JP6471256B1 - Deodorizing material and deodorizing sheet - Google Patents

Abstract

[PROBLEMS] To provide a deodorizing material that efficiently exhibits excellent acetaldehyde adsorption performance.
SOLUTION: An activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and a sulfuric acid supported on the activated carbon. Including deodorizing material,
The activated carbon is a deodorizing material having a pore volume of 0.6 cc / g or more and a pore volume of 0.65 nm or more and 2.0 nm or less.
[Selection figure] None

Description

  The present invention relates to a deodorizing material and a deodorizing sheet.

  In recent years, there has been an increasing interest in air purification, and there is a demand for an environment with less offensive odor in a room or the like. In addition, starting from the problem of sick house syndrome, countermeasures against volatile organic compounds (VOC) in the living environment are also required.

  For example, in vehicle interiors such as automobiles, bad odors of volatile organic compounds from interior resin parts such as seat pads, instrument panels, door trims, paints, adhesives, exhaust gases, fuel odors, tobacco, human bodies, etc. Many bad odors, such as food rots, can occur. Further, since the interior of the vehicle interior is narrower than that of a house, there is a problem that a bad odor tends to be filled when sealed.

Patent document 1 is a fibrous deodorizing material containing fibrous activated carbon, an aromatic amino acid, and sulfuric acid, and discloses a fibrous deodorizing material produced by a method including the following steps.
A step of immersing a fibrous activated carbon in an aqueous solution containing an aromatic amino acid and sulfuric acid to allow the fibrous activated carbon to carry the aromatic amino acid and sulfuric acid, wherein the mass ratio of the aromatic amino acid to the fibrous activated carbon is 10 mass. % To 20% by mass, and the step of making the mass ratio of sulfuric acid to fibrous activated carbon 5% to 25% by mass;
Removing the aqueous solution from the fibrous activated carbon carrying the aromatic amino acid and sulfuric acid;
A step of drying the fibrous activated carbon from which the aqueous solution has been removed.

JP 2011-72603 A

  The present inventor wanted to make the deodorizing material disclosed in Patent Document 1 exhibit more efficiently the adsorption performance of acetaldehyde by supporting an aromatic amino acid and sulfuric acid on activated carbon. That is, it was considered to improve the acetaldehyde adsorption performance when the same amount of aromatic amino acid and sulfuric acid were supported on activated carbon.

  Accordingly, the present invention provides a deodorizing material that solves the above-mentioned problems and efficiently exhibits the acetaldehyde adsorption performance of the deodorizing material when the activated carbon is loaded with an aromatic amino acid and sulfuric acid on the same immersion conditions to form a deodorizing material. The main purpose is to provide.

  The present inventor has intensively studied to solve such problems. As a result, when the aromatic amino acid and sulfuric acid were supported on activated carbon having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more, Excellent acetaldehyde adsorption compared to the case where sulfuric acid is supported on activated carbon other than the above activated carbon, that is, activated carbon having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. It has been found that it demonstrates its performance. The present invention has been completed by further studies based on these findings.

That is, this invention provides the invention of the aspect hung up below.
Item 1. A deodorizing material comprising activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid supported on the activated carbon. Because
The activated carbon is a deodorizing material having a pore volume of 0.6 cc / g or more and a pore volume of 0.65 nm or more and 2.0 nm or less.
Item 2. Item 2. The deodorizing material according to Item 1, wherein the activated carbon has a total pore volume (cc / g) of 1 to 2 times the pore volume of the pore diameter of 0.65 nm to 2.0 nm.
Item 3. Item 3. The deodorizing material according to Item 1 or 2, wherein the activated carbon has a pore volume of a pore diameter of 3 nm or more of 0.02 cc / g or less.
Item 4. Item 4. The deodorizing material according to any one of Items 1 to 3, wherein the activated carbon has a specific surface area of 1500 m ² / g or more.
Item 5. Item 5. The deodorizing material according to any one of Items 1 to 4, wherein the deodorizing material has a specific surface area of 400 to 1200 m ² / g.
Item 6. Item 6. The deodorizing material according to any one of Items 1 to 5, wherein a value obtained by subtracting the specific surface area of the deodorizing material from the specific surface area of the activated carbon is 800 to 1300 m ² / g.
Item 7. Item 7. The deodorizing material according to any one of Items 1 to 6, wherein an equilibrium adsorption amount (mg / g ACF) of acetaldehyde at an equilibrium concentration of 10 ppm is 35 mg / g ACF or more.
Item 8. Item 8. A deodorizing sheet comprising the deodorizing material according to any one of items 1 to 7.

  The deodorizing material of the present invention comprises activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon, or (B) an aromatic amine, a sulfate of the aromatic amine, and A deodorizing material containing sulfuric acid, wherein the activated carbon has a pore volume of 0.6 cc / g or more and a pore diameter of 0.6 nm or more and 2.0 nm or less, and has excellent acetaldehyde adsorption performance efficiently. It can be demonstrated. Moreover, the deodorizing sheet containing the deodorizing material of this invention can also exhibit the outstanding acetaldehyde adsorption performance efficiently.

  The deodorizing material of the present invention comprises activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon, or (B) an aromatic amine, a sulfate of the aromatic amine, and A deodorizing material containing sulfuric acid, wherein the activated carbon has a pore volume of 0.6 cc / g or more and a pore diameter of 0.65 nm or more and 2.0 nm or less. Hereinafter, the deodorizing material of the present invention and the deodorizing sheet using the same will be described in detail.

  Hereinafter, the pore volume refers to the pore volume calculated by the QSDFT method (quenched solid density functional method). The QSDFT method is an analytical method capable of calculating a pore size distribution from about 0.5 nm to about 40 nm for geometrically and chemically irregular microporous and mesoporous carbon pore size analysis. . In the QSDFT method, the influence of the roughness and nonuniformity of the pore surface is clearly taken into account, so that the accuracy of the pore diameter distribution analysis is greatly improved. In the present invention, measurement of nitrogen adsorption isotherm and pore size distribution analysis by QSDFT method are performed using “AUTOSORB-1-MP” manufactured by Quantachrome. By applying N2 at 77K on carbon [slit pore, QSDFT equilibrium model] as a calibration model to the nitrogen desorption isotherm measured at a temperature of 77 K, the pore size distribution is calculated to obtain a fine pore size range. The pore volume can be calculated.

