JP2008154915A - Deodorant - Google Patents

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JP2008154915A
JP2008154915A JP2006349337A JP2006349337A JP2008154915A JP 2008154915 A JP2008154915 A JP 2008154915A JP 2006349337 A JP2006349337 A JP 2006349337A JP 2006349337 A JP2006349337 A JP 2006349337A JP 2008154915 A JP2008154915 A JP 2008154915A
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deodorizing material
test
weight
carbodihydrazide
magnesium silicate
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JP2008154915A5 (en
JP5221871B2 (en
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Masanobu Okita
正信 大北
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Osaka Gas Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant which expresses high removal efficiency for aldehyde and can be used for a long period of time. <P>SOLUTION: A honeycomb molded body is obtained from a hydrated magnesium silicate clay mineral and a binding material, and carbohydrazide is added to the honeycomb molded body to obtain the deodorant. The carbohydrazide is added so as to be ≥1 pts.wt. and ≤15 pts.wt. to 100 pts.wt. of the honeycomb molded body to obtain the deodorant. Phosphoric acid is added so as to be ≥5 pts.wt. to 100 pts.wt. of the honeycomb molded body to obtain the deodorant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、特にホルムアルデヒドやアセトアルデヒドなどのアルデヒド類の臭い成分の除去性能に優れた脱臭材に関するものである。   The present invention relates to a deodorizing material excellent in removal performance of odorous components of aldehydes such as formaldehyde and acetaldehyde.

一般に、商業施設や工場、レストランなどで用いられる業務用の換気装置では、排気流路に脱臭材を配設して脱臭することが行われている。   In general, in a commercial ventilation apparatus used in commercial facilities, factories, restaurants, etc., deodorizing material is disposed in an exhaust passage to deodorize it.

従来より、この脱臭に用いる脱臭材としては、含水珪酸マグネシウム粘土鉱物を主成分とするハニカム通気孔の連続多孔構造体のものが知られている。(例えば、特許文献1参照)。
特開2005−305268号公報
2. Description of the Related Art Conventionally, as a deodorizing material used for this deodorization, a honeycomb porous continuous porous structure having a hydrous magnesium silicate clay mineral as a main component is known. (For example, refer to Patent Document 1).
JP-A-2005-305268

しかし、上記従来の脱臭材は、ガス状の有機化合物に対しては脱臭性能を有しているが、シックハウス症候群やタバコの刺激臭の原因となっているホルムアルデヒドやアセトアルデヒドその他のアルデヒド類の脱臭性能は、十分に発揮することができないといった不都合を生じていた。   However, the above-mentioned conventional deodorizing materials have deodorizing performance against gaseous organic compounds, but deodorizing performance of formaldehyde, acetaldehyde and other aldehydes that cause the irritating odor of sick house syndrome and tobacco. Caused the inconvenience that it could not be fully demonstrated.

本発明は係る実情に鑑みてなされたものであって、アルデヒド類への高い除去効率を発言し、かつ、長期間使用することができる脱臭材を提供することを目的としている。   The present invention has been made in view of the actual situation, and an object of the present invention is to provide a deodorizing material that can be used for a long period of time, which is highly effective for removing aldehydes.

本発明者等は、アルデヒド類の臭気成分の除去について鋭意研究を重ねたところ、含水珪酸マグネシウム組成物にカルボジヒドラジドを添着したものが優れた脱臭効果を発揮することを知見し、本発明に至ったものである。   As a result of intensive studies on the removal of odorous components from aldehydes, the present inventors have found that a hydrated magnesium silicate composition with carbodihydrazide exerts an excellent deodorizing effect, leading to the present invention. It is a thing.

すなわち、本発明は、含水珪酸マグネシウム組成物から得られるハニカム成形体にカルボジヒドラジドが添着されたことを特徴とする脱臭材である。   That is, the present invention is a deodorizing material characterized in that carbodihydrazide is attached to a honeycomb formed body obtained from a hydrous magnesium silicate composition.

