JP2009268510A - Antibacterial deodorant - Google Patents
Antibacterial deodorant Download PDFInfo
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本発明は抗菌性能と併せて揮発性有機化合物（ＶＯＣ）を分解することのできる抗菌消臭剤に関する。特に、ＶＯＣが含酸素有機化合物、なかでもアルデヒド基（−ＣＨＯ）を有する有機化合物の分解性能に優れた抗菌消臭剤に関する。 The present invention relates to an antibacterial deodorant capable of decomposing volatile organic compounds (VOC) in combination with antibacterial performance. In particular, the present invention relates to an antibacterial deodorant excellent in decomposing performance of an oxygen-containing organic compound, particularly an organic compound having an aldehyde group (—CHO).
近年、清潔志向、衛生志向、安全志向、快適志向等生活環境の向上が求められている。
従来、シリカゲル、複合酸化物、酸化チタン等の粉末、あるいはコロイド粒子に抗菌性を有する銀、銅、亜鉛等の金属成分を担持した抗菌性組成物が知られている。
In recent years, improvement of living environment such as cleanliness, hygiene, safety, and comfort has been demanded.
Conventionally, an antibacterial composition in which a metal component such as silver, copper, or zinc having antibacterial properties is supported on a powder of silica gel, composite oxide, titanium oxide, or colloidal particles is known.
例えば、本願出願人は無機酸化物コロイド粒子に抗菌性金属成分を付着せしめた抗菌剤（特開平６−８０５２７号公報：特許文献１）あるいはメタ珪酸アルミン酸マグネシウムに抗菌性を有する金属イオンをイオン交換した抗菌剤（特開平３−２７５６２７号公報：特許文献２）を開示している。
抗菌効果の持続性および抗菌物質の安定性を改善する目的で、抗菌性の金属イオンをゼオライトあるいはアルミノ珪酸塩に担持した抗菌性組成物も知られている（特開平１−２８３２０４号公報：特許文献３）。
For example, the applicant of the present application ionizes an antibacterial agent in which an antibacterial metal component is attached to inorganic oxide colloidal particles (Japanese Patent Laid-Open No. 6-80527: Patent Document 1) or metal ions having antibacterial properties in magnesium metasilicate aluminate. An exchanged antibacterial agent (JP-A-3-275627: Patent Document 2) is disclosed.
An antibacterial composition in which an antibacterial metal ion is supported on zeolite or aluminosilicate for the purpose of improving the durability of the antibacterial effect and the stability of the antibacterial substance is also known (Japanese Patent Laid-Open No. 1-283204: Patent). Reference 3).
また、本願出願人は、金属成分と該金属成分以外の無機酸化物とから構成される無機酸化物微粒子であって、前記無機酸化物が酸化チタンとシリカおよび／またはジルコニアとを含んでなり、該酸化チタンが結晶性酸化チタンである抗菌性消臭剤を開示している（特開２００５−３１８９９９号公報：特許文献４）。この抗菌性消臭剤は抗菌性能の他、揮発性有機化合物（ＶＯＣ）の分解による消臭性能を有することを開示している。 Further, the applicant of the present invention is an inorganic oxide fine particle composed of a metal component and an inorganic oxide other than the metal component, and the inorganic oxide comprises titanium oxide and silica and / or zirconia, An antibacterial deodorant in which the titanium oxide is crystalline titanium oxide is disclosed (Japanese Patent Laid-Open No. 2005-318999: Patent Document 4). It is disclosed that this antibacterial deodorant has a deodorizing performance due to decomposition of a volatile organic compound (VOC) in addition to the antibacterial performance.
この抗菌性消臭剤は、使用条件、対象臭気成分よってはさらに消臭性能の向上が求められている。
また、建材等に含まれるホルムアルデヒド、煙草喫煙時に発生するアセトアルデヒドは健康被害をもたらすといわれている。
The antibacterial deodorant is required to further improve the deodorizing performance depending on the use conditions and the target odor component.
Formaldehyde contained in building materials and acetaldehyde generated when smoking cigarettes are said to cause health damage.
これに対して、化学吸着剤により揮発性有機化合物（ＶＯＣ）の一種であるアルデヒド化合物を選択的に化学吸着により捕捉して悪臭、有害成分を低減させることも知られており、吸着剤（大塚化学（株）製、ケムキャッチＨ−６０００ＨＳ）が市販されている。
しかしながら、吸着による方法は飽和吸着量に近くなると吸着性能がなくなり、新規な吸着剤を補充したり取り替える必要がある。
また、当該吸着剤は対象臭気成分がアルデヒド化合物に限定されており、他の臭気成分例えば臭気性窒素化合物、臭気性硫黄化合物等に対して有用でなく、加えて、抗菌性能は有しておらず、生活環境の向上への寄与が限定的とならざるを得なかった。
On the other hand, it is also known that a chemical adsorbent selectively captures an aldehyde compound, which is a kind of volatile organic compound (VOC), by chemical adsorption to reduce malodor and harmful components. Chemical Co., Ltd., Chemcatch H-6000HS) is commercially available.
However, when the adsorption method is close to the saturated adsorption amount, the adsorption performance is lost, and it is necessary to replenish or replace a new adsorbent.
In addition, the adsorbent has a target odor component limited to aldehyde compounds and is not useful for other odor components such as odorous nitrogen compounds and odorous sulfur compounds, and in addition, has no antibacterial performance. Therefore, the contribution to improving the living environment had to be limited.
本発明者等は鋭意検討した結果、酸化チタン微粒子に抗菌消臭成分を担持した無機コロイド系の抗菌消臭剤にアミノ基を有するシラン化合物を担持すると抗菌性能を低下させることなく、揮発性有機化合物（ＶＯＣ）の一種であるアルデヒド化合物に対する分解性能が格段に向上すること見出して本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that when a silane compound having an amino group is supported on an inorganic colloidal antibacterial deodorant in which an antibacterial deodorant component is supported on titanium oxide fine particles, volatile organic compounds are not degraded without reducing the antibacterial performance The present invention was completed by finding that the decomposition performance for an aldehyde compound which is a kind of the compound (VOC) is remarkably improved.
本発明は、抗菌機能、臭気性窒素化合物、臭気性硫黄化合物等に対する消臭性能に加えて揮発性有機化合物（ＶＯＣ）の一種であるアルデヒド化合物を効率的に分解することができる抗菌消臭剤を提供することを目的としている。 The present invention provides an antibacterial deodorant capable of efficiently decomposing an aldehyde compound which is a kind of volatile organic compound (VOC) in addition to an antibacterial function, an odorous nitrogen compound, an odorous sulfur compound and the like. The purpose is to provide.
