JPH0347118A - Antimicrobial agent of hydroxyapatite and production thereof - Google Patents
Antimicrobial agent of hydroxyapatite and production thereofInfo
- Publication number
- JPH0347118A JPH0347118A JP2053857A JP5385790A JPH0347118A JP H0347118 A JPH0347118 A JP H0347118A JP 2053857 A JP2053857 A JP 2053857A JP 5385790 A JP5385790 A JP 5385790A JP H0347118 A JPH0347118 A JP H0347118A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyapatite
- antibacterial
- hinokitiol
- antimicrobial
- protamine
- 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
- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 41
- 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 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000004599 antimicrobial Substances 0.000 title abstract 6
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 claims abstract description 42
- TUFYVOCKVJOUIR-UHFFFAOYSA-N alpha-Thujaplicin Natural products CC(C)C=1C=CC=CC(=O)C=1O TUFYVOCKVJOUIR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229930007845 β-thujaplicin Natural products 0.000 claims abstract description 21
- 102000007327 Protamines Human genes 0.000 claims abstract description 12
- 108010007568 Protamines Proteins 0.000 claims abstract description 12
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940048914 protamine Drugs 0.000 claims abstract description 12
- 235000010199 sorbic acid Nutrition 0.000 claims abstract description 12
- 239000004334 sorbic acid Substances 0.000 claims abstract description 12
- 229940075582 sorbic acid Drugs 0.000 claims abstract description 12
- 239000001648 tannin Substances 0.000 claims abstract description 12
- 229920001864 tannin Polymers 0.000 claims abstract description 12
- 235000018553 tannin Nutrition 0.000 claims abstract description 12
- 102000016943 Muramidase Human genes 0.000 claims abstract description 11
- 108010014251 Muramidase Proteins 0.000 claims abstract description 11
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 claims abstract description 11
- 229960000274 lysozyme Drugs 0.000 claims abstract description 11
- 235000010335 lysozyme Nutrition 0.000 claims abstract description 11
- 239000004325 lysozyme Substances 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 10
- 239000003242 anti bacterial agent Substances 0.000 claims description 56
- 239000000463 material Substances 0.000 abstract description 8
- 210000000988 bone and bone Anatomy 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 2
- 230000000845 anti-microbial effect Effects 0.000 abstract 2
- 241000251468 Actinopterygii Species 0.000 abstract 1
- 241000283690 Bos taurus Species 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 11
- 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 11
- 238000000034 method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 244000063299 Bacillus subtilis Species 0.000 description 3
- 235000014469 Bacillus subtilis Nutrition 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- 229940078499 tricalcium phosphate Drugs 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 229940034610 toothpaste Drugs 0.000 description 2
- 239000000606 toothpaste Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003479 dental cement Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- -1 medical equipment Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/26—Phosphorus; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、生体親和性の良好な材料として、人工骨、人
工歯根、骨欠…部補填剤、歯科用セメント、歯磨き、お
よび化粧品など医科、歯科、衛生用品分野に広く使用さ
れているハイドロキシアパタイトに、ヒノキチオール、
タンニン、リゾチーム、プロタミン、ソルビン酸、アリ
ルイソチアシアネート等の有機系抗菌剤のうち、１種又
は２種以上を担持させた抗菌性ハイドロキシアパタイト
及びその製造法に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to medical applications such as artificial bones, artificial tooth roots, bone filling agents, dental cement, toothpaste, and cosmetics as a material with good biocompatibility. , hinokitiol, hydroxyapatite, which is widely used in the dental and sanitary products fields.
The present invention relates to antibacterial hydroxyapatite supported with one or more organic antibacterial agents such as tannin, lysozyme, protamine, sorbic acid, and allyl isothiacyanate, and to a method for producing the same.
（従来の技術）
抗菌剤は医薬品、医薬部外品、医療用具、化粧品、食品
、台所用品、包装材料、フィルター、衣料品、雑貨等の
あらゆる分野に使われており、特に飲食、吸入、接触す
るなど人の関与が激しい場所には抗菌剤、保存剤が多く
用いられている。(Conventional technology) Antibacterial agents are used in all fields such as pharmaceuticals, quasi-drugs, medical equipment, cosmetics, foods, kitchen utensils, packaging materials, filters, clothing, and miscellaneous goods, especially when used in food, drink, inhalation, and contact. Antibacterial agents and preservatives are often used in places where there is a lot of human interaction, such as when cleaning products.