含水珪酸マグネシウム組成物は、例えば、含水珪酸マグネシウム粘土鉱物を主成分とする成形材料を結合材とともに湿式混練した後、多数の六角形状、細格子状の連続孔を有するいわゆるハニカム成形体として任意の寸法形状に押し出し成形し、乾燥後に焼成して含水珪酸マグネシウムハニカム成形体として形成することができる。ここで用いる結合材はPVA樹脂、PTFE(ポリテトラフルオロエチレン)、PVDF(ポリフッ化ビニリデン)、PVC(ポリ塩化ビニル)、ポリアクリル酸エステル、エポキシ樹脂、フェノール樹脂、ポリエチレン、ポリプロピレン、ABS樹脂、ポリエステルなどのポリマー、シリカゾル、アルミナゾル、ベントナイト、カオリナイト等の粘土鉱物が挙げられる。   The hydrous magnesium silicate composition is, for example, a so-called honeycomb molded body having a large number of hexagonal and fine grid-like continuous pores after wet-kneading a molding material mainly composed of hydrous magnesium silicate clay mineral together with a binder. It can be extruded into a dimensional shape, fired after drying, and formed into a hydrous magnesium silicate honeycomb formed body. The binder used here is PVA resin, PTFE (polytetrafluoroethylene), PVDF (polyvinylidene fluoride), PVC (polyvinyl chloride), polyacrylic ester, epoxy resin, phenol resin, polyethylene, polypropylene, ABS resin, polyester. And polymers such as silica sol, alumina sol, bentonite and kaolinite.

含水珪酸マグネシウムハニカム成形体は、この成形体に一体的に形成された多数の空隙が連続して通気可能な通気孔を形成するように連続多孔構造となされたものであれば、特に限定されるものではない。また、セルサイズの異なるハニカム成形体を積層または組み合わせて配置したものであってもよい。なお、通気時の含水珪酸マグネシウム成形体と通気ガスとの接触を多くしようとして通気孔を細かくした場合、通気抵抗が増すこととなり、通気抵抗を低くした場合、含水珪酸マグネシウム成形体と通気ガスとを十分に接触させることができなくなる。したがって、これら含水珪酸マグネシウム成形体の大きさ、通気抵抗などは、用いる場所や許容される通気圧力損失などに応じたものが用いられる。   The hydrous magnesium silicate honeycomb molded body is particularly limited as long as it has a continuous porous structure so that a large number of voids integrally formed in the molded body form a vent hole that allows continuous ventilation. It is not a thing. Further, honeycomb molded bodies having different cell sizes may be laminated or combined. In addition, if the ventilation hole is made finer in order to increase the contact between the hydrous magnesium silicate molded product and the ventilation gas at the time of ventilation, the ventilation resistance will increase, and if the ventilation resistance is lowered, the hydrous magnesium silicate molded product and the ventilation gas Cannot be fully contacted. Accordingly, the size, ventilation resistance and the like of these hydrous magnesium silicate compacts are determined according to the place of use and the allowable ventilation pressure loss.

具体的な含水珪酸マグネシウム粘土鉱物としては、ホルマイト、ゼオライト、セピオライト、シロタイル、ラフリナイト、およびアタパルジャイト等が挙げられる。これらの含水珪酸マグネシウム粘土鉱物を用いた具体的な含水珪酸マグネシウムのハニカム成形体としては、例えば、株式会社カルモア社製「マグセライド( 商品名) 」などを用いることができる。   Specific hydrous magnesium silicate clay minerals include holmite, zeolite, sepiolite, sirotile, rafrinite, attapulgite and the like. As a specific hydrous magnesium silicate honeycomb formed body using these hydrous magnesium silicate clay minerals, for example, “Mugselide (trade name)” manufactured by Calmore Co., Ltd. can be used.

カルボジヒドラジドは、化学式H2 NOC- NHNH2 で表される。このカルボジヒドラジドは、含水珪酸マグネシウムハニカム成形体100重量部に対して1重量部以上15重量部以下、好ましくは5重量部以上10重量部以下となるように、上記含水珪酸マグネシウムハニカム成形体に添着される。 Carbodihydrazide is represented by the chemical formula H 2 NOC—NHNH 2 . The carbodihydrazide is attached to the hydrous magnesium silicate honeycomb molded body so as to be 1 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the hydrous magnesium silicate honeycomb molded body. Is done.

この添着は、上記含水珪酸マグネシウムハニカム成形体を、カルボジヒドラジドの薬剤中に含浸させて含水珪酸マグネシウムハニカム成形体にカルボジヒドラジドを添着することによって行うことができる。このカルボジヒドラジドは、含水珪酸マグネシウムハニカム成形体100重量部に対して1重量部未満の場合、アルデヒド類に対して十分な脱臭能力を得ることができず、一方、15重量部を超えると、アルデヒド類に対する脱臭能力が飽和するとともに、カルボジヒドラジド自体に含まれるアミノ基によって脱臭材自体から放散するアミン臭が強くなり使用する用途によっては好ましくない。   This attachment can be performed by impregnating the hydrated magnesium silicate honeycomb molded body into a carbodihydrazide chemical and attaching the carbodihydrazide to the hydrated magnesium silicate honeycomb molded body. When this carbodihydrazide is less than 1 part by weight relative to 100 parts by weight of the hydrous magnesium silicate honeycomb molded body, sufficient deodorizing ability cannot be obtained with respect to aldehydes. The deodorizing ability with respect to the odor is saturated, and the amine group contained in the carbodihydrazide itself increases the amine odor emitted from the deodorizing material itself.

