JPH0624921A - Antibacterial/antifungal fluorine-substituted calcium phosphate compound and its production - Google Patents
Antibacterial/antifungal fluorine-substituted calcium phosphate compound and its productionInfo
- Publication number
- JPH0624921A JPH0624921A JP18109592A JP18109592A JPH0624921A JP H0624921 A JPH0624921 A JP H0624921A JP 18109592 A JP18109592 A JP 18109592A JP 18109592 A JP18109592 A JP 18109592A JP H0624921 A JPH0624921 A JP H0624921A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- antibacterial
- fluorine
- calcium phosphate
- calcium
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、抗菌・防カビ性を有す
るフッ素置換リン酸カルシウム化合物およびその製造方
法に関するものであり、特に、耐薬品性にすぐれ、かつ
抗菌・防カビ性を有する、フッ素置換リン酸カルシウム
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 fluorine-substituted calcium phosphate compound having antibacterial and antifungal properties and a method for producing the same, and particularly to fluorine-substituted calcium phosphate compounds having excellent chemical resistance and antibacterial and antifungal properties. The present invention relates to a calcium phosphate compound and a method for producing the same.
【０００２】[0002]
【従来の技術】リン酸カルシウム系化合物、例えばハイ
ドロキシアパタイトは、陽イオン交換能を有し、鉛、
錫、カドミウムなどの有害重金属イオンの除去剤として
知られている。また、リン酸カルシウム系化合物の陽イ
オン交換能を利用して、そのカルシウム原子の一部分
を、抗菌性金属、例えば銀原子により置換して抗菌・防
カビ性を示す抗菌性金属担持リン酸カルシウム系化合物
を得ることができる。2. Description of the Related Art Calcium phosphate compounds, such as hydroxyapatite, have a cation exchange ability and lead,
It is known as a scavenger for harmful heavy metal ions such as tin and cadmium. Further, by utilizing the cation exchange ability of a calcium phosphate-based compound, a part of the calcium atom is replaced by an antibacterial metal, for example, a silver atom, to obtain an antibacterial metal-supported calcium phosphate-based compound exhibiting antibacterial and antifungal properties. You can
【０００３】しかし、上記のような抗菌性金属担持リン
酸カルシウム系化合物は、その母剤がリン酸カルシウム
系化合物、例えばハイドロキシアパタイトなどであるた
め、耐薬品性、特に耐酸性が不十分であって、低pH域に
おいて有効に使用することができないという問題があ
る。However, the above-mentioned antibacterial metal-supported calcium phosphate-based compound has insufficient chemical resistance, particularly acid resistance, since its mother material is a calcium phosphate-based compound, such as hydroxyapatite, and has a low pH. There is a problem that it cannot be used effectively in the area.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、リン酸カル
シウム系化合物を母剤とする抗菌・防カビ剤において、
そのすぐれた抗菌・防カビ性能を維持したまゝ、その耐
薬品性、特に耐酸性を高め、pH域においても実用を可能
にしようとするものである。DISCLOSURE OF THE INVENTION The present invention provides an antibacterial / antifungal agent comprising a calcium phosphate compound as a base material,
While maintaining its excellent antibacterial and antifungal properties, it aims to enhance its chemical resistance, especially acid resistance, and make it practical in the pH range.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
の解決のために、抗菌性金属担持リン酸カルシウム系化
合物の一部をフッ素で置換することがきわめて有効であ
ることを見出し本発明を完成した。In order to solve the above-mentioned problems, the present inventors have found that it is extremely effective to replace a part of the antibacterial metal-supported calcium phosphate compound with fluorine, and the present invention has been proposed. completed.
【０００６】すなわち、本発明の抗菌・防カビ性を有す
るフッ素置換リン酸カルシウム化合物は、リン酸カルシ
ウム化合物を母剤として含み、そのカルシウム原子の一
部分が、抗菌性金属原子によって置換されており、かつ
この塩化合物が、更にフッ素で置換されていることを特
徴とするものである。That is, the fluorine-substituted calcium phosphate compound having antibacterial / antifungal properties of the present invention contains a calcium phosphate compound as a base material, and a part of the calcium atom is replaced by an antibacterial metal atom, and this salt compound Is further substituted with fluorine.
