WO2018173534A1 - Adsorbent for removal of aldehyde, deodorizing material, and production method for same - Google Patents

Abstract

Provided is an adsorbent for removal of aldehydes which is able to highly efficiently remove aldehydes and exhibits excellent storage stability. This adsorbent for removal of aldehydes contains a porous carrier, a non-volatile strong acid, and one or more agents each containing a 1,2,4-triazol backbone with an electron donor group bonded to the N atom at position 4. The atom of the electron donor group bonded to the N atom at position 4 has an unshared electron pair.

Description

Adsorbent for removing aldehyde, deodorizing material, and production method thereof

The present invention relates to an adsorbent for aldehyde removal.

In recent years, indoor and in-vehicle environments are required to have less odor and dust. For example, regarding the in-vehicle environment, it is desired to remove odors originating from resin parts, exhaust gas from engines, fuel, tobacco, human bodies, and the like.

Japanese Patent Application Laid-Open No. 2006-75312 describes a deodorant composition comprising an inorganic porous material to which triazoles are attached. This deodorant composition efficiently deodorizes lower aldehydes such as formaldehyde at room temperature.

JP 2011-72603 A describes a fibrous deodorant containing fibrous activated carbon, p-aminobenzoic acid, and sulfuric acid. This fibrous deodorant makes it possible to remove odorous components such as volatile organic compounds such as ammonia and aldehydes with high efficiency and has excellent storage stability.

In addition, various deodorants are known as deodorizers for removing odors containing aldehydes (Japanese Patent Laid-Open Nos. 2005-137601, 11-004879, 2000-152979). JP, 2001-149456, JP 05-023588, and JP 2000-186212).

The present inventors have found that conventional deodorant compositions and fibrous deodorizers have room for improvement in terms of removal performance and storage stability of aldehydes such as formaldehyde and acetaldehyde.

Therefore, an object of the present invention is to provide an adsorbent for removing aldehyde that can remove aldehydes with high efficiency and has excellent storage stability.

According to the first aspect of the present invention, each of the porous carrier, the non-volatile strong acid, the 1,2,4-triazole skeleton, and the electron donating group bonded to the N atom at the 4-position thereof, An aldehyde-removing adsorbent comprising one or more agents in which the atoms bonded to the 4-position N atom have a lone pair of electrons is provided.

According to the second aspect of the present invention, there is provided a deodorizing material comprising the aldehyde removing adsorbent according to the first aspect and a substrate carrying the aldehyde removing adsorbent.

According to the third aspect of the present invention, the base material, the porous carrier supported on the base material, the non-volatile strong acid, the 1,2,4-triazole skeleton and the electron donation bonded to the N atom at the 4-position thereof There is provided a deodorizing material each comprising a functional group, wherein an atom bonded to the N atom at the 4-position of the electron donating group and one or more agents having an unshared electron pair are provided. The

According to the fourth aspect of the present invention, each of the non-volatile strong acid, the 1,2,4-triazole skeleton, and the electron donating group bonded to the N atom at the 4-position thereof, There is provided a method for producing an adsorbent for removing aldehyde, comprising a step of supporting a porous carrier with one or more drugs having an unshared electron pair in the atom bonded to the N atom at the position.

According to the fifth aspect of the present invention, there is provided a method for producing a deodorizing material including supporting an adsorbent for removing aldehyde according to the first aspect on a base material.

According to a sixth aspect of the present invention, there is provided a dispersion comprising a non-volatile strong acid, one or more drugs, a porous carrier and a dispersion medium, each of the one or more drugs being 1, 2, 4 A dispersion comprising a triazole skeleton and an electron donating group bonded to the N atom at the 4-position, wherein the atom bonded to the N atom at the 4-position of the electron donating group has an unshared electron pair There is provided a method for producing a deodorizing material comprising supplying a liquid to a base material and drying the base material supplied with the dispersion.

The figure which shows roughly an example of the deodorizing material which concerns on 1 aspect of this invention. The graph which shows the aldehyde removal rate of the adsorption agent for aldehyde removal using various chemical | medical agents. The graph which shows an example of the influence which the quantity of a sulfuric acid has on the aldehyde removal rate. The graph which shows an example of the influence which the quantity of a chemical | medical agent has on an aldehyde removal rate. The graph which shows an example of the influence which the kind of an acid and a chemical | medical agent has on storage stability. The graph which shows an example of the influence which pH has on the aldehyde removal rate.

Hereinafter, embodiments of the present invention will be described.
The adsorbent for removing aldehyde according to one embodiment of the present invention includes a porous carrier, a non-volatile strong acid, and one or more drugs.

The porous carrier is, for example, activated carbon, activated clay, talc, clay, molecular sieve, silica gel, bentonite, alumina, perlite, zeolite, or sepiolite. The kind of the porous carrier can be appropriately selected according to the kind of odor to be removed.

Preferably, the porous carrier is activated carbon. Since activated carbon has a large specific surface area, it can remove odor more efficiently. The raw material for the activated carbon is, for example, coconut shell, coal, or charcoal.

The shape of the porous carrier is, for example, granular, powdery, crushed, fibrous, spherical, sheet-like or honeycomb-like.

