JP2016080626A - Acetaldehyde odor indicator material - Google Patents
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Abstract
Description
本発明はアセトアルデヒド臭気インジケータ材料に関する。 The present invention relates to an acetaldehyde odor indicator material.
揮発性有機化合物（ＶＯＣ）であるアセトアルデヒドは人体に有害な臭気物質である。しかしながら、アセトアルデヒドは、空気中に高濃度で気体として存在していても視覚的に認知することはできない。そこで、アセトアルデヒドの存在を簡便に認知できる方法が必要とされている。
アルデヒド類の検出には、一般的にガスクロマトグラフィが用いられるが、大型の装置を必要とし、操作が煩雑であるという問題点がある。
また、ホルムアルデヒドを検出する方法として、アミンとアルデヒドのシッフ反応を利用してする方法が提案されている（特開２００５−３６７３号公報）。
Acetaldehyde, a volatile organic compound (VOC), is an odorous substance harmful to the human body. However, acetaldehyde cannot be visually recognized even if it exists as a gas at a high concentration in the air. Therefore, there is a need for a method that can easily recognize the presence of acetaldehyde.
For detection of aldehydes, gas chromatography is generally used, but there is a problem that a large apparatus is required and the operation is complicated.
As a method for detecting formaldehyde, a method using a Schiff reaction between an amine and an aldehyde has been proposed (Japanese Patent Laid-Open No. 2005-3673).
本発明は、アセトアルデヒドなどの臭気を簡便に認知できるインジケータ材料を提供することを目的とする。 An object of this invention is to provide the indicator material which can recognize odors, such as acetaldehyde, simply.
本発明は、シリカ中に含有するコバルト成分を変色成分として含有することを特徴とする臭気検知用インジケータ材料を提供する。
１つの実施態様において、本発明のインジケータ材料は、シリカ中にコバルト成分を含む。
また、１つの実施態様において、本発明のインジケータ材料は、検知対象臭気をアセトアルデヒドとする。
The present invention provides an indicator material for detecting odor, characterized by containing a cobalt component contained in silica as a color-changing component.
In one embodiment, the indicator material of the present invention comprises a cobalt component in silica.
Moreover, in one embodiment, the indicator material of this invention sets a detection target odor to acetaldehyde.
本発明により、アセトアルデヒドなどの臭気を簡便に認知できるインジケータ材料を提供することができる。特に、シリカとコバルト化合物を組み合わせることで、臭気に対して単独では発現しなかった呈色反応が生じる。また、呈色反応後に所定の温度で加熱すると呈色反応前の色に戻る。さらに、呈色反応と加熱を繰り返し行うことができる。また、インジケータ材料は微粉末状であり、塗料や樹脂、液体、ゲル状物質などと混合可能なことからインジケータ組成物を容易に得ることができる。 The present invention can provide an indicator material that can easily recognize odors such as acetaldehyde. In particular, by combining silica and a cobalt compound, a color reaction that has not been developed alone with respect to odor occurs. Further, when heated at a predetermined temperature after the color reaction, the color returns to the color before the color reaction. Further, the color reaction and heating can be repeated. In addition, since the indicator material is in the form of fine powder and can be mixed with paint, resin, liquid, gel substance, etc., the indicator composition can be easily obtained.
