JP3051019B2 - Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glaze - Google Patents
Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glazeInfo
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- JP3051019B2 JP3051019B2 JP6079064A JP7906494A JP3051019B2 JP 3051019 B2 JP3051019 B2 JP 3051019B2 JP 6079064 A JP6079064 A JP 6079064A JP 7906494 A JP7906494 A JP 7906494A JP 3051019 B2 JP3051019 B2 JP 3051019B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- glaze
- antifungal
- composition
- weight
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、陶器、磁器などの表面
に、抗菌性防カビ性を付与する抗菌防カビ性釉薬組成
物、および釉薬添加用抗菌防カビ性組成物と、これらを
用いた抗菌防カビ性窯業製品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the surface of ceramics, porcelain, etc.
To, antibacterial and antifungal glaze composition for imparting antimicrobial and antifungal properties
Objects, and the glaze additive antibacterial and antifungal composition relates to antibacterial and antifungal properties ceramic products using these.
【０００２】[0002]
【従来の技術】便器、洗面器、浴槽といった製品は、人
間が生活上直接肌を触れ、あるいは肌が極めて近づく機
会が多いことから、衛生的であること、さらに美観を備
えていることが要求されている。このような要求に応え
るべく、前記便器などの製品は従来、窯業製品によって
作られている。この理由は、窯業製品の表面が釉薬、す
なわちガラスでコーティングされているためであり、釉
薬によって形成される層が緻密で吸水性がなく、しかも
表面が滑らかで傷が付きにくいため、衛生面での要求や
美観の要求に十分に応えられるからである。2. Description of the Related Art Products such as toilets, washbasins, and bathtubs are required to be sanitary and have aesthetic appearance, since humans often come into direct contact with their skin in their daily lives or get very close to the skin. Have been. In order to meet such demands, products such as the above-mentioned toilets are conventionally made of ceramic products. The reason for this is that the surface of ceramic products is coated with glaze, that is, glass, and the layer formed by the glaze is dense and has no water absorption. This is because it can sufficiently meet the demands of the aesthetics and beauty.
【０００３】ところで、近年前記製品に加え、タイルや
衛生陶器などの窯業製品に対し、その衛生面での要求が
さらに高まってきている。すなわち、このような窯業製
品にあっても、細菌、カビなどが繁殖するため、十分な
清潔感が得られず、また菌の繁殖が汚れとなって現われ
るからであり、よって、このような菌の繁殖を防止する
ことが望まれているのである。[0003] In recent years, in addition to the above-mentioned products, ceramic products such as tiles and sanitary ware have been increasingly required in terms of hygiene. That is, even in such ceramic products, bacteria, molds, and the like propagate, so that a sufficient clean feeling cannot be obtained, and the propagation of the bacteria appears as dirt. It is desired to prevent breeding.
【０００４】従来、このような菌の繁殖を防止するため
に、抗菌防カビ力を有するもの、例えば銀、銅、酸化チ
タンなどを含有する薄膜を、抗菌防カビ性を付与させよ
うとするものの表面に形成させるということがなされて
きた。その具体的な方法として、例えば前記窯業製品の
表面に銀化合物を焼き付ける、または窯業製品の表面に
銅、銀などの還元メッキを施す、酸化チタンの液体原料
を吹き付けて焼成するなどの方法が挙げられる。Heretofore, in order to prevent the propagation of such bacteria, a thin film containing an antibacterial and / or antifungal agent, for example, a thin film containing silver, copper, titanium oxide, etc., is intended to be provided with an antibacterial and antifungal effect. It has been made to form on the surface. As a specific method, for example, a method of baking a silver compound on the surface of the ceramic product, or applying a reduction plating of copper, silver, or the like to the surface of the ceramic product, spraying a liquid material of titanium oxide, and firing. Can be
【０００５】しかしながら、銀化合物を表面に焼き付け
る方法では、抗菌成分を表面に析出させるのが困難で、
結果として所望する抗菌防カビ力を得ることができず、
メッキをする方法においては、得られた薄膜の強度や耐
薬品性が劣るなどの欠点があった。また、酸化チタンの
薄膜を形成させる方法においては、光還元反応にその抗
菌性を期待するため、光量による依存性が高くなり、安
定な抗菌性が維持されず、用途も極端に限定されるとい
う問題があった。However, in the method of baking a silver compound on a surface, it is difficult to deposit an antibacterial component on the surface.
As a result, the desired antibacterial and antifungal power cannot be obtained,
The plating method has disadvantages such as inferior strength and chemical resistance of the obtained thin film. In addition, in the method of forming a thin film of titanium oxide, since antibacterial properties are expected in the photoreduction reaction, dependence on the amount of light is increased, stable antibacterial properties are not maintained, and applications are extremely limited. There was a problem.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、これらの事
情に鑑みてなされたものであって、耐久性に優れ、長期
間に亙って優れた抗菌防カビ力を保持することのできる
抗菌防カビ性釉薬組成物と、釉薬添加用抗菌防カビ性組
成物と、これらを用いた抗菌防カビ性窯業製品を提供す
ることを目的としている。SUMMARY OF THE INVENTION The present invention has been made in view of these circumstances, and has excellent durability and can maintain excellent antibacterial and antifungal properties over a long period of time.
Antibacterial and antifungal glaze composition and antibacterial and antifungal antiglare composition for adding glaze
The purpose is to provide products and antibacterial and mold-proof ceramic products using them.