  The deodorizing material of the present invention comprises activated carbon and (A) “aromatic amine and sulfate of the aromatic amine” or (B) “aromatic amine, sulfate of the aromatic amine, and sulfuric acid”. Including. In the deodorizing material of the present invention, when activated carbon, an aromatic amine and a sulfate of the aromatic amine are included, (A) the aromatic amine and the sulfate of the aromatic amine are supported on the activated carbon. ing. When the deodorizing material of the present invention contains activated carbon and (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid, the aromatic amine, the sulfate of the aromatic amine, and Sulfuric acid is supported on the activated carbon.

  In the deodorizing material of the present invention, (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid (hereinafter collectively referred to as “the present invention”). The activated carbon that carries "the chemical contained in the deodorizing material") has a pore volume of 0.6 cc / g or more with a pore diameter of 0.65 nm or more and 2.0 nm or less. By using activated carbon having such a specific pore distribution, excellent acetaldehyde adsorption performance can be efficiently exhibited.

  In the deodorizing material of the present invention, the reason why the acetaldehyde adsorbing performance excellent by using the activated carbon having the specific pore distribution can be efficiently exhibited is as follows. That is, since acetaldehyde has a small molecular size, it was considered that small pores are preferable as the pores of activated carbon that adsorbs acetaldehyde. However, it has become clear that the drug contained in the deodorizing material of the present invention is easily supported by the pore diameter in the range of 0.65 to 2.0 nm of activated carbon according to the study of the present inventors. More specifically, when the activated carbon pore distribution before and after the drug loading was examined, the rate of decrease in the pore volume in the range of 0.65 to 2.0 nm was high. This is considered to indicate that a larger amount of the drug is supported in pores having a pore diameter in the above range among all pore diameters. Therefore, by using activated carbon having the specific pore distribution, it is easy to support the drug in the pores, the adsorption effect by the pores, and the contact between the drug and acetaldehyde by the support of the drug in the pores. It is likely that a synergistic effect with the area improvement effect is likely to occur, and as a result, excellent acetaldehyde adsorption performance can be efficiently exhibited.

  The pore volume having a pore diameter of 0.65 nm or more and 2.0 nm or less is preferably 0.7 cc / g or more, more preferably 0.75 cc / g or more, from the viewpoint of more efficiently exhibiting acetaldehyde adsorption performance. Moreover, although the upper limit of the pore volume is not particularly limited, for example, 1.2 cc / g or less is exemplified, and 1.0 cc / g or less is exemplified. In the present specification, unless otherwise specified, the description of the activated carbon is the one before carrying the chemical contained in the deodorizing material of the present invention.

  In the deodorizing material of the present invention, the total pore volume of the activated carbon is 0.65 nm or more from the viewpoint of further improving the acetaldehyde adsorption performance while ensuring a pore volume having a pore diameter of 0.65 nm or more and 2.0 nm or less. About 1-2 times the pore volume with a pore diameter of 2.0 nm or less, preferably about 1.1-1.4 times. Specifically, 0.7-2.0 cc / g is mentioned, for example, 0.7-1.2 cc / g is mentioned preferably.

  In the deodorizing material of the present invention, the ratio of the pore volume of the pore diameter of 0.65 nm to 2.0 nm to the total pore volume of the activated carbon (pore volume of the pore diameter of 0.65 nm to 2.0 nm / total Examples of the pore volume include 0.6 to 0.9, preferably 0.7 to 0.85, and more preferably 0.7 to 0.75.

  In the deodorizing material of the present invention, as the pore volume of activated carbon with a pore diameter of 2 nm or less, the acetaldehyde adsorption performance is further improved while ensuring a pore volume with a pore diameter of 0.65 nm or more and 2.0 nm or less. From the viewpoint, for example, 0.7 to 0.9 cc / g is preferable, and 0.85 to 0.9 cc / g is more preferable. Further, the ratio of the pore volume having a pore diameter of 2 nm or less to the total pore volume (pore volume of pore diameter of 2 nm or less / total pore volume) is 0.8 to 0.98 from the same viewpoint. Preferred examples are 0.80 to 0.85.

  In the deodorizing material of the present invention, the activated carbon has a pore volume of 0.65 nm or less with a pore volume of 0.65 nm or less and a pore volume of 0.65 nm or more and 2.0 nm or less, while further increasing the acetaldehyde adsorption performance. From the viewpoint of improving, for example, 0.05 to 0.12 cc / g is preferable, and 0.08 to 0.1 cc / g is more preferable. Further, the ratio of the pore volume having a pore diameter of 0.65 nm or less to the total pore volume (pore volume of pore diameter of 0.65 nm or less / total pore volume) is 0.05 to 0.20 is mentioned preferably and 0.05-0.12 is mentioned more preferably.

  In the deodorizing material of the present invention, as the pore volume of the activated carbon having a pore diameter of 2 nm or more and 3 nm or less, the acetaldehyde adsorption performance is improved while ensuring the pore volume of the pore diameter of 0.65 nm or more and 2.0 nm or less. From a viewpoint of improving, 0.01-0.2 cc / g is mentioned preferably and 0.15-0.2 cc / g is mentioned more preferably. The ratio of the pore volume having a pore diameter of 2 nm or more and 3 nm or less to the total pore volume (pore volume of pore diameter of 2 nm or more and 3 nm or less / total pore volume) is 0.01 to 0.20 is mentioned preferably and 0.15-0.20 is mentioned more preferably.

  In the deodorizing material of the present invention, the pore volume of the activated carbon with a pore diameter of 3 nm or more is secured to a pore volume with a pore diameter of 0.65 nm or more and 2.0 nm or less, and more From the viewpoint of facilitating loading of the chemical contained in the deodorizing material of the present invention, it is preferably 0.02 cc / g or less, more preferably 0.01 cc / g or less.

