JPH10273322A - Antifungal composite titanate and manufacture of the same - Google Patents
Antifungal composite titanate and manufacture of the sameInfo
- Publication number
- JPH10273322A JPH10273322A JP10016687A JP1668798A JPH10273322A JP H10273322 A JPH10273322 A JP H10273322A JP 10016687 A JP10016687 A JP 10016687A JP 1668798 A JP1668798 A JP 1668798A JP H10273322 A JPH10273322 A JP H10273322A
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- Prior art keywords
- antibacterial
- compound
- alkali metal
- titanate
- metal
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- Inorganic Compounds Of Heavy Metals (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Apparatus For Disinfection Or Sterilisation (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、抗菌作用，防汚，
防藻効果等にすぐれ、人体に対する安全性を有し、かつ
耐熱性，断熱性，耐摩耗性，補強性等を備えた抗菌性複
合チタン化合物およびその製造方法に関する。TECHNICAL FIELD The present invention relates to an antibacterial action, antifouling,
The present invention relates to an antibacterial composite titanium compound having an excellent antialgal effect and the like, having safety for the human body, and having heat resistance, heat insulation, abrasion resistance, reinforcement and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来の抗菌剤の多くは有機系抗菌剤であ
り、有機系抗菌剤は耐熱性に乏しく、比較的低い温度域
で分解・蒸発等により抗菌作用を減少ないし消失するも
のも多い。また人体に対する安全性の問題も指摘され始
めている。他方、銀（Ａｇ），銅（Ｃｕ）、亜鉛（Ｚ
ｎ）等の金属イオンが抗菌作用を有することはよく知ら
れており、近時はこれらの抗菌性金属なしいその塩を、
ゼオライト，燐酸ジルコニウム，ハイドロアパタイト，
活性炭，アルミナ，シリカゲル，炭酸塩等に吸着等によ
り担持させた無機系抗菌剤が開発されている。2. Description of the Related Art Many conventional antibacterial agents are organic antibacterial agents, and organic antibacterial agents have poor heat resistance, and many of them reduce or eliminate the antibacterial action by decomposition, evaporation, etc. in a relatively low temperature range. . In addition, safety issues to the human body have begun to be pointed out. On the other hand, silver (Ag), copper (Cu), zinc (Z
It is well known that metal ions such as n) have an antibacterial action, and recently these antibacterial metals or salts thereof are
Zeolite, zirconium phosphate, hydroapatite,
Inorganic antibacterial agents supported on activated carbon, alumina, silica gel, carbonate, and the like by adsorption or the like have been developed.
【０００３】[0003]
【発明が解決しようとする課題】抗菌性金属またはその
塩等をゼオライト，活性炭，その他の担体に吸着等で担
持させた従来の無機系抗菌剤は、抗菌効果の持続性，必
要な量の抗菌剤の安定保持等に一長一短あり、また耐熱
性や化学的安定性等の点においても十分なものとはいえ
ず、利用分野や適用形態等に種々の制約を受けるもので
あった。本発明は、無機系抗菌剤として、抗菌性金属イ
オンを安定に保持し、抗菌・殺菌，防黴が効果的に行わ
れ、その効果の持続性にすぐれ、耐熱性，化学的安定
性，補強性等をも具備し、広範な分野への適用および多
様な使用態様を可能とする抗菌性複合チタン化合物およ
びその製造方法を提供するものである。A conventional inorganic antibacterial agent in which an antibacterial metal or a salt thereof is supported on zeolite, activated carbon, or another carrier by adsorption or the like, has a sustained antibacterial effect and a required amount of antibacterial agent. It has advantages and disadvantages in terms of stable retention of the agent, and is not sufficient in terms of heat resistance, chemical stability, and the like, and is subject to various restrictions in fields of application and application forms. The present invention, as an inorganic antibacterial agent, stably retains antibacterial metal ions, effectively performs antibacterial, sterilization, and antifungal activities, has excellent sustained effects, and has heat resistance, chemical stability, and reinforcement. Another object of the present invention is to provide an antibacterial composite titanium compound which has properties and the like, and which can be applied to a wide range of fields and can be used in various ways, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明の抗菌性複合チタ
ン酸化合物は、トンネル型結晶構造を有する六チタン酸
アルカリ金属のアルカリ金属イオンの一部が抗菌性金属
イオンで置換された、次式: （Ａ，Ｂ）2 Ｔｉ6 Ｏ13 …〔１〕 〔式中，A:アルカリ金属 B:抗菌性金属 〕で示されるトンネル型結晶構造の六
チタン酸化合物の結晶と、チタニア（ＴｉＯ 2 ）の結晶
とが分散混在した混相化合物であることを特徴としてい
る。上記六チタン酸化合物〔１〕の抗菌性金属（Ｂ）
は、銀（Ａｇ），銅（Ｃｕ）、亜鉛（Ｚｎ），水銀（Ｈ
ｇ），錫（Ｓｎ），鉛（Ｐｂ），ビスマス（Ｂｉ），カ
ドムウム（Ｃｄ），クロム（Ｃｒ），タリウム（Ｔｌ）
等であり、その１種または２種以上がチタン酸化合物
〔１〕の結晶内に包含されている。SUMMARY OF THE INVENTION The antibacterial composite titer of the present invention
Acid compound is hexatitanic acid having a tunnel type crystal structure
Some of the alkali metal ions of the alkali metal are antibacterial metals
The following formula replaced with ions: (A, B)TwoTi6O13 … [1] [6] In the formula, A: alkali metal B: antibacterial metal
Crystals of titanate compound and titania (TiO Two) Crystal
Is a mixed phase compound in which
You. Antibacterial metal (B) of the above hexatitanate compound [1]
Are silver (Ag), copper (Cu), zinc (Zn), mercury (H
g), tin (Sn), lead (Pb), bismuth (Bi),
Domium (Cd), chromium (Cr), thallium (Tl)
Etc., one or more of which are titanate compounds
It is contained in the crystal of [1].