【０００７】[0007]
【課題を解決するための手段】かかる目的は、ＳｉＯ2
が４０〜５５重量％、Ａｌ2 Ｏ3 が５〜１０重量％、Ｂ
2 Ｏ3 が５〜１５重量％、ＣａＯが１〜７重量％、Ｓｒ
Ｏが７〜１２重量％、Ｎａ2 ＯとＫ2 Ｏが合計で５〜１
０重量％、Ａｇ2 Ｏが５〜２０重量％、Ｐ2Ｏ5が０．５
〜５重量％の組成からなる抗菌防カビ釉薬組成物および
上記組成の釉薬添加用抗菌防カビ性組成物によって解決
される。この際の前記Ａｇ2 ＯおよびＰ2Ｏ5の供給源
は、リン酸銀である。さらに、前記抗菌防カビ性釉薬組
成物を単独で、あるいは、前記釉薬添加用抗菌防カビ組
成物と釉薬とを混合して、窯業製品の表面に固着させ
て、抗菌防カビ性窯業製品とする。SUMMARY OF THE INVENTION The object of the present invention is to provide a method of forming an SiO 2
There 40-55 wt%, Al 2 O 3 is 5-10 wt%, B
2 O 3 is 5 to 15% by weight, CaO is 1 to 7% by weight, Sr
O is 7 to 12% by weight, and Na 2 O and K 2 O are 5 to 1 in total.
0% by weight, 5 to 20% by weight of Ag 2 O, 0.5% of P 2 O 5
An antibacterial and antifungal glaze composition comprising a composition of about 5% by weight and
Solved by the antibacterial and antifungal composition for adding glaze of the above composition
Is done. The source of the Ag 2 O and P 2 O 5 at this time is silver phosphate. Further, the antibacterial and antifungal properties glaze sets
Antibacterial and antifungal group for glaze addition
The product and glaze are mixed and adhered to the surface of the ceramic product to obtain an antibacterial and mold-proof ceramic product.
【０００８】[0008]
【作用】本発明の抗菌防カビ性釉薬組成物および釉薬添
加用抗菌防カビ性組成物は上記組成からなるものであ
り、加熱溶融中にリン酸銀がガラス中に均一に分散され
る。また、前記リン酸銀は、リン酸と銀との結合が強固
であり、ガラス中での酸性度が高く保持され、銀の還元
が防止できる。The antibacterial and antifungal glaze composition and glaze of the present invention
The added antibacterial and antifungal composition has the above composition, and silver phosphate is uniformly dispersed in glass during heating and melting. Further, the silver phosphate has a strong bond between phosphoric acid and silver, has a high acidity in the glass, and can prevent the reduction of silver.
【０００９】[0009]
【実施例】次に、本発明の抗菌防カビ性釉薬組成物また
は釉薬添加用抗菌防カビ性組成物の一例について詳しく
説明する。この抗菌防カビ性釉薬組成物および釉薬添加
用抗菌防カビ性組成物は、ホウケイ酸ガラスに、銀が分
散されてなるものである。そしてその組成は、ＳｉＯ2
が４０〜５５重量％、Ａｌ2 Ｏ3 が５〜１０重量％、Ｂ
2 Ｏ3 が５〜１５重量％、ＣａＯが１〜７重量％、Ｓｒ
Ｏが７〜１２重量％、Ｎａ2 ＯとＫ2 Ｏが合計で、５〜
１０重量％、Ａｇ2 Ｏが５〜２０重量％、Ｐ2 Ｏ5 が
０．５〜５重量％である。EXAMPLES Next, the antibacterial and antifungal glaze composition of the present invention or
Describes in detail an example of the antibacterial and antifungal composition for adding glaze . This antibacterial and antifungal glaze composition and glaze addition
The antibacterial and antifungal composition for use is obtained by dispersing silver in borosilicate glass. And the composition is SiO 2
There 40-55 wt%, Al 2 O 3 is 5-10 wt%, B
2 O 3 is 5 to 15% by weight, CaO is 1 to 7% by weight, Sr
O is 7 to 12 wt%, Na 2 O and K 2 O is in total, 5
10 wt%, Ag 2 O 5 to 20 wt%, P 2 O 5 is from 0.5 to 5 wt%.
【００１０】前記抗菌防カビ性釉薬組成物および釉薬添
加用抗菌防カビ性組成物において、ＳｉＯ2 の含有量が
４０〜５５重量％であるのは、４０重量％未満だと、ガ
ラスの主成分であるケイ酸分が乏しすぎ、また、５５重
量％を越えると、釉面が均一に形成できず、マットな仕
上がりとなって好ましくないからである。The above antibacterial and antifungal glaze composition and glaze additive
In the added antibacterial and antifungal composition, the content of SiO 2 is 40 to 55% by weight. If the content is less than 40% by weight, the content of silicic acid, which is the main component of glass, is too low, and 55% by weight. %, The glaze surface cannot be formed uniformly, resulting in a matte finish, which is not preferable.