In the deodorizing material of the present invention, the specific surface area of the activated carbon is 1500 m ² / from the viewpoint of improving the acetaldehyde adsorption performance while ensuring a pore volume having a pore diameter of 0.65 nm to 2.0 nm. g or more is preferable, and 1900 m ² / g or more is more preferable. Although an upper limit is not restrict | limited in particular, For example, 3500 m < ² > / g or less is mentioned, For example, 2500 m < ² > / g or less is mentioned. The specific surface area of the activated carbon is a value determined by the BET method (one-point method) described in JIS K1477.

  In the deodorizing material of the present invention, the form of activated carbon is not particularly limited, and examples thereof include granular activated carbon, powdered activated carbon, and fibrous activated carbon. From the viewpoint that the adsorption rate of acetaldehyde is relatively fast, it is more preferable to use fibrous activated carbon that is fibrous. In addition, as an average fiber diameter of fibrous activated carbon, Preferably it is 30 micrometers or less, More preferably, about 5-20 micrometers is mentioned. In addition, the average fiber diameter in this invention is the value measured with the image processing fiber diameter measuring apparatus (based on JISK1477). Moreover, as a particle size of granular activated carbon and powdered activated carbon, the integrated volume percentage D50 measured by the laser diffraction / scattering type method is 0.01-5 mm.

  The raw material species and form of the activated carbon precursor are not particularly limited. Examples of the raw material species of the activated carbon precursor include infusible or carbonized organic materials, curable resins such as phenol resins, and the like, for example, polyacrylonitrile, pitch, polyvinyl alcohol, cellulose, etc. Is mentioned. Also sawdust, wood chips, wood, peat, charcoal, coconut husk, coal, oil, carbonaceous materials (petroleum coke, coal coke, petroleum pitch, coal pitch, coal tar pitch, and composites thereof), synthesis Examples thereof include resins (phenol resins, polyacrylonitrile (PAN), polyimides, furan resins, etc.), cellulosic fibers (paper, cotton fibers, etc.), and composites thereof (paper-phenol resin laminates, etc.), fullerenes, and the like. Among these, in terms of the theoretical carbonization yield at the time of carbonization, pitch is preferable, and coal pitch is more preferable. Examples of the form of the activated carbon precursor include granular, powdery, and fibrous forms.

  The method for obtaining the activated carbon used for the deodorizing material of the present invention is not particularly limited. For example, the activated carbon precursor is adjusted by using steam to adjust the activation temperature and activation time so as to have a predetermined pore distribution. The method of obtaining is mentioned.

  In the deodorizing material of the present invention, the aromatic amine is not particularly limited, but in order to more effectively enhance the deodorizing ability with respect to toluene and ammonia in addition to acetaldehyde, and from the viewpoint of ease of handling in production and safety, halogen, sulfo An aromatic amine in which a group, an acetamide group or a carbonyl group is bonded to a benzene ring is preferred. Preferred examples of the aromatic amine having a halogen, a sulfo group, an acetamide group, or a carbonyl group bonded to a benzene ring include aminobenzoic acid, aminoacetanilide, aminosalicylic acid, and aminosulfanilic acid. Among these, aminobenzoic acid and its sulfate are preferable as the aromatic amine and the sulfate of the aromatic amine. That is, in the deodorizing material of the present invention, it is preferred that aminobenzoic acid and its sulfate are supported on fibrous activated carbon. In the deodorizing material of the present invention, at least a part of the aromatic amine forms a sulfate with sulfuric acid described later. The aromatic amine and the sulfate of the aromatic amine may be used alone or in combination of two or more.

  The aminobenzoic acid is not particularly limited, and at least one of p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid can be used. In addition to acetaldehyde, it is particularly preferable that p-aminobenzoic acid is supported in the deodorizing material of the present invention from the viewpoint of more effectively increasing the deodorizing ability with respect to toluene and ammonia.

  In the deodorizing material of this invention, a sulfuric acid may be carry | supported with said aromatic amine and sulfate of this aromatic amine. That is, the deodorizing material of the present invention comprises (A) an activated carbon on which an aromatic amine and a sulfate of the aromatic amine are supported (sulfuric acid may not be supported), or (B) an aromatic amine and the An activated carbon on which an aromatic amine sulfate and sulfuric acid are supported is provided.

  Sulfuric acid has a relatively high boiling point and is difficult to volatilize. Sulfuric acid promotes the dissolution of aminobenzoic acid in water, so that it is possible to uniformly carry an aromatic amine and a sulfate of the aromatic amine on activated carbon in the process of producing a deodorizing material as described later. . Furthermore, sulfuric acid exhibits the effect of suppressing the polymerization of aromatic amines and sulfates of aromatic amines in the deodorizing material.

  In the deodorizing material of the present invention, the total supported amount of the aromatic amine and the sulfate of the aromatic amine is not particularly limited, and for example, it may be 10 to 40 parts by mass with respect to 100 parts by mass of the activated carbon. From the viewpoint of further improving the acetaldehyde adsorption performance, 20 to 40 parts by mass are preferably exemplified, and 25 to 35 parts by mass are more preferably exemplified. Moreover, in the deodorizing material of the present invention, the total supported amount of the sulfate and sulfuric acid of the aromatic amine is not particularly limited, but for example, it may be 0.5 to 5 parts by mass with respect to 100 parts by mass of the activated carbon. Preferably, the content is 2 to 5 parts by mass.

Although it does not restrict | limit especially as a specific surface area (specific surface area after carrying | supporting the chemical | medical agent contained in the deodorizing material of this invention) of the deodorizing material of this invention, For example, 400-1200 m < ² > / g is mentioned, 500-1100 m < ² > / g>. g is preferable, and 700 to 1100 m ² / g is more preferable. Further, the specific surface area, for example, be a 900~1200m ² / g, may be 500~800m ² / g.