本発明に係る抗菌消臭剤は、銀、銅、亜鉛、錫、コバルト、ニッケル、マンガンから選ばれる１種または２種以上の抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物とからなることを特徴としている。
前記酸化チタン系微粒子にアミン系化合物が担持されていてもよい。
前記アミン系化合物が、１級アミン、２級アミン、３級アミン、４級アンモニウム塩、４級アンモニウムハイドロオキサイド、またはアミノ基を有する有機化合物およびアミノ基を有するシラン化合物から選ばれる１種または２種以上であることが好ましい。
前記アミン系化合物の重量（ＷA）と抗菌消臭成分が担持された酸化チタン系微粒子の重量（ＷT）との重量比（ＷA）／（ＷT）が０．０１〜０．５の範囲にあることが好ましい。
The antibacterial deodorant according to the present invention comprises titanium oxide-based fine particles carrying an antibacterial deodorant component selected from silver, copper, zinc, tin, cobalt, nickel, and manganese, and an amine compound. It is characterized by consisting of.
An amine compound may be supported on the titanium oxide fine particles.
The amine compound is one or two selected from a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt, a quaternary ammonium hydroxide, an organic compound having an amino group, and a silane compound having an amino group. It is preferable that it is a seed or more.
Weight (W A) and the weight of the titanium oxide-based fine particles antimicrobial deodorant component is carried (W T) and the weight ratio of said amine compound (W A) / (W T ) is 0.01 to 0.5 It is preferable that it exists in the range.
前記酸化チタン系微粒子の平均粒子径が２〜３００ｎｍの範囲にあることが好ましい。
前記抗菌消臭成分の担持量が酸化チタン系微粒子中に酸化物として０．１〜２０重量％の範囲にあることが好ましい。
前記抗菌成分が亜鉛であることが好ましい。
対象臭気成分がアルデヒド基（−ＣＨＯ）を有する有機化合物であることが好ましい。
The average particle diameter of the titanium oxide-based fine particles is preferably in the range of 2 to 300 nm.
The supported amount of the antibacterial and deodorant component is preferably in the range of 0.1 to 20% by weight as an oxide in the titanium oxide fine particles.
The antibacterial component is preferably zinc.
The target odor component is preferably an organic compound having an aldehyde group (—CHO).
本発明によれば、抗菌機能を有する抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物を混合または担持して併用することにより、抗菌機能、臭気性窒素化合物、臭気性硫黄化合物等に対する消臭性能に加えて揮発性有機化合物（ＶＯＣ）の一種であるアルデヒド化合物を効率的に分解することができる抗菌消臭剤を提供することができる。
According to the present invention, antibacterial function, odorous nitrogen compound, odorous sulfur compound, etc. can be obtained by mixing or supporting and combining titanium oxide-based fine particles carrying an antibacterial deodorant component having an antibacterial function and an amine compound. It is possible to provide an antibacterial deodorant capable of efficiently decomposing an aldehyde compound, which is a kind of volatile organic compound (VOC), in addition to the deodorizing performance against odor.
以下に、本発明に係る抗菌消臭剤について具体的に説明する。
本発明に係る抗菌消臭剤は、銀、銅、亜鉛、錫、コバルト、ニッケル、マンガンから選ばれる１種または２種以上の抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物とからなることを特徴としている。
Below, the antibacterial deodorant concerning this invention is demonstrated concretely.
The antibacterial deodorant according to the present invention comprises titanium oxide-based fine particles carrying an antibacterial deodorant component selected from silver, copper, zinc, tin, cobalt, nickel, and manganese, and an amine compound. It is characterized by consisting of.
酸化チタン系微粒子
本発明に用いる酸化チタン系微粒子としては酸化チタン微粒子、酸化チタン以外の酸化物を含む酸化チタン微粒子があり、該酸化チタン以外の酸化物としてはシリカおよび／またはジルコニアが挙げられる。
この時の酸化チタン系微粒子中の酸化チタンの含有量は５０重量％以上、さらには７０〜９５重量％の範囲にあることが好ましい。
酸化チタン系微粒子中の酸化チタンの含有量が５０重量％未満の場合は、充分な抗菌性能、消臭性能が得られないことがある。
Titanium oxide fine particles Titanium oxide fine particles used in the present invention include titanium oxide fine particles and titanium oxide fine particles containing an oxide other than titanium oxide. Examples of the oxide other than titanium oxide include silica and / or zirconia.
At this time, the content of titanium oxide in the titanium oxide-based fine particles is preferably 50% by weight or more, and more preferably in the range of 70 to 95% by weight.
When the content of titanium oxide in the titanium oxide fine particles is less than 50% by weight, sufficient antibacterial performance and deodorizing performance may not be obtained.
シリカを含むことによって、酸化チタン系微粒子分散液の安定性が向上し、また耐光性、耐候性が向上する傾向がある。また、ジルコニアを含むことによって酸化チタン系微粒子分散液の安定性が向上し、また耐光性、耐候性が向上する傾向があり、抗菌成分の種類によっては変色を抑制することができる。
上記した酸化チタン系微粒子は、本願出願人による特開昭６３−１８５８２０号公報、特開２００５−３１８９９９号公報（特許文献４）等に開示した方法に準じて得ることができる。
By including silica, the stability of the titanium oxide-based fine particle dispersion is improved, and the light resistance and weather resistance tend to be improved. In addition, the inclusion of zirconia improves the stability of the titanium oxide-based fine particle dispersion and also tends to improve the light resistance and weather resistance. Discoloration can be suppressed depending on the type of antibacterial component.
The titanium oxide-based fine particles described above can be obtained according to the methods disclosed in Japanese Patent Application Laid-Open Nos. 63-185820 and 2005-318999 (Patent Document 4) by the applicant of the present application.
酸化チタン系微粒子は、平均粒子径が概ね２〜３００ｎｍ、さらには５〜２００ｎｍの範囲にあることが好ましい。
酸化チタン系微粒子の平均粒子径が２ｎｍ未満の場合は、酸化チタン系微粒子が凝集する傾向があり、また結晶性が不充分となることから得られる抗菌消臭剤の消臭性能、抗菌性能が不充分となることがある。
酸化チタン系微粒子の平均粒子径が３００ｎｍを越えると、有効な粒子の外部表面積の低下により消臭性能、抗菌性能が不充分となることがある。
The titanium oxide-based fine particles preferably have an average particle diameter in the range of about 2 to 300 nm, more preferably 5 to 200 nm.
When the average particle diameter of the titanium oxide-based fine particles is less than 2 nm, the titanium oxide-based fine particles tend to aggregate and the crystallinity becomes insufficient. It may be insufficient.
If the average particle diameter of the titanium oxide fine particles exceeds 300 nm, the deodorizing performance and antibacterial performance may be insufficient due to a decrease in the external surface area of the effective particles.
抗菌消臭成分
抗菌消臭成分としては銀、銅、亜鉛、錫、コバルト、ニッケル、マンガンから選ばれる１種または２種以上の抗菌成分を含むことが好ましい。なかでも銀または亜鉛は抗菌機能に加えて揮発性有機化合物（ＶＯＣ）の一種で、臭気成分の一種でもあるアルデヒド化合物を効率的に分解することができるので好ましい。
このような抗菌消臭成分はイオン、酸化物、水酸化物等の化合物またはこれらの混合物のいずれの形態で存在していてもよい。抗菌性の観点からはイオンの形態が好ましく、酸化物であれば消臭性にも優れた抗菌消臭剤が得られる。
Antibacterial deodorant component The antibacterial deodorant component preferably contains one or more antibacterial components selected from silver, copper, zinc, tin, cobalt, nickel, and manganese. Among them, silver or zinc is preferable because it can efficiently decompose an aldehyde compound which is a kind of volatile organic compound (VOC) and also a kind of odor component in addition to an antibacterial function.