なお、この添着は、含浸添着に限定されるものではなく、上記含水珪酸マグネシウムハニカム成形体にカルボジヒドラジドの薬剤をスプレーによって噴霧することで添着するものであってもよいし、刷毛などで塗布することによって添着するものであってもよい。   Note that this attachment is not limited to impregnation attachment, and the hydrated magnesium silicate honeycomb molded body may be attached by spraying a carbodihydrazide agent by spraying, or may be applied with a brush or the like. It may be attached depending on the situation.

このようにして構成される脱臭材は、含水珪酸マグネシウムハニカム成形体に添着させたカルボジヒドラジドがアミノ基を有するため、脱臭材自体の臭気が発生することとなる。したがって、脱臭材自体のアミン臭を低減させる目的で、含水珪酸マグネシウムハニカム成形体100重量部に対して5重量部以上となるようにリン酸を添着してもよい。この場合、リン酸の添着は、含水珪酸マグネシウムハニカム成形体にカルボジヒドラジドを添着した後、同じ要領でリン酸を添着するものであってもよいし、含水珪酸マグネシウムハニカム成形体にリン酸を添着した後、同じ要領でカルボジヒドラジドを添着するものであってもよいし、含水珪酸マグネシウムハニカム成形体にカルボジヒドラジドとリン酸とを同時に添着するものであってもよい。このリン酸の添着量が、含水珪酸マグネシウムハニカム成形体100重量部に対して5重量部未満の場合には、このアミン臭低減効果が低く脱臭材自体の臭気を十分に除去することができない。また、5重量部以上では、アミン臭の除去効果が認められる。しかしながらリン酸添加量の増加に伴い、アセトアルデヒドの除去率が低下する現象があるため、したがって、含水珪酸マグネシウムハニカム成形体に添着させるリン酸の量としては、含水珪酸マグネシウムハニカム成形体100重量部に対して5重量部以上10重量部以下の範囲で、脱臭材に要求される脱臭能力に応じて適宜調整できる。このリン酸の添着についても、上記カルボジヒドラジドの添着と同様に含浸添着に限定されるものではなく、スプレーによる噴霧で添着するものであってもよいし、刷毛などによる塗布によって添着するものであってもよい。   In the deodorizing material configured in this manner, the odor of the deodorizing material itself is generated because the carbodihydrazide attached to the hydrous magnesium silicate honeycomb formed body has an amino group. Therefore, phosphoric acid may be added so as to be 5 parts by weight or more with respect to 100 parts by weight of the hydrous magnesium silicate honeycomb molded body for the purpose of reducing the amine odor of the deodorizing material itself. In this case, the phosphoric acid may be attached by adding carbodihydrazide to the hydrous magnesium silicate honeycomb molded body and then adding phosphoric acid in the same manner, or by attaching phosphoric acid to the hydrous magnesium silicate honeycomb molded body. Then, carbodihydrazide may be attached in the same manner, or carbodihydrazide and phosphoric acid may be attached simultaneously to the hydrous magnesium silicate honeycomb formed body. When the amount of phosphoric acid added is less than 5 parts by weight with respect to 100 parts by weight of the hydrous magnesium silicate honeycomb molded body, the amine odor reducing effect is low and the odor of the deodorizing material itself cannot be sufficiently removed. Moreover, the removal effect of an amine odor is recognized by 5 weight part or more. However, as the amount of phosphoric acid added increases, there is a phenomenon that the removal rate of acetaldehyde decreases. Therefore, the amount of phosphoric acid to be added to the hydrous magnesium silicate honeycomb molded body is 100 parts by weight of the hydrous magnesium silicate honeycomb molded body. On the other hand, in the range of 5 parts by weight or more and 10 parts by weight or less, it can be appropriately adjusted according to the deodorizing ability required for the deodorizing material. The addition of phosphoric acid is not limited to impregnation as in the case of carbodihydrazide, but may be applied by spraying with a spray, or by application with a brush or the like. May be.

このようにして構成される脱臭材は、アルデヒド類の臭気を高い除去効率で除去し、かつ、長期にわたって脱臭効果を維持することができるだけでなく、今までの含水珪酸マグネシウムハニカム成形体が有していた他の臭い成分の除去性能についてもそのまま維持することができる。したがって、他の臭い成分の中にアルデヒド類を含んだ複合臭気に対しても、この脱臭材一つで除去することが可能となる。   The deodorizing material constituted in this way can not only remove odors of aldehydes with high removal efficiency and maintain the deodorizing effect over a long period of time, but also the conventional hydrous magnesium silicate honeycomb molded body has The removal performance of other odorous components that have been present can also be maintained. Therefore, it is possible to remove even a complex odor containing aldehydes in other odor components with this single deodorizing material.