The non-volatile strong acid is, for example, sulfuric acid.
Nonvolatile acids are less likely to reduce in volume due to volatilization. That is, when a non-volatile acid is used, the storage stability of the aldehyde-removing adsorbent is better than when a volatile acid is used.

When a weak acid is used, a larger amount of acid must be used than a strong acid. When a large amount of acid is used, the pores of the porous carrier are blocked. On the other hand, strong acid can improve the aldehyde removal property of the adsorbent for aldehyde removal with a small amount. Therefore, when a strong acid is used, blockage of the pores of the porous carrier can be minimized. Therefore, when a strong acid is used, a reaction with an aldehyde can be caused more efficiently than when a weak acid is used.

Each of the drugs includes a 1,2,4-triazole skeleton and an electron donating group bonded to the 4-position N atom, and among the electron-donating groups, the atom bonded to the 4-position N atom is It is a compound having an unshared electron pair.

The atom bonded to the 4-position N atom in the electron donating group is, for example, an N atom, an O atom, or an S atom.

The electron donating group is preferably one that does not prevent the aldehyde from approaching the electron donating group due to its steric hindrance. The number of atoms other than hydrogen contained in the electron donating group is preferably 3 or less, and more preferably 2 or less.

The electron donating group is, for example, an amino group, a hydroxy group, a methoxy group, a thiol group, or a hydrazino group.

Each drug may have a substituent on at least one of the C atom at the 3-position and the C atom at the 5-position of the 1,2,4-triazole skeleton. The substituent bonded to the 3-position C atom and the substituent bonded to the 5-position C atom may be bonded to each other to form a ring together with the 1,2,4-triazole skeleton. . Further, each of these substituents preferably has 3 or less atoms, and more preferably 2 or less atoms other than hydrogen. Examples of these substituents include hydrazino group, mercapto group, amino group, hydroxy group, and methoxy group.

At least one of the drugs is preferably a compound represented by the following general formula (1). More preferably, all of the drugs are compounds represented by the following general formula (1).

Here, R ₁ and R ₂ are the same or different and each represents a hydrogen atom or a substituent having a number of atoms other than hydrogen in the range of 1 to 7, preferably in the range of 1 to 4. Yes. Examples of such a substituent include an alkyl group, an alkylamino group, an amino group, a hydroxy group, a methoxy group, and a thiol group.

R ₃ and R ₄ are the same or different and represent a hydrogen atom or a substituent having a number of atoms other than hydrogen in the range of 1 to 5, preferably in the range of 1 to 3. . Examples of such a substituent include an alkyl group, an alkylamino group, an amino group, a hydroxy group, a methoxy group, and a thiol group.

At least one of the drugs is preferably selected from the group consisting of 4-amino-1,2,4-triazole and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole. More preferably, all of the drugs are selected from the group consisting of 4-amino-1,2,4-triazole and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole.

This adsorbent for removing aldehyde is produced by supporting one or more drugs and a non-volatile strong acid on a porous carrier.
The non-volatile strong acid and the drug are supported on the porous carrier by, for example, the following method.
First, a treatment liquid is prepared by dissolving a drug and a non-volatile strong acid in a solvent.

Instead of preparing a treatment liquid containing both a chemical and a non-volatile strong acid, a treatment liquid containing a chemical and a treatment liquid containing a non-volatile strong acid may be prepared.
When preparing a treatment liquid by dissolving a drug and a non-volatile strong acid together in one solvent, the treatment liquid can be prepared by adding the drug and non-volatile strong acid to the solvent in any order and stirring. . As the solvent, for example, water can be used. In order to dissolve the drug in a solvent, an aqueous solution of a non-volatile strong acid may be heated or cooled to a temperature in the range of 0 to 100 ° C, for example. This treatment liquid may be used in a heated state or may be used after being cooled. The drug may be dissolved in an aqueous solution of a non-volatile strong acid sufficiently diluted with water, or may be dissolved in an aqueous solution containing a non-volatile strong acid at a relatively high concentration and then diluted with water. Good. The amount of the chemical and the non-volatile strong acid in the treatment liquid will be described later.

Next, the porous carrier is brought into contact with the treatment liquid.
The step of bringing the treatment liquid into contact with the porous carrier can be performed, for example, by immersing the porous carrier in the treatment liquid or by spraying the treatment liquid onto the porous carrier.
When immersing the porous carrier in the treatment liquid, for example, the porous carrier is uniformly dispersed in the treatment liquid.

Next, the solvent is removed from the porous carrier brought into contact with the treatment liquid.
The removal of the solvent is performed, for example, by drying the porous carrier. For this drying, for example, natural drying, ventilation drying, hot air drying, microwave heating drying or indirect heating drying is used.

This drying is performed so that the temperature of the porous carrier is maintained at a temperature that does not affect the drug, for example, 200 ° C. or lower, typically 150 ° C. or lower.
The adsorbent for aldehyde removal is obtained as described above. In addition, when preparing the process liquid containing a chemical | medical agent and the process liquid containing a non-volatile strong acid, these process liquids can be made to contact a porous support | carrier in arbitrary orders.

