JPH04327852A - Antibacterial composition and manufacture thereof - Google Patents
Antibacterial composition and manufacture thereofInfo
- Publication number
- JPH04327852A JPH04327852A JP12278391A JP12278391A JPH04327852A JP H04327852 A JPH04327852 A JP H04327852A JP 12278391 A JP12278391 A JP 12278391A JP 12278391 A JP12278391 A JP 12278391A JP H04327852 A JPH04327852 A JP H04327852A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- hydroxyapatite
- silver
- heat
- composition
- 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
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 35
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 34
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 150000002500 ions Chemical group 0.000 abstract description 3
- 230000002688 persistence Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 230000005923 long-lasting effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- -1 silver ions Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Apparatus For Disinfection Or Sterilisation (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、抗菌性組成物およびそ
の製造方法に関する。さらに詳しくは、本発明は、熱処
理を行った合成ハイドロキシアパタイトに抗菌性金属イ
オンを複合化させることにより得られる、変色しにくく
、微量でも抗菌力があり、耐熱性、安全性にすぐれ、か
つ抗菌力の保持能に優れた抗菌性組成物及びその製造方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial composition and a method for producing the same. More specifically, the present invention is a synthetic hydroxyapatite that is obtained by compounding antibacterial metal ions with heat-treated synthetic hydroxyapatite. The present invention relates to an antibacterial composition with excellent power retention ability and a method for producing the same.
【０００２】0002
【従来の技術】有機合成によって調製される抗菌剤は熱
に弱く殆んどが水に可溶であるため、熱加工が難かしく
、抗菌力の持続性に乏しく、安全性の面でも問題がある
。いっぽう、銀、銅、亜鉛やこれらのイオンが抗菌性を
有し、なかでも銀は抗菌力が非常に強いことが一般に知
られており、これらを用いた抗菌、殺菌方法が種々提案
されている。たとえば、銀イオンは硝酸銀溶液の形態で
使用されている。これは、溶液状態であるため取り扱い
が不便であり、抗菌力の持続性がなく、大量に使用する
ことは安全性の面で問題がある。活性炭やアルミナ、シ
リカゲル等の吸着物質に保持させて用いる方法も知られ
ているが、吸着物質に対する抗菌性金属イオンの保持量
、液相への金属イオンの流出による抗菌力の持続性に欠
けるなどの問題がある。また、ゼオライトやハイドロキ
シアパタイトの構造中にイオン交換反応を利用して銀イ
オン等を担持させる方法も提案されている。これらの方
法は抗菌力の持続性という点では優れているが、ゼオラ
イトについては、熱的に不安定であるために、耐熱性に
乏しく、また焼結により粉体を成形することができない
などの問題がある。[Prior Art] Antibacterial agents prepared by organic synthesis are weak against heat and most are soluble in water, making them difficult to heat process, lacking long-lasting antibacterial activity, and causing safety problems. be. On the other hand, it is generally known that silver, copper, zinc, and their ions have antibacterial properties, and silver in particular has very strong antibacterial properties, and various antibacterial and sterilization methods using these have been proposed. . For example, silver ions have been used in the form of silver nitrate solutions. Since it is in the form of a solution, it is inconvenient to handle, has no long-lasting antibacterial activity, and is problematic in terms of safety when used in large quantities. Methods of retaining the antibacterial metal ions in adsorbent materials such as activated carbon, alumina, and silica gel are also known, but the amount of antibacterial metal ions retained by the adsorbent materials and the sustainability of antibacterial activity due to metal ions leaking into the liquid phase are also known. There is a problem. Furthermore, a method has also been proposed in which silver ions and the like are supported in the structure of zeolite or hydroxyapatite by utilizing an ion exchange reaction. These methods are excellent in terms of long-lasting antibacterial activity, but zeolites have problems such as poor heat resistance because they are thermally unstable, and the inability to form powder by sintering. There's a problem.
【０００３】0003
【発明が解決しようとする課題】本発明は、上記事情に
かんがみ完成されたものであり、本発明の目的は、少量
でも効力があり、抗菌力の持続性、耐熱性に優れ、変色
を起こさず安定性に優れ、安全性が良好な抗菌剤を提供
するにある。[Problems to be Solved by the Invention] The present invention has been completed in view of the above circumstances, and the object of the present invention is to provide a product that is effective even in small amounts, has long-lasting antibacterial activity, is excellent in heat resistance, and does not cause discoloration. It is an object of the present invention to provide an antibacterial agent which has excellent stability and good safety.