以上述べたように、本発明の脱臭材によると、アルデヒド類の臭気を高い除去効率で除去し、かつ、長期にわたって脱臭効果を維持することができる。   As described above, according to the deodorizing material of the present invention, the odor of aldehydes can be removed with high removal efficiency, and the deodorizing effect can be maintained over a long period of time.

また、必要に応じリン酸を添着することにより、脱臭材自体の臭気も抑えることができるので、広い用途に適用可能となる。   Moreover, since the odor of the deodorizing material itself can be suppressed by adding phosphoric acid as necessary, it can be applied to a wide range of applications.

以下、本発明の実施例を挙げて具体的に説明する。
アセトアルデヒド1パス除去特性試験1
直径25φ×長さ60mm、重さ12〜14gの円柱状に形成され、断面に200セル/平方インチの通気孔を有する含水珪酸マグネシウムの押出成形ハニカム成形体を用意した。
Examples of the present invention will be specifically described below.
Acetaldehyde 1-pass removal characteristic test 1
An extruded honeycomb formed body of hydrous magnesium silicate having a diameter of 25φ × length of 60 mm and a weight of 12 to 14 g and having a vent of 200 cells / in 2 in a cross section was prepared.

この押出成形ハニカム成形体に、カルボジヒドラジド、アジピン酸ジヒドラジド、コハク酸ジヒドラジドをそれぞれ含浸添着して表1に示すように、実施例1〜実施例3、比較例1〜3の各試験脱臭材を用意した。   Carbodihydrazide, adipic acid dihydrazide, and succinic acid dihydrazide were impregnated and impregnated into this extruded molded honeycomb formed body, and as shown in Table 1, each test deodorizing material of Examples 1 to 3 and Comparative Examples 1 to 3 was added. Prepared.

各試験脱臭材の入口側から10ppmに調整したアセトアルデヒドガスを1.0m/sの線速度で供給し、各試験脱臭材を通過した後の出口側でアセトアルデヒドガスの濃度測定を行った。測定は、ガステック社製のガス検知管を使用してガス通過1分後、60分後、120分後のそれぞれについて行った。出口濃度から各試験脱臭材によって除去されたアセトアルデヒドガスの除去率を求めた。結果を表1に示す。   Acetaldehyde gas adjusted to 10 ppm from the inlet side of each test deodorizer was supplied at a linear velocity of 1.0 m / s, and the concentration of acetaldehyde gas was measured on the outlet side after passing through each test deodorizer. The measurement was performed using a gas detection tube manufactured by Gastec Co., Ltd., after 1 minute, 60 minutes, and 120 minutes after gas passage. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in Table 1.

Figure 2008154915
表1の結果から、ハニカム成形体100重量部に対して10重量部となるようにカルボジヒドラジドを含浸添着した実施例3の試験脱臭材は、1分後から120分後の長時間にわたって高い除去率を維持することが確認できた。また、ハニカム成形体100重量部に対して1重量部となるようにカルボジヒドラジドを含浸添着した実施例1の試験脱臭材でも、1分後から120分後の長時間にわたって、他の比較例と比べて良好な除去率を維持することが確認できた。
アセトアルデヒド1パス除去特性試験2
直径25φ×長さ60mmの円柱状に形成され、断面に200〜300セル/平方インチの通気孔を有する、含水珪酸マグネシウムのハニカム成形体と、活性炭のハニカム成形体とを用意した。
Figure 2008154915
From the results shown in Table 1, the test deodorizing material of Example 3 impregnated with carbodihydrazide so as to be 10 parts by weight with respect to 100 parts by weight of the honeycomb formed body was removed at a high rate over a long time from 1 minute to 120 minutes later. It was confirmed that the rate was maintained. Further, the test deodorizing material of Example 1 impregnated and impregnated with carbodihydrazide so as to be 1 part by weight with respect to 100 parts by weight of the honeycomb formed body was compared with other comparative examples over a long period of time after 1 minute to 120 minutes. It was confirmed that a good removal rate was maintained.
Acetaldehyde 1-pass removal characteristic test 2
A honeycomb formed body of hydrous magnesium silicate and a honeycomb formed body of activated carbon having a diameter of 25φ × length of 60 mm and having a vent of 200 to 300 cells / in 2 in a cross section were prepared.