本発明の臭気検知用インジケータ材料は、コバルト成分を変色成分として含有することを特徴とする。
コバルト成分としては、例えばコバルトイオン、コバルト酸化物、コバルト水酸化物、コバルト金属、ケイ酸コバルトなどが挙げられる。これらのコバルト成分は、単独であっても、２種以上が混合した形態であってもよい。インジケータ材料中のコバルト成分の含有量は、好ましくは０．００１〜５ｍｏｌ％であり、より好ましくは０．５〜２ｍｏｌ％である。この範囲より少ない場合も多い場合も、シリカとコバルト成分との相互作用が減少してしまい、シリカ単独の性質、もしくはコバルト化合物単独の性質に近くなり、インジケータとして呈色を示さない。コバルト成分の供給源としては、例えば硝酸コバルト、塩化コバルト、硫酸コバルト等の水溶性コバルト塩を用いることが可能で好ましくは硝酸コバルトを使用する。酸性水溶液に可溶なことが重要である。
本発明のインジケータ材料において、コバルト成分を含有する基材となるシリカの供給源としては、例えばアルコキシシランであるテトラメチルオルトシリケート、テトラエチルオルトシリケート、テトライソプロピルオルトシリケート、テトラ-ｎ-ブチルオルトシリケートやケイ酸ナトリウム等を用いることが可能で好ましくはテトラエチルオルトシリケート（ＴＥＯＳ）を使用する。酸触媒によって脱水縮合反応することが重要である。
本発明のインジケータ材料によって検知できる臭気としては、アセトアルデヒドやホルムアルデヒドなどの揮発性有機化合物（ＶＯＣ）、ギ酸や酢酸等の酸性臭気などのシリカ中に含有するコバルト成分と反応もしくは配位する臭気が挙げられる。
また、本発明のインジケータ材料は、加熱（例えば１００〜２００℃で２〜３時間）によりくりかえし使用することができる。
本発明のインジケータ材料は、コバルト成分を変色成分として含有する微粉末であり、そのまま微粉末状で用いることができるだけではなく、塗料と混合して塗工する形態、熱可塑性樹脂と混合して成形体にする形態、揮発性液体と混合してスプレー状に噴霧する形態、ゲル状物質と混合した形態など様々なインジケータ組成物を容易に得ることができる。各形態によって用いる材料は特に限定はされないが、インジケータ材料と臭気成分が接触して反応することから臭気成分が透過し易い材料を選択することが好ましい。成形体としては、粒状、ペレット、繊維、多孔質、フィルムなどが挙げられる。
The odor detection indicator material of the present invention is characterized by containing a cobalt component as a discoloration component.
Examples of the cobalt component include cobalt ions, cobalt oxide, cobalt hydroxide, cobalt metal, and cobalt silicate. These cobalt components may be used alone or in the form of a mixture of two or more. Content of the cobalt component in indicator material becomes like this. Preferably it is 0.001-5 mol%, More preferably, it is 0.5-2 mol%. When the amount is smaller or larger than this range, the interaction between the silica and the cobalt component is reduced, and the properties of silica alone or the properties of the cobalt compound are reduced, and no color is shown as an indicator. As a supply source of the cobalt component, for example, a water-soluble cobalt salt such as cobalt nitrate, cobalt chloride, and cobalt sulfate can be used. Preferably, cobalt nitrate is used. It is important that it is soluble in an acidic aqueous solution.
In the indicator material of the present invention, as a source of silica serving as a base material containing a cobalt component, for example, tetramethylorthosilicate, tetraethylorthosilicate, tetraisopropylorthosilicate, tetra-n-butylorthosilicate, which are alkoxysilanes, Sodium silicate or the like can be used, and tetraethylorthosilicate (TEOS) is preferably used. It is important to conduct a dehydration condensation reaction with an acid catalyst.
Odors that can be detected by the indicator material of the present invention include odors that react or coordinate with cobalt components contained in silica such as volatile organic compounds (VOC) such as acetaldehyde and formaldehyde, and acidic odors such as formic acid and acetic acid. It is done.
The indicator material of the present invention can be used repeatedly by heating (for example, at 100 to 200 ° C. for 2 to 3 hours).
The indicator material of the present invention is a fine powder containing a cobalt component as a discoloring component, and can be used as it is in the form of fine powder as it is, as well as a form in which it is mixed with a paint, a mixture with a thermoplastic resin, and a molding Various indicator compositions can be easily obtained, such as a body form, a form mixed with a volatile liquid and sprayed in a spray form, and a form mixed with a gel substance. Although the material used by each form is not specifically limited, Since an indicator material and an odor component contact and react, it is preferable to select the material which an odor component permeate | transmits easily. Examples of the molded body include granules, pellets, fibers, porous materials, and films.
