JPH04288006A - Antimicrobial calcium phosphate based ceramics - Google Patents
Antimicrobial calcium phosphate based ceramicsInfo
- Publication number
- JPH04288006A JPH04288006A JP7372991A JP7372991A JPH04288006A JP H04288006 A JPH04288006 A JP H04288006A JP 7372991 A JP7372991 A JP 7372991A JP 7372991 A JP7372991 A JP 7372991A JP H04288006 A JPH04288006 A JP H04288006A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- antibacterial
- metal
- oxide
- ceramics
- 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.)
- Granted
Links
- 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 title claims abstract description 9
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 8
- 239000000919 ceramic Substances 0.000 title abstract description 20
- 229910000389 calcium phosphate Inorganic materials 0.000 title abstract 5
- 235000011010 calcium phosphates Nutrition 0.000 title abstract 5
- 230000000845 anti-microbial effect Effects 0.000 title abstract 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- 239000002184 metal Substances 0.000 claims abstract description 72
- 150000003839 salts Chemical class 0.000 claims abstract description 50
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
- 239000011135 tin Substances 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims abstract description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 claims abstract description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 claims abstract description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims abstract description 3
- 229940078499 tricalcium phosphate Drugs 0.000 claims abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 57
- 239000004068 calcium phosphate ceramic Substances 0.000 claims description 37
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 8
- 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 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 claims description 2
- ROPDWRCJTIRLTR-UHFFFAOYSA-L calcium metaphosphate Chemical compound [Ca+2].[O-]P(=O)=O.[O-]P(=O)=O ROPDWRCJTIRLTR-UHFFFAOYSA-L 0.000 claims description 2
- 229940043256 calcium pyrophosphate Drugs 0.000 claims description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 claims description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical class [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 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000010828 elution Methods 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 description 23
- 239000003242 anti bacterial agent Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は抗菌性セラミックス、詳
しくは金属又はその塩を担持させたリン酸カルシウム系
セラミックスと、無機系酸化物とよりなり、場合によっ
ては、それを焼成することにより得られる抗菌性リン酸
カルシウム系セラミックスに関するものである。[Industrial Application Field] The present invention relates to antibacterial ceramics, specifically calcium phosphate ceramics supported with metals or their salts, and inorganic oxides, and in some cases antibacterial ceramics obtained by firing them. The present invention relates to calcium phosphate ceramics.
【０００２】0002
【従来の技術】銀、銅、亜鉛などの金属及びその塩が、
強い抗菌性を有することは古くから知られており、それ
を利用する方法が種々検討されている。然しながら、こ
れらは金属又は塩であるため、有機物への溶解性、分散
性がわるく、又水中に溶出する、光、熱、物質などによ
り変色するなどの性質を有するため、その用途が限定さ
れていた。[Prior Art] Metals such as silver, copper, and zinc and their salts are
It has been known for a long time that it has strong antibacterial properties, and various methods of utilizing it have been studied. However, since these are metals or salts, they have poor solubility and dispersibility in organic substances, and have properties such as being eluted into water and discoloring due to light, heat, substances, etc., so their uses are limited. Ta.
