JP2015505832A - Antibacterial composition, antibacterial glaze composition, and antibacterial article - Google Patents

Antibacterial composition, antibacterial glaze composition, and antibacterial article Download PDF

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JP2015505832A
JP2015505832A JP2014545081A JP2014545081A JP2015505832A JP 2015505832 A JP2015505832 A JP 2015505832A JP 2014545081 A JP2014545081 A JP 2014545081A JP 2014545081 A JP2014545081 A JP 2014545081A JP 2015505832 A JP2015505832 A JP 2015505832A
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秀紀 堀越
秀紀 堀越
孝子 矢澤
孝子 矢澤
正紘 野辺
正紘 野辺
振海 趙
振海 趙
斯毅 魏
斯毅 魏
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SUMILONG NANO TECHNOLOGY MATERIALS (SHENZHEN) Co Ltd
Sumilong Nano Technology Materials Shenzhen Co Ltd
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Sumilong Nano Technology Materials Shenzhen Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C03C2204/02—Antibacterial glass, glaze or enamel

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Abstract

本発明は抗菌性組成物及び抗菌性釉薬組成物並びに抗菌性物品を提供する。本発明の抗菌性組成物は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有している。この抗菌性組成物によれば、抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を少なくすることができる。【選択図】なしThe present invention provides antibacterial compositions and antibacterial glaze compositions and antibacterial articles. The antibacterial composition of the present invention is a silver-containing powder containing a silver component consisting of any one or two of silver metal and silver compound, and a glassy powder with metal silver and silver compound. A silver-containing vitreous powder containing one or two silver components in terms of metallic silver in an amount of 0.01% by mass or more and 50% by mass or less. According to this antibacterial composition, the antibacterial property can be improved and the amount of metallic silver or silver compound contained can be reduced. [Selection figure] None

Description

本発明は、抗菌性組成物及び抗菌性釉薬組成物並びに抗菌性物品に関し、特に詳しくは、衛生陶器、医療用品、琺瑯用品や各種容器や食器等の台所用品、タイル等の建材、自動車の各種部材、電気機器のパネル等の各種部材に好適に用いられ、優れた抗菌性を有する抗菌性組成物、及び、この抗菌性組成物と釉薬とを含有する抗菌性釉薬組成物、並びに、この抗菌性釉薬組成物により被膜を形成した抗菌性物品に関するものである。   The present invention relates to an antibacterial composition, an antibacterial glaze composition, and an antibacterial article, and in particular, sanitary ware, medical supplies, bowls, kitchenware such as various containers and tableware, building materials such as tiles, and various types of automobiles. An antibacterial composition having excellent antibacterial properties, an antibacterial glaze composition containing the antibacterial composition and a glaze, and the antibacterial composition, which are suitably used for various members such as members and panels of electrical equipment The present invention relates to an antibacterial article in which a film is formed with a glaze composition.

従来、抗菌成分としては、銀、銅、亜鉛等の金属が広く利用されている。これらの金属は、そのイオンが細菌等の細胞中の活性酵素へ作用することにより、細菌の増殖を妨げる働きがあるといわれている。   Conventionally, metals such as silver, copper, and zinc have been widely used as antibacterial components. These metals are said to have a function of hindering the growth of bacteria by their ions acting on active enzymes in cells such as bacteria.

この細菌の増殖を阻止するのに必要な抗菌成分の濃度は、最低発育阻止濃度（ＭＩＣ）で表され、一般的に、銀を含有する抗菌成分の場合では、例えば、大腸菌に対するＭＩＣが約２００ｐｐｍ程度とされている。   The concentration of the antibacterial component necessary to inhibit the growth of this bacterium is expressed as the minimum inhibitory concentration (MIC). Generally, in the case of an antibacterial component containing silver, for example, the MIC for E. coli is about 200 ppm. It is said to be about.

陶磁器や琺瑯製品に抗菌性を付与するには、従来より金属銀、酸化銀、金属銅、酸化銅、金属亜鉛、酸化亜鉛等の金属や金属酸化物を含む釉薬を用いることが知られており、実際に行われている（例えば、特許文献１〜３等参照）。   In order to impart antibacterial properties to ceramics and glaze products, it has been known to use glazes containing metals and metal oxides such as metal silver, silver oxide, metal copper, copper oxide, metal zinc, and zinc oxide. Actually, it is carried out (see, for example, Patent Documents 1 to 3).

これらの陶磁器や琺瑯製品に良好な抗菌性を付与するためには、陶磁器や琺瑯製品の表面に形成される釉薬層中に金属銀等の抗菌性を有する金属や金属酸化物を均一に分散させて、これらの金属や金属酸化物を陶磁器や琺瑯製品の表面に溶出させる必要がある。   In order to impart good antibacterial properties to these ceramics and glazed products, metal or metal oxides having antibacterial properties such as metallic silver are uniformly dispersed in the glaze layer formed on the surface of the ceramics and glazed products. Therefore, it is necessary to elute these metals and metal oxides on the surface of ceramics and pottery products.

例えば、銀イオンを陶磁器や琺瑯製品の表面に効率的に溶出させる方法として、燐酸成分を銀含有化合物と共存させることが提案されており（特許文献４）、この燐酸成分を銀含有化合物と共存させたものを陶磁器や琺瑯用釉薬等に用いたものも提案されている（特許文献５、６）。   For example, it has been proposed that a phosphoric acid component coexists with a silver-containing compound as a method of efficiently eluting silver ions on the surface of ceramics or porcelain products (Patent Document 4), and this phosphoric acid component coexists with a silver-containing compound. The thing using the made thing for ceramics, glazes for glazes, etc. is proposed (patent documents 5 and 6).

ところで、陶磁器や琺瑯製品においては、釉薬成分が表面で溶解し、強固な被膜を形成するためには、７００℃以上かつ１３００℃以下の温度にて１時間以上焼成することが一般的である。   By the way, in ceramics and glaze products, in order to dissolve the glaze component on the surface and form a strong film, it is generally fired at a temperature of 700 ° C. or higher and 1300 ° C. or lower for 1 hour or longer.

しかしながら、金属銀を抗菌剤として用いた場合、金属銀が焼成過程中に表面に拡散し、この表面から蒸発するために、得られた被膜中の銀の量が当初予定した量より少なくなり、その結果、被膜の抗菌性が低下するという問題点があった。   However, when metallic silver is used as an antibacterial agent, metallic silver diffuses to the surface during the firing process and evaporates from this surface, so the amount of silver in the resulting coating is less than originally planned, As a result, there is a problem that the antibacterial property of the coating is lowered.

そこで、被膜の抗菌性を低下させない方法として、銀の量を、蒸発による減少分を見越して増量した釉薬を用いる方法、あるいは、陶磁器素地の表面に釉薬を層状に施し、焼成することにより施釉陶磁器品を得るのに際し、陶磁器素地の表面と最表層の釉薬層との間に、銀を抗菌成分とする抗菌剤を層状に施し、その状態で焼成を行うことにより、陶磁器素地の表面に釉薬を層状に施した抗菌性陶磁器品の製造方法が提案されている（特許文献７）。   Therefore, as a method of not reducing the antibacterial properties of the coating, a method using a glaze in which the amount of silver is increased in anticipation of a decrease due to evaporation, or a glaze ceramic by applying a layer of glaze on the surface of the ceramic substrate and baking it. In order to obtain a product, a layer of an antibacterial agent containing silver as an antibacterial component is applied between the surface of the ceramic body and the outermost layer of the glaze layer, and firing is performed in this state, so that the glaze is applied to the surface of the ceramic body. A method for producing a layered antibacterial ceramic product has been proposed (Patent Document 7).

特開平６−３４０５１３号公報JP-A-6-340513 特開平７−１９６３８４号公報JP 7-196384 A 特開平７−２６８６５２号公報JP-A-7-268652 特開平３−３８５０４号公報JP-A-3-38504 特開平７−２９１６５８号公報JP-A-7-291658 特開２００４−３０００８６号公報Japanese Patent Laid-Open No. 2004-300086 特開平９−１７３１６２号公報JP-A-9-173162

ところで、金属銀や銀化合物を抗菌剤として用いた釉薬の場合、金属銀や銀化合物により抗菌性を発現させるためには、例えば、大腸菌の場合では、表面の銀濃度が５０〜２００ｐｐｍ程度（最低発育阻止濃度（ＭＩＣ））が必要である。   By the way, in the case of a glaze using metallic silver or a silver compound as an antibacterial agent, for example, in the case of Escherichia coli, the silver concentration on the surface is about 50 to 200 ppm (minimum). An inhibitory concentration (MIC)) is required.

本来ならば、釉薬全体量に対して金属銀換算で約０．０１〜０．０２質量％程度の金属銀や銀化合物を添加すれば良いのであるが、実際には、上述したように、銀成分の蒸発、あるいは陶磁器の下地（素地）への銀成分の拡散等により、被膜に含まれる銀の量が当初予定していた量より減少することとなる。したがって、被膜が所定の抗菌性を得るためには、当初予定していた量の数十倍以上の銀が必要となるという問題点があった。   Originally, it is only necessary to add about 0.01 to 0.02% by mass of metal silver or a silver compound in terms of metal silver with respect to the total amount of glaze. The amount of silver contained in the coating is reduced from the originally planned amount due to evaporation of the component or diffusion of the silver component into the ceramic base (base). Therefore, in order to obtain a predetermined antibacterial property, there is a problem that silver more than tens of times the amount originally planned is required.