本発明のインジケータ材料は、例えば酸性水溶液に、コバルト成分の供給源を溶解し、次いで基材材料であるシリカの供給源を加えて加熱してゲル状の生成物を得、さらにゲル状の生成物を焼成することによって得られる。上記酸としては、硝酸、塩酸などが挙げられる。上記加熱の条件としては、５０〜１５０℃で３０分〜１２時間、８０よりも高い温度で３０分〜２時間、８０℃よりも低い温度の場合で１時間〜１２時間であることが好ましい。インジケータ材料の生成方法は、このような方法に限定されない。上記焼成の条件としては、２００〜５５０℃で１〜１０時間、例えば３００℃で６時間、例えば４００℃で４時間の条件などが挙げられる。なお、インジケータ材料の生成方法は、上記方法に限定されない。
コバルト化合物の呈色は、塩化コバルトと水分との呈色などが知られているが、アルデヒド臭気と呈色する機構は提唱されていない。本発明のインジケータ機能は、シリカ中に含有するコバルト成分由来であり、シリカ単独でもコバルト化合物単独でも起こらない現象である。その発現機構の詳細までは捉えられていないが、シリカ中に散在する酸化コバルトもしくは水酸化コバルト、ケイ酸コバルトなどがアルデヒド臭気と配位もしくは錯体形成などの化学構造的な変化が生じることによる呈色であると考えている。従って、本発明のインジケータ材料は、シリカ中にコバルト成分を含有することで臭気成分と反応して呈色を示すと考えられる。
The indicator material of the present invention is obtained by, for example, dissolving a cobalt component source in an acidic aqueous solution, adding a silica source as a base material, and heating to obtain a gel product. It is obtained by firing the product. Examples of the acid include nitric acid and hydrochloric acid. The heating conditions are preferably 30 to 12 hours at 50 to 150 ° C, 30 minutes to 2 hours at a temperature higher than 80, and 1 to 12 hours at a temperature lower than 80 ° C. The method for generating the indicator material is not limited to such a method. Examples of the firing conditions include 200 to 550 ° C. for 1 to 10 hours, for example, 300 ° C. for 6 hours, for example, 400 ° C. for 4 hours, and the like. In addition, the production | generation method of indicator material is not limited to the said method.
As for the coloration of the cobalt compound, the coloration of cobalt chloride and moisture is known, but a mechanism for coloring with an aldehyde odor has not been proposed. The indicator function of the present invention is derived from a cobalt component contained in silica and is a phenomenon that does not occur with either silica alone or cobalt compound alone. Although the details of the mechanism of its development are not captured, it is suggested that cobalt oxide, cobalt hydroxide, cobalt silicate, etc. scattered in silica undergo chemical structural changes such as coordination or complex formation with aldehyde odor. I think it is color. Therefore, it is thought that the indicator material of this invention reacts with an odor component and shows a color by containing a cobalt component in a silica.
本発明のインジケータ材料は、臭気成分に反応して呈色することから視覚的に認知が可能であり、検知管、インジケーターテープ、インジケーターラベルなどの材料として用いることができる。また、スポーツウエア、介護衣類、被服、寝具、靴、ブーツに直接貼付して使用する。例えば、消臭成分を配合したものと配合しなかったものとを比較することで消臭能力を体感でき、販売促進等で使用することができる。 Since the indicator material of the present invention is colored in response to odor components, it can be visually recognized, and can be used as a material for detector tubes, indicator tapes, indicator labels, and the like. In addition, it is used directly on sportswear, nursing clothes, clothing, bedding, shoes and boots. For example, the deodorizing ability can be experienced by comparing a compound containing a deodorant component with a compound containing no deodorant component, which can be used for sales promotion or the like.
（実施例１）
０．０１ｍｏｌ／Ｌの硝酸水溶液に硝酸コバルトを溶解後、５．５ｍｏｌ／Ｌとなるようにテトラエトキシシランを加えて１００℃で攪拌子を６００ｒｐｍで回転させて攪拌した。コバルトの濃度をシリカに対して１ｍｏｌ％とした。全体がゲル状になったら攪拌を停止し、３００℃で６時間焼成して粉体試料を得た。撹拌温度と時間は１００℃１５分、１２０℃３０分及び１８０℃３分であった。
Example 1
After dissolving cobalt nitrate in a 0.01 mol / L nitric acid aqueous solution, tetraethoxysilane was added so as to be 5.5 mol / L, and the stirrer was rotated at 600 rpm and stirred. The concentration of cobalt was 1 mol% with respect to silica. When the whole became a gel, stirring was stopped and the powder sample was obtained by baking at 300 ° C. for 6 hours. The stirring temperature and time were 100 ° C. for 15 minutes, 120 ° C. for 30 minutes, and 180 ° C. for 3 minutes.
（実施例２）
硝酸コバルトを塩化コバルトとした以外は実施例１と同様に行った。
(Example 2)
The same procedure as in Example 1 was performed except that cobalt nitrate was changed to cobalt chloride.
