JP5765455B2 - Antibacterial ceramic product, ceramic surface treatment agent, and method for manufacturing antibacterial ceramic product - Google Patents
Antibacterial ceramic product, ceramic surface treatment agent, and method for manufacturing antibacterial ceramic product Download PDFInfo
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本発明は、衛生陶器、和洋食器等の陶磁器製品に代表される窯業製品の表面に、抗菌性を付与した抗菌性窯業製品と、前記抗菌性窯業製品を製造するために用いる窯業表面処理剤と、前記窯業表面処理剤を用いた抗菌性窯業製品の製造方法とに関するものである。 The present invention includes an antibacterial ceramic product imparted with antibacterial properties on the surface of ceramic products represented by ceramic products such as sanitary ware and Japanese and Western tableware, and a ceramic surface treatment agent used for producing the antibacterial ceramic product. The present invention relates to a method for producing an antibacterial ceramic product using the ceramic surface treatment agent.
窯業製品の表面に、抗菌性を付与するための抗菌剤としては、銀、銅、錫、亜鉛等の金属（以下、これらの金属を「抗菌性金属」と総称する場合がある）が用いられる。これらの抗菌性金属は、そのイオンが触媒として機能して、水中に溶け込んでいる酸素を活性酸素に変化させて、変化させた活性酸素の作用によって、菌やカビ等の繁殖を抑制する、いわゆるオリゴジナミー効果によって、抗菌性を発現することが知られている。前記抗菌性金属を用いて、窯業製品の表面に抗菌性を付与する場合には、できるだけ長期間に亘って、良好な抗菌性を持続させることを考慮して、窯業製品の素地（素焼き品等）の表面に形成する釉薬層や、あるいは、前記素地自体に、抗菌性金属を含有させるのが一般的である。 As an antibacterial agent for imparting antibacterial properties to the surface of ceramic products, metals such as silver, copper, tin and zinc (hereinafter, these metals may be collectively referred to as “antibacterial metals”) are used. . These antibacterial metals function as a catalyst, change the oxygen dissolved in water to active oxygen, and suppress the growth of fungi and fungi by the action of the changed active oxygen, so-called It is known to exhibit antibacterial properties due to the oligodynamic effect. When antibacterial properties are imparted to the surface of ceramic products using the antibacterial metal, considering that it will maintain good antibacterial properties for as long as possible, the base material of ceramic products (such as unglazed products) In general, an antibacterial metal is contained in the glaze layer formed on the surface) or the substrate itself.
例えば、特許文献１には、抗菌性金属が、焼成時に、釉薬成分の溶融物によって侵食されるのを防止するため、前記抗菌性金属を、ハイドロキシアパタイトに担持させて複合粒子を形成し、前記複合粒子を釉薬に添加した後、前記釉薬を、素地の表面に塗布し、焼成して、抗菌性金属を含む釉薬層を形成することが記載されている。また、特許文献２には、同様の目的で、抗菌性金属のイオンを、リン酸カルシウム化合物に含有させて複合粒子を形成し、前記複合粒子を釉薬に添加した後、前記釉薬を、素地の表面に塗布し、焼成して、抗菌性金属を含む釉薬層を形成することが記載されている。 For example, in Patent Document 1, in order to prevent the antibacterial metal from being eroded by the melt of the glaze component during firing, the antibacterial metal is supported on hydroxyapatite to form composite particles, After adding the composite particles to the glaze, it is described that the glaze is applied to the surface of the substrate and baked to form a glaze layer containing an antibacterial metal. Further, in Patent Document 2, for the same purpose, an antibacterial metal ion is contained in a calcium phosphate compound to form a composite particle, and after adding the composite particle to the glaze, the glaze is added to the surface of the substrate. It is described that it is applied and baked to form a glaze layer containing an antibacterial metal.
