JP2013075067A - Deodorant composition and deodorizing product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant composition that has excellent deodorizing performance with respect to various kinds of odor gas, in particular, aldehydes, and to provide a deodorizing product which contains the deodorant composition and also shows excellent deodorizing performance, the deodorant composition further enabling a house building material and an air cleaning filter, etc. containing the deodorant composition to show the maximum deodorizing effect without deteriorating quality and work efficiency of the building material and the air cleaning filter, etc. upon manufacturing them.SOLUTION: The deodorant composition has excellent deodorizing performance with respect to aldehydes by causing a carrier to carry at least one or more kinds of compounds selected from among organic compounds expressed by a general formula A-X-CH-Z (A indicates CHor CHNH, X indicates O or NH, Z indicates OH or NH, and at least one of A, X, Z contains amine).

Description

The present invention contains a deodorant composition exhibiting excellent deodorizing performance with respect to various odor gases, particularly a deodorant composition having excellent deodorizing performance with respect to aldehydes, and this deodorant composition. It relates to deodorant products.

In recent years, there has been a growing interest in health damage from the living environment called sick house syndrome due to residential building materials, and in the indoor environment such as VOC regulations. The cause of these pollutions is said to be largely due to formaldehyde generated from building materials. In addition, acetaldehyde, ammonia, hydrogen sulfide, acetic acid and other causative substances such as tobacco odor also cause pollution and discomfort in the indoor environment, and their removal from the living environment and indoor environments such as the interior of a car is desired. ing. From these facts, building materials with low generation of formaldehyde, building materials such as paints and adhesives, and interior materials are used, but they are not perfect. Moreover, although building materials such as wallpaper and interior materials imparted with deodorizing performance are used, the deodorizing performance is not satisfactory.

In air cleaning in the living environment and indoor environments such as in a car, odorous components such as aldehydes in the air, ammonia, hydrogen sulfide, acetic acid and organic substances are adsorbed by an adsorbent such as activated carbon as a method of purifying gases in the indoor environment. A technique for collecting substances and cleaning indoor air is generally used.
However, even if the activated carbon collects odorous components and the like, they are only adsorbed on the surface of the activated carbon and may be desorbed from the activated carbon by heating or the like and re-released into the air.

It is known that amine compounds have high reactivity with aldehydes, and aldehydes can be deodorized by contacting aldehydes with amine compounds. However, since the amine compound itself has an odor, low heat resistance, and is easily volatilized even if it is processed into a building material, it is difficult to obtain a deodorizing effect.

It is known that aminoguanidine compounds can deodorize aldehydes. A deodorant having an aminoguanidine compound supported on a carrier has a large effect on aldehydes, but has a weak effect on other odor components, particularly sulfur-based gases such as hydrogen sulfide.

JP 2009-39671 A JP 2006-130453 A WO2006 / 046611 Publication

It is an object of the present invention to provide a deodorant composition that increases the maximum deodorizing effect without deteriorating the quality and workability in producing a house building material or an air cleaning filter.

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される化合物から選ばれる少なくとも一種類以上を固形の担体に担持したことを特徴とする消臭剤組成物が、アルデヒド類に対する消臭性能に優れ、かつ担体に担持させたことによりそれ自身の臭気を低減し、表面積が大きくなることにより悪臭ガスとの接触機会が向上され、消臭製品への処理がし易くなることに加え、耐熱性の向上、および吸着した臭気が脱離し難くなることを見出し、本発明を完成させた。すなわち本発明は、（１）一般式（Ｉ）

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される有機化合物から選ばれる少なくとも１種以上を固形の担体に担持したことを特徴とする消臭剤組成物であり、（２）一般式（Ｉ）

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される有機化合物がジグリコールアミンであることを特徴とする消臭剤組成物であり、（３）担体が無機鉱物質または有機物固体である消臭剤組成物であり、（４）前記消臭剤組成物を、塗布、噴霧、または混合させて製造することを特徴とする消臭製品である。 In order to solve the above-mentioned problems, the present inventor has intensively studied to formula (I)