【０００５】[0005]
【発明の実施の形態】トンネル型結晶構造の六チタン酸
アルカリ金属は、式: Ａ2 Ｔｉ6 Ｏ13（Ａ:アルカリ金
属）で表され、このものは、ＴｉＯ6 八面体の連鎖によ
り構成されるトンネル枠の内部に、アルカリ金属（Ｌ
ｉ，Ｎａ，Ｋ，Ｒｂ，Ｃｓ等）のイオンが配位した構造
を有する。このトンネル枠内のアルカリ金属イオンの一
部を抗菌性金属イオンで置き換えられたチタン酸化合物
が、本発明の抗菌性複合チタン酸化合物の構成成分であ
る前記式〔１〕の六チタン酸化合物である。抗菌性金属
イオンを含有するトンネル型結晶構造の六チタン酸化合
物〔１〕は、具体的には次式: （Ａ1-X ＢX/N ）2 Ｔｉ6 Ｏ13 〔式中，0 ＜X ＜1, Nは抗菌性金属Ｂの原子価〕として
表すことができる。BEST MODE FOR CARRYING OUT THE INVENTION An alkali metal hexatitanate having a tunnel type crystal structure is represented by the formula: A 2 Ti 6 O 13 (A: alkali metal), which is constituted by a chain of TiO 6 octahedra. Alkali metal (L
i, Na, K, Rb, Cs, etc.). A titanate compound in which a part of the alkali metal ion in the tunnel frame is replaced with an antibacterial metal ion is a hexatitanate compound of the above formula [1], which is a component of the antibacterial composite titanate compound of the present invention. is there. The hexatitanate compound [1] having a tunnel-type crystal structure containing an antibacterial metal ion is specifically represented by the following formula: (A 1−X B X / N ) 2 Ti 6 O 13 [where 0 <X <1, N is the valence of antibacterial metal B].
【０００６】抗菌性金属イオンを含有する六チタン酸化
合物〔１〕は、トンネル枠内から極微量の抗菌性金属イ
オンが溶出し抗菌作用を発現する。本発明は、六チタン
酸アルカリ金属のトンネル枠内に抗菌性金属イオンを担
持させた構造を有するので、従来の抗菌剤、例えばゼオ
ライト等の表面に抗菌性金属イオンを吸着担持させた抗
菌剤に比し、抗菌性金属イオンが安定に保持され、抗菌
作用の持続性にすぐれる。しかも、トンネル構造の六チ
タン酸化合物は、熱的・化学的に安定であり、高温環境
下にも抗菌作用の衰えはなく、種々の使用環境・使用態
様のもとに高い抗菌作用が安定に維持される。[0006] The hexatitanate compound [1] containing an antibacterial metal ion exhibits an antibacterial action because a very small amount of the antibacterial metal ion is eluted from the inside of the tunnel frame. Since the present invention has a structure in which an antibacterial metal ion is supported in a tunnel frame of an alkali metal hexatitanate, a conventional antibacterial agent, for example, an antibacterial agent in which an antibacterial metal ion is adsorbed and supported on the surface of zeolite or the like. On the other hand, the antibacterial metal ion is stably retained, and the antibacterial effect is excellent. In addition, the hexatitanate compound having a tunnel structure is thermally and chemically stable, and its antibacterial action does not decline even in a high-temperature environment, and its high antibacterial action is stable under various use environments and usage modes. Will be maintained.
【０００７】本発明の抗菌性複合チタン化合物は、抗菌
性金属イオン含有六チタン酸化合物〔１〕の結晶に、チ
タニア（ＴｉＯ2 ）の結晶が分散混在した混相化合物で
ある。ＴｉＯ2 は、よく知られているように、光の照射
により強い酸化力を持つ正孔と強い還元力をもつ電子を
生成し、その酸化還元作用により空気中の酸素や水分を
活性酸素に変化させ、生成する活性酸素は細菌等を死滅
させるほか、汚れや悪臭物質を分解する機能を有してい
る。従って、本発明の抗菌性複合チタン化合物は、六チ
タン酸化合物〔１〕の抗菌作用と、チタニア結晶の光触
媒作用とが重畳した抗菌，防汚，防臭，防藻等の効果を
発現する。抗菌性金属イオン含有六チタン酸化合物
〔１〕とチタニア結晶の混在量比は、用途，使用環境，
要求特性に応じて任意に設定されるが、六チタン酸化合
物／チタニアの量比（重量）: 約９５／５〜５０／５０
の範囲内において、種々の用途に対する良好な抗菌，防
汚，防臭，防藻等の効果が得られる。The antibacterial composite titanium compound of the present invention is a mixed phase compound in which crystals of titania (TiO 2 ) are dispersed and mixed with crystals of the antibacterial metal ion-containing hexatitanate compound [1]. As is well known, TiO 2 generates holes with strong oxidizing power and electrons with strong reducing power when irradiated with light, and converts oxygen and moisture in the air into active oxygen by the redox action. The generated active oxygen kills bacteria and the like, and has a function of decomposing dirt and odorous substances. Therefore, the antibacterial composite titanium compound of the present invention exhibits effects such as antibacterial, antifouling, deodorant, and antialgal effects in which the antibacterial action of the hexatitanate compound [1] and the photocatalytic action of titania crystals are superimposed. The mixing ratio of the antimicrobial metal ion-containing hexatitanate compound [1] and the titania crystal depends on the application, usage environment,
It is arbitrarily set according to the required characteristics, but the amount ratio (weight) of hexatitanate compound / titania: about 95/5 to 50/50
Within the range, good effects such as antibacterial, antifouling, deodorizing, and antialgae for various uses can be obtained.
