JP3218605B2 - Antibacterial phosphate intercalation compound and method for producing the same - Google Patents
Antibacterial phosphate intercalation compound and method for producing the sameInfo
- Publication number
- JP3218605B2 JP3218605B2 JP40578390A JP40578390A JP3218605B2 JP 3218605 B2 JP3218605 B2 JP 3218605B2 JP 40578390 A JP40578390 A JP 40578390A JP 40578390 A JP40578390 A JP 40578390A JP 3218605 B2 JP3218605 B2 JP 3218605B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- phosphate
- metal
- amine
- producing
- 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
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、種々の細菌に対して抗
菌作用を有する新規かつ改良された抗菌性リン酸塩層間
化合物およびその製造方法に関し、更に詳しくは、それ
自体が経時的に変色せず、さらには樹脂などと混練して
抗菌性樹脂組成物とした場合にも経時的に変色すること
のない、抗菌性リン酸塩層間化合物およびその製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and improved antibacterial phosphate intercalation compound having an antibacterial activity against various bacteria and a method for producing the same, and more particularly to a method for discoloring itself over time. The present invention relates to an antibacterial phosphate interlayer compound which does not discolor over time even when kneaded with a resin or the like to form an antibacterial resin composition, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来、無機系の抗菌剤においては、抗菌
作用を有する銀などの金属やそれの化合物をゼオライ
ト、活性炭、活性アルミナ、シリカゲル等の吸着剤に吸
着させて抗菌目的に利用することが知られている。一
方、有機系の抗菌剤として種々の有機物質も提案されて
いる。しかし前者の無機系のものは、銀などの抗菌作用
を有する金属の安定性が不十分で抗菌効果の持続性等の
点で問題があった。また、後者の有機系では、耐熱性に
乏しい、蒸気圧が高い、毒性が比較的高い等の欠点があ
った。2. Description of the Related Art Conventionally, in the case of inorganic antibacterial agents, a metal such as silver having an antibacterial action or a compound thereof is adsorbed to an adsorbent such as zeolite, activated carbon, activated alumina, silica gel and used for antibacterial purposes. It has been known. On the other hand, various organic substances have been proposed as organic antibacterial agents. However, the former inorganic type has a problem in that the metal having an antibacterial effect such as silver has insufficient stability and the antibacterial effect is persistent. Further, the latter organic system has disadvantages such as poor heat resistance, high vapor pressure, and relatively high toxicity.
【０００３】このような従来の抗菌剤の持つ問題点を解
消するものの一つとして、水に不溶ないし難溶性のリン
酸塩または縮合リン酸塩に、重金属イオンを担持させて
なる抗菌性組成物が提案されている（特開平2-96508
）。この抗菌性組成物は、抗菌作用を有する金属が活
性な状態で安定に保持されており、抗菌作用の持続性に
優れ、耐熱性にも優れている。One of the solutions to the problems of the conventional antibacterial agents is to provide an antibacterial composition comprising a heavy metal ion supported on a water-insoluble or hardly soluble phosphate or condensed phosphate. (Japanese Patent Laid-Open No. 2-96508)
). This antibacterial composition has a metal having an antibacterial action stably maintained in an active state, and has excellent durability of the antibacterial action and excellent heat resistance.
【０００４】[0004]
【発明の解決しようとする問題点】しかしながら、上述
した従来の抗菌性組成物は、樹脂等と混練して抗菌性樹
脂組成物として用いる場合に、混練時に変色したり、混
練後の抗菌性樹脂組成物が経時的に徐々に変色するとい
う問題点があった。However, when the above-mentioned conventional antibacterial composition is kneaded with a resin or the like and used as an antibacterial resin composition, the discoloration at the time of kneading or the antibacterial resin after kneading occurs. There was a problem that the composition gradually changed color with time.
【０００５】そこで本発明は、それ自体は経時的に変色
せず、さらに樹脂等と混練して抗菌性樹脂組成物として
使用する場合に、樹脂との混練時に変色したり、混練後
の抗菌性樹脂組成物が経時的に変色することのない、抗
菌性リン酸塩層間化合物およびその製造方法を提供する
ことを目的としてなされたものである。[0005] Therefore, the present invention does not discolor itself with time, and when used as an antibacterial resin composition after being kneaded with a resin or the like, the discoloration may occur upon kneading with the resin or the antibacterial property after kneading. An object of the present invention is to provide an antibacterial phosphate interlayer compound and a method for producing the same, wherein the resin composition does not discolor over time.