（実施例３）
硝酸コバルトを硫酸コバルトとした以外は実施例１と同様に行った。
(Example 3)
The same procedure as in Example 1 was performed except that cobalt nitrate was changed to cobalt sulfate.
（比較例１）
硝酸コバルトを用いなかった以外は実施例１と同様に行った。
(Comparative Example 1)
The same procedure as in Example 1 was performed except that cobalt nitrate was not used.
（比較例２）
０．０１ｍｏｌ／Ｌの硝酸水溶液に硝酸コバルトを１．５ｍｏｌ／Ｌとなるように溶解後、３００℃で３０分かけて水分を蒸発させ、さらに３００℃で６時間焼成した。
(Comparative Example 2)
After dissolving cobalt nitrate in a 0.01 mol / L nitric acid aqueous solution so as to have a concentration of 1.5 mol / L, water was evaporated at 300 ° C. for 30 minutes, followed by baking at 300 ° C. for 6 hours.
（比較例３）
ガステック社製のアセトアルデヒド用検知管９２の内容試薬（有効成分としてリン酸ヒドロキシルアミン）を取り出して粉体試料を得た。
(Comparative Example 3)
The content reagent (hydroxylamine phosphate as an active ingredient) in the detector tube 92 for acetaldehyde manufactured by GASTECH was taken out to obtain a powder sample.
（試験方法）
（アセトアルデヒド水溶液滴下試験）
実施例１及び２並びに比較例１及び２で得られた粉体試料２０ｍｇに対してアセトアルデヒド計３ｃｍ3を３０回にわけて１分ごとに０．１ｃｍ3ずつ滴下して３０分かけて３ｃｍ3全てを使い切り、最初の滴下から１時間後の色を観察した。
（ギ酸滴下試験）
実施例１及び３並びに比較例１及び２で得られた粉体試料２０ｍｇに対してアセトアルデヒド０．１ｃｍ3を滴下して１時間後の色を観察した。
（酢酸滴下試験）
実施例１及び３並びに比較例１及び２で得られた粉体試料２０ｍｇに対して酢酸０．１ｃｍ3を滴下して１時間後の色を観察した。
（アセトアルデヒド曝露試験）
７００ｐｐｍのアセトアルデヒド含有空気５００ｍｌ中に、実施例１並びに比較例１及び２、３で得られた粉体試料５０ｍｇを曝して２時間後の色を観察した。
（くりかえし使用評価）
アセトアルデヒド曝露試験を行った試薬（色Ａ）を１７０℃で３時間加熱した後の色を観察した（色Ｂ）。また、再びアセトアルデヒド曝露試験を行って色を観察した（色Ｃ）。
(Test method)
(Acetaldehyde aqueous solution drop test)
Acetaldehyde total 3 cm 3 was dropped 30 times into 0.1 cm 3 every minute to 20 mg of the powder samples obtained in Examples 1 and 2 and Comparative Examples 1 and 2, and 3 cm 3 over 30 minutes. All were used up and the color 1 hour after the first addition was observed.
(Formic acid drop test)
0.1 cm 3 of acetaldehyde was added dropwise to 20 mg of the powder samples obtained in Examples 1 and 3 and Comparative Examples 1 and 2, and the color after 1 hour was observed.
(Acetic acid drop test)
Acetic acid 0.1 cm 3 was added dropwise to 20 mg of the powder samples obtained in Examples 1 and 3 and Comparative Examples 1 and 2, and the color after 1 hour was observed.
(Acetaldehyde exposure test)
50 mg of the powder sample obtained in Example 1 and Comparative Examples 1, 2, and 3 was exposed to 500 ml of 700 ppm acetaldehyde-containing air, and the color after 2 hours was observed.
(Repetitive use evaluation)
The color after the reagent (color A) subjected to the acetaldehyde exposure test was heated at 170 ° C. for 3 hours was observed (color B). Moreover, the acetaldehyde exposure test was performed again and the color was observed (color C).
（試験結果）
表１ アセトアルデヒド水溶液滴下試験
Table 1 Acetaldehyde drop test
表２ ギ酸滴下試験
表３ 酢酸滴下試験
表４ アセトアルデヒド曝露試験
表５ くりかえし使用評価
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| JPH0221869A (en) * | 1988-07-11 | 1990-01-24 | Takeda Chem Ind Ltd | Deodorizer incorporating use life indicating function |
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