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X, and Z includes an amine). The deodorant composition is characterized in that at least one kind is supported on a solid carrier, has excellent deodorizing performance against aldehydes, and reduces the odor of itself by supporting it on the carrier. In addition to improving the chances of contact with malodorous gases and increasing the ease of processing into deodorized products, it has been found that heat resistance is improved and adsorbed odors are difficult to desorb. Completed. That is, the present invention provides (1) general formula (I)

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X, and Z contains an amine) A deodorant composition comprising at least one selected from a solid carrier, (2) General formula (I)

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X and Z contains an amine) It is a deodorant composition characterized by being a diglycolamine, (3) a deodorant composition whose carrier is an inorganic mineral or an organic solid, and (4) the deodorant composition, It is a deodorizing product produced by applying, spraying, or mixing.

According to the present invention, it is possible to provide an aldehyde deodorant composition that is efficient and inexpensive and has high deodorizing performance.

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される有機化合物には、アルコキシアルカノールアミン、アルコキシアルキルアミンおよびアルカノールアミンが挙げられる。アルコキシアルカノールアミンとしては、例えばジグリコールアミン、２−（２−アミノエトキシ）プロパノールなどが挙げられ、アルコキシアルキルアミンとしては、例えば２−メトキシエチルアミン、３−メトキシプロピルアミン、３−エトキシプロピルアミンなど が挙げられ、アルカノールアミンとしては、例えばエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミンなどが挙げられる。これらの有機化合物のうち、アルコキシアルカノールアミン類が好ましく、ジグリコールアミンが特に好ましい。 The method for preparing the deodorant composition of the present invention is described in detail below. General formula (I) used in the present invention

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X and Z contains an amine) Include alkoxyalkanolamines, alkoxyalkylamines and alkanolamines. Examples of the alkoxyalkanolamine include diglycolamine and 2- (2-aminoethoxy) propanol. Examples of the alkoxyalkylamine include 2-methoxyethylamine, 3-methoxypropylamine, and 3-ethoxypropylamine. Examples of the alkanolamine include ethanolamine, N-methylethanolamine, N, N-dimethylethanolamine and the like. Of these organic compounds, alkoxyalkanolamines are preferable, and diglycolamine is particularly preferable.

The carrier carrying the amine deodorant used in the present invention may be any organic or inorganic carrier. When an inorganic carrier is used, it is preferably other than an acidic solid. It may be a natural product or a synthetic product. Specific examples include silicon dioxide such as silica, silicate compounds, zeolites, cyclodextrins, silica gels, crystalline layered phosphate compounds and activated carbon. These carriers may be used in combination of two or more.

The silicon dioxide used as a carrier in the present invention is not particularly limited, and amorphous silicon dioxide is particularly preferable.

There is no limitation in particular as a silicate compound used as a support | carrier in this invention, Any silicate compound can be used. Specifically, aluminum silicate or magnesium silicate is preferred, and these may be natural products or synthetic products.

The zeolite used as the carrier in the present invention is not particularly limited, and any type of zeolite can be used, and it may be a natural product or a synthetic product. Specific examples of natural zeolites and synthetic zeolites include P-type, A-type, X-type, and Y-type structures, and ionic species include sodium, calcium, iron, silver, and the like. Can be used.

The cyclodextrin used as the organic carrier in the present invention is not particularly limited, and any cyclodextrin can be used. Specific examples include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and those obtained by modifying sugars to these cyclodextrins can also be used.

Silica gel used as a carrier in the present invention has various characteristics such as surface area and / or pore diameter, and any of them can be used. Specific examples include A-type silica gel and B-type silica gel, and any of these can be used.

