JP2008086436A - Deodorizing filter - Google Patents
Deodorizing filter Download PDFInfo
- Publication number
- JP2008086436A JP2008086436A JP2006268681A JP2006268681A JP2008086436A JP 2008086436 A JP2008086436 A JP 2008086436A JP 2006268681 A JP2006268681 A JP 2006268681A JP 2006268681 A JP2006268681 A JP 2006268681A JP 2008086436 A JP2008086436 A JP 2008086436A
- Authority
- JP
- Japan
- Prior art keywords
- group
- solid
- deodorizing
- filter
- deodorizing filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001877 deodorizing effect Effects 0.000 title claims abstract description 59
- -1 hydroxy amine compound Chemical class 0.000 claims abstract description 80
- 239000007787 solid Substances 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
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- 238000004438 BET method Methods 0.000 claims description 2
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- 239000007789 gas Substances 0.000 abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 14
- 239000000194 fatty acid Substances 0.000 abstract description 14
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- 150000004665 fatty acids Chemical class 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
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- 239000000835 fiber Substances 0.000 description 27
- 235000019645 odor Nutrition 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
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Abstract
Description
本発明は、消臭フィルターに関し、詳しくは室内その他の空間において発生するタバコ臭等の生活臭に含まれる悪臭を消臭する機能を持つ消臭フィルターに関する。 The present invention relates to a deodorizing filter, and more particularly to a deodorizing filter having a function of deodorizing bad odors included in daily odors such as tobacco odor generated in a room or other space.
近年の生活環境の質の高度化に伴い、住環境についてもより質の高い快適さが求められている。この結果、最近の気密性の高い家屋では快適さを向上させている反面、臭いがこもりやすく、タバコ臭、体臭、ペット臭、トイレ臭、高齢者介護に伴う匂い、乳児の匂いを取り除きたいという要望が強まってきている。そのため、室温を調整するために加熱・冷却した空気を循環させる機能を持つエアコンや空気清浄機を中心に、運転時に循環する空気に対し消臭機能を付与したものが多くなっている。これらの多くは活性炭吸着による活性炭フィルターにより働くものである。 With the advancement of the quality of living environment in recent years, higher quality comfort is also required for the living environment. As a result, the recent high-tightness houses have improved comfort, but the odor is likely to be trapped, cigarette odor, body odor, pet odor, toilet odor, smell associated with elderly care, and infant odor Requests are getting stronger. For this reason, air conditioners and air purifiers that function to circulate heated and cooled air to adjust the room temperature, and more, have added a deodorizing function to air circulated during operation. Many of these work by activated carbon filters with activated carbon adsorption.
しかしながら、活性炭のみのフィルターは、臭気分子を吸着することによって脱臭するが、吸着量に限界があるため、吸着量が飽和すると活性炭に吸着した臭気分子は平衡によって脱離して再放出されるという問題が生じる。また、タバコの臭気には、アンモニア、アセトアルデヒド、低級脂肪酸、硫化水素等が含まれており、これらの臭気分子の中でも、特に多く含まれるアセトアルデヒド等のアルデヒド系のガスに対しては、活性炭フイルターでは脱臭性能が低いという問題点があった。 However, activated carbon-only filters deodorize by adsorbing odor molecules, but because the amount of adsorption is limited, when the adsorption amount is saturated, the odor molecules adsorbed on the activated carbon are desorbed by equilibrium and re-released. Occurs. In addition, the odor of tobacco contains ammonia, acetaldehyde, lower fatty acids, hydrogen sulfide, etc. Among these odor molecules, especially for the aldehyde gas such as acetaldehyde, which is abundantly contained, the activated carbon filter is used. There was a problem that the deodorizing performance was low.
アルデヒド系のガスに対する消臭剤としては、ジエタノールアミン等のエタノールアミンを用いる技術がある（例えば特許文献１）。しかし、アミン類は一般に特有の臭を有し、空気清浄機用のフィルターとしての使用には適さない。 As a deodorant for aldehyde gas, there is a technique using ethanolamine such as diethanolamine (for example, Patent Document 1). However, amines generally have a characteristic odor and are not suitable for use as a filter for an air cleaner.
従って、本発明は、種々の臭気成分、特にアルデヒド系ガスや低級脂肪酸等に対して効果的に安定した消臭性能を発揮する消臭フィルターを提供することを課題とする。 Accordingly, an object of the present invention is to provide a deodorizing filter that exhibits a stable deodorizing performance effectively against various odor components, particularly aldehyde-based gases and lower fatty acids.
本発明者らは、特定のヒドロキシアミン化合物を担持させた固体より構成される消臭フィルターが、上記課題を解決する上で極めて有効であることを見出し、本発明を完成するに到った。 The present inventors have found that a deodorizing filter composed of a solid on which a specific hydroxyamine compound is supported is extremely effective in solving the above problems, and have completed the present invention.
即ち、本発明は、下記一般式（１）で表されるヒドロキシアミン化合物を担持させた固体より構成される消臭フィルターを提供することにより上記課題を解決したものである。 That is, this invention solves the said subject by providing the deodorizing filter comprised from the solid which carry | supported the hydroxyamine compound represented by following General formula (1).
本発明によれば、種々の臭気成分、特にアルデヒド系ガスや低級脂肪酸等に対して効果的に安定した消臭性能を発揮する消臭フィルターを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the deodorizing filter which exhibits the stable deodorizing performance effectively with respect to various odor components, especially aldehyde type gas, a lower fatty acid, etc. can be provided.
以下、本発明の好ましい実施の形態に基づいて詳細に説明する。
本発明の消臭フィルターは、上記一般式（１）で表されるヒドロキシアミン化合物が担持された固体より構成される。
上記一般式（１）において、Ｒ1は、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基を示す。
上記炭素数１〜５のアルキル基は、直鎖又は分岐鎖のいずれであってもよく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基が挙げられる。
また、上記炭素数１〜５のヒドロキシアルキル基としては、ヒドロキシメチル基、２−ヒドロキシエチル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基、２−ヒドロキシブチル基、３−ヒドロキシブチル基、４−ヒドロキシブチル基等が挙げられる。
Ｒ1は、消臭性能及び入手性の観点から、上記の中では水素原子、メチル基、エチル基、ヒドロキシメチル基、２−ヒドロキシエチル基が好ましく、特に水素原子、ヒドロキシメチル基、２−ヒドロキシエチル基が好ましい。
Hereinafter, it demonstrates in detail based on preferable embodiment of this invention.
The deodorizing filter of this invention is comprised from the solid by which the hydroxyamine compound represented by the said General formula (1) was carry | supported.
In the general formula (1), R 1 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and various pentyl groups. .
Moreover, as said C1-C5 hydroxyalkyl group, a hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4 -A hydroxybutyl group etc. are mentioned.
R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, or a 2-hydroxyethyl group from the viewpoint of deodorizing performance and availability, and particularly a hydrogen atom, a hydroxymethyl group, or 2-hydroxy An ethyl group is preferred.
Ｒ2は、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基を示す。
上記炭素数１〜６のアルキル基は、直鎖状、分岐鎖状、環状のいずれであってもよく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
上記炭素数１〜５のヒドロキシアルキル基としては、上記Ｒ1の説明で例示したものが挙げられる。
Ｒ2は、消臭性能及び入手性の観点から、上記の中では水素原子、炭素数１〜３のアルキル基、ヒドロキシエチル基が好ましく、特に水素原子が好ましい。
Ｒ3及びＲ4は、炭素数１〜５のアルカンジイル基を示す。Ｒ3及びＲ4は、同一でも異なっていてもよい。炭素数１〜５のアルカンジイル基としては、メチレン基、エチレン基、トリメチレン基、プロパン−１，２−ジイル基、テトラメチレン基等が挙げられ、特にメチレン基が好ましい。
R 2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyls. Groups, various hexyl groups, cyclopentyl groups, cyclohexyl groups and the like.
Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include those exemplified in the description of R 1 above.
From the viewpoints of deodorizing performance and availability, R 2 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyethyl group, and particularly preferably a hydrogen atom.
R 3 and R 4 represent an alkanediyl group having 1 to 5 carbon atoms. R 3 and R 4 may be the same or different. Examples of the alkanediyl group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, and a tetramethylene group, and a methylene group is particularly preferable.
本発明に係る上記一般式（１）で表されるヒドロキシアミン化合物の具体例としては、例えば、２−アミノ−１，３−プロパンジオール、２−アミノ−２−メチル−１，３−プロパンジオール、２−アミノ−２−エチル−１，３−プロパンジオール、２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール、２−アミノ−２−ヒドロキシエチル−１，３−プロパンジオール、４−アミノ−４−ヒドロキシプロピル−１，７−ヘプタンジオール、２−（Ｎ−エチル）アミノ−１，３−プロパンジオール、２−（Ｎ−エチル）アミノ−２−ヒドロキシメチル−１，３−プロパンジオール、２−（Ｎ−デシル）アミノ−１，３−プロパンジオール、２−（Ｎ−デシル）アミノ−２−ヒドロキシメチル−１，３−プロパンジオール等が挙げられる。
これらの中では、消臭性能等の観点から、２−アミノ−１，３−プロパンジオール、２−アミノ−２−メチル−１，３−プロパンジオール、２−アミノ−２−エチル−１，３−プロパンジオール、２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール（トリス（ヒドロキシメチル）アミノメタン）、２−アミノ−２−ヒドロキシエチル−１，３−プロパンジオールから選ばれる１種以上が特に好ましい。
上記のヒドロキシアミン化合物は、単独で又は２種以上を混合して用いることができる。
Specific examples of the hydroxyamine compound represented by the general formula (1) according to the present invention include, for example, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol. 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, 4- Amino-4-hydroxypropyl-1,7-heptanediol, 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2-hydroxymethyl-1,3-propanediol 2- (N-decyl) amino-1,3-propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol, and the like. That.
Among these, from the viewpoint of deodorizing performance and the like, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3 One or more selected from propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol (tris (hydroxymethyl) aminomethane), 2-amino-2-hydroxyethyl-1,3-propanediol Is particularly preferred.
Said hydroxyamine compound can be used individually or in mixture of 2 or more types.
本発明の消臭フィルターを構成する固体には、さらに界面活性剤を含む消臭液を担持させることが好ましい。
上記消臭液は、本発明に係るヒドロキシアミン化合物を固体に担持させる前に、該ヒドロキシアミン化合物を均一に分散させるために調製される。
具体的には、水、溶剤、界面活性剤、多価アルコール類、ｐＨ調整剤等を溶解した消臭液が挙げられる。
界面活性剤や多価アルコール類は、水分保持効果が高く、本発明に係るヒドロキシアミン化合物の消臭効果を持続的に発現させることができる。
The solid constituting the deodorizing filter of the present invention preferably further carries a deodorizing liquid containing a surfactant.
The deodorizing liquid is prepared to uniformly disperse the hydroxyamine compound before the hydroxyamine compound according to the present invention is supported on a solid.
Specifically, a deodorizing solution in which water, a solvent, a surfactant, a polyhydric alcohol, a pH adjuster and the like are dissolved can be mentioned.
Surfactants and polyhydric alcohols have a high moisture retention effect and can continuously develop the deodorizing effect of the hydroxyamine compound according to the present invention.
上記界面活性剤としては、非イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤、陰イオン界面活性剤が挙げられる。
具体的には、非イオン界面活性剤としては、アルキルグリコシド、エチレン又はプロピレンオキサイド付加のポリオキシアルキレンアルキルエーテル、ポリオキシエチレンアルキルエステル、ポリオキシエチレングリセリド、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルアミド、アルキルアルカノールアミド等が挙げられる。
これらの中では、ポリオキシエチレンアルキルエーテルやアルキルアルカノールアミドが好ましい。
Examples of the surfactant include nonionic surfactants, cationic surfactants, amphoteric surfactants, and anionic surfactants.
Specifically, as the nonionic surfactant, alkylglycoside, ethylene or propylene oxide-added polyoxyalkylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene glyceride, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Examples include fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, and alkyl alkanol amides.
Among these, polyoxyethylene alkyl ether and alkyl alkanolamide are preferable.
陽イオン界面活性剤としては、第１級アミン塩、第２級アミン塩、第３級アミン塩、第４級アンモニウム塩が挙げられる。これらの中では、第４級アンモニウム塩が好ましい。 Examples of the cationic surfactant include primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts. Of these, quaternary ammonium salts are preferred.
両性界面活性剤としては、アルキルジメチルアミンオキサイド等（アルキルアミド型を含む）のアミンオキサイド型、ラウリルアミノ脂肪酸ベタインなどのアルキルベタイン型、アルキルジメチルアミノ脂肪酸ベタイン型、ラウロイルアミドプロピルベタインなどのアミドベタイン型、２−アルキル−Ｎ−カルボキシメチルイミダゾリニウムベタイン、２−アルキル−Ｎ−カルボキシエチルイミダゾリニウムベタイン、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニウムベタイン等のイミダゾリン型、Ｎ−２−ヒドロキシエチル−Ｎ−２−ラウリン酸アミドエチル−β−アラニン、Ｎ−２−ヒドロキシエチル−Ｎ−２−ヤシ油脂肪酸アミドエチル−β−アラニンなどのアミドアミン型、アルキルジエチレントリアミノ酢酸塩型等が挙げられる。
これらの中では、アルキルジメチルアミンオキシドが好ましく、例えばラウリルアミドプロピルアミン−Ｎ，Ｎ−ジメチル−Ｎ−オキサイド、ラウリルジメチルアミンオキサイド等が挙げられる。
Amphoteric surfactants include amine oxide types such as alkyldimethylamine oxide (including alkylamide type), alkylbetaine types such as laurylamino fatty acid betaine, alkyldimethylamino fatty acid betaine types, and amide betaine types such as lauroylamidopropylbetaine. Imidazoline type such as 2-alkyl-N-carboxymethylimidazolinium betaine, 2-alkyl-N-carboxyethylimidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N Amidoamine type such as 2-hydroxyethyl-N-2-lauric acid amidoethyl-β-alanine, N-2-hydroxyethyl-N-2-coconut oil fatty acid amidoethyl-β-alanine, alkyldiethylene triami Nonacetate type and the like.
Among these, alkyldimethylamine oxide is preferable, and examples thereof include laurylamidopropylamine-N, N-dimethyl-N-oxide and lauryldimethylamine oxide.
陰イオン界面活性剤としては、エチレン又はプロピレンオキサイド付加のポリオキシアルキレンアルキルエーテル硫酸ナトリウム、アルキル硫酸ナトリウム、ポリオキシエチレンアルキルエーテルリン酸カリウム、アルケニルコハク酸ジカリウム、アルカンスルホン酸ナトリウム、脂肪酸ナトリウム石鹸、脂肪酸カリウム石鹸等が挙げられる。
上記界面活性剤の中では、前記の非イオン界面活性剤及び両性界面活性剤が特に好ましい。
用いられる界面活性剤の量の比率は、ヒドロキシアミン１ｇに対して、好ましくは０．０５〜２ｇ、更に好ましくは０．１〜１ｇである。
Anionic surfactants include ethylene or propylene oxide added polyoxyalkylene alkyl ether sodium sulfate, sodium alkyl sulfate, polyoxyethylene alkyl ether potassium phosphate, alkenyl succinate dipotassium, alkane sulfonate sodium, fatty acid sodium soap, fatty acid A potassium soap etc. are mentioned.
Among the surfactants, the nonionic surfactant and the amphoteric surfactant are particularly preferable.
The ratio of the amount of the surfactant used is preferably 0.05 to 2 g, more preferably 0.1 to 1 g with respect to 1 g of hydroxyamine.