【０００８】次に、本発明の抗菌性チタン化合物の製造
法について説明する。Next, a method for producing the antibacterial titanium compound of the present invention will be described.
【原料物質】本発明の抗菌性チタン化合物は、下式: Ａ2 Ｔｉn Ｏ2n+1 …〔２〕 〔式中，A:アルカリ金属 n:２〜４〕で示される層状結晶構造のチタン酸アルカリ
金属を原料として製造される。原料化合物〔２〕の例と
して、二チタン酸アルカリ金属（K 2 Ti2 O 5,Li2 Ti 2
O 5 等）、三チタン酸アルカリ金属（Na2 Ti3 O
7 等），四チタン酸アルカリ金属（K 2 Ti4 O 9, Li 2
Ti4 O 9 等）が挙げられる。二チタン酸アルカリ金属
は、TiO 5 三角両錐体の連鎖が積層した層間にアルカリ
金属イオンが配位し, 三チタン酸アルカリ金属および四
チタン酸アルカリ金属は、TiO 6 八面体の連鎖が積層し
た層間にアルカリ金属イオンが配位した結晶構造を有す
る。層状構造チタン酸アルカリ金属〔２〕を原料とする
のは、層状構造であることにより、アルカリ金属と抗菌
性金属イオンのイオン交換処理を比較的容易に行うこと
ができるからである。[Raw material] The antibacterial titanium compound of the present invention has the following formula: ATwoTinO2n + 1 ... [2] [wherein A: alkali metal n: 2 to 4] an alkali titanate having a layered crystal structure
Manufactured from metal. Examples of starting compound [2]
And alkali metal dititanate (KTwoTiTwoOFive,LiTwoTi Two
OFiveEtc.), alkali metal trititanate (NaTwoTiThreeO
7Etc.), alkali metal tetratitanate (KTwoTiFourO9, LiTwo
TiFourO9Etc.). Alkali metal dititanate
Is TiOFiveAlkali between layers of triangular bipyramidal chains
Metal ions coordinate,Alkali metal trititanate and quaternary
Alkali metal titanate is TiO6Octahedral chains stacked
Has a crystal structure in which alkali metal ions are coordinated between layers
You. Starting from layered structure alkali metal titanate [2]
The fact that it has a layered structure makes it possible to
Performing ion exchange treatment of reactive metal ions relatively easily
Because it can be.
【０００９】[0009]
【アルカリ金属・抗菌性金属のイオン交換処理】出発原
料（チタン酸化合物〔２〕）のイオン交換処理は、下記
のように、アルカリ金属イオン溶出処理とそれにつづく
抗菌性金属イオン導入処理の２つの工程として行うこと
ができる。処理効率の点から、原料化合物は比較的細粒
に調整された粉末（粒径約 0.1〜100 μｍ）を使用する
のが好ましい。[Ion-exchange treatment of alkali metal and antibacterial metal] The ion-exchange treatment of the starting material (titanate compound [2]) is carried out by the following two processes: elution treatment of alkali metal ions and introduction treatment of antibacterial metal ions. It can be performed as a process. From the viewpoint of the processing efficiency, it is preferable to use a powder (particle size: about 0.1 to 100 μm) adjusted to relatively fine particles as the raw material compound.
【００１０】[0010]
上記水和チタン酸化合物〔３〕は、具体的には下式: （Ａ1-X ＨX ）2 Ｔｉn Ｏ2n+1・ｍＨ2 Ｏ 〔式中，0 ＜ｘ＜ 1，ｎおよびｍは前記と同義〕のよう
に表すことができる。The hydrated titanic acid compound [3], the following formula is specifically: (A 1-X H X ) 2 Ti n O 2n + 1 · mH 2 O wherein, 0 <x <1, n and m Is as defined above).
【００１１】[0011]
【抗菌性金属Ｂイオン導入処理】上記水和チタン酸化合
物〔３〕に対する抗菌性金属イオン導入処理は、抗菌性
金属の塩類の１種ないし２種以上を含有する溶液を処理
液として行われる。その処理は、水和チタン酸化合物
〔３〕を含む上記溶出処理液に、抗菌性金属塩溶液を添
加する方法、または水和チタン酸化合物〔３〕を溶出処
理液から回収し、脱水乾燥した後、抗菌性金属塩溶液と
接触させる方法を採用することができる。[Antimicrobial metal B ion introduction treatment] The antimicrobial metal ion introduction treatment for the hydrated titanate compound [3] is performed using a solution containing one or more salts of antibacterial metals. The treatment is carried out by adding an antibacterial metal salt solution to the above-mentioned elution solution containing the hydrated titanate compound [3], or collecting the hydrated titanate compound [3] from the elution solution and dehydrating and drying the solution. Thereafter, a method of contacting with an antibacterial metal salt solution can be adopted.
【００１２】抗菌性金属塩溶液は、目的とする抗菌性チ
タン酸化合物の組成に応じて調製され、例えば、銀（Ａ
ｇ）イオンは，硝酸銀，硫酸銀，過塩素酸銀，酢酸銀，
ジアミン銀硝酸塩等、銅（Ｃｕ）イオンは，硝酸銅，硫
酸銅，過塩素酸銅，酢酸銅等、亜鉛（Ｚｎ）イオンは，
硝酸亜鉛，硫酸亜鉛，過塩素酸亜鉛，チオシアン酸亜
鉛，酢酸亜鉛等、水銀（Ｈｇ）イオンは，硝酸水銀，過
塩素酸水銀，酢酸水銀等，錫（Ｓｎ）イオンは，硫酸
錫、鉛（Ｐｂ）イオンは，硫酸鉛，硝酸鉛等，ビスマス
（Ｂｉ）イオンは，塩化ビスマス，沃化ビスマス等，カ
ドミウム（Ｃｄ）イオンは，過塩素酸カドミウム，硫酸
カドミウム，硝酸カドミウム等、クロム（Ｃｒ）イオン
は，過塩素酸クロム，硫酸クロム，硫酸アンモニウムク
ロム，硝酸クロム等、タリウム（Ｔｌ）イオンは，硫酸
タリウム，過塩素酸タリウム，硝酸タリウム，酢酸タリ
ウム等の塩類の溶液が使用される。The antibacterial metal salt solution is prepared according to the composition of the target antibacterial titanate compound.