In the deodorizing material of the present invention, the specific surface area (= specific surface area of activated carbon before supporting−specific surface area of the deodorizing material after supporting) reduced by loading of the chemical contained in the deodorizing material of the present invention is, for example, 800 to 1300 m. ² / g is mentioned, and 900-1200 m < ² > / g is mentioned. Further, in the deodorizing material of the present invention, the reduction rate of the specific surface area of the activated carbon due to the loading of the drug contained in the deodorizing material of the present invention (= specific surface area of the deodorizing material after loading / specific surface area of the activated carbon before loading × 100 ( %)) Includes, for example, 30 to 60%.

  In the deodorizing material of the present invention, the equilibrium adsorption amount (mg / g ACF) of acetaldehyde at an equilibrium concentration of 10 ppm is preferably 35 mg / g ACF or more, more preferably 45 to 70 mg / g ACF, particularly preferably 50 to 60 mg / g ACF. It is done. In addition, the measuring method of the equilibrium adsorption amount of acetaldehyde in the equilibrium concentration of 10 ppm of the deodorizing material of the present invention is as follows.

(Measurement of equilibrium adsorption amount of acetaldehyde)
A sample piece of an arbitrary weight and 3 L of 100 ppm acetaldehyde gas are sealed in a sealed container and allowed to stand in an environment of 25 ° C. After 24 hours, the gas concentration in the container is measured and the amount of adsorption is calculated. Measure the weight of multiple samples, plot the correlation between concentration and adsorption amount on the graph from each calculation result, and calculate the equilibrium adsorption amount (mg / g ACF) of acetaldehyde at any equilibrium concentration from the obtained relational expression. Lead. Gas chromatography or a gas detector tube is used for measuring the concentration of acetaldehyde.

  The deodorizing material of this invention can be manufactured as follows, for example. First, activated carbon having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of 0.6 cc / g or more is prepared. The method for obtaining the activated carbon is as described above. Next, a treatment liquid containing an aromatic amine and / or salt thereof, sulfuric acid and / or salt thereof, and water is prepared. Aromatic amines and / or salts thereof may be dissolved in an aqueous solution of sulfuric acid and / or its salt sufficiently diluted with water, and dissolved in an aqueous solution containing sulfuric acid and / or its salt at a relatively high concentration. Then, it may be diluted with water to form a treatment liquid. As sulfuric acid, concentrated sulfuric acid or dilute sulfuric acid may be used. Also, in order to dissolve the aromatic amine and / or salt thereof in water, an aqueous solution of sulfuric acid and / or salt thereof is heated to a temperature in the range of, for example, 50 to 80 ° C., where the aromatic amine and / or The salt may be mixed. As the aromatic amine, those described above are used. Although it does not restrict | limit especially as a salt of an aromatic amine, For example, the sulfate of the said aromatic amine etc. are mentioned.

  The amount of the aromatic amine and / or salt thereof charged in the treatment liquid is not particularly limited as long as the amount of the aromatic amine and / or salt thereof in the deodorizing material of the present invention is set within a desired range. For example, what is necessary is just to set it as about 12-40 mass parts with respect to 100 mass parts of activated carbon immersed later. In addition, the amount of sulfuric acid and / or salt thereof charged in the treatment liquid may be selected from the aromatic amine and sulfate of the aromatic amine, or the aromatic amine and sulfate of sulfuric acid and sulfuric acid in the deodorizing material of the present invention. If it sets so that content of may become a desired range, it will not restrict | limit in particular, What is necessary is just about 12-40 mass parts with respect to 100 mass parts of activated carbon to immerse later.

  Next, the activated carbon prepared is immersed in the treatment liquid, and the activated amine carries the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine, the sulfate of the aromatic amine, and the sulfuric acid. For example, activated carbon is uniformly dispersed in the treatment liquid, and then this dispersion liquid is allowed to stand for a sufficient time. The time for immersing the activated carbon in the treatment liquid is, for example, about 1 hour or more. The ratio between the mass of the activated carbon and the volume of the treatment liquid is, for example, in the range of 5 to 50 g / L. When this ratio is too small, it takes a longer time to support the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine, the sulfate of the aromatic amine and the sulfuric acid on the activated carbon. On the other hand, when this ratio is too large, it becomes difficult to uniformly carry the aromatic amine and the sulfate of the aromatic amine, or the aromatic amine, the sulfate of the aromatic amine and the sulfuric acid on the activated carbon. If the time for which the activated carbon is in contact with the aqueous solution is sufficiently long, this ratio is the aromatic amine supported on the activated carbon and the sulfate of the aromatic amine, or the aromatic amine and the sulfate of the aromatic amine. The effect on the amount of sulfuric acid is negligible. In addition, the processing liquid which immerses activated carbon may be used in the state heated at the time of preparation of said aromatic amine and / or its salt, and may be used after cooling the heated processing liquid.

  Next, the treatment liquid is removed from the activated carbon on which the aromatic amine and the sulfate of the aromatic amine or the aromatic amine, the sulfate of the aromatic amine and the sulfuric acid are supported. The method for removing the treatment liquid is not particularly limited, and can be performed, for example, by pulling up activated carbon from the treatment liquid. Prior to the removal of the treatment liquid from the aromatic amine and the sulfate of the aromatic amine or the activated liquid carrying the aromatic amine, the sulfate of the aromatic amine and the sulfuric acid, the treatment liquid is diluted with water. May be.

  Thereafter, the activated carbon from which the treatment liquid has been removed is dried. For this drying, for example, natural drying, ventilation drying, hot air drying, microwave heating drying, indirect heating drying, or the like can be used. Drying is performed so that the temperature of the activated carbon is maintained at, for example, 130 ° C. or lower, preferably 80 ° C. or lower. As described above, the deodorizing material of the present invention can be produced.

  Next, the deodorizing sheet of the present invention will be described in detail. The deodorizing sheet of the present invention uses the above-described deodorizing material of the present invention, and includes the deodorizing material of the present invention. Specifically, the deodorizing sheet of the present invention is, for example, a sheet in which the above-mentioned deodorizing material is formed. Although it does not specifically limit as a form of a sheet | seat, A nonwoven fabric is mentioned preferably. The deodorizing sheet of this invention may contain the binder as needed for the purpose of shape | molding said deodorizing material in a sheet form. The binder is not particularly limited as long as the activated carbon constituting the deodorizing material can be bonded to each other. For example, (a fibrous binder is mentioned, and a commercial product of fibrous binder is trade name Melty manufactured by Unitika Ltd.) Can be used.

