JP2008148804A - Deodorant with excellent tobacco odor removal performance - Google Patents

Abstract

The present invention relates to aldehydes such as formaldehyde and acetaldehyde, VOC, and a deodorizing performance particularly excellent for removing tobacco odors containing them, durability for long lasting deodorizing effect, and removal in a short time. To provide a deodorant excellent in immediate effect.
SOLUTION: A hydrazine derivative is fixed in the pores of an inorganic porous material so that a hydrazine derivative effective for deodorization of aldehydes such as acetaldehyde and activated carbon exhibiting an adsorption ability to a gas such as VOC are not in direct contact with each other. By doing so, the acetaldehyde adsorption ability of the hydrazine derivative is not lowered due to the influence of activated carbon, and there is provided a deodorant that is durable and particularly effective for tobacco odor.
[Selection figure] None

Description

  The present invention is particularly effective in removing aldehydes such as formaldehyde and acetaldehyde, VOC, and tobacco odors containing these, deodorizing performance that lasts for a long time, and immediate effect for removing in a short time. It is a technology related to excellent deodorants.

  Recently built houses with good secrecy have been developed and have become energy-saving houses that are efficient for cooling and heating. However, because of its good confidentiality, various living odors can be trapped indoors, and a small amount of VOC gas that is thought to be generated from building materials can adversely affect the human body. The technology to remove is attracting interest. Among them, the tobacco odor is an unpleasant odor not only for non-smokers but also for smokers, and there is a strong demand for a technique for deodorizing tobacco odors because of people's desire for cleanliness. Tobacco odor is known to contain acetaldehyde as the main component and more than 100 types of VOC gas as subcomponents. To deodorize tobacco odor, both the acetaldehyde and VOC gas should be deodorized. It is indispensable to do it at the same time, and it has been found that the deodorization of either one will change to a bad odor for humans.

  However, there is no deodorant effective for all offensive odor gases, and a method of deodorizing by combining effective deodorants with various odorous gases is performed. In general, as a method of removing malodor, adsorption type using an adsorbent such as activated carbon and zeolite, catalyst type that decomposes and removes malodorous substances by ozone, photocatalyst, metal phthalocyanine complex, etc., or combination of this adsorption type and catalyst type Can be divided into two types. Among these, for example, a technique using the excellent adsorption action of activated carbon is well known, but activated carbon is excellent in the action of adsorbing various types of VOC gas and lowering the concentration of surrounding VOC gas. Adsorption of aldehydes such as was not sufficient, and it had to be used in combination with other deodorants to remove the tobacco odor.

  Patent Document 1 discloses a deodorant obtained by mixing a hydrazide having a water solubility of 1 g / 100 ml or less at 30 ° C. and activated carbon in an aqueous solvent, and adsorbs aldehydes such as formaldehyde and other malodorous substances. Although a deodorant that has a deodorizing effect that lasts for a long period of time has been described, the aldehyde adsorption activity of hydrazides decreases due to the direct contact between hydrazides and activated carbon, and therefore a longer period of time. There is a need for deodorants that have an adsorption effect.

  Patent Document 2 discloses a deodorant in which a compound having a primary amino group in the molecule is supported on porous silicon dioxide, and has a high deodorizing function for aldehydes such as acetaldehyde and formaldehyde itself. In addition, even when mixed with other deodorants, a mixed deodorant that can sufficiently exhibit the original deodorant function of each deodorant is described, but removal of VOC gas. It was inferior in ability.

  In addition, the applicant has applied for Patent Document 3, and a structure in which a deodorizing composition containing a hydrazine derivative, a metal phthalocyanine complex, and a porous inorganic substance is supported on a support is ammonia, hydrogen sulfide, methyl mercaptan, acetic acid. Although it is disclosed as having excellent deodorizing performance against many types of bad odors such as acetaldehyde, it is still insufficient for VOC gas removal ability.

JP2001-218824 JP 2002-200149 A JP 2003-275288 A

  These conventional techniques are a combination of an adsorbent and an adsorbent and a catalyst, which adsorbs and decomposes aldehydes and VOC gas, respectively, and deodorizes them, and is a useful method for efficient deodorization. For odors that do not exhibit the deodorizing effect unless both aldehydes such as tobacco odor, which are typical odors, and VOC gas are deodorized at the same time, they have a stronger deodorizing effect, immediate effect, and durability. A deodorant is needed.