このような理由と、銀自体が高価であることから、この銀を含む被膜を用いることによる製品の製造コストの上昇等の理由から、本来、抗菌性が必要な箇所への採用が見送られたり、あるいは、銀の含有量が少ない被膜を用いることにより、実環境における清潔性が損なわれ、その結果、細菌の増殖に起因する病原性大腸菌等による発病等の社会的な問題が発生している。   For these reasons and because the silver itself is expensive, the use of this silver-containing coating increases the production cost of the product, etc. Or, by using a film with a low silver content, cleanliness in the real environment is impaired, and as a result, social problems such as pathogenesis due to pathogenic Escherichia coli caused by bacterial growth have occurred. .

本発明は、上記事情に鑑みてなされたものであって、従来よりも少量の金属銀または銀化合物を用いることによっても、抗菌性を向上させることができる抗菌性組成物及び抗菌性釉薬組成物並びに抗菌性物品を提供することを目的とする。   The present invention has been made in view of the above circumstances, and an antibacterial composition and an antibacterial glaze composition that can improve antibacterial properties by using a smaller amount of metallic silver or a silver compound than conventional ones. An object is to provide an antibacterial article.

本発明者等は、上記課題を解決するために鋭意検討を行った結果、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有した組成物とすれば、この組成物中においては、従来よりも少量の金属銀または銀化合物を用いて、従来以上の抗菌性を発現させることができることを見出し、本発明を完成するに至った。   As a result of intensive studies to solve the above problems, the present inventors have found that a silver-containing powder containing a silver component composed of any one or two of metallic silver and a silver compound, and a vitreous powder A silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less of a silver component composed of any one or two of silver and silver compounds in terms of metal silver in the body As a result, the present inventors have found that the antibacterial property higher than that in the conventional composition can be expressed using a smaller amount of metallic silver or silver compound than in the conventional composition, and the present invention has been completed.

すなわち、本発明の抗菌性組成物は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなることを特徴とする。   That is, the antibacterial composition of the present invention includes a silver-containing powder containing a silver component of any one or two of metallic silver and a silver compound, and a glassy powder containing metallic silver and a silver compound. Silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less of any one or two types of silver components in terms of metallic silver.

本発明の抗菌性組成物では、前記銀含有ガラス質粉体の軟化点は、３００℃以上かつ１５００℃以下であることが好ましい。   In the antibacterial composition of the present invention, the softening point of the silver-containing vitreous powder is preferably 300 ° C. or higher and 1500 ° C. or lower.

さらに、軟化点が３００℃以上かつ１５００℃以下の第２のガラス質粉体を含有してなることが好ましい。   Furthermore, it is preferable to contain the 2nd glassy powder whose softening point is 300 degreeC or more and 1500 degrees C or less.

前記銀含有ガラス質粉体または前記第２のガラス質粉体は、銀の融点以下の軟化点を有するガラス質粉体を１種または２種以上含有してなることが好ましい。   The silver-containing vitreous powder or the second vitreous powder preferably contains one or more vitreous powders having a softening point not higher than the melting point of silver.

前記銀化合物は、リン酸銀、酸化銀、炭酸銀、硝酸銀、塩化銀、硫化銀、酢酸銀の群から選択される１種または２種以上であることが好ましい。   The silver compound is preferably one or more selected from the group consisting of silver phosphate, silver oxide, silver carbonate, silver nitrate, silver chloride, silver sulfide and silver acetate.

本発明の抗菌性釉薬組成物は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなる抗菌性組成物と、釉薬と、を含有してなる抗菌性釉薬組成物であって、前記抗菌性組成物の含有量は、前記釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下であることを特徴とする。   The antibacterial glaze composition of the present invention includes a silver-containing powder containing a silver component composed of any one or two of metallic silver and a silver compound, and a glassy powder that is either of metallic silver or a silver compound. Or an antibacterial composition containing a silver component containing 0.01% by mass or more and 50% by mass or less of a silver component consisting of one or two types in terms of metallic silver, and a glaze, An antibacterial glaze composition comprising: the content of the antibacterial composition is 0.01% by mass or more and 5% by mass or less in terms of metallic silver with respect to the glaze. To do.

本発明の抗菌性物品は、本発明の抗菌性釉薬組成物により被膜を形成してなることを特徴とする。   The antibacterial article of the present invention is formed by forming a film with the antibacterial glaze composition of the present invention.

本発明の抗菌性組成物によれば、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有したので、抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を少なくすることができる。   According to the antibacterial composition of the present invention, a silver-containing powder containing a silver component composed of any one or two of silver metal and silver compound, and a glassy powder containing metal silver and silver compound. Since the silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less of any one or two kinds of silver components in terms of metallic silver is contained, antibacterial properties can be improved. In addition, the amount of metallic silver or silver compound contained can be reduced.

本発明の抗菌性釉薬組成物によれば、本発明の抗菌性組成物と、釉薬と、を含有し、この抗菌性組成物の含有量を、釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下としたので、釉薬の抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を少なくすることができる。   According to the antibacterial glaze composition of the present invention, the antibacterial composition of the present invention and a glaze are contained, and the content of this antibacterial composition is 0.01 mass in terms of metallic silver with respect to the glaze. % Or more and 5% by mass or less, the antibacterial properties of the glaze can be improved, and the amount of metallic silver or silver compound contained can be reduced.

本発明の抗菌性物品によれば、本発明の抗菌性釉薬組成物により被膜を形成したので、この抗菌性物品の表面の抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を少なくすることができる。   According to the antibacterial article of the present invention, since the film is formed by the antibacterial glaze composition of the present invention, the antibacterial property of the surface of the antibacterial article can be improved, and the metallic silver or silver compound contained therein The amount of can be reduced.

本発明の一実施形態の銀含有ガラス質粉体の一例を示す断面図である。It is sectional drawing which shows an example of the silver containing glassy powder of one Embodiment of this invention. 本発明の一実施形態の銀含有ガラス質粉体の他の一例を示す断面図である。It is sectional drawing which shows another example of the silver containing glassy powder of one Embodiment of this invention. 本発明の一実施形態の銀含有ガラス質粉体のさらに他の一例を示す断面図である。It is sectional drawing which shows another example of the silver containing glassy powder of one Embodiment of this invention.

本発明の抗菌性組成物及び抗菌性釉薬組成物並びに抗菌性物品を実施するための形態について説明する。 The form for implementing the antibacterial composition and antibacterial glaze composition of this invention, and an antibacterial article is demonstrated.

なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。   This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

［抗菌性組成物］
本実施形態の抗菌性組成物は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなる組成物である。 [Antimicrobial composition]
The antibacterial composition of the present embodiment includes a silver-containing powder containing a silver component composed of either one or two of metallic silver and a silver compound, and any of metallic silver and a silver compound in a vitreous powder. Or a silver-containing vitreous powder containing one or two silver components in terms of metallic silver in an amount of 0.01% by mass or more and 50% by mass or less.

この抗菌性組成物中における、銀含有粉体の質量（ＭＡｇ）と、銀含有ガラス質粉体の質量（ＭＧ）との比（ＭＡｇ：ＭＧ）は、１：０．１〜１：１００の範囲内であることが好ましい。 The ratio (M Ag : M G ) of the mass (M Ag ) of the silver-containing powder and the mass (M G ) of the silver-containing vitreous powder in this antibacterial composition was 1: 0.1 It is preferably within the range of 1: 100.

ここで、銀含有粉体の質量（ＭＡｇ）を１とした場合の銀含有ガラス質粉体の質量（ＭＧ）が０．１未満であると、銀含有ガラス質粉体が少なすぎてしまい、抗菌性を向上させる効果がなくなるので、好ましくない。一方、銀含有粉体の質量（ＭＡｇ）を１とした場合の銀含有ガラス質粉体の質量（ＭＧ）が１００を超えると、銀の総量が少なすぎてしまい、抗菌効果に必要な銀量を満たさないので、好ましくない。 Here, when the mass (M G ) of the silver-containing vitreous powder when the mass (M Ag ) of the silver-containing powder is 1, the silver-containing vitreous powder is too small. Therefore, the effect of improving antibacterial properties is lost, which is not preferable. On the other hand, when the mass (M G ) of the silver-containing vitreous powder when the mass (M Ag ) of the silver-containing powder is 1, the total amount of silver is too small, which is necessary for the antibacterial effect. Since the amount of silver is not satisfied, it is not preferable.

次に、本実施形態の抗菌性組成物の成分である銀含有粉体及び銀含有ガラス質粉体について説明する。   Next, the silver-containing powder and the silver-containing vitreous powder that are components of the antibacterial composition of the present embodiment will be described.

「銀含有粉体」
この銀含有粉体は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する粉体である。ここで、銀化合物としては、リン酸銀、酸化銀、炭酸銀、硝酸銀、塩化銀、硫化銀、酢酸銀の群から選択される１種または２種以上であることが好ましい。特に、融点が比較的高い金属銀粉体（ｍ．ｐ．＝９６１．９３℃）、リン酸銀粉体（ｍ．ｐ．＝８４９℃）を用いることで、安定した抗菌性を発現することができるので、より好ましい。 "Silver-containing powder"
This silver-containing powder is a powder containing a silver component composed of one or two of metallic silver and a silver compound. Here, the silver compound is preferably one or more selected from the group consisting of silver phosphate, silver oxide, silver carbonate, silver nitrate, silver chloride, silver sulfide, and silver acetate. In particular, by using a metallic silver powder (mp = 961.93 ° C.) and a silver phosphate powder (mp = 849 ° C.) having a relatively high melting point, stable antibacterial properties are exhibited. Is more preferable.

この銀含有粉体の平均一次粒子径は、０．１μｍ以上かつ３０μｍ以下が好ましく、より好ましくは１μｍ以上かつ１５μｍ以下である。   The average primary particle size of the silver-containing powder is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less.

