JP3489136B2 - Method for producing deodorant - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to air cleaning dexterity filter, deodorizing sheet, a process for the <br/> manufacturing deodorizing agent used in the deodorizing decorative material or the like.

[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 obtained by mixing activated carbon carrying malic acid and activated carbon carrying iron salt (Japanese Examined Patent Publication No. 3-41187) has a strong adsorbing power for lower fatty acid aldehydes and is a petroleum stove. It is suitable for removing the odor immediately after digestion. Further, a deodorizing agent obtained by mixing activated carbon carrying an aniline phosphate and activated carbon carrying phosphoric acid (Japanese Patent Laid-Open No. 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. The invention according view of the conventional problems, is intended to provide a method of manufacturing a superior deodorizing agent stability over time.

[0004]

The present invention has a feature as an acid gas adsorbent.
A silicon compound is used and the organosilicon compound is
Using the lanol group, the surface of the carrier is linked by a silanol bond.
Three-dimensional network structure while firmly immobilizing inside the surface pores
To form a first carrier which is carried on a carrier,
Separately from the first carrier, a basic gas adsorbent is added to make it hydrophobic.
Is strongly supported by the intermolecular force inside the pores on the surface of the carrier.
To prepare a second carrier, and then wet mix both carriers.
Manufacture of deodorant characterized by combining, molding and drying
On the way .

In the present invention, the above organosilicon compound is
It is used as an acid gas adsorbent and has a silanol group. Examples of the organic silicon compound include 3-aminopropyltrihydrosilane (hereinafter referred to as AS), γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) -γ.
-Aminopropyltrimethoxysilane, dimethyltrimethyl-silylamine, N- (β-aminoethyl) -γ-
Examples include amino group-containing organosilicon compounds such as aminopropyl-trimethoxysilane.

As the above-mentioned basic gas adsorbent, one having an extremely small ionization constant such as a carboxyl group-containing organic substance is used. Examples of the carboxyl group-containing organic substances include aromatic carboxylic acids such as salicylic acid and benzoic acid, pyridinecarboxylic acids such as picolinic acid, and aromatic polycarboxylic acids such as phthalic 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 such as ultrafine particles of titanium oxide, aluminum oxide and silicon dioxide obtained by a vapor phase method. Etc. An acidic gas adsorbent or a basic gas adsorbent is carried on the surface and pores of the carrier.

[0007]

When mixing the first carrier and the second carrier, 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 fiber include rayon, 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. . In addition, when the first carrier and the second carrier are mixed and molded,
It is possible to carry out a wet papermaking method in which both of the above-mentioned carriers are scooped up from water by a round net, a flat net or the like to form a thin sheet. This makes it possible to produce a paper-like thin deodorant.

[0010]

FUNCTION AND EFFECT In the deodorant obtained in the present invention , the functional groups of the acidic gas adsorbent and the basic gas adsorbent are independently present in the active state (see FIGS. 1 and 2). for that reason,
The basic gas such as ammonia, which is the gas to be adsorbed, depends on the functional groups of the basic gas adsorbent, and hydrogen sulfide,
Acid gases such as acetaldehyde are chemically adsorbed by the neutralization reaction by the functional groups of the acid gas adsorbent.

Since a proper amount of gas adsorbent is carried on the surface of the pores of the carrier, a proper space is opened in the pores (see FIG. 4). 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.

Next, in the first carrier, the organosilicon compound serving as the acidic gas adsorbent is firmly immobilized by the silanol bond with the hydroxyl group on the carrier surface to form a three-dimensional network structure (FIG. 1). reference). Further, in the second carrier, the basic gas adsorbent has an extremely small ionization constant and has a hydrophobic property. Therefore, it is firmly supported by the intermolecular force on the hydrophobic carrier surface (see FIG. 2). Therefore, both adsorbents do not separate from the carrier and can exhibit stable gas adsorption performance for a long period of time. Therefore, the deodorant of the present invention has excellent stability over time.

Next, in the above method for producing a deodorant,
As described above, the acidic gas adsorbent or the basic gas adsorbent is firmly fixed to the carrier. Therefore, even if the first carrier and the second carrier are mixed under harsh conditions such as wet mixing, the gas adsorbents carried on both carriers rarely fall off the carrier. Therefore, the neutralization reaction of both gas adsorbents by acids and bases is negligible.

It is also conceivable that the first carrier and the second carrier may come into contact and react during molding. However, most of the gas adsorbents are carried inside the pores on the surface of the carrier. Therefore, even if the outer surfaces of both supports contact with each other during mixing, the insides of the pores do not contact each other. Therefore, there is no performance deterioration during mixing and molding, and a deodorant having excellent adsorption performance can be obtained. As described above, according to the present invention, it is possible to provide a manufacturing method excellent deodorant over time stability and gas adsorption properties.