また、特許文献３には、抗菌性金属を保持させた、複合粒子としての無機顔料を、釉薬に添加し、前記釉薬を、素地の表面に塗布した後、焼成して、抗菌性金属を含む釉薬層を形成したり、前記無機顔料を、窯業製品の素地のもとになる陶土や磁土に添加し、前記陶土等を、窯業製品の形状に成型した後、焼成して、前記素地自体に抗菌性金属を含有させたりすることが記載されている。さらに、特許文献４には、酸化銀、金属銀、もしくは任意の銀化合物を下絵具に添加し、前記下絵具を用いて、窯業製品の素地の表面や、前記表面に形成した釉薬層の表面に下絵を描いて焼成したり、前記酸化銀等を釉薬に添加し、前記釉薬を、素地の表面や、前記表面に形成した釉薬層の表面に塗布して焼成したりすることで、抗菌性金属を含む下絵や釉薬層等を形成することが記載されている。 Patent Document 3 includes an antibacterial metal-containing inorganic pigment as composite particles added to the glaze, and the glaze is applied to the surface of the substrate and then fired to contain the antibacterial metal. A glaze layer is formed, or the inorganic pigment is added to the clay or magnetic earth that is the basis of the ceramic product base. After the ceramic clay is molded into the shape of the ceramic product, it is baked and applied to the base itself. It describes that an antibacterial metal is contained. Furthermore, in Patent Document 4, silver oxide, metallic silver, or an arbitrary silver compound is added to the lower paint, and the surface of the ceramic product base or the glaze layer formed on the surface using the lower paint. It is antibacterial by drawing a sketch on the surface, adding the silver oxide or the like to the glaze, and applying the glaze to the surface of the substrate or the surface of the glaze layer formed on the surface. It describes the formation of a metal-containing sketch or glaze layer.
ところが、前記従来の窯業製品は、いずれも、抗菌性金属の利用効率が低いため、抗菌
性金属の使用量に見合う十分な抗菌性が得られず、高い抗菌性を得るためには、抗菌性金属の使用量を多くしなければならないため、例えば、釉薬層や下絵が所定の色目にならなかったり（所定の色目より黒ずんだ色目になったりする場合が多い）、窯業製品のコストアップに繋がったりするといった問題を生じるおそれがある。
However, all of the above conventional ceramic products have low antibacterial metal utilization efficiency, so that sufficient antibacterial property corresponding to the amount of antibacterial metal used cannot be obtained. Since the amount of metal used must be increased, for example, the glaze layer and background may not have a predetermined color (often darker than the predetermined color), leading to an increase in the cost of ceramic products. May cause problems.
本発明の目的は、抗菌性金属の利用効率が高いため、前記抗菌性金属の使用量を、現状より少なくしても、十分な抗菌性を得ることができる、新規な抗菌性窯業製品と、前記抗菌性窯業製品を製造するために用いることができる窯業表面処理剤と、前記窯業表面処理剤を用いた抗菌性窯業製品の製造方法とを提供することにある。 The object of the present invention is a novel antibacterial ceramic product that can obtain sufficient antibacterial properties even when the amount of the antibacterial metal used is less than the current amount because the use efficiency of the antibacterial metal is high, and An object of the present invention is to provide a ceramic surface treatment agent that can be used to produce the antibacterial ceramic product, and a method for producing an antibacterial ceramic product using the ceramic surface treatment agent.
抗菌性金属による、先に説明したオリゴジナミー効果に基づく抗菌性は、製造される窯業製品の表面、例えば、釉薬層を有する窯業製品であれば、前記釉薬層の表面に露出した抗菌性金属と、水との接触面積が大きいほど強くなり、前記接触面積は、抗菌性金属の粒子径が小さく、比表面積が大きいほど、大きくなる傾向がある。ところが、発明者の検討によると、従来の窯業製品は、いずれも、その表面に露出している抗菌性金属の粒子径が大きく、比表面積が小さいため、抗菌性金属の利用効率が低くなって、使用した抗菌性金属の量に見合う、十分な抗菌性が得られないのである。 The antibacterial property based on the oligodynamic effect described above by the antibacterial metal is the surface of the ceramic product to be manufactured, for example, a ceramic product having a glaze layer, and the antibacterial metal exposed on the surface of the glaze layer, The larger the contact area with water, the stronger, and the contact area tends to increase as the particle size of the antibacterial metal decreases and the specific surface area increases. However, according to the inventor's study, all the conventional ceramic products have a large particle size of the antibacterial metal exposed on the surface and a small specific surface area, so the utilization efficiency of the antibacterial metal is low. However, sufficient antibacterial properties corresponding to the amount of antibacterial metal used cannot be obtained.