In the treatment liquid, a total of one or more drugs is preferably within a range of 2 to 30 parts by mass, more preferably 3 to 30 parts by mass with respect to 100 parts by mass of the porous carrier. In the range of 3 parts by mass to 10 parts by mass. When this ratio is reduced, the initial performance of the aldehyde-removing adsorbent is lowered.

In addition, the treatment liquid contains a non-volatile strong acid, preferably in the range of 0.5 to 12 parts by mass, more preferably 0.6 to 7 parts by mass with respect to 100 parts by mass of the porous carrier. In the range of 0.8 parts by mass, more preferably in the range of 0.8 parts by mass to 5 parts by mass, and most preferably in the range of 0.8 parts by mass to 4 parts by mass. Since the reaction between the drug and the aldehyde tends to be activated in a strongly acidic environment, increasing this ratio can remove malodorous components with higher efficiency. However, if this ratio is excessively increased, the initial performance of the aldehyde removing adsorbent is lowered.

The adsorbent for aldehyde removal obtained by the above method has a pH obtained according to JIS K1474: 2014, for example, in the range of 1.5 to 4.5, preferably in the range of 1.9 to 4.1. Is in.

In addition, when sulfuric acid is used as the non-volatile strong acid, the aldehyde-removing adsorbent obtained by the above-described method has a sulfur content of, for example, 0.1% by mass to 2% by mass, preferably 0.2% by mass to 1%. .4 mass%, more preferably 0.2 to 1 mass%. The amount of sulfur contained in the aldehyde removing adsorbent is a value obtained by performing measurement by a UniQuant measurement method in a vacuum atmosphere using a fluorescent X-ray analyzer.

The adsorbent for removing aldehyde obtained by the above-mentioned method can remove malodorous components such as volatile organic compounds such as ammonia and aldehydes from the gas phase with high efficiency. In addition, the aldehyde-removing adsorbent is excellent in storage stability. That is, this aldehyde removing adsorbent exhibits excellent performance regardless of the time from the completion of production to the start of use. The present inventors consider that the reason is as follows.

In the presence of an acid, H ⁺ is bonded to the oxygen atom of the carbonyl group of the aldehyde, and the aldehyde has a state in which the carbon atom of the carbonyl group is positively charged and a state in which the oxygen atom of the carbonyl group is positively charged. It changes reversibly between. As a result, the aldehyde activates the carbonyl carbon and increases the reactivity with the drug.

The unshared electron pair possessed by the electron donating group of the drug contributes to the reaction with the aldehyde. This unshared electron pair is likely to be deactivated by binding to H ^{+ in} the presence of an acid. However, the above-mentioned drug can stably hold electrons contributing to the reaction with the aldehyde even in the presence of an acid by the mechanism described below, and therefore can maintain the reactivity with the aldehyde. it is conceivable that.

In addition, the drug used here can take at least three states as shown below, for example, due to resonance of the 1,2,4-triazole skeleton.

Here, in the states (A) to (C), among the compounds represented by the general formula (1), all of R ₁ , R ₂ , R ₃ , and R ₄ are hydrogen atoms. Is a possible state. The electron donating group of this drug contains an atom with an unshared electron pair, here an N atom.

In state (A), H ⁺ bonds to this atom tend to occur. And when this coupling | bonding arises, the reactivity with the aldehyde of a chemical | medical agent will fall.

In the states (B) and (C), the bond between H ⁺ and an atom having an unshared electron pair of an electron donating group, in this case, an N atom is weaker than in the state (A). Therefore, when the change from the state (A) to the state (B) or (C) occurs, the bond between H ⁺ and the atom (N atom) can be broken.

When the stability of the states (B) and (C) is low, the frequency of change from the state (A) to the state (B) or (C) is low, and the frequency at which the above-described bond is broken is low. However, in this drug, since the electron donating group is bonded to the 4-position N atom of the 1,2,4-triazole skeleton, the electron density at the 4-position N atom is low (B) and (C) To stabilize. That is, this drug has high stability in the states (B) and (C). For this reason, this chemical | medical agent has the high frequency of the change from a state (A) to a state (B) or (C), and the frequency which the coupling | bonding mentioned above is cut | disconnected is also high.

Therefore, even if this drug produces a bond of H ⁺ to an atom having an unshared electron pair of an electron donating group, this bond is quickly cleaved and shows high activity.

Thus, the drug remains reactive with the aldehyde even in the presence of acid. In addition, as described above, aldehydes are highly reactive with drugs in the presence of acids. Therefore, as a whole, the reaction between the drug and the aldehyde is promoted in the presence of an acid.

Also, when a weak acid is used instead of a strong acid, a larger amount of acid must be used than when a strong acid is used. When a large amount of acid is used, the pores of the porous carrier are blocked. On the other hand, strong acid can improve the aldehyde removal property of the adsorbent for aldehyde removal with a small amount. Therefore, when a strong acid is used, blockage of the pores of the porous carrier can be minimized. Therefore, when a strong acid is used, the reaction between the drug and the aldehyde can be caused more efficiently than when a weak acid is used.