[0015]

EXAMPLES Example 1 A deodorant obtained by the present invention will be described with reference to FIGS. The deodorant 7 of this example is as shown in FIG.
It is a mixture of the first carrier 1 and the second carrier 2. In the first carrier 1, as shown in FIG. 1, an organosilicon compound as the acidic gas adsorbent 10 is supported on the carrier 5 by utilizing the silanol groups 12 thereof. AS (3-aminopropyltrihydrosilane) was used as the acidic gas adsorbent 10.

In the second carrier 2, as shown in FIG. 2, the basic gas adsorbent 20 is carried on the carrier 5.
As the basic gas adsorbent 20, salicylic acid having an extremely small ionization constant was used. As the carrier 5, FIG.
As shown in Fig. 5, it has a large number of pores 50 and a specific surface area of 800
˜1500 m ² / g of activated carbon fiber (AFC) 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. First, in step A of the loading step, 0.01 to 0.1 mol / liter AS aqueous solution 11
Was prepared. Then, the AS solution 11 is
1 to 10 times the weight of the carrier 5 with respect to the weight of the
React. As a result, the first carrier 1 in which the silanol group of AS is bonded to the hydroxyl group on the surface of the carrier is obtained.

In step B of the supporting step, 0.0
A salicylic acid aqueous solution 21 of 1 to 0.1 mol / liter was prepared. Then, in the salicylic acid aqueous solution 21, the above step A is performed.
Similarly to, the carrier 5 is added and these are reacted. As a result, the second carrier 2 in which salicylic acid is carried on the carrier is obtained.

Next, in a mixing step, the first carrier 1 and the second carrier 2 are mixed in water 90 at a weight ratio of 1: 1 to obtain a deodorant material. Next, with respect to the weight of the material, 5% by weight of binder and 15% by weight of reinforcing fiber are mixed and formed into a paper by a wet papermaking method. Vinylon is used as the binder and rayon is used as the reinforcing fiber. Next, the molded body was dried with a drum dryer at 120 ° C. for 10 minutes. As a result, the above deodorant is obtained.

Next, the function and effect of this example will be described.
As shown in FIGS. 1 and 2, the deodorant of this example has an amino group of AS as an acid gas adsorbent and a carboxyl group of salicylic acid as a basic gas adsorbent independently present in an active state. There is. Therefore, the basic gas that is the adsorbed gas is chemically adsorbed by the amino group, and the acidic gas of the adsorbed gas is chemically adsorbed by the carboxyl group by the neutralization reaction.

Further, as shown in FIG. 4, the pores 5 of the carrier 5 are
Since an appropriate amount of the acidic gas adsorbent 10 or the basic gas adsorbent 20 is carried on the 0 surface, a proper space is opened in the pore 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, as shown in FIG. 1, in the first carrier 1, AS as the acidic gas adsorbent 10 is strongly immobilized by the hydroxyl groups on the surface of the carrier 5 and silanol bonds to form a three-dimensional network structure. Is forming. In addition, as shown in FIG. 2, in the second carrier 2, the basic gas adsorbent 20
Since the salicylic acid as described above has an extremely small ionization constant and has a hydrophobic property, it is strongly supported by being supported by the intermolecular force on the surface of the hydrophobic carrier 5.

Therefore, both adsorbents 10 and 20 can exhibit stable gas adsorption performance for a long period of time without being separated from the carrier 5. Therefore, the deodorant of this example has excellent stability over time.

Next, in the above method for producing a deodorant,
As indicated above, it is firmly fixed from the acid gas adsorbent 10 or the basic gas adsorbent 20 to the carrier 5. for that reason,
Even if the first carrier 1 and the second carrier 2 are mixed under severe conditions such as wet mixing, the gas adsorbents 10 and 20 carried on the both carriers 1 and 2 can be mixed with the carrier 5 Very few are dropped from Therefore, the neutralization reaction between the two gas adsorbents due to acid and base is negligible.

It is also conceivable that the first carrier 1 and the second carrier 2 may contact and react during molding. However, Figure 4
As shown in, most of the gas adsorbents 10 and 20 are carried inside the pores 50 on the surface of the carrier 5. for that reason,
Even if the outer surfaces of both carriers 1 and 2 come into contact during mixing, the pores 5
0 Internal comrades never come into contact with each other. Therefore, there is no performance deterioration during mixing and molding, and a deodorant having excellent gas adsorption performance can be obtained.