ここで、銀含有粉体の平均一次粒子径が０．１μｍ未満では、銀含有粉体の比表面積が大きくなり、また、嵩密度も低くなることから、後述する抗菌性釉薬組成物を作製する場合に、銀含有粉体が、銀含有ガラス質粉体及び釉薬と共に均一に分散させることが難かしいばかりだけでなく、銀含有粉体の比表面積が増大することにより、抗菌性組成物あるいは抗菌性釉薬組成物を焼成する過程で蒸発が促進される虞があるので好ましくない。   Here, when the average primary particle diameter of the silver-containing powder is less than 0.1 μm, the specific surface area of the silver-containing powder increases and the bulk density also decreases, so that an antibacterial glaze composition described later is prepared. In some cases, the silver-containing powder is not only difficult to disperse uniformly with the silver-containing glassy powder and the glaze, but also because the specific surface area of the silver-containing powder increases, This is not preferable because evaporation may be accelerated in the process of baking the glaze composition.

「銀含有ガラス質粉体」
この銀含有ガラス質粉体は、ガラス質粉体に、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下、好ましくは０．０５質量％以上かつ３０質量％以下含有する粉体である。 "Silver-containing glassy powder"
This silver-containing vitreous powder is obtained by adding 0.01% by mass or more and 50% by mass or less of a silver component consisting of any one or two of metallic silver and a silver compound in terms of metallic silver. A powder containing 0.05% by mass or more and 30% by mass or less is preferable.

ここで、この銀含有ガラス質粉体中の銀成分の含有量を金属銀換算で０．０１質量％以上かつ５０質量％以下とした理由は、この銀含有ガラス質粉体中の銀成分の含有量が金属銀換算で０．０１質量％未満であると、銀含有ガラス質粉体の添加による抗菌効果の向上が得られないので好ましくないからであり、一方、この銀含有ガラス質粉体中の銀成分の含有量が金属銀換算で５０質量％を超えると、ガラス質粉体が銀を安定した状態で含有する量を超えることとなり、銀の多くが銀単体の状態で析出する等の不具合が生じるとともに、銀の多くが無駄になるので好ましくない。   Here, the reason why the content of the silver component in the silver-containing vitreous powder is 0.01% by mass or more and 50% by mass or less in terms of metallic silver is that the silver component in the silver-containing vitreous powder is If the content is less than 0.01% by mass in terms of metallic silver, the antibacterial effect cannot be improved by the addition of the silver-containing vitreous powder. On the other hand, this silver-containing vitreous powder is not preferable. If the content of the silver component exceeds 50% by mass in terms of metallic silver, the vitreous powder will exceed the amount of silver contained in a stable state, and most of the silver will precipitate in the form of silver alone. This is not preferable because a large amount of silver is wasted.

この銀含有ガラス質粉体の平均一次粒子径は、０．１μｍ以上かつ３０μｍ以下が好ましく、より好ましくは１μｍ以上かつ１５μｍ以下である。   The average primary particle diameter of the silver-containing vitreous powder is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less.

ここで、銀含有ガラス質粉体の平均一次粒子径が０．１μｍ未満では、銀含有ガラス質粉体の比表面積が大きくなり、また、嵩密度も低くなることから、後述する抗菌性釉薬組成物を作製する場合に、銀含有ガラス質粉体が、銀含有粉体及び釉薬と共に均一に分散させることが難かしいばかりだけでなく、銀含有ガラス質粉体の比表面積が増大することにより、抗菌性組成物あるいは抗菌性釉薬組成物を焼成する過程で蒸発が促進される虞があるので好ましくない。   Here, when the average primary particle diameter of the silver-containing vitreous powder is less than 0.1 μm, the specific surface area of the silver-containing vitreous powder is large and the bulk density is also low. When producing a product, not only is it difficult to uniformly disperse the silver-containing vitreous powder together with the silver-containing powder and the glaze, but the specific surface area of the silver-containing vitreous powder increases, This is not preferable because evaporation may be accelerated in the process of baking the antibacterial composition or the antibacterial glaze composition.

この銀含有ガラス質粉体は、ガラス質粉体中の銀成分の分布状態が様々な形態を取り得る。この銀成分の分布状態としては、銀イオンの状態、銀化合物の状態、銀の微粒子あるいは微結晶の状態、のいずれか１種のみ、または２種以上の組み合わせの状態が挙げられる。   The silver-containing vitreous powder can take various forms in the distribution state of the silver component in the vitreous powder. Examples of the distribution state of the silver component include a state of silver ions, a state of a silver compound, a state of silver fine particles or a microcrystal, and a state of a combination of two or more.

ここで、ガラス質粉体中に、銀化合物の状態、銀の微粒子あるいは微結晶の状態、のいずれか１種または２種以上の組み合わせの状態で分布している場合、様々な分布状態がある。ここで、これらの分布状態の例を挙げて説明する。   Here, there are various distribution states in the vitreous powder when it is distributed in a state of any one or a combination of two or more of a silver compound state, a silver fine particle state or a microcrystal state. . Here, an example of these distribution states will be described.

図１は、本実施形態の銀含有ガラス質粉体の一例を示す断面図であり、この銀含有ガラス質粉体１は、ガラス質粉体２中に微粒子状の銀成分３が分散している状態である。   FIG. 1 is a cross-sectional view showing an example of the silver-containing vitreous powder of the present embodiment. This silver-containing vitreous powder 1 has a particulate silver component 3 dispersed in a vitreous powder 2. It is in a state.

図２は、本実施形態の銀含有ガラス質粉体の他の一例を示す断面図であり、この銀含有ガラス質粉体１１は、ガラス質粉体２の表面に扁平状または微粒子状の銀成分１２が付着・固定している状態である。   FIG. 2 is a cross-sectional view showing another example of the silver-containing vitreous powder according to the present embodiment. This silver-containing vitreous powder 11 is flat or fine-grained silver on the surface of the vitreous powder 2. In this state, the component 12 is adhered and fixed.

図３は、本実施形態の銀含有ガラス質粉体のさらに他の一例を示す断面図であり、この銀含有ガラス質粉体２１は、ガラス質粉体２の内部に粒子状の銀成分２２が埋め込まれている状態である。   FIG. 3 is a cross-sectional view showing still another example of the silver-containing vitreous powder of the present embodiment. The silver-containing vitreous powder 21 has a particulate silver component 22 inside the vitreous powder 2. Is embedded.

この銀含有ガラス質粉体は、上記の様な様々な形態を取ることが可能であるから、例えば、銀含有ガラス質粉体１と銀含有ガラス質粉体１１とを組み合わせる、あるいは銀含有ガラス質粉体１１と銀含有ガラス質粉体２１とを組み合わせる等、仕様及び用途に合わせてその形状や分布状態を様々に変更可能である。   Since this silver-containing vitreous powder can take various forms as described above, for example, a combination of the silver-containing vitreous powder 1 and the silver-containing vitreous powder 11 or a silver-containing glass. The shape and distribution state can be variously changed in accordance with the specification and application, such as combining the powdery powder 11 and the silver-containing glassy powder 21.

なお、これらの銀含有ガラス質粉体１、１１、２１は、銀イオンを含んでいてもよい。   In addition, these silver containing glassy powders 1, 11, and 21 may contain silver ion.

この銀含有ガラス質粉体の軟化点は、３００℃以上かつ１５００℃以下であることが好ましく、より好ましくは５００℃以上かつ１３００℃以下である。   The softening point of the silver-containing vitreous powder is preferably 300 ° C. or higher and 1500 ° C. or lower, more preferably 500 ° C. or higher and 1300 ° C. or lower.

この銀含有ガラス質粉体は、軟化点が３００℃以上かつ１５００℃以下の第２のガラス質粉体を含有したこととしてもよい。   This silver-containing vitreous powder may contain a second vitreous powder having a softening point of 300 ° C. or higher and 1500 ° C. or lower.

ここで、銀含有ガラス質粉体、第２のガラス質粉体それぞれの軟化点を３００℃以上かつ１５００℃以下と限定した理由は、軟化点が３００℃未満では、ガラス自体の耐水性等が低下するので好ましくなく、一方、軟化点が１５００℃を超えると、一般に用いられる陶磁器等の焼成温度を超えることとなり、ガラス質が溶融しない可能性があり、特に、この銀含有ガラス質粉体を釉薬の成分として用いた場合、釉薬中のガラス質が溶融せずに残ってしまい、釉薬の品質に悪影響を及ぼす可能性があるので、好ましくない。   Here, the reason why the softening points of the silver-containing vitreous powder and the second vitreous powder are limited to 300 ° C. or more and 1500 ° C. or less is that if the softening point is less than 300 ° C., the water resistance of the glass itself is. On the other hand, if the softening point exceeds 1500 ° C., it may exceed the firing temperature of commonly used ceramics and the like, and the vitreous material may not melt. When used as a glaze component, the vitreous in the glaze remains unmelted and may adversely affect the quality of the glaze.

このようなガラス質粉体または第２のガラス質粉体としては、リン酸ガラス（軟化点：３００〜５００℃）、ホウケイ酸ガラス（軟化点：４００〜１０００℃）、ホウケイ酸亜鉛ガラス（軟化点：５００〜８００℃）、ソーダ石灰ガラス（軟化点：５００〜７００℃）、アルミナケイ酸ガラス（軟化点：８００〜１０００℃）等から選択された１種のみ、または２種以上からなる粉体を混合して用いることができる。   Examples of such vitreous powder or second vitreous powder include phosphate glass (softening point: 300 to 500 ° C.), borosilicate glass (softening point: 400 to 1000 ° C.), and zinc borosilicate glass (softening). Point: 500 to 800 ° C.), soda lime glass (softening point: 500 to 700 ° C.), alumina silicate glass (softening point: 800 to 1000 ° C.), etc. The body can be mixed and used.