Such an antibacterial deodorant component may be present in any form of compounds such as ions, oxides, hydroxides, or mixtures thereof. From the viewpoint of antibacterial properties, an ionic form is preferable, and if it is an oxide, an antibacterial deodorant excellent in deodorizing properties can be obtained.
また、抗菌消臭成分は酸化チタン系微粒子の表層に存在するか、酸化チタン系微粒子の内部まで比較的均一に分布していることが好ましい。
抗菌消臭成分を酸化チタン系微粒子に担持する方法としては、例えば前記特開２００５−３１８９９９号公報に開示した方法を採用することができる。
具体的には、例えば、負の電荷を有する酸化チタン微粒子が分散した分散液に、抗菌消臭性成分の金属塩水溶液を添加する方法が挙げられる。
The antibacterial deodorant component is preferably present in the surface layer of the titanium oxide-based fine particles or distributed relatively uniformly throughout the titanium oxide-based fine particles.
As a method for supporting the antibacterial and deodorant component on the titanium oxide-based fine particles, for example, the method disclosed in JP-A-2005-318999 can be employed.
Specifically, for example, a method of adding a metal salt aqueous solution of an antibacterial deodorant component to a dispersion in which titanium oxide fine particles having a negative charge are dispersed may be mentioned.
前記金属塩水溶液はアンミン錯塩水溶液が好ましい。アンミン錯塩水溶液を用いると酸化チタン系微粒子分散液の安定性を低下させたり、ゲル化させることなく長期にわたって安定な抗菌消臭剤を製造することができる。安定性が低下した抗菌消臭剤、ゲル化した抗菌消臭剤は用途が制限されたり、抗菌性能、消臭性能が不充分となることがある。
好適なアンミン錯塩水溶液は、例えば、酸化亜鉛、酸化銀あるいは酸化銅などをアンモニア水に溶解することによって、亜鉛、銀あるいは銅等のアンミン錯塩水溶液を調製することができる。
The metal salt aqueous solution is preferably an ammine complex salt aqueous solution. When an aqueous solution of an ammine complex salt is used, a stable antibacterial deodorant can be produced over a long period of time without lowering the stability of the titanium oxide fine particle dispersion or causing it to gel. The antibacterial deodorant with reduced stability and the gelled antibacterial deodorant may have limited applications or may have insufficient antibacterial and deodorant performance.
As a suitable aqueous solution of ammine complex salt, for example, an aqueous solution of ammine complex salt such as zinc, silver or copper can be prepared by dissolving zinc oxide, silver oxide or copper oxide in ammonia water.
なお、前記した方法での抗菌消臭剤の調製に際し、水を分散媒とする酸化チタン系微粒子分散液の濃度は酸化物として５重量％以下、好ましくは、０．５重量％〜３重量％の範囲にあることが好ましい。
前述の方法で得られた水を分散媒とする抗菌消臭成分を担持した酸化チタン微粒子分散液は、公知の方法、例えば限外濾過膜を用いて、所望の濃度に調整される。
また、上記抗菌消臭成分を担持した酸化チタン微粒子分散液の分散媒である水は公知の方法により有機溶媒と置換して、有機溶媒を分散媒とする分散液とすることも可能である。
In the preparation of the antibacterial deodorant by the above-described method, the concentration of the titanium oxide-based fine particle dispersion using water as a dispersion medium is 5% by weight or less, preferably 0.5% by weight to 3% by weight as an oxide. It is preferable that it exists in the range.
The titanium oxide fine particle dispersion liquid carrying the antibacterial deodorant component using water as a dispersion medium obtained by the above-described method is adjusted to a desired concentration using a known method, for example, an ultrafiltration membrane.
Further, water, which is a dispersion medium of the titanium oxide fine particle dispersion carrying the antibacterial and deodorant components, can be replaced with an organic solvent by a known method to obtain a dispersion using the organic solvent as a dispersion medium.
酸化チタン系微粒子中の抗菌消臭成分の含有量は酸化物として０．１〜２０重量％、さらには１〜１５重量％の範囲にあることが好ましい。
抗菌消臭成分の含有量が０．１重量％よりも少ない場合には充分な消臭性能および抗菌性能が得られにくい。
抗菌消臭成分の含有量が２０重量％よりも多い場合には、さらに消臭性能および抗菌性能が向上することもなく、むしろ抗菌成分が凝集するためかこれら性能が低下する場合がある。
The content of the antibacterial deodorizing component in the titanium oxide-based fine particles is preferably in the range of 0.1 to 20% by weight, more preferably 1 to 15% by weight as an oxide.
When the content of the antibacterial deodorant component is less than 0.1% by weight, it is difficult to obtain sufficient deodorant performance and antibacterial performance.
When the content of the antibacterial deodorant component is more than 20% by weight, the deodorant performance and the antibacterial performance are not further improved, but rather the performance may be decreased due to aggregation of the antibacterial component.
アミン系化合物
本発明に用いるアミン系化合物としては、１級アミン、２級アミン、３級アミン、４級アンモニウム塩、４級アンモニウムハイドロオキサイド、またはアミノ基を有する有機化合物およびアミノ基を有するシラン化合物から選ばれる１種または２種以上が挙げられる。
Amine-based compounds The amine-based compounds used in the present invention include primary amines, secondary amines, tertiary amines, quaternary ammonium salts, quaternary ammonium hydroxides, organic compounds having amino groups, and silane compounds having amino groups. 1 type (s) or 2 or more types selected from are mentioned.
具体的には、アスパラギン酸、グルタミン酸、リシン、アルギニン、ヒスチジン、グリシン、アラニン、バリン、ロイシン、イソロイシン、セリン、トレオニン、システイン、メチオニン、アスパラギン、グルタミン、プロリン、フェニルアラニン、チロシン、トリプトファンなどのアミノ酸、ペプチド、タンパク質；テトラメチルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラプロピルアンモニウムブロマイド、テトラメチルアンモニウムハイドロオキサイド；およびγ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−（フェニル）γ−アミノプロピルトリメトキシシラン等が挙げられる。 Specifically, amino acids and peptides such as aspartic acid, glutamic acid, lysine, arginine, histidine, glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, asparagine, glutamine, proline, phenylalanine, tyrosine, tryptophan Tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium bromide, tetramethylammonium hydroxide; and γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- (phenyl) γ-amino Trimethoxysilane, and the like.
本発明の抗菌消臭剤は前記抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物とからなることを特徴としている。
抗菌消臭剤は、抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物の混合物であってもよく、抗菌消臭成分が担持された酸化チタン系微粒子にアミン系化合物が担持された物であってもよい。
The antibacterial deodorant of the present invention is characterized by comprising titanium oxide-based fine particles carrying an antibacterial deodorant component and an amine compound.
The antibacterial deodorant may be a mixture of a titanium oxide fine particle carrying an antibacterial deodorant component and an amine compound, and the amine compound is carried on a titanium oxide fine particle carrying an antibacterial deodorant component. It may be a thing.