そこで、発明者は、抗菌性金属の利用効率を高めるため、窯業製品の表面に露出する抗菌性金属の粒子径の範囲を規定することを検討した結果、前記抗菌性金属が、平均粒子径２００ｎｍ以下の金属ナノ粒子として、窯業製品の表面に存在していればよいことを見出した。したがって、請求項１に記載の発明は、表面に、少なくとも銀を含む、平均粒子径２００ｎｍ以下の金属ナノ粒子が存在していることを特徴とする抗菌性窯業製品である。 Then, in order to improve the utilization efficiency of an antibacterial metal, the inventor examined defining the range of the particle diameter of the antibacterial metal exposed on the surface of the ceramic product. As a result, the antibacterial metal has an average particle diameter of 200 nm. It discovered that it should just exist on the surface of ceramic products as the following metal nanoparticles. Therefore, the invention according to claim 1 is an antibacterial ceramic product characterized in that metal nanoparticles containing at least silver and having an average particle diameter of 200 nm or less are present on the surface.
また発明者は、先に説明した平均粒子径２００ｎｍ以下の金属ナノ粒子を、窯業製品の表面に、できるだけ多く露出させて、前記金属ナノ粒子を構成する抗菌性金属の利用効率を、さらに高めることを検討した。その結果、分散媒中に、粒度分布の９０％累積径Ｄ90が１５０ｎｍ以下の金属ナノ粒子をコロイド分散させた窯業表面処理剤を、釉薬層を形成するための釉薬や、下絵を形成するための下絵具等として用いればよいことを見出した。したがって、請求項２に記載の発明は、分散媒中に、粒度分布の９０％累積径Ｄ90が１５０ｎｍ以下の金属ナノ粒子が、コロイド分散していることを特徴とする窯業表面処理剤である。 The inventor further increases the utilization efficiency of the antibacterial metal constituting the metal nanoparticles by exposing the metal nanoparticles having an average particle diameter of 200 nm or less as described above to the surface of the ceramic product as much as possible. It was investigated. As a result, a ceramic surface treatment agent in which metal nanoparticles having a 90% cumulative diameter D 90 of particle size distribution of 150 nm or less are colloidally dispersed in a dispersion medium is used to form a glaze for forming a glaze layer or a sketch. It has been found that it may be used as a lower paint for the above. Therefore, the invention described in claim 2 is a ceramic surface treatment agent characterized in that metal nanoparticles having a 90% cumulative diameter D 90 of particle size distribution of 150 nm or less are colloidally dispersed in a dispersion medium. .
抗菌性金属による抗菌性は、窯業製品の表面、例えば釉薬層を有する窯業製品であれば、前記釉薬層の表面に露出して、水と接触可能な抗菌性金属においてのみ発現し、釉薬層等の内部に存在する抗菌性金属は、抗菌性の付与には、殆ど寄与しない。そのため、抗菌性金属の利用効率を高めるためには、釉薬層等の表面に露出しない抗菌性金属の割合をできるだけ少なくして、相対的に、前記表面に露出する抗菌性金属の割合を多くすることが肝要である。ところが、先に説明した特許文献１〜３に記載された、抗菌性金属を担持した複合粒子や、特許文献４に記載された酸化銀、水に不溶性、難溶性の銀化合物等は、釉薬中で凝集しやすい上、凝集を生じると沈降を生じやすい。また、特許文献４に記載された金属銀は、釉薬成分よりも比重が大きいため、やはり釉薬中で沈降を生じやすい。 Antibacterial properties due to antibacterial metals, such as ceramic products that have a glaze layer, such as ceramic products that are exposed on the surface of the glaze layer and can be contacted with water, such as glaze layers The antibacterial metal present in the inside hardly contributes to imparting antibacterial properties. Therefore, in order to increase the utilization efficiency of the antibacterial metal, the proportion of the antibacterial metal not exposed on the surface of the glaze layer or the like is reduced as much as possible, and the proportion of the antibacterial metal exposed on the surface is relatively increased. It is important. However, the composite particles supporting the antibacterial metal described in Patent Documents 1 to 3 described above, the silver oxide described in Patent Document 4, water-insoluble, poorly soluble silver compounds, and the like are contained in the glaze. It is easy to agglomerate, and when it agglomerates, it tends to settle. Moreover, since metallic silver described in Patent Document 4 has a specific gravity greater than that of the glaze component, it is likely to cause sedimentation in the glaze.