これら抗菌剤は大別して金属などの無機物と、天然や合
成の有機物に分けられるが、実際に用いられている抗菌
剤は、有機物がそのほとんどを占めている。従来、金属
及びそれらの塩は、それらの金属イオンによって抗菌力
が生ずるため溶液中でないと使用できない、毒性が強い
、着色、変色する等の欠点を有しており、あまり使用さ
れなかったが、現在では金属イオンをハイドロキシアパ
タイトやゼオライトなどのセラミックスに担持させるこ
とにより、安全に、しかも取り扱いやすい無機物抗菌剤
が使用され始めている。又、現在抗菌剤の主要部を占め
ている有機系抗菌剤は、有機物であるために揮発性が高
い、熱に弱い、着色する、有機溶媒や水に溶解しやすい
等の欠点があり、使用方法が限られていた。そこで抗菌
剤の着色を防止するため種々の方法が考えられている。These antibacterial agents can be broadly divided into inorganic substances such as metals, and natural and synthetic organic substances, but most of the antibacterial agents actually used are organic substances. In the past, metals and their salts had drawbacks such as being unable to be used unless they were in a solution, being highly toxic, and being colored or discolored due to the antibacterial activity produced by their metal ions, and were not used much. Currently, inorganic antibacterial agents that are safe and easy to handle are beginning to be used by supporting metal ions on ceramics such as hydroxyapatite and zeolite. In addition, organic antibacterial agents, which currently make up the majority of antibacterial agents, have disadvantages such as being highly volatile, sensitive to heat, colored, and easily soluble in organic solvents and water because they are organic substances, making them difficult to use. Methods were limited. Therefore, various methods have been considered to prevent antibacterial agents from discoloring.
例えばヒノキチオールの着色を防ぐため、明ばんやカル
シウム塩と共に添加する方法（特開昭５９−２２４６７
７号公報）、塩又は包接化合物として使用する方法（特
開昭６１−１０８３５９号公報）などが考えられている
。然しなから抗菌性金属をセラミックスに担持させた無
機物抗菌剤は、安全な抗菌剤とはいえ金属の毒性が強く
、溶出の可能性も考えられるため、食品や医療関係には
使用しにくい。又、有機系で安全性が高い抗菌剤であっ
ても、やはり直接食品等に添加する方法は使用制限を受
けるばかりでなく、安全性、味、臭い、変色などの点で
問題がある。又、有機系抗菌剤溶液を、紙、布、吸水性
ポリマーなどの基材に含浸、吸着させて含浸物とすると
、乾燥時に抗菌剤が昇華して抗菌力が失われたり、或は
使用時含浸物表面から抗菌剤が揮発、溶出または析出し
て、思わぬ薬害を生じる可能性があるなど、安定性、安
全性の点から、作成された含浸物の保存法、使用法など
にむつかしい問題を含んでいる。その他、フィルムや樹
脂の成型体に抗菌性を与えるために熱に弱い有機系抗菌
剤を樹脂中に直接添加すると、加工時に分解、昇華など
が起こり抗菌力が失なわれる可能性が高く、抗菌力を損
なわないで加工することは難しい。For example, to prevent hinokitiol from coloring, it is added together with alum or calcium salt (Japanese Patent Application Laid-Open No. 59-22467
7), and the method of using it as a salt or clathrate compound (Japanese Patent Application Laid-Open No. 108359/1983). However, although inorganic antibacterial agents in which antibacterial metals are supported on ceramics are safe antibacterial agents, the metals are highly toxic and there is a possibility of elution, making them difficult to use in food and medical applications. Furthermore, even if an antibacterial agent is organic and highly safe, adding it directly to food etc. is not only subject to usage restrictions, but also poses problems in terms of safety, taste, odor, discoloration, etc. Furthermore, if an organic antibacterial agent solution is impregnated and adsorbed onto a base material such as paper, cloth, or a water-absorbing polymer, the antibacterial agent may sublimate during drying and lose its antibacterial activity, or the antibacterial activity may be lost during use. Difficult problems in storage and usage of impregnated materials from the standpoint of stability and safety, such as the possibility of antibacterial agents volatilizing, eluting, or precipitating from the surface of impregnated materials, resulting in unexpected drug damage. Contains. In addition, if heat-sensitive organic antibacterial agents are directly added to the resin to impart antibacterial properties to films and resin moldings, there is a high possibility that the antibacterial properties will be lost due to decomposition and sublimation during processing. It is difficult to process without losing strength.