混合物の場合は、抗菌消臭成分が担持された酸化チタン系微粒子とアミン系化合物とを常法によって混合すればよく、例えば、酸化チタン系微粒子分散液にアミン系化合物が可溶性であれば、溶解して、また、不溶性であれば、懸濁して混合する。
また、抗菌消臭成分が担持された酸化チタン系微粒子にアミン系化合物が担持された物の場合は、例えば、抗菌消臭成分が担持された酸化チタン系微粒子分散液にアミン系化合物を溶解したり、アミン化合物水溶液を混合し、ついで、必要に応じて熟成し、ついで乾燥することによって担持することができる。
In the case of a mixture, the titanium oxide fine particles carrying the antibacterial deodorant component and the amine compound may be mixed by a conventional method. For example, if the amine compound is soluble in the titanium oxide fine particle dispersion, it is dissolved. If it is insoluble, suspend and mix.
In the case of an amine compound supported on a titanium oxide fine particle carrying an antibacterial deodorant component, for example, the amine compound is dissolved in a titanium oxide fine particle dispersion carrying an antibacterial deodorant component. Alternatively, it can be supported by mixing an aqueous amine compound solution, then aging if necessary, and then drying.
このときの、アミン系化合物の重量（ＷA）と抗菌消臭成分が担持された酸化チタン系微粒子の重量（ＷT）との混合重量比（ＷA）／（ＷT）が０．０１〜０．５、さらには０．０２〜０．３の範囲にあることが好ましい。
ここで、酸化チタン系微粒子の重量（ＷT）は固形分としての重量であり、アミン系化合物の重量（ＷA）は化合物としての重量である。
In this case, the mixing weight ratio of the weight (W A) and the weight of the titanium oxide-based fine particles antimicrobial deodorant component is carried (W T) of the amine compound (W A) / (W T ) is 0.01 It is preferable to be in the range of -0.5, more preferably 0.02-0.3.
Here, the weight (W T ) of the titanium oxide-based fine particles is a weight as a solid content, and the weight (W A ) of the amine-based compound is a weight as a compound.
混合重量比（ＷA）／（ＷT）が０．０１未満の場合は、アルデヒド化合物の吸着能力が低いために、抗菌消臭成分が担持された酸化チタン系微粒子によるアルデヒド化合物の分解も抑制され、本願発明のアルデヒド基（−ＣＨＯ）を有する有機化合物の除去性能が不充分となる場合がある。
混合重量比（ＷA）／（ＷT）が０．５を越えても抗菌消臭成分が担持された酸化チタン系微粒子によるアルデヒド化合物の分解性能が追随できないためか、アルデヒド基（−ＣＨＯ）を有する有機化合物の除去性能がさらに向上することもなく、むしろ、抗菌性能、他の臭気成分も含めて除去性能が低下する場合がある。
When the mixing weight ratio (W A ) / (W T ) is less than 0.01, the adsorption ability of the aldehyde compound is low, so that the decomposition of the aldehyde compound by the titanium oxide fine particles carrying the antibacterial deodorant component is also suppressed. In some cases, the removal performance of the organic compound having an aldehyde group (—CHO) of the present invention is insufficient.
Aldehyde group (—CHO) is probably because the decomposition performance of aldehyde compounds by titanium oxide-based fine particles carrying antibacterial deodorant components cannot follow even if the mixing weight ratio (W A ) / (W T ) exceeds 0.5. The removal performance of the organic compound having odor may not be further improved, but rather the removal performance may be deteriorated including antibacterial performance and other odor components.
本発明の抗菌消臭剤において抗菌の対象となる菌類としては、黄色ブドウ球菌、連鎖球菌、大腸菌、緑膿菌、プロテウス菌、肺炎桿菌、枯草菌等が挙げられる。
また、消臭の対象となる臭気成分としては、法定悪臭８物質（硫化水素、メチルメルカプタン、硫化メチル、二硫化ジメチル、アンモニア、トリメチルアミン、アセトアルデヒド、スチレン）、炭化水素、ケトン・アルデヒド、アルコール類、エステル類、窒素化合物、硫黄化合物、低級脂肪酸等が挙げられる。
Examples of fungi to be antibacterial in the antibacterial deodorant of the present invention include Staphylococcus aureus, Streptococcus, Escherichia coli, Pseudomonas aeruginosa, Proteus, Neisseria pneumoniae, Bacillus subtilis and the like.
The odor components that are subject to deodorization include eight legal malodorous substances (hydrogen sulfide, methyl mercaptan, methyl sulfide, dimethyl disulfide, ammonia, trimethylamine, acetaldehyde, styrene), hydrocarbons, ketones / aldehydes, alcohols, Examples include esters, nitrogen compounds, sulfur compounds, and lower fatty acids.
本発明の抗菌消臭剤は、特に揮発性有機化合物（ＶＯＣ）の分解除去に有効である。なかでも、含酸素有機化合物、例えば、アルコール類、アルデヒド類、ケトン類、エーテル類、エステル類等の分解除去に有効である。特に、一般式［Ｒ−ＣＨＯ］で表されるアルデヒド類の分解除去には有効である。
アルデヒド化合物としては、ホルムアルデヒド、アセトアルデヒド、グリセルアルデヒド、ベンズアルデヒド等が挙げられる。
以下に実施例を示し、本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。
The antibacterial deodorant of the present invention is particularly effective for decomposing and removing volatile organic compounds (VOC). Among these, it is effective for decomposing and removing oxygen-containing organic compounds such as alcohols, aldehydes, ketones, ethers and esters. In particular, it is effective for decomposing and removing aldehydes represented by the general formula [R-CHO].
Examples of the aldehyde compound include formaldehyde, acetaldehyde, glyceraldehyde, benzaldehyde and the like.
Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
抗菌消臭剤(1)の調製
酸化チタン微粒子（T-1）分散液の調製
塩化チタン水溶液を純水で希釈してＴiＯ2として濃度５重量％の塩化チタン水溶液を調製した。この水溶液を、温度を５℃に調節した濃度１５重量％のアンモニア水に添加して中和・加水分解した。塩化チタン水溶液添加後のｐＨは１０.５であった。ついで、生成したゲルを濾過洗浄し、ＴiＯ2として濃度１０重量％のオルソチタン酸のゲルを得た。
このオルソチタン酸のゲルを１２０℃で１６時間乾燥し、純水２９０００ｇに分散させた後、濃度３５重量％の過酸化水素水８０００ｇを加えてペルオキソチタン酸水溶液とした後、１６０℃で１６時間加熱し、ＴiＯ2としての濃度が３.０重量％の酸化チタン微粒子（T-1）分散液を調製した。
Preparation of antibacterial deodorant (1)
Preparation of Titanium Oxide Fine Particle (T-1) Dispersion A titanium chloride aqueous solution was diluted with pure water to prepare a titanium chloride aqueous solution having a concentration of 5% by weight as TiO 2 . This aqueous solution was neutralized and hydrolyzed by adding it to 15% by weight ammonia water whose temperature was adjusted to 5 ° C. The pH after addition of the aqueous titanium chloride solution was 10.5. Next, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 10% by weight as TiO 2 .