g) The ions are silver nitrate, silver sulfate, silver perchlorate, silver acetate,
Copper (Cu) ions such as diamine silver nitrate are copper nitrate, copper sulfate, copper perchlorate, copper acetate, etc. Zinc (Zn) ion is
Mercury (Hg) ions, such as zinc nitrate, zinc sulfate, zinc perchlorate, zinc thiocyanate, and zinc acetate; mercury nitrate, mercury perchlorate, and mercury acetate; tin (Sn) ions, tin sulfate and lead ( Pb) ions are lead sulfate, lead nitrate, etc., bismuth (Bi) ions are bismuth chloride, bismuth iodide, etc., cadmium (Cd) ions are cadmium perchlorate, cadmium sulfate, cadmium nitrate, etc., chromium (Cr). As the ion, a solution of salts such as thallium sulfate, thallium perchlorate, thallium nitrate, and thallium acetate is used as the thallium (Tl) ion.
【００１３】上記イオン導入処理により、水和チタン酸
化合物〔３〕の結晶内の水素イオンおよび／またはアル
カリ金属イオンの一部が抗菌性金属イオンに置換され
た、下式〔４〕で示される抗菌性金属イオン含有水和チ
タン酸化合物を得る。その化学組成は、処理液として使
用される抗菌性金属塩溶液の濃度，ｐＨ，処理時間等に
より調整される。 （Ａ，Ｂ，Ｈ）2 Ｔｉn Ｏ2n+1・ｍＨ2 Ｏ…〔４〕 〔式中，A.B.ｍは前記と同義，ｎ:2〜4 〕 この抗菌性金属イオン含有水和チタン酸化合物は、より
具体的には下式: ((Ａ1-X ＨX ) 1-Y ＢY/N ) 2 Ｔｉn Ｏ2n+1・ｍＨ2 Ｏ 〔式中，0 ＜Y ＜1, X, N,ｎおよびｍは前記と同義〕の
ように表される。この水和チタン酸化合物におけるＨ組
成比〔 X(1-Y) 〕は、製品抗菌剤（抗菌性六チタン酸化
合物とチタニアの混相化合物）のチタニアの生成を確保
するために、出発原料（チタン酸アルカリ金属）の種類
に応じて調節される。出発原料を四チタン酸アルカリ金
属とする場合、X(1-Y)＞0.33、三チタン酸アルカリ金属
の場合は、X(1-Y)＞0.5 、二チタン酸アルカリ金属の場
合は、X(1-Y)＞0.67、にそれぞれ調節すればよい。The hydrogen ion and / or alkali metal ions in the crystals of the hydrated titanate compound [3] are partially replaced by antibacterial metal ions by the above-mentioned ion introduction treatment, and are represented by the following formula [4]. An antibacterial metal ion-containing hydrated titanate compound is obtained. The chemical composition is adjusted by the concentration, pH, treatment time, etc. of the antibacterial metal salt solution used as the treatment liquid. (A, B, H) wherein, ABm are as defined above, n: 2 to 4] 2 Ti n O 2n + 1 · mH 2 O ... [4] The antibacterial metal ion-containing hydrated titanic acid compound , more specifically the following formula: ((a 1-X H X) 1-Y B Y / n) 2 Ti n O 2n + 1 · mH 2 O wherein, 0 <Y <1, X , n , n and m are as defined above]. The H composition ratio [X (1-Y)] in this hydrated titanic acid compound is determined based on the starting material (titanium) in order to ensure the production of titania as a product antibacterial agent (a mixed phase compound of an antibacterial hexatitanate compound and titania). (Alkali metal acid). When the starting material is an alkali metal tetratitanate, X (1-Y)> 0.33, in the case of an alkali metal trititanate, X (1-Y)> 0.5, and in the case of an alkali metal dititanate, X ( 1-Y)> 0.67.
【００１４】[0014]
【焼成処理（結晶構造変換）】上記イオン交換処理で得
た水和チタン酸化合物〔４〕を、脱水乾燥の後、焼成処
理に付す。その焼成処理（結晶構造変換反応）により、
水和チタン酸化合物〔４〕の TiO2 成分と (A,B)2 O 成
分の等モル量の反応により、抗菌性金属イオン含有トン
ネル構造六チタン酸化合物〔１〕（TiO 2 / (A,B) 2 O
＝６〕が析出生成し、残余のＴｉＯ2 分はチタニア結晶
として析出生成する。この焼成反応生成物として、目的
物である抗菌性複合化合物を得る。[Baking treatment (Crystal structure conversion)] The hydrated titanate compound [4] obtained by the above-mentioned ion exchange treatment is subjected to a baking treatment after dehydration and drying. By the firing process (crystal structure conversion reaction),
By reacting the equimolar amounts of the TiO 2 component and the (A, B) 2 O component of the hydrated titanate compound [4], an antibacterial metal ion-containing tunnel structure hexatitanate compound [1] (TiO 2 / (A, B) 2 O
= 6] is precipitated and the remaining TiO 2 is precipitated and formed as titania crystals. An antibacterial composite compound, which is the target, is obtained as a product of the calcination reaction.