これらのガラス質粉体または第２のガラス質粉体には、長石、ケイ砂、ホウ砂、ケイ酸塩鉱物等のガラス原料と、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分とを混合して溶融したガラス材料を含むこととしてもよい。   These glassy powders or second glassy powders include glass raw materials such as feldspar, silica sand, borax, silicate minerals, and any one or two of metallic silver and silver compounds. It is good also as including the glass material which mixed and fuse | melted the silver component which becomes.

この銀含有ガラス質粉体または第２のガラス質粉体は、銀の融点（９６１．９３℃）以下の軟化点を有するガラス質粉体を１種または２種以上含有してなることが好ましい。   The silver-containing vitreous powder or the second vitreous powder preferably contains one or more vitreous powders having a softening point not higher than the melting point of silver (961.93 ° C.). .

このようなガラス質粉体の組み合わせとしては、例えば、銀の融点以下の軟化点を有するリン酸ガラス、ソーダ石灰ガラス等の低軟化点ガラスと、銀の融点を超える軟化点を有するホウケイ酸ガラス、ホウケイ酸亜鉛ガラス、アルミナケイ酸ガラス等の高軟化点ガラスとの組み合わせが挙げられる。   As a combination of such glassy powders, for example, a low softening point glass such as phosphate glass or soda lime glass having a softening point below the melting point of silver, and a borosilicate glass having a softening point exceeding the melting point of silver And combinations with high softening point glass such as zinc borosilicate glass and alumina silicate glass.

特に、銀含有粉体として金属銀粉体を用いる場合には、軟化点や成分の異なる複数種のガラス質粉体のうち少なくとも１種は、その軟化点が金属銀粉体の融点（９６１．９３℃）以下のガラス質粉体であることが必要である。例えば、軟化点が３５０℃のリン酸ガラスと、軟化点が１２００℃の珪酸塩鉱物との組み合わせが挙げられる。   In particular, when metallic silver powder is used as the silver-containing powder, at least one of a plurality of types of glassy powders having different softening points and components has a softening point of the melting point of the metallic silver powder (961. 93 ° C.) or lower glassy powder. For example, a combination of a phosphate glass having a softening point of 350 ° C. and a silicate mineral having a softening point of 1200 ° C. can be mentioned.

［抗菌性組成物の製造方法］
本実施形態の抗菌性組成物の製造には、一般的に行われているガラス粉体（フリットガラス）の製造工程を適用することができる。 [Method for producing antibacterial composition]
For the production of the antibacterial composition of the present embodiment, a glass powder (frit glass) production process that is generally performed can be applied.

まず、ガラス質粉体またはその原料と、所定量の金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分とを、ボールミル等の混合手段を用いて混合し、次いで、電気炉等の加熱手段を用いて７００℃以上かつ１２００℃以下の温度にて１０分以上かつ１０時間以下加熱して溶融させた後、冷却し、得られた塊状物をボールミル等の混合・粉砕手段を用いて平均粒子径が０．１μｍ以上かつ３０μｍ以下となるように粉砕する。これにより、所望の平均粒子径の銀含有ガラス質粉体が得られる。   First, glassy powder or a raw material thereof and a predetermined amount of metallic silver and a silver component composed of one or two of silver compounds are mixed using a mixing means such as a ball mill, and then an electric furnace Using a heating means such as 700 ° C. or higher and 1200 ° C. or lower for 10 minutes or more and 10 hours or less to melt and then cooling, and the resulting lump is mixed and pulverized by a ball mill or the like. And pulverizing so that the average particle size is 0.1 μm or more and 30 μm or less. Thereby, a silver-containing vitreous powder having a desired average particle diameter is obtained.

一方、銀含有粉体の原料となる金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を、ボールミル等の混合・粉砕手段を用いて平均粒子径が０．１μｍ以上かつ３０μｍ以下となるように粉砕する。これにより、所望の平均粒子径の銀含有粉体が得られる。   On the other hand, an average particle size of 0.1 μm or more and 30 μm of a silver component composed of any one or two of silver metal and silver compound as a raw material for the silver-containing powder using a mixing / pulverizing means such as a ball mill. Grind to the following. Thereby, the silver containing powder of a desired average particle diameter is obtained.

次いで、銀含有粉体と、銀含有ガラス質粉体とを、この銀含有粉体の質量（ＭＡｇ）と銀含有ガラス質粉体の質量（ＭＧ）との比（ＭＡｇ：ＭＧ）が１：０．１〜１：１００の範囲内となるように秤量し、ボールミル等の混合手段を用いて混合する。 Next, the silver-containing powder and the silver-containing vitreous powder are ratios (M Ag : M G ) between the mass (M Ag ) of the silver-containing powder and the mass (M G ) of the silver-containing vitreous powder. ) Is in a range of 1: 0.1 to 1: 100 and mixed using a mixing means such as a ball mill.

以上により、平均粒子径が０．１μｍ以上かつ３０μｍ以下の抗菌性組成物が得られる。   As described above, an antibacterial composition having an average particle size of 0.1 μm or more and 30 μm or less is obtained.

［抗菌性釉薬組成物］
本実施形態の抗菌性釉薬組成物は、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなる抗菌性組成物と、釉薬と、を含有してなる抗菌性釉薬組成物であり、この抗菌性組成物の含有量は、釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下が好ましく、より好ましくは０．０５質量％以上かつ３質量％以下である。 [Antimicrobial glaze composition]
The antibacterial glaze composition of the present embodiment includes a silver-containing powder containing a silver component composed of any one or two of silver metal and silver compound, and a glassy powder containing metal silver and silver compound. A silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less of a silver component composed of any one or two of them in terms of metallic silver, and a glaze. The content of the antibacterial composition is preferably 0.01% by mass or more and 5% by mass or less in terms of metallic silver with respect to the glaze, more preferably 0. 0.05 mass% or more and 3 mass% or less.

この抗菌性釉薬組成物に用いられる抗菌性組成物については、上述した抗菌性組成物と同様であるから説明を省略する。   About the antibacterial composition used for this antibacterial glaze composition, since it is the same as that of the antibacterial composition mentioned above, description is abbreviate | omitted.

ここで、抗菌性組成物の含有量を釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下とした理由は、抗菌性組成物の含有量が金属銀換算で０．０１質量％未満であると、抗菌性組成物に含まれる銀の量が少なすぎて抗菌性が低下してしまい、その結果、所望の抗菌性を発現することができず、抗菌性組成物としての抗菌性が低下するので好ましくない。一方、抗菌性組成物の含有量が金属銀換算で５質量％を超えると、所望の抗菌性を発現する以上に銀が含まれることとなり、銀の多くが無駄になるので好ましくない。   Here, the reason why the content of the antibacterial composition is 0.01% by mass or more and 5% by mass or less in terms of metallic silver with respect to the glaze is that the content of the antibacterial composition is 0.01 in terms of metallic silver. If the amount is less than% by mass, the amount of silver contained in the antibacterial composition is too small and the antibacterial property is lowered. As a result, the desired antibacterial property cannot be expressed, and the antibacterial composition Since antibacterial property falls, it is not preferable. On the other hand, if the content of the antibacterial composition exceeds 5% by mass in terms of metallic silver, it is not preferable because silver is contained more than desired antibacterial properties and much of silver is wasted.

この抗菌性釉薬組成物は、この抗菌性組成物を釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下含有したことにより、釉薬に抗菌性を付与することができ、しかも、含まれる金属銀または銀化合物の量を少なくすることが可能である。   The antibacterial glaze composition can impart antibacterial properties to the glaze by containing the antibacterial composition in an amount of 0.01% by mass to 5% by mass in terms of metallic silver with respect to the glaze. It is possible to reduce the amount of metallic silver or silver compound contained.

したがって、この抗菌性釉薬組成物を陶磁器製品や琺瑯製品に塗布し、熱処理することにより、陶磁器製品や琺瑯製品に抗菌性を付与することができる。   Therefore, the antibacterial properties can be imparted to the ceramic product or the glaze product by applying this antibacterial glaze composition to the ceramic product or the glaze product and heat-treating it.

［抗菌性物品］
本実施形態の抗菌性物品は、本実施形態の抗菌性釉薬組成物により被膜を形成した物品であり、これらの物品としては、洗面所、トイレ、台所、浴室等の細菌による汚れを防止すべき箇所や、病院、食品加工施設、公共施設等の細菌から人命を守る必要がある箇所に用いられる物品、例えば、衛生陶器、容器、食器、タイル、陶器等の陶磁器製品、容器、パネル、調理器具、電化製品、建材部材等の琺瑯製品が挙げられる。 [Antimicrobial products]
The antibacterial article of the present embodiment is an article in which a film is formed by the antibacterial glaze composition of the present embodiment, and these articles should prevent contamination by bacteria such as a washroom, toilet, kitchen, bathroom, etc. Goods used in places and places where it is necessary to protect human lives from bacteria such as hospitals, food processing facilities, public facilities, etc., for example, ceramic products such as sanitary ware, containers, tableware, tiles, pottery, containers, panels, cooking utensils , And appliances such as electrical appliances and building materials.

これらの陶磁器製品や琺瑯製品の表面の少なくとも必要な箇所に、本実施形態の抗菌性釉薬組成物により被膜を形成したことにより、この物品の表面の抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を少なくすることができる。   By forming a film with the antibacterial glaze composition of the present embodiment on at least necessary portions of the surface of these ceramic products and glazed products, the antibacterial properties of the surface of this article can be improved and included. The amount of metallic silver or silver compound produced can be reduced.

以上説明したように、本実施形態の抗菌性組成物によれば、金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有したので、抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を従来のものよりも少なくすることができる。   As described above, according to the antibacterial composition of the present embodiment, the silver-containing powder containing a silver component composed of any one or two of silver metal and silver compound, and the vitreous powder. Since silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less of a silver component composed of any one or two of metallic silver and silver compound in terms of metallic silver is contained, antibacterial The amount of metallic silver or silver compound contained can be reduced as compared with the conventional one.