Example 2 In this example, the adsorption rate of a single component gas was measured for the deodorant of the present invention. In the measurement, the deodorant for measurement was stored in a thermo-hygrostat at a temperature of 25 ° C. and a humidity of 60% for 150 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.

As the above-mentioned deodorant for measurement, a solution having a concentration of AS of 5 for acid gas adsorbent and salicylic acid for basic gas adsorbent of 0.05 mol / liter was used, and a specific surface area of 120
0 m ² / g of activated carbon fiber was used. The carrier was used 5 times by weight with respect to AS and 5 times by weight with respect to salicylic acid. This deodorant is a sheet having a basis weight of 120 g / m ² and a thickness of 1 mm. For comparison, the gas adsorption rate of untreated activated carbon fibers (comparative example) 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 results are shown in Table 1. It can be seen from Table 1 that the deodorant of the present invention has significantly better initial performance than the comparative example for all the various unit gases, and that the adsorption rate hardly deteriorates even after 150 days.

[0030]

[Table 1]

Example 3 In this example, instead of the AS used in Example 1, the following various amino group-containing organic substances were used, and otherwise the deodorant was prepared in the same manner as in Example 1. Examples of the amino group-containing organic substance include γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N
-Β (aminoethyl) -γ-aminopropyltrimethoxysilane, dimethyltrimethyl-silylamine, N-
Either (β-aminoethyl) -γ-aminopropyl-trimethoxysilane was used. As a result of measuring the gas adsorption rate of each of the deodorants of this example, the same effect as in Example 1 could be obtained.

Example 4 In this example, as the carrier, powdered activated carbon, granular activated carbon, zeolite, silica gel, or titanium oxide, aluminum oxide, or silicon dioxide in the form of ultrafine particles obtained by the gas phase method was used, and the others were used. A deodorant was prepared in the same manner as in Example 1. Also in this example, the same effect as in Example 1 could be obtained.

Example 5 In this example, the following binders and reinforcing fibers were used in place of the binders and reinforcing fibers used in Example 1,
A deodorant was produced in the same manner as in Example 1 except for the above. As the binder, any water-soluble polymer such as acrylic emulsion, vinyl chloride, acrylic styrene copolymer, ether-ester polyurethane resin, polyester urethane, urethane resin, polyvinyl alcohol, or acrylic is used.

As the reinforcing fiber, any one of polyester, nylon, pulp, linter pulp and Manila hemp is used. When the time-dependent stability of the gas adsorption rate was measured for each deodorant of this example, the same effect as that of the deodorant of Example 1 was obtained.

[Brief description of drawings]

FIG. 1 is an explanatory view showing a state in which an acidic gas adsorbent is supported on the surface of a carrier and the surface of pores in a first carrier of Example 1.

FIG. 2 is an explanatory view showing a state in which a basic gas adsorbent is carried on the surface and pores of the carrier in the second carrier of Example 1.

FIG. 3 is an explanatory diagram showing a state where the carriers are assembled in Example 1.

FIG. 4 is an explanatory view showing a state in which an acidic gas adsorbent or a basic gas adsorbent is carried on the surface of a carrier and the surface of pores in Example 1.

FIG. 5 is an explanatory view showing a method for producing a deodorant in Example 1.

[Explanation of symbols]

1. ． ． First carrier, 10. ． ． Acid gas adsorbent, 12. ． ． Silanol group, 2. ． ． Second carrier, 20. ． ． Basic gas adsorbent, 5. ． ． Carrier, 50. ． ． pore, 7. ． ． Deodorant,

Continuation of front page (56) Reference JP-A-6-304233 (JP, A) JP-A-57-72651 (JP, A) JP-A-4-180834 (JP, A) JP-A-6-327751 (JP , A) JP 6-7634 (JP, A) JP 7-815 (JP, A) JP 5-17687 (JP, A) JP 1-198549 (JP, A) JP 3-41187 (JP, A) JP-A-2-160042 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61L 9/01 A61L 9/16

Claims (2)

(57) [Claims] 1. An organic silicon compound is used as an acid gas adsorbent, and the silanol group is used to firmly fix the organic silicon compound to the inside of the pores on the surface of the support by a silanol bond and to form a three-dimensional network structure. To form a first carrier on which a carrier is supported, and a basic gas adsorbent is added separately from the first carrier to the intermolecular force inside the pores on the surface of the hydrophobic carrier. A method for producing a deodorant characterized in that a second carrier which is more strongly supported is produced, and then both carriers are wet mixed, molded and dried. 2. The method for producing a deodorant according to claim 1, wherein reinforcing fibers and a binder are mixed when the first carrier and the second carrier are mixed.