そのため、これらの成分を含有する釉薬を用いて形成した釉薬層を有する従来の窯業製品は、前記釉薬層の表面に露出しない抗菌性金属の割合が多くなりやすく、先に説明したように、表面に露出した抗菌性金属の粒子径が大きいことと相まって、前記抗菌性金属の利用効率が大きく低下してしまう。また、前記のように、凝集したり沈降したりしやすい成分を含む釉薬を、窯業製品の製造に使用する場合には、かく拌して凝集物を解砕したり、沈降物を再分散させたりする操作を頻繁に行う必要がある。しかも、それでもなお、凝
集や沈降によって、釉薬の組成が刻々と変化するため、前記釉薬を用いて形成した釉薬層の表面における、抗菌性金属の露出量や粒子径と、それに伴う抗菌性能とが、製造した窯業製品ごとにばらつきやすいという問題もある。
Therefore, conventional ceramic products having a glaze layer formed using a glaze containing these components tend to increase the proportion of antibacterial metals that are not exposed on the surface of the glaze layer. Combined with the large particle diameter of the antibacterial metal exposed to the surface, the utilization efficiency of the antibacterial metal is greatly reduced. In addition, as described above, when a glaze containing a component that easily aggregates or settles is used in the manufacture of ceramic products, the agglomerates are crushed by stirring or the sediment is redispersed. Frequent operations are required. Moreover, since the composition of the glaze is constantly changing due to aggregation and sedimentation, the amount and particle diameter of the antibacterial metal on the surface of the glaze layer formed using the glaze and the associated antibacterial performance There is also a problem that it varies easily for each manufactured ceramic product.
一方、特許文献４に記載された水溶性の銀化合物は、通常は水性である釉薬中に、均一に溶解するため、凝集や沈降等は生じない。しかし、焼成した際に、前記銀化合物が熱分解することで発生した銀の原子を析出の核として、次々と銀の原子が析出して、銀粒子が徐々に成長するという経過を辿るため、特に、釉薬層の表面において、銀粒子が、十分な大きさに成長する前の段階で、焼成の熱によって揮発して、失われてしまいやすい。そのため、釉薬層の表面に露出する銀の割合が少なくなって、前記銀の、抗菌性金属としての利用効率が大きく低下してしまう。また、釉薬層中に析出した銀によって、前記釉薬層が所定の色目にならなかったりする場合も多い。 On the other hand, since the water-soluble silver compound described in Patent Document 4 is uniformly dissolved in a glaze that is usually aqueous, no aggregation or sedimentation occurs. However, when firing, the silver compound generated by thermal decomposition of the silver compound as a nucleus of precipitation, silver atoms are deposited one after another, and the course of silver particles gradually growing, In particular, on the surface of the glaze layer, silver particles are liable to be volatilized and lost by the heat of baking at a stage before growing to a sufficient size. Therefore, the ratio of silver exposed on the surface of the glaze layer decreases, and the utilization efficiency of the silver as an antibacterial metal is greatly reduced. In addition, the silver layer deposited in the glaze layer often fails to give the glaze layer a predetermined color.
