added to the AS aqueous solution 11 in an amount of 1 to 10 times the weight of the AS, and the mixture is impregnated with the stirring blade 9 for 5 minutes to 2 hours to cause a reaction.
Then, vacuum suction filtration is performed, and drying is performed at 120 ° C. for 3 hours. As a result, the acidic gas adsorbent (A
The first carrier 1 carrying S) is obtained.

Further, in the step B of the supporting step, 0.
The L-tartaric acid aqueous solution 21 of 05-0.5 mol / liter was prepared. Then, in the L-tartaric acid aqueous solution 21, the L
-Add 1 to 10 times the amount of carrier 5 to the weight of tartaric acid,
The reaction is performed in the same manner as in the above step A, and filtration and drying are performed.
As a result, the second carrier 2 in which the basic gas adsorbent (L-tartaric acid) is carried on the surface of the carrier 5 is obtained.

Next, in the mixing step, 0.01 mol /
The first supporting body 1 and the second supporting body 2 are put into a liter of β-alanine aqueous solution 31 at a weight ratio of 1: 1 to obtain a deodorant material. The total weight of both carriers is 10 to 100 times the weight of β-alanine.

Next, 5% by weight of binder and 15% by weight of reinforcing fiber were mixed with the weight of this material, and the mixture was formed into a paper by a wet papermaking method. Vinylon was used as the binder and rayon was used as the reinforcing fiber. Next, the above-mentioned molded body is subjected to 12 by a drum dryer.
It was dried at 0 ° C for 10 minutes. As a result, the above deodorant was obtained.

Next, the function and effect of this example will be described.
As shown in FIG. 3, the deodorant of this example has pores 50 of the carrier 5.
On the surface, the functional groups of the acidic gas adsorbent 10 and the basic gas adsorbent 20 are independently present in an active state. for that reason,
Hydrogen sulfide, acid gas of the gas to be adsorbed is acid gas adsorbent 10
On the other hand, the basic gas of the gas to be adsorbed is chemically adsorbed by the functional groups of the basic gas adsorbent 20 by the neutralization reaction.

Since a proper amount of the acidic gas adsorbent 10 or the basic gas adsorbent 20 is carried on the surface of the pores 50 of the carrier 5, a proper space is secured in the pores 50. . Therefore, the neutral gas of the adsorbed gas is physically trapped in this space. Therefore, the deodorant of this example can exhibit a multi-type high adsorption capacity adapted to the adsorption of all acidic, basic and neutral gases.

Next, the carrier 5 is hydrophobic and the amphoteric compound 3 is hydrophilic. Therefore, as shown in FIG. 3, the amphoteric compound 3 is less likely to enter the pores 50 of the carrier 5 and is less likely to be adsorbed. Therefore, it is possible to secure an adsorption space for gas components. In addition, the acidic gas adsorbent 10 and the basic gas adsorbent 20 in which the amphoteric compound 3 is supported in the pores 50.
Since the reaction with the above is blocked, the excellent gas adsorption capacity of both gas adsorbents 10 and 20 can be maintained for a long period of time.

That is, since the amphoteric compound 3 exists between the first carrier 2 and the second carrier 2, the gas adsorption capacities of both carriers are kept stable, and the excellent gas adsorption capability is stable for a long period of time. Can be maintained at. Therefore, it has excellent stability over time.

Next, when the deodorant is mixed and molded, the electrolytic amphoteric compound 3 is released from the functional groups of the acidic gas adsorbent 10 and the basic gas adsorbent 20 and the carrier 5, as shown in FIG. The released components of both gas adsorbents are neutralized. Therefore, the functional groups of both gas adsorbents 10 and 20 can be maintained in an active state without causing a neutralization reaction. Therefore, the destructive decrease in adsorption capacity can be suppressed.

Further, since the functional groups of both gas adsorbents 10 and 20 carried on the surface of the carrier 5 form an ionic bond with the functional groups of the amphoteric compound 3, both gas adsorbents are not attracted to each other. Therefore, the elution of both gas adsorbents can be prevented. Therefore, as described above, a deodorant having excellent adsorption performance can be produced.

Example 2 In this example, the change with time of the gas adsorption rate of the deodorant of the present invention was measured. At the time of measurement, put the deodorant for measurement in a thermo-hygrostat at a temperature of 25 ° C and a humidity of 60%.
Stored for days. During that time, the required amount of the above deodorant for measurement was taken out as appropriate, and the gas adsorption rate was measured by the following method.

The above deodorant for measurement is a 0.01 mol / liter AS aqueous solution for an acidic gas adsorbent, a 0.05 mol / liter L-tartaric acid aqueous solution for a basic gas adsorbent, and a β-for an amphoteric compound. Alanine was used and produced in the same manner as in Example 1. As the carrier, activated carbon fiber having a specific surface area of 1200 m ² / g was used. The carrier is 5 times as much as AS, L-
It was used in an amount of 5 times the weight of tartaric acid. The amphoteric compound was used 10 times by weight. This deodorant has a basis weight of 120 g /
It is a sheet with m ² and a thickness of 1 mm. For comparison,
With respect to the activated carbon fiber carrying the same acidic gas adsorbent and basic gas adsorbent as in Example 1 (Comparative Example) without using the amphoteric compound, the change with time in the gas adsorption rate was measured in the same manner as above.

Next, a method of measuring the gas adsorption rate will be described. That is, 0.25 g of the deodorant for measurement is placed in a closed chamber filled with the initial concentration (R) of the single component gas at 25 ° C. for 1 hour to adsorb the single component gas. During this time, the single-component gas in the closed chamber is constantly circulated. Then, the residual concentration (Q) of the single component gas remaining in the closed chamber is measured by a gas chromatograph (GC-9A, Shimadzu Corporation).