上記多価アルコール類としては、例えば、グリセリン、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等が挙げられる。これらの中では、グリセリン、ジエチレングリコール、ジプロピレングリコールが好ましい。
用いられる多価アルコール類の量の比率は、ポリヒドロキシアミン１ｇに対して、好ましくは０．１〜２ｇである。
Examples of the polyhydric alcohols include glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol. Among these, glycerin, diethylene glycol, and dipropylene glycol are preferable.
The ratio of the amount of polyhydric alcohol used is preferably 0.1 to 2 g with respect to 1 g of polyhydroxyamine.
上記ｐＨ調整剤としては、酸又は塩基を添加することにより調整することができる。
酸としては、塩酸、硫酸、硝酸、リン酸、乳酸、コハク酸、リンゴ酸、クエン酸等が挙げられる。塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム等が挙げられ、水酸化ナトリウム、水酸化カリウムが好ましい。
消臭液を調製する上で、好ましくはｐＨ６．０〜１２である。 ｐＨ６以上で脂肪酸類、アルデヒドに対する消臭効果が高くなる。ｐＨ１０以上にするとさらに硫化水素に対する消臭効果が高くなる。ｐＨ９．５以下でアミンに対する消臭効果が高まる。
種々の生活臭の全てに対する効果、及び皮膚刺激低減の観点から、より好ましくはｐＨ７．０〜１０である。
As said pH adjuster, it can adjust by adding an acid or a base.
Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, lactic acid, succinic acid, malic acid, citric acid and the like. Examples of the base include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like, and sodium hydroxide and potassium hydroxide are preferable.
In preparing the deodorant liquid, the pH is preferably 6.0 to 12. When the pH is 6 or higher, the deodorizing effect on fatty acids and aldehydes is enhanced. When the pH is 10 or more, the deodorizing effect on hydrogen sulfide is further increased. The deodorizing effect with respect to amine increases at pH 9.5 or less.
The pH is preferably 7.0 to 10 from the viewpoint of the effect on all of the various life odors and the reduction of skin irritation.
＜ヒドロキシアミン化合物を担持させる固体＞
本発明に係るヒドロキシアミン化合物を担持させる固体の材質は、有機物、無機物のいずれであっても良い。
有機物の具体例として、木炭、竹炭、わら炭、活性炭、デキストリン、セルロース、発泡セルロース、カルボキシメチルセルロース、ポリビニルアルコール、アルギン酸ゲル、カラギーナンゲル、ポリエステル樹脂、ポリメタクリル酸系樹脂、ポリアクリル酸系樹脂、ジビニルベンゼン系樹脂、スチレン系樹脂、ウレタン樹脂などがあり、
無機物の具体例として、シリカ、シリカゲル、ケイ酸カルシウム、ゼオライト、ハイシリカゼオライト（疎水性ゼオライト）、酸化アルミニウム（アルミナ）、酸化銅、酸化チタン、酸化鉄、酸化銅、セピオライト、水和酸化ジルコニウム、雲母等がある。
<Solid on which a hydroxyamine compound is supported>
The solid material for supporting the hydroxyamine compound according to the present invention may be either organic or inorganic.
Specific examples of organic substances include charcoal, bamboo charcoal, straw charcoal, activated carbon, dextrin, cellulose, foamed cellulose, carboxymethylcellulose, polyvinyl alcohol, alginic acid gel, carrageenan gel, polyester resin, polymethacrylic acid resin, polyacrylic acid resin, divinyl. There are benzene resin, styrene resin, urethane resin, etc.
Specific examples of inorganic substances include silica, silica gel, calcium silicate, zeolite, high silica zeolite (hydrophobic zeolite), aluminum oxide (alumina), copper oxide, titanium oxide, iron oxide, copper oxide, sepiolite, hydrated zirconium oxide, There are mica.
さらに本発明に係るヒドロキシアミン化合物を担持する固体は比表面積の大きいものが好ましい。
上記固体の好ましい比表面積は、窒素吸着量から算出するＢＥＴ法による値として、１〜２０００ｍ2／ｇ、特に１０〜２０００ｍ2／ｇ、さらに５０〜２０００ｍ2／ｇである。
好ましい担持する固体名及び比表面積（かっこ内、ｍ2／ｇ）は、無機物では、シリカ（５０〜４００）、シリカゲル（５００〜７００）、ケイ酸カルシウム（１００〜１５０）、ゼオライト（４００〜７００）、ハイシリカゼオライト（３００〜７５０）、酸化アルミニム（１００〜３００）、セピオライト（２００〜４００）、酸化亜鉛（１〜３０）、酸化チタン（１〜３０）である。
有機物では活性炭（７００〜２０００）、発泡セルロース（１〜４０）である。
これらの中で特に好ましいのは、シリカ、シリカゲル、ケイ酸カルシウム、ゼオライト、酸化アルミニウム、セピオライト、活性炭、発泡セルロースである。
Further, the solid carrying the hydroxyamine compound according to the present invention preferably has a large specific surface area.
Preferred specific surface area of the solid, as a value measured by the BET method of calculating the amount of nitrogen adsorbed, 1~2000m 2 / g, especially 10~2000m 2 / g, a further 50~2000m 2 / g.
Preferred supported solid names and specific surface areas (in parentheses, m 2 / g) are silica (50 to 400), silica gel (500 to 700), calcium silicate (100 to 150), zeolite (400 to 700) in the case of inorganic substances. ), High silica zeolite (300 to 750), aluminum oxide (100 to 300), sepiolite (200 to 400), zinc oxide (1 to 30), and titanium oxide (1 to 30).
Among organic substances, activated carbon (700 to 2000) and foamed cellulose (1 to 40).
Of these, silica, silica gel, calcium silicate, zeolite, aluminum oxide, sepiolite, activated carbon, and foamed cellulose are particularly preferable.
本発明に係るヒドロキシアミン化合物を担持させる固体の形状は、粉体、顆粒状、破砕粒状、繊維状、シート状、網目状又はダンボール構造が挙げられる。 Examples of the solid shape on which the hydroxyamine compound according to the present invention is supported include powder, granule, crushed granule, fiber, sheet, network, or cardboard structure.
担持する固体が粉体、顆粒状、破砕粒状であった場合の大きさは１μ〜３０ｍｍ、好ましくは１０μ〜１０ｍｍ、さらに好ましくは３０μ〜５ｍｍである。 When the supported solid is powder, granular, or crushed, the size is 1 to 30 mm, preferably 10 to 10 mm, and more preferably 30 to 5 mm.
担持する固体が繊維状であった場合、活性炭繊維や、活性炭繊維よりなるシートが好ましい。 When the solid to be supported is fibrous, activated carbon fiber or a sheet made of activated carbon fiber is preferable.
本発明に係るヒドロキシアミン化合物を担持する固体の含水率は、好ましくは０．１〜４０重量％であり、より好ましくは８〜１５重量％である。粉体の含水率は、ＪＩＳ Ｋ７１２０〜７１２２に準じて容易に測定できる。 The water content of the solid carrying the hydroxyamine compound according to the present invention is preferably 0.1 to 40% by weight, more preferably 8 to 15% by weight. The moisture content of the powder can be easily measured according to JIS K7120-7122.
ヒドロキシアミン化合物の固体に対する担持量は、固体１ｇ当たり、ヒドロキシアミン化合物を、好ましくは０．０１〜３ｇであり、より好ましくは０．１〜２ｇである。担持量が少な過ぎると、アルデヒドガスなどの悪臭の吸収能が低く、担持量が多過ぎると、アルデヒドガスへの効果のみが高くなり、他の悪臭への効果が相対的に低下する。 The amount of the hydroxyamine compound supported on the solid is preferably 0.01 to 3 g, more preferably 0.1 to 2 g of the hydroxyamine compound per 1 g of the solid. When the loading amount is too small, the ability to absorb malodors such as aldehyde gas is low, and when the loading amount is too large, only the effect on aldehyde gas is high and the effect on other malodors is relatively lowered.