【００１１】また、Ａｌ2 Ｏ3 は、通常のホウケイ酸ガ
ラスにも含有されている成分の一つであり、ケイ酸成分
による失透傾向を抑制し、分相化を防止する働きを持
つ。ここで、前記Ａｌ2 Ｏ3 の含有量を５〜１０重量％
としたのは、５重量％未満であると、後述するＢ2 Ｏ3
成分により融点が下がりすぎ、失透傾向が見られ、ま
た、１０重量％を越えると、耐火度が上昇し、ＳｉＯ2
の場合と同様マットな仕上がりとなって好ましくないか
らである。Further, Al 2 O 3 is one of the components contained in ordinary borosilicate glass, and has a function of suppressing the tendency to devitrify due to the silicate component and preventing phase separation. Here, the content of Al 2 O 3 is 5 to 10% by weight.
Is less than 5% by weight when B 2 O 3
Depending on the components, the melting point is too low and the tendency to devitrify is observed. If it exceeds 10% by weight, the fire resistance is increased and SiO 2
This is because the matte finish is not preferable as in the case of the above.
【００１２】また、Ｂ2 Ｏ3 も前記Ａｌ2 Ｏ3 と同様、
ホウケイ酸ガラスに元来含有されている成分の一つであ
る。このＢ2 Ｏ3 は、一般にホウケイ酸ガラス中では、
融剤として働き、Ｂ2 Ｏ3 の含有量が多いと融点が低下
し、Ｂ2 Ｏ3 の含有量が少ないと融点が上昇するとされ
ており、本発明においては、５〜１５重量％である。こ
れは、５重量％未満となると、釉面の仕上がり状態が悪
くなるからである。一方、１５重量％を越えると、水に
対する溶解性が高くなり、このような抗菌防カビ性釉薬
組成物、または釉薬添加用抗菌防カビ性組成物と釉薬と
の混合物を用いて形成された釉面の耐久性が低下して好
ましくないからである。Also, B 2 O 3 is similar to Al 2 O 3 described above.
It is one of the components originally contained in borosilicate glass. This B 2 O 3 is generally used in borosilicate glass.
It acts as a flux, and it is said that the melting point decreases when the content of B 2 O 3 is large, and increases when the content of B 2 O 3 is small. In the present invention, the content is 5 to 15% by weight. . This is because when the content is less than 5% by weight, the finished state of the glaze surface deteriorates. On the other hand, if it exceeds 15% by weight, the solubility in water becomes high, and such an antibacterial and antifungal glaze is used.
A composition, or an antibacterial and antifungal composition for glaze addition and a glaze
This is because the durability of the glaze surface formed by using the mixture of the above is lowered, which is not preferable.
【００１３】また、ＣａＯも、ホウケイ酸ガラス中に元
来含有されている成分の一つであるが、本発明の抗菌防
カビ性釉薬組成物および釉薬添加用抗菌防カビ性組成物
においては、その一部がＳｒＯに置換されている。この
ＣａＯとＳｒＯの比は、ＣａＯ：ＳｒＯ＝１：２である
ことが好ましい。これは、１：２よりもＣａＯの含有量
が多くなると水に対する溶解度が大きくなって好ましく
なく、また、１：２よりもＣａＯの含有量が少なくなる
と、この抗菌防カビ性釉薬組成物、または釉薬添加用抗
菌防カビ性組成物を添加した釉薬からなる釉面の耐酸性
が極度に低下するからである。この際のＣａＯの含有量
は１〜７重量％であり、これは、７重量％を越えるとＢ
2 Ｏ3 の場合と同様、水に対する溶解性が高くなり、前
記釉面の耐久性が低下して好ましくなく、また、１重量
％未満であると先に述べた釉面の耐酸性の低下を促すか
らである。一方、ＳｒＯの含有量は、前記ＣａＯの含有
量から、２〜１４重量％であればよいが、特に７〜１２
重量％であることが好ましい。これは、耐水溶性および
耐酸性の両方を十分に発揮でき、合わせて適度な耐火度
を有すものであるからである。[0013] CaO is also one of the components originally contained in the borosilicate glass, but the antibacterial and antifungal glaze composition of the present invention and the antibacterial and antifungal composition for adding a glaze. In>, a part is replaced by SrO. The ratio between CaO and SrO is preferably CaO: SrO = 1: 2. This is because the solubility in water is increased when the content of CaO is larger than 1: 2, and it is not preferable. When the content of CaO is smaller than 1: 2, this antibacterial and antifungal glaze composition, or Glaze additive
This is because the acid resistance of the glaze surface made of the glaze to which the fungicidal composition has been added is extremely reduced. At this time, the content of CaO is 1 to 7% by weight.
As in the case of 2 O 3, the solubility in water is increased, and the durability of the glaze surface is reduced, which is not preferable. In addition, the decrease in acid resistance of the glaze surface, which is less than 1% by weight, is reduced. It is because it urges. On the other hand, the content of SrO may be 2 to 14% by weight based on the content of CaO, but is more preferably 7 to 12% by weight.
% By weight. This is because both the water resistance and the acid resistance can be sufficiently exhibited, and in addition, it has an appropriate degree of fire resistance.
【００１４】また、Ｎａ2 ＯとＫ2 Ｏの含有量は、その
合計で、５〜１０重量％である。これは、５重量％未満
であると溶融しにくく、ガラスとしての性質を著しく損
ない、１０重量％を越えると、耐火度が低下し、融点調
節に支障を与えるからである。The total content of Na 2 O and K 2 O is 5 to 10% by weight. This is because if it is less than 5% by weight, it is difficult to melt, the properties as glass are remarkably impaired, and if it exceeds 10% by weight, the fire resistance is reduced and the melting point is hindered.