本実施形態の抗菌性釉薬組成物によれば、本実施形態の抗菌性組成物と、釉薬と、を含有し、この抗菌性組成物の含有量を、釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下としたので、釉薬の抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を従来のものよりも少なくすることができる。   According to the antibacterial glaze composition of this embodiment, the antibacterial composition of this embodiment and the glaze are contained, and the content of this antibacterial composition is set to 0. 0 in terms of metallic silver relative to the glaze. Since the content is set to 01% by mass or more and 5% by mass or less, the antibacterial properties of the glaze can be improved, and the amount of metallic silver or silver compound contained can be reduced as compared with the conventional one.

本実施形態の抗菌性物品によれば、本実施形態の抗菌性釉薬組成物により被膜を形成したので、この抗菌性物品の表面の抗菌性を向上させることができ、しかも、含まれる金属銀または銀化合物の量を従来のものよりも少なくすることができる。   According to the antibacterial article of the present embodiment, the antibacterial property of the surface of the antibacterial article can be improved because the coating is formed by the antibacterial glaze composition of the present embodiment. The amount of the silver compound can be reduced as compared with the conventional one.

以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.

Ａ．抗菌性組成物、抗菌性釉薬組成物、抗菌性陶磁器板の作製及び評価
［実施例１］
「抗菌性組成物の作製」
銀化合物としてリン酸銀を、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、リン酸銀４５ｇとガラス質粉体１４５５ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が８μｍ、銀の含有量が金属銀換算で２．３質量％の銀含有ガラス質粉体を得た。 A. Preparation and Evaluation of Antibacterial Composition, Antibacterial Glaze Composition, and Antibacterial Ceramic Plate [Example 1]
"Preparation of antibacterial composition"
Using silver phosphate as the silver compound and vitreous powder mainly composed of a borosilicate glass component having a softening point of 650 ° C. as the vitreous powder, 45 g of silver phosphate and 1455 g of vitreous powder are put into a ball mill. 3 hours, and then heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the resulting lump was put into a ball mill and crushed for 25 hours, with a softening point of 650 A silver-containing vitreous powder having an average particle size of 8 ° C. and a silver content of 2.3 mass% in terms of metallic silver was obtained.

一方、リン酸銀をボールミルに投入して１５時間粉砕し、平均粒子径が１０μｍのリン酸銀粉体を得た。   On the other hand, silver phosphate was put into a ball mill and pulverized for 15 hours to obtain silver phosphate powder having an average particle diameter of 10 μm.

次いで、リン酸銀粉体と銀含有ガラス質粉体との質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、実施例１の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は８μｍ、銀の含有量は金属銀換算で２７質量％であった。   Subsequently, the silver phosphate powder and the silver-containing vitreous powder were weighed so that the mass ratio was 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Example 1. . This antibacterial composition had an average particle size of 8 μm and a silver content of 27% by mass in terms of metallic silver.

「抗菌性釉薬組成物の作製」
釉薬原料として、下記の組成を有する釉薬原料を用いた。
ＳｉＯ２ ５５質量％
Ａｌ２Ｏ３ １０質量％
ＺｒＯ２ １０質量％
ＣａＯ １０質量％
ＺｎＯ １０質量％
Ｋ２Ｏ ４質量％
Ｎａ２Ｏ １質量％ "Preparation of antibacterial glaze composition"
As the glaze material, a glaze material having the following composition was used.
SiO 2 55% by mass
Al 2 O 3 10% by mass
ZrO 2 10% by mass
CaO 10% by mass
ZnO 10 mass%
K 2 O 4% by mass
Na 2 O 1% by mass

この釉薬原料に、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加し、これらの合計量６０質量部に対して水が４０質量部となるようにボールミルに投入して１５時間分散し、実施例１の抗菌性釉薬組成物を得た。   The antibacterial composition is added to the glaze raw material so that the amount of the antibacterial composition is 0.30% by mass with respect to the glaze raw material, and the total amount of water is 40 parts by mass. Thus, it put into the ball mill and disperse | distributed for 15 hours, and the antimicrobial glaze composition of Example 1 was obtained.

「抗菌性陶磁器板の作製」
縦５０ｍｍ×横５０ｍｍ×厚み５ｍｍの陶磁器板を用意し、上記の抗菌性釉薬組成物を、この陶磁器板上に３０ｇ／ｍ２の塗布量にてスプレー塗布し、乾燥後、１２００℃の温度にて１時間、焼成し、実施例１の抗菌性陶磁器板を得た。 "Production of antibacterial ceramic plates"
A ceramic plate having a length of 50 mm, a width of 50 mm, and a thickness of 5 mm is prepared. The antibacterial glaze composition is spray-applied at a coating amount of 30 g / m 2 on the ceramic plate, dried, and brought to a temperature of 1200 ° C. And baked for 1 hour to obtain an antibacterial ceramic plate of Example 1.

「抗菌性陶磁器板の評価」
上記の抗菌性陶磁器板の抗菌性を、ＩＳＯ２２１９６「Plastics-Measurement of antibacterial activity on plastics surface」にて評価し、以下の計算式から抗菌活性値を求めた。 "Evaluation of antibacterial ceramic plates"
The antibacterial property of the above antibacterial ceramic plate was evaluated by ISO 22196 “Plastics-Measurement of antibacterial activity on plastics surface”, and the antibacterial activity value was determined from the following formula.

抗菌活性値（Ｒ）＝（Ｕｔ−Ｕ０）−（Ａｔ−Ｕ０）＝Ｕｔ−Ａｔ
Ｕ０：無加工試験片の接種直後の生菌数の平均値（個）
Ｕｔ：無加工試験片の２４時間後の生菌数の平均値（個）
Ａｔ：抗菌加工試験片の２４時間後の生菌数の平均値（個） Antibacterial activity value (R) = (U t −U 0 ) − (A t −U 0 ) = U t −A t
U 0 : Average number of viable bacteria immediately after inoculation of unprocessed test piece (pieces)
U t : Average value of viable cell count after 24 hours of unprocessed test piece (pieces)
A t: average value of the number of viable bacteria after 24 hours of antibacterial test piece (number)

ここでは、大腸菌と黄色ブドウ球菌について試験を行い、それぞれの抗菌性能の有無について評価した。評価は、日本工業規格ＪＩＳ Ｚ ２８００「抗菌加工製品−抗菌性試験方法・抗菌効果」により、大腸菌及び黄色ブドウ球菌の双方の抗菌活性値が２．０以上であれば合格とし、大腸菌及び黄色ブドウ球菌のいずれか一方または双方が２．０未満であれば不合格とした。   Here, E. coli and Staphylococcus aureus were tested, and the presence or absence of each antibacterial performance was evaluated. Evaluation is passed if the antibacterial activity value of both Escherichia coli and Staphylococcus aureus is 2.0 or more according to Japanese Industrial Standard JIS Z 2800 “Antimicrobial Processed Products-Antibacterial Test Method / Antimicrobial Effect”. If either one or both of the cocci were less than 2.0, the test was rejected.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

「外観評価」
得られた抗菌性陶磁器板の外観を、抗菌性組成物を含まない陶磁器板との目視検査により、変色、凹凸、異物析出、気泡などの有無を確認し、著しい外観不良が認められるものを不合格とした。 "Appearance evaluation"
The appearance of the obtained antibacterial ceramic board is visually inspected with a ceramic board that does not contain the antibacterial composition, and the presence or absence of discoloration, unevenness, foreign matter precipitation, bubbles, etc. is confirmed. Passed.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例２］
「抗菌性組成物の作製」
金属銀と、ガラス質粉体として軟化点が９５０℃のアルミノケイ酸ガラス成分を主としたガラス質粉体を用い、銀１ｇとガラス質粉体１４９９ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１１００℃にて１時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が９５０℃、平均粒子径が１０μｍ、銀の含有量が金属銀換算で０．０５質量％の銀含有ガラス質粉体を得た。 [Example 2]
"Preparation of antibacterial composition"
Using a vitreous powder mainly composed of metallic silver and an aluminosilicate glass component having a softening point of 950 ° C. as a vitreous powder, 1 g of silver and 1499 g of the vitreous powder are put into a ball mill and mixed for 3 hours. Next, after heating and melting at 1100 ° C. for 1 hour using an electric furnace, the mixture was cooled, and the resulting mass was put into a ball mill and pulverized for 25 hours. The softening point was 950 ° C. and the average particle size was A silver-containing vitreous powder having a thickness of 10 μm and a silver content of 0.05% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。   On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.

次いで、銀粉体と銀含有ガラス質粉体との質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、実施例２の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は７μｍ、銀の含有量は金属銀換算で３３質量％であった。   Subsequently, the silver powder and the silver-containing vitreous powder were weighed so as to have a mass ratio of 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Example 2. This antibacterial composition had an average particle size of 7 μm and a silver content of 33% by mass in terms of metallic silver.

この抗菌性組成物を用いて、実施例１に準じて、実施例２の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Using this antibacterial composition, an antibacterial glaze composition and an antibacterial ceramic plate of Example 2 were produced according to Example 1, and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例３］
「抗菌性組成物の作製」
金属銀と、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、銀２２ｇとガラス質粉体１４７８ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が６μｍ、銀の含有量が金属銀換算で１．０質量％の銀含有ガラス質粉体を得た。 [Example 3]
"Preparation of antibacterial composition"
Using a vitreous powder mainly composed of metallic silver and a borosilicate glass component having a softening point of 650 ° C. as a vitreous powder, 22 g of silver and 1478 g of the vitreous powder are put into a ball mill and mixed for 3 hours. Next, the mixture was heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the obtained lump was put into a ball mill and pulverized for 25 hours. The softening point was 650 ° C. and the average particle size was A silver-containing vitreous powder having 6 μm and a silver content of 1.0% by mass in terms of metallic silver was obtained.