  When the deodorizing sheet of the present invention contains a binder, the mass ratio (binder / deodorizing material) between the binder and the deodorizing material of the present invention is preferably about 75/25 to 25/75. Further, when the density of the deodorizing sheet to be described later is low, the deodorizing ability with respect to acetaldehyde is further improved, so that the mass ratio of the activated carbon is easily reduced, for example, the binder and the present invention. As a mass ratio (binder / deodorizing material) to the deodorizing material, it becomes easy to be about 75/25 to 65/35.

The density of the deodorizing sheet of the present invention is not particularly limited, but is preferably, for example, 0.05 to 0.3 g / cm ³ from the viewpoint of further improving the deodorizing ability with respect to acetaldehyde. 05 to 0.20 g / cm ³ is more preferable, and 0.08 to 0.15 g / cm ³ is particularly preferable. In addition, the thickness of the deodorizing sheet of the present invention is, for example, 0.15 to 0.80 mm, preferably 0.3 to 0.7 mm. It becomes easy to accommodate. As a method for obtaining a sheet having a low density and / or a thinness as described above, for example, a thin nonwoven fabric having a basis weight of about 1 to 8 g / m ² is manufactured, and a plurality of the nonwoven fabrics are stacked and subjected to needle punch processing to be integrated. Can be obtained.

  The deodorizing sheet of the present invention can be produced, for example, by molding the above-mentioned deodorizing material into a sheet shape, and an aromatic amine and a sulfate of the aromatic amine or an aromatic amine on a fibrous activated carbon. After forming the fibrous activated carbon before supporting the sulfate and sulfuric acid of the aromatic amine into a sheet, the sheet is immersed in a treatment solution in the same manner as described above, and the aromatic amine and the aromatic are added to the fibrous activated carbon. It can also be produced by supporting an aromatic amine sulfate or an aromatic amine, an aromatic amine sulfate and sulfuric acid.

  When the deodorizing sheet of the present invention is used as an air purification sheet, a dust removing sheet such as an electret nonwoven sheet, a high efficiency particulate air (HEPA) filter, or an ULPA (ultra low penetration air) filter is pasted on the deodorizing sheet. Thus, it is possible to obtain a laminated body having a dust removal effect. Such a laminate can be suitably used in an air purifier that performs air purification and dust removal.

  Since the deodorizing sheet of the present invention contains the above-described deodorizing material of the present invention, acetaldehyde can be removed from the gas phase with high efficiency. Therefore, the deodorizing sheet of the present invention can be widely used in a living environment, and can also be suitably used for interior materials such as automobiles, trains, ships and airplanes. Especially, the deodorizing sheet of this invention can be accommodated and used in the cover of the seat of a vehicle interior as a motor vehicle interior material which can remove acetaldehyde from a gaseous phase with high efficiency. That is, it can be set as a vehicle interior seat including the deodorizing sheet of the present invention. Moreover, the deodorizing material of this invention has a deodorizing ability also with respect to lower aldehydes, such as formaldehyde, besides acetaldehyde.

  Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

[Test Example A]
<Example 1A>
Preparation of activated carbon Granular coal pitch was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 875 ° C. for 70 minutes to obtain fibrous activated carbon. . The obtained fibrous activated carbon had a pore volume of 0.781 cc / g with a pore diameter of 0.65 nm to 2.0 nm. The total pore volume is 1.058 cc / g, the pore volume of 2 nm or less is 0.877 cc / g, the specific surface area is 2069 m ² / g, and the pore volume of 0.65 nm or less is 0. The pore volume of pore diameters of 0.096 cc / g and 2 nm or more and 3 nm or less was 0.174 cc / g, and the pore volume of pore diameters of 3 nm or more was 0.007 cc / g. In Examples, the pore volume having a pore diameter of 2 nm or more and 3 nm or less is obtained by subtracting the pore volume having a pore diameter of 2 nm or less from the pore volume. Determined by The pore volume having a pore diameter of 3 nm or more was determined by subtracting the pore volume having a pore diameter of 3 nm or less from the total pore volume.

Preparation of drug solution A contained in deodorizing material of the present invention First, an aqueous sulfuric acid solution containing sulfuric acid at a concentration of 75% by mass was prepared. After stirring this sulfuric acid aqueous solution at a temperature of 65 ° C. or more and adding p-aminobenzoic acid as an aromatic amine to the aqueous solution and completely dissolving it, the ratio of the mass of activated carbon to the volume of the treatment liquid is 20 g / L. Water was added to obtain a treatment solution. The amount of aromatic amine and sulfuric acid charged was 15.0 parts by mass with respect to 100 parts by mass of activated carbon. In addition, the said preparation amount (mass part) of a sulfuric acid shows the quantity (mass part) of only the sulfuric acid except a pure water in 75 mass% sulfuric acid aqueous solution.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution A. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 1A. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( (Mass part) was measured as follows.

Measurement of total supported amount (mass part) of aromatic amine and sulfate of aromatic amine with respect to 100 parts by mass of activated carbon About the total supported amount of aromatic amine and sulfate of aromatic amine supported on activated carbon, Measure the organic concentration of the solution before immersing the activated carbon and the concentration after immersing the activated carbon using a total organic concentration (TOC) meter. From the difference in organic concentration before and after the immersing operation, the total supported amount Was measured. Specifically, first, using a total organic matter concentration (TOC) meter (TOC-5000 manufactured by Shimadzu Corporation), the concentration of organic matter (mgC / L) converted to carbon (C) for the drug solution before and after the dipping operation. And the difference in concentration before and after the operation was determined. Separately, weighed and prepared a known concentration of aromatic amine aqueous solution to measure the total organic matter concentration in the same manner, and a calibration curve representing the correspondence between the organic matter concentration (mgC / L) and the aromatic amine concentration (mg aromatic amine / L). It was created. Using the prepared calibration curve, the difference (mg C / L) in the organic matter concentration before and after the attaching operation was converted to the difference in the aromatic amine concentration (mg aromatic amine / L). The difference in aromatic amine mass was calculated by multiplying the determined concentration difference by the amount of processing solution (L). The calculated value is converted into mass parts per 100 parts by mass of activated carbon before being immersed in the drug solution, and the obtained mass part is the sum of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon. The supported amount (parts by mass) was used.