＜ヒドロキシアミン化合物を固体に担持させる方法＞
ヒドロキシアミン化合物を担持させる方法は、特に限定されないが、ヒドロキシアミン化合物を、水やエタノールに溶解や分散させて、担持させる固体と液状で混合し、加熱乾燥すれば容易に均一に担持できる。加熱温度は、例えば５０℃〜１２０℃で乾燥すれば、短時間で乾燥を終えることができる。
<Method for supporting a hydroxyamine compound on a solid>
The method for supporting the hydroxyamine compound is not particularly limited, but it can be easily and uniformly supported by dissolving or dispersing the hydroxyamine compound in water or ethanol, mixing the supported solid with a liquid, and drying by heating. If the heating temperature is, for example, 50 ° C. to 120 ° C., the drying can be completed in a short time.
本発明に係るヒドロキシアミン化合物は、アルデヒドや低級脂肪酸、硫化水素等のガスに対して有効であり、特にアルデヒド系ガスに対して有効である。すなわち、アセトアルデヒドを含むタバコ臭、ノネナール、ノナナールを含む体臭や加齢臭、デカジエナールなどを含む加熱調理油のニオイなどに有効である。対象とするガスによって、その他の消臭剤と併用することも可能である The hydroxyamine compound according to the present invention is effective for gases such as aldehydes, lower fatty acids, and hydrogen sulfide, and is particularly effective for aldehyde-based gases. That is, it is effective for the smell of tobacco cooking oil containing acetaldehyde, nonenal, body odor containing nonanal, aging odor, cooking oil odor including decadienal and the like. Depending on the target gas, it can be used in combination with other deodorants.
その他の消臭剤の例としては、
酸化鉄、硫酸鉄、塩化鉄、酸化亜鉛、硫酸亜鉛、塩化亜鉛、酸化銀、酸化銅等の金属化合物、
乳酸、コハク酸、リンゴ酸、クエン酸、マレイン酸、マロン酸、エチレンジアミンポリ酢酸、アルカン・アルケン−１，２−ジカルボン酸、シクロアルカン・アルケン−１，２−ジカルボン酸、ナフタレンスルホン酸等のカルボン酸類
ウンデシレン酸亜鉛、２−エチルヘキサン酸亜鉛、リシノール亜鉛などの脂肪酸金属類、カテキン、ポリフェノール、緑茶抽出物、マッシュルームエキス、木酢液、竹酢液等の植物抽出物系の消臭剤、
鉄、銅などの金属クロロフィリンナトリウム、鉄、銅、コバルトなどの金属フタロシアニン、鉄、銅、コバルト等のテトラスルホン酸フタロシアニン等、二酸化チタン、可視光応答型ニ酸化チタン（窒素ドープ型など）の触媒型消臭剤、
α、β、γ―シクロデキストリン、そのメチル誘導体、ヒドロキシプロピル誘導体、グルコシル誘導体、マルトシル誘導体等のシクロデキストリン類、
ミリスチン酸エステル類、パルミチン酸エステル類、フタル酸エステル類、アジピン酸エステル類、セバシン酸エステル類、クエン酸エステル類等の悪臭の保留効果があるとされるエステル油剤、
アクリル酸ポリマー、マレイン酸ポリマー、ナフタレンスルホン酸ホルマリン縮合物、芳香族スルフォン酸ホルマリン縮合物等のポリマー、
多孔メタクリル酸ポリマー、多孔アクリル酸ポリマー等のアクリル酸系ポリマー、多孔ジビニルベンゼンポリマー、多孔スチレン−ジビニルベンゼンービニルピリジンポリマー、多孔ジビニルベンゼンービニルピリジンポリマー等の芳香族系ポリマー、それらの共重合体等の合成の多孔質ポリマー、
キチン、キトサン等の天然の多孔質ポリマー、
シリカ、二酸化ケイ素（シリカゲル）、ケイ酸カルシウム、ハイシリカゼオライト（疎水性ゼオライト）、セピオライト、カンクリナイト、ゼオライト、水和酸化ジルコニウム等の無機多孔質物質、
銀担持ゼオライト、銀担持カンクリナイト、銀担持多孔スチレン−ジビニルベンゼンービニルピリジンポリマー等金属担持多孔質、
これらその他の消臭剤は、単独で用いても良く、さらに組み合わせて使うこともできる。
Examples of other deodorants include
Metal compounds such as iron oxide, iron sulfate, iron chloride, zinc oxide, zinc sulfate, zinc chloride, silver oxide, copper oxide,
Carboxyl such as lactic acid, succinic acid, malic acid, citric acid, maleic acid, malonic acid, ethylenediamine polyacetic acid, alkane alkene-1,2-dicarboxylic acid, cycloalkane alkene-1,2-dicarboxylic acid, naphthalenesulfonic acid, etc. Acids Fatty acid metals such as zinc undecylenate, zinc 2-ethylhexanoate, and ricinol zinc, catechin, polyphenol, green tea extract, mushroom extract, wood extract, bamboo vinegar and other plant extract deodorants,
Metal chlorophyllin sodium such as iron and copper, metal phthalocyanine such as iron, copper and cobalt, tetrasulfonic acid phthalocyanine such as iron, copper and cobalt, etc., titanium dioxide, visible light responsive titanium dioxide (such as nitrogen doped type) catalyst Mold deodorant,
cyclodextrins such as α, β, γ-cyclodextrin, its methyl derivatives, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives,
Ester oils that are said to have an effect of retaining bad odors such as myristic acid esters, palmitic acid esters, phthalic acid esters, adipic acid esters, sebacic acid esters, citrate esters,
Polymers such as acrylic acid polymer, maleic acid polymer, naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate,
Acrylic acid polymers such as porous methacrylic acid polymer and porous acrylic acid polymer, porous divinylbenzene polymer, porous styrene-divinylbenzene-vinylpyridine polymer, aromatic polymer such as porous divinylbenzene-vinylpyridine polymer, and copolymers thereof Synthetic porous polymer, etc.
Natural porous polymers such as chitin and chitosan,
Inorganic porous materials such as silica, silicon dioxide (silica gel), calcium silicate, high silica zeolite (hydrophobic zeolite), sepiolite, cancrinite, zeolite, hydrated zirconium oxide,
Metal-supported porous materials such as silver-supported zeolite, silver-supported cancrinite, silver-supported porous styrene-divinylbenzene-vinylpyridine polymer,
These other deodorants may be used alone or in combination.
他の機能性の剤、例えば抗菌剤、防カビ剤、抗ウイルス剤、昆虫忌避剤、香料等も各種用途に応じて組み合わせて使うことができる。 Other functional agents such as antibacterial agents, fungicides, antiviral agents, insect repellents, fragrances and the like can be used in combination according to various applications.
本発明の消臭フィルターの代表的な構成としては、本発明に係るヒドロキシアミン化合物をフィルターである繊維に直接担持したもの、及び本発明に係るヒドロキシアミン化合物を担持した固体をフィルターである繊維に固定化したもの等が挙げられる。 As a typical structure of the deodorizing filter of the present invention, a hydroxyamine compound according to the present invention is directly supported on a fiber that is a filter, and a solid that supports the hydroxyamine compound according to the present invention is a fiber that is a filter. Immobilized ones are listed.
消臭フィルターに使用される繊維の材質は、合成樹脂繊維、無機繊維、不織布、天然パルプ、紙、和紙等、あるいはこれらの複合物が挙げられる。 Examples of the fiber material used in the deodorizing filter include synthetic resin fibers, inorganic fibers, non-woven fabrics, natural pulp, paper, Japanese paper, and the like, or composites thereof.