一方、リン酸銀をボールミルに投入して１５時間粉砕し、平均粒子径が１０μｍのリン酸銀粉体を得た。   On the other hand, silver phosphate was put into a ball mill and pulverized for 15 hours to obtain silver phosphate powder having an average particle diameter of 10 μm.

また、第２のガラス質粉体として、軟化点が９５０℃のアルミノケイ酸ガラス成分を主としたガラス質粉体を用いた。   Further, as the second vitreous powder, a vitreous powder mainly composed of an aluminosilicate glass component having a softening point of 950 ° C. was used.

次いで、リン酸銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例３の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は７μｍ、銀の含有量は金属銀換算で２５質量％であった。   Next, the silver phosphate powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. 3 antimicrobial composition was obtained. This antibacterial composition had an average particle size of 7 μm and a silver content of 25% by mass in terms of metallic silver.

この抗菌性組成物を用いて、実施例１に準じて、実施例３の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Using this antibacterial composition, an antibacterial glaze composition and an antibacterial ceramic plate of Example 3 were produced according to Example 1, and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例４］
「抗菌性組成物の作製」
金属銀と、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、銀２２ｇとガラス質粉体１４７８ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が６μｍ、銀の含有量が金属銀換算で１．０質量％の銀含有ガラス質粉体を得た。 [Example 4]
"Preparation of antibacterial composition"
Using a vitreous powder mainly composed of metallic silver and a borosilicate glass component having a softening point of 650 ° C. as a vitreous powder, 22 g of silver and 1478 g of the vitreous powder are put into a ball mill and mixed for 3 hours. Next, the mixture was heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the obtained lump was put into a ball mill and pulverized for 25 hours. The softening point was 650 ° C. and the average particle size was A silver-containing vitreous powder having 6 μm and a silver content of 1.0% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。   On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.

また、第２のガラス質粉体として、軟化点が３５０℃のリン酸ガラス成分を主としたガラス質粉体を用いた。   Further, as the second vitreous powder, a vitreous powder mainly composed of a phosphate glass component having a softening point of 350 ° C. was used.

次いで、銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例４の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は８μｍ、銀の含有量は金属銀換算で２５質量％であった。   Subsequently, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. An antibacterial composition was obtained. This antibacterial composition had an average particle size of 8 μm and a silver content of 25% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．１０質量％となるように添加した他は、実施例１に準じて、実施例４の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added so as to be 0.10% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 4 were produced and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例５］
「抗菌性組成物の作製」
実施例２に準じて、銀含有ガラス質粉体及び銀粉体を得た。 [Example 5]
"Preparation of antibacterial composition"
In accordance with Example 2, a silver-containing vitreous powder and a silver powder were obtained.

また、第２のガラス質粉体として、軟化点が５００℃のソーダ石灰ガラス成分を主としたガラス質粉体を用いた。   Further, as the second vitreous powder, a vitreous powder mainly containing a soda-lime glass component having a softening point of 500 ° C. was used.

次いで、銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例５の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は７μｍ、銀の含有量は金属銀換算で２５質量％であった。   Subsequently, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. An antibacterial composition was obtained. This antibacterial composition had an average particle size of 7 μm and a silver content of 25% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．０５質量％となるように添加した他は、実施例１に準じて、実施例５の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added to 0.05% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 5 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例６］
「抗菌性組成物の作製」
実施例３に準じて、銀含有ガラス質粉体を得た。 [Example 6]
"Preparation of antibacterial composition"
A silver-containing vitreous powder was obtained according to Example 3.

一方、硝酸銀をボールミルに投入して１５時間粉砕し、平均粒子径が１５μｍの硝酸銀粉体を得た。   On the other hand, silver nitrate was put into a ball mill and pulverized for 15 hours to obtain silver nitrate powder having an average particle size of 15 μm.

次いで、硝酸銀粉体と銀含有ガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、実施例６の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は１０μｍ、銀の含有量は金属銀換算で２１質量％であった。   Subsequently, the silver nitrate powder and the silver-containing vitreous powder were weighed so that the mass ratio was 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Example 6. This antibacterial composition had an average particle size of 10 μm and a silver content of 21% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．１０質量％となるように添加した他は、実施例１に準じて、実施例６の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added so as to be 0.10% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 6 were produced and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例７］
「抗菌性組成物の作製」
実施例４に準じて、実施例６の銀含有ガラス質粉体及び銀粉体を得た。 [Example 7]
"Preparation of antibacterial composition"
The silver-containing vitreous powder and silver powder of Example 6 were obtained according to Example 4.

また、第２のガラス質粉体として、軟化点が１２００℃のケイ酸塩鉱物を主としたガラス質粉体を用いた。   As the second vitreous powder, a vitreous powder mainly composed of a silicate mineral having a softening point of 1200 ° C. was used.

次いで、銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例７の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は１５μｍ、銀の含有量は金属銀換算で２５質量％であった。   Next, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. An antibacterial composition was obtained. This antibacterial composition had an average particle size of 15 μm and a silver content of 25% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、実施例７の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added to 0.30% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 7 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例８］
「抗菌性組成物の作製」
金属銀と、ガラス質粉体として軟化点が１２００℃のケイ酸塩鉱物を主としたガラス質粉体を用い、銀４５０ｇとガラス質粉体１０５０ｇとをボールミルに投入して５時間混合し、次いで、電気炉を用いて１５００℃にて１時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が１２００℃、平均粒子径が１５μｍ、銀の含有量が金属銀換算で３０質量％の銀含有ガラス質粉体を得た。 [Example 8]
"Preparation of antibacterial composition"
Using a vitreous powder mainly composed of metallic silver and a silicate mineral having a softening point of 1200 ° C. as a vitreous powder, 450 g of silver and 1050 g of the vitreous powder are put into a ball mill and mixed for 5 hours. Next, after heating and melting at 1500 ° C. for 1 hour using an electric furnace, the mixture was cooled, and the resulting mass was put into a ball mill and pulverized for 25 hours. The softening point was 1200 ° C. and the average particle size was A silver-containing vitreous powder having a content of 15 μm and a silver content of 30% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。   On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.

また、第２のガラス質粉体として、軟化点が６５０℃のホウケイ酸ガラスを主としたガラス質粉体を用いた。   As the second vitreous powder, a vitreous powder mainly composed of borosilicate glass having a softening point of 650 ° C. was used.

次いで、銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例８の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は１５μｍ、銀の含有量は金属銀換算で４０質量％であった。   Subsequently, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. An antibacterial composition was obtained. This antibacterial composition had an average particle size of 15 μm and a silver content of 40% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、実施例８の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added to 0.30% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 8 were produced and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例９］
「抗菌性組成物の作製」
実施例３に準じて、銀含有ガラス質粉体及びリン酸銀粉体を得た。 [Example 9]
"Preparation of antibacterial composition"
According to Example 3, a silver-containing vitreous powder and a silver phosphate powder were obtained.

次いで、リン酸銀粉体と銀含有ガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、実施例９の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は８μｍ、銀の含有量は金属銀換算で２６質量％であった。   Subsequently, the silver phosphate powder and the silver-containing vitreous powder were weighed so as to have a mass ratio of 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Example 9. This antibacterial composition had an average particle size of 8 μm and a silver content of 26% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．１０質量％となるように添加した他は、実施例１に準じて、実施例９の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above-mentioned antibacterial composition was added so as to be 0.10% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 9 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例１０］
実施例９に準じて、実施例１０の抗菌性組成物を得た。 [Example 10]
The antibacterial composition of Example 10 was obtained according to Example 9.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して３．０質量％となるように添加した他は、実施例１に準じて、実施例１０の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added in an amount of 3.0% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and antibacterial ceramic plate of Example 10 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例１１］
実施例９に準じて、実施例１１の抗菌性組成物を得た。 [Example 11]
The antibacterial composition of Example 11 was obtained according to Example 9.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して５．０質量％となるように添加した他は、実施例１に準じて、実施例１１の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added so as to be 5.0% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and antibacterial ceramic plate of Example 11 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例１２］
「抗菌性組成物の作製」
銀化合物として硝酸銀を、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、硝酸銀３５ｇとガラス質粉体１４６５ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が６μｍ、銀の含有量が金属銀換算で１．５質量％の銀含有ガラス質粉体を得た。 [Example 12]
"Preparation of antibacterial composition"
Using silver nitrate as the silver compound, and vitreous powder mainly composed of a borosilicate glass component having a softening point of 650 ° C. as the vitreous powder, 35 g of silver nitrate and 1465 g of the vitreous powder are charged into a ball mill and mixed for 3 hours. Then, the mixture was heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the obtained lump was put into a ball mill and pulverized for 25 hours. The softening point was 650 ° C. and the average particle size A silver-containing vitreous powder having a diameter of 6 μm and a silver content of 1.5% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。   On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.