これに対し、請求項２に記載の発明の窯業表面処理剤においては、粒度分布の９０％累積径Ｄ90が１５０ｎｍ以下の金属ナノ粒子が、分散媒中に、均一かつ安定的にコロイド分散しており、凝集したり、沈降したりしにくいため、前記本発明の窯業表面処理剤を、釉薬や下絵具等として、窯業製品の製造に使用した場合には、かく拌して凝集物を解砕したり、沈降物を再分散させたりする操作を頻繁に行う必要がない上、前記操作を行わなくても、抗菌性金属の露出量や粒子径と、それに伴う抗菌性能とが一定した抗菌性窯業製品を製造することができる。 In contrast, in the ceramic surface treatment agent of the invention according to claim 2, metal nanoparticles having a 90% cumulative diameter D 90 of particle size distribution of 150 nm or less are uniformly and stably colloidally dispersed in a dispersion medium. Therefore, when the ceramics surface treatment agent of the present invention is used as a glaze or a lower paint for the production of ceramics products, it is stirred to dissolve the aggregates. There is no need to frequently perform operations such as crushing or redispersing sediment, and even without the above operations, the antibacterial metal exposure and particle size and the antibacterial performance associated therewith are constant. It is possible to produce a natural ceramic product.
また、前記金属ナノ粒子は、焼成の熱に曝されても揮発して失われずに、製造後の抗菌性窯業製品の表面に残留しやすいため、残留した金属ナノ粒子の平均粒子径が２００ｎｍ以下であって、先に説明したように比表面積、ひいては水との接触面積が大きいことと相まって、前記抗菌性窯業製品における、金属ナノ粒子を構成する抗菌性金属の利用効率を、これまでより向上することもできる。そのため、請求項２に記載の発明の窯業表面処理剤によれば、抗菌性金属の使用量を、現状より少なくしても、十分な抗菌性を得ることが可能となる。また、釉薬層や下絵が所定の色目にならなかったり、窯業製品のコストアップに繋がったりするのを、確実に防止することもできる。 In addition, the metal nanoparticles are not volatilized and lost even when exposed to the heat of firing, and are likely to remain on the surface of the antibacterial ceramic product after manufacture, so the average particle size of the remaining metal nanoparticles is 200 nm or less However, as described above, combined with the large specific surface area and thus the large contact area with water, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles in the antibacterial ceramic product is improved. You can also Therefore, according to the ceramics surface treatment agent of the invention described in claim 2, it is possible to obtain sufficient antibacterial properties even if the amount of the antibacterial metal used is smaller than the current amount. In addition, it is possible to reliably prevent the glaze layer and the background from becoming a predetermined color or increasing the cost of ceramic products.
金属ナノ粒子を形成する抗菌性金属としては、先に例示した抗菌性金属の中でも、オリゴジナミー効果に基づく抗菌性に優れた銀が好ましい。したがって、請求項３に記載の発明は、金属ナノ粒子が、少なくとも銀を含んでいることを特徴とする請求項２に記載の窯業表面処理剤である。また、分散媒が水である場合に、金属ナノ粒子の、分散媒中でのコロイド分散を、より安定的に維持するためには、前記金属ナノ粒子が、親水性基を有する分散剤によって被覆された状態で、コロイド分散しているのが好ましい。したがって、請求項４に記載の発明は、金属ナノ粒子が、親水性基を有する分散剤によって被覆された状態で、分散媒としての水中にコロイド分散していることを特徴とする請求項２または３に記載の窯業表面処理剤である。 As the antibacterial metal forming the metal nanoparticles, among the antibacterial metals exemplified above, silver excellent in antibacterial properties based on the oligodynamic effect is preferable. Therefore, the invention according to claim 3 is the ceramics surface treatment agent according to claim 2, wherein the metal nanoparticles contain at least silver. In addition, when the dispersion medium is water, in order to more stably maintain the colloidal dispersion of the metal nanoparticles in the dispersion medium, the metal nanoparticles are coated with a dispersant having a hydrophilic group. In this state, it is preferable that the colloidal dispersion be performed. Therefore, the invention according to claim 4 is characterized in that the metal nanoparticles are colloidally dispersed in water as a dispersion medium in a state where the metal nanoparticles are coated with a dispersant having a hydrophilic group. 3. A ceramic surface treatment agent according to 3.