This orthotitanic acid gel was dried at 120 ° C. for 16 hours and dispersed in 29000 g of pure water, and then 8000 g of hydrogen peroxide solution having a concentration of 35% by weight was added to form a peroxotitanic acid aqueous solution, and then at 160 ° C. for 16 hours. By heating, a dispersion of titanium oxide fine particles (T-1) having a concentration of 3.0% by weight as TiO 2 was prepared.
消臭抗菌成分の担持
別途、硝酸銀(AgNO3)７．９ｇに水４９２．１ｇを加えて、濃度１．０重量％の硝酸銀水溶液を調製した。
ＴｉＯ2濃度を１．０重量％に調整した酸化チタン微粒子（T-1）分散液９．５ｋｇを調合タンクに採取し、これを攪拌しながら５０℃に加温した。ついで、酸化チタン微粒子（T-1）分散液のｐＨが９．０になるようにアンモニアを添加した後、前記硝酸銀水溶液をペリスターポンプで１０ｇ／ｍｉｎの速度で添加した。硝酸銀水溶液の添加により酸化チタン微粒子（T-1）分散液のｐＨが低下し始めたところで、陰イオン交換樹脂（三菱化学製）をｐＨ８．５に維持するように少量ずつ添加し、全硝酸銀水溶液の添加が終了するまで、この操作を継続した。陰イオン交換樹脂の全使用量は３１０ｇであり、また酸化チタン微粒子（T-1）分散液の最終ｐＨは８．１であった。
Separately carrying deodorant antibacterial components 492.1 g of water was added to 7.9 g of silver nitrate (AgNO 3 ) to prepare a silver nitrate aqueous solution having a concentration of 1.0% by weight.
9.5 kg of a titanium oxide fine particle (T-1) dispersion whose TiO 2 concentration was adjusted to 1.0% by weight was collected in a preparation tank and heated to 50 ° C. while stirring. Next, ammonia was added so that the pH of the titanium oxide fine particle (T-1) dispersion was 9.0, and then the aqueous silver nitrate solution was added at a rate of 10 g / min with a peristaltic pump. When the pH of the titanium oxide fine particle (T-1) dispersion began to drop due to the addition of the aqueous silver nitrate solution, anion exchange resin (Mitsubishi Chemical) was added in small portions so as to maintain the pH at 8.5. This operation was continued until the addition of was completed. The total amount of anion exchange resin used was 310 g, and the final pH of the titanium oxide fine particle (T-1) dispersion was 8.1.
酸化チタン微粒子（T-1）分散液からイオン交換樹脂を分離した後、冷却し、ついで、限外濾過膜装置でＴｉＯ2 重量に対して２００倍の水で洗浄した後、限外濾過膜装置で濃縮して、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液を得た。銀を担持した酸化チタン微粒子（T-1）中のＡｇ2Ｏの担持量は５．０重量％であった。
銀を担持した酸化チタン微粒子（T-1）の平均粒子径は、超遠心式自動粒度分布測定装置（ＣＡＰＡ−７００）で測定したところ、１０ｎｍであった。また、Ｘ線回折によりアナターゼ型であった。
The ion exchange resin is separated from the titanium oxide fine particle (T-1) dispersion, cooled, and then washed with 200 times the weight of TiO 2 in the ultrafiltration membrane device, and then the ultrafiltration membrane device. To obtain a titanium oxide fine particle (T-1) dispersion carrying silver having a solid concentration of 10% by weight. The supported amount of Ag 2 O in the titanium oxide fine particles (T-1) supporting silver was 5.0% by weight.
The average particle size of the titanium oxide fine particles (T-1) supporting silver was 10 nm as measured with an ultracentrifugal automatic particle size distribution analyzer (CAPA-700). It was anatase type by X-ray diffraction.
ついで、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液９００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(1)を調製した。 Next, 10 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 900 g of a dispersion of titanium oxide fine particles (T-1) supporting silver having a solid content concentration of 10% by weight. The antibacterial deodorant (1) was prepared by drying at 16 ° C. for 16 hours.
抗菌性能・消臭性能の評価
抗菌消臭剤(1)について、抗菌性能および消臭性能を以下の方法および基準で評価し、結果を表１に示した。
抗菌性能評価用試料の調製
抗菌消臭剤(1)６ｇ（乾燥粉末）と水系アクリル系樹脂（日本純薬製；ジュリマーＦＣ６５、濃度４０重量％）２０ｇとを混合して、抗菌性コート剤を調製した。このコート剤１．０ｇを１０ｃｍ×１０ｃｍのガラス板に厚さ１０μｍのバーコートを用いて塗布し、１００℃で乾燥して塗膜を形成し、抗菌性能評価用試料(1)とした。
Evaluation of antibacterial performance and deodorant performance The antibacterial and deodorant performance of the antibacterial deodorant (1) was evaluated by the following methods and standards. The results are shown in Table 1.
Preparation of antibacterial performance evaluation sample Antibacterial deodorant (1) 6g (dry powder) and aqueous acrylic resin (manufactured by Nippon Pure Chemicals; Julimer FC65, concentration 40% by weight) 20g are mixed to prepare an antibacterial coating agent. Prepared. 1.0 g of this coating agent was applied to a 10 cm × 10 cm glass plate using a 10 μm-thick bar coat, dried at 100 ° C. to form a coating film, and used as a sample (1) for antibacterial performance evaluation.
抗菌性の評価(JIS Z2801)
抗菌性能評価用試料(1)に菌懸濁液、０．４ｍｌを接種し、その上に被覆フイルムを被せて蓋をした後、３５±１℃、ＲＨ９０以上で２４時間放置後、菌懸濁液を回収して生菌数を測定し、次式（１）の殺菌活性値により抗菌性能を評価した。結果を表２に示した。
試験菌には、黄色ぶどう球菌、大腸菌、およびＭＲＳＡを用い、菌懸濁液の栄養として、肉エキス（３ｇ／Ｌ）＋ペプトン（１０ｇ／Ｌ）＋塩化ナトリウム（５ｇ／Ｌ）を１００倍に薄めたものを使用した。
殺菌活性値＝Ｌｏｇ（植菌数）−Ｌｏｇ（試験片生菌数）・・・（１）
Antibacterial evaluation (JIS Z2801)
Antimicrobial performance evaluation sample (1) was inoculated with 0.4 ml of bacterial suspension, covered with a coating film and covered, then left at 35 ± 1 ° C, RH90 or more for 24 hours, and then the bacterial suspension The liquid was collected, the number of viable bacteria was measured, and the antibacterial performance was evaluated by the bactericidal activity value of the following formula (1). The results are shown in Table 2.
Staphylococcus aureus, Escherichia coli, and MRSA are used as test bacteria. Meat extract (3 g / L) + peptone (10 g / L) + sodium chloride (5 g / L) is multiplied by 100 as nutrients for the bacterial suspension. A diluted one was used.