次いで、銀粉体と銀含有ガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、実施例１２の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は６μｍ、銀の含有量は金属銀換算で２５質量％であった。   Next, the silver powder and the silver-containing vitreous powder were weighed so that the mass ratio was 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Example 12. This antibacterial composition had an average particle size of 6 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３質量％となるように添加した他は、実施例１に準じて、実施例１２の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as a glaze raw material, and the antibacterial composition was added in an amount of 0.3% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and antibacterial ceramic plate of Example 12 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例１３］
「抗菌性組成物の作製」
金属銀と、銀化合物としてリン酸銀を、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、銀２２ｇとリン酸銀２０ｇとガラス質粉体１４５８ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が６μｍ、銀の含有量が金属銀換算で２．０質量％の銀含有ガラス質粉体を得た。 [Example 13]
"Preparation of antibacterial composition"
Using metallic silver, silver phosphate as a silver compound, and vitreous powder mainly composed of a borosilicate glass component having a softening point of 650 ° C. as vitreous powder, 22 g of silver, 20 g of silver phosphate and vitreous powder 1458 g was put into a ball mill and mixed for 3 hours, then heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the resulting mass was put into a ball mill for 25 hours. By pulverization, a silver-containing vitreous powder having a softening point of 650 ° C., an average particle diameter of 6 μm, and a silver content of 2.0% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。   On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.

また、第２のガラス質粉体として、軟化点が３５０℃のリン酸ガラスを主としたガラス質粉体を用いた。   Further, as the second vitreous powder, a vitreous powder mainly composed of phosphate glass having a softening point of 350 ° C. was used.

次いで、銀粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例１３の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は８μｍ、銀の含有量は金属銀換算で２６質量％であった。   Next, the silver powder, the silver-containing vitreous powder, and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill, and mixed for 5 hours. An antibacterial composition was obtained. This antibacterial composition had an average particle size of 8 μm and a silver content of 26% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、実施例１３の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added to 0.30% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 13 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［実施例１４］
「抗菌性組成物の作製」
実施例３に準じて、銀含有ガラス質粉体を得た。 [Example 14]
"Preparation of antibacterial composition"
A silver-containing vitreous powder was obtained according to Example 3.

一方、金属銀とリン酸銀の質量比が１：１となるように秤量し、これらをボールミルに投入して１５時間粉砕し、平均粒子径が８μｍの銀含有粉体を得た。   On the other hand, it was weighed so that the mass ratio of metallic silver to silver phosphate was 1: 1, and these were put into a ball mill and pulverized for 15 hours to obtain a silver-containing powder having an average particle size of 8 μm.

また、第２のガラス質粉体として、軟化点が６５０℃のホウケイ酸ガラスを主としたガラス質粉体を用いた。   As the second vitreous powder, a vitreous powder mainly composed of borosilicate glass having a softening point of 650 ° C. was used.

次いで、銀含有粉体と銀含有ガラス質粉体と第２のガラス質粉体の質量比が１：２：１となるように秤量し、ボールミルに投入して５時間混合し、実施例１４の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は６μｍ、銀の含有量は金属銀換算で２５質量％であった。   Next, the silver-containing powder, the silver-containing vitreous powder and the second vitreous powder were weighed so that the mass ratio was 1: 2: 1, put into a ball mill and mixed for 5 hours. Example 14 An antibacterial composition was obtained. This antibacterial composition had an average particle size of 6 μm and a silver content of 25% by mass in terms of metallic silver.

「抗菌性釉薬組成物及び抗菌性陶磁器板の作製、評価」
釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、実施例１４の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。 "Production and evaluation of antibacterial glaze composition and antibacterial ceramic plate"
According to Example 1, except that the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added to 0.30% by mass with respect to the glaze raw material in terms of metallic silver. The antibacterial glaze composition and the antibacterial ceramic plate of Example 14 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例１］
釉薬原料として実施例１の釉薬原料を用い、リン酸銀粉体を金属銀換算で上記の釉薬原料に対して０．３０質量％となるように添加した抗菌性釉薬組成物を作製した。 [Comparative Example 1]
The glaze raw material of Example 1 was used as a glaze raw material, and an antibacterial glaze composition was prepared by adding silver phosphate powder so as to be 0.30% by mass with respect to the above glaze raw material in terms of metallic silver.

この抗菌性釉薬組成物を用いて、実施例１に準じて比較例１の抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Using this antibacterial glaze composition, an antibacterial ceramic plate of Comparative Example 1 was produced according to Example 1, and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例２］
銀粉体として金属銀を、第２のガラス質粉体として軟化点が１２００℃のケイ酸塩鉱物を主としたガラス質粉体を用い、銀粉体と第２のガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、比較例２の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は１５μｍ、銀の含有量は金属銀換算で２５質量％であった。 [Comparative Example 2]
Metallic silver is used as the silver powder, and a vitreous powder mainly composed of a silicate mineral having a softening point of 1200 ° C. is used as the second vitreous powder, and the mass of the silver powder and the second vitreous powder. The antibacterial composition of Comparative Example 2 was obtained by weighing the mixture so that the ratio was 1: 2, putting it in a ball mill and mixing for 5 hours. This antibacterial composition had an average particle size of 15 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、比較例２の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the antibacterial composition was added in an amount of 0.30% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and the antibacterial ceramic plate of Comparative Example 2 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例３］
銀粉体として金属銀を、第２のガラス質粉体として軟化点が３５０℃のリン酸ガラスを主としたガラス質粉体を用い、銀粉体と第２のガラス質粉体の質量比が１：４となるように秤量し、ボールミルに投入して５時間混合し、比較例３の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は８μｍ、銀の含有量は金属銀換算で２５質量％であった。 [Comparative Example 3]
Metallic silver is used as the silver powder, and a vitreous powder mainly composed of phosphate glass having a softening point of 350 ° C. is used as the second vitreous powder, and the mass ratio of the silver powder to the second vitreous powder. Was weighed so as to be 1: 4, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Comparative Example 3. This antibacterial composition had an average particle size of 8 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．５０質量％となるように添加した他は、実施例１に準じて、比較例３の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added so as to be 0.50% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and the antibacterial ceramic plate of Comparative Example 3 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例４］
釉薬原料として実施例１の釉薬原料を用い、銀粉体として金属銀を金属銀換算で上記の釉薬原料に対して０．３０質量％となるように添加した抗菌性釉薬組成物を作製した。 [Comparative Example 4]
Using the glaze raw material of Example 1 as a glaze raw material, an antibacterial glaze composition was prepared by adding metal silver as a silver powder to 0.30% by mass with respect to the above glaze raw material in terms of metal silver.

この抗菌性釉薬組成物を用いて、実施例１に準じて比較例１の抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Using this antibacterial glaze composition, an antibacterial ceramic plate of Comparative Example 1 was produced according to Example 1, and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例５］
銀粉体として金属銀を、第２のガラス質粉体として軟化点が１６００℃のシリカガラスを主としたガラス質粉体を用い、銀粉体と第２のガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、比較例５の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は１０μｍ、銀の含有量は金属銀換算で２５質量％であった。 [Comparative Example 5]
Metallic silver is used as the silver powder, and vitreous powder mainly composed of silica glass having a softening point of 1600 ° C. is used as the second vitreous powder, and the mass ratio between the silver powder and the second vitreous powder is The sample was weighed so as to be 1: 2, and put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Comparative Example 5. This antibacterial composition had an average particle size of 10 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．３０質量％となるように添加した他は、実施例１に準じて、比較例５の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the antibacterial composition was added in an amount of 0.30% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and the antibacterial ceramic plate of Comparative Example 5 were prepared and evaluated according to Example 1.

評価結果を表１に示す。   The evaluation results are shown in Table 1.

［比較例６］
金属銀と、ガラス質粉体として軟化点が１６００℃のシリカガラスを主としたガラス質粉体を用い、銀２２ｇとガラス質粉体１４７８ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１６５０℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が１６００℃の銀含有ガラス質粉体を得た。 [Comparative Example 6]
Using a vitreous powder mainly composed of metallic silver and silica glass having a softening point of 1600 ° C. as a vitreous powder, 22 g of silver and 1478 g of vitreous powder are put into a ball mill and mixed for 3 hours, It was heated and melted at 1650 ° C. for 4 hours using an electric furnace, cooled, and the obtained lump was put into a ball mill and ground for 25 hours, and a silver-containing vitreous powder having a softening point of 1600 ° C. Got.

この銀含有ガラス質粉体を目視にて観察したところ、銀は蒸発により失われており、シリカガラス中には存在していなかった。   When this silver-containing vitreous powder was visually observed, silver was lost by evaporation and was not present in the silica glass.

［比較例７］
金属銀と、ガラス質粉体として軟化点が１２００℃のケイ酸塩鉱物を主としたガラス質粉体を用い、銀８２５ｇとガラス質粉体６７５ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１５００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が１２００℃の銀含有ガラス質粉体を得た。 [Comparative Example 7]
Using glassy powder mainly composed of metallic silver and silicate mineral having a softening point of 1200 ° C. as glassy powder, 825 g of silver and 675 g of glassy powder are put into a ball mill and mixed for 3 hours. Next, after heating and melting at 1500 ° C. for 4 hours using an electric furnace, the mixture was cooled, and the obtained lump was put into a ball mill and pulverized for 25 hours, and a silver-containing glassy material having a softening point of 1200 ° C. A powder was obtained.

この銀含有ガラス質粉体を目視にて観察したところ、銀とガラス質粉体とが分離しており、均一なガラス質粉体を得ることができなかった。   When this silver-containing vitreous powder was visually observed, silver and vitreous powder were separated, and a uniform vitreous powder could not be obtained.

Figure 2015505832
Figure 2015505832

表１によれば、実施例１〜１４の抗菌性陶磁器板では、大腸菌に対する抗菌活性値及び黄色ブドウ球菌に対する抗菌活性値のいずれにおいても、良好な抗菌性を有することが分かった。   According to Table 1, it was found that the antibacterial ceramic plates of Examples 1 to 14 have good antibacterial properties in both the antibacterial activity value against Escherichia coli and the antibacterial activity value against Staphylococcus aureus.