【００１５】さらに、Ａｇ2 Ｏの含有量は５〜２０重量
％、Ｐ2 Ｏ5 の含有量は０．５〜５重量％である。これ
は、Ａｇ2 Ｏが５重量％未満、Ｐ2 Ｏ5 の含有量が０．
５重量％未満であると、安定した抗菌防カビ効果を発揮
することができず、またＡｇ2 Ｏが２０重量％、Ｐ2Ｏ5
が５重量％を越えると、コスト面に支障を来すほか、リ
ン酸銀の有する黄色が残存し、色調に変化を与えるため
用途が狭まるなどの問題が生じるからである。Further, the content of Ag 2 O is 5 to 20% by weight, and the content of P 2 O 5 is 0.5 to 5% by weight. This means that the content of Ag 2 O is less than 5% by weight and the content of P 2 O 5 is 0.1%.
If the content is less than 5% by weight, a stable antibacterial and antifungal effect cannot be exhibited, and 20% by weight of Ag 2 O and P 2 O 5
If the content exceeds 5% by weight, not only the cost will be hindered, but also the yellow color of the silver phosphate will remain, giving rise to a change in the color tone and causing problems such as a narrowed application.
【００１６】また、前記Ａｇ2 ＯおよびＰ2 Ｏ5 の供給
源は、リン酸銀であることが好ましい。これは、銀を単
に担持させたアパタイトなどとは異なり、銀とリン酸成
分の結合が強く、ガラス中でも酸性度が高く保持され、
容易に銀が還元されないからである。The source of Ag 2 O and P 2 O 5 is preferably silver phosphate. This is different from apatite, which simply supports silver, in which the bond between silver and the phosphoric acid component is strong, and the acidity is kept high even in glass,
This is because silver is not easily reduced.
【００１７】このような組成の抗菌防カビ性釉薬組成物
および釉薬添加用抗菌防カビ性組成物は、原材料を混
合、加熱、溶融して冷却し、フリットとしたものであっ
てもよいし、また、原材料を混合しただけの生釉の状態
のものであってもよい。また、本発明の抗菌防カビ性釉
薬組成物および釉薬添加用抗菌防カビ性組成物は、先の
例に限られるものではなく、微細な融点調整のため、長
石、カオリン、フッ化カルシウムなどを添加したもので
あってもよい。An antibacterial and antifungal glaze composition having such a composition
The antibacterial and antifungal composition for adding glaze may be a frit obtained by mixing, heating, melting and cooling the raw materials, or may be a raw glaze obtained by mixing the raw materials only. There may be. Further, the antibacterial / antifungal glaze composition and the antibacterial / antifungal composition for adding glaze of the present invention are not limited to the above examples, and may be made of feldspar, kaolin, calcium fluoride, etc. for fine melting point adjustment. It may be added.
【００１８】このような抗菌防カビ性釉薬組成物および
釉薬添加用抗菌防カビ性組成物はＳｉＯ2が４０〜５５
重量％、Ａｌ2Ｏ3が５〜１０重量％、Ｂ2 Ｏ3 が５〜１
５重量％、ＣａＯが１〜７重量％、ＳｒＯが７〜１２重
量％、Ｎａ2 ＯとＫ2 Ｏが合計で５〜１０重量％、Ａｇ
2 Ｏが５〜２０重量％、Ｐ2 Ｏ5 が０．５〜５重量％の
組成からなるものであるので、このものの融点はリン酸
銀の融点より高いことから、加熱溶融中にリン酸銀が均
一に分散され、効果ムラの無い安定した抗菌防カビ力を
有するものとなる。また、Ａｇ2 ＯおよびＰ2 Ｏ5 の供
給源としてリン酸銀を用いているので、ガラス中での酸
性度が高く保持され、銀の還元が防止できるため、優れ
た抗菌力を長期にわたって維持することができるととも
に、前記抗菌防カビ性釉薬組成物および釉薬添加用抗菌
防カビ性組成物はもちろん、これらを用いて作製された
釉面においても変色などが生じにくい。Such an antibacterial and antifungal glaze composition and
Glaze additive antibacterial and antifungal composition SiO 2 is 40 to 55
% By weight, 5 to 10% by weight of Al 2 O 3 , 5 to 1% of B 2 O 3
5 wt%, CaO 1 to 7 wt%, SrO 7 to 12 wt%, 5-10 wt% Na 2 O and K 2 O is in total, Ag
Since the composition of 2 O is 5 to 20% by weight and P 2 O 5 is 0.5 to 5% by weight, its melting point is higher than that of silver phosphate. Silver is uniformly dispersed, and has a stable antibacterial and antifungal ability without unevenness of effect. Further, since silver phosphate is used as a supply source of Ag 2 O and P 2 O 5 , the acidity in the glass is kept high, and the reduction of silver can be prevented, so that excellent antibacterial activity is maintained for a long time. The antibacterial and antifungal glaze composition and the antibacterial for glaze addition
Antifungal compositions, of course, also is less likely to occur, such as color change in釉面made using these.