Measurement of Total Amount of Aromatic Amine Sulfate and Sulfuric Acid (Mass Part) with respect to 100 parts by Mass of Activated Carbon The same applies to the total amount of aromatic amine sulfate and sulfuric acid supported on activated carbon before immersing the activated carbon. The concentration of sulfate ion (mg / L) was measured in accordance with the ion chromatographic method specified in JIS K 0101: 1998 42.4 for the drug solution after immersion in activated carbon and the drug solution after the activated carbon was immersed. The loading was calculated. Specifically, the sulfate ion concentration (mg / L) of the drug solution before and after the dipping operation was measured using a calibration curve, and the difference in sulfate ion concentration before and after the operation (mg / L) was determined. Multiply the difference in sulfate ion concentration before and after the operation (mg / L) by the ratio between the molecular weight of sulfuric acid (98.08 g / mol) and the molecular weight of sulfate ion (96.06 g / mol) to convert to the difference in sulfuric acid concentration. did. The difference in sulfuric acid before and after the operation was calculated by multiplying the difference in sulfuric acid concentration by the amount of processing solution (L). The calculated difference in sulfuric acid before and after the operation was converted to mass parts per 100 parts by mass of activated carbon before immersing in the drug solution, and the obtained mass parts were obtained by using an aromatic amine sulfate and sulfuric acid with respect to 100 parts by mass of activated carbon. The total supported amount (parts by mass) was used.

<Comparative Example 1A>
Preparation of activated carbon Granular coal pitch was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 875 ° C. for 30 minutes to obtain a fibrous activated carbon. . The resulting fibrous activated carbon had a pore volume of 0.116 cc / g with a pore diameter of 0.65 nm to 2.0 nm. Further, the total pore volume is 0.315 cc / g, the pore volume of 2 nm or less is 0.315 cc / g, the specific surface area is 825 m ² / g, and the pore volume of 0.65 nm or less is 0. 199 cc / g The pore volume of pore diameters of 2 nm or more and 3 nm or less was 0.000 cc / g, and the pore volume of pore diameters of 3 nm or more was 0.000 cc / g.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1A. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2A>
Preparation of activated carbon Granular coal pitch was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat treating it at an ambient temperature of 875 ° C. for 40 minutes to obtain a fibrous activated carbon. . The resulting fibrous activated carbon had a pore volume of 0.255 cc / g with a pore diameter of 0.65 nm to 2.0 nm. The total pore volume is 0.476 cc / g, the pore volume of 2 nm or less is 0.476 cc / g, the specific surface area is 1232 m ² / g, and the pore volume of 0.65 nm or less is 0. 0.21 cc / g, the pore volume having a pore diameter of 2 nm or more and 3 nm or less was 0.000 cc / g, and the pore volume having a pore diameter of 3 nm or more was 0.000 cc / g.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2A. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3A>
Preparation of activated carbon As an organic material, a mixture of 1.3 parts by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch with a softening point of 280 ° C. is supplied to a melt extruder at a melting temperature of 320 ° C. Pitch fibers were obtained by melt mixing and spinning at a discharge rate of 20 g / min. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 900 ° C. for 20 minutes to obtain a fibrous activated carbon. . The obtained fibrous activated carbon had a pore volume of a pore diameter of 0.65 nm to 2.0 nm of 0.335 cc / g. Also, the total pore volume is 0.572 cc / g, the pore volume of 2 nm or less is 0.395 cc / g, the specific surface area is 1078 m ² / g, and the pore volume of 0.65 nm or less is 0. The pore volume of pore diameters of 0.075 cc / g, 2 nm or more and 3 nm or less was 0.113 cc / g, and the pore volume of pore diameters of 3 nm or more was 0.050 cc / g.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution A prepared in Example 1A. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3A. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

  Using the deodorizing materials obtained in Example 1A and Comparative Examples 1A to 3A, the specific surface area and the acetaldehyde equilibrium adsorption amount were measured according to the methods described above. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorizing material, and the specific surface area decreased due to the loading of the aromatic amine and sulfuric acid was calculated. Moreover, the said acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 1.

<Summary of Test Example A>
Example 1A includes activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid supported on the activated carbon. The activated carbon has a pore volume of 0.65 nm to 2.0 nm in pore diameter of 0.6 cc / g or more, so that the aromatic amino acid and sulfuric acid are used under the same immersion conditions. In comparison with the case where the activated carbon other than the activated carbon, that is, the activated carbon of Comparative Examples 1A to 3A having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g, It exhibited excellent acetaldehyde adsorption performance.

[Test Example B]
<Example 1B>
Preparation of activated carbon The activated carbon obtained in Example 1A was prepared.

