JP2988811B2 - Antibacterial agent - Google Patents
Antibacterial agentInfo
- Publication number
- JP2988811B2 JP2988811B2 JP5198894A JP19889493A JP2988811B2 JP 2988811 B2 JP2988811 B2 JP 2988811B2 JP 5198894 A JP5198894 A JP 5198894A JP 19889493 A JP19889493 A JP 19889493A JP 2988811 B2 JP2988811 B2 JP 2988811B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- metal component
- solution
- weight
- silver
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は抗菌剤に関し、特に、樹
脂、塗料、繊維または化粧品などに添加または塗布して
抗菌性、防黴性、消臭効果を発揮する抗菌剤に関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial agent, and more particularly to an antibacterial agent which exerts antibacterial, antifungal and deodorant effects when added or applied to resins, paints, fibers or cosmetics.
【０００２】[0002]
【従来技術およびその問題点】従来、例えば、特開平２
−２２５４０２号公報等には、ゼオライトやシリカゲ
ル、酸化チタンなどの粉末に抗菌性を有する金属成分を
担持した抗菌性組成物が知られている。2. Description of the Related Art Conventionally, for example, Japanese Unexamined Patent Publication No.
JP-A-225402 and the like disclose an antibacterial composition in which a metal component having an antibacterial property is supported on a powder such as zeolite, silica gel, and titanium oxide.
【０００３】しかしながら、従来公知の粉末状の抗菌性
組成物には、次のような問題点があった。 樹脂、塗料、繊維、化粧品などに添加したときの分
散性が悪い。 抗菌性が効果的に発現しにくく、所望の抗菌活性を
得るためには、多量の抗菌性組成物を添加する必要があ
る。However, conventionally known powdery antibacterial compositions have the following problems. Poor dispersibility when added to resins, paints, fibers, cosmetics, etc. Antibacterial properties are hardly exhibited effectively, and it is necessary to add a large amount of an antibacterial composition in order to obtain a desired antibacterial activity.
【０００４】 添加量が多くなると粉末の凝集が生じ
易く、また、金属成分の含有量も多くなるので、銀など
の抗菌性金属成分を用いた組成物では変色が起こる。 繊維の原料樹脂に抗菌性組成物を混合して紡糸する
場合には、粒子径の大きい粉末状の組成物では糸切れを
引き起こす原因となる。 樹脂などの材料の表面に粉末状の抗菌性組成物を含
有する塗料を塗布して塗膜を形成し、抗菌性を付与する
場合には、塗膜が厚くなり膜強度の低下を生じ、また、
剥離が起きやすい。さらに透明性が要求される場合には
適用できない。[0004] When the amount of addition increases, powder agglomeration is likely to occur, and the content of the metal component also increases. Therefore, discoloration occurs in a composition using an antibacterial metal component such as silver. When the antibacterial composition is mixed with the raw material resin of the fiber and spun, a powdery composition having a large particle diameter causes thread breakage. When a coating containing a powdery antibacterial composition is applied to the surface of a material such as a resin to form a coating film and impart antibacterial properties, the coating film becomes thicker and causes a decrease in film strength, and ,
Peeling easily occurs. Not applicable when transparency is required.
【０００５】そこで、本願の発明者等は特願平２−７４
０８８号（特開平３−２７５６２７号）により、無機の
オキソ酸の塩の金属イオンを、抗菌性を有する金属イオ
ンでイオン交換してなる新規な抗菌性組成物を提案した
が、前述の問題点を解決する上で必ずしも満足のいくも
のではなかった。Accordingly, the inventors of the present application have disclosed in Japanese Patent Application No. 2-74.
No. 088 (JP-A-3-275627) has proposed a novel antibacterial composition obtained by ion-exchanging a metal ion of an inorganic oxo acid salt with a metal ion having antibacterial properties. Was not always satisfactory in solving the problem.
【０００６】また、特開平１−２５８７９２号公報に
は、アルミナゾル中の酸化アルミニウムの表面に、抗菌
作用を有する金属又はその化合物が付着した抗菌性を有
するアルミナゾルを含有する抗菌剤が提案されている。
当該発明はアルミナゾルの有する塗膜形成機能を利用し
て、上記問題点を解消したもののようであるが、〜
に掲げた問題点は依然として残されていた。Japanese Unexamined Patent Publication (Kokai) No. 1-258792 proposes an antibacterial agent containing an antibacterial alumina sol in which a metal having an antibacterial action or a compound thereof is adhered to the surface of aluminum oxide in the alumina sol. .
The present invention seems to have solved the above problems by utilizing the coating film forming function of alumina sol.
The problems listed in (1) still remained.
【０００７】さらに、特開平４−３２１６２８号公報に
は、抗菌性の高い銀コロイド粒子からなる抗菌剤が提案
されているが、該コロイド溶液は灰褐色に着色してお
り、透明性に欠け、また、銀成分そのものがコロイド粒
子であるため、凝集し易く安定性に欠けるという問題点
を有している。Furthermore, Japanese Patent Application Laid-Open No. Hei 4-321628 proposes an antibacterial agent comprising silver colloid particles having high antibacterial properties. However, the colloid solution is colored grayish brown and lacks transparency. Further, since the silver component itself is a colloidal particle, there is a problem that the silver component is easily aggregated and lacks stability.
【０００８】[0008]
【発明の目的】本発明は、前述の様な粉末状の抗菌性組
成物に特有な問題点を解決した上で、新規な抗菌性無機
酸化物コロイド溶液からなる抗菌剤を提供することを目
的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide an antibacterial agent comprising a novel antibacterial inorganic oxide colloid solution after solving the problems inherent in the powdery antibacterial composition as described above. It is assumed that.