【００１９】次に、本発明の抗菌防カビ性窯業製品の一
例について説明する。この抗菌防カビ性窯業製品は、陶
器、磁器などの窯業製品の表面に、前記抗菌防カビ性釉
薬組成物を単独で、または、前記釉薬添加用抗菌防カビ
性組成物と釉薬との混合物で施釉、焼成、固着されてな
るものである。前記固着させるための方法としては、公
知の任意の方法でよく、例えば、前記抗菌防カビ性釉薬
組成物、または釉薬添加用抗菌防カビ性組成物を含有す
る釉薬を、水などの適宜な溶媒に分散させた懸濁液を、
抗菌防カビ性を付与したい窯業製品の表面に吹き付けた
後、これを焼成し、前記窯業製品の表面に抗菌防カビ性
を有する釉面を形成させるなどの方法が挙げられる。ま
た、この際の塗布方法は吹き付け、流しかけ、浸しが
け、塗布など任意であり、また、焼成時の条件、例えば
焼成温度なども、得ようとする窯業製品の用途などによ
って任意とすることができる。Next, an example of the antibacterial and mold-proof ceramic product of the present invention will be described. This antibacterial / mildew-proof ceramic product is obtained by coating the above antibacterial / mildew-proof glaze composition alone or on the surface of ceramic products such as ceramics and porcelain,
Facilities glaze with a mixture of sex composition and glaze firing are those formed by sticking. The method for fixing may be any known method, for example, the antibacterial and antifungal glaze.
A suspension obtained by dispersing the composition, or the glaze containing the antibacterial and antifungal composition for glaze addition, in an appropriate solvent such as water,
After spraying onto the surface of a ceramic product to which antibacterial and fungicidal properties are desired to be imparted, the method is baked to form a glaze surface having antibacterial and fungicidal properties on the surface of the ceramic product. In addition, the application method at this time is optional such as spraying, pouring, soaking, applying, and the like, and the conditions at the time of firing, such as the firing temperature, may be optional depending on the intended use of the ceramic product to be obtained. it can.
【００２０】前記釉薬としては、本発明の抗菌防カビ性
釉薬組成物単独でも、前記釉薬添加用抗菌防カビ性組成
物を、他の市販されている釉薬に混合したものであって
もよい。さらに、前記釉薬添加用抗菌防カビ性組成物を
市販の釉薬に混合して用いる場合、その配合量は、市販
の釉薬の種類や組成によって、任意の量とすることがで
きるが、通常は１〜５重量％とされる。[0020] Examples of the glaze, in antibacterial and antifungal glaze composition alone of the present invention, antibacterial and antifungal composition for the glaze additives
The product may be mixed with other commercially available glazes. Further, when the antibacterial and antifungal composition for adding a glaze is used by being mixed with a commercially available glaze, the compounding amount can be any amount depending on the type and composition of the commercially available glaze. , Usually 1 to 5% by weight.
【００２１】このような抗菌防カビ性窯業製品は、本発
明の抗菌防カビ性釉薬組成物、または、釉薬添加用抗菌
防カビ性組成物と釉薬との混合物を含んでなる釉面が表
面に形成されてなるものであるので、抗菌防カビ効果を
有する銀が、前記抗菌防カビ性釉薬組成物、または釉薬
添加用抗菌防カビ性組成物と釉薬との混合物を含んでな
る釉面に均一に分散され、前記銀の一部は確実に、前記
釉面の表面に存在するため、効率よく抗菌防カビ効果を
発揮する。また、仮に、前記釉面の表面が損傷を受けた
場合でも、銀はその内部にまで存在しているため、抗菌
防カビ力が失われることはない。また、このような抗菌
防カビ性窯業製品を得るには特別な工程は要せず、前記
抗菌防カビ性釉薬組成物、または、釉薬添加用抗菌防カ
ビ性組成物と釉薬との混合物を含有する釉薬をその表面
に塗布した後、焼成させるという、公知の陶器、磁器の
製法を用いることができるため、窯業製品製造において
工程変更を必要としない。[0021] Such an antibacterial and fungicidal ceramic product is an antibacterial and fungicidal glaze composition of the present invention or an antibacterial and antifungal for glaze addition.
Since the glaze surface comprising a mixture of the antifungal composition and the glaze is formed on the surface, silver having an antibacterial and antifungal effect is used as the antibacterial and antifungal glaze composition, or the glaze.
The additive antibacterial and fungicidal composition is uniformly dispersed on the glaze surface comprising a mixture of the glaze, and a part of the silver is surely present on the surface of the glaze surface. Demonstrate. Even if the glaze surface is damaged, the antibacterial and antifungal ability is not lost because silver is present even inside the glaze surface. No special process is required to obtain such an antibacterial and fungicidal ceramic product, and the antibacterial and fungicidal glaze composition or the antibacterial and fungicide for adding glaze is not required.
A known method of making pottery and porcelain, in which a glaze containing a mixture of a vitreous composition and a glaze is applied to the surface and then fired, can be used, so that no process change is required in the manufacture of ceramic products.
【００２２】（実施例１） 以下、具体例を示し、本発明の効果を明らかにする。Ｓ
ｒＯ成分を含有する市販のホウケイ酸ガラスフリット
に、ケイ砂、脱水ホウ砂を加えた。さらに、これに対
し、９：１の割合でリン酸銀を添加した。このものをよ
く混合した後ルツボに入れ、１２００℃にて３０分間溶
融させた後、前記ルツボから溶融状態のまま水中に投下
し、冷却固化したものを粗粉砕し、本発明の抗菌防カビ
性釉薬組成物を得た。(Example 1) Hereinafter, specific examples will be shown to clarify the effects of the present invention. S
Silica sand and dehydrated borax were added to a commercially available borosilicate glass frit containing an rO component. Further, silver phosphate was added at a ratio of 9: 1. This mixture was mixed well, put into a crucible, melted at 1200 ° C. for 30 minutes, dropped into water in a molten state from the crucible, cooled and solidified, coarsely pulverized, and then subjected to the antibacterial and antifungal properties of the present invention. A glaze composition was obtained.