【０００３】近年、これらの金属及び金属塩を、安全に
、そして広範囲に使用できるようにした抗菌性材料とし
て、ゼオライト、ハイドロキシアパタイト、シリカ、ア
ルミナ、酸化チタンなどのセラミックスに、これらの金
属又は金属塩を吸着又はイオン交換により担持させた抗
菌剤が種々提案されている。これらの方法によりえられ
た抗菌剤は、有機物質への分散性、混合性、抗菌性金属
又は金属塩の水中への溶出性が改善されているので、従
来のものより安全に、広く使用されえるが、これらの方
法によってえられた抗菌剤でも、抗菌性金属や金属塩の
変色や、水中への溶出が完全に解決されているとは云え
ず、長期間の使用で、担持された抗菌性金属や金属塩が
僅かづつ水中に溶出したり、変色したりするため、抗菌
剤の性質が徐々に変化し、長期間の使用に適し難い。[0003] In recent years, these metals and metal salts have been used in ceramics such as zeolite, hydroxyapatite, silica, alumina, and titanium oxide as antibacterial materials that have become safe and widely usable. Various antibacterial agents have been proposed in which salts are supported by adsorption or ion exchange. Antibacterial agents obtained by these methods are safer and more widely used than conventional agents because they have improved dispersibility in organic substances, mixability, and elution of antibacterial metals or metal salts into water. However, even with the antibacterial agents obtained by these methods, discoloration of antibacterial metals and metal salts and elution into water cannot be said to be completely resolved, and with long-term use, the carried antibacterial agents may deteriorate. Since the antibacterial metals and metal salts gradually dissolve into the water or change color, the properties of the antibacterial agent gradually change, making it difficult to use it for a long period of time.
【０００４】そこで抗菌性金属又はその塩の変色及び水
中への溶出が殆んどなく、有機物との混合、分散性が良
好で、抗菌力の低下がなく、安全に長期間有機物に混合
して使用できる無機性抗菌剤の製法を種々検討した結果
、銀、銅、亜鉛などの金属及びその塩を担持させたセラ
ミックスを、８００℃以上に焼成することにより、担持
された金属又は塩がセラミックスに強く結合され、抗菌
性金属又はその塩の変色、水中への溶出がなくなり、有
機物への混合、分散性も良好であるので、安全に長期間
使用できる抗菌性セラミックスがえられることを確め、
特願平２−２２６７３８号として特許出願した。この方
法によりえられた抗菌剤は、有機物への混合、分散性も
良く、抗菌性金属又は塩の変色、水中への溶出がなく、
熱に対しても安定で変質しないので、合成樹脂、合成繊
維などに分散させ安全に長期間使用できる。[0004] Antibacterial metals or their salts hardly discolor or elute into water, have good mixing and dispersibility with organic substances, do not reduce antibacterial activity, and can be safely mixed with organic substances for a long period of time. As a result of examining various methods for producing usable inorganic antibacterial agents, we found that by firing ceramics on which metals such as silver, copper, zinc, and their salts are supported, at a temperature of 800°C or higher, the supported metals or salts are transferred to the ceramics. It has been confirmed that antibacterial ceramics can be obtained that can be used safely for a long period of time because it is strongly bonded, prevents discoloration of antibacterial metals or their salts, and does not elute into water, and has good mixing and dispersibility with organic substances.
A patent application was filed as Japanese Patent Application No. 2-226738. The antibacterial agent obtained by this method has good mixing and dispersibility in organic matter, no discoloration of antibacterial metals or salts, no elution into water,
It is stable against heat and does not change in quality, so it can be dispersed into synthetic resins, synthetic fibers, etc. and used safely for long periods of time.
【０００５】然しながら、抗菌性物質として、銀、銅、
亜鉛及びそれらの塩を、セラミックスに担持させた後焼
成するため、焼成工程を必要とする上、高価な銀塩を使
用したり、焼成したりするので、焼成により、担持され
た抗菌性金属又は塩が、担体より揮発、遊離、放散した
りすることがあり、製造法が複雑で、コスト高になり、
抗菌力が焼成により低下する可能性がある。特にリン酸
カルシウム系セラミックスを担体として使用すると、焼
成後抗菌力が低下するという好ましくない現象を生じる
。リン酸カルシウム系化合物は、有機物への混合、分散
性がよく、生体無害の物質であり、各種の医薬、栄養剤
として使用されているものである。従って、金属又はそ
の塩を担持させた抗菌性リン酸カルシウム系セラミック
スで、焼成することなしに担持された金属及びその塩が
、変色、水中へ溶出することがなく、又焼成しても抗菌
力が低下しない抗菌剤が製造できれば、抗菌剤として好
ましいと云える。However, as antibacterial substances, silver, copper,
Since zinc and its salts are fired after being supported on ceramics, a firing process is required, and expensive silver salts are used and firing is required. The salt may volatilize, be liberated, or dissipate from the carrier, making the manufacturing method complicated and expensive.