【００１５】このように本発明の抗菌性複合チタン化合
物を構成する、抗菌性金属イオン含有トンネル構造六チ
タン酸化合物〔１〕と、チタニア（ＴｉＯ2 ）結晶との
混相量比は、水和チタン酸化合物〔４〕の化学組成に依
存する。換言すれば、本発明の複合チタン化合物の混相
量比は、原料（層状構造チタン酸アルカリ金属〔２〕）
のアルカリ金属溶出処理条件および水和チタン酸化合物
〔３〕の抗菌性金属イオン導入処理条件により任意に調
整できるということである。焼成処理は、温度７００〜
１３００℃に適当時間（約１〜４Ｈｒ）保持することに
より達成される。７００℃に満たない処理温度では、ト
ンネル構造六チタン酸化合物〔１〕およびチタニア（Ｔ
ｉＯ2 ）の結晶の析出生成反応を効率よく行わせること
が困難であり、他方１３００℃を越えると、六チタン酸
化合物〔１〕に溶融を生じ、目的とする混相抗菌性化合
物の収率の低下をきたす。As described above, the antimicrobial metal ion-containing tunnel structure hexatitanate compound [1] constituting the antimicrobial composite titanium compound of the present invention and the titania (TiO 2 ) crystal have a mixed phase ratio of titanium hydrate. It depends on the chemical composition of the acid compound [4]. In other words, the mixed phase ratio of the composite titanium compound of the present invention depends on the raw material (layer-structured alkali metal titanate [2]).
Can be arbitrarily adjusted by the alkali metal elution treatment condition and the antibacterial metal ion introduction treatment condition of the hydrated titanate compound [3]. The firing process is performed at a temperature of 700 to
This is achieved by maintaining the temperature at 1300 ° C. for an appropriate time (about 1 to 4 hours). At a processing temperature lower than 700 ° C., the tunnel structure hexatitanate compound [1] and titania (T
It is difficult to efficiently carry out the precipitation and formation reaction of iO 2 ) crystals. On the other hand, when the temperature exceeds 1300 ° C., the hexatitanate compound [1] is melted, and the yield of the target multiphase antibacterial compound is reduced. Causes a decline.
【００１６】上記工程を経て収得される抗菌性複合チタ
ン化合物は、原料として使用したチタン酸アルカリ金属
の粒子形態とほぼ同じ形態を有する。このものは、粉末
のまま、またはそれを素材とする圧粉成形体として、あ
るいは粉末に樹脂，その他の異材種を配合して調製され
る組成物・混合物等として、種々の形態で使用すること
ができる。本発明の抗菌性チタン酸化合物は、一般細
菌，真菌，藻類等，微生物の発生増殖防止，防臭，防汚
等を必要とする種々の分野に利用することができ、例え
ば、水系分野では、浄水器，クーリングタワー水，各種
冷却水の抗菌・防藻剤として使用され、塗料分野では、
油性塗料，樹脂塗料，水系・粉体系等の各種塗料に混合
し，または塗膜表面にコーティングして塗膜に抗菌・抗
黴・抗藻機能等を付与し、建築分野では、目地材，壁
材，タイル等に混合し，もしくはその表面にコーティン
グして抗菌・抗黴・抗藻機能をもたせ、製紙分野では、
濡れティッシュ，包装紙，ダンボール，電気掃除器用パ
ックフィルタ，敷紙，鮮度保持紙に混抄し、もしくは表
面にコーティングして抗菌・抗黴・抗藻機能を付与する
ことができ、その他、化粧料分野（メイクアップ料，フ
ァンデーション等）、衣料分野（病院衣，スポーツウエ
アー，作業衣等）、空気調和装置のフィルタ、厨房機器
類等の分野において種々の形態で適用し，抗菌，防黴，
防臭，防汚機能を付与することすることができる。The antibacterial composite titanium compound obtained through the above steps has substantially the same form as the particle form of the alkali metal titanate used as a raw material. This product may be used in various forms, either as a powder or as a green compact using it as a raw material, or as a composition or mixture prepared by blending resin and other dissimilar materials with the powder. Can be. The antibacterial titanate compound of the present invention can be used in various fields requiring prevention of the growth and growth of microorganisms, such as general bacteria, fungi, and algae, as well as deodorization and antifouling. It is used as an antibacterial and anti-algal agent for containers, cooling tower water and various types of cooling water.
It is mixed with various paints such as oil paints, resin paints, water-based and powder-based paints, or coated on the surface of the paint film to impart antibacterial, anti-fungal and anti-algal functions to the paint film. Mixed with wood, tile, etc., or coated on the surface to provide antibacterial, antifungal and antialgal functions.
It can be mixed with wet tissue, wrapping paper, cardboard, pack filters for vacuum cleaners, wrapping paper, freshness preserving paper, or coated on the surface to provide antibacterial, antifungal and antialgal functions. (Make-up fee, foundation, etc.), clothing (hospital clothing, sportswear, work clothing, etc.), filters for air conditioners, kitchen appliances, etc.
A deodorant and antifouling function can be provided.
【００１７】[0017]
〔実施例１〕 （１）原料 二チタン酸カリウム粉末，粒径: 0.1 〜10μｍ（後記参
考例１による） （２）イオン交換処理 (2.1)アルカリ金属イオン溶出処理 原料粉末100gを、蒸留水 400mLに浸漬する。これに１mo
l/L の硝酸をｐＨを確認しながら徐々に添加し、緩和な
攪拌流下に、２Hrを要して結晶層間のＫイオンの一部を
溶出すると共に、ｐＨを6 〜6.5 に調整する。 (2.2)抗菌性金属イオン導入処理 上記スラリーに、1 mol/L の硝酸銀溶液 20ml を加え、
緩和な攪拌流下に１Hrを要して、抗菌性イオン含有水和
チタン酸化合物に組成変換する。[Example 1] (1) Raw material potassium dititanate powder, particle size: 0.1 to 10 µm (according to Reference Example 1 described later) (2) Ion exchange treatment (2.1) Alkali metal ion elution treatment 100 g of the raw material powder was mixed with 400 mL of distilled water. Soak in This is 1mo
1 / L nitric acid is gradually added while confirming the pH, and under a gentle stirring flow, a part of K ions between the crystal layers is eluted with 2Hr, and the pH is adjusted to 6 to 6.5. (2.2) Antimicrobial metal ion introduction treatment To the above slurry, add 20 ml of 1 mol / L silver nitrate solution,
The composition is converted to a hydrated titanate compound containing an antibacterial ion by requiring 1 hour under a gentle stirring flow.