【０００７】本発明に係る、抗菌・防カビ性を有するフ
ッ素置換リン酸カルシウム化合物を製造する方法は、リ
ン酸水溶液と、抗菌性金属の水溶性化合物の水溶液とを
混合し、この混合水溶液を、カルシウム化合物の水懸濁
液に混合し、次に、この混合反応系に、フッ素イオン含
有水溶液を添加することを特徴とするものである。The method for producing a fluorine-substituted calcium phosphate compound having antibacterial / antifungal properties according to the present invention comprises mixing an aqueous solution of phosphoric acid and an aqueous solution of a water-soluble compound of an antibacterial metal, and mixing the mixed aqueous solution with calcium. It is characterized in that it is mixed with an aqueous suspension of the compound, and then a fluorine ion-containing aqueous solution is added to this mixed reaction system.
【０００８】[0008]
【作用】本発明において、リン酸カルシウム系化合物
は、例えば、ＣａＨＰＯ4 ，Ｃａ 3(ＰＯ4)2 ，Ｃａ5(Ｐ
Ｏ4)3 ＯＨ，Ｃａ4 Ｏ（ＰＯ4)2 ，Ｃａ10（ＰＯ4)6(Ｏ
Ｈ)2，ＣａＰ4 Ｏ11，Ｃａ（ＰＯ3)2 ，Ｃａ2 Ｐ
2 Ｏ7 ，およびＣａ（Ｈ2 ＰＯ4) 2 ・Ｈ2 Ｏなどを包含
する。In the present invention, calcium phosphate-based compound
Is, for example, CaHPOFour, Ca 3(POFour)2, CaFive(P
OFour)3OH, CaFourO (POFour)2, CaTen(POFour)6(O
H)2, CaPFourO11, Ca (PO3)2, Ca2P
2O7, And Ca (H2POFour) 2・ H2Including O etc.
To do.
【０００９】本発明において、抗菌性金属とは、銀（Ａ
ｇ）、銅（Ｃｕ）、および亜鉛（Ｚｎ）を包含する。In the present invention, the antibacterial metal means silver (A
g), copper (Cu), and zinc (Zn).
【００１０】本発明のリン酸カルシウム−抗菌性金属塩
化合物においては、上記リン酸カルシウム系化合物のカ
ルシウム原子の一部分が、抗菌性金属によって置換され
ているが、抗菌性金属の含有量は、０．１〜１０．０％
であることが好ましく、０．５〜５．０％であることが
より好ましい。上記含有量が０．１％未満であると、得
られる化合物の抗菌・防カビ性能が不満足なものとなる
ことがあり、また、それが１０％より多くなると、抗菌
性金属が高価であるため経済的メリットがなく、又、リ
ン酸カルシウム化合物のカルシウムをこれ以上置換する
ことが難しいためである。In the calcium phosphate-antibacterial metal salt compound of the present invention, a part of the calcium atom of the calcium phosphate compound is replaced by the antibacterial metal, but the content of the antibacterial metal is 0.1-10. 0.0%
Is preferable, and more preferably 0.5 to 5.0%. If the content is less than 0.1%, the antibacterial and antifungal properties of the resulting compound may be unsatisfactory, and if it exceeds 10%, the antibacterial metal is expensive. This is because there is no economic merit and it is difficult to further replace the calcium in the calcium phosphate compound.
【００１１】本発明方法において、抗菌性金属の水溶性
化合物としては、抗菌性金属の硝酸塩、例えば、硝酸
銀、硝酸銅、硝酸亜鉛が好適に用いられる。In the method of the present invention, as the water-soluble compound of the antibacterial metal, nitrate of the antibacterial metal, for example, silver nitrate, copper nitrate or zinc nitrate is preferably used.
【００１２】本発明方法において、出発化合物として用
いられるカルシウム化合物は、例えば、水酸化カルシウ
ム、硝酸カルシウム、および炭酸カルシウムなどから選
ぶことができる。カルシウム化合物の水懸濁液における
カルシウム化合物の濃度は３０〜２００ｇ／リットルで
あることが好ましい。In the method of the present invention, the calcium compound used as the starting compound can be selected from, for example, calcium hydroxide, calcium nitrate and calcium carbonate. The concentration of the calcium compound in the aqueous suspension of the calcium compound is preferably 30 to 200 g / liter.
【００１３】リン酸−抗菌性金属化合物混合水溶液にお
いて、リン酸は１〜５０重量％の濃度を有することが好
ましく、また、抗菌性金属化合物の含有量は、金属イオ
ンに換算して０．０５〜１．０％（重量）であることが
好ましく、また、使用されるカルシウム化合物の重量に
対し、０．５〜１０％であることが好ましい。In the phosphoric acid-antibacterial metal compound mixed aqueous solution, phosphoric acid preferably has a concentration of 1 to 50% by weight, and the content of the antibacterial metal compound is 0.05 in terms of metal ions. ˜1.0% (weight), and preferably 0.5 to 10% with respect to the weight of the calcium compound used.