Antibacterial activity may decrease due to baking. In particular, when calcium phosphate ceramics are used as a carrier, an undesirable phenomenon occurs in that the antibacterial activity decreases after firing. Calcium phosphate compounds have good mixing and dispersibility in organic substances, are harmless to living organisms, and are used as various medicines and nutritional supplements. Therefore, with antibacterial calcium phosphate ceramics that support metals or their salts, the metals and their salts supported without firing will not discolor or elute into water, and the antibacterial activity will decrease even after firing. If it is possible to produce an antibacterial agent that does not cause oxidation, it can be said to be preferable as an antibacterial agent.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、安価に製造
でき、焼成せずとも金属又はその塩の変色、水中への溶
出がないので、長期間安全に使用できる金属又はその塩
を担持させた抗菌性リン酸カルシウム系セラミックスを
提供することを第１の目的としている。[Problems to be Solved by the Invention] The present invention provides a method for supporting metals or their salts that can be produced at low cost, and can be safely used for a long period of time because the metals or their salts do not change color or elute into water without firing. The first objective is to provide antibacterial calcium phosphate ceramics.
【０００７】更に焼成しても、抗菌力の低下がみられな
い抗菌性リン酸カルシウム系セラミックスを提供するこ
とを第２の目的としている。A second object of the present invention is to provide an antibacterial calcium phosphate ceramic whose antibacterial activity does not deteriorate even after firing.
【０００８】更に、銀、銅、亜鉛、ニッケル、白金、錫
、ヒ素、鉛、カドミウム、クロムより選ばれた少くとも
１種の金属又はその塩を担持したリン酸カルシウム系セ
ラミックスであり、焼成せずとも担持した金属又は金属
塩の変色、水中への溶出がなく、又焼成しても抗菌力の
低下しない抗菌性リン酸カルシウム系セラミックスを提
供することを目的としている。Furthermore, it is a calcium phosphate ceramic supporting at least one metal selected from silver, copper, zinc, nickel, platinum, tin, arsenic, lead, cadmium, and chromium, or a salt thereof, and can be used without firing. The object of the present invention is to provide antibacterial calcium phosphate ceramics in which the supported metal or metal salt does not discolor or dissolve into water, and its antibacterial activity does not decrease even after firing.
【０００９】[0009]
【課題を解決するための手段及び作用】前記の課題を解
決するため、本発明は、上記した金属又は金属塩を担持
したリン酸カルシウム系セラミックスと、無機系酸化物
とよりなる抗菌性リン酸カルシウム系セラミックスを提
案する。更に、得られた抗菌性カルシウム系セラミック
スを８００℃以上で焼成することも可能であり、又は８
００℃以上で焼成した上記金属又は金属塩担持リン酸カ
ルシウム系セラミックスに、無機系酸化物を添加するこ
とも可能である。[Means and effects for solving the problems] In order to solve the above problems, the present invention provides an antibacterial calcium phosphate ceramic made of a calcium phosphate ceramic supporting the metal or metal salt described above and an inorganic oxide. suggest. Furthermore, it is also possible to sinter the obtained antibacterial calcium-based ceramics at 800°C or higher, or 800°C or higher.
It is also possible to add an inorganic oxide to the above metal or metal salt supported calcium phosphate ceramics fired at 00°C or higher.