合成樹脂繊維としては具体的には、ポリプロピレン繊維、ポリエチレン繊維、ポリエチレンテレフタレート繊維、ポリ塩化ビニル繊維、ポリスチレン繊維等が挙げられる。
無機繊維としては具体的には、アルミナ繊維、活性炭繊維、炭素繊維、ガラス繊維、ジルコニア繊維、アルミナ・シリカ繊維等が挙げられる。
不織布としては具体的には、スパンボンド法、メルトブロー法、遠心力法、フラッシュ紡糸法、高電圧乾式紡糸法、フィルム法等の直接製布法、エアレイ法、カード法、ガーネット機（反毛機）法等の乾式法、抄紙と同様の湿式法により製造される不織布が挙げられ、繊維間の結合方法としては接着剤法、熱融着法、超音波接着法、ニードルパンチ法、スパンレース法、ステッチボンド法等が挙げられる。
天然パルプとしては具体的には、木材パルプ、靭皮繊維、葦パルプ、バガスパルプ、ワラパルプ、竹パルプ等が挙げられる。
紙としては具体的には、複雑紙、薄葉紙（例えば、ティシュペーパー、トイレットペーパー、ナプキン、タオル紙及び生理紙）、包装紙、塗工紙（例えば、アート紙、コート）、非塗工紙、印刷紙、図面紙、ラミネート紙等があり、板紙としては、ダンボール構造紙、ハニカム構造紙、白板紙、黄板紙、チップボール紙、コルゲート紙、紙幣原紙及び台紙等が挙げられる。
繊維以外にも、樹脂、金属、活性炭等のフィルム、シート等の成形品を使用することも可能である。
Specific examples of the synthetic resin fiber include polypropylene fiber, polyethylene fiber, polyethylene terephthalate fiber, polyvinyl chloride fiber, and polystyrene fiber.
Specific examples of the inorganic fiber include alumina fiber, activated carbon fiber, carbon fiber, glass fiber, zirconia fiber, and alumina / silica fiber.
Specific examples of non-woven fabric include spunbonding, melt-blowing, centrifugal force, flash spinning, high-voltage dry spinning, direct spinning such as film, airlay, card, garnet ) And other non-woven fabrics produced by wet methods similar to papermaking. Adhesive method, thermal fusion method, ultrasonic bonding method, needle punch method, spunlace method And stitch bond method.
Specific examples of natural pulp include wood pulp, bast fiber, straw pulp, bagasse pulp, straw pulp, bamboo pulp and the like.
Specific examples of paper include complex paper, thin paper (for example, tissue paper, toilet paper, napkin, towel paper and physiological paper), wrapping paper, coated paper (for example, art paper, coat), non-coated paper, There are printing paper, drawing paper, laminate paper, and the like. Examples of the paperboard include cardboard structured paper, honeycomb structured paper, white paperboard, yellow paperboard, chipboard paper, corrugated paper, banknote base paper, and backing paper.
In addition to fibers, it is also possible to use molded articles such as films, sheets of resins, metals, activated carbon and the like.
本発明のヒドロキシアミン化合物を担持した固体より構成される消臭フィルターを作成する方法は、１．ヒドロキシアミン化合物をフィルターの繊維等に直接担持する方法、２．フィルターに担持用の固体を固定化した後に、ヒドロキシアミン化合物を固体に担持する方法、３．ヒドロキシアミン化合物を担持用の固体に担持した後に、固体をフィルターに固定化する方法が挙げられる。これらの方法について以下に具体的に説明する。 A method for producing a deodorizing filter composed of a solid carrying a hydroxyamine compound of the present invention is as follows. 1. a method for directly supporting a hydroxyamine compound on a fiber of a filter; 2. a method of supporting a hydroxyamine compound on a solid after immobilizing the support solid on the filter; An example is a method of immobilizing a solid on a filter after the hydroxyamine compound is supported on the supporting solid. These methods will be specifically described below.
＜１．ヒドロキシアミン化合物をフィルターの繊維等に直接担持する方法＞
ヒドロキシアミン化合物をフィルターに直接担持する方法として、例えば、後加工で担持させる場合には、ヒドロキシアミン化合物を含有した消臭液を、塗布、吹き付け、含浸等の方法でフィルターを構成する活性炭繊維などの多孔質繊維表面に付着させ、水や溶媒を除去することによりフィルター表面に担持することができる。
<1. Method of directly supporting a hydroxyamine compound on a filter fiber>
As a method of directly supporting the hydroxyamine compound on the filter, for example, when supporting it by post-processing, an activated carbon fiber constituting the filter by a method such as coating, spraying, impregnation, etc., with a deodorizing liquid containing the hydroxyamine compound It can be carried on the surface of the filter by attaching it to the surface of the porous fiber and removing water and solvent.
＜２．フィルターに担持用の固体を固定化した後に、ヒドロキシアミン化合物を固体に担持する方法＞
抄紙法などにおいて予めヒドロキシアミン化合物を担持可能な固体を固定化した後に、最終乾燥工程の直前に、ヒドロキシアミン化合物を含んだ消臭液を、塗布、吹き付け、含浸して乾燥させる。
<2. Method of supporting hydroxyamine compound on solid after fixing supporting solid on filter>
After immobilizing a solid capable of supporting a hydroxyamine compound in a papermaking method or the like, a deodorizing solution containing the hydroxyamine compound is applied, sprayed, impregnated and dried immediately before the final drying step.
抄紙工程自体は公知の方法に従って行えばよく、例えば、所定の割合で担持用の固体、パルプ及びバインダーを含むスラリーに、カチオン性及びアニオン性の凝集剤をそれぞれ全スラリー重量の５重量%以下添加して凝集体を生成する。次いで、この凝集体を公知の方法によって抄紙を行うと共に、これを温度１００〜１９０℃で乾燥させることにより、担持用の固体が固定化された紙を得ることができる。 The paper making process itself may be carried out in accordance with a known method. For example, a cationic and anionic flocculant is added in an amount of 5% by weight or less of the total slurry weight to a slurry containing a supporting solid, pulp and binder at a predetermined ratio To produce aggregates. Next, the aggregate is subjected to papermaking by a known method, and dried at a temperature of 100 to 190 ° C., thereby obtaining a paper on which a supporting solid is fixed.
好ましいカチオン性の無機凝集剤として、硫酸アルミニウム、水酸化亜鉛等があり、好ましいカチオン性有機凝集剤として、カチオン性デンプン、ポリアクリルアミド−カチオン性モノマー共重合体、ポリビニルベンジルトリメチル、アンモニウムクロライド、ポリビニルピリジン塩、縮合型高分子凝集剤としての陽性ポリアミド、水溶性尿素樹脂、ポリチオ尿素塩、陽性ポリ尿素、ポリアミノトリアゾール、アミン−エピクロルヒドリン重縮合物塩、アンモニアエピクロルヒドリン重縮合部塩等があり、好ましいアニオン性有機凝集剤として、重合型高分子のカルボキシル−メチル−スターチ（ＣＭＳ）、カルボキシル−メチル−セルロース（ＣＭＣ）、ポリアクリルアミド−カチオン性モノマー共重合体、ポリスチレンスルホン酸ナトリウム、マレイン酸共重合体等がある。尚、上記以外の凝集剤としてポリアクリルアミド系等のノニオン系或いは両性凝集剤も使用することができる。 Preferred cationic inorganic flocculants include aluminum sulfate and zinc hydroxide, and preferred cationic organic flocculants include cationic starch, polyacrylamide-cationic monomer copolymer, polyvinylbenzyltrimethyl, ammonium chloride, and polyvinylpyridine. Salt, positive polyamide as condensation polymer flocculant, water-soluble urea resin, polythiourea salt, positive polyurea, polyaminotriazole, amine-epichlorohydrin polycondensate salt, ammonia epichlorohydrin polycondensation salt, etc., preferable anionic As organic flocculants, polymerization type polymer carboxyl-methyl-starch (CMS), carboxyl-methyl-cellulose (CMC), polyacrylamide-cationic monomer copolymer, polystyrene sulfonate sodium Beam, there is a maleic acid copolymers. Non-ionic or amphoteric flocculants such as polyacrylamide can be used as flocculants other than those described above.