Bactericidal activity value = Log (number of inoculated bacteria)-Log (number of viable test pieces) (1)
消臭性の評価
５Lテトラパックに抗菌消臭剤（１）１ｇと、初期濃度１００ｐｐｍのアンモニア試験臭３L、初期濃度４ｐｐｍの硫化水素試験臭３L、初期濃度２０ｐｐｍのアセトアルデヒド試験臭３Ｌを各々封入して２時間放置した後、検知管にて試験臭濃度を測定し、次式（２）により消臭率を求めた。測定結果を表１に示す。
消臭率（％）＝１００×（初期濃度−２時間後の濃度）／初期濃度・・・（２）
なお、アセトアルデヒドの消臭性の評価では、紫外線を照射して、発生するＣＯ2濃度も表１に示した。
ＣＯ2発生量％＝ＣＯ2発生量／完全酸化された理論上のＣＯ2発生量×１００
Evaluation of deodorization 5L tetrapack is filled with 1g of antibacterial deodorant (1), 3L of ammonia test odor with initial concentration of 100ppm, 3L of hydrogen sulfide test odor with initial concentration of 4ppm, and 3L of acetaldehyde test odor with initial concentration of 20ppm. The test odor concentration was measured with a detector tube, and the deodorization rate was determined by the following formula (2). The measurement results are shown in Table 1.
Deodorization rate (%) = 100 × (initial concentration−concentration after 2 hours) / initial concentration (2)
In addition, in the evaluation of the deodorizing property of acetaldehyde, Table 1 also shows the CO 2 concentration generated by irradiating ultraviolet rays.
CO 2 emissions% = CO 2 generation amount / on fully oxidized stoichiometric amount of produced CO 2 × 100
抗菌消臭剤(2)の調製
実施例１において、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液９５０ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）５ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(2)を調製した。
抗菌性能・消臭性能の評価
抗菌消臭剤(2)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Preparation of antibacterial deodorant (2) In Example 1, an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch) was added to 950 g of a titanium oxide fine particle (T-1) dispersion supporting silver having a solid concentration of 10% by weight. 5 g of H-6000HS) was dissolved, and then dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (2).
Evaluation of antibacterial performance and deodorant performance The antibacterial and deodorant performance of the antibacterial deodorant (2) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(3)の調製
実施例１において、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液８００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）２０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(3)を調製した。
抗菌性能・消臭性能の評価
抗菌消臭剤(3)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Preparation of antibacterial deodorant (3) In Example 1, an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch) was added to 800 g of a titanium oxide fine particle (T-1) dispersion supporting silver having a solid concentration of 10% by weight. 20 g of H-6000HS) was dissolved, and then dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (3).
Evaluation of antibacterial performance and deodorant performance The antibacterial deodorant (3) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(4)の調製
実施例１において、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液９００ｇにアミン系化合物（三木理研工業（株）製：リケンレヂンＦＣ−３０）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(4)を調製した。
抗菌性能・消臭性能の評価
抗菌消臭剤(4)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Preparation of antibacterial deodorant (4) In Example 1, an amine compound (manufactured by Miki Riken Kogyo Co., Ltd .: Riken Resin) was added to 900 g of a titanium oxide fine particle (T-1) dispersion supporting silver having a solid concentration of 10% by weight. FC-30) 10 g was dissolved and then dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (4).
Evaluation of antibacterial performance / deodorant performance The antibacterial deodorant (4) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(5)の調製
実施例１と同様にして調製した固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液９００ｇを限外濾過膜法にてエタノールに溶媒置換し、これに、γ−アミノプロピルトリメトキシシラン（信越化学工業（株）製：ＫＢＭ９０３）１０ｇを加え、５０℃で加熱処理を行い、再び限外濾過膜を用いて溶媒をエタノールに置換した固形分濃度１０重量％の抗菌消臭剤(5)のアルコール分散液を調製し、ついで１２０℃で１６時間乾燥して抗菌消臭剤(5)を調製した。
Preparation of antibacterial deodorant (5) 900 g of titanium oxide fine particle (T-1) dispersion supporting silver having a solid content of 10% by weight prepared in the same manner as in Example 1 was made into ethanol by ultrafiltration membrane method. The solvent was replaced, 10 g of γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM903) was added thereto, heat treatment was performed at 50 ° C., and the solvent was replaced with ethanol again using an ultrafiltration membrane. An alcohol dispersion of the antibacterial deodorant (5) having a solid content concentration of 10% by weight was prepared, and then dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (5).
抗菌性能・消臭性能の評価
抗菌消臭剤(5)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance and deodorant performance The antibacterial and deodorant performance of the antibacterial deodorant (5) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(6)の調製
酸化チタン微粒子（T-2）分散液の調製
塩化チタン水溶液を純水で希釈してＴiＯ2として濃度５重量％の塩化チタン水溶液を調製した。この水溶液を、温度を５℃に調節した濃度１５重量％のアンモニア水に添加して中和・加水分解した。塩化チタン水溶液添加後のｐＨは１０.５であった。ついで、生成したゲルを濾過洗浄し、ＴiＯ2として濃度１０重量％のオルソチタン酸のゲルを得た。
このオルソチタン酸のゲル１０００ｇを純水２９０００ｇに分散させた後、濃度３５重量％の過酸化水素水８０００ｇを加えてペルオキソチタン酸水溶液とした後、攪拌しながら、８５℃で３時間加熱し、ＴiＯ2としての濃度が３.０重量％の酸化チタン微粒子（T-2）分散液を調製した。
Preparation of antibacterial deodorant (6)
Preparation of Titanium Oxide Fine Particle (T-2) Dispersion A titanium chloride aqueous solution was diluted with pure water to prepare a titanium chloride aqueous solution having a concentration of 5% by weight as TiO 2 . This aqueous solution was neutralized and hydrolyzed by adding it to 15% by weight ammonia water whose temperature was adjusted to 5 ° C. The pH after addition of the aqueous titanium chloride solution was 10.5. Next, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 10% by weight as TiO 2 .
After 1000 g of this orthotitanic acid gel was dispersed in 29000 g of pure water, 8000 g of a hydrogen peroxide solution having a concentration of 35% by weight was added to form a peroxotitanic acid aqueous solution, followed by heating at 85 ° C. for 3 hours while stirring. A dispersion of titanium oxide fine particles (T-2) having a concentration of 3.0% by weight as TiO 2 was prepared.
消臭抗菌成分の担持
別途、硝酸銀(AgNO3)７．９ｇに水４９２．１ｇを加えて、濃度１．０重量％の硝酸銀水溶液を調製した。
ＴｉＯ2濃度を１．０重量％に調整した酸化チタン微粒子（T-2）分散液９．５ｋｇを調合タンクに採取し、これを攪拌しながら５０℃に加温した。ついで、酸化チタン微粒子（T-2）分散液のｐＨが９．０になるようにアンモニアを添加した後、前記硝酸銀水溶液をペリスターポンプで１０ｇ／ｍｉｎの速度で添加した。硝酸銀水溶液の添加により酸化チタン微粒子（T-2）分散液のｐＨが低下し始めたところで、陰イオン交換樹脂（三菱化学製）をｐＨ８．５に維持するように少量ずつ添加し、全硝酸銀水溶液の添加が終了するまで、この操作を継続した。陰イオン交換樹脂の全使用量は３１０ｇであり、また酸化チタン微粒子（T-2）分散液の最終ｐＨは８．１であった。
Separately carrying deodorant antibacterial components 492.1 g of water was added to 7.9 g of silver nitrate (AgNO 3 ) to prepare a silver nitrate aqueous solution having a concentration of 1.0% by weight.