【００１０】本発明に使用されるリン酸カルシウム系セ
ラミックスは、リン酸３カルシウム、リン酸水素カルシ
ウム、ピロリン酸カルシウム、メタリン酸カルシウム、
ハイドロキシアパタイト及びハロゲン化アパタイトなど
、歯磨き研磨剤として使用されているものより任意に選
択されるが、ハイドロキシアパタイトは骨、歯の成分で
無害であり、有機物への混合、分散性も極めて良好であ
るので特に好ましいと云える。Calcium phosphate ceramics used in the present invention include tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate,
It is arbitrarily selected from those used as toothpaste abrasives, such as hydroxyapatite and halogenated apatite, but hydroxyapatite is a harmless component of bones and teeth, and has extremely good mixing and dispersibility in organic matter. Therefore, it can be said that it is particularly preferable.
【００１１】これらリン酸カルシウム系セラミックスに
担持させる金属又はその塩は、銀、亜鉛、銅、ニッケル
、白金、錫、ヒ素、鉛、カドミウム、及びクロムより選
ばれた１種又は２種以上の金属塩より選択され、これら
金属塩水溶液をリン酸カルシウム系セラミックスに、常
法により吸着又はイオン交換により金属又は金属塩を担
持させて金属又は金属塩担持したリン酸カルシウム系セ
ラミックスをえる。担持する金属塩の量は、処理する金
属塩水溶液濃度により任意に選択できるが、一般に担持
した金属塩の量は、使用したリン酸カルシウム系セラミ
ックスに対し、重量で０．００１％以上、好ましくは０
．１〜１５％程度になるように水溶液濃度を選択する。The metal or its salt supported on these calcium phosphate ceramics is one or more metal salts selected from silver, zinc, copper, nickel, platinum, tin, arsenic, lead, cadmium, and chromium. The selected metal salt aqueous solution is allowed to support the metal or metal salt on the calcium phosphate ceramic by adsorption or ion exchange using a conventional method to obtain a calcium phosphate ceramic supporting the metal or metal salt. The amount of supported metal salt can be arbitrarily selected depending on the concentration of the metal salt aqueous solution to be treated, but generally the amount of supported metal salt is 0.001% or more by weight, preferably 0.001% or more by weight, based on the calcium phosphate ceramic used.
．． The concentration of the aqueous solution is selected to be about 1 to 15%.
【００１２】このようにしてえられた金属又は金属塩を
担持したリン酸カルシウム系セラミックスに、無機系酸
化物を添加する。使用される無機系酸化物は、ジルコニ
ア、アルミナ、シリカ、珪酸、酸化鉄、酸化チタン、酸
化カルシウム、酸化マグネシウム、酸化亜鉛、酸化銅及
びゼオライトよりなる群から選ばれた１種又は２種以上
の酸化物であり、その金属又は金属塩を担持したリン酸
カルシウム系セラミックスに対する添加割合は、担持さ
せた抗菌性金属又は金属塩の量により変化させるが、一
般に金属又は金属塩を担持したリン酸カルシウム系セラ
ミックスに対し重量で０．１％以上、好ましくは１〜９
９％である。An inorganic oxide is added to the calcium phosphate ceramic supporting the metal or metal salt thus obtained. The inorganic oxide used is one or more selected from the group consisting of zirconia, alumina, silica, silicic acid, iron oxide, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, and zeolite. It is an oxide, and the ratio of addition to calcium phosphate ceramics supporting metals or metal salts varies depending on the amount of antibacterial metals or metal salts supported, but in general, it is added to calcium phosphate ceramics supporting metals or metal salts. 0.1% or more by weight, preferably 1 to 9
It is 9%.