【０００６】[0006]
【問題点を解決するための手段】すなわち本発明の抗菌
性リン酸塩層間化合物は、アンモニアおよび／またはア
ミンと抗菌作用を有する金属イオンとをインターカレー
トした層状リン酸塩からなることを特徴とするものであ
る。この抗菌性リン酸塩層間化合物は、抗菌効果の持続
性、抗菌物質の安定性、耐熱性等といった優れた特性を
失うことなく、しかも、経時的に変色しにくく、樹脂等
と混練して抗菌性樹脂組成物として使用する場合にも、
樹脂等と混練させる際の変色、さらには混練後の抗菌性
樹脂組成物の経時的な変色も少ない。That is, the antibacterial phosphate intercalation compound of the present invention comprises a layered phosphate obtained by intercalating ammonia and / or an amine with a metal ion having an antibacterial action. It is assumed that. This antibacterial phosphate intercalation compound does not lose excellent properties such as persistence of the antibacterial effect, stability of the antibacterial substance, heat resistance, etc., and is hardly discolored over time. When used as a conductive resin composition,
Discoloration during kneading with a resin or the like, and further, discoloration over time of the antibacterial resin composition after kneading are small.
【０００７】上記した本発明の抗菌性リン酸塩層間化合
物は、抗菌作用を有する金属のアンミン錯体溶液および
／またはアミン錯体溶液と層状リン酸塩とを接触させる
ことにより、単一操作で容易に製造することができる。The above-mentioned antibacterial phosphate intercalation compound of the present invention can be easily prepared in a single operation by contacting an ammine complex solution and / or amine complex solution of a metal having an antibacterial action with a layered phosphate. Can be manufactured.
【０００８】本発明で用いる抗菌作用を有する金属イオ
ンとしては、銀イオン、銅イオン、亜鉛イオン等が好ま
しく使用でき、これらの金属イオンは１種だけでなく数
種を層状リン酸塩にインターカレートさせてもよい。As the metal ions having an antibacterial action used in the present invention, silver ions, copper ions, zinc ions and the like can be preferably used, and not only one kind of these metal ions but also several kinds thereof are intercalated into a layered phosphate. May be
【０００９】アンモニアおよびアミンについても、これ
らのうちの一方だけでなく両方を層状リン酸塩にインタ
ーカレートさせることができる。アミンとしては、メチ
ルアミン、エチルアミン、プロピルアミン、イソプロピ
ルアミン、ｎ−ブチルアミン、イソブチルアミン、ｓｅ
ｃ−ブチルアミン、ｔｅｒｔ−ブチルアミン、アミルア
ミン、ジメチルアミン、ジエチルアミン、ジプロピルア
ミン、トリメチルアミン、トリエチルアミン、アリルア
ミン、エチレンジアミン、プロピレンジアミン、テトラ
メチレンジアミン、モノエタノールアミン、ピリジン、
ピペリジン等の水溶性アミンが好ましく使用できる。[0009] With respect to ammonia and amines, not only one but also both of them can be intercalated into the layered phosphate. As the amine, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, isobutylamine, se
c-butylamine, tert-butylamine, amylamine, dimethylamine, diethylamine, dipropylamine, trimethylamine, triethylamine, allylamine, ethylenediamine, propylenediamine, tetramethylenediamine, monoethanolamine, pyridine,
A water-soluble amine such as piperidine can be preferably used.