9.5 kg of a titanium oxide fine particle (T-2) dispersion whose TiO 2 concentration was adjusted to 1.0% by weight was collected in a preparation tank and heated to 50 ° C. while stirring. Next, ammonia was added so that the pH of the titanium oxide fine particle (T-2) dispersion was 9.0, and then the aqueous silver nitrate solution was added at a rate of 10 g / min with a peristaltic pump. When the pH of the titanium oxide fine particle (T-2) dispersion began to drop due to the addition of the aqueous silver nitrate solution, anion exchange resin (Mitsubishi Chemical) was added in small portions to maintain the pH at 8.5, and the total aqueous silver nitrate solution was added. This operation was continued until the addition of was completed. The total amount of anion exchange resin used was 310 g, and the final pH of the titanium oxide fine particle (T-2) dispersion was 8.1.
酸化チタン微粒子（T-2）分散液からイオン交換樹脂を分離した後、９５℃で３時間加熱後、冷却し、ついで、限外濾過膜装置でＴｉＯ2 重量に対して２００倍の水で洗浄した後、限外濾過膜装置で濃縮して、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-2）分散液を得た。銀を担持した酸化チタン微粒子（T-2）中のＡｇ2Ｏの担持量は５．０重量％であった。また、銀を担持した酸化チタン微粒子（T-2）の平均粒子径は５ｎｍであった。また、Ｘ線回折によりアモルファス型であった。 After separating the ion exchange resin from the titanium oxide fine particle (T-2) dispersion, heating at 95 ° C. for 3 hours, cooling, and then washing with 200 times water with respect to TiO 2 weight in an ultrafiltration membrane device. After that, it was concentrated with an ultrafiltration membrane device to obtain a titanium oxide fine particle (T-2) dispersion carrying silver having a solid concentration of 10% by weight. The supported amount of Ag 2 O in the titanium oxide fine particles (T-2) supporting silver was 5.0% by weight. The average particle diameter of the titanium oxide fine particles (T-2) supporting silver was 5 nm. Moreover, it was an amorphous type by X-ray diffraction.
ついで、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-2）分散液９００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(6)を調製した。 Next, 10 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 900 g of a dispersion of titanium oxide fine particles (T-2) supporting silver having a solid content concentration of 10% by weight. The antibacterial deodorant (6) was prepared by drying at 16 ° C. for 16 hours.
抗菌性能・消臭性能の評価
抗菌消臭剤(6)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance / deodorant performance The antibacterial deodorant (6) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(7)の調製
酸化チタン微粒子（T-3）分散液の調製
塩化チタン水溶液を純水で希釈してＴiＯ2として濃度５重量％の塩化チタン水溶液を調製した。この水溶液を、温度を５℃に調節した濃度１５重量％のアンモニア水に添加して中和・加水分解した。塩化チタン水溶液添加後のｐＨは１０.５であった。ついで、生成したゲルを濾過洗浄し、ＴiＯ2として濃度１０重量％のオルソチタン酸のゲルを得た。
このオルソチタン酸のゲルを２５０℃で１６時間乾燥し、純水２９０００ｇに分散させた後、濃度３５重量％の過酸化水素水８０００ｇを加えてペルオキソチタン酸水溶液とした後、攪拌しながら、８５℃で３時間加熱し、ＴiＯ2としての濃度が３.０重量％の酸化チタン微粒子（T-3）分散液を調製した。
Preparation of antibacterial deodorant (7)
Preparation of Titanium Oxide Fine Particle (T-3) Dispersion A titanium chloride aqueous solution was diluted with pure water to prepare a titanium chloride aqueous solution having a concentration of 5% by weight as TiO 2 . This aqueous solution was neutralized and hydrolyzed by adding it to 15% by weight ammonia water whose temperature was adjusted to 5 ° C. The pH after addition of the aqueous titanium chloride solution was 10.5. Next, the produced gel was washed by filtration to obtain an orthotitanic acid gel having a concentration of 10% by weight as TiO 2 .
This orthotitanic acid gel was dried at 250 ° C. for 16 hours and dispersed in 29000 g of pure water. Then, 8000 g of hydrogen peroxide having a concentration of 35% by weight was added to form a peroxotitanic acid aqueous solution. The mixture was heated at 0 ° C. for 3 hours to prepare a dispersion of titanium oxide fine particles (T-3) having a concentration of 3.0% by weight as TiO 2 .
消臭抗菌成分の担持
別途、硝酸銀(AgNO3)７．９ｇに水４９２．１ｇを加えて、濃度１．０重量％の硝酸銀水溶液を調製した。
ＴｉＯ2濃度を１．０重量％に調整した酸化チタン微粒子（T-3）分散液９．５ｋｇを調合タンクに採取し、これを攪拌しながら５０℃に加温した。ついで、酸化チタン微粒子（T-3）分散液のｐＨが９．０になるようにアンモニアを添加した後、前記硝酸銀水溶液をペリスターポンプで１０ｇ／ｍｉｎの速度で添加した。硝酸銀水溶液の添加により酸化チタン微粒子（T-1）分散液のｐＨが低下し始めたところで、陰イオン交換樹脂（三菱化学製）をｐＨ８．５に維持するように少量ずつ添加し、全硝酸銀水溶液の添加が終了するまで、この操作を継続した。陰イオン交換樹脂の全使用量は３１０ｇであり、また酸化チタン微粒子（T-3）分散液の最終ｐＨは８．１であった。
Separately carrying deodorant antibacterial components 492.1 g of water was added to 7.9 g of silver nitrate (AgNO 3 ) to prepare an aqueous silver nitrate solution having a concentration of 1.0 wt%.
9.5 kg of a titanium oxide fine particle (T-3) dispersion having a TiO 2 concentration adjusted to 1.0% by weight was collected in a preparation tank and heated to 50 ° C. while stirring. Next, ammonia was added so that the pH of the titanium oxide fine particle (T-3) dispersion was 9.0, and then the aqueous silver nitrate solution was added at a rate of 10 g / min with a peristaltic pump. When the pH of the titanium oxide fine particle (T-1) dispersion began to drop due to the addition of the aqueous silver nitrate solution, anion exchange resin (Mitsubishi Chemical) was added in small portions so as to maintain the pH at 8.5. This operation was continued until the addition of was completed. The total amount of anion exchange resin used was 310 g, and the final pH of the titanium oxide fine particle (T-3) dispersion was 8.1.