Specific examples of the crystalline layered phosphate compound used as a carrier in the present invention include crystalline layered aluminum phosphate such as aluminum tripolyphosphate and aluminum metaphosphate, crystalline layered zirconium phosphate, and the like. Or it can be used in combination of two or more. Particularly preferred is crystalline layered zirconium phosphate.

As the activated carbon used as a carrier in the present invention, any known one can be used, such as one obtained by treating wood with an activating agent such as zinc chloride or phosphoric acid and dry distillation, or one obtained by activating charcoal with steam.

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される有機化合物の少なくとも一種類以上の原液、あるいは希釈溶液を滴下などにより混合した後、これらのアミン類の分解温度以下で加熱し、乾燥することで消臭剤組成物を得ることが出来る。具体的な温度範囲は８０℃から２００℃である。希釈溶液は水溶液でもアルコールなどの有機溶媒を用いても良いが、水溶液が好ましい。 There are various methods for preparing the deodorant composition of the present invention. For example, the general formula (I) is used while stirring the carrier.

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X and Z contains an amine) A deodorant composition can be obtained by mixing at least one kind of undiluted solution or dilute solution by dropping or the like, and then heating at or below the decomposition temperature of these amines and drying. A specific temperature range is 80 ° C to 200 ° C. The diluted solution may be an aqueous solution or an organic solvent such as alcohol, but an aqueous solution is preferred.

Although the deodorant composition of the present invention may be used as it is, it is usually used after being formulated. The type of the preparation is not particularly limited, but a liquid preparation is preferable from the viewpoint of ease of handling. Examples of liquid preparations include flowable agents. The above preparation can be prepared in the same manner as a normal preparation. Furthermore, it can be used by mixing with other deodorants, photocatalysts, etc. for reinforcing the deodorant function.

（ＡはＣＨ_３またはＣ_２Ｈ_４ＮＨ_２、ＸはＯまたはＮＨ、ＺはＯＨまたはＮＨ_２を示し、Ａ、Ｘ、Ｚの内少なくとも一つはアミンを含む）で表される少なくとも一種類以上の化合物の希釈溶液を滴下、噴霧、および浸漬処理することも可能である。 In order to prepare a deodorant product, there are a method of applying the deodorant composition of the present application to the surface of a substrate or a covering, and a method of kneading into a substrate. In addition, after the carrier is previously attached to the deodorant product, the general formula (I)

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X and Z contains an amine) It is also possible to drop, spray, and soak the diluted solution of the above compound.

When processing chemicals on the surface of a substrate or coating, it may be mixed with a surface treatment agent such as paint and sprayed, mixed with brush, roll or ink, and gravure printing, etc. In addition, a method suitable for the substrate or coating may be appropriately selected.

[Example 1]
10 parts by weight of silicon dioxide (Carplex # 80 manufactured by Evonik Tegusa Japan Co., Ltd.) was stirred and 20 parts by weight of 50% diglycolamine (2- (2-aminoethoxy) ethanol manufactured by Wako Pure Chemical Industries, Ltd.) was stirred. ) Aqueous solution was added at room temperature. After the addition, the mixture was stirred until uniform and dried at 100 ° C. for 1 hour to obtain a deodorant composition.

[Example 2]
10 parts by weight of silicon dioxide (Carplex # 80 manufactured by Evonik Tegusa Japan Co., Ltd.) was stirred, and 20 parts by weight of 50% diethylenetriamine (diethylenetriamine manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was added thereto at room temperature. After the addition, the mixture was stirred until uniform and dried at 100 ° C. for 1 hour to obtain a deodorant composition.

[Comparative Example 1]
10 parts by weight of distilled water was added to 10 parts by weight of diglycolamine. Stir until homogeneous after addition.

[Comparative Example 2]
10 parts by weight of distilled water was added to 10 parts by weight of diethylenetriamine. Stir until homogeneous after addition.

[Comparative Example 3]
Only silicon dioxide (Evonik Degussa Japan Co., Ltd .: Carplex # 80).