Furthermore, the amount of non-volatile acid is less likely to decrease due to volatilization. That is, when a non-volatile acid is used, the storage stability of the aldehyde-removing adsorbent is better than when a volatile acid is used.

Therefore, the adsorbent for aldehyde removal described above can remove aldehydes with high efficiency and has excellent storage stability.

The adsorbent for removing aldehyde described above can be used, for example, in a deodorizing material.

In FIG. 1, an example of the deodorizing material which concerns on 1 aspect of this invention is shown roughly.
A deodorizing material 1 shown in FIG. 1 includes an aldehyde removing adsorbent 2 and a base material 3. The base material 3 carries the aldehyde removing adsorbent 2. The base material 3 is a nonwoven fabric here. In FIG. 1, reference numeral 4 indicates a non-woven fiber.

The base material 3 may not be a non-woven fabric. The substrate 3 may be, for example, a foam, a porous polyurethane, a curtain, a carpet, a woven fabric such as an automobile seat fabric, paper, corrugated paper, or various fibrous materials.

This deodorizing material can be obtained by supporting an adsorbent for removing aldehyde on a base material. For example, the deodorizing material can be obtained by spraying, applying, or impregnating a dispersion containing an aldehyde-removing adsorbent and a dispersion medium and drying the dispersion. As the dispersion medium, for example, polar solvents such as water, ethanol and acetone, or a mixed solution thereof can be used.

Since this deodorizing material contains the aldehyde removing adsorbent described above, it is possible to remove malodorous components such as volatile organic compounds such as ammonia and aldehydes from the gas phase with high efficiency. In addition, since this deodorizing material is unlikely to cause deterioration of the aldehyde removing adsorbent, it has excellent storage stability. That is, this deodorizing material exhibits excellent performance regardless of the time from the completion of production until the start of use.

The deodorizing material can also be obtained by the following method. First, a dispersion containing the components described above for the aldehyde-removing adsorbent, that is, a non-volatile strong acid, one or more drugs, a porous carrier, and a dispersion medium is prepared. Next, this dispersion is supplied to the substrate. For example, the dispersion is sprayed, applied, or impregnated onto the substrate. Then it is dried.

In the deodorizing material obtained by this method, the porous carrier is supported on the base material. The non-volatile strong acid and the one or more drugs are supported on at least one of the base material and the porous carrier. For example, a part of the aldehyde removing adsorbent other than the porous carrier is supported on the porous carrier, and the rest is supported on the substrate. Such a deodorizing material also exhibits excellent performance regardless of the time from the completion of production to the start of use.

The components preferably used in this deodorizing material are the same as those described above for the aldehyde removing adsorbent. Moreover, the suitable quantity of each component in this deodorizing material is the same as that mentioned above about the adsorbent for aldehyde removal.

As for the aldehyde removal adsorbent, a suitable amount of a specific component, for example, sulfur is described as a ratio to the amount of the aldehyde removal adsorbent. In this deodorizing material, the proportion of the specific component in the total of the porous carrier, the non-volatile strong acid, and the one or more drugs is preferably the above-described ratio of the specific component in the adsorbent for aldehyde removal. Is in range.

Moreover, this deodorizing material has a pH of preferably within the range described above for the aldehyde-removing adsorbent using the method defined in JIS K1474: 2014. In JIS K1474: 2014, a pH measurement method is defined for a powder sample or a granular sample. In order to measure the pH of the deodorizing material, the deodorizing material has a solid content other than the nonwoven fabric of 3 g, that is, the total amount of the porous carrier, the non-volatile strong acid, and one or more drugs is 3 g. A sample cut in this manner is used as a sample.

In addition, the components suitably used in the dispersion used in the production of the deodorizing material are the same as the components suitably used in the treatment liquid described above for the aldehyde-removing adsorbent. And the suitable quantity of each component in this dispersion liquid is the same as that of what was mentioned above about the processing liquid mentioned above.

Examples of the present invention will be described below.
<Effect of drug type on aldehyde removal rate>
(Example 1)
An aldehyde removing adsorbent was prepared by the following method.
To 50 parts by mass of water, 5 parts by mass of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass and 3 parts by mass of 4-amino-1,2,4-triazole were added. This solution was stirred and 4-amino-1,2,4-triazole was completely dissolved in an aqueous solution to prepare a treatment solution.

Next, 100 parts by mass of activated carbon was prepared. As the activated carbon, coconut shell activated carbon having a BET specific surface area of 1000 m ² / g was used.
Subsequently, the treatment liquid was sprayed on the activated carbon to uniformly adhere the treatment liquid to the activated carbon.
Thereafter, the activated carbon was dried at 80 ° C. for 10 hours using a dryer.
As described above, an adsorbent for removing aldehyde was obtained.

(Example 2)
In the same manner as described in Example 1 except that 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole was used instead of 4-amino-1,2,4-triazole. An aldehyde removal adsorbent was prepared.

(Comparative Example 1)
An adsorbent for removing aldehyde was produced in the same manner as described in Example 1 except that 3-amino-1,2,4-triazole was used instead of 4-amino-1,2,4-triazole. did.