これらのハニカム成形体に、カルボジヒドラジドをそれぞれ含浸添着し、ハニカム成形体100重量部に対して10重量部となるようにカルボジヒドラジドを含浸添着した含水珪酸マグネシウムのハニカム成形体からなる実施例4の試験脱臭材と、ハニカム成形体100重量部に対して5重量部となるようにカルボジヒドラジドを含浸添着した活性炭のハニカム成形体からなる比較例4の試験脱臭材と、ハニカム成形体100重量部に対して10重量部となるようにカルボジヒドラジドを含浸添着した活性炭のハニカム成形体からなる比較例5の試験脱臭材をそれぞれ用意した。   The honeycomb molded body of Example 4 comprising a honeycomb molded body of hydrous magnesium silicate impregnated with carbodihydrazide and impregnated with carbodihydrazide so as to be 10 parts by weight with respect to 100 parts by weight of the honeycomb molded body. The test deodorizing material, the test deodorizing material of Comparative Example 4 comprising a honeycomb molded body of activated carbon impregnated with carbodihydrazide so as to be 5 parts by weight with respect to 100 parts by weight of the honeycomb molded body, and 100 parts by weight of the honeycomb molded body On the other hand, a test deodorizing material of Comparative Example 5 comprising a honeycomb formed body of activated carbon impregnated with carbodihydrazide so as to be 10 parts by weight was prepared.

各試験脱臭材の入口側から10ppmに調整したアセトアルデヒドガスを1.0m/sの線速度で供給し、各試験脱臭材を通過した後の出口側でアセトアルデヒドガスの濃度測定を行った。測定は、ガステック社製のガス検知管を使用してガス通過 2時間毎に行った。出口濃度から各試験脱臭材によって除去されたアセトアルデヒドガスの除去率を求めた。結果を図1のグラフに示す。   Acetaldehyde gas adjusted to 10 ppm from the inlet side of each test deodorizer was supplied at a linear velocity of 1.0 m / s, and the concentration of acetaldehyde gas was measured on the outlet side after passing through each test deodorizer. The measurement was performed every 2 hours through the gas passage using a gas detector manufactured by Gastec. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in the graph of FIG.

図1の結果から、カルボジヒドラジドを活性炭のハニカム構造体に含浸添着しても十分な除去率を得ることができないが、カルボジヒドラジドを含水珪酸マグネシウムのハニカム成形体に含浸添着した場合には、除去率が飛躍的に向上することが確認できた。
アルデヒド平衡吸着量評価試験
実施例3の試験脱臭材と、実施例3のカルボジヒドラジドをアジピン酸ジヒドラジドに変更し、それ以外は実施例3と同様に構成した比較例6の試験脱臭材と、実施例3のカルボジヒドラジドをコハク酸ジヒドラジドに変更し、それ以外は実施例3と同様に構成した比較例7の試験脱臭材とをそれぞれ用意した。また、他社製品として、比較例8に係るアニリン系添着剤の試験脱臭材、比較例9に係る過マンガン酸カリ系添着剤の試験脱臭材、比較例10に係るモルフォリン系添着剤の試験脱臭材をそれぞれ用意した。
From the results shown in FIG. 1, it is not possible to obtain a sufficient removal rate even when carbodihydrazide is impregnated and impregnated into the activated carbon honeycomb structure. However, when carbodihydrazide is impregnated and impregnated into a hydrous magnesium silicate honeycomb structure, it is removed. It was confirmed that the rate improved dramatically.
Aldehyde Equilibrium Adsorption Evaluation Test Test deodorizing material of Example 3 and test deodorizing material of Comparative Example 6 constructed in the same manner as in Example 3 except that carbodihydrazide of Example 3 was changed to adipic acid dihydrazide, and The carbodihydrazide of Example 3 was changed to succinic acid dihydrazide, and the test deodorizing material of Comparative Example 7 was prepared in the same manner as in Example 3 except that. Further, as other company's products, the test deodorizing material of the aniline-based additive according to Comparative Example 8, the test deodorizing material of the potassium permanganate-based additive according to Comparative Example 9, and the test deodorizing of the morpholine-based additive according to Comparative Example 10 Each material was prepared.

各試験脱臭材を22リットル容量の密閉循環式平衡吸着量評価装置に投入し、5リットル/分の循環風量で、50ppmのアセトアルデヒドと50ppmのホルムアルデヒドとの混合ガスを循環させた。ガステック社製のガス検知管を使用して混合ガスの濃度測定を行い、濃度変化が無く平衡するまで循環させた後、最終測定濃度から各試験脱臭材の平衡吸着量を評価した。結果を表2、図2、図3に示す。   Each test deodorizing material was put into a 22 liter capacity closed circulation type equilibrium adsorption amount evaluation apparatus, and a mixed gas of 50 ppm acetaldehyde and 50 ppm formaldehyde was circulated at a circulation air flow rate of 5 liters / minute. The concentration of the mixed gas was measured using a gas detection tube manufactured by Gastec Co., Ltd., and the mixture was circulated until equilibration without any change in concentration. Then, the equilibrium adsorption amount of each test deodorizing material was evaluated from the final measured concentration. The results are shown in Table 2, FIG. 2 and FIG.