【０００４】0004
【課題を解決するための手段】本発明は、熱処理を行っ
て結晶性を高めたハイドロキシアパタイトのカルシウム
は、銀イオン等とイオン交換してこれを結晶構造中に安
定化させ、ＮａＣｌ水溶液やアルカリによって変色を起
こさないこと、さらにこの組成物は少量でも抗菌力があ
り、抗菌力の持続性、耐熱性に優れ、焼結させることも
できるとの知見に基づいて完成されたものであって、本
発明の抗菌性組成物は熱処理を行った合成ハイドロキシ
アパタイトに抗菌性金属イオンが複合化されてなること
を特徴とする。[Means for Solving the Problems] In the present invention, the calcium of hydroxyapatite, which has been heat-treated to improve crystallinity, is stabilized in the crystal structure by ion exchange with silver ions, etc. This composition was developed based on the knowledge that it does not cause discoloration, and that even a small amount of this composition has antibacterial activity, has long-lasting antibacterial activity, excellent heat resistance, and can be sintered. The antibacterial composition of the present invention is characterized in that it is made of heat-treated synthetic hydroxyapatite combined with antibacterial metal ions.
【０００５】本発明で用いられるハイドロキシアパタイ
トは、熱処理を行ってその結晶性を高めたものでなけれ
ばならない。ハイドロキシアパタイト自体は常法により
合成されるものでよく、ハイドロキシアパタイトの水酸
基の一部がフッ素またはヨウ素で置換されたものでもよ
い。ハイドロキシアパタイトとしては、通常、カルシウ
ムとリンのモル比が１．５〜１．８の範囲にある組成の
ものが用いられる。本発明で用いられる抗菌性金属イオ
ンは、好ましくは銀イオン単独であるか、または銀イオ
ンと、銅イオン、亜鉛イオンのような他の金属イオンと
の混合物である。The hydroxyapatite used in the present invention must be heat-treated to enhance its crystallinity. Hydroxyapatite itself may be synthesized by a conventional method, and some of the hydroxyl groups of hydroxyapatite may be substituted with fluorine or iodine. As hydroxyapatite, one having a composition in which the molar ratio of calcium to phosphorus is in the range of 1.5 to 1.8 is usually used. The antibacterial metal ion used in the present invention is preferably silver ion alone or a mixture of silver ion and other metal ions such as copper ion or zinc ion.
【０００６】本発明の抗菌性組成物は、上記のハイドロ
キシアパタイトを熱処理し、これに抗菌性金属イオンの
１種または２種以上を複合化させることにより製造され
る。熱処理はハイドロキシアパタイトの結晶性を高める
ことができる温度で行われ、通常６００〜１３００℃の
範囲で選択される。この熱処理を行なうことによって、
常法により合成されたハイドロキシアパタイトは結晶性
を高められ、抗菌性金属イオンとの複合化において、抗
菌性金属のリン酸塩や抗菌性金属そのものの析出といっ
た副反応を起こさずにイオン交換し、抗菌性金属イオン
を安定に結晶構造中に取り込むことができる。その結果
、得られる抗菌性組成物は変色を起こしにくく、微量で
も抗菌力があり、抗菌力の持続性、耐熱性に優れたもの
となる。The antibacterial composition of the present invention is produced by heat-treating the above hydroxyapatite and compounding it with one or more antibacterial metal ions. The heat treatment is performed at a temperature that can improve the crystallinity of hydroxyapatite, and is usually selected in the range of 600 to 1300°C. By performing this heat treatment,
Hydroxyapatite synthesized by conventional methods has increased crystallinity, and when combined with antibacterial metal ions, it exchanges ions without causing side reactions such as phosphate of the antibacterial metal or precipitation of the antibacterial metal itself. Antibacterial metal ions can be stably incorporated into the crystal structure. As a result, the antibacterial composition obtained is resistant to discoloration, has antibacterial activity even in a small amount, and has excellent long-lasting antibacterial activity and heat resistance.
【０００７】抗菌性金属イオンを複合化させる具体的方
法としては、熱処理を行なったハイドロキシアパタイト
を水に懸濁させ、これに抗菌性金属の水溶性塩を添加し
、所定時間攪拌してハイドロキシアパタイト中のカルシ
ウムと抗菌性金属とをイオン交換させたのち、濾過、十
分に水洗を行ない、乾燥させる手法が採られる。抗菌性
金属の水溶性塩としては、銀塩単独または銀塩と銅、亜
鉛等の他の金属の塩との混合物が用いられ、通常は硝酸
塩、硫酸塩等の形態で用いられる。水洗は十分に行なわ
ないと、余剰の抗菌性金属がハイドロキシアパタイト粒
子の表面に付着していたり、水溶性塩の形でそのまま残
ることがあり、変色しにくく、安定性、安全性良好な抗
菌性組成物が得られないことがある。A specific method for compounding antibacterial metal ions is to suspend heat-treated hydroxyapatite in water, add a water-soluble salt of an antibacterial metal, and stir for a predetermined period of time to form hydroxyapatite. After ion-exchanging the calcium inside with antibacterial metals, it is filtered, thoroughly washed with water, and dried. As water-soluble salts of antibacterial metals, silver salts alone or mixtures of silver salts and salts of other metals such as copper and zinc are used, and are usually used in the form of nitrates, sulfates, etc. If washing with water is not done sufficiently, excess antibacterial metals may adhere to the surface of the hydroxyapatite particles or may remain in the form of water-soluble salts, resulting in less discoloration, stability, and safety. The composition may not be obtained.