【００２３】そして前記抗菌防カビ性釉薬組成物の組成
はＳｉＯ2 が４９重量％、Ａｌ2Ｏ3が８重量％、ＣａＯ
が５重量％、Ｂ2 Ｏ3 が１０重量％、Ｎａ2 Ｏが５重量
％、Ｋ2 Ｏが２重量％、ＳｒＯが１０重量％、Ａｇ2 Ｏ
が８重量％、Ｐ2 Ｏ5 が２重量％、その他の成分が１重
量％であった。The composition of the antibacterial and antifungal glaze composition is 49% by weight of SiO 2 , 8% by weight of Al 2 O 3 , and CaO
5% by weight, 10% by weight of B 2 O 3 , 5% by weight of Na 2 O, 2 % by weight of K 2 O, 10% by weight of SrO, Ag 2 O
Was 8% by weight, P 2 O 5 was 2% by weight, and other components were 1% by weight.
【００２４】ついで、前記抗菌防カビ性釉薬組成物と水
を１：１の割合にて混合して、遠心ボールミルに入れた
後粉砕し、沈降性のスラリーとした。以下、このスラリ
ーを単独スラリーと記す。このものを、既に市販のジル
コン系の白色釉薬を施釉したタイルに吹き付け、電気炉
にて１２００℃、３０分間焼成した。これを試験片と
し、大腸菌を用い、１／５０濃度ブイヨンを添加した静
置生菌法による抗菌試験を行った。結果を表１に示す。Then, the antibacterial and antifungal glaze composition and water were mixed at a ratio of 1: 1 and put into a centrifugal ball mill and pulverized to obtain a sedimentable slurry. Hereinafter, this slurry is referred to as a single slurry. This was sprayed onto a tile already glazed with a commercially available zircon-based white glaze and fired in an electric furnace at 1200 ° C. for 30 minutes. This was used as a test piece, and an antibacterial test was performed using Escherichia coli using a stationary live bacteria method to which a 1/50 concentration broth was added. Table 1 shows the results.
【００２５】（実施例２） 実施例１で作製した抗菌防カビ性釉薬組成物と同様の組
成の釉薬添加用抗菌防カビ性組成物を、実施例１と同様
の市販の釉薬に、５重量％添加し、同量の水とともに遠
心ボールミルにて粉砕混合し、スラリーとした。以下、
このスラリーを混合スラリーと記す。この混合スラリー
を直接タイル素地に吹き付け、実施例１と同様の条件で
焼成させたものを試験片とし、実施例１と同様の抗菌試
験を行った。結果を表１に示す。(Example 2) A set similar to the antibacterial and antifungal glaze composition prepared in Example 1
The resulting antibacterial and antifungal composition for adding glaze was added to a commercially available glaze in the same manner as in Example 1 by 5% by weight, and crushed and mixed with the same amount of water in a centrifugal ball mill to obtain a slurry. Less than,
This slurry is referred to as a mixed slurry. This mixed slurry was directly sprayed on a tile base and fired under the same conditions as in Example 1 to obtain a test piece, and the same antibacterial test as in Example 1 was performed. Table 1 shows the results.
【００２６】（比較例１） リン酸銀を添加しない他は、実施例１と同様の試験片を
作製し、同様の試験を行った。結果を表１に示す。Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that silver phosphate was not added, and a similar test was performed. Table 1 shows the results.
【００２７】[0027]
【表１】 [Table 1]
【００２８】（実施例３） 実施例１にて冷却固化された塊状および粉砕された粉末
状の抗菌防カビ性釉薬組成物を用い、ハロー試験を行っ
た。普通寒天培地上に菌液を塗布し、その中に５×５×
５ｍｍの塊状および０．０５ｇの粉末を設置し、一晩放
置して、前記塊状および粉末状の抗菌防カビ性釉薬組成
物の周囲に形成されたハローの幅を計測した。結果を表
２に示す。また、表２中の数値は、ハローの大きさｍｍ
で表わしたものである。(Example 3) A halo test was performed using the lumpy and pulverized powdery antibacterial and antifungal glaze compositions cooled and solidified in Example 1. Bacterial solution is spread on an ordinary agar medium, and 5 × 5 ×
5 mm lump and 0.05 g of powder were placed and left overnight, and the lump and powder antibacterial and antifungal glaze composition
The width of the halo formed around the object was measured. Table 2 shows the results. The values in Table 2 are the size of the halo mm
It is represented by.
【００２９】（実施例４） 実施例２と同様の混合スラリーを乾燥し、ルツボ内で溶
融、冷却後、固化したものについて、実施例３と同様に
ハロー試験を行った。(Example 4) The same mixed slurry as in Example 2 was dried, melted in a crucible, cooled, and then solidified, and a halo test was performed in the same manner as in Example 3.