【００１３】このように、本発明の抗菌性リン酸カルシ
ウム系セラミックスは、金属又はその塩を担持したリン
酸カルシウム系セラミックスと無機系酸化物とよりえら
れているので、金属又は塩として高価な材料を使用して
も、全体として安価に製造することができる上、担持し
た金属又は金属塩は、共存する無機系酸化物の影響によ
り、変色、水中への溶出が少くなるとともに、無機系酸
化物を添加しない抗菌性リン酸カルシウム系セラミック
スと仝等又はそれ以上の抗菌力を示す。無機系酸化物の
共存により、かかる利点を示す理由は明らかでないが、
金属イオンによる抗菌作用が、抗菌性金属の表面酸化や
、活性酸素によると考えられているので、無機系酸化物
の共存により金属表面酸化や、活性酸素の作用が増強さ
れる、或は又、これら使用する無機系酸化物が、遠赤外
線放射セラミックスであるので、加熱などして遠赤外線
を放射させていないが、共存する無機系酸化物の物理的
化学的性質により、金属イオンの抗菌性が増加され、抗
菌性金属イオンの水中への溶出が妨害されているものと
考えられる。[0013] As described above, the antibacterial calcium phosphate ceramic of the present invention is obtained from a calcium phosphate ceramic supporting a metal or its salt and an inorganic oxide, so that it does not require the use of expensive materials as the metal or salt. However, it can be manufactured at low cost as a whole, and the supported metals or metal salts are less likely to change color or elute into water due to the influence of coexisting inorganic oxides, and do not add inorganic oxides. Shows antibacterial activity equal to or greater than antibacterial calcium phosphate ceramics. Although it is not clear why the coexistence of inorganic oxides provides such advantages,
The antibacterial effect of metal ions is thought to be due to the surface oxidation of antibacterial metals and active oxygen, so the coexistence of inorganic oxides may enhance the metal surface oxidation and the action of active oxygen, or Since the inorganic oxides used are far-infrared emitting ceramics, far-infrared rays are not emitted by heating, etc. However, due to the physical and chemical properties of the coexisting inorganic oxides, the antibacterial properties of the metal ions can be improved. It is thought that this increases the amount of antibacterial metal ions and prevents the elution of antibacterial metal ions into water.
【００１４】このようにしてえられた本発明の抗菌性リ
ン酸カルシウム系セラミックスは、８００℃以上で焼成
しても抗菌力の低下がみられない。このことは共存する
無機系酸化物により、焼成しても抗菌性金属又は塩の揮
発、遊離、放散がさまたげられているためと考えられる
。このように無機系酸化物の共存が、金属又は金属塩を
担持したリン酸カルシウム系セラミックスの抗菌性に著
しい利点をもたらすことは本願で初めて明らかになった
ものであるとともに、金属又は金属塩を担持したリン酸
カルシウム系セラミックスに限らず、担体としてゼオラ
イト、シリカ、酸化チタンなどを用いた抗菌性金属又は
金属塩担持抗菌剤に対しても、これら無機系酸化物の共
存が、有効に作用するであろうことをこれらの結果は示
唆しているものと云える。以下に実施例を示して、具体
的に本発明を説明する。The antibacterial calcium phosphate ceramic of the present invention thus obtained does not show any decrease in antibacterial activity even when fired at 800° C. or higher. This is thought to be because the coexisting inorganic oxide prevents the antibacterial metal or salt from volatilizing, liberating, and dissipating even after firing. In this way, it has been revealed for the first time in this application that the coexistence of inorganic oxides brings a significant advantage to the antibacterial properties of calcium phosphate ceramics that support metals or metal salts. The coexistence of these inorganic oxides will work effectively not only on calcium phosphate ceramics but also on antibacterial metal- or metal salt-supported antibacterial agents using zeolite, silica, titanium oxide, etc. as carriers. These results can be said to suggest that. EXAMPLES The present invention will be specifically described below with reference to Examples.
【００１５】例１）
銀１％、亜鉛０．５％を担持したハイドロキシアパタイ
ト抗菌剤（以後１−３という）９９部に対し、ジルコニ
ア６５％、シリカ３３％、酸化第二鉄２％を混合したセ
ラミックス粉末（１−２）を１部添加し、良く混合する
（１−１）。Example 1) 99 parts of a hydroxyapatite antibacterial agent (hereinafter referred to as 1-3) carrying 1% silver and 0.5% zinc was mixed with 65% zirconia, 33% silica, and 2% ferric oxide. Add 1 part of the prepared ceramic powder (1-2) and mix well (1-1).