【０００８】本発明の抗菌性組成物中の抗菌性金属の含
有量は、抗菌性金属がハイドロキシアパタイトの結晶構
造の中に安定に存在していて、ハイドロキシアパタイト
粒子表面に付着していたりすることがなく、抗菌効果を
十分に発揮することができるかぎり特に制限はないが、
通常０．００１〜１０重量％、好ましくは０．００２〜
５重量％の範囲で選択される。The content of the antibacterial metal in the antibacterial composition of the present invention is such that the antibacterial metal stably exists in the crystal structure of hydroxyapatite and is attached to the surface of the hydroxyapatite particles. There are no particular restrictions as long as the antibacterial effect can be fully demonstrated without any
Usually 0.001-10% by weight, preferably 0.002-10% by weight
It is selected within the range of 5% by weight.
【０００９】本発明の抗菌性組成物は、そのまま、ある
いはさらに熱処理を加えたものについて、粉体状態のま
ま単身で用いてもよく、または、他のものに混ぜ込んだ
りして複合化させて用いることもできる。例えば、合成
高分子化合物やセメント組成物に練り込むことにより、
繊維や塗料、紙、壁材等として用いることができる。ま
た、通常のセラミックスと同じように焼結により成形加
工して用いることもできる。[0009] The antibacterial composition of the present invention may be used alone as it is or after heat treatment, in powder form, or it may be mixed with other substances to form a compound. It can also be used. For example, by incorporating it into synthetic polymer compounds or cement compositions,
It can be used as fiber, paint, paper, wall material, etc. Furthermore, it can be molded and used by sintering in the same way as ordinary ceramics.
【００１０】0010
【実施例】以下、実施例について、本発明をさらに詳細
に説明する。
実施例１
常法により合成したカルシウムとリンのモル比１．６７
のハイドロキシアパタイトを６００、９００、１０００
、１１００℃の各温度でそれぞれ１時間熱処理を行なっ
た。それぞれ１０ｇを２００ｍｌの蒸留水に懸濁し、硝
酸銀０．１６ｇと硝酸亜鉛０．４５ｇを添加し、２４時
間攪拌してイオン交換処理を行なった。それぞれの懸濁
液を濾過し、十分に水洗を行なったのち、６０℃で乾燥
して本発明の抗菌性組成物を得た。それぞれの組成物は
白色の粉体であり、化学分析を行なったところカルシウ
ム、リン、銀、亜鉛が検出された。また、粉末Ｘ線回折
分析を行なったところ、いずれもハイドロキシアパタイ
トのみで他の鉱物相は認められず、銀および亜鉛はハイ
ドロキシアパタイト構造中に安定に保持されていた。[Examples] The present invention will be explained in more detail with reference to Examples below. Example 1 Mole ratio of calcium and phosphorus synthesized by conventional method 1.67
Hydroxyapatite of 600, 900, 1000
, 1100° C. for 1 hour. 10 g of each was suspended in 200 ml of distilled water, 0.16 g of silver nitrate and 0.45 g of zinc nitrate were added, and ion exchange treatment was performed by stirring for 24 hours. Each suspension was filtered, thoroughly washed with water, and then dried at 60°C to obtain an antibacterial composition of the present invention. Each composition was a white powder, and chemical analysis detected calcium, phosphorus, silver, and zinc. Furthermore, when powder X-ray diffraction analysis was performed, only hydroxyapatite was observed, and no other mineral phases were observed, and silver and zinc were stably retained in the hydroxyapatite structure.
【００１１】比較例１
実施例１の１０００℃で１時間熱処理を行なったハイド
ロキシアパタイトを用いた。抗菌性金属イオンは複合化
させなかった。Comparative Example 1 The hydroxyapatite of Example 1 which had been heat treated at 1000° C. for 1 hour was used. Antibacterial metal ions were not combined.