【００３０】（比較例２） 銀成分を含有しない他は、実施例３と同様のスラリーを
用いて、同様の試験を行った。結果を表２に示す。Comparative Example 2 A similar test was conducted using the same slurry as in Example 3 except that the silver component was not contained. Table 2 shows the results.
【００３１】[0031]
【表２】 [Table 2]
【００３２】[0032]
【発明の効果】以上説明したように、本発明の抗菌防カ
ビ性釉薬組成物および釉薬添加用抗菌防カビ性組成物
は、ＳｉＯ2 が４０〜５５重量％、Ａｌ2 Ｏ3 が５〜１
０重量％、Ｂ2 Ｏ3 が５〜１５重量％、ＣａＯが１〜７
重量％、Ｓ ｒＯが７〜１２重量％、Ｎａ2 ＯとＫ2 Ｏ
が合計で５〜１０重量％、Ａｇ2 Ｏが５〜２０重量％、
Ｐ2 Ｏ5 が０．５〜５重量％の組成からなるものである
ので、このものの融点はリン酸銀の融点より高く、加熱
溶融中にリン酸銀が均一に分散されるため、効果ムラの
無い安定した抗菌防カビ力を有するものとなる。また、
Ａｇ2 ＯおよびＰ2 Ｏ5 の供給源としてリン酸銀を用い
ているので、ガラス中での酸性度が高く保持され、銀の
還元が防止されるため、優れた抗菌力を長期にわたって
維持することができる。さらに、本発明の抗菌防カビ性
窯業製品は、前記抗菌防カビ性釉薬組成物または、釉薬
添加用抗菌防カビ性組成物と釉薬との混合物をその表面
に固着してなるものであるので、効率よく抗菌防カビ効
果を発揮する。さらに銀の還元が生じにくいので、変色
などが生じない。また、このような抗菌防カビ性窯業製
品を得るには特別な工程は要せず、前記抗菌防カビ性釉
薬組成物、または釉薬添加用抗菌防カビ性組成物と釉薬
との混合物を含有する釉薬をその表面に施釉した後、焼
成させるという、従来通りの陶器、磁器の製法を用いる
ことができるため、窯業製品製造において工程変更を必
要としないなどの効果も得られる。As described above, the antibacterial and antibacterial effects of the present invention are as described above.
Bi-glazeComposition and antibacterial and antifungal composition for adding glaze
Is SiOTwoIs 40 to 55% by weight, AlTwo OThree Is 5 to 1
0% by weight, BTwo OThree Is 5 to 15% by weight, and CaO is 1 to 7
% By weight, SrO 7 to 12% by weight, NaTwo O and KTwo O
Is 5 to 10% by weight in total, AgTwoO is 5 to 20% by weight,
PTwo OFive Has a composition of 0.5 to 5% by weight.
Because the melting point of this product is higher than that of silver phosphate,
Because silver phosphate is uniformly dispersed during melting,
It has no stable antibacterial and antifungal power. Also,
AgTwoO and PTwo OFive Using silver phosphate as a source of
So that the acidity in the glass is kept high and the silver
Excellent antibacterial activity over a long period of time because reduction is prevented
Can be maintained. Furthermore, the antibacterial and antifungal properties of the present invention
Ceramic products are the antibacterial and antifungal glazesComposition or glaze
A mixture of the antibacterial and antifungal composition for addition and glazeIts surface
Antibacterial and antifungal effect
Demonstrate fruit. Furthermore, discoloration occurs because silver is hardly reduced.
Does not occur. In addition, such antibacterial and mold-proof ceramics
No special process is required to obtain the product, and the antibacterial and
medicineComposition, or antibacterial and antifungal composition for adding glaze and glaze
Mixture withAfter glazing the surface with a glaze containing
Use the traditional method of making pottery and porcelain
Need to change processes in the manufacture of ceramic products.
There are also effects such as not being required.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢澤 孝子 千葉県船橋市豊富町585番地 住友セメ ント株式会社中央研究所内 (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 (56)参考文献 特開 平６−100329（ＪＰ，Ａ) 特開 平６−127975（ＪＰ，Ａ) 特開 平８−91871（ＪＰ，Ａ) 特開 平５−201747（ＪＰ，Ａ) 特開 平７−315866（ＪＰ，Ａ) 特開 平８−59291（ＪＰ，Ａ) 特開 平６−340513（ＪＰ，Ａ) 「日本防菌防黴学会第19回年次大会要 旨集」、ｐ．65、1992．５．11発行 (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 1/00 - 14/00 C04B 41/86 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takako Yazawa 585 Tomicho, Funabashi-shi, Chiba Sumitomo Cement Co., Ltd. (72) Inventor Nobuyuki Kumakura 585 Tomicho, Funabashi-shi, Chiba Sumitomo Cement Co., Ltd. Central Research Laboratory (56) References JP-A-6-100329 (JP, A) JP-A-6-127975 (JP, A) JP-A-8-91871 (JP, A) JP-A-5-201747 (JP, A A) JP-A-7-315866 (JP, A) JP-A-8-59291 (JP, A) JP-A-6-340513 (JP, A) "Summary of the 19th Annual Meeting of the Japanese Society of Antimicrobial and Mold Control" Shu, "p. 65, issued 192.5.11 (58) Fields investigated (Int. Cl. 7 , DB name) C03C 1/00-14/00 C04B 41/86
Claims (6)
3 が５〜１０重量％、Ｂ2 Ｏ3 が５〜１５重量％、Ｃａ
Ｏが１〜７重量％、ＳｒＯが７〜１２重量％、Ｎａ2Ｏ
とＫ2Ｏが合計で５〜１０重量％、Ａｇ2 Ｏが５〜２０
重量％、Ｐ2Ｏ5が０．５〜５重量％の組成からなること
を特徴とする抗菌防カビ性釉薬組成物。 1. A SiO 2 is 40 to 55 wt%, Al 2 O
3 is 5-10 wt%, B 2 O 3 is 5-15 wt%, Ca
O is 1-7 wt%, SrO 7 to 12 wt%, Na 2 O
And K 2 O in total of 5 to 10% by weight, and Ag 2 O in 5 to 20% by weight.