金属ナノ粒子の、コロイド分散の安定化の度合いとしては、前記金属ナノ粒子を含む分散液を調製後、２４時間、経過した時点での、前記金属ナノ粒子の沈降量が、その総量の０．１重量％以下であることが好ましい。したがって、請求項５に記載の発明は、調製後、２４時間、経過した時点での金属ナノ粒子の沈降量が、前記金属ナノ粒子の総量の０．１重量％以下である分散液を用いて調製されたことを特徴とする請求項２ないし４のいずれかに記載の窯業表面処理剤である。また、請求項６に記載の発明は、窯業製品の表面に、請求項２ないし５のいずれかに記載の窯業表面処理剤を塗布した後、８００〜１６００℃で焼成する工程を含むことを特徴とする抗菌性窯業製品の製造方法である。前記本発明の製造方法によれば、本発明の窯業表面処理剤を、窯業製品の表面に塗布して、前記温度範囲で焼成するだけで、表面に、平均粒子径２００ｎｍ以下の金属ナノ粒子が存在してい
る本発明の抗菌性窯業製品を、生産性よく製造することができる。
The degree of stabilization of the colloidal dispersion of the metal nanoparticles is that the sedimentation amount of the metal nanoparticles at the time when 24 hours have elapsed after preparing the dispersion containing the metal nanoparticles is 0. It is preferably 1% by weight or less. Therefore, the invention according to claim 5 uses the dispersion liquid in which the amount of sedimentation of the metal nanoparticles after the lapse of 24 hours is 0.1% by weight or less of the total amount of the metal nanoparticles. The ceramic surface treatment agent according to any one of claims 2 to 4, which is prepared. The invention according to claim 6 includes a step of firing at 800 to 1600 ° C. after applying the ceramic surface treatment agent according to any of claims 2 to 5 to the surface of the ceramic product. It is a manufacturing method of antibacterial ceramics products. According to the production method of the present invention, the metal nanoparticles having an average particle diameter of 200 nm or less are formed on the surface simply by applying the ceramic surface treatment agent of the present invention to the surface of the ceramic product and firing in the temperature range. The existing antibacterial ceramic product of the present invention can be produced with high productivity.
本発明によれば、抗菌性金属の利用効率が高いため、前記抗菌性金属の使用量を、現状より少なくしても、十分な抗菌性を得ることができる、新規な抗菌性窯業製品と、前記抗菌性窯業製品を製造するために用いることができる窯業表面処理剤と、前記窯業表面処理剤を用いた抗菌性窯業製品の製造方法とを提供することができる。 According to the present invention, since the utilization efficiency of the antibacterial metal is high, even if the amount of the antibacterial metal used is less than the current amount, a novel antibacterial ceramic product that can obtain sufficient antibacterial properties, There can be provided a ceramic surface treatment agent that can be used for producing the antibacterial ceramic product, and a method for producing an antibacterial ceramic product using the ceramic surface treatment agent.
《窯業表面処理剤》
本発明の抗菌性窯業製品を製造するために用いる、本発明の窯業表面処理剤は、分散媒中に、粒度分布の９０％累積径Ｄ90が１５０ｎｍ以下の金属ナノ粒子が、コロイド分散していることを特徴とするものである。金属ナノ粒子の、粒度分布の９０％累積径Ｄ90が１５０ｎｍ以下に限定されるのは、前記範囲を超える、大きな金属ナノ粒子を含む窯業表面処理剤を、例えば、下絵具や釉薬として使用して、窯業製品の素地の表面や、前記表面に形成した釉薬層の表面に塗布して焼成したとしても、その表面に、平均粒子径２００ｎｍ以下の、微小な金属ナノ粒子が存在し、かつ、抗菌性金属の利用効率が高い、本発明の抗菌性窯業製品を製造できないためである。
《Ceramic surface treatment agent》
The ceramic surface treatment agent of the present invention used for producing the antibacterial ceramic product of the present invention is obtained by colloidally dispersing metal nanoparticles having a 90% cumulative diameter D 90 of a particle size distribution of 150 nm or less in a dispersion medium. It is characterized by being. The reason why the 90% cumulative diameter D 90 of the particle size distribution of the metal nanoparticles is limited to 150 nm or less is that a ceramic surface treatment agent containing large metal nanoparticles exceeding the above range is used, for example, as a base paint or glaze. Even if it is applied to the surface of the ceramic product base or the surface of the glaze layer formed on the surface and fired, fine metal nanoparticles having an average particle diameter of 200 nm or less are present on the surface, and This is because the antibacterial ceramic product of the present invention, in which the use efficiency of the antibacterial metal is high, cannot be produced.