そこで、ゼオライトに有機系抗菌剤を吸着させて取り扱
いやすくする方法が考えられているが、ゼオライトは抗
菌剤を保持する量が少なかったり、吸着した抗菌剤を保
持する力が強い為に抗菌性を示さないなどの問題がある
。又、二酸化珪素、炭酸カルシウム、リン酸３カルシウ
ムなどのセラミックスは抗菌剤の保持量に問題がある為
、これらのセラミックスに抗菌剤を添加しても水や溶媒
でほとんど？容出してしまい、これらのセラミックス中
に溶出しない状態で保持されている抗菌剤はわずかな量
となってしまう。そのため、このように抗菌剤を溶出し
ない状態でわずかに保持したセラミックス自身は抗菌効
果を持つものの、この抗菌性セラミックスを化粧品、樹
脂、繊維、紙、フィルター等の抗菌性を必要とする製品
に少量添加しても抗菌力を得る事ができない。従って、
これらの抗菌性セラミックスを多量に製品中に添加する
事により抗菌性を得なければならないが、セラミックス
を多量に添加すると製品の品質を低下させる事が多く、
多量の添加ができない為に抗菌力を得られない場合が多
い。又、抗菌力を高めるためにこれらのセラミックスに
抗菌剤を多量に添加した場合、上記したように、これら
のセラミックスは多量に添加された抗菌剤のすべてを保
持することができないため、しっかりとセラミックスに
保持されていない抗菌剤が、有機系抗菌剤を直接用いた
時と同様の、抗菌剤の揮発、溶出、析出、劣化などの問
題を起こす。Therefore, a method has been considered to make zeolite easier to handle by adsorbing organic antibacterial agents, but zeolite retains only a small amount of antibacterial agents or has a strong ability to retain adsorbed antibacterial agents. There are problems such as not being displayed. In addition, ceramics such as silicon dioxide, calcium carbonate, and tricalcium phosphate have problems with the amount of antibacterial agents they retain, so even if antibacterial agents are added to these ceramics, most of them can be washed with water or solvents. Only a small amount of the antibacterial agent is retained in these ceramics without being eluted. Therefore, although ceramics that retain a small amount of antibacterial agents without eluting them have an antibacterial effect, small amounts of these antibacterial ceramics are used in products that require antibacterial properties such as cosmetics, resins, fibers, paper, and filters. Even if added, antibacterial activity cannot be obtained. Therefore,
Antibacterial properties must be obtained by adding large amounts of these antibacterial ceramics to products, but adding large amounts of ceramics often reduces the quality of the product.
In many cases, antibacterial activity cannot be obtained because large amounts cannot be added. In addition, when a large amount of antibacterial agent is added to these ceramics to increase their antibacterial power, as mentioned above, these ceramics cannot retain all of the added antibacterial agent, so Antibacterial agents that are not retained in the organic antibacterial agent cause the same problems as when organic antibacterial agents are used directly, such as volatilization, elution, precipitation, and deterioration of the antibacterial agent.
（発明が解決しようとする課題）
本発明は簡単に製造でき、抗菌力が強いので少量の添加
で充分で、揮発、昇華などにより或は析出、溶出などに
より抗菌力が失われたり、薬害を生じたりすることがな
く、加えて安定で、変質せず、安全であり、他の物質と
混合して任意の形状で使用できる長期間抗菌性を有する
粉体抗菌剤及びその製造法を提供するものである。(Problems to be solved by the invention) The present invention is easy to manufacture and has strong antibacterial activity, so it is sufficient to add a small amount, and it does not cause loss of antibacterial activity or chemical damage due to volatilization, sublimation, precipitation, elution, etc. To provide a powder antibacterial agent that does not cause any oxidation, is stable, does not deteriorate, is safe, and has long-term antibacterial properties that can be mixed with other substances and used in any form, and a method for producing the same. It is something.
（課題を解決するための手段及び作用）ハイドロキシア
パタイトは骨の主成分であり、人工骨、人工歯根、カル
シウム剤などに使用されている無害な物質であるととも
に、タンパク質、アミノ酸などの有機物を特異的に強く
吸着するので、これらの分離精製用の充填剤として使用
されている。(Means and actions for solving the problem) Hydroxyapatite is a main component of bone, and is a harmless substance used in artificial bones, artificial tooth roots, calcium preparations, etc., and is also a unique substance for organic substances such as proteins and amino acids. Because it strongly adsorbs substances, it is used as a packing material for separation and purification of these substances.
そこで本発明者らはハイドロキシアパタイトの安全性と
タンパク質やアミノ酸などの有機物を特異的に強く吸着
する性質に着目した。Therefore, the present inventors focused on the safety of hydroxyapatite and its ability to specifically and strongly adsorb organic substances such as proteins and amino acids.
ヒノキチオール、タンニン、リゾチーム、プロタミン、
ソルビン酸、アリルイソチアシアネートは従来より抗菌
剤として使用されているものであるがヒノキチオールは
比較的揮発性を有し、タンニン及びヒノキチオールは空
気中で酸化される可能性があり、金属の存在で著しい変
色を示し抗菌性を変化させる。このため長期の保存に関
しては特殊な保存法を講する必要があった。リゾチーム
は塩基性の酵素であるため、取扱いがむつかしい。hinokitiol, tannin, lysozyme, protamine,
Sorbic acid and allyl isothiacyanate have traditionally been used as antibacterial agents, but hinokitiol is relatively volatile, tannins and hinokitiol can be oxidized in the air, and the presence of metals Shows significant discoloration and alters antibacterial properties. For this reason, it was necessary to use special preservation methods for long-term preservation. Because lysozyme is a basic enzyme, it is difficult to handle.
プロタミンは水溶性であるため、使用範囲が限られる。Since protamine is water-soluble, its range of use is limited.
ソルビン酸は空気中で酸化されて着色する。Sorbic acid is oxidized in the air and becomes colored.
又この水？ｇ ｆ＆を加熱するとソルビン酸が水蒸気と
共に揮散する等の問題があった。然しなからこれらの抗
菌剤をハイドロキシアパタイトで処理することにより、
これらの抗菌剤がハイドロキシアパタイトに特異的に強
く吸着され、吸着された抗菌剤は溶液中に溶出、析出す
ることがなく、熱にも安定で、変質せず、長期間抗菌性
を有することを見出した。即ち、本発明はヒノキチオー
ル、タンニン、リゾチーム、プロタミン、ソルビン酸、
アリルイソチアシアネートのうち１種又は２種以上を担
持させた安全で取り扱い易く、且つ製造が簡単な抗菌性
ハイドロキシアパタイトを提供するものである。This water again? There were problems such as sorbic acid volatilizing together with water vapor when gf& was heated. However, by treating these antibacterial agents with hydroxyapatite,
These antibacterial agents are specifically and strongly adsorbed to hydroxyapatite, and the adsorbed antibacterial agents do not elute or precipitate into the solution, are stable under heat, do not change in quality, and have long-term antibacterial properties. I found it. That is, the present invention uses hinokitiol, tannin, lysozyme, protamine, sorbic acid,
The object of the present invention is to provide antibacterial hydroxyapatite that supports one or more allyl isothiacyanates and is safe, easy to handle, and easy to manufacture.
物又は常法により製造された合成物のどちらでもよい。Either a compound or a compound produced by a conventional method may be used.
粒子の大きさはできるだけ微粒子であることが望まれ、
一般に０．０２〜３０μｍ程度に微粉砕されたものが良
い。担持させる抗菌剤はヒノキチオール、タンニン、リ
ゾチーム、プロタミン、ソルビン酸、アリルイソチアシ
アネートのうち選ばれた１種又は２種以上の抗菌剤を水
又は溶媒もしくはこれらの混合溶液で溶解して用いる。It is desired that the particle size is as fine as possible,
Generally, it is preferable to use finely pulverized particles of about 0.02 to 30 μm. The antibacterial agent to be supported is one or more selected from hinokitiol, tannin, lysozyme, protamine, sorbic acid, and allyl isothiacyanate, dissolved in water, a solvent, or a mixed solution thereof.
ハイドロキシアパタイト粉末にこの抗菌剤を溶解した溶
液を含浸させた後、水又は溶媒もしくはこれらの混合溶
液でこの粉末を洗浄してハイドロキシアパタイトに担持
していない抗菌剤を洗い流し、乾燥して粉末化する。或
はハイドロキシアパタイトを常法により湿式合成する際
に抗菌剤を共存させることにより抗菌剤を担持させるこ
とができる。After impregnating hydroxyapatite powder with a solution in which the antibacterial agent is dissolved, the powder is washed with water, a solvent, or a mixed solution of these to wash away the antibacterial agent not supported on the hydroxyapatite, and then dried and powdered. . Alternatively, the antibacterial agent can be supported by allowing the antibacterial agent to coexist when wet-synthesizing hydroxyapatite using a conventional method.
ハイドロキシアパタイトに担持させる抗菌剤の量は、担
持させる抗菌剤の種類、溶液の濃度、製造したハイドロ
キシアパタイト抗菌剤の使用方法などにより任意に選択
することができるが、ハイドロキシアパタイトに担持す
る抗菌剤の量に限度があるため、抗菌剤の量はハイドロ
キシアパタイトに対して１０％以下であり、又抗菌力を
得るために０．０１％以上が好ましい。The amount of antibacterial agent supported on hydroxyapatite can be arbitrarily selected depending on the type of antibacterial agent to be supported, the concentration of the solution, the usage method of the produced hydroxyapatite antibacterial agent, etc. Since there is a limit to the amount, the amount of antibacterial agent is 10% or less based on hydroxyapatite, and preferably 0.01% or more to obtain antibacterial activity.
このようにして得られた抗菌性ハイドロキシアパタイト
は長期間抗菌性を保持し、水やアルコールに対する溶出
は検出されず、安全に使用され、そのまま用いるか他の
材料に５０％以下、好ましくは０．１〜２０％程度添加
することにより充分な抗菌力を発渾する。The antibacterial hydroxyapatite thus obtained maintains its antibacterial properties for a long time, and no elution in water or alcohol is detected, so it is safe to use, and can be used as is or added to other materials by 50% or less, preferably 0%. Sufficient antibacterial activity is developed by adding about 1 to 20%.
以下実施例を示して本発明を具体的に説明する。The present invention will be specifically described below with reference to Examples.
例１）
ヒノキチオール１．５ｇを５０Ｏｎ＋１のエタノールに
溶解し、ハイドロキシアパタイト１００ｇを加えて攪拌
する。生成物をエタノール及び蒸留水で良く洗い、乾燥
、粉砕を行ない、ヒノキチオールを１．５％担持した抗
菌性ハイドロキシアパタイト粉末を得た。Example 1) Dissolve 1.5 g of hinokitiol in 50 On+1 ethanol, add 100 g of hydroxyapatite, and stir. The product was thoroughly washed with ethanol and distilled water, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 1.5% hinokitiol.
例２）
ヒノキチオール１．０ｇとタンニン０．４ｇを５００１
１１のエタノールに溶解し、ハイドロキシアバタイ）１
００ｇを加えて攪拌する。生成物を蒸留水及びエタノー
ルで良く洗い、乾燥、粉砕を行ない、ヒノキチオールを
１．０％およびタンニンを０．４％担持した抗菌性ハイ
ドロキシアパタイト粉末を得た。Example 2) 1.0g hinokitiol and 0.4g tannin in 5001
Hydroxyabatai) dissolved in 11 ethanol
Add 00g and stir. The product was thoroughly washed with distilled water and ethanol, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 1.0% hinokitiol and 0.4% tannin.
例３）
リゾチーム５ｇを５００ｍ＃の蒸留水に溶解し、ハイド
ロキシアパタイト１００ｇを加えて攪拌する。生成物を
エタノール及び蒸留水で良く洗い、乾燥、粉砕を行ない
、リゾチームを５％担持した抗菌性ハイドロキシアパタ
イト粉末を得た。Example 3) Dissolve 5 g of lysozyme in 500 m# of distilled water, add 100 g of hydroxyapatite, and stir. The product was thoroughly washed with ethanol and distilled water, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 5% lysozyme.
例４）
プロタミン２．０ｇを５００ｎ＋ｊ！の蒸留水に溶解し
、ハイドロキシアパタイト１００ｇを加えて攪拌する。Example 4) 2.0g of protamine for 500n+j! Dissolve in distilled water, add 100 g of hydroxyapatite, and stir.
生成物を蒸留水で良く洗い、乾燥、粉砕を行ない、プロ
タミンを２％担持した抗菌性ハイドロキシアパタイト粉
末を得た。The product was thoroughly washed with distilled water, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 2% protamine.
例５）
ソルビンＭ２．Ｏｇを５００ｍ１のエタノールに溶解し
、ハイドロキシアパタイト１００ｇを加えて攪拌する。Example 5) Sorvin M2. Dissolve Og in 500 ml of ethanol, add 100 g of hydroxyapatite, and stir.
生成物をエタノールおよび蒸留水で良く洗い、乾燥、粉
砕を行ない、ソルビン酸を２％担持した抗菌性ハイドロ
キシアパタイト粉末を得た。The product was thoroughly washed with ethanol and distilled water, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 2% sorbic acid.
例６）
１Ｍ水酸化カルシウム溶液ｉｆ中にヒノキチオール１０
％溶液を５０Ｉ１１加え、０．２ Ｍリン酸溶液を添加
して攪拌し、常法によりハイドロキシアパタイトを合成
した。生成物を蒸留水及びエタノールで良く洗い、乾燥
、粉砕を行ない、ヒノキチオールを５％担持した抗菌性
ハイドロキシアパタイト粉末を得た。Example 6) Hinokitiol 10 in 1M calcium hydroxide solution if
A 50I11% solution was added thereto, a 0.2 M phosphoric acid solution was added and stirred, and hydroxyapatite was synthesized by a conventional method. The product was thoroughly washed with distilled water and ethanol, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 5% hinokitiol.
例７）
アリルイソチアシアネート０．４ ｇを５００＋ｎ１の
エタノールに溶解し、ハイドロキシアパタイト１００ｇ
を加えて攪拌する。生成物を蒸留水及びエタノールで良
く洗い、乾燥、粉砕を行ない、アリルイソチアシアネー
トを０．４％担持した抗菌性ハイドロキシアパタイト粉
末を得た。Example 7) Dissolve 0.4 g of allyl isothiacyanate in 500+n1 ethanol and prepare 100 g of hydroxyapatite.
Add and stir. The product was thoroughly washed with distilled water and ethanol, dried, and ground to obtain antibacterial hydroxyapatite powder carrying 0.4% allyl isothiacyanate.
例８）抗菌剤溶出試験
上記のように作成した抗菌剤担持ハイドロキシアバタイ
ｌ−Ｌｏｇを蒸留水１００ｍＪ中に入れて攪拌し、抗菌
剤の溶出量を測定した。その結果、いずれの場合も抗菌
剤が検出されなかった。Example 8) Antibacterial agent elution test The antibacterial agent-supported hydroxyabatai l-Log prepared as described above was placed in 100 mJ of distilled water and stirred, and the amount of antibacterial agent eluted was measured. As a result, no antibacterial agents were detected in any case.
例９）実施例１）〜５）及び実施例７）の作成物を用い
て抗菌性の試験を行なった。Example 9) Antibacterial tests were carried out using the products of Examples 1) to 5) and Example 7).
国名
実施例１） 大腸菌
実施例２） 大腸菌
実施例３） 枯草菌
実施例４） 枯草菌
実施例５） 枯草菌
０時間 ２４時間後
４．１ｘｌＯ５１０以下
３、２ ＸＩＯ’ １０ 以下
５、 ＯｘｌＯ’ ２．６ ｘｌＯ’６、９ ｘｌＯ
ｈ８．４ ｘｌＯ’
９、５ ｘｌＯ’ ２．１ ＸＩＯ’実施例７）
大腸菌 ５．５ｘｌＯＳ１０ 以下例１０）実施例
６）の作成物を、ハイドロキシアパタイト１００ｇに蒸
留水２００ｍｊ！加えたスラリー中にそれぞれ０．２％
、１．０％添加して大腸菌に対する抗菌性の試験を行な
った。Country Example 1) Escherichia coli Example 2) Escherichia coli Example 3) Bacillus subtilis Example 4) Bacillus subtilis Example 5) Bacillus subtilis 0 hours 4.1xlO510 or less after 24 hours 3, 2 XIO' 10 or less 5, OxlO' 2 .6 xlO'6, 9 xlO
h8.4 xlO' 9, 5 xlO' 2.1 XIO' Example 7)
Escherichia coli 5.5xlOS10 Example 10) The preparation of Example 6) was added to 100 g of hydroxyapatite and 200 mj of distilled water! 0.2% of each in the added slurry
, 1.0% was added to conduct an antibacterial test against E. coli.
添加量 ０時間 ２４時間後０．２％
１． ＯＸＩＯ” １．５ ＸＩＯ”
１．０％ １．０Ｘ１０’６ １０以下コン
トロール １．０Ｘ１０１０２．３Ｘ１０”例９）、
例１０）の抗菌試験において、ハイドロキシアパタイト
抗菌剤の静菌又は抗菌力が認められた。Addition amount 0 hours 0.2% after 24 hours
1. OXIO" 1.5 XIO"
1.0% 1.0X10'6 10 or less control 1.0X10102.3X10"Example 9),
In the antibacterial test of Example 10), the bacteriostatic or antibacterial activity of the hydroxyapatite antibacterial agent was observed.
参考例１）
各種濃度のヒノキチオール溶液中にセラミックス粉末（
ハイドロキシアパタイト、リン酸−水素カルシウム、リ
ン酸二水素カルシウム、リン酸三カルシウム、ピロリン
酸カルシウム、ゼオライト）を加え、攪拌することによ
りヒノキチオールを含浸させ、その後エタノール及び蒸
留水で良（洗浄して、セラミックス粉末に担持じていな
いヒノキチオールを洗い流すという簡単な操作により、
それらセラミックス粉末にヒノキチオールを担持させ、
その担持量を測定して最大担持量を求めた。Reference example 1) Ceramic powder (
Hydroxyapatite, calcium hydrogen phosphate, calcium dihydrogen phosphate, tricalcium phosphate, calcium pyrophosphate, zeolite) are added and stirred to impregnate hinokitiol. By the simple operation of washing away hinokitiol that is not carried in the powder,
By supporting hinokitiol on these ceramic powders,
The amount supported was measured to determine the maximum amount supported.
その結果を表１に示す。The results are shown in Table 1.
表 １
参考例２）
参考例１）と同様の簡単な操作によりその他の有機系抗
菌剤がハイドロキシアパタイト、リン酸三カルシウム、
ゼオライトに担持する最大量を測定した。その結果を表
２に示す。Table 1 Reference Example 2) Other organic antibacterial agents such as hydroxyapatite, tricalcium phosphate, and
The maximum amount supported on zeolite was measured. The results are shown in Table 2.
参考例１）及び２）の結果はハイドロキシアパタイトが
他のセラミックスに比較して各種の有機系抗菌剤のうち
ヒノキチオール、タンニン、リゾチーム、プロタミン、
ソルビン酸、アリルイソチアシアネートを特異的に多量
に吸着、保持する事を示している。The results of Reference Examples 1) and 2) show that hydroxyapatite is more effective than other ceramics in terms of hinokitiol, tannin, lysozyme, protamine, and other organic antibacterial agents.
This shows that it specifically adsorbs and retains large amounts of sorbic acid and allyl isothiacyanate.
（発明の効果）
本発明によるハイドロキシアパタイト抗菌剤は、生体親
和性が高く安全であるため、食品、生体材料、化粧品、
紙、繊維、プラスチック、フィルム、フィルター、吸水
性樹脂など抗菌性を必要とする多くの分野に用いること
ができる。又、歯磨き、口内用の洗浄剤などに用いると
、ハイドロキシアパタイトの蛋白除去、微小充填効果の
他に薬剤がハイドロキシアパタイトと供に歯面上に長く
留まるため、薬剤のミュータンス増殖抑制等の抗う蝕効
果が加わり、効果の高い虫歯予防剤となる。(Effect of the invention) The hydroxyapatite antibacterial agent according to the present invention has high biocompatibility and is safe, so it can be used in foods, biomaterials, cosmetics, etc.
It can be used in many fields that require antibacterial properties, such as paper, fibers, plastics, films, filters, and water-absorbing resins. In addition, when used in toothpaste, oral cleansing agents, etc., in addition to the protein removal and microfilling effects of hydroxyapatite, the drug remains on the tooth surface for a long time together with hydroxyapatite, resulting in anti-causal effects such as suppression of mutans proliferation. With the added caries effect, it becomes a highly effective caries prevention agent.
Claims (3)
イソチアシアネート、プロタミン及びソルビン酸、で示
される抗菌剤のうち１種又は２種以上をハイドロキシア
パタイトに担持させたことを特徴とするハイドロキシア
パタイト抗菌剤。(1) A hydroxyapatite antibacterial agent characterized in that hydroxyapatite supports one or more of the following antibacterial agents: hinokitiol, tannin, lysozyme, allyl isothiacyanate, protamine, and sorbic acid.
し１０〜０．０１重量％である請求項（１）記載のハイ
ドロキシアパタイト抗菌剤。(2) The hydroxyapatite antibacterial agent according to claim 1, wherein the amount of the antibacterial agent supported is 10 to 0.01% by weight based on hydroxyapatite.
イソチアシアネート、プロタミン及びソルビン酸で示さ
れる抗菌剤のうち１種又は２種以上をハイドロキシアパ
タイトに吸着させることを特徴とするハイドロキシアパ
タイト抗菌剤の製造法。(3) A method for producing a hydroxyapatite antibacterial agent, which comprises adsorbing one or more antibacterial agents of hinokitiol, tannin, lysozyme, allyl isothiacyanate, protamine, and sorbic acid onto hydroxyapatite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2053857A JPH085782B2 (en) | 1989-04-14 | 1990-03-07 | Hydroxyapatite antibacterial agent and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1-92999 | 1989-04-14 | ||
| JP9299989 | 1989-04-14 | ||
| JP2053857A JPH085782B2 (en) | 1989-04-14 | 1990-03-07 | Hydroxyapatite antibacterial agent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0347118A true JPH0347118A (en) | 1991-02-28 |
| JPH085782B2 JPH085782B2 (en) | 1996-01-24 |
Family
ID=26394575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2053857A Expired - Lifetime JPH085782B2 (en) | 1989-04-14 | 1990-03-07 | Hydroxyapatite antibacterial agent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH085782B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999013716A1 (en) * | 1997-09-16 | 1999-03-25 | Showa Denko K.K. | Antibiotic preparations and use of the same |
| US6541042B1 (en) * | 1999-10-27 | 2003-04-01 | Bogar Ag | Therapeutically effective combination |
| DE10252956A1 (en) * | 2002-11-14 | 2004-06-03 | Nutrinova Nutrition Specialties & Food Ingredients Gmbh | New lysozyme sorbate, useful as antimicrobial agent, especially as preservative in foodstuffs or animal feed or as additive in detergents, cleaning agents or packaging |
| JP2007045799A (en) * | 2005-08-12 | 2007-02-22 | Sangi Co Ltd | Composition for oral ingestion |
| US7618658B2 (en) | 2002-06-13 | 2009-11-17 | Hououdou Co., Ltd. | Anti-microbial agent and anti-microbial composition |
| JP2013532157A (en) * | 2010-06-24 | 2013-08-15 | プライオン エス．エー． | Stabilized active compounds |
| JP2013163655A (en) * | 2012-02-10 | 2013-08-22 | Kanagawa Academy Of Science & Technology | Antimicrobial material |
| JP2016533325A (en) * | 2013-09-25 | 2016-10-27 | クレデンティス・アクチェンゲゼルシャフトＣｒｅｄｅｎｔｉｓ ＡＧ | Dental care products for whitening teeth |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147401A (en) * | 1984-08-13 | 1986-03-07 | Shiraishi Chuo Kenkyusho:Kk | Calcium phosphate based sustained release substance |
| JPS62143672A (en) * | 1985-12-14 | 1987-06-26 | Shigeo Inamine | Preservative for food |
-
1990
- 1990-03-07 JP JP2053857A patent/JPH085782B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6147401A (en) * | 1984-08-13 | 1986-03-07 | Shiraishi Chuo Kenkyusho:Kk | Calcium phosphate based sustained release substance |
| JPS62143672A (en) * | 1985-12-14 | 1987-06-26 | Shigeo Inamine | Preservative for food |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999013716A1 (en) * | 1997-09-16 | 1999-03-25 | Showa Denko K.K. | Antibiotic preparations and use of the same |
| US6541042B1 (en) * | 1999-10-27 | 2003-04-01 | Bogar Ag | Therapeutically effective combination |
| US7618658B2 (en) | 2002-06-13 | 2009-11-17 | Hououdou Co., Ltd. | Anti-microbial agent and anti-microbial composition |
| DE10252956A1 (en) * | 2002-11-14 | 2004-06-03 | Nutrinova Nutrition Specialties & Food Ingredients Gmbh | New lysozyme sorbate, useful as antimicrobial agent, especially as preservative in foodstuffs or animal feed or as additive in detergents, cleaning agents or packaging |
| JP2007045799A (en) * | 2005-08-12 | 2007-02-22 | Sangi Co Ltd | Composition for oral ingestion |
| JP2013532157A (en) * | 2010-06-24 | 2013-08-15 | プライオン エス．エー． | Stabilized active compounds |
| JP2013163655A (en) * | 2012-02-10 | 2013-08-22 | Kanagawa Academy Of Science & Technology | Antimicrobial material |
| JP2016533325A (en) * | 2013-09-25 | 2016-10-27 | クレデンティス・アクチェンゲゼルシャフトＣｒｅｄｅｎｔｉｓ ＡＧ | Dental care products for whitening teeth |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH085782B2 (en) | 1996-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5009898A (en) | Antimicrobial hydroxyapatite powders and methods for preparing them | |
| US5268174A (en) | Antimicrobial hydroxyapatite powders containing hinokitiol, protamine or sorbic acid | |
| GB2238044A (en) | Antibacterial ceramic material | |
| JP2012533568A (en) | Particles containing antibacterial substances | |
| JPH0347118A (en) | Antimicrobial agent of hydroxyapatite and production thereof | |
| Pihl et al. | Osseointegration and antibacterial effect of an antimicrobial peptide releasing mesoporous titania implant | |
| JPH0383905A (en) | Antimicrobial agent | |
| JPS5925751A (en) | Sterilization of pobidon | |
| Milan et al. | Effects of mangosteen peel phenolic compounds on tilapia skin collagen-based mineralized scaffold properties | |
| DE69414521T2 (en) | METHOD FOR THE PRODUCTION OF IODIZED BIOPOLYMERS WITH DISINFECTING AND SCARF-PROMOTING EFFECT, AND THEREFORE PRODUCED IODATED BIOPOLYMERS | |
| JP4388285B2 (en) | Functional molded body for improving environmental atmosphere | |
| KR0143396B1 (en) | Dentifrice containing antibacterial material | |
| JP4210037B2 (en) | Antibacterial composition | |
| JP2649388B2 (en) | Antimicrobial composition | |
| JPH02180270A (en) | Antibacterial hydroxyapatite and manufacturing method thereof | |
| CN112955009A (en) | Composition, sprayer and wiping cloth | |
| JPH0413605A (en) | Inorganic antimicrobial agent and production thereof | |
| KR102253875B1 (en) | Antibacterial deodorant composition | |
| JP2859181B2 (en) | Antibacterial tribasic calcium phosphate and method for producing the same | |
| JP2762423B2 (en) | Antibacterial ceramic material | |
| JPH02273165A (en) | Freshness retaining agent for food | |
| KR20220123952A (en) | Silver ion anti-oxidation processing method and silver ion antibacterial solution production method Silver ion antibacterial solution and silver ion-containing products containing the antibacterial solution | |
| JP3051315B2 (en) | Antibacterial material | |
| KR101020178B1 (en) | Processing method for preventing oxidation of silver ions and sterilizing textiles with silver ions manufactured thereby | |
| JPH04288006A (en) | Antimicrobial calcium phosphate based ceramics |