【００１４】抗菌性金属として１価の金属、例えばＡｇ
を用いる場合、置換される金属の価数調製のために、ア
ルミニウム（Ａｌ）イオンを添加してもよい。As the antibacterial metal, a monovalent metal such as Ag
When using, aluminum (Al) ions may be added to adjust the valence of the metal to be replaced.
【００１５】本発明方法において、カルシウム化合物懸
濁液に、リン酸−抗菌性金属化合物含有混合溶液を滴
し、これらを反応させ、リン酸カルシウム−抗菌性金属
複合塩化合物を生成させる。この滴下操作の際、混合反
応系のpHを管理し、その値が約８．０になったとき（す
なわち原料カルシウム化合物のほゞ全量が消尽したと
き）、上記リン酸−抗菌性金属化合物混合水溶液の滴下
をやめる。In the method of the present invention, a mixed solution containing phosphoric acid-antibacterial metal compound is added dropwise to the calcium compound suspension, and these are reacted to produce a calcium phosphate-antibacterial metal complex salt compound. During the dropping operation, the pH of the mixed reaction system is controlled, and when the value becomes about 8.0 (that is, when the total amount of the raw material calcium compound is exhausted), the phosphoric acid-antibacterial metal compound mixture is added. Stop dropping the aqueous solution.
【００１６】次に、混合反応系に生成するリン酸カルシ
ウム−抗菌性金属複合塩化合物の重量に対し、１〜５％
のフッ素イオンを含むフッ素化合物水溶液を添加する。
このフッ素化合物としては水溶性の高いもの、例えば、
ＮａＦを用いることが好ましい。上記フッ素化合物添加
により、混合反応系のpHが変動し、例えばＮａＦを用い
た場合、混合反応系のpHは約９．０に上昇する。この場
合、アルミニウムに換算して０．０５ｇ／mlの硝酸アル
ミニウム水溶液を混合反応系に添加し、そのpHを６．０
〜８．０に調整することが好ましい。Next, 1 to 5% of the weight of the calcium phosphate-antibacterial metal complex salt compound formed in the mixed reaction system
An aqueous solution of a fluorine compound containing the above fluorine ion is added.
As the fluorine compound, one having high water solubility, for example,
It is preferable to use NaF. The addition of the fluorine compound causes the pH of the mixed reaction system to fluctuate. For example, when NaF is used, the pH of the mixed reaction system rises to about 9.0. In this case, 0.05 g / ml of aluminum nitrate aqueous solution in terms of aluminum was added to the mixed reaction system, and the pH was adjusted to 6.0.
It is preferable to adjust to ~ 8.0.
【００１７】次に、この混合反応系を攪拌しながら、常
温において１〜２４時間熟成する。この熟成液を濾過
し、得られた濾過ケーキを蒸留水により水洗し、乾燥し
て、抗菌・防カビ性を有する抗菌性金属含有フッ素置換
リン酸カルシウム化合物を得ることができる。Next, the mixed reaction system is aged at room temperature for 1 to 24 hours while stirring. This aged liquid is filtered, and the obtained filter cake is washed with distilled water and dried to obtain an antibacterial metal-containing fluorine-substituted calcium phosphate compound having antibacterial and antifungal properties.
【００１８】このリン酸カルシウム−抗菌性金属複合塩
フッ素化物におけるフッ素含有量は、０．１〜４．０重
量％であることが好ましい。このフッ素含有量が０．１
重量％未満のときは、得られた製品の耐薬品性、特に耐
酸性が不十分になり、また、それが４．０重量％をこえ
て多量になると未反応のフッ素化合物が生成し抗菌・防
カビ性を低下させることがある。The content of fluorine in the calcium phosphate-antibacterial metal complex salt fluorinated product is preferably 0.1 to 4.0% by weight. This fluorine content is 0.1
If it is less than 10% by weight, the chemical resistance of the obtained product, particularly acid resistance, becomes insufficient, and if it exceeds 4.0% by weight, a large amount of unreacted fluorine compound is formed, and antibacterial It may reduce the mold resistance.
【００１９】上記本発明方法により得られたフッ素化物
は、その母剤がリン酸カルシウム系化合物であるにも拘
らず、良好な耐薬品性、特に高耐酸性を示し、従って、
抗菌性金属の溶出がきわめて少ないというすぐれた特性
を示すものである。The fluorinated product obtained by the above-mentioned method of the present invention exhibits good chemical resistance, particularly high acid resistance, even though the matrix is a calcium phosphate compound, and therefore,
It has the excellent property that the elution of antibacterial metal is extremely small.