  The present invention provides the following means in order to provide a deodorant having a greater deodorizing effect, immediate effect, and durability, particularly with respect to tobacco odor among bad odors.

[1] A deodorant comprising an inorganic porous material in which a hydrazine derivative is fixed in pores and activated carbon as active ingredients.

[2] The deodorizer according to item 1, wherein the inorganic porous material is an inorganic porous material having a pore diameter of 0.6 nm to 20 nm.

[3] The deodorizer according to item 1 or 2, wherein the inorganic porous material is a hydrophobic zeolite.

[4] The deodorizer according to any one of items 1 to 3, wherein the hydrazine derivative comprises an acid hydrazide compound having 4 to 8 carbon atoms.

[5] The deodorizer according to any one of items 1 to 4, wherein the supported amount of the hydrazine derivative is 5 to 500 mg with respect to 1 g of the inorganic porous material.

[6] The deodorizer according to any one of items 1 to 5, wherein the inorganic porous material has an average particle size of 0.1 μm to 30 μm.

[7] The foregoing items 1 to 6, wherein the inorganic porous material having the hydrazine derivative fixed in the pores is composed of 5 to 50% by mass with respect to the deodorant 100 and 50 to 95% by mass of activated carbon. The deodorizer of any one of these.

  In the invention of [1], since it contains an inorganic porous substance in which the hydrazine derivative is fixed in the pores and activated carbon as active ingredients, it is an adsorption and deodorant effect excellent in tobacco odor such as ammonia, acetaldehyde, acetic acid, VOC gas, etc. Can be demonstrated. In particular, acetaldehyde, which is a typical malodorous gas of tobacco odor, is difficult to be adsorbed by activated carbon, but hydrazine derivatives have a property of immediate chemical adsorption, so they do not re-release acetaldehyde odor and are durable. High deodorant performance can be demonstrated. Activated carbon is not effective for aldehydes, but is effective for many other gases. For example, it exhibits excellent adsorption performance for acetic acid, hydrogen sulfide, VOC gas (toluene, etc.). In the present invention, since the hydrazine derivative is fixed in the pores of the inorganic porous material so that the hydrazine derivative and the activated carbon are not in direct contact with each other, the acetaldehyde adsorption ability of the hydrazine derivative decreases due to the influence of the activated carbon. It can be made into a durable deodorant without any problems.

  In the invention of [2], since the inorganic porous material is an inorganic porous material having a pore diameter of 0.6 nm to 20 nm, the hydrazine derivative can be fixed in the pores, and the hydrazine derivative and activated carbon are in direct contact with each other. Therefore, it is possible to provide a durable deodorant that does not lower the acetaldehyde adsorption ability of the hydrazine derivative.

In the invention of [3], since the inorganic porous material is a hydrophobic zeolite, the hydrazine derivative fixed in the pores hardly leaves even when in contact with water, and is excellent in ammonia, acetaldehyde, acetic acid and the like. Adsorption and deodorization effect can be exhibited.

  In the invention of [4], since the hydrazine derivative is an acid hydrazide compound having 4 to 8 carbon atoms, the solubility in water is about 20 g / 100 ml, and even when it comes into contact with water, it hardly leaves, and ammonia, acetaldehyde In addition, it exhibits an adsorption deodorizing effect excellent in acetic acid and the like, and can be made into a deodorant excellent in immediate effect and durability for deodorizing in a short time.

  In the invention of [5], since the supported amount of the hydrazine derivative is 5 to 500 mg with respect to 1 g of the inorganic porous material, it is a deodorant exhibiting an excellent adsorption and deodorizing effect on ammonia, acetaldehyde, acetic acid and the like. be able to.

  In the invention of [6], since the average particle diameter of the inorganic porous material is 0.1 μm to 30 μm, a sufficient amount of hydrazine derivative can be fixed in the pores of the inorganic porous material, and the aldehyde adsorption effect is high. Can be realized. Moreover, even if the deodorizer of the present invention is fixed to the fiber structure, it can be made free of roughness.

  In the invention of [7], since the inorganic porous material in which the hydrazine derivative is fixed in the pores consists of 5 to 50% by mass and activated carbon 50 to 95% by mass with respect to the deodorant 100, ammonia, acetaldehyde Adsorption and deodorization effects sufficient for tobacco odors such as acetic acid and VOC gas can be exerted, and a deodorant having immediate effect and durability can be obtained.

  The deodorant of the present invention is, for example, fixed to a fiber structure such as a curtain, carpet, wallpaper, chair upholstery, etc. in a room with a binder resin or the like, and deodorizes tobacco odor in a natural convection environment. The deodorizer of the present invention may be carried on a filter such as an air purifier or an air conditioner, and the cigarette odor may be deodorized while forcibly circulating the air with a fan, or in a directly breathable container. It can also be used as a deodorant for simultaneously deodorizing both aldehydes and VOC gas.

  The deodorizer of the present invention contains an inorganic porous material in which a hydrazine derivative is fixed in the pores and activated carbon as active ingredients.

  Examples of inorganic porous materials include zeolite, barley stone, and silica gel. Among them, hydrophobic zeolite is fine even if it is dispersed in water once the hydrazine derivative is fixed in the pores and dried. This is preferable because the hydrazine derivative in the pores is not retained and released. The pore diameter of the inorganic porous material is preferably 0.6 nm to 20 nm. If the pore diameter is less than 0.6 nm, the hydrazine derivative is difficult to enter the pores of the inorganic porous material, and if the pore diameter exceeds 20 nm, the hydrazine derivative is detached when washed with water.

  Moreover, it is preferable that the particle size of an inorganic porous material is 0.1 micrometer-30 micrometers. When the thickness is less than 0.1 μm, it is not preferable because the hydrazine derivative is hardly supported in the pores of the inorganic porous material and the cost is increased. On the other hand, when the thickness exceeds 30 μm, it is not preferable because a rough feeling is generated when the fiber structure is supported.

  In the present invention, the hydrazine derivative is a deodorant that is effective for chemical adsorption of aldehyde components such as acetaldehyde, which is considered to be contained in a large amount of tobacco odor, and is excellent in immediate effect, and is preferably water-soluble hydrazine. For example, hydrazine hydrate, carbonate hydrazine, hydrazine sulfate, hydrazine hydrochloride, hydrazine hydrobromide, adipic acid hydrazide, phenyl hydrazide, carbodihydrazide, isophthalic acid dihydrazide, sebacic acid hydrazide, dodecanedihydrazide, benzophenone hydrazide, stearic acid dihydrazide, Examples include acid dihydrazide, succinic dihydrazide, maleic hydrazide, maleic hydrazide monopotassium, maleic hydrazide monosodium, benzenesulfonyl hydrazide, monomethyl hydrazine, citric hydrazide and p-toluenesulfonyl hydrazide. Since it is water-soluble, it can be easily fixed in the pores of the inorganic porous material. More desirably, the acid hydrazide compound having 4 to 8 carbon atoms is preferably a hydrazine derivative having a water solubility of about 20 g / 100 ml. Specifically, adipic acid hydrazide can be mentioned as a particularly preferable one. The hydrazine derivative may be used alone or as a mixture.

  Although hydrazine derivatives are very effective for aldehyde deodorization, it has been found that when a hydrazine derivative and activated carbon are in direct contact, the aldehyde deodorizing ability of the hydrazine derivative is extremely reduced and it is not durable. Although the reason is not clearly clarified, in the present invention, in order to avoid direct contact between the hydrazine derivative and the activated carbon, the hydrazine derivative is fixed in the pores of the inorganic porous material, and then the VOC gas of the activated carbon is used. In addition to the adsorption performance, the deodorizer has a strong deodorizing effect, immediate effect and durability against tobacco odor.

  As the activated carbon, activated carbon-based carbon porous bodies such as coconut shell activated carbon, petroleum pitch-based spherical activated carbon, activated carbon fiber, and wood-based activated carbon are preferably used because of their very large specific adsorption surface area. Although effective for adsorptivity, it is also effective for deodorization of other malodorous gases such as VOC gas generated from building materials and the like, rotting odors of raw garbage, pet odors and the like. Among them, coconut shell activated carbon is particularly preferable because of its high adsorption effect. Moreover, since activated carbon is black, it is difficult to use it on the surface of general clothing and interior merchandise, but it can be supported on the back surface with a binder resin or mixed with a backing agent. In addition, filter materials that do not affect color may be mixed in the manufacturing process of the filter, or may be used by being supported on the surface of the filter with a binder resin.

Further, the deodorant of the present invention is preferably composed of 5 to 50% by mass of an inorganic porous material in which a hydrazine derivative is fixed in the pores with respect to the deodorant 100, and 50 to 95% by mass of activated carbon. Adsorption and deodorization effects sufficient for tobacco odors such as ammonia, acetaldehyde, acetic acid, and VOC gas can be exhibited. When the inorganic porous material having the hydrazine derivative fixed in the pores is less than 5% by mass, sufficient adsorption and deodorizing effects such as ammonia, acetaldehyde and acetic acid cannot be exhibited. If it exceeds 50% by mass, the surface of the activated carbon is covered with the inorganic porous material, and the adsorption performance of the activated carbon itself is impaired, which is not preferable. More preferably, it is 10-30 mass%. Moreover, when activated carbon is less than 50 mass% with respect to the deodorizer 100, it cannot exhibit a strong immediate effect and durable deodorizing effect with respect to VOC gas or the like. If it exceeds 95% by mass, the amount of the inorganic porous material having the hydrazine derivative fixed in the pores becomes too small, and the deodorizing effect sufficient for ammonia, acetaldehyde, acetic acid and the like cannot be exhibited. More preferably, it is 70-90 mass%.

  Moreover, in the deodorizer of this invention, you may employ | adopt the structure which carry | supported other deodorizer, an odor adsorption agent, various additives, etc. in the range which does not prevent invention. For example, when zinc oxide is added, bad odors such as hydrogen sulfide can be eliminated in addition to tobacco odor. Next, the present invention will be described specifically by way of examples. Various performance tests of the present invention were performed as follows.

(Deodorization performance test)
An aqueous dispersion of the deodorant of the present invention is placed on a petri dish, dried, and placed in a test bag (volume 10 l) as it is. Various malodorous gases 5 l (acetaldehyde, ammonia, acetic acid, toluene) are fixed in the bag. (Acetaldehyde 100 ppm, Ammonia 100 ppm, Acetic acid 100 ppm, Toluene 20 ppm) The concentration after thirty minutes was measured with a detector tube to obtain the deodorization rate (%). , “◯” when the removal rate is 85% or more and less than 90%, “△” when the removal rate is 80% or more and less than 85%, and “X” when the removal rate is less than 80%, “○” or higher was evaluated as acceptable.

(Durability test)
“◎” when the removal rate after repeating this 50 times is 90% or more, “◯” when the removal rate is 85% or more and less than 90%, and removal rate is 80% or more and less than 85%. The case where “△” was given, the case where the removal rate was less than 80% was made “X”, and the case where “◯” or more was evaluated as pass was evaluated.

(Immediate performance test)
The deodorant of the present invention is placed on a petri dish and placed in a test bag (volume 10 l), and 5 l (acetaldehyde, ammonia, acetic acid, toluene) of various malodorous gases (acetaldehyde 100 ppm, ammonia 100 ppm, acetic acid 100 ppm) in the bag. , Toluene 20ppm), and the concentration after 10 minutes is measured with a detector tube to determine the deodorization rate (%). The removal rate is 85% or more, “◎”, the removal rate is 80% or more and less than 85% Were evaluated as “◯”, those with a removal rate of 75% or more and less than 80% as “Δ”, those with a removal rate of less than 75% as “X”, and “○” or more as pass.

<Example 1>
Add 300 mg of adipic acid hydrazide to 100 cc of water, dissolve well by stirring, add 1 g of hydrophobic zeolite with a pore size of 10 nm and an average particle size of 15 μm, impregnate well, perform suction filtration, and wash on filter paper After drying, 1 g of an inorganic porous material having 200 mg of hydrazine derivative fixed in the pores was obtained. Next, 0.1 g of the inorganic porous material and 0.1 g of coconut pattern activated carbon were dispersed in 4 cc of water, sufficiently stirred, and dried on a petri dish. Next, the deodorization performance test, the durability performance test, and the immediate effect performance test were performed, and the removal rate is shown in Table 1.

<Example 2>
Next, 150 mg of adipic acid hydrazide was added to obtain 1 g of an inorganic porous material in which 100 mg of the hydrazine derivative was fixed in the pores. Inorganic porous material in which the hydrazine derivative was fixed in the pores in the same manner as in Example 1. A material was obtained. Each performance test was performed and the removal rate is shown in Table 1.

<Example 3>
In Example 1, each performance test was conducted in the same manner as in Example 1 except that 0.01 g of the inorganic porous material and 0.1 g of the coconut pattern activated carbon were dispersed in 4 cc of water, sufficiently stirred and dried on a petri dish. The removal rates are listed in Table 1.

<Example 4>
In Example 1, each performance test was carried out in the same manner as in Example 1 except that maleic hydrazide (acid hydrazide having 4 carbon atoms) was used instead of adipic acid hydrazide.