(Comparative Example 2)
An aldehyde-removing adsorbent was produced in the same manner as described in Example 1 except that 1,2,4-triazole was used instead of 4-amino-1,2,4-triazole.

(Comparative Example 3)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that p-aminobenzoic acid was used in place of 4-amino-1,2,4-triazole.

(Comparative Example 4)
Instead of 3 parts by mass of 4-amino-1,2,4-triazole, 5 parts by mass of adipic acid dihydrazide was used, and instead of 5 parts by mass of sulfuric acid containing 75 parts by mass of sulfuric acid, 4 parts by mass An aldehyde-removing adsorbent was produced in the same manner as described in Example 1 with the exception of using calcium chloride.

(Comparative Example 5)
Instead of 3 parts by weight of 4-amino-1,2,4-triazole, 5 parts by weight of adipic acid dihydrazide was used instead of 5 parts by weight of sulfuric acid aqueous solution containing 75 parts by weight of sulfuric acid. An aldehyde-removing adsorbent was produced in the same manner as described in Example 1 except that sodium acetate was used.

(Performance evaluation)
For each of the adsorbents for aldehyde removal obtained in Examples 1 and 2 and Comparative Examples 1 to 5, the aldehyde removal performance was evaluated according to the following method.

First, 2.94 mL of an adsorbent for removing aldehyde was packed in a 30 mm diameter column. Next, the column packed with the adsorbent for aldehyde removal was adjusted to a temperature of 23 ± 5 ° C. and a humidity of 60 ± 10% RH, and a gas containing acetaldehyde at a concentration of 10 ppm was added to 2.35 L / It was circulated for 60 minutes at a flow rate of min and a space velocity of 48000 / h. After 60 minutes, the concentration of acetaldehyde at the inlet and outlet of the column was measured. The initial acetaldehyde removal rate was defined as a percentage of the difference between the measured value at the column inlet and the measured value at the column outlet and the measured value at the column inlet.

(PH measurement)
About each of the adsorption agent for aldehyde removal obtained in Example 1 and Example 2 and Comparative Example 1 thru | or Comparative Example 5, pH was measured according to JISK1474: 2014. That is, 100 ml of water was added to 3 g of the aldehyde-removing adsorbent, boiled, cooled, and then the pH was measured with a pH meter.
These results are summarized in Table 1 below and FIG.

FIG. 2 is a graph showing the aldehyde removal rate of the aldehyde removal adsorbent using various chemicals. The horizontal axis of this graph indicates the numbers of the example and the comparative example, and the vertical axis indicates the initial acetaldehyde removal rate.

As shown in Table 1 and FIG. 2, Examples 1 and 2 achieved an excellent initial acetaldehyde removal rate as compared with Comparative Examples 1 to 3. That is, when 4-amino-1,2,4-triazole or 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole is used as a drug used in combination with sulfuric acid, 3-amino-1 Excellent initial acetaldehyde removal rate was achieved compared to the use of 1,2,4-triazole, 1,2,4-triazole, or p-aminobenzoic acid. Further, Examples 1 and 2 achieved an excellent initial acetaldehyde removal rate as compared with Comparative Examples 4 and 5. That is, when 4-amino-1,2,4-triazole or 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole is used in combination with sulfuric acid, adipic acid dihydrazide is mixed with calcium chloride or sodium acetate. Excellent initial acetaldehyde removal rate was achieved compared with the case of using together.

<Effect of drug and acid amount on aldehyde removal rate>
(Example 3)
An aldehyde-removing adsorbent was prepared in the same manner as described for Example 1 except that the amount of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 1 part by mass.

(Example 4)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of the sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 2 parts by mass.

(Example 5)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 9 parts by mass.

(Example 6)
An aldehyde removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of 4-amino-1,2,4-triazole was changed from 3 parts by mass to 5 parts by mass.

(Example 7)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of 4-amino-1,2,4-triazole was changed from 3 parts by mass to 10 parts by mass.

(Example 8)
An aldehyde-removing adsorbent was prepared in the same manner as described for Example 1 except that the amount of 4-amino-1,2,4-triazole was changed from 3 parts by mass to 20 parts by mass.

(Example 9)
An aldehyde-removing adsorbent was prepared in the same manner as described for Example 1 except that the amount of 4-amino-1,2,4-triazole was changed from 3 parts by weight to 30 parts by weight.

(Example 10)
An adsorbent for aldehyde removal was prepared in the same manner as described in Example 1 except that the amount of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 0.75 parts by mass. did.

(Example 11)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of the sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 12 parts by mass.

(Example 12)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that the amount of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was changed from 5 parts by mass to 15 parts by mass.

(Example 13)
An aldehyde-removing adsorbent was prepared in the same manner as described for Example 1 except that the amount of 4-amino-1,2,4-triazole was changed from 3 parts by weight to 2 parts by weight.

(Comparative Example 6)
An adsorbent for aldehyde removal was prepared in the same manner as described for Example 1 except that no sulfuric acid aqueous solution was used.

(Performance evaluation)
For each of the aldehyde-removing adsorbents obtained in Examples 3 to 13 and Comparative Example 6, the initial acetaldehyde removal rate was determined by the same method as described above.