【００１６】例２）
（１−３）１部に対し、アルミナ５０％、酸化チタン４
７％、酸化カルシウム３％を混合したセラミックス粉末
（２−２）を９９部添加し、良く混合する（２−１）。Example 2) (1-3) 1 part, 50% alumina, 4 parts titanium oxide
Add 99 parts of ceramic powder (2-2) containing 7% calcium oxide and 3% calcium oxide, and mix well (2-1).
【００１７】例３）
（１−３）５０部に対し、酸化マグネシウム５０％、酸
化亜鉛４９％、酸化銅１％を混合したセラミックス粉末
（３−２）を５０部添加し、良く混合する（３−１）。Example 3) To 50 parts of (1-3), add 50 parts of ceramic powder (3-2), which is a mixture of 50% magnesium oxide, 49% zinc oxide, and 1% copper oxide, and mix well ( 3-1).
【００１８】例４）
（１−３）９０部に対し、ゼオライト（４−２）を１０
部添加して良く混合する（４−１）。Example 4) 10 parts of zeolite (4-2) was added to 90 parts of (1-3).
Add 100% and mix well (4-1).
【００１９】例５）抗菌力試験
（１−１）〜（４−１）の試料を０．００１重量％加え
たリン酸緩衝液に、大腸菌の菌液を添加して大腸菌に対
する抗菌力を測定した。比較として同様に（１−２）〜
（４−２）の無機系酸化物の抗菌力試験を行なった。
又、銀１％、亜鉛０．５％を担持したハイドロキシアパ
タイト抗菌剤について０．０１重量％及び０．００１重
量％加えたリン酸緩衝液で抗菌力試験を行なった。その
結果を表１に示すExample 5) Antibacterial activity test The antibacterial activity against E. coli was measured by adding E. coli bacterial solution to a phosphate buffer solution containing 0.001% by weight of the samples from (1-1) to (4-1). did. Similarly (1-2) for comparison
An antibacterial activity test was conducted on the inorganic oxide (4-2). Furthermore, an antibacterial activity test was conducted using a phosphate buffer solution containing 0.01% by weight and 0.001% by weight of a hydroxyapatite antibacterial agent carrying 1% silver and 0.5% zinc. The results are shown in Table 1.
【００２０】[0020]
【表１】[Table 1]
【００２１】この結果より、銀１％、亜鉛０．５％を担
持したハイドロキシアパタイト抗菌剤と（１−２）〜（
４−２）の無機系酸化物を０．００１％添加した抗菌試
験では抗菌力が見られなかったが、（１−１）〜（４−
１）の試料では抗菌力が認められた。この事より、抗菌
性金属含有リン酸カルシウム系セラミックスに無機系酸
化物を混合することにより抗菌力の増強が認められた。From this result, it was found that hydroxyapatite antibacterial agent carrying 1% silver and 0.5% zinc and (1-2) to (
No antibacterial activity was observed in the antibacterial test with the addition of 0.001% of the inorganic oxide in (1-1) to (4-2).
Antibacterial activity was observed in sample 1). From this, it was confirmed that the antibacterial activity was enhanced by mixing an inorganic oxide with antibacterial metal-containing calcium phosphate ceramics.
【００２２】又、抗菌性金属として銅、ニッケル、白金
、錫、ヒ素、鉛、カドミウム、クロム等を用いた場合に
も同様の結果が得られた。Similar results were also obtained when copper, nickel, platinum, tin, arsenic, lead, cadmium, chromium, etc. were used as antibacterial metals.