Figure 2008154915
これらの結果から、カルボジヒドラジドを含水珪酸マグネシウムのハニカム成形体に含浸添着した本願発明に係る脱臭材の場合には、他の脱臭材と比べても、アセトアルデヒド、ホルムアルデヒドの双方に対して優れた平衡吸着量を有することが確認できた。
Figure 2008154915
From these results, in the case of the deodorizing material according to the present invention in which carbodihydrazide was impregnated and impregnated into a honeycomb formed body of hydrous magnesium silicate, an excellent equilibrium with respect to both acetaldehyde and formaldehyde as compared with other deodorizing materials. It was confirmed that it had an adsorption amount.

また、この試験で使用したカルボジヒドラジド、アジピン酸ジヒドラジド、コハク酸ジヒドラジド、モルフォリンのそれぞれの添着剤5gを、3リットルの密閉バックに封入し、各添着剤の臭気の強弱を3人のパネラーで官能評価した。   In addition, 5 g of each additive of carbodihydrazide, adipic acid dihydrazide, succinic acid dihydrazide, and morpholine used in this test was sealed in a 3-liter sealed bag, and the odor intensity of each additive was controlled by three panelists. Sensory evaluation was performed.

その結果、モルフォリン>アジピン酸ジヒドラジド>コハク酸ジヒドラジド>カルボジヒドラジドの順で、アミン臭気が低下することが確認できた。
アセトアルデヒド1パス除去特性試験3
実施例3の試験脱臭材に、リン酸を含浸添着して表3に示すように、実施例3、実施例5〜7の各試験脱臭材を用意した。
As a result, it was confirmed that the amine odor decreased in the order of morpholine> adipic acid dihydrazide> succinic acid dihydrazide> carbodihydrazide.
Acetaldehyde 1-pass removal characteristic test 3
The test deodorizing material of Example 3 was impregnated with phosphoric acid and impregnated with phosphoric acid to prepare each test deodorizing material of Example 3 and Examples 5-7 as shown in Table 3.

各試験脱臭材のアミン臭気の有無を3人のパネラーで官能評価した。その結果、ハニカム成形体100重量部に対して5重量部以上となるようにリン酸を含浸添着した場合、アミン臭気が気にならないといった結果が得られた。   Each panel deodorizer was subjected to sensory evaluation on the presence or absence of amine odor by three panelists. As a result, when the phosphoric acid was impregnated and added so as to be 5 parts by weight or more with respect to 100 parts by weight of the honeycomb formed body, a result that the amine odor was not a concern was obtained.

次に、このようにしてリン酸を含浸添着した各試験脱臭材について、各試験脱臭材の入口側から10ppmに調整したアセトアルデヒドガスを1.0m/sの線速度で供給し、各試験脱臭材を通過した後の出口側でアセトアルデヒドガスの濃度測定を行った。測定は、ガステック社製のガス検知管を使用してガス通過120分後のそれぞれについて行った。出口濃度から各試験脱臭材によって除去されたアセトアルデヒドガスの除去率を求めた。結果を図4に示す。   Next, for each test deodorizing material impregnated and impregnated with phosphoric acid, acetaldehyde gas adjusted to 10 ppm from the inlet side of each test deodorizing material was supplied at a linear velocity of 1.0 m / s, and each test deodorizing material was supplied. The concentration of acetaldehyde gas was measured on the outlet side after passing through the. The measurement was performed for each gas passage 120 minutes after using a gas detection tube manufactured by Gastec. The removal rate of the acetaldehyde gas removed by each test deodorizing material was determined from the outlet concentration. The results are shown in FIG.

図4の結果から、リン酸の含浸添着量が増加するに伴って除去率の低下はあるもののアミン臭気を低減できることを見出した。ハニカム成形体100重量部に対して15重量部以上となるようにリン酸を含浸添着した場合でも、アセトアルデヒド除去性能としては30%の良好な除去率を維持することが確認できた。
複合臭気(厨房臭気)1パス除去特性試験
実施例3の試験脱臭材と比較例1の試験脱臭材とを用意した。
From the results shown in FIG. 4, it was found that the amine odor can be reduced although the removal rate decreases as the amount of impregnated and impregnated phosphoric acid increases. Even when phosphoric acid was impregnated and added so as to be 15 parts by weight or more with respect to 100 parts by weight of the honeycomb formed body, it was confirmed that a good removal rate of 30% was maintained as the acetaldehyde removal performance.
Compound odor (kitchen odor) 1-pass removal characteristic test A test deodorizing material of Example 3 and a test deodorizing material of Comparative Example 1 were prepared.