【００２０】よって、本発明の抗菌・防カビ剤は、ホウ
ロウ組成物、釉組成物、樹脂材料、塗料、および接着剤
などの広い用途に好適に用いることができる。Therefore, the antibacterial / antifungal agent of the present invention can be suitably used for a wide variety of applications such as enamel composition, glaze composition, resin material, paint and adhesive.
【００２１】[0021]
【実施例】本発明を、下記実施例により更に説明する。実施例１ ２０ｇの水酸化カルシウムを２００mlの蒸留水に懸濁し
た。別に、濃度５０ml／リットルのリン酸水溶液２００
mlに、濃度０．１ｇ／mlの硝酸銀水溶液４mlを混合し
た。The present invention will be further described by the following examples. Example 1 20 g of calcium hydroxide was suspended in 200 ml of distilled water. Separately, 200 ml of phosphoric acid aqueous solution with a concentration of 50 ml / liter
4 ml of an aqueous solution of silver nitrate having a concentration of 0.1 g / ml was mixed with ml.
【００２２】上記混合水溶液を、水酸化カルシウム懸濁
液に、攪拌しながら滴下した。混合反応系のpHを管理
し、それが８．０に達したとき、混合水溶液の滴下を中
止し、これに０．６％フッ化ナトリウム水溶液１００ml
を添加した。この反応系を攪拌しながら、１時間熟成
し、固体生成物を濾過し、洗浄した。The above mixed aqueous solution was added dropwise to the calcium hydroxide suspension while stirring. The pH of the mixed reaction system was controlled, and when it reached 8.0, the dropping of the mixed aqueous solution was stopped, and 100 ml of a 0.6% aqueous sodium fluoride solution was added to this.
Was added. The reaction system was aged for 1 hour while stirring, and the solid product was filtered and washed.
【００２３】上記操作により得られた固形物を乾燥し、
１０００℃において１時間焼成し、この焼成物を粉砕し
た。銀含有フッ素アパタイトからなる抗菌・防カビ剤が
得られた。The solid obtained by the above operation is dried,
The product was baked at 1000 ° C. for 1 hour, and the baked product was crushed. An antibacterial / antifungal agent composed of silver-containing fluoroapatite was obtained.
【００２４】この抗菌・防カビ剤を、黄色ブドウ球菌、
枯草菌、大腸菌、サルモネラ菌、肺炎桿菌、および緑膿
菌を用いてハロー試験に供した。その結果を表１に示
す。This antibacterial / antifungal agent is treated with Staphylococcus aureus,
A halo test was performed using Bacillus subtilis, Escherichia coli, Salmonella, Klebsiella pneumoniae, and Pseudomonas aeruginosa. The results are shown in Table 1.
【００２５】[0025]
【表１】 [Table 1]
【００２６】実施例２および比較例１ 実施例２において、実施例１において得られた銀含有フ
ッ素アパタイトからなる抗菌・防カビ剤を、５重量％の
添加量でシリコーン系ゴム材料に混合分布させた。この
材料を、厚さ１mmのシートに形成し、このシートから、
直径５mmのペレット状物を作製した。このペレット状物
を、１０％塩酸水溶液中に、室温において３０秒間浸漬
し、これを取り出して水洗し乾燥した。 Example 2 and Comparative Example 1 In Example 2, the antibacterial / antifungal agent made of silver-containing fluoroapatite obtained in Example 1 was mixed and distributed in a silicone rubber material in an amount of 5% by weight. It was This material is formed into a sheet with a thickness of 1 mm, and from this sheet,
A pellet having a diameter of 5 mm was prepared. The pellets were immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 seconds, taken out, washed with water and dried.
【００２７】この乾燥ペレットを、前記各種菌を用いて
ハロー試験に供した。このハロー試験において阻止円の
形成が認められた。すなわち本発明の抗菌・防カビ剤
は、すぐれた耐酸性を有することが確認された。The dried pellets were subjected to a halo test using the above-mentioned various bacteria. In this halo test, formation of a blocking circle was recognized. That is, it was confirmed that the antibacterial / antifungal agent of the present invention has excellent acid resistance.