Preparation of drug solution B contained in deodorizing material of the present invention First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was prepared. After stirring this sulfuric acid aqueous solution at a temperature of 65 ° C. or more and adding p-aminobenzoic acid as an aromatic amine to the aqueous solution and completely dissolving it, the ratio of the mass of activated carbon to the volume of the treatment liquid is 20 g / L. Water was added to obtain a treatment solution. The amount of the aromatic amine and sulfuric acid charged was 22.5 parts by mass with respect to 100 parts by mass of the activated carbon. In addition, the said preparation amount (mass part) of a sulfuric acid shows the quantity (mass part) of only the sulfuric acid except a pure water in 75 sulfuric acid aqueous solution.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 1B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Example 2B>
Preparation of activated carbon Granular coal pitch was supplied to a melt extruder, melted and mixed at a melting temperature of 320 ° C., and spun at a discharge rate of 20 g / min to obtain pitch fibers. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat treating it at an ambient temperature of 875 ° C. for 50 minutes to obtain fibrous activated carbon. . The fibrous activated carbon obtained had a pore volume of 0.622 cc / g with a pore diameter of 0.65 nm to 2.0 nm. The total pore volume is 0.753 cc / g, the pore volume of 2 nm or less is 0.728 cc / g, the specific surface area is 1731 m ² / g, and the pore volume of 0.65 nm or less is 0. The pore volume of pore diameters of .106 cc / g, 2 nm or more and 3 nm or less was 0.025 cc / g, and the pore volume of pore diameters of 3 nm or more was 0.000 cc / g.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 2B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 1B>
Preparation of activated carbon The activated carbon obtained in Comparative Example 1A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2B>
Preparation of activated carbon The activated carbon obtained in Comparative Example 2A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3B>
Preparation of activated carbon The activated carbon obtained in Comparative Example 3A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 4B>
Preparation of activated carbon As an organic material, a mixture of 1.3 parts by mass of trisacetylacetonatoyttrium with 100 parts by mass of granular coal pitch with a softening point of 280 ° C. is supplied to a melt extruder at a melting temperature of 320 ° C. Pitch fibers were obtained by melt mixing and spinning at a discharge rate of 20 g / min. The pitch fiber thus obtained was heated in the air at a rate of 1 to 30 ° C./min for 54 minutes from room temperature to 354 ° C. to obtain an activated carbon precursor which was an infusible pitch fiber. The obtained activated carbon precursor was activated by continuously introducing a gas having an H ₂ O concentration of 100% by volume into an activation furnace and heat-treating it at an ambient temperature of 900 ° C. for 25 minutes to obtain a fibrous activated carbon. . The resulting fibrous activated carbon had a pore volume of a pore diameter of 0.65 nm to 2.0 nm of 0.337 cc / g. The total pore volume is 1.039 cc / g, the pore volume of 2 nm or less is 0.395 cc / g, the specific surface area is 1248 m ² / g, and the pore volume of 0.65 nm or less is 0. The pore volume of pore diameters of 0.059 cc / g, 2 nm or more and 3 nm or less was 0.194 cc / g, and the pore volume of pore diameters of 3 nm or more was 0.450 cc / g.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution B prepared in Example 1B. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 4B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of activated carbon ( Mass part) was measured in the same manner as in Example 1A.

  Using the deodorizing materials obtained in Example 1B, Example 2B, and Comparative Examples 1B to 4B, the specific surface area and the acetaldehyde equilibrium adsorption amount were measured according to the methods described above. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorizing material, and the specific surface area decreased due to the loading of the aromatic amine and sulfuric acid was calculated. Moreover, the said acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 2.

<Summary of Test Example B>
Examples 1B and 2B include activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon, or (B) an aromatic amine, a sulfate of the aromatic amine, and A deodorizing material containing sulfuric acid, wherein the activated carbon has a pore volume of 0.6 cc / g or more and a pore size of 0.6 cc / g or more. Compared to the case where sulfuric acid is supported on activated carbon other than the above activated carbon, that is, activated carbons of Comparative Examples 1B to 4B having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. In addition, it exhibited excellent acetaldehyde adsorption performance.

[Test Example C]
<Example 1C>
Preparation of activated carbon The activated carbon obtained in Example 1A was prepared.

Preparation of drug solution C contained in deodorizing material of the present invention First, a sulfuric acid aqueous solution containing sulfuric acid at a concentration of 75% by mass was prepared. After stirring this sulfuric acid aqueous solution at a temperature of 65 ° C. or more and adding p-aminobenzoic acid as an aromatic amine to the aqueous solution and completely dissolving it, the ratio of the mass of activated carbon to the volume of the treatment liquid is 20 g / L. Water was added to obtain a treatment solution. The amount of aromatic amine and sulfuric acid charged was 30.0 parts by mass with respect to 100 parts by mass of activated carbon. In addition, the said preparation amount (mass part) of a sulfuric acid shows the quantity (mass part) of only the sulfuric acid except a pure water in 75 sulfuric acid aqueous solution.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 1C. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Example 2C>
Preparation of activated carbon The activated carbon obtained in Example 2B was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain the deodorizing material of Example 2C. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 1C>
Preparation of activated carbon The activated carbon obtained in Comparative Example 1A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 1B. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 2C>
Preparation of activated carbon The activated carbon obtained in Comparative Example 2A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 2C. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 3C>
Preparation of activated carbon The activated carbon obtained in Comparative Example 3A was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 3C. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

<Comparative Example 4C>
Preparation of activated carbon The activated carbon obtained in Comparative Example 4B was prepared.

Loading of the drug contained in the deodorizing material of the present invention on activated carbon Next, 100 parts by mass of the obtained activated carbon was immersed in the drug solution C prepared in Example 1C. Subsequently, the solution was stirred for 10 minutes to disperse the activated carbon uniformly in the solution. Thereafter, this dispersion was allowed to stand. After leaving still for 8 hours or more, the activated carbon was pulled up from the solution and dried at 80 ° C. for 3 hours using a dryer to obtain a deodorizing material of Comparative Example 4C. In addition, in the deodorizing material, the total supported amount (mass part) of the aromatic amine and sulfate of the aromatic amine with respect to 100 parts by mass of the activated carbon, and the total supported amount of sulfate and sulfuric acid of the aromatic amine with respect to 100 parts by mass of the activated carbon ( Mass part) was measured in the same manner as in Example 1A.

  Using the deodorizing materials obtained in Example 1C, Example 2C, and Comparative Examples 1C to 4C, the specific surface area and the acetaldehyde equilibrium adsorption amount were measured according to the methods described above. Further, the specific surface area of the activated carbon was subtracted from the specific surface area of the obtained deodorizing material, and the specific surface area decreased due to the loading of the aromatic amine and sulfuric acid was calculated. Moreover, the said acetaldehyde equilibrium adsorption amount was evaluated by the ratio when the equilibrium adsorption amount of Comparative Example 2A was 1. The results are shown in Table 3.