【００１８】（３）焼成処理 処理液から粉末を回収し、脱水乾燥後、電気炉内で焼成
乾燥（800 ℃×1Hr)して製品粉末を得る。得られた粉末
の結晶構造（Ｘ線回折）および銀イオン含有量（蛍光Ｘ
線分析）は下記のとおりである。 結晶構成: 六チタン酸カリウム銀〔(K,Ag)2 Ti6 O 13〕
/ チタニア(TiO 2 ) 混相量比: 83.1/ 16.9（重量比） 銀イオン濃度: 約４重量％(3) Firing treatment The powder is recovered from the processing liquid, dehydrated and dried, and then fired and dried (800 ° C. × 1 hr) in an electric furnace to obtain a product powder. The crystal structure (X-ray diffraction) and silver ion content (fluorescent X
Line analysis) is as follows. Crystal structure: Potassium hexatitanate [(K, Ag) 2 Ti 6 O 13 ]
/ Titania (TiO 2 ) Mixed phase ratio: 83.1 / 16.9 (weight ratio) Silver ion concentration: about 4% by weight
【００１９】〔実施例２〕 （１）原料 三チタン酸ナトリウム, 粒径: 0.1 〜10μｍ（後記参考
例２による） （２）イオン交換処理 (2.1) アルカリ金属イオン溶出処理 原料粉末100gを、1.5 mol/L 硝酸１Ｌに浸漬する。緩和
な攪拌流下に、４Hrを要して結晶層間のナトリウムイオ
ンの一部を溶出し、水和三チタン酸ナトリウムに組成変
換し、これを液中から回収し、脱水乾燥する。Example 2 (1) Raw material sodium trititanate, particle size: 0.1 to 10 μm (according to Reference Example 2 described later) (2) Ion exchange treatment (2.1) Alkali metal ion elution treatment Immerse in 1 L of mol / L nitric acid. Under mild stirring flow, a part of sodium ions between the crystal layers is eluted with 4Hr, and the composition is converted into hydrated sodium trititanate, which is recovered from the liquid and dehydrated and dried.
【００２０】(2.2) 抗菌性金属イオン導入処理 上記水和三チタン酸ナトリウム粉末を蒸留水 400mlに浸
漬し、これに 1mol/L硝酸銀溶液 10mL を添加する。緩
和な攪拌下に5 Hrを要して銀イオン含有水和チタン酸化
合物に組成変換する。 （３）焼成処理 処理液から回収した粉末を、脱水乾燥後、電気炉内で焼
成処理（温度: 900 ℃, 時間: 1 Hr) して製品粉末を得
る。 結晶構成: 六チタン酸カリウム銀〔(Na,Ag) 2 Ti6 O
13〕/ チタニア(TiO2 ) 混相量比: 74.4 / 25.6 （重量比） 銀イオン濃度: 約１重量％(2.2) Antimicrobial metal ion introduction treatment The above hydrated sodium trititanate powder is immersed in 400 ml of distilled water, and 10 ml of a 1 mol / L silver nitrate solution is added thereto. The composition is converted into a hydrated titanate compound containing silver ions by using 5 Hr under gentle stirring. (3) Firing treatment The powder recovered from the treatment liquid is dehydrated and dried, and then fired in an electric furnace (temperature: 900 ° C., time: 1 Hr) to obtain a product powder. Crystal structure: Potassium hexatitanate [(Na, Ag) 2 Ti 6 O
13 ] / Titania (TiO 2 ) mixed phase ratio: 74.4 / 25.6 (weight ratio) Silver ion concentration: about 1% by weight
【００２１】参考例−層状構造チタン酸アルカリ金属の
製造− 〔参考例１（二チタン酸カリウム粉末の製造）〕酸化チ
タン（ＴｉＯ2 ）粉末（精製アナターゼ粉末）と炭酸カ
リウム（Ｋ2 ＣＯ3 ）粉末とを、ＴｉＯ2 ／Ｋ2 Ｏ（モ
ル比）が２となる割合に混合し、これを電気炉中で焼成
処理（８００℃×１Ｈｒ）する。焼成反応生成物は二チ
タン酸カリウム（K 2 Ti2 O 5 ) の結晶粒からなる固化
物であり、これを高速ハンマーミルで粉砕して粒径0.1
〜10μｍの二チタン酸カリウム粉末を得る。REFERENCE EXAMPLE-Production of Layered Structure Alkali Metal Titanate [Reference Example 1 (Production of Potassium Dititanate Powder)] Titanium oxide (TiO 2 ) powder (purified anatase powder) and potassium carbonate (K 2 CO 3 ) The powder and TiO 2 / K 2 O (molar ratio) are mixed at a ratio of 2 and the mixture is fired (800 ° C. × 1 hr) in an electric furnace. The sintering reaction product is a solidified product composed of crystal grains of potassium dititanate (K 2 Ti 2 O 5 ), which is pulverized by a high-speed hammer mill to a particle size of 0.1.
A potassium dititanate powder of の 10 μm is obtained.