上記バインダーとしては以下のものがある。すなわち、天然樹脂、天然樹脂誘導体、フェノール樹脂、キシレン樹脂、尿素樹脂、メラミン樹脂、ケトン樹脂、クマロン・インデン樹脂、石油樹脂、テルペン樹脂、環化ゴム、塩化ゴム、アルキド樹脂、ポリアミド樹脂、ポリ塩化ビニル、アクリル樹脂、塩化ビニル、酢酸ビニル共重合樹脂、ポリ酢酸ビニル、ポリビニルアルコール、ポリビニルブチラール、塩素化ポリプロピレン、スチレン樹脂、エポキシ樹脂、ウレタン及びセルロース誘導体等である。尚、アルミナ繊維等の無機繊維を用いる場合、紙100重量部あたり５重量部以内のＮＢＲラテックスあるいはＳＢＲラテックス等の結合剤を併用することが好ましい。
次に、この紙をヒドロキシアミン化合物を溶解した水溶液に所定時間浸漬させたり、該水溶液を紙にスプレーして含浸させる等の方法で固体に担持させ、次いで乾燥させることで本発明のフィルターが得られる。担持させるヒドロキシアミン化合物の量は、水溶液の濃度、浸漬時間、スプレー量等で調整可能である。
Examples of the binder include the following. That is, natural resin, natural resin derivative, phenol resin, xylene resin, urea resin, melamine resin, ketone resin, coumarone / indene resin, petroleum resin, terpene resin, cyclized rubber, chlorinated rubber, alkyd resin, polyamide resin, polychlorinated resin Examples thereof include vinyl, acrylic resin, vinyl chloride, vinyl acetate copolymer resin, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, chlorinated polypropylene, styrene resin, epoxy resin, urethane, and cellulose derivatives. When inorganic fibers such as alumina fibers are used, it is preferable to use a binder such as NBR latex or SBR latex within 5 parts by weight per 100 parts by weight of paper.
Next, the filter of the present invention is obtained by immersing this paper in an aqueous solution in which a hydroxyamine compound is dissolved for a predetermined time, or by supporting the aqueous solution on a solid by spraying the paper to impregnate the paper, followed by drying. It is done. The amount of the hydroxyamine compound to be supported can be adjusted by the concentration of the aqueous solution, the immersion time, the spray amount, and the like.
＜３．ヒドロキシアミン化合物を担持用の固体に担持した後に、フィルターに固定化する方法＞
前記＜ヒドロキシアミン化合物を担持させる固体＞及び前記＜ヒドロキシアミン化合物を固体に担持させる方法＞にて記載したヒドロキシアミン化合物が担持された固体を、フィルターを構成する不織布などの表面に、散布、充填した後、不織布などでサンドイッチ状に挟み込んで固定化する。また、その際に、固定化を確実にするためにバインダー溶液を散布することができる。多くの層で積層することによってフィルター中のヒドロキシアミン化合物の増やすことができる。
<3. Method of Immobilizing Hydroxyamine Compound on Supporting Solid and then Immobilizing on Filter>
Scattering and filling the solid supported with the hydroxyamine compound described in the above <Solid for supporting a hydroxyamine compound> and <Method for supporting a hydroxyamine compound on a solid> on the surface of a nonwoven fabric constituting a filter After that, it is sandwiched between non-woven fabrics and fixed. At that time, a binder solution can be sprayed to ensure fixation. By laminating with many layers, the hydroxyamine compound in the filter can be increased.
本発明の消臭フィルター中におけるヒドロキシアミン化合物の担持量は、好ましくは１ｇ〜２０００ｇ／ｍ2、更に好ましくは、１０〜１０００ｇ／ｍ2である。 The amount of the hydroxyamine compound supported in the deodorizing filter of the present invention is preferably 1 g to 2000 g / m 2 , more preferably 10 to 1000 g / m 2 .
本発明の消臭フィルターの形態は、パイプ、ハニカム、箱、巻き物、袋および折り紙で作られる各種形態等がある。 The form of the deodorizing filter of the present invention includes various forms made of pipes, honeycombs, boxes, rolls, bags and origami.
本発明の消臭フィルターは、空気清浄機やエアコンに搭載する際には、粒子除去を目的とするＨＥＰＡフィルターのなどのフィルターや、抗菌、抗ウィルスを目的とカテキンフィルターなどのフィルターと一体化することもできる。 The deodorizing filter of the present invention is integrated with a filter such as a HEPA filter for the purpose of removing particles, or a filter such as a catechin filter for the purpose of antibacterial and antiviral when mounted on an air cleaner or an air conditioner. You can also.
本発明の消臭剤の用途として、タバコ臭、体臭、調理油臭、排泄物臭などの生活悪臭の消臭効果が望まれる分野で利用可能であり、
電力を使うものとして家庭用、施設用、自動車用の空気清浄機、エアコンディショナー、電池式の据え置き消臭剤、コンセントイン方式の消臭機など、
電力を使わないものとして家庭用、施設用の換気口取り付けタイプの消臭フィルター、据え置き型の消臭剤などに有用である。
As a use of the deodorant of the present invention, it can be used in fields where the deodorizing effect of life malodor such as tobacco odor, body odor, cooking oil odor, excrement odor is desired,
For households, facilities, automobiles, air cleaners, air conditioners, battery-powered deodorants, outlet-in deodorizers, etc.
It is useful for household and facility use as a deodorant filter with a ventilation opening, and a stationary deodorant, as it does not use electricity.
以下、実施例及び比較例により本発明を更に詳細に説明する。しかしながら、本発明は以下の実施例等により制限されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples.
＜抄紙タイプフィルター＞
（実施例１）
＜原料組成物配合＞
ガラス繊維 ６．０ｇ
微粉活性炭（粒径４５μｍ、比表面積：１０００ｍ2／ｇ） ４．８ｇ
ポリビニアルコール（ＰＶＡ）繊維 １．２ｇ
上記配合の原料組成物を１リットルの水に分散し、原料組成物１００重量部に対し、凝集剤としてカルボキシメチルセルロースナトリウム２．０重量部、及びポリアミドアミンエピクロロヒドリン樹脂０．８重量部を添加し、原料スラリーを得た。
そして、ＪＩＳ Ｐ８２０９に準じてシートマシン及び８０ｍｅｓｈ抄紙ネットを用いて抄紙を行い、回転型乾燥機を用いて、含水率が１質量％以下となるように乾燥を行った。得られたシートの坪量はおおよそ１７０ｇ／ｍ2前後であった。その後、トリス（ヒドロキシメチル）アミノメタン３．５％溶液（ｐＨ１０．５）を含浸させ、回転型乾燥機を用いて乾燥を行い、抄紙タイプの消臭フィルターを試作した。この際の、トリス（ヒドロキシメチル）アミノメタン添着量は添着前フィルターの２０％であった。尚、作成した抄紙タイプの消臭フィルタの概略構成を図１に示す。
<Paper making type filter>
(Example 1)
<Combination of raw material composition>
Glass fiber 6.0g
Fine activated carbon (particle size 45 μm, specific surface area: 1000 m 2 / g) 4.8 g
Polyvinyl alcohol (PVA) fiber 1.2g
The raw material composition having the above composition was dispersed in 1 liter of water, and 100 parts by weight of the raw material composition was mixed with 2.0 parts by weight of sodium carboxymethylcellulose as a flocculant and 0.8 parts by weight of polyamidoamine epichlorohydrin resin. This was added to obtain a raw material slurry.
Then, paper was made using a sheet machine and an 80 mesh paper making net according to JIS P8209, and dried using a rotary dryer so that the water content was 1% by mass or less. The basis weight of the obtained sheet was approximately 170 g / m 2 . Thereafter, tris (hydroxymethyl) aminomethane 3.5% solution (pH 10.5) was impregnated and dried using a rotary drier to produce a paper-making type deodorizing filter. At this time, the amount of tris (hydroxymethyl) aminomethane added was 20% of the pre-attached filter. In addition, the schematic structure of the created papermaking type deodorizing filter is shown in FIG.