【００１０】抗菌作用を有する金属イオンとアンモニア
および／またはアミンとの保持体となる層状リン酸塩と
しては、リン酸ジルコニウムやリン酸チタン等の４価金
属のリン酸塩、トリポリリン酸アルミニウム等が好まし
く利用できる。４価金属のリン酸塩は、A. Clearfield
，G. Alberti及びU. Constantino，“Inorganic Ion E
xchange Materials”，A. Clearfield 編，CRC Press
社，ＵＳＡ，第３章（1982）に大要が述べられている
が、Ｍ4 （ＨＰＯ4 ）2 ・ｎＨ2 Ｏ（Ｍ4 は４価金属を
示す）のように表わされ、１水和物のα型、２水和物の
γ型などが一般的によく知られている。これらは水に難
溶の固体酸で陽イオン交換能を持つ。イオン交換能はリ
ン酸水素基（ＨＰＯ4 2-）のプロトンが担っており、理
論的イオン交換容量はα型リン酸ジルコニウム（以下α
−ＺｒＰと略記）が6.64 meq/g、α型リン酸チタン（以
下α−ＴｉＰと略記）が7.76 meq/g、γ型リン酸ジルコ
ニウム（以下γ−ＺｒＰと略記）が6.27 meq/g、γ型リ
ン酸チタン（以下γ−ＴｉＰと略記）が7.25 meq/gであ
る。また、トリポリリン酸アルミニウムはＡｌＨ2 Ｐ3
Ｏ10・２Ｈ2 Ｏ（以下ＡｌＰと略記）で表わされ、理論
的イオン交換容量は6.29meq/gである。Examples of the layered phosphate serving as a support for a metal ion having an antibacterial action and ammonia and / or an amine include phosphates of tetravalent metals such as zirconium phosphate and titanium phosphate, and aluminum tripolyphosphate. It can be used preferably. Phosphates of tetravalent metals are available from A. Clearfield
, G. Alberti and U. Constantino, “Inorganic Ion E
xchange Materials ", edited by A. Clearfield, CRC Press
The outline is described in Sharp, USA, Chapter 3 (1982), which is expressed as M 4 (HPO 4 ) 2 .nH 2 O (M 4 represents a tetravalent metal). The α-form of a hydrate and the γ-form of a dihydrate are generally well known. These are solid acids which are hardly soluble in water and have cation exchange ability. The proton exchange capacity of the hydrogen phosphate group (HPO 4 2- ) is responsible for the ion exchange capacity, and the theoretical ion exchange capacity is α-type zirconium phosphate (hereinafter referred to as α).
-ZrP) is 6.64 meq / g, α-type titanium phosphate (hereinafter abbreviated as α-TiP) is 7.76 meq / g, γ-type zirconium phosphate (hereinafter abbreviated as γ-ZrP) is 6.27 meq / g, γ Type titanium phosphate (hereinafter abbreviated as γ-TiP) is 7.25 meq / g. Aluminum tripolyphosphate is AlH 2 P 3
It is represented by O 10 .2H 2 O (hereinafter abbreviated as AlP), and has a theoretical ion exchange capacity of 6.29 meq / g.
【００１１】層状リン酸塩に抗菌作用を有する金属イオ
ンがインターカレートする反応はリン酸水素基のプロト
ンとのイオン交換反応と考えられ、アンモニアおよび／
またはアミンがインターカレートする反応はリン酸水素
基のプロトンとプロトン化することで説明される。さら
に、金属アンミン錯イオン又は金属アミン錯イオンとし
てプロトンとイオン交換することも考えられる。The reaction in which a metal ion having an antibacterial action is intercalated into the layered phosphate is considered to be an ion exchange reaction with a proton of a hydrogen phosphate group, and ammonia and / or
Alternatively, the reaction in which an amine is intercalated is explained by protonation with a proton of a hydrogen phosphate group. Further, ion exchange with proton as a metal ammine complex ion or a metal amine complex ion is also conceivable.
【００１２】本発明の抗菌性リン酸塩層間化合物の製造
に当たっては、まず抗菌作用を有する金属の水溶性塩の
水溶液にアンモニアおよび／またはアミンを加えてアン
ミン錯体および／またはアミン錯体の水溶液とする。次
に、この溶液に層状リン酸塩を加え撹拌あるいは振盪す
ることなどにより接触させ、層状リン酸塩に抗菌作用を
有する金属イオンおよびアンモニアおよび／またはアミ
ンをインターカレートさせ、固相を濾別・水洗して未反
応のイオンを除去した後乾燥することにより、抗菌作用
を有する金属とアンモニアおよび／またはアミンとをイ
ンターカレートさせた層状リン酸塩すなわち抗菌性リン
酸塩層間化合物が得られる。In producing the antibacterial phosphate intercalation compound of the present invention, first, ammonia and / or an amine are added to an aqueous solution of a water-soluble salt of a metal having an antibacterial action to form an aqueous solution of an ammine complex and / or an amine complex. . Next, the layered phosphate is added to the solution, and the solution is brought into contact with the solution by stirring or shaking, and the layered phosphate is intercalated with a metal ion having an antibacterial action and ammonia and / or amine, and the solid phase is separated by filtration. By drying after removing unreacted ions by washing with water, a layered phosphate in which a metal having an antibacterial action is intercalated with ammonia and / or an amine, that is, an antibacterial phosphate intercalation compound is obtained. .