【００１２】比較例２
カルシウムとリンのモル比１．６７の未熱処理ハイドロ
キシアパタイト１０ｇを２００ｍｌの蒸留水に懸濁し、
硝酸銀０．１６ｇおよび硝酸亜鉛０．４５ｇを添加し、
２４時間攪拌した。この懸濁液を濾過し、十分に水洗を
行なったのち、６０℃にて乾燥を行なった。この粉末Ｘ
線回折分析を行なったところ、ハイドロキシアパタイト
の他にリン酸銀が認められた。Comparative Example 2 10 g of unheated hydroxyapatite with a molar ratio of calcium to phosphorus of 1.67 was suspended in 200 ml of distilled water.
Add 0.16 g of silver nitrate and 0.45 g of zinc nitrate,
Stirred for 24 hours. This suspension was filtered, thoroughly washed with water, and then dried at 60°C. This powder
When line diffraction analysis was performed, silver phosphate was observed in addition to hydroxyapatite.
【００１３】比較例３
比較例２で得られた硝酸銀と硝酸亜鉛を含む組成物を１
０００℃にて１時間熱処理を行なった。この粉末Ｘ線回
折分析を行なったところ、ハイドロキシアパタイトの他
に銀、酸化亜鉛が認められた。Comparative Example 3 The composition containing silver nitrate and zinc nitrate obtained in Comparative Example 2 was
Heat treatment was performed at 000°C for 1 hour. When this powder X-ray diffraction analysis was performed, silver and zinc oxide were observed in addition to hydroxyapatite.
【００１４】実施例２
実施例１において９００℃で１時間熱処理を行なったが
未だ硝酸銀および硝酸亜鉛を添加していないハイドロキ
シアパタイト１０ｇを２００ｍｌの蒸留水に懸濁し、フ
ッ化銀０．１２ｇを添加し、２４時間攪拌を行なった。
この懸濁液を濾過し、十分に水洗を行なったのち６０℃
にて乾燥を行なった。得られた組成物は白色の粉体であ
り、化学分析を行なったところカルシウム、リン、銀、
フッ素が検出された。また、粉末Ｘ線回折分析を行なっ
たところハイドロキシアパタイト以外の鉱物相は認めら
れず、銀、フッ素はアパタイト結晶構造中に安定に保持
されていた。Example 2 10 g of hydroxyapatite, which had been heat treated at 900° C. for 1 hour in Example 1 but to which no silver nitrate or zinc nitrate had been added, was suspended in 200 ml of distilled water, and 0.12 g of silver fluoride was added. The mixture was stirred for 24 hours. This suspension was filtered, thoroughly washed with water, and then heated to 60°C.
It was dried at. The resulting composition was a white powder, and chemical analysis revealed calcium, phosphorus, silver,
Fluorine was detected. Further, when powder X-ray diffraction analysis was performed, no mineral phase other than hydroxyapatite was observed, and silver and fluorine were stably retained in the apatite crystal structure.
【００１５】実施例３
カルシウムとリンのモル比１．６のハイドロキシアパタ
イトを１０００℃で１時間熱処理を行なった。この熱処
理品１０ｇを２００ｍｌの蒸留水に懸濁し、硝酸銀０．
３２ｇおよび硝酸銅０．３５ｇを添加し、２４時間攪拌
を行なった。この懸濁液を濾過し、十分に水洗を行なっ
たのち６０℃にて乾燥を行なった。得られた組成物は淡
青色の粉体であり、化学分析を行なったところカルシウ
ム、リン、銀、銅が検出された。また、粉末Ｘ線回折分
析を行なったところハイドロキシアパタイト、リン酸三
カルシウム以外の鉱物相は認められず、銀、銅は安定に
保持されていた。Example 3 Hydroxyapatite with a molar ratio of calcium to phosphorus of 1.6 was heat treated at 1000° C. for 1 hour. 10 g of this heat-treated product was suspended in 200 ml of distilled water, and 0.0 g of silver nitrate was suspended in 200 ml of distilled water.
32 g and 0.35 g of copper nitrate were added and stirred for 24 hours. This suspension was filtered, thoroughly washed with water, and then dried at 60°C. The resulting composition was a pale blue powder, and chemical analysis detected calcium, phosphorus, silver, and copper. Further, when powder X-ray diffraction analysis was performed, no mineral phases other than hydroxyapatite and tricalcium phosphate were observed, and silver and copper were stably retained.