【００２２】〔参考例２（三チタン酸ナトリウム粉末の
製造）〕酸化チタン（ＴｉＯ2 ）粉末（精製アナターゼ
粉末）と炭酸ナトリウム（Ｎａ 2 ＣＯ3 ）粉末とを、Ｔ
ｉＯ2 ／Ｎａ2 Ｏのモル比が３となる割合に混合し、電
気炉中で焼成処理（１０００℃×１Ｈｒ）する。 焼成
反応生成物は、三チタン酸ナトリウム（Na2 Ti3 O 7 ）
の結晶粒かなる固形物である。これを高速ハンマーミル
で粉砕して粒径0.1 〜10μｍの三チタン酸ナトリウム粉
末を得る。[Reference Example 2 (of sodium trititanate powder)
Production)] Titanium oxide (TiOTwo) Powder (purified anatase
Powder) and sodium carbonate (Na TwoCOThree) Powder and T
iOTwo/ NaTwoO was mixed at a molar ratio of 3
A baking treatment (1000 ° C. × 1 hour) is performed in an air furnace. Firing
The reaction product is sodium trititanate (NaTwoTiThreeO7)
Is a solid consisting of crystal grains. This is a high-speed hammer mill
Sodium trititanate powder with a particle size of 0.1 to 10 μm
Get the end.
【００２３】[0023]
【抗菌性試験】上記実施例の抗菌剤および比較抗菌剤等
について、菌に対する最少発育阻止濃度（Minimum Inhi
bitory Concentration: MIC ）を測定し、表１に示す結
果を得た。比較例 No.1 は六チタン酸カリウム（K 2 Ti
6 O 13) 結晶，比較例No.2は六チタン酸ナトリウム（Na
2 Ti6 O 13) 結晶（いずれも抗菌性金属を含まない）、
比較例No.3は、ゼオライトに銀イオンを吸着担持した市
販品無機系抗菌剤（銀ゼオライト）である。本発明の抗
菌剤は、すぐれた抗菌作用を有している。[Antibacterial test] For the antibacterial agent of the above example and the comparative antibacterial agent, the minimum inhibitory concentration against bacteria (Minimum Inhi
bitory Concentration: MIC) was measured, and the results shown in Table 1 were obtained. Comparative Example No. 1 was potassium hexatitanate (K 2 Ti
6 O 13 ) crystal, Comparative Example No. 2 is sodium hexatitanate (Na
2 Ti 6 O 13 ) crystal (both do not contain antibacterial metal),
Comparative Example No. 3 is a commercially available inorganic antibacterial agent (silver zeolite) in which silver ions are adsorbed and supported on zeolite. The antibacterial agent of the present invention has an excellent antibacterial action.
【００２４】（試験菌株） 大腸菌 (Escherihia coli) IFO 3301 緑膿菌 (Pseudomonas aeruginosa）IFO 3452 黄色ブドウ球菌 (Staphylococcus aureus) IFO 12732 黒こうじカビ(Aspergillus niger) IFO 6341 オーレオバシディウム (Aureobasidium pululans) IF
O 6353(Test strain) Escherichia coli (Escherihia coli) IFO 3301 Pseudomonas aeruginosa IFO 3452 Staphylococcus aureus IFO 12732 Aspergillus niger IFO 6341 Aureobasidium pululans IF
O 6353
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明の抗菌性チタン酸化合物は、六チ
タン酸化合物のトンネル結晶構造内に保持された抗菌性
金属イオンの抗菌作用とチタニア結晶の光触媒作用との
重畳作用により、高度の抗菌作用，防黴，防臭，防汚等
にすぐれた効果を発揮する。本発明の抗菌性チタン酸化
合物は、粉末，成形体として，また樹脂，その他の異種
材との混合物，組成物，その他各種の形態で使用され、
一般細菌，真菌，藻類等，微生物の発生増殖防止，防
臭，防汚等を必要とする種々の分野に利用することがで
き、耐熱性，断熱性，強度，補強効果に優れていること
により、例えば、建築分野、水系分野、塗料分野、製紙
分野、化粧料分野、衣料分野、空気調和装置、厨房機器
類等の分野において種々の形態で適用し，抗菌，防黴，
防臭，防汚機能を付与することすることができる。The antibacterial titanate compound of the present invention has a high antibacterial effect due to the superposition of the antibacterial action of the antibacterial metal ion held in the tunnel crystal structure of the hexatitanate compound and the photocatalytic action of the titania crystal. It has excellent effects on action, fungicide, deodorant, antifouling, etc. The antibacterial titanate compound of the present invention is used as a powder, a molded article, a resin, a mixture with other dissimilar materials, a composition, and various other forms.
It can be used in various fields that require the prevention and growth of microorganisms such as general bacteria, fungi, and algae, as well as deodorization and antifouling, and is excellent in heat resistance, heat insulation, strength, and reinforcing effect. For example, it is applied in various forms in the fields of architecture, water-based field, paint field, papermaking field, cosmetic field, clothing field, air conditioner, kitchen equipment, etc.
A deodorant and antifouling function can be provided.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ａ０１Ｎ 59/20 Ａ０１Ｎ 59/20 Ｚ Ａ６１Ｌ 2/16 Ａ６１Ｌ 2/16 Ｚ // Ａ６１Ｋ 33/24 ＡＤＺ Ａ６１Ｋ 33/24 ＡＤＺ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI A01N 59/20 A01N 59/20 Z A61L 2/16 A61L 2/16 Z // A61K 33/24 ADZ A61K 33/24 ADZ
Claims (3)
アルカリ金属のアルカリ金属イオンの一部が抗菌性金属
イオンで置換された、次式: （Ａ，Ｂ）2 Ｔｉ6 Ｏ13 …〔１〕 〔式中，Ａ: アルカリ金属 Ｂ: 抗菌性金属 〕で示されるトンネル型結晶構造の
六チタン酸化合物の結晶と、チタニア（ＴｉＯ 2 ）の結
晶とが分散混在した混相化合物であることを特徴とする
抗菌性複合チタン酸化合物。1. A hexatitanic acid having a tunnel type crystal structure
Some of the alkali metal ions of the alkali metal are antibacterial metals
The following formula replaced with ions: (A, B)TwoTi6O13 ... [1] [wherein A: alkali metal B: antibacterial metal]
Crystals of hexatitanate compound and titania (TiO Two)
It is characterized by being a mixed phase compound in which crystals and dispersion are mixed.