【００２８】比較例１において、実施例２と同様にして
シリコーンゴムペレットを作成し、これをハロー試験に
供した。但し、抗菌・防カビ剤の調製において、フッ素
置換処理を行わなかった。ハロー試験において、阻止円
の形成は認められなかった。すなわち、非フッ素置換抗
菌・防カビ剤の耐酸性は、きわめて低いものであった。In Comparative Example 1, silicone rubber pellets were prepared in the same manner as in Example 2 and subjected to a halo test. However, fluorine substitution treatment was not performed in the preparation of the antibacterial / antifungal agent. In the halo test, formation of an inhibition circle was not observed. That is, the acid resistance of the non-fluorine-substituted antibacterial / antifungal agent was extremely low.
【００２９】[0029]
【発明の効果】本発明により、耐薬品性、特に耐酸性に
すぐれ、かつ高い抗菌・防カビ性を有する無機抗菌・防
カビ性フッ素置換リン酸カルシウム化合物を高効率で得
ることが可能になった。また、本発明の抗菌・防カビ剤
は生物に対し無害であって、耐熱性および耐久性にもす
ぐれているため、ホーロー、釉、樹脂材料、塗料および
接着剤などの広い用途に用いることができる。INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to highly efficiently obtain an inorganic antibacterial / antifungal fluorine-substituted calcium phosphate compound having excellent chemical resistance, particularly acid resistance, and high antibacterial / antifungal properties. Further, since the antibacterial and antifungal agent of the present invention is harmless to living organisms and has excellent heat resistance and durability, it can be used in a wide range of applications such as enamels, glazes, resin materials, paints and adhesives. it can.
フロントページの続き (72)発明者 熊倉 信幸 千葉県船橋市豊富町585番地 住友セメン ト株式会社中央研究所内 (72)発明者 矢澤 孝子 千葉県船橋市豊富町585番地 住友セメン ト株式会社中央研究所内Front Page Continuation (72) Inventor Nobuyuki Kumakura 585 Tomimachi, Funabashi, Chiba Central Research Institute, Sumitomo Cement (72) Inventor Takako Yazawa 585, Tomimachi Funabashi, Chiba Central Research Institute, Sumitomo
Claims (2)
含み、そのカルシウム原子の一部分が抗菌性金属原子に
よって置換されており、かつ、この塩化合物が更にフッ
素化されている、抗菌・防カビ性を有するフッ素置換リ
ン酸カルシウム化合物。1. An antibacterial / antifungal property comprising a calcium phosphate-based compound as a base material, part of the calcium atoms of which is replaced by an antibacterial metal atom, and this salt compound is further fluorinated. Fluorine-substituted calcium phosphate compound.
合物の水溶液とを混合し、この混合水溶液を、カルシウ
ム化合物の水懸濁液に混合し、次に、この混合物反応系
に、フッ素イオン含有水溶液を添加することを特徴とす
る、抗菌・防カビ性を有するフッ素置換リン酸カルシウ
ム化合物の製造方法。2. A phosphoric acid aqueous solution and an aqueous solution of an antibacterial metal water-soluble compound are mixed, the mixed aqueous solution is mixed with an aqueous suspension of a calcium compound, and then the mixture reaction system is treated with fluorine. A method for producing a fluorine-substituted calcium phosphate compound having antibacterial and antifungal properties, which comprises adding an ion-containing aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18109592A JPH0624921A (en) | 1992-07-08 | 1992-07-08 | Antibacterial/antifungal fluorine-substituted calcium phosphate compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18109592A JPH0624921A (en) | 1992-07-08 | 1992-07-08 | Antibacterial/antifungal fluorine-substituted calcium phosphate compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0624921A true JPH0624921A (en) | 1994-02-01 |
Family
ID=16094749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18109592A Pending JPH0624921A (en) | 1992-07-08 | 1992-07-08 | Antibacterial/antifungal fluorine-substituted calcium phosphate compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0624921A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07127215A (en) * | 1993-11-05 | 1995-05-16 | Towa Shiyuuseizai Kogyo Kk | Antibacterial structural body and spray for coating forming the same |
| KR100984669B1 (en) * | 2007-12-24 | 2010-10-01 | 이대희 | The preparation method for silver bonded or substitution hydroxyaphatite with electric ion exchange |
-
1992
- 1992-07-08 JP JP18109592A patent/JPH0624921A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07127215A (en) * | 1993-11-05 | 1995-05-16 | Towa Shiyuuseizai Kogyo Kk | Antibacterial structural body and spray for coating forming the same |
| KR100984669B1 (en) * | 2007-12-24 | 2010-10-01 | 이대희 | The preparation method for silver bonded or substitution hydroxyaphatite with electric ion exchange |
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