すなわち、９０％累積径Ｄ90が前記範囲を超える、粒子径の大きな金属ナノ粒子は、窯業表面処理剤中で、安定にコロイド分散させることができず、凝集したり沈降したりしやすいため、製造される抗菌性窯業製品の表面に露出する金属ナノ粒子の割合が少なくなる。しかも前記粒子径の大きな金属ナノ粒子を含む窯業表面処理剤を用いた場合には、抗菌性窯業製品の表面に形成される金属ナノ粒子の平均粒子径を２００ｎｍ以下にすることが困難である。そのため、抗菌性窯業製品の表面に露出する金属ナノ粒子の割合が少ないことと、露出した金属ナノ粒子の平均粒子径が２００ｎｍを超えて、比表面積が小さいこととが相まって、前記抗菌性窯業製品における、金属ナノ粒子を構成する抗菌性金属の利用効率が低下するのである。なお、９０％累積径Ｄ90は、前記範囲内でも４０ｎｍ以上であるのが好ましい。また、金属ナノ粒子の、粒度分布のメジアン径Ｄ50は、１００ｎｍ以下であるのが好ましい。金属ナノ粒子の、粒度分布の９０％累積径Ｄ90、およびメジアン径Ｄ50は、本発明では、レーザードップラー法を応用した粒度分布測定装置を用いて測定される、金属ナノ粒子の粒度分布から求めることとする。 That is, the 90% cumulative diameter D 90 exceeds the above range, and the metal nanoparticles having a large particle diameter cannot be stably colloidally dispersed in the ceramic surface treatment agent, and are likely to aggregate or settle. The proportion of metal nanoparticles exposed on the surface of the manufactured antibacterial ceramic product is reduced. In addition, when the ceramic surface treatment agent containing metal nanoparticles having a large particle diameter is used, it is difficult to make the average particle diameter of the metal nanoparticles formed on the surface of the antibacterial ceramic product 200 nm or less. Therefore, the antibacterial ceramic product is combined with the fact that the ratio of the metal nanoparticles exposed on the surface of the antibacterial ceramic product is small and the average particle diameter of the exposed metal nanoparticles exceeds 200 nm and the specific surface area is small. In this case, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles is reduced. Incidentally, 90% cumulative diameter D 90 is preferably in the range 40nm or even within the above range. Further, the metal nanoparticles, the median diameter D 50 of the particle size distribution is preferably not 100nm or less. In the present invention, the 90% cumulative diameter D 90 and the median diameter D 50 of the particle size distribution of the metal nanoparticles are measured from the particle size distribution of the metal nanoparticles measured by using a particle size distribution measuring apparatus applying a laser Doppler method. We will ask for it.