Antibacterial composite titanate compound.
ｎ，Ｈｇ，Ｓｎ，Ｐｂ，Ｂｉ，Ｃｄ，Ｃｒ，Ｔｌの群か
ら選ばれる１種ないし２種以上の金属であることを特徴
とする請求項１に記載の抗菌性複合チタン酸化合物。2. The antibacterial metal (B) is composed of Ag, Cu, Z
The antibacterial composite titanate compound according to claim 1, wherein the compound is one or more metals selected from the group consisting of n, Hg, Sn, Pb, Bi, Cd, Cr, and Tl.
ン交換処理に付し、層間のイオンの一部を抗菌性金属イ
オンに置換して、次式: （Ａ，Ｂ，Ｈ）2 Ｔｉn Ｏ2n+1・ｍＨ2 Ｏ 〔式中，Ａ: 前記と同義 Ｂ: 抗菌性金属 ｎ: ２〜４，ｍ: 正数 〕で示される水和チタン
酸化合物に組成変換し、脱水乾燥の後、焼成処理に付し
て、トンネル型結晶構造の六チタン酸化合物およびチタ
ニア（ＴｉＯ2 ）の結晶を析出生成することを特徴とす
る請求項１または請求項２に記載の抗菌性複合チタン酸
化合物の製造方法。3. A having a layered crystal structure, the following formula: A 2 Ti n O 2n + 1 wherein, A: an alkali metal n: 2 to 4] The alkali metal titanate represented by, with the ion-exchange process and, by replacing part of the interlayer ions in the antimicrobial metal ions, the following formula: (a, B, H) 2 Ti n O 2n + 1 · mH 2 O [wherein, a: as defined above B: Antibacterial metal n: 2 to 4, m: positive number] The composition is converted to a hydrated titanate compound represented by the formula: dehydrated and dried, and then subjected to a baking treatment to obtain a tunnel type crystal structure hexatitanate compound and titania. The method for producing an antibacterial composite titanate compound according to claim 1 or 2, wherein (TiO 2 ) crystals are precipitated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10016687A JPH10273322A (en) | 1997-01-30 | 1998-01-29 | Antifungal composite titanate and manufacture of the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1603097 | 1997-01-30 | ||
| JP9-16030 | 1997-01-30 | ||
| JP10016687A JPH10273322A (en) | 1997-01-30 | 1998-01-29 | Antifungal composite titanate and manufacture of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10273322A true JPH10273322A (en) | 1998-10-13 |
Family
ID=26352269
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10016687A Withdrawn JPH10273322A (en) | 1997-01-30 | 1998-01-29 | Antifungal composite titanate and manufacture of the same |
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| JP (1) | JPH10273322A (en) |
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| WO2005110598A1 (en) * | 2004-05-13 | 2005-11-24 | Fujitsu Limited | Apatite and method for production thereof, and apatite base material |
| JP2008171621A (en) * | 2007-01-10 | 2008-07-24 | Konica Minolta Holdings Inc | Photoelectric conversion element, and dye-sensitized solar cell |
| JP2010100527A (en) * | 2010-01-28 | 2010-05-06 | Kubota Corp | Titanic acid compound powder and cosmetic |
| JP2010222266A (en) * | 2009-03-19 | 2010-10-07 | Panasonic Corp | Antibacterial agent composition |
| WO2016042913A1 (en) * | 2014-09-19 | 2016-03-24 | 昭和電工株式会社 | Antibacterial/antiviral composition, antibacterial/antiviral agent, photocatalyst, and bacteria/virus inactivation method |
| JP2021031450A (en) * | 2019-08-27 | 2021-03-01 | 学校法人同志社 | Antibacterial titanium oxide powder and method for producing the same |
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-
1998
- 1998-01-29 JP JP10016687A patent/JPH10273322A/en not_active Withdrawn
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| JP2004010464A (en) * | 2002-06-11 | 2004-01-15 | Kubota Corp | Titanic acid compound powder and cosmetic |
| WO2005110598A1 (en) * | 2004-05-13 | 2005-11-24 | Fujitsu Limited | Apatite and method for production thereof, and apatite base material |
| JP2008171621A (en) * | 2007-01-10 | 2008-07-24 | Konica Minolta Holdings Inc | Photoelectric conversion element, and dye-sensitized solar cell |
| JP2010222266A (en) * | 2009-03-19 | 2010-10-07 | Panasonic Corp | Antibacterial agent composition |
| JP2010100527A (en) * | 2010-01-28 | 2010-05-06 | Kubota Corp | Titanic acid compound powder and cosmetic |
| WO2016042913A1 (en) * | 2014-09-19 | 2016-03-24 | 昭和電工株式会社 | Antibacterial/antiviral composition, antibacterial/antiviral agent, photocatalyst, and bacteria/virus inactivation method |
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| JPWO2016042913A1 (en) * | 2014-09-19 | 2017-04-27 | 昭和電工株式会社 | Antibacterial / antiviral composition, antibacterial / antiviral agent, photocatalyst, and bacteria / virus inactivation method |
| JP2021185154A (en) * | 2016-03-08 | 2021-12-09 | ユニバーシティー オブ ユタ リサーチ ファウンデーションUniversity of Utah Research Foundation | Cross-linking agents and associated methods |
| JP2021031450A (en) * | 2019-08-27 | 2021-03-01 | 学校法人同志社 | Antibacterial titanium oxide powder and method for producing the same |
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