<Example 5>
In Example 1, each performance test was carried out in the same manner as in Example 1 except that mesoporous silica having a pore diameter of 18 nm and an average particle diameter of 25 μm was used instead of the hydrophobic zeolite, and the removal rate is shown in Table 1.

<Example 6>
Next, 600 mg of adipic acid hydrazide was added to obtain 1 g of an inorganic porous material in which 400 mg of the hydrazine derivative was fixed in the pores. Inorganic porous material in which the hydrazine derivative was fixed in the pores in the same manner as in Example 1. A material was obtained. Each performance test was performed and the removal rate is shown in Table 1.

<Comparative Example 1>
In Example 1, except that 0.2 g of adipic acid hydrazide and 0.1 g of coconut pattern activated carbon were directly dispersed in 4 cc of water without fixing the hydrazine derivative to the inorganic porous material, and the mixture was sufficiently stirred and dried on a petri dish. Each performance test was conducted in the same manner as in Example 1, and the removal rate is shown in Table 2.

<Comparative example 2>
In Example 1, 0.1 g of an inorganic porous material to which adipic acid hydrazide is not fixed and 0.1 g of coconut pattern activated carbon are dispersed in 4 cc of water, sufficiently stirred, dried on a petri dish, and subjected to each performance test. The removal rates are listed in Table 2.

<Comparative Example 3>
In Example 1, 0.2 g of inorganic porous material and 0.1 g of coconut pattern activated carbon were dispersed in 4 cc of water, stirred thoroughly, dried on a petri dish, and dried in the same manner as in Example 1 to perform each performance test. The removal rates are listed in Table 2.

<Comparative Example 4>
In Example 1, except that 0.08 g of the inorganic porous material and 2 g of coconut pattern activated carbon were dispersed in 4 cc of water, sufficiently stirred, dried on a petri dish and then dried in the same manner as in Example 1. Are listed in Table 2.

<Comparative Example 5>
In Example 1, each performance test was carried out in the same manner as in Example 1 except that a hydrophobic zeolite having a pore size of 30 nm and an average particle size of 15 μm was used.

  As shown in Tables 1 and 2, in Comparative Example 1 in which the hydrazine derivative and the cocoon pattern activated carbon were in direct contact, the deodorizing ability with respect to acetaldehyde was extremely reduced. Moreover, in the comparative example 2 which consists only of an inorganic porous substance and activated carbon, it was a thing without the deodorizing capability with respect to acetaldehyde. In Comparative Example 3 in which the amount of the inorganic porous material exceeded 50% by mass with respect to the deodorant 100, the effect of activated carbon was inhibited, and the adsorption effect of toluene was reduced. Moreover, in the comparative example 4 in which the quantity of an inorganic porous material is less than 5 mass% with respect to the deodorizer 100, the deodorizing capability of acetaldehyde has fallen. In Comparative Example 5, the pore diameter of the inorganic porous material exceeded 20 nm, and the hydrazine derivative was detached when the mixture was dispersed in water and sufficiently stirred and dried on a petri dish to reduce the deodorizing ability against acetaldehyde. .

  The present invention exhibits odor eliminating performance particularly excellent for removing aldehydes such as formaldehyde and acetaldehyde, VOC, and tobacco odors containing them, and filter materials for home or commercial air conditioners, air cleaners, etc. Widely used as a textile fabric that efficiently removes tobacco odor.

Claims (7)

A deodorant comprising an inorganic porous material in which a hydrazine derivative is fixed in pores and activated carbon as active ingredients. The deodorizer according to claim 1, wherein the inorganic porous material is an inorganic porous material having a pore diameter of 0.6 nm to 20 nm. The deodorant according to claim 1 or 2, wherein the inorganic porous material is a hydrophobic zeolite. The deodorizer according to any one of claims 1 to 3, wherein the hydrazine derivative comprises an acid hydrazide compound having 4 to 8 carbon atoms. The deodorizer according to any one of claims 1 to 4, wherein the supported amount of the hydrazine derivative is 5 to 500 mg with respect to 1 g of the inorganic porous material. The deodorant according to any one of claims 1 to 5, wherein an average particle size of the inorganic porous material is 0.1 µm to 30 µm. 7. The inorganic porous material in which the hydrazine derivative is fixed in the pores is composed of 5 to 50% by mass with respect to the deodorant 100 and 50 to 95% by mass of activated carbon. The deodorizer according to claim 1.