The adsorption rate (S) of the single component gas is calculated by the following formula. S (%) = 100 × (R−Q) / R The above various single component gases are hydrogen sulfide (H ₂ S), acetaldehyde (CH ₃ CHO), toluene (C ₇ H ₈ ), ammonia (NH ₃ ). is there. The initial concentrations of these gases are
100 ppm for H ₂ S, CH ₃ CHO, NH ₃
And 1000 ppm for C ₇ H ₈ .

The measurement results are shown in Table 1. From Table 1, it can be seen that the deodorant of the present invention has a remarkably superior initial adsorption performance as compared with the comparative example, and that the adsorption rate hardly deteriorates even after 150 days. In particular, H ₂ S, CH ₃ CH
It can be seen that this tendency is large in O and NH ₃ .

[0035]

[Table 1]

Example 3 In this example, a deodorant was prepared in the same manner as in Example 1 except that the following various acidic gas adsorbents were used instead of AS used in Example 1. The acid gas adsorbent is
γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, dimethyltrimethylsilylamine, N- (β-aminoethyl) -γ- Aminopropyl-trimethoxysilane. As a result of measuring the gas adsorption rates of the deodorants of this example, the same effects as in Example 1 could be obtained.

Example 4 In this example, the following various basic gas adsorbents were used in place of the L-tartaric acid used in Example 1, and the deodorant was prepared in the same manner as in Example 1. . The basic gas adsorbent is succinic acid, maleic acid, citric acid, gluconic acid, malic acid, fumaric acid, glutamic acid, glital acid,
It is one of m-hydroxybenzoic acid, pimelic acid, picolinic acid, itaconic acid, adipic acid, salicylic acid, glyceric acid, and gallic acid. With respect to the deodorizing agents of this example, the results of measuring the gas adsorption rates thereof were all Examples 1
It was possible to obtain the same effect as.

Example 5 In this example, a deodorant was prepared in the same manner as in Example 1 except that the following amphoteric compounds were used in place of β-alanine used in Example 1. The above amphoteric compound is
Azaserine, L-asparagine, L-α-aminobutyric acid,
γ-aminobutyric acid, L-alanine, L-arginine, L-
Allotreonine, ergotineine, L-ornithine, L
-Canavarin, L-kynurenine, glycine, L-glutamine, creatine, L-cysteine, L-citrulline,
It is any one of L-serine, L-tryptophan, L-threonine, norvaline, L-propyne, and L-lanthionine. As a result of measuring the gas adsorption rates of the deodorants of this example, the same effects as in Example 1 could be obtained.

Example 6 In this example, instead of the activated carbon fiber used in Example 1, the following various carriers were used, and otherwise the deodorant was prepared in the same manner as in Example 1. The carrier is powdered activated carbon,
It is one of granular activated carbon, zeolite, silica gel, or ultrafine particulate titanium oxide, aluminum oxide, or silicon dioxide obtained by the vapor phase method. As a result of measuring the gas adsorption rates of the deodorants of this example, the same effects as in Example 1 could be obtained.

Example 7 In this example, instead of the binder (vinylon) and the reinforcing fiber (rayon) used in Example 1, the following various binders and reinforcing fibers were used, and the others were the same as in Example 1. To produce a deodorant. The binder is acrylic emulsion, vinyl chloride, acrylic styrene copolymer, ether-ester polyurethane resin, polyester urethane, urethane resin, polyvinyl alcohol,
It is one of water-soluble polymers such as acrylic.

The reinforcing fiber is any one of polyester, nylon, pulp, linter pulp and Manila hemp. As a result of measuring the gas adsorption rates of the deodorants of this example, the same effects as in Example 1 could be obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the action and effect of the deodorant of Example 1.

FIG. 2 is an explanatory view showing a collection state of carriers in Example 1.

FIG. 3 is an explanatory view showing the surface of the first carrier and the second carrier and the state of pores in Example 1.

FIG. 4 is an explanatory view showing a method for producing a deodorant of Example 1.

[Explanation of symbols] 1. ． ． First carrier, 10. ． ． Acid gas adsorbent, 2. ． ． Second carrier, 20. ． ． Basic gas adsorbent, 3. ． ． Amphoteric compounds, 5. ． ． Carrier, 50. ． ． pore,

Claims (8)

[Claims] 1. A mixture of a first carrier having an acidic gas adsorbent carried on a carrier and a second carrier having a basic gas adsorbent carried on a carrier, and an amphoteric compound between the two carriers. A deodorant characterized by being present. 2. The compound according to claim 1, wherein the amphoteric compound is 1
A deodorant having an amino group and a carboxyl group in the molecule. 3. The deodorant according to claim 1, wherein the acidic gas adsorbent is an amino group-containing organic substance. 4. The deodorant according to claim 1, wherein the basic gas adsorbent is a carboxyl group-containing organic substance. 5. The deodorant according to claim 1, wherein the carrier is a porous body or ultrafine particles. 6. A first carrier having an acidic gas adsorbent supported on a carrier and a second carrier having a basic gas adsorbent supported on a carrier are prepared in advance, and then in a solution containing an amphoteric compound. A method for producing a deodorant, which comprises mixing the first carrier and the second carrier, then molding and drying. 7. The compound according to claim 6, wherein the amphoteric compound is 1
A method for producing a deodorant having an amino group and a carboxyl group in the molecule. 8. The method for producing a deodorant according to claim 6, wherein reinforcing fibers and a binder are mixed during the mixing.