【００１６】実施例４
実施例１、比較例１、２、３の各組成物について、５％
ＮａＣｌ水溶液および１０％のＣａ（ＯＨ）２ 懸濁液
を添加したときの粉体の色の変化を観察した。表１に結
果を示したが、実施例１、比較例１、３の組成物にはほ
とんど色の変化は認められなかったが、比較例２の組成
物は黒灰色に変化した。Example 4 For each composition of Example 1 and Comparative Examples 1, 2, and 3, 5%
The color change of the powder was observed when adding NaCl aqueous solution and 10% Ca(OH)2 suspension. The results are shown in Table 1.Although almost no color change was observed in the compositions of Example 1 and Comparative Examples 1 and 3, the composition of Comparative Example 2 turned black and gray.
【００１７】[0017]
【表１】[Table 1]
【００１８】実施例５
実施例１、比較例１、２、３の各組成物について、抗菌
力の評価として２４時間培養後の生存菌数の測定を行な
った。１００ｍｌのエレンマイヤーフラスコに実施例１
、比較例１、２、３の各組成物をそれぞれ２ｍｇずつ入
れた。これに、リン酸緩衝食塩水を用いて菌数が１０６
個／ｍｌになるように調製した大腸菌の懸濁液を２０
ｍｌずつ加え、２７℃で振盪培養した。２４時間後にフ
ラスコ内の生存菌数を測定した。表２に結果を示したが
、実施例１、比較例２の組成物では菌が検出されず、強
い抗菌性を示した。比較例３の組成物では菌があまり減
少せず、抗菌力は弱かった。比較例１の組成物は菌数が
減少せず、抗菌性は認められなかった。Example 5 For each of the compositions of Example 1 and Comparative Examples 1, 2, and 3, the number of viable bacteria after 24-hour cultivation was measured to evaluate the antibacterial activity. Example 1 in a 100 ml Ellenmeyer flask
, 2 mg of each of the compositions of Comparative Examples 1, 2, and 3 were added. To this, the number of bacteria was reduced to 106 using phosphate buffered saline.
A suspension of E. coli prepared at 20 cells/ml
ml each was added and cultured with shaking at 27°C. After 24 hours, the number of viable bacteria in the flask was measured. The results are shown in Table 2, and no bacteria were detected in the compositions of Example 1 and Comparative Example 2, indicating strong antibacterial properties. The composition of Comparative Example 3 did not significantly reduce bacteria and had weak antibacterial activity. In the composition of Comparative Example 1, the number of bacteria did not decrease, and no antibacterial properties were observed.
【００１９】[0019]
【表２】[Table 2]
Claims (5)
イトに抗菌性金属イオンを複合化させてなることを特徴
とする抗菌性組成物。1. An antibacterial composition comprising heat-treated hydroxyapatite combined with antibacterial metal ions.
範囲から選択される請求項１記載の抗菌性組成物。2. The antibacterial composition according to claim 1, wherein the temperature of the heat treatment is selected from the range of 600 to 1300°C.
ルシウムとリンのモル比が１．５〜１．８の範囲にある
組成のものである請求項１記載の抗菌性組成物。3. The antibacterial composition according to claim 1, which has a composition in which the molar ratio of calcium to phosphorus in hydroxyapatite is in the range of 1.5 to 1.8.
は銀イオンと他の金属イオンとの混合物である請求項１
記載の抗菌性組成物。Claim 4: Claim 1 wherein the antibacterial metal ion is silver ion alone or a mixture of silver ion and other metal ions.
Antimicrobial compositions as described.
タイトの懸濁液に抗菌性金属の水溶性塩を添加して、ハ
イドロキシアパタイトのカルシウムの一部を抗菌性金属
とイオン交換させることを特徴とする請求項１記載の抗
菌性組成物の製造方法。5. A claim characterized in that a water-soluble salt of an antibacterial metal is added to a suspension of heat-treated synthetic hydroxyapatite to cause ion exchange of part of the calcium in the hydroxyapatite with the antibacterial metal. Item 1. A method for producing an antibacterial composition according to item 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12278391A JPH04327852A (en) | 1991-04-26 | 1991-04-26 | Antibacterial composition and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12278391A JPH04327852A (en) | 1991-04-26 | 1991-04-26 | Antibacterial composition and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04327852A true JPH04327852A (en) | 1992-11-17 |
Family
ID=14844503
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12278391A Pending JPH04327852A (en) | 1991-04-26 | 1991-04-26 | Antibacterial composition and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04327852A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09303576A (en) * | 1996-05-14 | 1997-11-25 | Ngk Spark Plug Co Ltd | Ceramic valve |
-
1991
- 1991-04-26 JP JP12278391A patent/JPH04327852A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09303576A (en) * | 1996-05-14 | 1997-11-25 | Ngk Spark Plug Co Ltd | Ceramic valve |
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