【００２３】[0023]
【発明の効果】以上説明したように、金属又は金属塩を
担持したリン酸カルシウム系セラミックスと無機系酸化
物とよりなる本発明による抗菌性リン酸カルシウム系セ
ラミックスは、金属又は塩の変色、水中への溶出がない
ので、焼成して使用する必要がなく、又焼成しても抗菌
力の低下がない。加えて無機系酸化物の共存によりその
抗菌力が増加しているので、少量の金属又は金属塩の担
持量で、強い抗菌力を有する抗菌剤がえられる。又焼成
する必要がないので簡単に製造できる。Effects of the Invention As explained above, the antibacterial calcium phosphate ceramic of the present invention, which is composed of a calcium phosphate ceramic supporting a metal or metal salt and an inorganic oxide, does not cause discoloration of the metal or salt and elution into water. Therefore, there is no need to bake it before use, and the antibacterial activity does not decrease even if it is baked. In addition, the antibacterial activity is increased by the coexistence of inorganic oxides, so an antibacterial agent with strong antibacterial activity can be obtained even with a small amount of metal or metal salt supported. Moreover, since there is no need for firing, it can be manufactured easily.
Claims (4)
ヒ素、鉛、カドミウム及びクロムよりなる群から選ばれ
た少くとも１種の金属又は金属塩を担持したリン酸３カ
ルシウム、リン酸水素カルシウム、ピロリン酸カルシウ
ム、メタリン酸カルシウム、ハイドロキシアパタイト及
びハロゲン化アパタイトよりなる群から選ばれた少くと
も１種のリン酸カルシウム系セラミックスと、ジルコニ
ア、アルミナ、シリカ、珪酸、酸化鉄、酸化チタン、酸
化カルシウム、酸化マグネシウム、酸化亜鉛、酸化銅及
びゼオライトよりなる群から選ばれた少くとも１種の無
機系酸化物とよりなることを特徴とする抗菌性リン酸カ
ルシウム系セラミックス。[Claim 1] Silver, copper, zinc, nickel, platinum, tin,
Consisting of tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate, calcium metaphosphate, hydroxyapatite, and halogenated apatite supporting at least one metal or metal salt selected from the group consisting of arsenic, lead, cadmium, and chromium. at least one type of calcium phosphate ceramic selected from the group consisting of zirconia, alumina, silica, silicic acid, iron oxide, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, and zeolite. Antibacterial calcium phosphate ceramics characterized by being composed of one kind of inorganic oxide.
カルシウム系セラミックスと無機系酸化物との割合が重
量で９９：１〜１：９９である請求項１の抗菌性リン酸
カルシウム系セラミックス。2. The antibacterial calcium phosphate ceramic according to claim 1, wherein the ratio of the calcium phosphate ceramic supporting the metal or metal salt to the inorganic oxide is 99:1 to 1:99 by weight.
カルシウム系セラミックスの重量に対し０．００１〜１
５％である請求項１又は２の抗菌性リン酸カルシウム系
セラミックス。3. The amount of the supported metal or metal salt is 0.001 to 1 based on the weight of the calcium phosphate ceramic.
The antibacterial calcium phosphate ceramic according to claim 1 or 2, wherein the antibacterial calcium phosphate ceramic has a content of 5%.