【０００９】[0009]
【発明の概要】本発明の抗菌剤は、銀、銅、亜鉛、錫、
鉛、ビスマス、カドミウム、クロム、水銀の中から選択
される１種以上の抗菌性金属成分と該抗菌性金属成分以
外の無機酸化物とから構成される微粒子が分散してなる
抗菌性無機酸化物コロイド溶液であって、当該コロイド
溶液中の抗菌性金属成分の重量をＡ、該コロイド溶液を
超遠心分離処理して遊離した抗菌性金属成分の重量をＢ
としたとき、Ｂ／Ａで表される抗菌性金属成分の結合力
指数Ｉの値が１．０×１０-3以下であることを特徴とす
るものである。前記抗菌性無機酸化物コロイド溶液の分
散媒は、水または有機溶媒であることが好ましい。SUMMARY OF THE INVENTION The antimicrobial agent of the present invention comprises silver, copper, zinc, tin,
Antibacterial inorganic oxide in which fine particles composed of at least one antibacterial metal component selected from lead, bismuth, cadmium, chromium, and mercury and an inorganic oxide other than the antibacterial metal component are dispersed. The weight of the antimicrobial metal component in the colloid solution is A, and the weight of the antimicrobial metal component released by ultracentrifugation of the colloid solution is B.
Wherein the value of the binding strength index I of the antibacterial metal component represented by B / A is 1.0 × 10 −3 or less. The dispersion medium of the antibacterial inorganic oxide colloid solution is preferably water or an organic solvent.
【００１０】[0010]
【発明の具体的な説明】本発明に係る抗菌剤は、抗菌性
金属成分と該抗菌性金属成分以外の無機酸化物とから構
成される微粒子（コロイド粒子）が分散したコロイド溶
液であって、抗菌性金属成分は、無機酸化物と混合物ま
たは化合物の形でコロイド粒子を形成するか、あるい
は、無機酸化物コロイド粒子の表面に結合している。抗
菌性金属成分としては、銀、銅、亜鉛、錫、鉛、ビスマ
ス、カドミウム、クロム、水銀の中から１種以上が選択
される。特に、銀、銅、亜鉛から選択される１種以上の
抗菌性金属成分は、抗菌作用、変色及び人体に対する安
全性などの観点から好ましい。DETAILED DESCRIPTION OF THE INVENTION The antibacterial agent according to the present invention is a colloid solution in which fine particles (colloid particles) composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed, The antimicrobial metal component forms colloidal particles in the form of a mixture or compound with the inorganic oxide, or is bound to the surface of the inorganic oxide colloidal particles. As the antibacterial metal component, one or more kinds are selected from silver, copper, zinc, tin, lead, bismuth, cadmium, chromium, and mercury. In particular, one or more antibacterial metal components selected from silver, copper, and zinc are preferable from the viewpoints of antibacterial action, discoloration, and safety to the human body.
【００１１】抗菌性成分としての銅イオンは青色を呈す
るが、銀イオンはそもそも無色である。しかし、銀イオ
ンは光化学反応や酸化作用により金属銀の凝集体あるい
は酸化物となり、褐色または黒色に変色する。特に紫外
線の光化学反応による銀成分の変色を防止するために
は、チタン、ジルコニウム、セリウム、亜鉛などを銀成
分と組合わせて使用することが望ましい。これは、チタ
ン、ジルコニウム、セリウムおよび亜鉛成分が紫外線吸
収剤として作用して、銀成分の変色を防止する効果を有
しているからである。[0011] Copper ions as antibacterial components exhibit a blue color, whereas silver ions are originally colorless. However, silver ions become aggregates or oxides of metallic silver by a photochemical reaction or an oxidizing action, and change to brown or black. In particular, in order to prevent discoloration of the silver component due to the photochemical reaction of ultraviolet rays, it is desirable to use titanium, zirconium, cerium, zinc, or the like in combination with the silver component. This is because the titanium, zirconium, cerium and zinc components act as ultraviolet absorbers and have the effect of preventing discoloration of the silver component.
【００１２】本発明に係る抗菌剤中の抗菌性金属成分の
量は、固形分を基準として酸化物換算で０．１〜２５重
量％の範囲内であることが望ましい。抗菌性金属成分が
０．１重量％よりも少ない場合は、抗菌作用が十分に発
現しない。また、抗菌性金属成分を２５重量％よりも多
くしても、２５重量％の場合と比較して抗菌性作用に大
差がなく、また、銀成分などでは、結合量が多くなると
変色しやすい。好ましい抗菌性金属成分の量は、酸化物
換算で０．１〜１５重量％の範囲である。The amount of the antibacterial metal component in the antibacterial agent according to the present invention is desirably in the range of 0.1 to 25% by weight in terms of oxide based on the solid content. When the amount of the antibacterial metal component is less than 0.1% by weight, the antibacterial effect is not sufficiently exhibited. Further, even if the antibacterial metal component is more than 25% by weight, the antibacterial effect is not much different from the case of 25% by weight, and the silver component or the like is liable to be discolored when the binding amount is increased. The preferred amount of the antibacterial metal component is in the range of 0.1 to 15% by weight in terms of oxide.
【００１３】一方、本発明の抗菌性金属成分以外の無機
酸化物としては、一般に知られているコロイド溶液を構
成する無機酸化物を挙げることができ、無機酸化物コロ
イド粒子としては、単一または複合酸化物コロイド粒
子、あるいはこれらの混合物を用いることが可能であ
る。On the other hand, examples of the inorganic oxide other than the antibacterial metal component of the present invention include generally known inorganic oxides constituting a colloid solution. It is possible to use composite oxide colloid particles or a mixture thereof.