酸化チタン微粒子（T-3）分散液からイオン交換樹脂を分離した後、９５℃で３時間加熱後、冷却し、ついで、限外濾過膜装置でＴｉＯ2 重量に対して２００倍の水で洗浄した後、限外濾過膜装置で濃縮して、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-3）分散液を得た。銀を担持した酸化チタン微粒子（T-3）中のＡｇ2Ｏの担持量は５．０重量％であった。
銀を担持した酸化チタン微粒子（T-3）の平均粒子径は２０ｎｍであった。また、Ｘ線回折によりアモルファス型であった。
After separating the ion exchange resin from the titanium oxide fine particle (T-3) dispersion, heating at 95 ° C. for 3 hours, cooling, and then washing with 200 times water with respect to TiO 2 weight in an ultrafiltration membrane device. After that, it was concentrated with an ultrafiltration membrane device to obtain a dispersion of titanium oxide fine particles (T-3) carrying silver having a solid concentration of 10% by weight. The supported amount of Ag 2 O in the titanium oxide fine particles (T-3) supporting silver was 5.0% by weight.
The average particle diameter of the titanium oxide fine particles (T-3) supporting silver was 20 nm. Moreover, it was an amorphous type by X-ray diffraction.
ついで、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-3）分散液９００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(7)を調製した。 Next, 10 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 900 g of a dispersion of titanium oxide fine particles (T-3) supporting silver having a solid content concentration of 10% by weight. The antibacterial deodorant (7) was prepared by drying at 0 ° C. for 16 hours.
抗菌性能・消臭性能の評価
抗菌消臭剤(7)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance and deodorizing performance The antibacterial deodorizing agent (7) was evaluated for antibacterial performance and deodorizing performance in the same manner as in Example 1, and the results are shown in Table 1.
消臭抗菌剤(8)の調製
実施例１において、硝酸銀(AgNO3)の代わりに、硝酸亜鉛六水和物［Zn(NO3)2・6H2O］１９．８ｇに水４９２．１ｇを加えて、濃度１．０重量％の硝酸亜鉛水溶液を調製して使用した以外は同様にして、固形分濃度１０重量％の亜鉛を担持した酸化チタン微粒子（T-１）分散液を得た。亜鉛を担持した酸化チタン微粒子（T-１）中のＺｎＯの担持量は５．０重量％であった。
Preparation of Deodorant Antibacterial Agent (8) In Example 1, instead of silver nitrate (AgNO 3 ), 492.1 g of water was added to 19.8 g of zinc nitrate hexahydrate [Zn (NO 3 ) 2 · 6H 2 O]. In addition, a titanium oxide fine particle (T-1) dispersion carrying zinc having a solid concentration of 10% by weight was obtained in the same manner except that an aqueous zinc nitrate solution having a concentration of 1.0% by weight was prepared and used. The amount of ZnO supported in the titanium oxide fine particles (T-1) supporting zinc was 5.0% by weight.
ついで、固形分濃度１０重量％の亜鉛を担持した酸化チタン微粒子（T-1）分散液９００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(8)を調製した。 Next, 10 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 900 g of a titanium oxide fine particle (T-1) dispersion supporting zinc having a solid content concentration of 10% by weight. The antibacterial deodorant (8) was prepared by drying at 16 ° C. for 16 hours.
抗菌性能・消臭性能の評価
抗菌消臭剤(8)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance and deodorant performance The antibacterial and deodorant performance of the antibacterial deodorant (8) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(R1)
抗菌消臭剤分散液（触媒化成工業（株）製：ATOMYBALL-(UA)、ＳiＯ2・Ａｌ2Ｏ3、平均粒子径１５ｎｍ、Ａｇ2Ｏ＝５．０重量％、固形分濃度１．５重量％）を濃縮して固形分濃度１０重量％の銀を担持したシリカ・アルミナ微粒子分散液を得た。
Antibacterial deodorant (R1)
Antibacterial deodorant dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .: ATOMYBALL- (UA), SiO 2 · Al 2 O 3 , average particle size 15 nm, Ag 2 O = 5.0 wt%, solid content concentration 1.5 The silica / alumina fine particle dispersion carrying silver having a solid content of 10% by weight was obtained.
ついで、固形分濃度１０重量％の銀を担持したシリカ・アルミナ微粒子分散液９００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(R1)を調製した。 Next, 10 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 900 g of a silica / alumina fine particle dispersion supporting silver having a solid content concentration of 10% by weight, and then at 120 ° C. for 16 hours. Antibacterial deodorant (R1) was prepared by drying.
抗菌性能・消臭性能の評価
抗菌消臭剤(R1)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance / deodorant performance The antibacterial deodorant (R1) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(R2)
実施例１と同様にして、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液を得た。
ついで、１２０℃で１６時間乾燥して抗菌消臭剤(R2)を調製した。
Antibacterial deodorant (R2)
In the same manner as in Example 1, a titanium oxide fine particle (T-1) dispersion carrying silver having a solid concentration of 10% by weight was obtained.
Subsequently, it was dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (R2).
抗菌性能・消臭性能の評価
抗菌消臭剤(R2)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance / deodorant performance The antibacterial deodorant (R2) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
抗菌消臭剤(R3)
実施例１において、固形分濃度１０重量％の銀を担持した酸化チタン微粒子（T-1）分散液１００ｇにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）９０ｇを溶解し、ついで、１２０℃で１６時間乾燥して抗菌消臭剤(R3)を調製した。
Antibacterial deodorant (R3)
In Example 1, 90 g of an amine compound (manufactured by Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was dissolved in 100 g of a titanium oxide fine particle (T-1) dispersion supporting silver having a solid concentration of 10% by weight. Subsequently, it was dried at 120 ° C. for 16 hours to prepare an antibacterial deodorant (R3).
抗菌性能・消臭性能の評価
抗菌消臭剤(R3)について、実施例１と同様にして抗菌性能および消臭性能を評価し、結果を表１に示した。
Evaluation of antibacterial performance / deodorant performance The antibacterial deodorant (R3) was evaluated for antibacterial performance and deodorant performance in the same manner as in Example 1, and the results are shown in Table 1.
消臭性の評価
５Lテトラパックに、抗菌消臭剤の代わりにアミン系化合物（大塚化学（株）製；ケムキャッチＨ−６０００ＨＳ）１００ｇを封入した以外は実施例１と同様にしてケムキャッチＨ−６０００ＨＳの消臭性を評価した。測定結果を表１に示す。
Evaluation of deodorant ChemCatch H in the same manner as in Example 1 except that 100 g of an amine compound (Otsuka Chemical Co., Ltd .; Chemcatch H-6000HS) was encapsulated in a 5 L tetrapack instead of an antibacterial deodorant. The deodorizing property of -6000HS was evaluated. The measurement results are shown in Table 1.
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| JP2014033776A (en) * | 2012-08-08 | 2014-02-24 | Jgc Catalysts & Chemicals Ltd | Titanium oxide-based antibacterial deodorant, fluid dispersion thereof and product including the titanium oxide-based antibacterial deodorant |
| CN106498392A (en) * | 2016-11-03 | 2017-03-15 | 北京工商大学 | A kind of titanium nitride of argentiferous/copper nanometer multilayer antibacterial film and its preparation technology |
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| WO2019065134A1 (en) * | 2017-09-29 | 2019-04-04 | 富士フイルム株式会社 | Deodorant composition |
| WO2022244244A1 (en) | 2021-05-21 | 2022-11-24 | 株式会社原田伸銅所 | Phosphor bronze alloy and article using same |
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