（比較例１）
トリス（ヒドロキシメチル）アミノメタン溶液を含浸させないこと以外は、実施例１と同様の方法にてガラス繊維、微粉活性炭（４５μｍ）、ＰＶＡ繊維を用いて抄紙タイプの消臭フィルターを作成した。
(Comparative Example 1)
A papermaking type deodorizing filter was prepared using glass fiber, finely divided activated carbon (45 μm), and PVA fiber in the same manner as in Example 1 except that the tris (hydroxymethyl) aminomethane solution was not impregnated.
＜消臭試験方法＞
２つのプラスティック製５０ｍＬ注射筒（長さ１１ｃｍ×３ｃｍ、開口部の直径３ｃｍ）を用いて実施例１、比較例１の消臭フィルタ（６×４ｃｍ）を挟み込み固定した。注射筒の先端をシリコンチューブを介してパーミエーター（悪臭ガス発生装置；ガステック製）に接続し、悪臭ガスを０．２Ｌ／分の速度で流入後、ガスの入り口濃度とフィルター通過後の濃度を経時的に測定した。ガス濃度は、ガス検知管（ガステック製）を用いて測定し、入り口濃度との差分より消臭率（％）を求めた。ガスの入り口濃度はそれぞれアセトアルデヒド３０ｐｐｍ、酢酸４０ｐｐｍであった。試験結果を下記表１に示す。
<Deodorization test method>
The deodorizing filters (6 × 4 cm) of Example 1 and Comparative Example 1 were sandwiched and fixed using two plastic 50 mL syringes (length 11 cm × 3 cm, opening diameter 3 cm). Connect the tip of the syringe barrel to a permeator (smell gas generator; manufactured by Gastec) via a silicon tube, and then flow the malodorous gas at a rate of 0.2 L / min, then the gas inlet concentration and the concentration after passing through the filter. Was measured over time. The gas concentration was measured using a gas detector tube (manufactured by Gastec), and the deodorization rate (%) was determined from the difference from the inlet concentration. The gas inlet concentrations were 30 ppm acetaldehyde and 40 ppm acetic acid, respectively. The test results are shown in Table 1 below.
＜不織布タイプフィルター＞
（実施例２）
＜消臭液Ａ配合＞
２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール（トリス） １５質量％
３０％ラウリルアミドプロピルアミン−Ｎ，Ｎ−ジメチル−Ｎ−オキサイド １５質量％
ｐＨ調整剤（塩酸） 適量
イオン交換水 バランス
合計 １００質量％
微粉活性炭（粒径４５μｍ、比表面積：１０００ｍ2／ｇ）：消臭液Ａ＝１：６の割合で、消臭液A（ｐＨ９．５に調整）を微粉活性炭に含浸させ、１２０℃で２時間乾燥させることでトリス含有の消臭粉体を作成した。
上記トリス含有の消臭粉体をニードルパンチ不織布（ＰＥＴ繊維、ＰＰ／ＰＥ繊維混綿、６５ｇ／ｍ2）上に２８０ｇ／ｍ2相当積層し、一枚の消臭粉体を保持したシートを得る。このシートを６枚積層した後、メルトブローン不織布（ＰＰ樹脂製、１０ｇ／ｍ2）にて包み込み、更にニードルパンチ不織布（ＰＥＴ繊維、ＰＰ／ＰＥ繊維混綿、６５ｇ／ｍ2）にて包み込んだ後、積層した消臭粉体の外周部をヒートシールすることで一体化した不織布タイプの消臭フィルターを作成した。尚、作成した不織布タイプの消臭フィルターの概略構成を図２に示す。
<Nonwoven fabric type filter>
(Example 2)
<Deodorant A formulation>
2-Amino-2-hydroxymethyl-1,3-propanediol (Tris) 15% by mass
30% laurylamidopropylamine-N, N-dimethyl-N-oxide 15% by mass
pH adjuster (hydrochloric acid)
Ion exchange water balance
Total 100% by mass
Fine powder activated carbon (particle size 45 μm, specific surface area: 1000 m 2 / g): Deodorant liquid A (adjusted to pH 9.5) is impregnated in fine powder activated carbon at a ratio of deodorant liquid A = 1: 6, and 2 at 120 ° C. Tris-containing deodorized powder was prepared by drying for a period of time.
The tris-containing deodorant powder is laminated on a needle punched nonwoven fabric (PET fiber, PP / PE fiber blend cotton, 65 g / m 2 ) equivalent to 280 g / m 2 to obtain a sheet holding one deodorant powder. . After laminating 6 sheets of this sheet, it was wrapped with a melt blown nonwoven fabric (made of PP resin, 10 g / m 2 ), and further wrapped with a needle punch nonwoven fabric (PET fiber, PP / PE fiber mixed cotton, 65 g / m 2 ). A non-woven fabric type deodorizing filter integrated by heat-sealing the outer periphery of the laminated deodorant powder was prepared. In addition, the schematic structure of the produced nonwoven fabric type deodorizing filter is shown in FIG.
（比較例２）
実施例２の消臭粉体を全て等量の微粉活性炭（４５μｍ）で置き換えた他は、同様の方法にて不織布タイプの消臭フィルターを作成した。
(Comparative Example 2)
A non-woven fabric type deodorizing filter was prepared in the same manner except that all of the deodorizing powder in Example 2 was replaced with an equal amount of finely divided activated carbon (45 μm).
＜消臭試験方法＞
抄紙タイプフィルターの消臭試験方法と同様の方法で、さらに硫化水素（入り口濃度２０ｐｐｍ）に対する効果も加えて、実施例２、比較例２の消臭フィルターについて試験を行なった。試験結果を下記表２に示す。
<Deodorization test method>
The deodorization filters of Example 2 and Comparative Example 2 were tested in the same manner as the deodorization test method of the papermaking type filter, with the addition of an effect on hydrogen sulfide (inlet concentration 20 ppm). The test results are shown in Table 2 below.
＜ダンボール構造タイプフィルター＞
（実施例３〜５、比較例３及び４）
＜実施例及び比較例で使用する粉体もしくは顆粒状の固体＞
実施例３の粉体：２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール１５％水溶液：ケイ酸カルシウム（サイズ：１ｍｍ、比表面積：１３０ｍ2／ｇ）＝２：１の割合で、該水溶液をケイ酸カルシウムに含浸させ、１２０℃で２時間乾燥させた粉体。
実施例４の粉体：２−アミノ−２−エチル−１，３−プロパンジオール１５％水溶液：ケイ酸カルシウム（サイズ：１ｍｍ、比表面積：１３０ｍ2／ｇ）＝２：１の割合で、該水溶液をケイ酸カルシウムに含浸させ、１２０℃で２時間乾燥させた粉体。
実施例５の粉体：２−アミノ−２−メチル−１，３−プロパンジオール１５％水溶液：ケイ酸カルシウム（サイズ：１ｍｍ、比表面積：１３０ｍ2／ｇ）＝２：１の割合で、該水溶液をケイ酸カルシウムに含浸させ、１２０℃で２時間乾燥させた粉体。
比較例３の粉体：ジエタノールアミン１５％水溶液：ケイ酸カルシウム（サイズ１ｍｍ：比表面積１３０ｍ2／ｇ）＝２：１の割合で、該水溶液をケイ酸カルシウムに含浸させ、１２０℃で２時間乾燥させた粉体。
比較例４の固体：顆粒活性炭（３×５ｍｍ：比表面積１３００ｍ2／ｇ）のみを１２０℃で２時間乾燥させたもの。
上記方法により作成した粉体もしくは顆粒状の固体を、１ｃｍにスライスしたダンボール加工紙の中に充填した（各０．８ｇ）。脱落防止のためポリオレフィン製の不織布をスライス面に接着させ、ダンボール構造タイプのフィルターを作成した。尚、作成したダンボール構造タイプの消臭フィルターの模式図を図３に示す。
<Cardboard structure type filter>
(Examples 3-5, Comparative Examples 3 and 4)
<Powder or granular solid used in Examples and Comparative Examples>
Powder of Example 3: 2-amino-2-hydroxymethyl-1,3-propanediol 15% aqueous solution: calcium silicate (size: 1 mm, specific surface area: 130 m 2 / g) = 2: 1 Powder obtained by impregnating the aqueous solution with calcium silicate and drying at 120 ° C. for 2 hours.