一方、比較例１〜４の抗菌性陶磁器板では、大腸菌に対する抗菌活性値及び黄色ブドウ球菌に対する抗菌活性値のいずれか一方が合格圏外であるか、または双方とも合格圏外であり、実施例１〜１４の抗菌性陶磁器板と比べて抗菌性に劣っていることが分かった。   On the other hand, in the antibacterial ceramic plates of Comparative Examples 1 to 4, either one of the antibacterial activity value against Escherichia coli and the antibacterial activity value against Staphylococcus aureus is out of the acceptable range, or both are out of the acceptable range. It was found to be inferior in antibacterial properties compared to 14 antibacterial ceramic plates.

比較例５の抗菌性陶磁器板では、表面に異物が析出しており、外観を著しく損ねていた。   In the antibacterial ceramic plate of Comparative Example 5, foreign matters were deposited on the surface, and the appearance was remarkably impaired.

比較例６の銀含有ガラス質粉体では、銀が蒸発により失われており、比較例７の銀含有ガラス質粉体では、銀とガラス質粉体とが分離しており、いずれにしても抗菌性を有する均一なガラス質粉体を得ることができなかった。   In the silver-containing vitreous powder of Comparative Example 6, silver is lost due to evaporation, and in the silver-containing vitreous powder of Comparative Example 7, the silver and the vitreous powder are separated. A uniform glassy powder having antibacterial properties could not be obtained.

Ｂ．本発明の範囲外の抗菌性釉薬組成物の作製、抗菌性陶磁器板の作製及び評価
ここでは、本発明の範囲外の抗菌性釉薬組成物を作製し、この抗菌性釉薬組成物を用いて、実施例１に準じて抗菌性陶磁器板を作製し評価した。 B. Production of antibacterial glaze composition outside the scope of the present invention, production and evaluation of antibacterial ceramic plate Here, an antibacterial glaze composition outside the scope of the present invention was produced, and using this antibacterial glaze composition, In accordance with Example 1, an antibacterial ceramic plate was produced and evaluated.

［比較例８］
金属銀と、ガラス質粉体として軟化点が６５０℃のホウケイ酸ガラス成分を主としたガラス質粉体を用い、銀２２ｇとガラス質粉体１４７８ｇとをボールミルに投入して３時間混合し、次いで、電気炉を用いて１０００℃にて４時間加熱して溶融させた後、冷却し、得られた塊状物をボールミルに投入して２５時間粉砕し、軟化点が６５０℃、平均粒子径が６μｍ、銀の含有量が金属銀換算で１．０質量％の銀含有ガラス質粉体を得た。 [Comparative Example 8]
Using a vitreous powder mainly composed of metallic silver and a borosilicate glass component having a softening point of 650 ° C. as a vitreous powder, 22 g of silver and 1478 g of the vitreous powder are put into a ball mill and mixed for 3 hours. Next, the mixture was heated and melted at 1000 ° C. for 4 hours using an electric furnace, cooled, and the obtained lump was put into a ball mill and pulverized for 25 hours. The softening point was 650 ° C. and the average particle size was A silver-containing vitreous powder having 6 μm and a silver content of 1.0% by mass in terms of metallic silver was obtained.

一方、金属銀をボールミルに投入して１５時間粉砕し、平均粒子径が６μｍの銀粉体を得た。
次いで、銀粉体と銀含有ガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、比較例８の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は６μｍ、銀の含有量は金属銀換算で２５質量％であった。 On the other hand, metallic silver was put into a ball mill and pulverized for 15 hours to obtain a silver powder having an average particle diameter of 6 μm.
Subsequently, the silver powder and the silver-containing vitreous powder were weighed so that the mass ratio was 1: 2, put into a ball mill and mixed for 5 hours to obtain an antibacterial composition of Comparative Example 8. This antibacterial composition had an average particle size of 6 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して０．００５質量％となるように添加した他は、実施例１に準じて、比較例８の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the antibacterial composition was added in an amount of 0.005% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and the antibacterial ceramic plate of Comparative Example 8 were prepared and evaluated according to Example 1.

評価結果を表２に示す。   The evaluation results are shown in Table 2.

［比較例９］
比較例８に準じて作製した銀含有ガラス質粉体及び銀粉体を用いて、銀粉体と銀含有ガラス質粉体の質量比が１：２となるように秤量し、ボールミルに投入して５時間混合し、比較例９の抗菌性組成物を得た。この抗菌性組成物の平均粒子径は６μｍ、銀の含有量は金属銀換算で２５質量％であった。 [Comparative Example 9]
Using the silver-containing vitreous powder and the silver powder prepared according to Comparative Example 8, the mass ratio of the silver powder and the silver-containing vitreous powder is weighed to be 1: 2, and put into a ball mill. For 5 hours to obtain an antibacterial composition of Comparative Example 9. This antibacterial composition had an average particle size of 6 μm and a silver content of 25% by mass in terms of metallic silver.

次いで、釉薬原料として実施例１の釉薬原料を用い、上記の抗菌性組成物を金属銀換算で釉薬原料に対して１０．０質量％となるように添加した他は、実施例１に準じて、比較例９の抗菌性釉薬組成物及び抗菌性陶磁器板を作製し、実施例１に準じて評価を行った。   Subsequently, the glaze raw material of Example 1 was used as the glaze raw material, and the above antibacterial composition was added in an amount of 10.0% by mass with respect to the glaze raw material in terms of metallic silver, according to Example 1. The antibacterial glaze composition and the antibacterial ceramic plate of Comparative Example 9 were produced and evaluated according to Example 1.

評価結果を表２に示す。   The evaluation results are shown in Table 2.

Figure 2015505832
Figure 2015505832

表２によれば、比較例８の抗菌性陶磁器板では、大腸菌に対する抗菌活性値及び黄色ブドウ球菌に対する抗菌活性値のいずれにおいても、抗菌性を発現しなかった。   According to Table 2, the antibacterial ceramic plate of Comparative Example 8 did not exhibit antibacterial activity in any of the antibacterial activity value against Escherichia coli and the antibacterial activity value against Staphylococcus aureus.

比較例９の抗菌性陶磁器板では、塗膜が着色しており、透明性が低下していた。   In the antibacterial ceramic plate of Comparative Example 9, the coating film was colored and the transparency was lowered.

１ 銀含有ガラス質粉体
２ ガラス質粉体
３ 微粒子状の銀成分
１１ 銀含有ガラス質粉体
１２ 扁平状または微粒子状の銀成分
２１ 銀含有ガラス質粉体
２２ 粒子状の銀成分 DESCRIPTION OF SYMBOLS 1 Silver-containing vitreous powder 2 Vitreous powder 3 Fine-grained silver component 11 Silver-containing vitreous powder 12 Flat or fine-grained silver component 21 Silver-containing vitreous powder 22 Particulate silver component

Claims (7)

金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなることを特徴とする抗菌性組成物。   A silver-containing powder containing a silver component consisting of any one or two of metallic silver and a silver compound, and a silver component consisting of either one or two of metallic silver and a silver compound in a vitreous powder And a silver-containing vitreous powder containing 0.01 mass% or more and 50 mass% or less in terms of metallic silver. 前記銀含有ガラス質粉体の軟化点は、３００℃以上かつ１５００℃以下であることを特徴とする請求項１記載の抗菌性組成物。   The antibacterial composition according to claim 1, wherein a softening point of the silver-containing vitreous powder is 300 ° C or higher and 1500 ° C or lower. さらに、軟化点が３００℃以上かつ１５００℃以下の第２のガラス質粉体を含有してなることを特徴とする請求項１または２記載の抗菌性組成物。   The antibacterial composition according to claim 1 or 2, further comprising a second vitreous powder having a softening point of 300 ° C or higher and 1500 ° C or lower. 前記銀含有ガラス質粉体または前記第２のガラス質粉体は、銀の融点以下の軟化点を有するガラス質粉体を１種または２種以上含有してなることを特徴とする請求項１ないし３のいずれか１項記載の抗菌性組成物。   2. The silver-containing vitreous powder or the second vitreous powder contains one or more vitreous powders having a softening point not higher than the melting point of silver. 4. The antibacterial composition according to any one of items 3 to 3. 前記銀化合物は、リン酸銀、酸化銀、炭酸銀、硝酸銀、塩化銀、硫化銀、酢酸銀の群から選択される１種または２種以上であることを特徴とする請求項１ないし４のいずれか１項記載の抗菌性組成物。   5. The silver compound according to claim 1, wherein the silver compound is one or more selected from the group consisting of silver phosphate, silver oxide, silver carbonate, silver nitrate, silver chloride, silver sulfide, and silver acetate. The antimicrobial composition of any one of Claims. 金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を含有する銀含有粉体と、ガラス質粉体に金属銀及び銀化合物のうちいずれか１種または２種からなる銀成分を金属銀換算で０．０１質量％以上かつ５０質量％以下含有する銀含有ガラス質粉体と、を含有してなる抗菌性組成物と、釉薬と、を含有してなる抗菌性釉薬組成物であって、
前記抗菌性組成物の含有量は、前記釉薬に対して金属銀換算で０．０１質量％以上かつ５質量％以下であることを特徴とする抗菌性釉薬組成物。 A silver-containing powder containing a silver component consisting of any one or two of metallic silver and a silver compound, and a silver component consisting of either one or two of metallic silver and a silver compound in a vitreous powder An antibacterial glaze composition comprising: an antibacterial composition containing a silver-containing vitreous powder containing 0.01% by mass or more and 50% by mass or less in terms of metallic silver; Because
Content of the said antibacterial composition is 0.01 to 5 mass% in conversion of metallic silver with respect to the said glaze, The antibacterial glaze composition characterized by the above-mentioned. 請求項６記載の抗菌性釉薬組成物により被膜を形成してなることを特徴とする抗菌性物品。   An antibacterial article comprising a film formed of the antibacterial glaze composition according to claim 6.
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