【００１４】単一の酸化物コロイド粒子としては、Ｓｉ
Ｏ2 、ＴｉＯ2 、ＺｒＯ2 、Ｆｅ2Ｏ3 、Ｓｂ2 Ｏ5 、
ＷＯ3 、などが例示され、複合酸化物コロイド粒子とし
ては、前記各酸化物と他の無機酸化物の複合酸化物コロ
イド粒子、例えば、ＳｉＯ2・Ａｌ2 Ｏ3 、ＳｉＯ2 ・
Ｂ2 Ｏ3 、ＳｉＯ2 ・Ｐ2 Ｏ5 、ＴｉＯ2 ・ＣｅＯ2、
ＴｉＯ2 ・ＺｒＯ2 、ＳｉＯ2 ・ＺｒＯ2 、ＳｎＯ2 ・
Ｓｂ2 Ｏ5 、ＳｉＯ2・Ａｌ2 Ｏ3 ・ＴｉＯ2 、ＳｉＯ
2 ・ＴｉＯ2 ・ＣｅＯ2 、ＴｉＯ2 ・ＳｉＯ2・ＺｒＯ
2 、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・ＭｇＯ、ＳｉＯ2 ・Ａｌ2
Ｏ3 ・ＣａＯ、ＳｉＯ2 ・ＴｉＯ2 ・Ｆｅ2 Ｏ3 などを
挙げることができる。The single oxide colloid particles include Si
O 2 , TiO 2 , ZrO 2 , Fe 2 O 3 , Sb 2 O 5 ,
WO 3 , and the like. Examples of the composite oxide colloid particles include composite oxide colloid particles of the above oxides and other inorganic oxides, for example, SiO 2 .Al 2 O 3 , SiO 2.
B 2 O 3 , SiO 2 .P 2 O 5 , TiO 2 .CeO 2 ,
TiO 2 .ZrO 2 , SiO 2 .ZrO 2 , SnO 2.
Sb 2 O 5 , SiO 2 · Al 2 O 3 · TiO 2 , SiO
2・ TiO 2・ CeO 2 、 TiO 2・ SiO 2・ ZrO
2 , SiO 2 · Al 2 O 3 · MgO, SiO 2 · Al 2
O 3 .CaO, SiO 2 .TiO 2 .Fe 2 O 3 and the like can be mentioned.
【００１５】抗菌性金属成分と該抗菌性金属成分以外の
無機酸化物とから構成される微粒子（コロイド粒子）の
平均粒子径は、５００ｎｍ以下であることが望ましい。
コロイド粒子の平均粒子径が大きくなるにつれて、抗菌
性無機酸化物コロイド溶液の透明性は悪くなる傾向にあ
り、従って、コロイド粒子の平均粒子径が５００ｎｍよ
り大きい抗菌性無機酸化物コロイド溶液から調製した塗
料を、樹脂などの材料の表面に塗布して塗膜を形成する
際、塗膜の透明性が要求される用途には適当でない。透
明性が要求される用途にはコロイド粒子の平均粒子径
は、好ましくは３００ｎｍ以下、更に好ましくは３〜２
５０ｎｍの範囲であることが望ましい。The average particle diameter of fine particles (colloidal particles) composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component is desirably 500 nm or less.
As the average particle size of the colloidal particles increases, the transparency of the antibacterial inorganic oxide colloid solution tends to deteriorate. Therefore, the colloidal particles were prepared from an antibacterial inorganic oxide colloid solution having an average particle size larger than 500 nm. When a paint is applied to the surface of a material such as a resin to form a coating film, it is not suitable for applications requiring transparency of the coating film. For applications requiring transparency, the average particle size of the colloid particles is preferably 300 nm or less, more preferably 3 to 2 nm.
It is desirable to be in the range of 50 nm.
【００１６】本発明における抗菌性金属成分の結合力指
数（Ｉ）は、次の方法により求める。すなわち、抗菌性
無機酸化物コロイド溶液中の抗菌性金属成分の重量をプ
ラズマ発光分光分析装置により、金属原子を定量して求
め、次いで、所定量の該抗菌性無機酸化物コロイド溶液
を回転数４５，０００ｒｐｍの超遠心分離機にて１時間
処理して固形分と溶液に分離し、この分離された溶液中
に含まれる抗菌性金属成分の金属原子をプラズマ発光分
析装置で定量して、遊離した抗菌性金属成分の重量とす
る。The bonding strength index (I) of the antibacterial metal component in the present invention is determined by the following method. That is, the weight of the antibacterial metal component in the antibacterial inorganic oxide colloid solution was determined by quantifying the metal atoms by a plasma emission spectrometer, and then a predetermined amount of the antibacterial inorganic oxide colloid solution was rotated at 45 rpm. The mixture was treated with an ultracentrifuge at 2,000 rpm for 1 hour to separate the solid content and the solution, and the metal atom of the antibacterial metal component contained in the separated solution was quantified by a plasma emission analyzer and released. The weight of the antibacterial metal component.