(PH measurement)
About each of the adsorption agent for aldehyde removal obtained in Example 3 thru | or Example 13 and the comparative example 6, pH was measured by the method similar to having demonstrated above.

(Measurement of sulfur content)
For each of the aldehyde-removing adsorbents obtained in Example 1 and Examples 3 to 13, sulfur was measured by a UniQuant measurement method in a vacuum atmosphere using Axios (registered trademark) manufactured by PANalytical, which is an X-ray fluorescence analyzer. The amount was measured.
These results are summarized in Table 2 below and FIGS. 3 and 4.

FIG. 3 is a graph showing an example of the influence of the amount of sulfuric acid contained in the aldehyde removal adsorbent on the aldehyde removal rate. The horizontal axis of this graph indicates the ratio of sulfur contained in the aldehyde-removing adsorbent, and the vertical axis indicates the initial acetaldehyde removal rate. This figure shows data obtained when the amount of 4-amino-1,2,4-triazole is 3 parts by mass.

FIG. 4 is a graph showing an example of the effect of the amount of 4-amino-1,2,4-triazole on the aldehyde removal rate of the aldehyde removal adsorbent. The horizontal axis of this graph represents the amount of 4-amino-1,2,4-triazole, and the vertical axis represents the initial acetaldehyde removal rate. In addition, this figure has shown the data obtained when the quantity of 75 mass% sulfuric acid aqueous solution was 5 mass parts.

As shown in Table 2 and FIG. 3, Example 1, Example 3 to Example 5, and Example 10 to 12 achieved superior initial performance as compared with Comparative Example 6. That is, the aldehyde-removing adsorbent has superior initial performance when it contains 4-amino-1,2,4-triazole together with sulfuric acid, compared to when it contains 4-amino-1,2,4-triazole alone. Achieved. In addition, Example 1, Example 3 to Example 5, and Example 10 achieved better initial performance as compared with Example 11 and Example 12. That is, when the amount of sulfuric acid contained in the aldehyde-removing adsorbent is sufficiently small, excellent initial performance can be achieved as compared with the case where the amount of sulfuric acid is large.

As shown in Table 2 and FIG. 4, Example 1 and Examples 6 to 9 achieved superior initial performance as compared with Example 13. That is, when the amount of 4-amino-1,2,4-triazole is sufficiently large, excellent initial performance can be achieved as compared with the case where the amount of 4-amino-1,2,4-triazole is small.

<Effects of drug and acid type on storage stability>
(Comparative Example 7)
Example 1 was the same as that described for Example 1 except that 9 parts by mass of hydrochloric acid containing hydrogen chloride at a concentration of 35% by mass was used instead of 5 parts by mass of sulfuric acid aqueous solution containing 75% by mass of sulfuric acid. The adsorbent for aldehyde removal was prepared by the method.

(Comparative Example 8)
An aldehyde-removing adsorbent was prepared in the same manner as described in Example 1 except that 10 parts by mass of acetic acid was used instead of 5 parts by mass of sulfuric acid containing 75 parts by mass of sulfuric acid. .

(Comparative Example 9)
For removal of aldehyde by the same method as described in Example 1 except that 7 parts by mass of iron chloride tetrahydrate was used instead of 5 parts by mass of sulfuric acid solution containing sulfuric acid at a concentration of 75% by mass. An adsorbent was prepared.

(Comparative Example 10)
For removal of aldehyde by the same method as described in Example 1 except that 7 parts by mass of iron sulfide heptahydrate was used instead of 5 parts by mass of sulfuric acid solution containing sulfuric acid at a concentration of 75% by mass. An adsorbent was prepared.

(PH measurement)
About each of the adsorption agent for aldehyde removal obtained by the comparative example 7 thru | or the comparative example 10, pH was measured by the method similar to having demonstrated above.

(Evaluation of storage stability)
Each of the aldehyde-removing adsorbents obtained in Examples 1 and 4 and Comparative Examples 3 and 6 to 10 was subjected to a storage stability acceleration test described below.

First, 50 g of an adsorbent for removing aldehyde was placed in a 200 ml beaker and allowed to stand in a thermostatic bath at 70 ° C. for 7 days and 14 days. For each of the aldehyde-removing adsorbents after 7 days and 14 days, the acetaldehyde removal rate was determined by the same method as described for the initial acetaldehyde removal rate.

The value representing the ratio between the aldehyde removal rate after the storage stability acceleration test and the initial acetaldehyde removal rate as a percentage was defined as “storage stability”.
These results are summarized in Table 3 below and FIG.

FIG. 5 is a graph showing an example of the influence of the type of acid and drug on the storage stability of the aldehyde removal adsorbent. The horizontal axis of this graph represents the number of days that have passed since the aldehyde-removing adsorbent was subjected to the acceleration test, and the vertical axis represents the acetaldehyde removal rate. This figure shows data obtained when the amount of 4-amino-1,2,4-triazole is 3 parts by mass.