Powder of Example 4: 2-amino-2-ethyl-1,3-propanediol 15% aqueous solution: calcium silicate (size: 1 mm, specific surface area: 130 m 2 / g) = 2: 1 Powder obtained by impregnating an aqueous solution with calcium silicate and drying at 120 ° C. for 2 hours.
Powder of Example 5: 2-amino-2-methyl-1,3-propanediol 15% aqueous solution: calcium silicate (size: 1 mm, specific surface area: 130 m 2 / g) = 2: 1 Powder obtained by impregnating an aqueous solution with calcium silicate and drying at 120 ° C. for 2 hours.
Powder of Comparative Example 3: Diethanolamine 15% aqueous solution: calcium silicate (size 1 mm: specific surface area 130 m 2 / g) = 2: 1 The aqueous solution was impregnated with calcium silicate and dried at 120 ° C. for 2 hours. Powder.
Solid of Comparative Example 4: Granular activated carbon (3 × 5 mm: specific surface area 1300 m 2 / g) only dried at 120 ° C. for 2 hours.
The powder or granular solid prepared by the above method was filled into corrugated cardboard paper sliced into 1 cm (each 0.8 g). A non-woven fabric made of polyolefin was bonded to the sliced surface to prevent falling off, and a cardboard structure type filter was made. In addition, the schematic diagram of the produced cardboard structure type deodorizing filter is shown in FIG.
＜消臭試験方法＞
ポリエステル製の３Ｌニオイ袋の中に、実施例３〜５、比較例３及び４で作成した消臭フィルター０．８ｇ分とアセトアルデヒドガスを注入し（袋内で５０ｐｐｍになる）、６０分放置する。ガス濃度をアセトアルデヒド用検知管にて測定し、ブランクとの差分から消臭率を求める。試験結果を下記表３に示す。
<Deodorization test method>
In a 3 L odor bag made of polyester, 0.8 g of the deodorizing filter prepared in Examples 3 to 5 and Comparative Examples 3 and 4 and acetaldehyde gas were injected (50 ppm in the bag) and left for 60 minutes. . The gas concentration is measured with an acetaldehyde detector tube, and the deodorization rate is obtained from the difference from the blank. The test results are shown in Table 3 below.
本発明の消臭フィルターは、表１〜３の結果から明らかなように、比較品であるトリス（ヒドロキシメチル）アミノメタンが担持されていない消臭フィルターに比べて、抄紙タイプ、不織布タイプ及びダンボール構造タイプの何れの形状においても、アセトアルデヒドの消臭性能に優れ、また経時的にも安定的な消臭性能を発揮することが確認された。 As is clear from the results of Tables 1 to 3, the deodorizing filter of the present invention is a papermaking type, non-woven fabric type and cardboard as compared with a deodorizing filter that does not carry tris (hydroxymethyl) aminomethane as a comparative product. It was confirmed that in any shape of the structure type, the deodorization performance of acetaldehyde was excellent and stable deodorization performance was exhibited over time.
（実施例６）
微粉シリカ（粒径１００μｍ、比表面積２００ｍ2／ｇ）：実施例２の消臭液Ａ＝１：６の割合で、該水溶液を微粉シリカに含浸させ、１２０℃で２時間乾燥させた粉体を、１ｃｍにスライスしたダンボール加工紙の中に充填した（各０．２ｇ）。脱落防止のためポリオレフィン製の不織布をスライス面に接着させ、ダンボール構造タイプのフィルターを作成した。
(Example 6)
Finely divided silica (particle size 100 μm, specific surface area 200 m 2 / g): powder obtained by impregnating the aqueous solution with finely divided silica at a ratio of deodorizing liquid A = 1: 6 in Example 2 and drying at 120 ° C. for 2 hours Were filled into corrugated cardboard paper sliced into 1 cm (0.2 g each). A non-woven fabric made of polyolefin was bonded to the sliced surface to prevent falling off, and a cardboard structure type filter was made.
＜他のアルデヒド系悪臭に対する消臭試験＞
他のアルデヒド系悪臭成分として、ノナナール（体臭）、ノネナール（加齢臭）、２，４−デカジエナール（加熱油臭）２μＬをヘッドスペースガスクロマトグラフ（ＨＳ-ＧＣ）用２０ｍＬバイアル瓶に入れる。さらに、本発明の消臭フィルターを０．２ｇを添加し密栓した後、ＨＳ-ＧＣを行った。なお、消臭剤なしで悪臭のみのサンプルをブランクとした。
試験結果を下記表４に示す。
<Deodorization test for other aldehyde odors>
As other aldehyde-based malodorous components, 2 μL of nonanal (body odor), nonenal (aged odor), and 2,4-decadienal (heated oil odor) are placed in a 20 mL vial for a headspace gas chromatograph (HS-GC). Furthermore, 0.2 g of the deodorizing filter of the present invention was added and sealed, and then HS-GC was performed. In addition, the sample of only a bad odor without a deodorizer was made into the blank.
The test results are shown in Table 4 below.
＜ＨＳ-ＧＣ分析条件＞
ＨＳ-オートサンプラー；ＰＥＲＫＩＮ ＥＬＭＥＲ製 ＨＳ４０ＸＬ
バイアル保温時間；３５℃３０分保温後、加圧２分、注入０．３分
ＧＣ；ＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ５８９０
カラム液相；（５％フェニル）メチルポリシロキサン 無極性
カラム長さ；３０ｍ、内径；０．３２ｍｍ、膜厚；０．２５μｍ
昇温条件；４０℃（８℃／分）-６０℃（４℃／分）-２００℃
消臭率（％）は下記〔数１〕により求めた。
<HS-GC analysis conditions>
HS-Autosampler; manufactured by PERKIN ELMER HS40XL
Vial incubation time: 35 ° C. for 30 minutes, pressurization 2 minutes, injection 0.3 minutes GC; HEWLETT PACKARD 5890
Column liquid phase: (5% phenyl) methylpolysiloxane Nonpolar Column length: 30 m, inner diameter: 0.32 mm, film thickness: 0.25 μm
Temperature rising conditions: 40 ° C (8 ° C / min) -60 ° C (4 ° C / min) -200 ° C
The deodorization rate (%) was determined by the following [Equation 1].
本発明の消臭フィルターは、表４の結果から明らかなように、他のアセトアルデヒド系ガスにおいても優れた消臭性能を発揮することが確認された。 As is clear from the results in Table 4, the deodorizing filter of the present invention was confirmed to exhibit excellent deodorizing performance even in other acetaldehyde-based gases.
１ ガラス繊維
２ ヒドロキシアミン化合物が担持された活性炭
３ Needle Punch製法による不織布（ポリオレフィン系＋PET繊維）
４ Melt Blown製法による不織布（ポリオレフィン系繊維）
５ ヒドロキシアミン化合物が担持された活性炭
６ ヒドロキシアミン化合物が担持されたケイ酸カルシウム
1 Glass fiber 2 Activated carbon loaded with a hydroxyamine compound 3 Nonwoven fabric produced by Needle Punch (polyolefin-based + PET fiber)
4 Nonwoven fabric (polyolefin fiber) by Melt Blown manufacturing method
5 Activated carbon loaded with a hydroxyamine compound 6 Calcium silicate loaded with a hydroxyamine compound
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