Wt%, antibacterial and antifungal glaze composition P 2 O 5 is characterized in that it consists of 0.5 to 5% by weight of the composition.
が、リン酸銀であることを特徴とする請求項１記載の抗
菌防カビ性釉薬組成物。 2. A supply source of the Ag 2 O and P 2 O 5 is, antibacterial and antifungal glaze composition according to claim 1, characterized in that the silver phosphate.
の抗菌防カビ性釉薬組成物が、表面に固着されたことを
特徴とする抗菌防カビ性窯業製品。Wherein antibacterial and antifungal glaze composition according to any one of claims 1 or 2, antibacterial and antifungal properties ceramic product characterized in that it is adhered to the surface.
3Three が５〜１０重量％、Ｂ Is 5 to 10% by weight, B 2 Two ＯO 3 Three が５〜１５重量％、ＣａIs 5 to 15% by weight, Ca
Ｏが１〜７重量％、ＳｒＯが７〜１２重量％、Ｎａ1 to 7% by weight of O, 7 to 12% by weight of SrO, Na 2Two ＯO
とＫAnd K 2Two Ｏが合計で５〜１０重量％、ＡｇO is 5 to 10% by weight in total, Ag 2Two Ｏが５〜２０ O is 5-20
重量％、ＰWt%, P 2Two ＯO 5Five が０．５〜５重量％の組成からなることHas a composition of 0.5 to 5% by weight.
を特徴とする釉薬添加用抗菌防カビ性組成物。An antibacterial and antifungal composition for adding glaze, characterized by comprising:
が、リン酸銀であることを特徴とする請求項４記載の釉5. The glaze according to claim 4, wherein the glass is silver phosphate.
薬添加用抗菌防カビ性組成物。An antibacterial and antifungal composition for drug addition.
の釉薬添加用抗菌防カビ性組成物と釉薬との混合物が、The mixture of antibacterial and antifungal composition for adding glaze and glaze
表面に固着されたことを特徴とする抗菌防カビ性窯業製Made of antibacterial and mold-proof ceramics, fixed to the surface
品。Goods.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6079064A JP3051019B2 (en) | 1994-04-18 | 1994-04-18 | Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glaze |
| DE0653161T DE653161T1 (en) | 1993-05-31 | 1994-05-31 | ANTIBACTERIAL AND MOLD-REPELLENT GLAZE COMPOSITION FOR CERAMIC PRODUCTS. |
| PCT/JP1994/000873 WO1994027442A1 (en) | 1993-05-31 | 1994-05-31 | Antibacterial mildewproof glaze composition for ceramic products |
| EP94916428A EP0653161B1 (en) | 1993-05-31 | 1994-05-31 | Antibacterial mildewproof glaze composition for ceramic products |
| DE69408096T DE69408096T2 (en) | 1993-05-31 | 1994-05-31 | ANTIBACTERIAL AND MOLD-REPELLENT GLAZE COMPOSITION FOR CERAMIC PRODUCTS |
| US08/523,880 US5882808A (en) | 1993-05-31 | 1995-09-06 | Anti-bacterial and anti-fungal ceramic product |
| US08/567,155 US5807641A (en) | 1993-05-31 | 1995-12-05 | Anti-bacterial and anti-fungal glaze composition for ceramic products |
| HK98102694A HK1003589A1 (en) | 1993-05-31 | 1998-03-30 | Antibacterial mildewproof glaze composition for ceramic products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6079064A JP3051019B2 (en) | 1994-04-18 | 1994-04-18 | Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glaze |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291658A JPH07291658A (en) | 1995-11-07 |
| JP3051019B2 true JP3051019B2 (en) | 2000-06-12 |
Family
ID=13679463
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6079064A Expired - Fee Related JP3051019B2 (en) | 1993-05-31 | 1994-04-18 | Antibacterial and antifungal glaze composition and antibacterial and antifungal composition for adding glaze |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3051019B2 (en) |
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|---|---|---|---|---|
| CN105613582B (en) * | 2014-10-31 | 2019-11-22 | 住友大阪水泥股份有限公司 | Anti-bacterial composition and antibiotic property glaze compositions and antibacterial articles |
| CN113929497B (en) * | 2020-07-13 | 2023-01-24 | 蒙娜丽莎集团股份有限公司 | Antibacterial and antiskid ceramic tile and preparation method thereof |
-
1994
- 1994-04-18 JP JP6079064A patent/JP3051019B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 「日本防菌防黴学会第１９回年次大会要旨集」、ｐ．６５、１９９２．５．１１発行 |
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| Publication number | Publication date |
|---|---|
| JPH07291658A (en) | 1995-11-07 |
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