いわゆる4大悪臭といわれるアンモニア、トリメチルアミン、メチルメルカプタン、硫化水素の他、アルデヒド類や揮発性有機化合物(VOC)、低級脂肪酸を含んでいる厨房臭気を、現実の店舗においてガスバックに採取した。   In addition to ammonia, trimethylamine, methyl mercaptan, and hydrogen sulfide, which are the so-called four major malodors, kitchen odors containing aldehydes, volatile organic compounds (VOC), and lower fatty acids were collected in gas bags at actual stores.

次に、用意した実施例3および比較例1の各試験脱臭材について、各試験脱臭材の入口側から厨房臭気を1.0m/sの線速度で供給し、各試験脱臭材を通過した後の出口側で臭気強度(濃度)の測定を行った。測定は、新コスモス電気社製の「においセンサーXP329」(商品名)を使用し、測定器の表示値による判定を行った。結果を表3に示す。   Next, for each test deodorant prepared in Example 3 and Comparative Example 1, after supplying the kitchen odor from the entrance side of each test deodorant at a linear velocity of 1.0 m / s and passing through each test deodorant The odor intensity (concentration) was measured at the outlet side of the. For the measurement, “Odor sensor XP329” (trade name) manufactured by Shin Cosmos Electric Co., Ltd. was used, and the determination was made based on the display value of the measuring instrument. The results are shown in Table 3.

Figure 2008154915
表3の結果から、カルボジヒドラジドを含水珪酸マグネシウムのハニカム成形体に含浸添着した本願発明に係る脱臭材の場合には、複合臭気に対しても優れた脱臭性能を有することが確認できた。
清浄空気1パス除去特性試験
実施例3の試験脱臭材を用意した。また、この実施例3の試験脱臭材にリン酸を5%含浸添着し、それ以外は実施例3と同様に構成した実施例8の試験脱臭材と、実施例3の試験脱臭材におけるカルボジヒドラジドの添加量を15重量部に変更し、それ以外は実施例3と同様に構成した実施例9の試験脱臭材と、実施例9の試験脱臭材にリン酸を5%含浸添着し、それ以外は実施例9と同様に構成した実施例10の試験脱臭材と、実施例3の試験脱臭材におけるカルボジヒドラジドの添加量を20重量部に変更し、それ以外は実施例3と同様に構成した比較例11の試験脱臭材と、この比較例11の試験脱臭材にリン酸を5%含浸添着し、それ以外は比較例11と同様に構成した比較例12の試験脱臭材とを用意した。
Figure 2008154915
From the results shown in Table 3, it was confirmed that the deodorizing material according to the present invention in which carbodihydrazide was impregnated and impregnated into a honeycomb formed body of hydrous magnesium silicate had excellent deodorizing performance even with respect to composite odor.
Clean air 1-pass removal characteristic test The test deodorizing material of Example 3 was prepared. Further, the test deodorizer of Example 3 was impregnated with 5% phosphoric acid, and the test deodorizer of Example 8 was constructed in the same manner as in Example 3, and the carbodihydrazide in the test deodorizer of Example 3 The test deodorizing material of Example 9 and the test deodorizing material of Example 9 were impregnated with 5% phosphoric acid, and the rest was changed to 15 parts by weight. The test deodorizing material of Example 10 configured in the same manner as in Example 9 and the amount of carbodihydrazide added in the test deodorizing material of Example 3 were changed to 20 parts by weight, and the other configurations were the same as in Example 3. A test deodorizing material of Comparative Example 11 and a test deodorizing material of Comparative Example 12 configured in the same manner as Comparative Example 11 except that 5% phosphoric acid was impregnated and impregnated into the test deodorizing material of Comparative Example 11 were prepared.

次に、用意した実施例3、実施例8ないし実施例10、比較例11および比較例12の各試験脱臭材12〜14gを、25mmφの円筒状容器に充填し、各試験脱臭材の入口側から清浄空気を1.0m/sの線速度で供給し、各試験脱臭材を通過した後の出口側で臭気強度(濃度)の測定を行った。測定は、新コスモス電気社製の「においセンサーXP329」(商品名)を使用し、測定器の表示値による判定を行った。結果を表4に示す。   Next, 12 to 14 g of each test deodorizing material prepared in Example 3, Example 8 to Example 10, Comparative Example 11 and Comparative Example 12 was filled into a 25 mmφ cylindrical container, and the inlet side of each test deodorizing material. Clean air was supplied at a linear velocity of 1.0 m / s, and the odor intensity (concentration) was measured on the exit side after passing through each test deodorizing material. For the measurement, “Odor sensor XP329” (trade name) manufactured by Shin Cosmos Electric Co., Ltd. was used, and the determination was made based on the display value of the measuring instrument. The results are shown in Table 4.