【００１３】[0013]
【実施例】次に、実施例によりこの発明を詳細に説明す
るが、実施例は単に例示のために記すものであり、本発
明はこれらに実施例によって制限されるものではない。Next, the present invention will be described in detail with reference to examples. However, the examples are merely for illustrative purposes, and the present invention is not limited to these examples.
【００１４】実施例１ （本発明の抗菌性リン酸塩層間化合物の製造） 表１に示した組成の抗菌作用を有する金属の硝酸塩（Ａ
ｇＮＯ3 ，Ｃｕ（ＮＯ3 ）2 ，Ｚｎ（ＮＯ3 ）2 ）水溶
液 400mlに、アンモニア水あるいはアミン溶液を少しづ
つ、沈澱物が生成した後再び透明になるまで添加した。
こうして調製した抗菌作用を有する金属のアンミン又は
アミン錯体溶液に層状リン酸塩20ｇを加えて約６時間撹
拌接触させて、アンモニアあるいはアミンと抗菌作用を
有する金属イオンとを層状リン酸塩にインターカレート
させた。次に固相を濾別、水洗後100 〜110 ℃で５時間
乾燥し、本発明の抗菌性リン酸塩層間化合物を得た。 Example 1 (Production of Antibacterial Phosphate Intercalation Compound of the Present Invention) Metal nitrate having the composition shown in Table 1 and having an antibacterial action (A
gNO 3 , Cu (NO 3 ) 2 , Zn (NO 3 ) 2 ) To 400 ml of an aqueous solution, an aqueous ammonia solution or an amine solution was added little by little until a precipitate was formed, and the solution became transparent again.
20 g of layered phosphate is added to the ammine or amine complex solution of a metal having an antibacterial action thus prepared, and the mixture is stirred and contacted for about 6 hours to intercalate ammonia or an amine and a metal ion having an antibacterial action into the layered phosphate. Let me go. Next, the solid phase was separated by filtration, washed with water and dried at 100 to 110 ° C. for 5 hours to obtain the antibacterial phosphate interlayer compound of the present invention.
【００１５】比較例１ （アンモニアまたはアミンを含まない従来の抗
菌性組成物の製造） 表１に示した組成の抗菌作用を有する金属の硝酸塩水溶
液 400mlを使用して、アンモニア水あるいはアミン溶液
を添加しなかったこと以外は実施例１と同様にして、ア
ンモニアまたはアミンを含まない従来の抗菌性組成物を
調製した。以上の実施例１および比較例１で調製したサ
ンプルの抗菌作用を有する金属およびアンモニアまたは
アミンの含有量についても表１に示す。 Comparative Example 1 (Production of Conventional Antibacterial Composition Containing No Ammonia or Amine) Ammonia water or an amine solution was prepared by using 400 ml of an aqueous solution of a metal nitrate having an antibacterial action having the composition shown in Table 1. A conventional antimicrobial composition containing no ammonia or amine was prepared in the same manner as in Example 1 except that no addition was made. Table 1 also shows the content of the metal having an antibacterial action and the content of ammonia or amine in the samples prepared in Example 1 and Comparative Example 1 described above.
【００１６】 [0016]
【００１７】実施例２（抗菌試験） 抗菌試験は次のような方法でおこなった：滅菌シャーレ
に、試験菌種を一様に接種した寒天培地を１０ml作製す
る。この寒天培地上に直径２０mmのディスク状に成形し
た実施例１および比較例１で得られたサンプルを静置
し、３７℃で２４時間後の阻止円の大きさを測定した。 Example 2 (Antibacterial test) The antibacterial test was carried out by the following method: A sterilized petri dish was prepared by uniformly inoculating the test strain with 10 ml of an agar medium. The samples obtained in Example 1 and Comparative Example 1 each formed into a disk having a diameter of 20 mm on this agar medium were allowed to stand, and the size of the inhibition circle after 24 hours at 37 ° C. was measured.
【００１８】試験菌種は、Staphylococcus aureus （黄
色ブドウ球菌）およびEscherichiacoli（大腸菌）を使
用した。表２に結果を示す。この表から、本発明品は従
来品と同等以上の抗菌力があることがわかる。The test bacteria species were used Staphylococcus aureus (S. aureus) and Es ch erichiacoli (E. coli). Table 2 shows the results. From this table, it can be seen that the product of the present invention has antibacterial activity equal to or higher than that of the conventional product.