[Deodorization test method]
0.5 g of Examples 1 and 2 and Comparative Examples 1 to 3 were collected and placed in a flexible sampler (capacity 3 liters) manufactured by Omi Odo Air Service Co., Ltd., and filled with formaldehyde gas and acetaldehyde gas prepared to a predetermined concentration. The gas concentration was quantified using a gas detector tube for formaldehyde and a gas detector tube for acetaldehyde manufactured by Gastec Co., Ltd. every predetermined time. The deodorizing performance was evaluated from the concentration fluctuation. The results are shown in Tables 1 and 2.

Example 3
Example 1 0.1 part by weight of Example 1 was added to 10 parts by weight of an aqueous vinyl chloride emulsion (Vinibran T-888 manufactured by Nissin Chemical Industry Co., Ltd.) Was used as a deodorizing filter.

[Comparative Example 4]
0.1 part by weight of Comparative Example 1 was added to 10 parts by weight of the aqueous PVC emulsion, and the same deodorant filter was prepared as in Example 3.

[Deodorization test method]
1 g of Example 3 and Comparative Example 4 were collected, put into a flexible sampler (capacity 3 liters) manufactured by Omi Odo Air Service Co., Ltd., and filled with formaldehyde gas and acetaldehyde gas prepared to a predetermined concentration. The aldehyde gas concentration was quantified with a detector tube for formaldehyde and acetaldehyde manufactured by Gastec Co., Ltd. every predetermined time. The deodorizing performance was evaluated from the concentration fluctuation. The results are shown in Tables 3 and 4.

Example 4
0.1 parts by weight of Example 1 was added to 10 parts by weight of an aqueous PVC emulsion, and the result was applied to the surface of the PVC wallpaper at 10 g / square meter and dried to obtain a deodorant wallpaper.

[Comparative Example 5]
0.1 parts by weight of Comparative Example 3 was added to 10 parts by weight of an aqueous vinyl chloride emulsion, and the same deodorized wallpaper was prepared as in Example 4.

[Deodorization test method]
Example 4 and Comparative Example 5 were cut to 140 square centimeters, and the ends folded in half with aluminum tape were put into a flexible sampler (capacity 3 liters) manufactured by Omi Odo Air Service Co., Ltd., and prepared to a predetermined concentration. Formaldehyde gas and acetaldehyde gas were filled. Aldehyde concentrations were quantitatively determined with a gas detector tube for formaldehyde and acetaldehyde manufactured by Gastec Co., Ltd. every predetermined time. The deodorizing performance was evaluated from the concentration fluctuation. The results are shown in Tables 5 and 6.

[Re-release confirmation test method]
About Example 4, the gas in a flex sampler was expelled after completion | finish of the deodorizing test with respect to aldehydes, and nitrogen gas was inject | poured. After performing this operation twice, nitrogen gas corresponding to about 20% of the flex sampler capacity was injected, and after sealing, this was put in a thermostat at 60 ° C. Two hours later, the flex sampler was taken out and filled with nitrogen gas, and the gas concentration in the flex sampler was immediately measured with a gas detector tube. The results are shown in Table 7.

The deodorant composition of this invention is excellent in the deodorizing performance with respect to formaldehyde and acetaldehyde. The deodorant composition of the present invention can impart excellent deodorizing performance effects to fibers, paints, sheets, molded products, processed products, filters, and the like, and these can be used as deodorant products. .

Claims (4)

Formula (I)

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X, and Z contains an amine) A deodorant composition comprising at least one selected from a solid carrier. The general formula (I) according to claim 1

(A is CH ₃ or C ₂ H ₄ NH ₂ , X is O or NH, Z is OH or NH _2, and at least one of A, X and Z contains an amine) The deodorant composition according to claim 1, which is diglycolamine. The deodorant composition according to claim 1 or 2, wherein the carrier is an inorganic mineral or an organic solid. A deodorant product produced by applying, spraying, or mixing the deodorant composition according to any one of claims 1 to 3.