【００１７】結合力指数（Ｉ）が１．０×１０-3より大
きい場合には、抗菌性金属成分の無機酸化物コロイド粒
子への結合力が弱いため、抗菌性無機酸化物コロイド溶
液の溶媒中に抗菌性金属成分が溶出しやすく、抗菌効果
の持続性に劣り、また、抗菌性金属成分として銀を用い
た場合には変色の原因ともなるので好ましくない。抗菌
性金属成分の結合力指数（Ｉ）は、好ましくは５．０×
１０-4以下、特に、１．０×１０-4以下であることが望
BR>ましい。抗菌剤の抗菌性金属成分が２種以上の場合
には、それぞれの抗菌性金属成分の結合力指数が１．０
×１０-3以下であることを要する。When the bonding strength index (I) is larger than 1.0 × 10 -3 , the bonding strength of the antibacterial metal component to the inorganic oxide colloid particles is weak, so that the solvent of the antibacterial inorganic oxide colloid solution is The antibacterial metal component is easily eluted therein, and the durability of the antibacterial effect is poor. Further, when silver is used as the antibacterial metal component, it is not preferable because it causes discoloration. The binding index (I) of the antibacterial metal component is preferably 5.0 ×
10 -4, in particular, Nozomu be at 1.0 × 10 -4 or less
BR> Good. When two or more antibacterial metal components of the antibacterial agent are used, the bonding strength index of each antibacterial metal component is 1.0.
It is required to be not more than × 10 −3 .
【００１８】なお、本発明の抗菌性無機酸化物コロイド
溶液の濃度は、通常のコロイド溶液の濃度に調節可能で
あるが、コロイド溶液の安定性から言えば、酸化物とし
て１〜１０重量％の範囲とすることが好ましい。The concentration of the colloidal solution of the antibacterial inorganic oxide of the present invention can be adjusted to the concentration of a usual colloidal solution. However, from the viewpoint of the stability of the colloidal solution, 1 to 10% by weight of the oxide is used. It is preferable to set the range.
【００１９】次に本発明に係る抗菌剤の好ましい製造方
法を説明する。本発明の抗菌剤である抗菌性無機酸化物
コロイド溶液は、例えば、特開平５−１３２３０９号公
報に記載された複合酸化物コロイド溶液の製造方法に準
じて調製することができる。即ち、アルカリ金属、アン
モニウムまたは有機塩基の珪酸塩と、アルカリ可溶の無
機化合物と、抗菌性金属成分の水溶液とを、ｐＨ１０以
上のアルカリ水溶液中に同時に添加し、抗菌性金属成分
を含有する無機酸化物コロイド粒子を生成させる。Next, a preferred method for producing the antibacterial agent according to the present invention will be described. The antibacterial inorganic oxide colloid solution as the antibacterial agent of the present invention can be prepared, for example, according to the method for producing a composite oxide colloid solution described in JP-A-5-132309. That is, a silicate of an alkali metal, ammonium or an organic base, an alkali-soluble inorganic compound, and an aqueous solution of an antibacterial metal component are simultaneously added to an aqueous alkaline solution having a pH of 10 or more, and an inorganic solution containing an antibacterial metal component is added. Generate oxide colloid particles.
【００２０】また、特開昭６３−２７０６２０号公報に
記載された製造方法に準じて調製することもできる。即
ち、含水チタン酸のゲルまたはゾルに過酸化水素を加え
て得られるチタン酸水溶液と抗菌性金属成分の水溶液と
を、ケイ素化合物および／またはジルコニウム化合物の
存在下で加熱処理して調製する方法である。Further, it can be prepared according to the production method described in JP-A-63-270620. That is, a method of preparing an aqueous solution of titanic acid obtained by adding hydrogen peroxide to a gel or sol of hydrous titanic acid and an aqueous solution of an antibacterial metal component by heat treatment in the presence of a silicon compound and / or a zirconium compound. is there.
【００２１】更に、本願の出願人が先に出願した特願平
４−２５７３６４号に記載した抗菌性無機酸化物コロイ
ド溶液からなる抗菌剤の製造方法において、負の電荷を
有する無機酸化物コロイド粒子が分散したコロイド溶液
に抗菌性金属成分の水溶液を添加した後、該コロイド溶
液を６０℃以上、好ましくは１００〜２００℃で加熱処
理する方法も例示することができる。Further, in the method for producing an antibacterial agent comprising an antibacterial inorganic oxide colloid solution described in Japanese Patent Application No. 4-257364 previously filed by the applicant of the present invention, inorganic oxide colloid particles having a negative charge After adding an aqueous solution of the antibacterial metal component to the colloid solution in which is dispersed, the colloid solution is subjected to heat treatment at 60 ° C. or higher, preferably 100 to 200 ° C.
【００２２】上記製造方法において用いられる抗菌性金
属成分の水溶液としては、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して得られる亜
鉛、銀あるいは銅などのアンミン錯塩水溶液を用いるの
が好適である。As the aqueous solution of the antibacterial metal component used in the above production method, for example, an aqueous solution of an ammine complex salt of zinc, silver or copper obtained by dissolving zinc oxide, silver oxide or copper oxide in aqueous ammonia is used. Is preferred.
【００２３】上記方法で得られた抗菌性無機酸化物コロ
イド溶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抗菌性無機酸化物
コロイド溶液からなる抗菌剤とすることも可能である。
また、これらの抗菌性無機酸化物コロイド溶液は、限外
濾過膜などを用いる公知の方法により所望の濃度に調整
される。Water, which is a dispersion medium of the antibacterial inorganic oxide colloid solution obtained by the above method, is replaced with an organic solvent by a known method, and is composed of an antibacterial inorganic oxide colloid solution using an organic solvent as a dispersion medium. It can also be an antimicrobial agent.
Further, these antibacterial inorganic oxide colloid solutions are adjusted to a desired concentration by a known method using an ultrafiltration membrane or the like.
【００２４】[0024]
【実施例】以下に実施例を示し、本発明を更に具体的に
説明する。The present invention will be described more specifically with reference to the following examples.
【００２５】〔抗菌性無機酸化物コロイド溶液の調製〕実施例１ 硫酸チタンを純水に溶解し、ＴｉＯ2 として１．０重量
％を含む水溶液を得た。この水溶液を撹拌しながら、１
５重量％アンモニア水を徐々に添加し、白色スラリー液
を得、このスラリー液を濾過、洗浄し、含水チタン酸の
ケーキを得た。このケーキ３１．４ｇに、純水と３３重
量％過酸化水素水２１９．８ｇを加えた後、８０℃で１
４時間加熱し、ＴｉＯ2 として１．０重量％の溶液３１
３６ｇを得た。このチタン酸溶液は、黄褐色透明でｐＨ
は８．２であった。[0025] The [antimicrobial preparation of inorganic oxide colloidal solution] Example 1 titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 1.0 wt% as TiO 2. While stirring this aqueous solution, 1
A 5% by weight aqueous ammonia was gradually added to obtain a white slurry, which was filtered and washed to obtain a wet titanic acid cake. To 31.4 g of this cake, 219.8 g of pure water and 33% by weight of hydrogen peroxide were added,
Heat for 4 hours to obtain a 1.0% by weight solution of TiO 2 31
36 g were obtained. This titanic acid solution is tan, transparent and pH
Was 8.2.
【００２６】次いで、１５重量％アンモニア水２１．３
ｇを純水６１８．１ｇで希釈したアンモニア水中で酸化
銀０．６４ｇを溶解して、銀のアンミン錯塩水溶液と
し、さらにこの水溶液に炭酸ジルコニウムアンモニウム
１５．４ｇを純水１６９．９ｇに溶解したものを添加し
た。この混合水溶液を前記チタン酸溶液に加え、次に、
２０重量％シリカゾル３８．７ｇを加えた後、１５０℃
で３６時間加熱した。この溶液は初期黄褐色液であった
が、３６時間後に淡乳白色透明なコロイド溶液となっ
た。この銀成分を含む複合酸化物コロイド溶液のｐＨは
７．５で、固形分濃度は１２．０重量％であり、コロイ
ド粒子の平均粒径は５．５ｎｍであった。Then, 21.3% by weight of 15% aqueous ammonia was added.
g was diluted with 618.1 g of pure water to dissolve 0.64 g of silver oxide in an aqueous solution of silver ammine complex, and further dissolved 15.4 g of ammonium zirconium carbonate in 169.9 g of pure water. Was added. This mixed aqueous solution is added to the titanic acid solution, and then
After adding 38.7 g of 20% by weight silica sol, 150 ° C.
For 36 hours. This solution was initially a tan liquid, but turned into a pale milky white transparent colloid solution after 36 hours. The pH of the composite oxide colloid solution containing the silver component was 7.5, the solid content concentration was 12.0% by weight, and the average particle size of the colloid particles was 5.5 nm.
【００２７】実施例２ ＳｉＯ2 濃度２０重量％のコロイド溶液２０ｇと純水３
８０ｇの混合物を８０℃に加温した。この反応母液のｐ
Ｈは１０．７であり、同母液にＳｉＯ2 として１．５重
量％の珪酸ソーダ水溶液１５００ｇとＡｌ2 Ｏ3 として
０．５重量％のアルミン酸ソーダ水溶液１５００ｇとを
同時に添加して、ｐＨ１２．３のシリカ・アルミナ複合
酸化物コロイド溶液とした後、限外濾過膜で濃縮して固
形分濃度２２．２重量％のコロイド溶液を調製した。一
方、酸化銀特級試薬０．０８ｇを約２０ｇの水に懸濁
し、次いで１５重量％のアンモニア水を酸化銀が溶解す
るまで加えて、銀アンミン錯塩水溶液を調製した。ま
た、同様の方法で酸化亜鉛特級試薬０．３０ｇを溶解し
て亜鉛アンミン錯塩水溶液を調製した。 Example 2 20 g of a colloid solution having a SiO 2 concentration of 20% by weight and pure water 3
80 g of the mixture was warmed to 80 ° C. P of this reaction mother liquor
H is 10.7, and 1500 g of a 1.5 wt% aqueous sodium silicate solution as SiO 2 and 1500 g of a 0.5 wt% aqueous sodium aluminate solution as Al 2 O 3 are simultaneously added to the mother liquor to obtain a pH of 12.2. The silica / alumina composite oxide colloid solution of No. 3 was then concentrated by an ultrafiltration membrane to prepare a colloid solution having a solid content of 22.2% by weight. Separately, 0.08 g of a silver oxide special-grade reagent was suspended in about 20 g of water, and then 15% by weight of aqueous ammonia was added until silver oxide was dissolved to prepare a silver ammine complex salt aqueous solution. In the same manner, 0.30 g of zinc oxide special grade reagent was dissolved to prepare a zinc ammine complex salt aqueous solution.
【００２８】上記銀アンミン錯塩水溶液と亜鉛アンミン
錯塩水溶液とを混合し、更に、水を添加して銀酸化物お
よび亜鉛酸化物としての合計酸化物濃度が０．５重量％
となるように濃度調整した。この混合アンミン錯塩水溶
液を前記コロイド溶液に添加して十分に撹拌し、次い
で、オートクレーブにて１５０℃で６時間加熱した。こ
のコロイド溶液のｐＨは９．０であり、固形分濃度は
５．０重量％であった。The above aqueous solution of silver ammine complex salt and aqueous solution of zinc ammine complex salt are mixed, and water is added thereto so that the total oxide concentration as silver oxide and zinc oxide is 0.5% by weight.