【００１９】 [0019]
【００２０】実施例３（変色試験） 変色試験は以下のような方法で行なった： 1) 樹脂混練変色試験 低密度ポリエチレン粉末100 部に対し、実施例１および
比較例１で得られたサンプル各々５部及び酸化チタン５
部を加えてよく混合し、るつぼ中で190 ℃２０分間加熱
溶触した。放冷直後およびフェードオメーターを用いて
５０時間光照射した後の色の変化を比較した。色は、マ
ンセル色票と照合し、マンセル値にて表示した。表３に
結果を示す。 Example 3 (Discoloration test) The discoloration test was carried out by the following method: 1) Resin kneading discoloration test 100 parts of the low-density polyethylene powder were used for each of the samples obtained in Example 1 and Comparative Example 1. 5 parts and titanium oxide 5
The mixture was mixed well and heated and welded in a crucible at 190 ° C. for 20 minutes. The change in color immediately after cooling and after the light irradiation for 50 hours using a fadeometer was compared. The color was compared with the Munsell color chart and indicated by the Munsell value. Table 3 shows the results.
【００２１】 [0021]
【００２２】 2) 抗菌性リン酸塩層間化合物自身の変色試験 調製直後およびフェードオメーターで５０時間光照射後
の色の変化を比較した。色は樹脂混練試験と同様にマン
セル値にて表示した。表４に結果を示す。2) Discoloration test of antibacterial phosphate intercalation compound itself The change in color immediately after preparation and after 50 hours of light irradiation with a fadeometer was compared. The color was represented by the Munsell value as in the resin kneading test. Table 4 shows the results.
【００２３】 [0023]
【００２４】[0024]
【発明の効果】本発明の抗菌性リン酸塩層間化合物は、
従来のアンモニアまたは／およびアミンを含まない抗菌
性組成物と同等以上の抗菌力を有し、しかも従来品と比
較してそれ自体の経時的な変色が少なく、さらに樹脂等
と混練して抗菌性樹脂組成物として使用する場合にも、
樹脂等と混練させる際の変色や混練後の抗菌性樹脂組成
物の経時的な変色が従来品と比較してはるかに少ない
（表３および表４参照）。The antibacterial phosphate intercalation compound of the present invention comprises:
It has antibacterial activity equal to or higher than that of conventional antimicrobial compositions containing no ammonia and / or amine, and its discoloration over time is less than that of conventional products. Even when used as a resin composition,
Discoloration during kneading with a resin or the like and discoloration over time of the antibacterial resin composition after kneading are far less than those of conventional products (see Tables 3 and 4).
【００２５】また、アンモニアまたはアミンを金属イオ
ンと同時に層状リン酸塩にインターカレートさせる本発
明の製造方法においては、金属イオンのみをインターカ
レートさせる従来法に比べて金属イオンとくに銀イオン
の歩留まりが向上する（表１参照）。Further, in the production method of the present invention in which ammonia or amine is intercalated into a layered phosphate simultaneously with metal ions, the yield of metal ions, particularly silver ions, is lower than in the conventional method in which only metal ions are intercalated. (See Table 1).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｋ 3/32 Ｃ０８Ｋ 3/32 (56)参考文献 特開 平１−282109（ＪＰ，Ａ) 特開 平２−169027（ＪＰ，Ａ) 特開 平２−96508（ＪＰ，Ａ) 特開 平２−145408（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 25/37 A01N 59/26 C01B 25/40 C01B 25/45 C08K 3/32 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification symbol FI C08K 3/32 C08K 3/32 (56) References JP-A-1-282109 (JP, A) JP-A-2-169027 (JP) JP-A-2-96508 (JP, A) JP-A-2-145408 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 25/37 A01N 59/26 C01B 25/40 C01B 25/45 C08K 3/32
Claims (2)
および／またはアミン錯体溶液と層状リン酸塩とを接触
させることを特徴とする抗菌性リン酸塩層間化合物の製
造方法。 1. An ammine complex solution of a metal having an antibacterial action.
And / or contacting amine complex solution with layered phosphate
Producing an antibacterial phosphate intercalation compound characterized by the following:
Construction method.
亜鉛から選ばれる請求項１に記載の抗菌性リン酸塩層間
化合物の製造方法。 2. The metal having the antibacterial action is silver, copper or
The antibacterial phosphate interlayer according to claim 1, which is selected from zinc.