<Summary of Test Example C>
Examples 1C and 2C include activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine supported on the activated carbon, or (B) an aromatic amine, a sulfate of the aromatic amine, and A deodorizing material containing sulfuric acid, wherein the activated carbon has a pore volume of 0.6 cc / g or more and a pore size of 0.6 cc / g or more. Compared to the case where sulfuric acid is supported on activated carbon other than the above activated carbon, that is, activated carbons of Comparative Examples 1C to 4C having a pore volume of 0.65 nm or more and 2.0 nm or less and a pore volume of less than 0.6 cc / g. In addition, it exhibited excellent acetaldehyde adsorption performance.

  For Examples 1C and 2C in Test Example C, the pore distributions of the activated carbon before loading the drug and the deodorizing material after loading were measured. Table 4 and Table 5 show the measured pore distribution.

  From Table 4 and Table 5, it became clear that the decreasing rate of the pore volume in the range of 0.65 to 2.0 nm was high. This is considered to indicate that a larger amount of the drug is supported in pores having a pore diameter in the above range among all pore diameters.

[Test Example D]
(Example 1D (production of deodorizing sheet))
The deodorizing material obtained in Example 2B and the binder fiber (trade name Melty 4080, manufactured by Unitika Ltd.) were mixed so that the mass ratio (binder / deodorizing material) was 25/75, and the nonwoven fabric web was formed by the carding method. Formed. A predetermined number of the obtained non-woven webs were laminated, and the fibers were entangled by needle punching, then heated at a temperature of 110 ° C. to melt the binder fibers, and the binder fibers and the deodorizing material were fused to obtain a thickness of 0. A deodorizing sheet having a density of 65 mm and a density of 0.12 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 56 g / m ² .

(Example 2D)
The deodorizing material obtained in Example 2C and the binder fiber (trade name Melty 4080, manufactured by Unitika Ltd.) were mixed so that the mass ratio (binder / deodorizing material) was 25/75, and the nonwoven fabric web was formed by the carding method. Formed. A predetermined number of the obtained non-woven webs were laminated, and the fibers were entangled by needle punching, then heated at a temperature of 110 ° C. to melt the binder fibers, and the binder fibers and the deodorizing material were fused to obtain a thickness of 0. A deodorizing sheet having a density of 65 mm and a density of 0.12 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 56 g / m ² .

(Example 3D)
The deodorizing material obtained in Example 2C and the binder fiber (trade name Melty 4080, manufactured by Unitika Ltd.) were mixed so that the mass ratio (binder / deodorizing material) was 72/28, and the nonwoven fabric web was formed by the carding method. Formed. A predetermined number of the obtained non-woven webs were laminated, and the fibers were entangled by needle punching, then heated at a temperature of 110 ° C. to melt the binder fibers, and the binder fibers and the deodorizing material were fused to obtain a thickness of 0. A deodorizing sheet having a density of 35 mm and a density of 0.14 g / cm ³ was obtained. The basis weight of the deodorizing material in the deodorizing sheet was 14 g / m ² .

(Performance evaluation of deodorizing sheet)
A sample piece of an arbitrary weight of the obtained deodorizing sheet and 3 L of 100 ppm acetaldehyde gas were sealed in a sealed container and allowed to stand in an environment of 40 ° C. After 24 hours, the gas concentration in the container was measured and the adsorption amount was calculated. Measure the weight of multiple samples, plot the correlation between concentration and adsorption amount on the graph from each calculation result, and calculate the equilibrium adsorption amount (mg / g ACF) of acetaldehyde at any equilibrium concentration from the obtained relational expression. lead. The concentration of acetaldehyde was measured by gas chromatography.

  The results of Examples 1D to 3D are shown in Table 6.

  As shown in Table 6, the deodorizing sheets of Examples 1D to 3D included the deodorizing material of the present invention, and thus exhibited the acetaldehyde adsorption performance efficiently.

Claims (9)

A deodorizing material comprising activated carbon and (A) an aromatic amine and a sulfate of the aromatic amine, or (B) an aromatic amine, a sulfate of the aromatic amine, and sulfuric acid supported on the activated carbon. Because
The activated carbon before supporting (A) or (B) has a total pore volume of 0.7 to 2.0 cc / g,
Activated carbon before carrying said (A) or (B) state, and are more than 2.0nm or less of the pore volume of pore diameters 0.6 cc / g or more 0.65 nm,
The activated carbon before supporting the (A) or (B) has a pore volume ratio of 0.6 to 0.9 to 0.6 to 0.9 nm with respect to the total pore volume,
Wherein (A) or (B) activated carbon before carrying is, 0.65 nm Ru pore volume 0.05~0.12cc / g der the following pore diameters, acetaldehyde or deodorant formaldehyde. The total carrying amount of the aromatic amine and sulfate of the aromatic amine is 25 to 35 parts by mass with respect to 100 parts by mass of the activated carbon before carrying the (A) or (B), and the fragrance The deodorizing material according to claim 1, wherein the total supported amount of the sulfate and sulfuric acid of the group amine is 2 to 5 parts by mass with respect to 100 parts by mass of the activated carbon before supporting (A) or (B). The activated carbon before supporting ( A) or (B) has a total pore volume (cc / g) of 1 to 2 times the pore volume of the pore diameter of 0.65 nm to 2.0 nm, The deodorizing material according to claim 1 or 2 . The deodorizing material according to any one of claims 1 to 3 , wherein a pore volume having a pore diameter of 3 nm or more of the activated carbon before supporting the ( A) or (B) is 0.02 cc / g or less. The deodorizing material according to any one of claims 1 to 4 , wherein a specific surface area of the activated carbon before supporting the ( A) or (B) is 1500 m ² / g or more. The deodorizing material according to any one of claims 1 to 5 , wherein the deodorizing material has a specific surface area of 400 to 1200 m ² / g. The value which reduced the specific surface area of the said deodorizing material from the specific surface area of the activated carbon before carrying said ( A) or (B) is 800-1300m < ² > / g, It is any one of Claims 1-6. Deodorizing material. The deodorizing material according to any one of claims 1 to 7 , wherein an equilibrium adsorption amount (mg / g ACF) of acetaldehyde at an equilibrium concentration of 10 ppm is 35 mg / g ACF or more. A deodorizing sheet of acetaldehyde or formaldehyde containing the deodorizing material according to any one of claims 1 to 8 .