The density was adjusted so that This mixed ammine complex salt aqueous solution was added to the colloid solution, stirred sufficiently, and then heated at 150 ° C. for 6 hours in an autoclave. The pH of this colloid solution was 9.0, and the solid content concentration was 5.0% by weight.
【００２９】実施例３ ＳｉＯ2 濃度２０重量％のコロイド溶液２０ｇと純水３
８０ｇの混合物を８０℃に加温した。この反応母液のｐ
Ｈは１０．７であり、同母液にＳｉＯ2 として１．５重
量％の珪酸ソーダ水溶液１５００ｇとＡｌ2 Ｏ3 として
０．５重量％のアルミン酸ソーダ水溶液１５００ｇとを
同時に添加して、ｐＨ１２．３のシリカ・アルミナ複合
酸化物コロイド溶液とした後、限外濾過膜で濃縮して固
形分濃度２２．２重量％のコロイド溶液を調製した。 Example 3 20 g of a colloid solution having a SiO 2 concentration of 20% by weight and pure water 3
80 g of the mixture was warmed to 80 ° C. P of this reaction mother liquor
H is 10.7, and 1500 g of a 1.5 wt% aqueous sodium silicate solution as SiO 2 and 1500 g of a 0.5 wt% aqueous sodium aluminate solution as Al 2 O 3 are simultaneously added to the mother liquor to obtain a pH of 12.2. The silica / alumina composite oxide colloid solution of No. 3 was then concentrated by an ultrafiltration membrane to prepare a colloid solution having a solid content of 22.2% by weight.
【００３０】一方、酸化銀０．０８ｇを約２０ｇの水に
懸濁し、次いで１５重量％のアンモニア水を酸化銀が溶
解するまで加え、銀の酸化物としての濃度が０．５重量
％となる様に水を加えて調整した。この銀アンミン錯塩
水溶液を前記コロイド溶液に添加して十分に撹拌し、銀
成分とシリカ・アルミナ複合酸化物コロイド粒子とから
なるコロイド溶液を調製した。このコロイド溶液を限外
濾過膜で濃縮して、３重量％のシリカ・アルミナコロイ
ド溶液を得た。On the other hand, 0.08 g of silver oxide is suspended in about 20 g of water, and then 15% by weight of aqueous ammonia is added until the silver oxide is dissolved, so that the concentration of silver as an oxide becomes 0.5% by weight. Water was added in the same manner as above. This aqueous solution of silver ammine complex was added to the above colloid solution and stirred sufficiently to prepare a colloid solution comprising a silver component and silica / alumina composite oxide colloid particles. The colloid solution was concentrated with an ultrafiltration membrane to obtain a 3% by weight silica-alumina colloid solution.
【００３１】実施例４ メタノール１７８８．３ｇと実施例１で得られた１２．
０重量％の水ゾル２４９ｇとを混合し、この混合溶液中
にメチルトリメトキシシラン５．９６ｇを添加した。こ
の混合溶液を還流器付ガラス容器に入れ、６５℃で１８
時間加熱処理した後、これを限外濾過膜で約１０重量％
まで濃縮した。次いで、メタノールを添加しながら混合
液中の水を連続的に限外濾過装置で溶媒置換した。置換
後のオルガノゾル中の残存水分量は０．４重量％で、固
形分濃度は１１．５重量％であった。 Example 4 1788.3 g of methanol and 12.1 obtained in Example 1.
249 g of a 0% by weight water sol were mixed, and 5.96 g of methyltrimethoxysilane was added to the mixed solution. This mixed solution was placed in a glass container equipped with a reflux condenser, and was placed at 65 ° C.
After heat treatment for an hour, this is treated with an ultrafiltration membrane to about 10% by weight.
Concentrated. Subsequently, the solvent in the water in the mixed solution was continuously replaced by an ultrafiltration device while adding methanol. The residual water content in the organosol after the replacement was 0.4% by weight, and the solid content concentration was 11.5% by weight.
【００３２】〔コロイド溶液の性状測定〕実施例５ 実施例１〜実施例４で得られた抗菌性無機酸化物コロイ
ド溶液の性状を下記のようにして測定した。結果を表１
に示す。 （１）抗菌性金属成分の重量は、プラズマ発光分光分析
装置（セイコー社製）により、抗菌性金属成分の金属原
子を定量して求めた。 （２）無機酸化物コロイド溶液の超遠心分離処理は、久
保田商事（株）製の超遠心分離機（KUBOTA KR/180B）を
用いて、回転数４５０００ｒｐｍで１時間処理した。 （３）コロイド粒子の平均粒子径は、レーザー散乱粒子
径測定装置（ナイコンプ社製）を使用して測定した。[Measurement of Properties of Colloid Solution] Example 5 The properties of the antibacterial inorganic oxide colloid solutions obtained in Examples 1 to 4 were measured as follows. Table 1 shows the results
Shown in (1) The weight of the antibacterial metal component was determined by quantifying the metal atom of the antibacterial metal component using a plasma emission spectrometer (manufactured by Seiko). (2) The ultracentrifugation treatment of the inorganic oxide colloid solution was performed for 1 hour at 45,000 rpm using an ultracentrifuge (KUBOTA KR / 180B) manufactured by Kubota Corporation. (3) The average particle size of the colloid particles was measured using a laser scattering particle size measuring device (manufactured by Nicomp).
【００３３】[0033]
【表１】 なお、実施例２の欄において( )内は、ZnO についての
数値である。[Table 1] In the column of Example 2, the values in parentheses are the values for ZnO.