Figure 2008154915
表4の結果から、含水珪酸マグネシウムのペレット状物100重量部に対してカルボジヒドラジドを10重量部および15重量部とした脱臭材の場合には、リン酸を5%含浸添着させたか否かに関係無く、脱臭性能を有することが確認できるが、カルボジヒドラジドの含浸添着量が20重量部までになると、測定値が上昇してしまう。恐らくカルボジヒドラジドのアミン臭が脱離発生している可能性が考えられる。
Figure 2008154915
From the results of Table 4, in the case of a deodorizing material in which carbodihydrazide was 10 parts by weight and 15 parts by weight with respect to 100 parts by weight of hydrous magnesium silicate pellets, whether or not 5% phosphoric acid was impregnated and impregnated. Regardless, it can be confirmed that it has deodorizing performance. However, when the amount of impregnated carbodihydrazide is up to 20 parts by weight, the measured value increases. Probably the amine odor of carbodihydrazide may be eliminated.

各種換気装置などに装着する脱臭材として利用できる。   It can be used as a deodorizing material to be installed in various ventilation devices.

ハニカム構造体の相違によるアセトアルデヒドの除去率の経時的変化を示すグラフである。It is a graph which shows the time-dependent change of the removal rate of acetaldehyde by the difference in a honeycomb structure. 含浸添着薬剤の違いによるアセトアルデヒドの平衡吸着量の違いを示すグラフである。It is a graph which shows the difference in the amount of equilibrium adsorption of acetaldehyde by the difference in an impregnating agent. 含浸添着薬剤の違いによるホルムアルデヒドの平衡吸着量の違いを示すグラフである。It is a graph which shows the difference in the amount of equilibrium adsorption of formaldehyde by the difference in an impregnating agent. リン酸添着量の相違によるアセトアルデヒドの除去率の違いを示すグラフである。It is a graph which shows the difference in the removal rate of acetaldehyde by the difference in the amount of phosphoric acid addition.

Claims (4)

含水珪酸マグネシウム粘土鉱物と結着材とから得られるハニカム成形体であって、ハニカム成形体にカルボジヒドラジドが添着されたことを特徴とする脱臭材。   A deodorizing material comprising a honeycomb formed body obtained from a hydrous magnesium silicate clay mineral and a binder, wherein carbodihydrazide is attached to the honeycomb formed body. 含水珪酸マグネシウム粘土鉱物がホルマイト、ゼオライト、セピオライト、シロタイル、ラフリナイト、アタパルジャイトから選ばれる少なくとも1種である請求項1記載の脱臭材。   2. The deodorizing material according to claim 1, wherein the hydrous magnesium silicate clay mineral is at least one selected from holmite, zeolite, sepiolite, sirotile, rafrinite, attapulgite. カルボジヒドラジドが、ハニカム成形体100重量部に対して1重量部以上15重量部以下となるように添着された請求項1または2記載の脱臭材。   The deodorizing material according to claim 1 or 2, wherein the carbodihydrazide is attached in an amount of 1 to 15 parts by weight with respect to 100 parts by weight of the honeycomb formed body. ハニカム成形体100重量部に対して5重量部以上となるようにリン酸が添着された請求項1ないし3の何れか1記載の脱臭材。   The deodorizing material according to any one of claims 1 to 3, wherein phosphoric acid is added so as to be 5 parts by weight or more with respect to 100 parts by weight of the honeycomb formed body.
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JP2012115737A (en) * 2010-11-30 2012-06-21 Nisshinbo Holdings Inc Adsorptive molding
CN114984914A (en) * 2022-05-31 2022-09-02 西安科技大学 Coal gangue-based adsorption material, coal gangue-based adsorption odor removal material and application

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JP2006075312A (en) * 2004-09-09 2006-03-23 Otsuka Chemical Co Ltd Deodorant composition having superior heat resistance and molding using the same

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JPH10235129A (en) * 1997-02-25 1998-09-08 Matsushita Electric Works Ltd Filter
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JP2004275520A (en) * 2003-03-17 2004-10-07 Aisin Seiki Co Ltd Aldehydes removing material
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JP2012115737A (en) * 2010-11-30 2012-06-21 Nisshinbo Holdings Inc Adsorptive molding
CN114984914A (en) * 2022-05-31 2022-09-02 西安科技大学 Coal gangue-based adsorption material, coal gangue-based adsorption odor removal material and application
CN114984914B (en) * 2022-05-31 2023-09-26 西安科技大学 Gangue-based adsorption material, gangue-based adsorption deodorizing material and application

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