ミックスがハイドロキシアパタイト、担持された金属又
は金属塩が、銀、亜鉛及び銅より選ばれた少くとも１種
である請求項１乃至３いずれか１項記載の抗菌性リン酸
カルシウム系セラミックス。4. The calcium phosphate ceramic as a carrier is hydroxyapatite, and the supported metal or metal salt is at least one selected from silver, zinc, and copper. Antibacterial calcium phosphate ceramics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07372991A JP3174589B2 (en) | 1991-03-14 | 1991-03-14 | Antibacterial calcium phosphate ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07372991A JP3174589B2 (en) | 1991-03-14 | 1991-03-14 | Antibacterial calcium phosphate ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04288006A true JPH04288006A (en) | 1992-10-13 |
| JP3174589B2 JP3174589B2 (en) | 2001-06-11 |
Family
ID=13526615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07372991A Expired - Fee Related JP3174589B2 (en) | 1991-03-14 | 1991-03-14 | Antibacterial calcium phosphate ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3174589B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476881A (en) * | 1993-02-15 | 1995-12-19 | Suh; Kang I. | Antimicrobial composition for manufacturing nipples |
| DE4445881A1 (en) * | 1994-12-22 | 1996-06-27 | Toni Gradl | Active agent for inhibiting microorganism growth on surfaces |
| US5713987A (en) * | 1994-12-22 | 1998-02-03 | Gradl; Toni | Method as well as active substance for preventing microbial growth on surfaces, as well as compound for surface coating or finishing |
| KR100232986B1 (en) * | 1997-07-26 | 1999-12-01 | 이장무 | Hydroxyapatite composite material |
| CN114538914A (en) * | 2022-03-14 | 2022-05-27 | 成都理工大学 | Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof |
-
1991
- 1991-03-14 JP JP07372991A patent/JP3174589B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5476881A (en) * | 1993-02-15 | 1995-12-19 | Suh; Kang I. | Antimicrobial composition for manufacturing nipples |
| DE4445881A1 (en) * | 1994-12-22 | 1996-06-27 | Toni Gradl | Active agent for inhibiting microorganism growth on surfaces |
| US5713987A (en) * | 1994-12-22 | 1998-02-03 | Gradl; Toni | Method as well as active substance for preventing microbial growth on surfaces, as well as compound for surface coating or finishing |
| DE4445881C2 (en) * | 1994-12-22 | 2003-04-17 | Gradl Grams Marianne | Agents for preventing microbial growth on surfaces |
| KR100232986B1 (en) * | 1997-07-26 | 1999-12-01 | 이장무 | Hydroxyapatite composite material |
| CN114538914A (en) * | 2022-03-14 | 2022-05-27 | 成都理工大学 | Zinc-doped calcium phosphate ceramic microsphere with antibacterial function and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3174589B2 (en) | 2001-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR950014709B1 (en) | Antibacterial ceramic | |
| IL96313A (en) | Antibacterial ceramic material | |
| JP2007507408A (en) | Antibacterial glass surface of glass powder | |
| JPH0687714A (en) | Germicidal ceramic | |
| JP6010834B2 (en) | Antibacterial ceramic body | |
| CN103768643A (en) | Silver ion alginate sustained-release antibacterial gel and preparation method thereof | |
| JPH04288006A (en) | Antimicrobial calcium phosphate based ceramics | |
| JP2519143B2 (en) | Bactericidal ceramic composition | |
| JP3051228B2 (en) | Antibacterial tricalcium phosphate | |
| JPH061708A (en) | Antibacterial calcium phosphate ceramics | |
| JPH05229911A (en) | Antimicrobial aluminum phosphate | |
| JPH0413605A (en) | Inorganic antimicrobial agent and production thereof | |
| JP4130950B2 (en) | Silver-based antibacterial composition and method for producing the same | |
| JP2002293705A (en) | Silver-based antibacterial agent and method for producing the same | |
| JP2762423B2 (en) | Antibacterial ceramic material | |
| JP4059326B2 (en) | Inorganic antibacterial agent | |
| JPH05154A (en) | Antibacterial ceramic material | |
| JP2773612B2 (en) | Antimicrobial ceramic and method for producing the same | |
| JPH09157119A (en) | Antibacterial agent | |
| JPH07247205A (en) | Antimicrobial agent | |
| KR20100119985A (en) | Sericite exchanged metal ion having anti-bacteria and preparing methods for thereof | |
| JPH08165213A (en) | Antimicrobial agent | |
| KR980007982A (en) | Method for producing inorganic antibacterial agent | |
| CN112938925B (en) | Novel antibacterial silver compound titanium oxide silver phosphate and preparation method thereof | |
| JPH0687713A (en) | Zinc silicate germicide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |