JPH06298616A - Antifungal and antimold agent and its production - Google Patents

Antifungal and antimold agent and its production

Info

Publication number
JPH06298616A
JPH06298616A JP9140793A JP9140793A JPH06298616A JP H06298616 A JPH06298616 A JP H06298616A JP 9140793 A JP9140793 A JP 9140793A JP 9140793 A JP9140793 A JP 9140793A JP H06298616 A JPH06298616 A JP H06298616A
Authority
JP
Japan
Prior art keywords
silver
antibacterial
calcium phosphate
antifungal
glass
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
Application number
JP9140793A
Other languages
Japanese (ja)
Other versions
JP3251376B2 (en
Inventor
Keijiro Shigeru
啓二郎 茂
Takako Yazawa
矢澤孝子
Tomohiko Iijima
飯島智彦
Nobuyuki Kumakura
熊倉信幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Cement Co Ltd
Original Assignee
Sumitomo Cement Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Cement Co Ltd filed Critical Sumitomo Cement Co Ltd
Priority to JP09140793A priority Critical patent/JP3251376B2/en
Publication of JPH06298616A publication Critical patent/JPH06298616A/en
Application granted granted Critical
Publication of JP3251376B2 publication Critical patent/JP3251376B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

PURPOSE:To provide an antifungal and antimold composition by fixing metallic ions having oligodynamic action including silver to an inorganic ion exchanger firmly and its production process. CONSTITUTION:The objective antifungal and antimold agent is composed of 0.01 to 10wt.% of at least one selected from silver, copper and zinc, 1 to 50wt.% of calcium phosphate and the remaining of glass phase.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、抗菌、防カビ剤及びそ
の製法に関する。更に詳しくは、本発明は、プラスチッ
ク、繊維、セメント、コンクリート、陶磁器等の工業製
品に、抗菌、防カビ処理を行なうに当って使用する抗
菌、防カビ剤及びその製法に関する。
TECHNICAL FIELD The present invention relates to an antibacterial and antifungal agent and a method for producing the same. More specifically, the present invention relates to an antibacterial and antifungal agent which is used for performing antibacterial and antifungal treatments on industrial products such as plastics, fibers, cement, concrete and ceramics, and a method for producing the same.

【0002】[0002]

【従来の技術】従来、抗菌、防カビ剤は、有機系のもの
が多く用いられてきた。然し乍ら、近年、銀、銅、亜鉛
等のオリゴジナミー効果を利用した無機系のものが、安
全性及び耐久性の点ですぐれているため、適用する機会
が増大してきた。
2. Description of the Related Art Conventionally, organic antibacterial and antifungal agents have been widely used. However, in recent years, inorganic materials such as silver, copper, and zinc which utilize the oligodynamic effect are excellent in safety and durability, and therefore the opportunities for application have increased.

【0003】無機系の抗菌,防カビ剤は,大別して2種
類に分類される。その1つは、無機物イオン交換体に水
溶液中でオリゴジナミー金属イオンを、イオン交換反応
で担持したものである。もう1つは、水溶性ガラス中に
オリゴジナミー金属イオンを溶解させたものである。前
者のイオン交換担持のものは、イオン交換体に担持され
たオリゴジナミー金属イオンが、抗菌,防カビ性を発揮
し,そして,後者の水溶性ガラス中に溶解させたもの
は、ガラスの溶解に伴って放出されたオリゴジナミー金
属イオンが、抗菌、防カビ性を発揮すると考えられる。
Inorganic antibacterial and antifungal agents are roughly classified into two types. One of them is an inorganic ion exchanger in which an oligodynamic metal ion is supported in an aqueous solution by an ion exchange reaction. The other is a solution of oligodinamy metal ions dissolved in water-soluble glass. The former ion-exchange-supported one, in which the oligodinamy metal ion supported on the ion-exchanger exhibits antibacterial and antifungal properties, and the latter one dissolved in water-soluble glass, is accompanied by the dissolution of the glass. It is considered that the released oligodynamic metal ions exert antibacterial and antifungal properties.

【0004】このような従来の無機系抗菌、防カビ剤の
問題点は、銀イオンを含有した場合、これの溶出に伴
い、色が変化することにある。無機物イオン交換体に水
溶液反応で担持された銀イオンは、担持の結合力が弱い
ため、溶出し、変色する。この改善のために、イオン交
換体を高温で処理すれば、結合力が強くなり、変色はや
や小さくなるが、未だ十分なものではない。更に、水溶
性ガラスに銀イオンを溶解させたものは、ガラスの溶解
に伴い銀イオンを溶出するため、変色を避け得ないもの
である。
A problem with such conventional inorganic antibacterial and antifungal agents is that when silver ions are contained, the color changes as the silver ions elute. The silver ion carried by the aqueous solution reaction on the inorganic ion exchanger has a weak binding force for carrying, and is eluted and discolored. If the ion exchanger is treated at a high temperature for this improvement, the binding force will be increased and the discoloration will be slightly reduced, but it is still not sufficient. Further, the one in which silver ions are dissolved in water-soluble glass cannot avoid discoloration because silver ions are eluted as the glass is dissolved.

【0005】[0005]

【発明が解決しようとする課題】従って、本発明は、前
記のような種々の問題を解決するために発明されたもの
であり、ここで、銀等の金属イオンを無機物イオン交換
体に、従来よりも強固に結合させることができれば、変
色はほとんど認められなくなると考えられることに基づ
いて、無機物イオン交換体に、強固に、銀を始めとする
オリゴジナミー効果を有する金属イオンを固定できる抗
菌、防カビ剤の組成物、並びに、その製造方法を提供す
ることを目的とする。
Therefore, the present invention has been invented to solve the above-mentioned various problems, in which a metal ion such as silver is used as an inorganic ion exchanger. Based on the fact that if it can be bound more firmly, discoloration is considered to be hardly observed, based on the fact that the inorganic ion exchanger can firmly fix metal ions having an oligodynamic effect such as silver, antibacterial and preventive It is an object of the present invention to provide a mold composition and a method for producing the same.

【0006】[0006]

【課題を解決するための手段】本発明は、上記の技術的
な課題の解決のために、銀、銅、亜鉛から選択された少
なくとも1つの金属の含有量が、0.01〜10重量
%、リン酸カルシウムの含有量が1〜50重量%、残り
がガラス相から構成される抗菌、防カビ剤を提供する。
更に、本発明は、リン酸カルシウムに銀を水溶液中で担
持させた後、これをガラス粉と混合し、この混合物を7
00℃以上の高温に加熱して、ガラス成分が流動化する
ようになった後、この混合物を急冷して得ることを特徴
とする抗菌、防カビ剤の製法であり、また、リン酸カル
シウム、銀化合物、ガラス粉を混合し、この混合物を、
700℃以上の高温に加熱して、ガラス成分が流動化す
るようになった後、この混合物を急冷して得ることを特
徴とする、抗菌、防カビ剤の製法である。
According to the present invention, in order to solve the above technical problems, the content of at least one metal selected from silver, copper and zinc is 0.01 to 10% by weight. The present invention provides an antibacterial and antifungal agent having a calcium phosphate content of 1 to 50% by weight and the rest being a glass phase.
Further, according to the present invention, after calcium phosphate is supported with silver in an aqueous solution, this is mixed with glass powder, and the mixture is mixed with 7
A method for producing an antibacterial and antifungal agent, which comprises heating the mixture to a high temperature of 00 ° C. or higher to fluidize the glass component, and then rapidly cooling the mixture, and a calcium phosphate and a silver compound. , Glass powder is mixed, and this mixture is
It is a method for producing an antibacterial and antifungal agent, which comprises heating the mixture to a high temperature of 700 ° C. or higher to fluidize the glass component and then rapidly cooling the mixture.

【0007】即ち、抗菌、防カビ剤の製法としては、2
通りある。その1つは、リン酸カルシウムに先ず銀等の
金属を担持させるものである。即ち、リン酸カルシウム
と水溶性銀化合物、例えば、AgNO3又はAgFを水
溶液中で混合する。次に、これとガラス粉を混合する。
ガラス粉の組成に特に限定はないが、ホウケイ酸塩ガラ
スのフリットが、溶融時の流動性が良いために、好適で
ある。これらの混合物を、700℃以上の高温に、好適
には、1000〜1200℃の温度に加熱して、ガラス
成分を充分に溶解し、流動化せしめる。この後、これを
急冷し、好適には水中に急冷すると、抗菌、防カビ剤が
得られる。この抗菌、防カビ剤は、必要に応じて微粉砕
して使用する。
That is, there are two methods for producing antibacterial and antifungal agents:
There is a street. One of them is to support a metal such as silver on calcium phosphate. That is, calcium phosphate and a water-soluble silver compound such as AgNO 3 or AgF are mixed in an aqueous solution. Next, this and glass powder are mixed.
The composition of the glass powder is not particularly limited, but frit of borosilicate glass is preferable because it has good fluidity when melted. These mixtures are heated to a high temperature of 700 ° C. or higher, preferably to a temperature of 1000 to 1200 ° C. to sufficiently dissolve and fluidize the glass component. Then, this is rapidly cooled, preferably in water, to obtain an antibacterial and antifungal agent. The antibacterial and antifungal agents are used after finely pulverized as needed.

【0008】ここで、銀、銅、亜鉛から選択された少な
くとも1つの金属の含有量が、0.01〜10重量%の
範囲である。0.01重量%未満では、充分な効果が得
られず、10重量%を超えると、変色性が生じることと
なる。リン酸カルシウムの含有量は、1〜50重量%が
好適である。1重量%未満では、抗菌、防カビ効果が充
分でなく、50重量%を超えると、変色するためであ
る。また、リン酸カルシウムの組成は、CaとPのモル
比が、Ca/P=1.5〜1.7が好適である。これ
に、更に、3〜4重量%のフッ素を含有させると、好適
である。
Here, the content of at least one metal selected from silver, copper and zinc is in the range of 0.01 to 10% by weight. If it is less than 0.01% by weight, a sufficient effect cannot be obtained, and if it exceeds 10% by weight, discoloration occurs. The content of calcium phosphate is preferably 1 to 50% by weight. This is because if it is less than 1% by weight, the antibacterial and antifungal effects are not sufficient, and if it exceeds 50% by weight, discoloration occurs. The composition of calcium phosphate is preferably such that the molar ratio of Ca and P is Ca / P = 1.5 to 1.7. It is preferable to further contain 3 to 4% by weight of fluorine.

【0009】もう1つの製造方法は、リン酸カルシウ
ム、銀等の化合物(例えば、リン酸銀、塩化銀)、ガラ
ス粉(好適には、ホウケイ酸ガラスのフリットで、10
00〜1200℃で流動化するもの)を混合し、700
℃以上の高温に加熱して、ガラス粉を溶融、流動化せし
め、これを急冷し、好適には水冷するものである。
Another method is to prepare a compound such as calcium phosphate, silver (eg, silver phosphate, silver chloride), glass powder (preferably a frit of borosilicate glass, 10
(Which fluidizes at 00 to 1200 ° C) are mixed, and 700
The glass powder is melted and fluidized by heating it to a high temperature of ℃ or more, and this is rapidly cooled, preferably water cooled.

【0010】[0010]

【作用】本発明の抗菌、防カビ剤において、銀、銅、亜
鉛の金属成分の役割は、抗菌、防カビ性の発現であり、
リン酸カルシウムの役割は、銀等の金属の担持体になる
ことである。また、ガラス相の役割は、銀等の金属が、
リン酸カルシウムに担持されるのを助ける溶媒になるこ
とである。
In the antibacterial and antifungal agent of the present invention, the role of the metal components of silver, copper and zinc is the expression of antibacterial and antifungal properties,
The role of calcium phosphate is to become a carrier for metals such as silver. In addition, the role of the glass phase, metal such as silver,
It is a solvent that helps the calcium phosphate to be supported.

【0011】リン酸カルシウムは、水溶液中の反応で
も、銀等の金属を担持することができるが、これでの結
合力が小さいため、銀等の金属が遊離しやすく、変色し
易くなる。然し乍ら、本発明の抗菌、防カビ剤のよう
に、溶融したガラス中で担持させると、結合力が大きく
なり、銀等の金属が、遊離し難くなるために、変色し難
くなる。
Calcium phosphate can support a metal such as silver even in a reaction in an aqueous solution, but its binding force is small, so that the metal such as silver is easily liberated and discolored easily. However, like the antibacterial and antifungal agent of the present invention, when it is carried in molten glass, the binding force becomes large, and the metal such as silver is less likely to be liberated, so that discoloration is less likely to occur.

【0012】この方法は、単なる加熱による結合力と
は、本質的に異なり、ガラス溶融液中で、イオン交換反
応を起こし、強固な結合力を得るためのものである。こ
のように、本発明の抗菌、防カビ剤の特徴は、ガラス溶
融液中で、銀等の金属イオンを無機物イオン交換体に担
持させることにより、変色しない抗菌、防カビ剤を得る
ことができる。
This method is essentially different from the binding force by heating, and is for obtaining a strong binding force by causing an ion exchange reaction in the glass melt. As described above, the feature of the antibacterial and antifungal agent of the present invention is that an antibacterial and antifungal agent which does not discolor can be obtained by supporting a metal ion such as silver on an inorganic ion exchanger in a glass melt. .

【0013】そして、銀等の金属イオンのオリゴジナミ
ー効果は、これの溶出に伴って発現するものではない。
即ち、担持された状態の銀イオン等の金属イオンを、触
媒として活性酸素が生成され,その活性酸素が存在する
と、オリゴジナミー効果が発現するものである。従っ
て、本発明の抗菌,防カビ剤のように、溶出しない銀イ
オン等の金属イオンを担持している無機物イオン交換体
であっても、抗菌、防カビ効果を発揮することが可能で
ある。
The oligodynamic effect of metal ions such as silver does not appear with the elution of the ions.
That is, the active oxygen is generated by using the supported metal ions such as silver ions as a catalyst, and when the active oxygen is present, the oligodynamic effect is exhibited. Therefore, even an inorganic ion exchanger carrying metal ions such as silver ions that do not elute like the antibacterial and antifungal agent of the present invention can exhibit antibacterial and antifungal effects.

【0014】次に、本発明を具体的に実施例により説明
するが、本発明はそれらによって限定されるものではな
い。
Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

【0015】[0015]

【実施例】リン酸カルシウムの合成 水酸化カルシウム スラリーにリン酸を滴下して、リン
酸カルシウムを合成した。Ca/Pモル比は、1.5と
1.67とした2種類のものを作成した。また、1.6
7のものには、フッ素を4重量%(NaF添加による)
添加したものも作成した。
Example Synthesis of calcium phosphate Phosphoric acid was added dropwise to a calcium hydroxide slurry to synthesize calcium phosphate. Two Ca / P molar ratios of 1.5 and 1.67 were prepared. Also, 1.6
7: 4% by weight of fluorine (by adding NaF)
The added one was also created.

【0016】水溶液での銀の担持(水溶液中銀担持法) 上記のようにして合成した3種のリン酸カルシウムに銀
を担持させた。担持法は、リン酸カルシウム水懸濁液中
に、硝酸銀を添加し、24時間撹拌処理して行なった。
銀の担持量は、固形分に対して1重量%とした。
Loading of Silver in Aqueous Solution (Method of Loading Silver in Aqueous Solution ) Silver was loaded on the three types of calcium phosphate synthesized as described above. The supporting method was carried out by adding silver nitrate to an aqueous suspension of calcium phosphate and stirring for 24 hours.
The amount of silver supported was 1% by weight based on the solid content.

【0017】ガラス粉との混合 上記のリン酸カルシウムの合成で作成した3種のリン酸
カルシウムに、各々、リン酸銀を、リン酸カルシウムに
対して銀が1重量%になる配合で、そして、ホウケイ酸
ガラスのフリットを、リン酸カルシウムの4倍量添加
し、ボールミルで混合した(直接混合法)。更に、水溶
液中銀担持法で作成した3種の銀担持のリン酸カルシウ
ムに、各々、ホウケイ酸ガラスのフリットを、リン酸カ
ルシウムの4倍量添加し、ボールミルで混合した。
Mixing with glass powder To each of the three types of calcium phosphate prepared by the above-mentioned synthesis of calcium phosphate, silver phosphate is added in such a manner that the silver content is 1% by weight based on calcium phosphate, and the frit of borosilicate glass is used. Was added by 4 times the amount of calcium phosphate and mixed by a ball mill (direct mixing method). Further, to each of the three types of silver-supported calcium phosphate prepared by the silver-supported method in an aqueous solution, a borosilicate glass frit was added in an amount four times that of calcium phosphate and mixed by a ball mill.

【0018】ガラスの溶融及び冷却 以上で作成した6種類の混合物を、各々、1100℃に
加熱して、ガラス成分混合物を溶融した。この溶融物を
水中に投下して冷却した。得られた固化物は、ボールミ
ルで平均粒子径10μmに粉砕した。
Melting and Cooling of Glass Each of the six types of mixtures prepared above was heated to 1100 ° C. to melt the glass component mixture. The melt was dropped in water and cooled. The obtained solidified product was pulverized with a ball mill to an average particle size of 10 μm.

【0019】変色性の試験 以上作成した6種類の粉体試料の変色性を試験した。試
験法は、粉体試料1gを、100gのアクリル エマル
ジョン樹脂に練り込み、太陽光を24時間照射し、目視
で変色を観察した。この試験法では、銀が溶出し易い抗
菌、防カビ剤では、試験すると変色するものである。試
験の結果は、表1に示す。
Color Change Test The color change properties of the 6 types of powder samples prepared above were tested. In the test method, 1 g of a powder sample was kneaded into 100 g of an acrylic emulsion resin, irradiated with sunlight for 24 hours, and the discoloration was visually observed. According to this test method, antibacterial and antifungal agents, which easily dissolve silver, are discolored when tested. The test results are shown in Table 1.

【0020】[0020]

【表1】 [Table 1]

【0021】実施例で説明した、原料、作成法は、一例
であって、本発明の目的にかなうものであれば、使用す
る原料、作成法、作成過程など種々を組合わせたり、異
なるものを用いても良い。
The raw materials and preparation methods described in the examples are merely examples, and as long as they meet the purpose of the present invention, various combinations of raw materials to be used, preparation methods, preparation processes and the like may be used. You may use.

【0022】[0022]

【発明の効果】以上説明したように、本発明の抗菌、防
カビ剤及びその製法及びそれを用いた構造により、次の
ような顕著な技術的効果が得られた。無機物イオン交換
体に強固に、銀を始めとするオリゴジナミー効果を有す
る金属イオンを固定できる抗菌、防カビ剤の組成物並び
に、その製造方法を提供した。即ち、銀等の金属イオン
を無機物イオン交換体に、従来よりも強固に結合させる
ことができ、変色はほとんど認められなくなる、抗菌、
防カビ剤及びその製法を提供する。
As described above, the following remarkable technical effects are obtained by the antibacterial and antifungal agent of the present invention, the method for producing the same, and the structure using the same. Provided are a composition of an antibacterial and antifungal agent capable of firmly fixing a metal ion having an oligodynamic effect such as silver to an inorganic ion exchanger, and a method for producing the same. That is, a metal ion such as silver can be bound to an inorganic ion exchanger more firmly than before, and discoloration is hardly observed.
An antifungal agent and a method for producing the same are provided.

フロントページの続き (72)発明者 熊倉信幸 千葉県船橋市豊富町585番地 住友セメン ト株式会社中央研究所内Front page continuation (72) Inventor Nobuyuki Kumakura 585 Tomicho, Funabashi, Chiba Sumitomo Cement Co., Ltd. Central Research Laboratory

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 銀、銅、亜鉛から選択された少なくとも
1つの金属の含有量が、0.01〜10重量%、リン酸
カルシウムの含有量が1〜50重量%、残りがガラス相
から構成されることを特徴とする抗菌、防カビ剤。
1. The content of at least one metal selected from silver, copper and zinc is 0.01 to 10% by weight, the content of calcium phosphate is 1 to 50% by weight, and the rest is composed of a glass phase. An antibacterial and antifungal agent characterized by
【請求項2】リン酸カルシウムに、銀を水溶液中で担持
させた後、これをガラス粉と混合し、この混合物を70
0℃以上の高温に加熱して、ガラス成分が流動化するよ
うになった後、この混合物を急冷して得ることを特徴と
する請求項1に記載の抗菌、防カビ剤の製法。
2. Silver is supported on calcium phosphate in an aqueous solution, which is then mixed with glass powder to obtain 70 parts of the mixture.
The method for producing an antibacterial and antifungal agent according to claim 1, which is obtained by heating the mixture to a high temperature of 0 ° C or higher to fluidize the glass component and then rapidly cooling the mixture.
【請求項3】リン酸カルシウム、銀化合物、ガラス粉を
混合し、この混合物を、700℃以上の高温に加熱し
て、ガラス成分が流動化するようになった後、この混合
物を急冷して得ることを特徴とする請求項1に記載の抗
菌、防カビ剤の製法。
3. A method in which calcium phosphate, a silver compound and glass powder are mixed, the mixture is heated to a high temperature of 700 ° C. or higher to fluidize the glass component, and then the mixture is rapidly cooled. The method for producing an antibacterial and antifungal agent according to claim 1, characterized in that
JP09140793A 1993-04-19 1993-04-19 Antibacterial and antifungal agent and its manufacturing method Expired - Fee Related JP3251376B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP09140793A JP3251376B2 (en) 1993-04-19 1993-04-19 Antibacterial and antifungal agent and its manufacturing method

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6752867B1 (en) * 2002-11-29 2004-06-22 Sinanen Zeomic Co., Ltd. Antibacterial agent for concrete, concrete compositions and concrete products
CN116143418A (en) * 2023-04-21 2023-05-23 山东孟友新材料科技有限责任公司 Antibacterial toughened glass and preparation method thereof
CN116143417A (en) * 2023-04-18 2023-05-23 山东孟友新材料科技有限责任公司 Nanometer inorganic antibacterial agent for toughened glass and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6752867B1 (en) * 2002-11-29 2004-06-22 Sinanen Zeomic Co., Ltd. Antibacterial agent for concrete, concrete compositions and concrete products
CN116143417A (en) * 2023-04-18 2023-05-23 山东孟友新材料科技有限责任公司 Nanometer inorganic antibacterial agent for toughened glass and preparation method thereof
CN116143417B (en) * 2023-04-18 2023-09-01 山东孟友新材料科技有限责任公司 Nanometer inorganic antibacterial agent capable of being tempered together with glass to prepare tempered glass and preparation method thereof
CN116143418A (en) * 2023-04-21 2023-05-23 山东孟友新材料科技有限责任公司 Antibacterial toughened glass and preparation method thereof
CN116143418B (en) * 2023-04-21 2023-08-18 山东孟友新材料科技有限责任公司 Antibacterial toughened glass and preparation method thereof

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