【００３４】〔抗菌剤の評価〕実施例６ 実施例１〜実施例４で得られた抗菌性無機酸化物コロイ
ド溶液に関し、下記項目につい評価した。結果を表２に
示す。[Evaluation of antibacterial agent] Example 6 The antibacterial inorganic oxide colloid solutions obtained in Examples 1 to 4 were evaluated for the following items. Table 2 shows the results.
【００３５】（１）抗菌性の評価 実施例１〜実施例４で得られた各コロイド溶液を純水で
希釈して、濃度１重量％とし、このコロイド溶液からな
る抗菌剤６ｇ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１２μｍのバー
コートを用いて塗布し、１００℃で乾燥して塗膜を形成
した。このガラス板表面の塗膜を抗菌活性測定の試料と
して抗菌性を評価した。緑膿菌および大腸菌を生理食塩
水中に懸濁させ、その３０μｌを上記各試料のガラス面
に滴下し、２８℃で２４時間放置後、生菌数を測定して
式１により死滅率を求めた。(1) Evaluation of antibacterial activity Each of the colloid solutions obtained in Examples 1 to 4 was diluted with pure water to a concentration of 1% by weight. 20 g of a resin (manufactured by Nippon Pure Chemical Co., Ltd .; Julimer FC65, concentration: 40% by weight) was mixed to prepare an antibacterial coating agent. 1.0 g of this coating agent
Was applied to a glass plate of 10 cm × 10 cm using a bar coat having a thickness of 12 μm, and dried at 100 ° C. to form a coating film. The antibacterial property was evaluated using the coating film on the surface of the glass plate as a sample for measuring the antibacterial activity. Pseudomonas aeruginosa and Escherichia coli were suspended in physiological saline, and 30 μl of the suspension was dropped on the glass surface of each of the above samples. After standing at 28 ° C. for 24 hours, the number of viable bacteria was measured, and the mortality was determined by Formula 1. .
【００３６】[0036]
【式１】死滅率（％）＝１００×（初期生菌数−２４時
間後の生菌数）／初期生菌数Formula 1: Death rate (%) = 100 × (initial viable cell count−viable cell count after 24 hours) / initial viable cell count
【００３７】（２）耐候性 ウエザーメーター（ガス試験機器（株）製）を用いて１
００時間の耐候試験を行い、変色度合いを観察した。 ○・・・変色が見られないもの △・・・変色が僅かに見られるもの ×・・・変色が見られるもの(2) Weather resistance 1 was measured using a weather meter (manufactured by Gas Testing Instruments Co., Ltd.).
A weathering test for 00 hours was performed to observe the degree of discoloration.・ ・ ・: No discoloration is observed △: slight discoloration is observed ×: discoloration is observed
【００３８】（３）変色性 １重量％コロイド溶液に１０ｃｍ×１０ｃｍのガーゼを
浸し、太陽光のもとで乾燥した。乾燥過程で紫外線のた
めに遊離Ａｇイオンが還元されてＡｇとなり、褐色乃至
黒色に変化する度合いを観察した。 ○・・・変色が見られないもの。 △・・・変色が僅かに見られるもの ×・・・変色が見られるもの。(3) Discoloration A gauze of 10 cm × 10 cm was immersed in a 1% by weight colloid solution and dried under sunlight. During the drying process, it was observed that free Ag ions were reduced to Ag by ultraviolet rays and changed to brown or black.・ ・ ・: No discoloration is observed. Δ: Discoloration is slightly observed X: Discoloration is observed.
【００３９】（４）コロイド溶液の安定性 コロイド溶液を３ヶ月間放置して沈殿物生成の有無を観
察した。 ○・・・沈殿物の生成が見られないもの。 △・・・沈殿物の生成が僅かに見られるもの ×・・・沈殿物の生成が見られるもの。(4) Stability of Colloid Solution The colloid solution was allowed to stand for three months, and the presence or absence of formation of a precipitate was observed.・ ・ ・: No precipitate is observed. Δ: Slight formation of a precipitate is observed X: Slight formation of a precipitate is observed.
【００４０】[0040]
【表２】 [Table 2]
【００４１】[0041]
【発明の効果】本発明の抗菌剤は無機酸化物と抗菌性金
属成分とが強固に結合した微粒子が分散したコロイド溶
液であるため、少量の使用量でも抗菌性が高く、その抗
菌効果が持続する。また、コロイド粒子の分散性がよ
く、耐候性、変色性およびコロイド粒子の安定性に優れ
ている。The antimicrobial agent of the present invention is a colloidal solution in which fine particles in which an inorganic oxide and an antimicrobial metal component are firmly bonded are dispersed, so that even a small amount of the antimicrobial agent has high antimicrobial properties, and its antimicrobial effect is maintained. I do. Further, the dispersibility of the colloid particles is good, and the weather resistance, the discoloration property and the stability of the colloid particles are excellent.