A method for producing a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40578390A JP3218605B2 (en) | 1990-12-25 | 1990-12-25 | Antibacterial phosphate intercalation compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40578390A JP3218605B2 (en) | 1990-12-25 | 1990-12-25 | Antibacterial phosphate intercalation compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04243908A JPH04243908A (en) | 1992-09-01 |
| JP3218605B2 true JP3218605B2 (en) | 2001-10-15 |
Family
ID=18515392
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40578390A Expired - Lifetime JP3218605B2 (en) | 1990-12-25 | 1990-12-25 | Antibacterial phosphate intercalation compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3218605B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9155311B2 (en) * | 2013-03-15 | 2015-10-13 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4226810C1 (en) * | 1992-08-13 | 1994-01-27 | Theodor Dipl Ing Krall | Hoses and other objects made of plastic for medical use, which are not colonized by germs and processes for their manufacture |
| JP3186908B2 (en) * | 1993-07-15 | 2001-07-11 | テイカ株式会社 | Rust prevention pigment composition |
| CA2201934C (en) * | 1994-10-05 | 2008-03-18 | Makoto Hayakawa | Antimicrobial solid material, process for producing the same, and method of utilizing the same |
| DE19936059A1 (en) | 1999-07-30 | 2001-02-01 | J Peter Guggenbichler | Production of antimicrobial plastic articles, especially catheters, involves pretreatment with colloidal metal, especially colloidal silver, before the final moulding process |
| KR100411178B1 (en) * | 2000-10-09 | 2003-12-18 | 한국화학연구원 | Novel antibacterial agents, and antibacterial and deordorizing solution comprising them |
| WO2013158509A1 (en) * | 2012-04-16 | 2013-10-24 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9078445B2 (en) | 2012-04-16 | 2015-07-14 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| JP7365078B1 (en) * | 2022-05-30 | 2023-10-19 | ミテジマ化学株式会社 | Antiviral layered aluminum phosphate and antiviral composition containing the same |
-
1990
- 1990-12-25 JP JP40578390A patent/JP3218605B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9155311B2 (en) * | 2013-03-15 | 2015-10-13 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US20160029641A1 (en) * | 2013-03-15 | 2016-02-04 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
| US9955700B2 (en) * | 2013-03-15 | 2018-05-01 | Bunge Amorphic Solutions Llc | Antimicrobial chemical compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04243908A (en) | 1992-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3218605B2 (en) | Antibacterial phosphate intercalation compound and method for producing the same | |
| JPH0640829A (en) | Production of antimicrobial agent | |
| CN1541536A (en) | Inorganic antiseptic of phosphate containing high valence Ag and its preparation method | |
| JP3525523B2 (en) | Antibacterial agent and method for producing the same | |
| RU2088234C1 (en) | Water-soluble bactericidal composition and a method of its preparing | |
| JPS60202162A (en) | Antiseptic and mildewproofing paint composition | |
| JP3205968B2 (en) | Antibacterial phosphate intercalation compound | |
| JP3684634B2 (en) | Antibacterial composition and method for producing the same | |
| JPS6256163B2 (en) | ||
| JPH0413605A (en) | Inorganic antimicrobial agent and production thereof | |
| KR101871963B1 (en) | Antibiotic compound and manufacturing method thereof | |
| JPH11246213A (en) | Antibacterial composition | |
| JP2559125B2 (en) | Method for producing antibacterial zeolite | |
| JPH0764685B2 (en) | Stabilized aqueous composition of β'-type copper oxynate | |
| JP3176054B2 (en) | Antibacterial aluminum silicate composition and method for producing the same | |
| JP2909676B2 (en) | Antibacterial and antifungal ceramics and method for producing the same | |
| JPH1025206A (en) | Antibacterial composition and its production | |
| JP3177039B2 (en) | Phosphate antibacterial agent and method for producing the same | |
| JP3467447B2 (en) | Inorganic antibacterial material using calcium silicates | |
| CN115108544B (en) | Preparation method, product and application of silver-loaded zirconium phosphate cubic block powder | |
| JP3243814B2 (en) | Method for producing antibacterial phosphate intercalation compound | |
| JP5023258B2 (en) | Method for producing organic-inorganic composite material having bioactive function | |
| JPH08165213A (en) | Antimicrobial agent | |
| JP2524893B2 (en) | Antibacterial / antifungal phosphate double salt and method for producing the same | |
| JPH06157014A (en) | Antimicrobial pigment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100810 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100810 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110810 Year of fee payment: 10 |