As shown in Table 3 and FIG. 5, Example 1 and Example 4 achieved superior storage stability compared to Comparative Example 6. That is, when 4-amino-1,2,4-triazole was used in combination with sulfuric acid, excellent storage stability was achieved as compared with the case where it was not used in combination with sulfuric acid. In addition, Examples 1 and 4 achieved excellent storage stability as compared with Comparative Example 3. That is, when 4-amino-1,2,4-triazole was used as a drug used in combination with sulfuric acid, excellent storage stability was achieved compared to the case where p-aminobenzoic acid was used. In addition, Examples 1 and 4 achieved excellent storage stability as compared with Comparative Example 7. That is, when sulfuric acid was used as the acid, excellent storage stability was achieved compared to the case where hydrochloric acid was used. In addition, Examples 1 and 4 achieved excellent storage stability as compared with Comparative Example 8. That is, when sulfuric acid was used as the acid, excellent initial performance and excellent storage stability were achieved compared to the case where acetic acid was used. In addition, Examples 1 and 4 achieved excellent storage stability as compared with Comparative Example 9. That is, when sulfuric acid was used as the acid, excellent storage stability was achieved compared to the case where iron chloride was used. In addition, Examples 1 and 4 achieved excellent storage stability as compared with Comparative Example 10. That is, when sulfuric acid was used as the acid, excellent storage stability was achieved compared to the case where iron sulfide was used.

<Effect of pH of aldehyde removal adsorbent on aldehyde removal rate>
FIG. 6 is a graph showing an example of the effect of the pH of the aldehyde removal adsorbent on the aldehyde removal rate. The horizontal axis of this graph indicates the pH value of the aldehyde removing adsorbent, and the vertical axis indicates the initial acetaldehyde removal rate. This figure shows data obtained when the amount of 4-amino-1,2,4-triazole is 3 parts by mass.

As shown in FIG. 6, Examples 1, 3 to 5 and Examples 10 to 12 achieved an excellent initial acetaldehyde removal rate as compared with Comparative Example 6. Among them, Example 1 and Examples 3 to 5 achieved particularly excellent initial performance.

<Manufacture and evaluation of deodorizing material>
(Example 14)
First, an aldehyde removing adsorbent was prepared by the following method.
To 250 g of water, 1.3 g of sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass and 8 g of 4-amino-1,2,4-triazole were added. This solution was stirred and 4-amino-1,2,4-triazole was completely dissolved in the aqueous solution to prepare a treatment solution.

Next, 100 g of activated carbon was added to the treatment liquid. As the activated carbon, coconut shell activated carbon having a BET specific surface area of 1000 m ² / g and a median diameter (D50) of 25 μm was used.
The dispersion was sufficiently stirred, and 2 g of hydroxyethyl cellulose and 61 g of an acrylic binder were added thereto. The dispersion was further stirred to prepare a slurry.

Subsequently, this slurry was applied to a nonwoven fabric having a basis weight of 95 g / m ² . The application of the slurry was performed so that the basis weight of the solid content contained in the slurry was 260 g / m ² .

Thereafter, this was heated at 100 ° C. for 1 hour and dried.
A deodorizing material was obtained as described above.

(Comparative Example 11)
A deodorizing material was produced in the same manner as described for Example 14 except that no sulfuric acid aqueous solution was used.

(PH measurement)
About each of the deodorizing material obtained in Example 14 and Comparative Example 11, pH was measured using the method prescribed | regulated in JISK1474: 2014. That is, the deodorizing material was cut so that the solid content other than the nonwoven fabric was 3 g, and 100 ml of water was added thereto and boiled. After cooling, the pH was measured with a pH meter. The results are shown in Table 4 below.

(Performance evaluation)
Each of the deodorizing materials obtained in Example 14 and Comparative Example 11 was evaluated for aldehyde removal performance according to the following method.

First, each deodorizing material was cut into five pieces having different sizes. These pieces were enclosed in separate bags. Here, a bag having a capacity of 5 L was used.

Next, acetaldehyde was injected into each bag so as to have a concentration of 1000 ppm, and this was left under the conditions of 25 ° C. and 50% RH until the concentration of acetaldehyde reached saturation. Moreover, the bag which inject | poured the same quantity of aldehyde as the above was prepared, without enclosing the fragment | piece of a deodorizing material, and the acetaldehyde density | concentration in this bag was measured. Then, the difference between the acetaldehyde concentration and the saturated concentration of the acetaldehyde was determined, and the mass of the deodorizing material adsorbed by the fragments was calculated from the difference and the volume of gas in the bag. By dividing this mass by the area of the fragment, the amount of acetaldehyde adsorbed by the deodorizing material per unit area was determined.

Next, a relational expression between the saturated concentration of acetaldehyde and the acetaldehyde adsorption amount of the deodorizing material per unit area was obtained. And from this relational expression, the acetaldehyde adsorption amount of the deodorizing material per unit area when the saturation concentration was 300 μg / m ³ , that is, the initial acetaldehyde adsorption amount was determined. The results are shown in Table 4 below.

(Evaluation of storage stability)
Each of the deodorizing materials obtained in Example 14 and Comparative Example 11 was subjected to a storage stability acceleration test described below.