【００４２】従って、樹脂組成物や塗料組成物中に配合
される抗菌剤として好適であり、特に、樹脂、ガラス、
繊維などの表面に塗布される抗菌性塗料の配合剤として
最適である。また、抗菌効果、フケ・かゆみ防止効果、
防臭・消臭効果等の要求される抗菌性化粧料や、ビルの
冷却塔水等、水中微生物の殺菌、抗菌を目的とする浄水
剤としても有用である。さらに、粉末状の抗菌性組成物
が使用されている各種の用途にも、勿論使用することが
できる。Accordingly, it is suitable as an antibacterial agent to be incorporated in a resin composition or a coating composition, and particularly, a resin, glass,
It is most suitable as a compounding agent for antibacterial paint applied to the surface of fibers and the like. In addition, antibacterial effect, dandruff / itch prevention effect,
It is also useful as an antibacterial cosmetic which is required for deodorizing and deodorizing effects, and as a water purifier for disinfecting and antibacterial microorganisms in water, such as cooling tower water of buildings. Furthermore, it can of course be used for various applications in which the powdery antibacterial composition is used.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ａ６１Ｋ 33/38 Ａ６１Ｋ 33/38 (56)参考文献 特開 昭63−270620（ＪＰ，Ａ) 特開 昭63−97234（ＪＰ，Ａ) 特開 平３−8448（ＪＰ，Ａ) 特開 平３−52804（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) A01N 59/16 ＷＰＩ（ＤＩＡＬＯＧ)──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI A61K 33/38 A61K 33/38 (56) References JP-A-63-270620 (JP, A) JP-A-63-97234 (JP) JP-A-3-8448 (JP, A) JP-A-3-52804 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) A01N 59/16 WPI (DIALOG)
Claims (2)
ミウム、クロム、水銀の中から選択される１種以上の抗
菌性金属成分と該抗菌性金属成分以外の無機酸化物とか
ら構成される微粒子が分散してなる抗菌性無機酸化物コ
ロイド溶液であって、当該コロイド溶液中の抗菌性金属
成分の重量をＡ、該コロイド溶液を超遠心分離処理して
遊離した抗菌性金属成分の重量をＢとしたとき、Ｂ／Ａ
で表される抗菌性金属成分の結合力指数Ｉの値が１．０
×１０-3以下であることを特徴とする抗菌剤。(1) silver, copper, zinc, tin, lead, bismuth, and cad
An antibacterial inorganic oxidation obtained by dispersing fine particles composed of at least one antibacterial metal component selected from the group consisting of mium, chromium, and mercury and an inorganic oxide other than the antibacterial metal component. When the weight of the antimicrobial metal component in the colloid solution is A and the weight of the antimicrobial metal component released by ultracentrifugation of the colloid solution is B, B / A
The binding strength index I of the antibacterial metal component represented by
An antibacterial agent characterized by being at most 10-3 .
散媒が水または有機溶媒である請求項１記載の抗菌剤。2. The antibacterial agent according to claim 1, wherein the dispersion medium of the antibacterial inorganic oxide colloid solution is water or an organic solvent.
Priority Applications (1)
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|---|---|---|---|
| JP5198894A JP2988811B2 (en) | 1993-07-16 | 1993-07-16 | Antibacterial agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5198894A JP2988811B2 (en) | 1993-07-16 | 1993-07-16 | Antibacterial agent |
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| Publication Number | Publication Date |
|---|---|
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Family
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| JP3095960B2 (en) * | 1994-10-05 | 2000-10-10 | 触媒化成工業株式会社 | Antibacterial agent |
| US5929133A (en) * | 1996-02-16 | 1999-07-27 | Hitachi Chemical Filtec, Inc. | Anti-bacterial film suitable for food packaging |
| JP3558460B2 (en) * | 1996-07-05 | 2004-08-25 | 触媒化成工業株式会社 | Antibacterial agent |
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JPH1180617A (en) * | 1997-09-05 | 1999-03-26 | Catalysts & Chem Ind Co Ltd | Antimicrobial treatment method |
| JPH11323213A (en) * | 1998-05-13 | 1999-11-26 | Catalysts & Chem Ind Co Ltd | Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith |
| JP3982953B2 (en) * | 1999-07-28 | 2007-09-26 | 触媒化成工業株式会社 | Antibacterial coating film and substrate with coating film |
| JP2001114610A (en) * | 1999-08-11 | 2001-04-24 | Catalysts & Chem Ind Co Ltd | Antimicrobial fatty acid compound and method for produsing the same |
| JP2002080303A (en) * | 2000-09-06 | 2002-03-19 | Catalysts & Chem Ind Co Ltd | Antibacterial agent and method for producing the same |
| JP2002145717A (en) * | 2000-11-01 | 2002-05-22 | Catalysts & Chem Ind Co Ltd | Antimicrobial cosmetic |
| JP4255318B2 (en) * | 2002-06-13 | 2009-04-15 | 日揮触媒化成株式会社 | Method for producing antibacterial / deodorant polyester resin or antibacterial / deodorant polyurethane resin |
| JP4849778B2 (en) * | 2004-05-07 | 2012-01-11 | 日揮触媒化成株式会社 | Antibacterial deodorant and method for producing the same |
| JP4619075B2 (en) * | 2004-09-21 | 2011-01-26 | 日揮触媒化成株式会社 | Method for producing antibacterial and deodorant titanium oxide colloidal solution |
| US8486433B2 (en) | 2004-05-07 | 2013-07-16 | Jgc Catalysts And Chemicals Ltd. | Antibacterial deodorant |
| JP4846268B2 (en) * | 2005-05-25 | 2011-12-28 | 花王株式会社 | Liquid detergent composition for clothing |
| JP4964331B2 (en) * | 2010-06-02 | 2012-06-27 | 日揮触媒化成株式会社 | Method for producing antibacterial deodorant |
| JP5935133B2 (en) * | 2012-03-29 | 2016-06-15 | フジコピアン株式会社 | Hard coat film |
| US9144237B2 (en) * | 2012-08-10 | 2015-09-29 | Tsukasa Sakurada | Sterilizing and deodorizing agents, their method of manufacture and uses |
-
1993
- 1993-07-16 JP JP5198894A patent/JP2988811B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0733616A (en) | 1995-02-03 |
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