First, each deodorizing material was cut into five pieces having different sizes. Subsequently, these fragments were allowed to stand in a thermostat at 70 ° C. for 7 days and 14 days. The acetaldehyde adsorption amount was determined by the same method as described for the initial acetaldehyde adsorption amount using the fragments after 7 days and 14 days.

And the value which expressed the ratio of the acetaldehyde adsorption amount obtained using the fragments after 14 days and the initial acetaldehyde adsorption amount as a percentage was defined as “storage stability”. *

As shown in Table 4, Example 14 achieved superior storage stability compared to Comparative Example 11. That is, when sulfuric acid was used in combination with 4-amino-1,2,4-triazole, excellent storage stability was achieved as compared with the case where sulfuric acid was not used.

Claims (14)

1. A porous carrier;
   A non-volatile strong acid;
   Each includes a 1,2,4-triazole skeleton and an electron donating group bonded to the N atom at the 4-position thereof, and the atom bonded to the N atom at the 4-position of the electron donating group is an unshared electron An adsorbent for aldehyde removal comprising one or more drugs having a pair.
2. The adsorbent for aldehyde removal according to claim 1, wherein at least one of the one or more drugs is a compound represented by the following general formula (1).
   

   

   (Wherein R1 and R2 are the same or different and each represents a hydrogen atom or a substituent having a number of atoms other than hydrogen in the range of 1 to 7, and R3 and R4 are the same or different and represent a hydrogen atom, Or a substituent having a number of atoms other than hydrogen in the range of 1 to 4.
3. At least one of the one or more agents is selected from the group consisting of 4-amino-1,2,4-triazole and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole Item 3. Adsorbent for removing aldehyde according to item 1 or 2.
4. The adsorbent for aldehyde removal is
   A solvent,
   A non-volatile strong acid;
   Each includes a 1,2,4-triazole skeleton and an electron donating group bonded to the N atom at the 4-position thereof, and the atom bonded to the N atom at the 4-position of the electron donating group is an unshared electron Contacting a porous carrier with a treatment liquid containing one or more drugs having a pair;
   And removing the solvent from the porous carrier.
   The aldehyde removal agent according to any one of claims 1 to 3, wherein the treatment liquid contains the one or more drugs in a range of 2 to 30 parts by mass with respect to 100 parts by mass of the porous carrier. Adsorbent.
5. The aldehyde removal adsorbent according to claim 4, wherein the treatment liquid contains the nonvolatile strong acid in a range of 0.5 to 12 parts by mass with respect to 100 parts by mass of the porous carrier.
6. The adsorbent for aldehyde removal according to claim 4, wherein the non-volatile strong acid is sulfuric acid.
7. The aldehyde-removing adsorbent according to claim 6, wherein the aldehyde-removing adsorbent contains 0.1 to 2% by mass of sulfur.
8. The adsorbent for aldehyde removal is
   A solvent,
   A non-volatile strong acid;
   Each includes a 1,2,4-triazole skeleton and an electron donating group bonded to the N atom at the 4-position thereof, and the atom bonded to the N atom at the 4-position of the electron donating group is an unshared electron Contacting a porous carrier with a treatment liquid containing one or more drugs having a pair;
   And removing the solvent from the porous carrier.
   The aldehyde removal agent according to any one of claims 1 to 3, wherein the treatment liquid contains the non-volatile strong acid in a range of 0.5 to 12 parts by mass with respect to 100 parts by mass of the porous carrier. Adsorbent.
9. A deodorizing material comprising the aldehyde-removing adsorbent according to any one of claims 1 to 8, and a base material carrying the aldehyde-removing adsorbent.
10. A substrate;
    A porous carrier carried on the substrate;
    A non-volatile strong acid;
    Each includes a 1,2,4-triazole skeleton and an electron donating group bonded to the N atom at the 4-position thereof, and the atom bonded to the N atom at the 4-position of the electron donating group is an unshared electron A deodorizing material comprising one or more drugs having a pair.
11. A non-volatile strong acid;
    Each includes a 1,2,4-triazole skeleton and an electron donating group bonded to the N atom at the 4-position thereof, and the atom bonded to the N atom at the 4-position of the electron donating group is an unshared electron A method for producing an adsorbent for removing aldehyde, comprising a step of supporting one or more drugs having a pair on a porous carrier.
12. The step of supporting the non-volatile strong acid and the one or more drugs on the porous carrier,
    A solvent,
    The non-volatile strong acid;
    Contacting the porous carrier with a treatment liquid containing the one or more agents;
    12. The method of claim 11, comprising removing the solvent from the porous support.
13. A method for producing a deodorizing material, comprising supporting an adsorbent for removing aldehyde according to any one of claims 1 to 8 on a base material.
14. A dispersion comprising a non-volatile strong acid, one or more drugs, a porous carrier, and a dispersion medium, each of the one or more drugs comprising a 1,2,4-triazole skeleton and an N at the 4-position Supplying a dispersion liquid containing an electron donating group bonded to an atom, wherein the atom bonded to the N atom at the 4-position of the electron donating group has a lone pair When,
    A method for producing a deodorizing material, comprising drying the base material supplied with the dispersion.

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