金属ナノ粒子は、先に説明したように、銀、銅、錫、亜鉛等の、オリゴジナミー効果によって抗菌性を発現することができる抗菌性金属の１種単体、または２種以上の合金によって形成できる他、前記抗菌性金属の１種または２種以上と、他の金属との合金によって形成することもできる。特に、先に説明したように、オリゴジナミー効果に基づく抗菌性に優れた銀単体、もしくは銀を含む合金によって金属ナノ粒子を形成するのが好ましい。金属ナノ粒子が、銀と、他の抗菌性金属や、他の金属との合金からなる場合には、銀による抗菌性を、より有効に発現させることを考慮すると、銀の含有割合は、合金の総量中の５０重量％以上、特に８０重量％以上であるのが好ましい。 As described above, the metal nanoparticles can be formed of a single element of an antibacterial metal such as silver, copper, tin, zinc or the like that can exhibit antibacterial properties by an oligodynamic effect, or two or more alloys. In addition, it can also be formed by an alloy of one or more of the antibacterial metals and other metals. In particular, as described above, it is preferable to form the metal nanoparticles from silver alone or an alloy containing silver excellent in antibacterial properties based on the oligodynamic effect. When the metal nanoparticles are composed of silver and other antibacterial metals or alloys with other metals, considering that the antibacterial properties due to silver are expressed more effectively, the silver content is It is preferably 50% by weight or more, particularly 80% by weight or more, based on the total amount.
銀と共に合金を形成する、抗菌性金属以外の他の金属としては、白金、パラジウム、ロジウム、イリジウム、ニッケル、鉄等が挙げられる。これらの金属は、いずれも、銀よりも融点が高いため、合金の融点を高めて、金属ナノ粒子が、焼成時の熱によって融着する等して成長するのを抑制して、抗菌性窯業製品の表面に露出される金属ナノ粒子の平均粒
子径が大きくなり過ぎるのを防止する働きをする。また、前記金属は、銀と合金を形成することで、酸化したり、いわゆるマイグレーションを生じたりするのを防止して、長期間に亘って、銀による抗菌性を維持する働きもする。なお、金属ナノ粒子は、任意の金属からなる芯材粒子の表面を、前記銀や、銀を含む合金等からなる表皮層で被覆した複合構造を有していてもよい。
Platinum, palladium, rhodium, iridium, nickel, iron, etc. are mentioned as metals other than an antibacterial metal which form an alloy with silver. All of these metals have a higher melting point than silver, so the melting point of the alloy is increased, and the metal nanoparticles are prevented from growing by fusing with heat during firing. It works to prevent the average particle size of the metal nanoparticles exposed on the surface of the product from becoming too large. Further, the metal forms an alloy with silver, thereby preventing oxidation or so-called migration and maintaining antibacterial properties due to silver over a long period of time. The metal nanoparticles may have a composite structure in which the surface of core particles made of any metal is covered with a skin layer made of silver, an alloy containing silver, or the like.
金属ナノ粒子は、含浸法と呼ばれる高温処理法や、液相還元法、気相法などの、従来公知の種々の方法によって製造することができる。このうち、液相還元法によって金属ナノ粒子を製造するためには、例えば、水に、金属ナノ粒子を形成する金属のイオンのもとになる水溶性の金属化合物と、分散剤とを溶解すると共に、還元剤を加えて、好ましくは、かく拌下、一定時間、金属のイオンを還元反応させればよい。また、液相還元法によって、合金からなる金属ナノ粒子を製造するためには、前記合金を形成する、少なくとも２種の金属のイオンのもとになる、２種以上の水溶性の金属化合物を併用すればよい。さらに、複合構造を有する金属ナノ粒子を製造するためには、芯材粒子の析出と、前記芯材粒子の表面への被覆層の析出とを、液相還元法によって、順に行えばよい。液相還元法によって製造される金属ナノ粒子は、形状が球状ないし粒状で揃っていると共に、粒度分布がシャープで、しかも、粒子径が小さいという特徴を有している。 The metal nanoparticles can be produced by various conventionally known methods such as a high temperature treatment method called an impregnation method, a liquid phase reduction method, and a gas phase method. Among these, in order to produce metal nanoparticles by the liquid phase reduction method, for example, a water-soluble metal compound that is a source of metal ions forming the metal nanoparticles and a dispersant are dissolved in water. At the same time, a reducing agent is added, and the metal ions are preferably allowed to undergo a reduction reaction with stirring for a certain period of time. In addition, in order to produce metal nanoparticles made of an alloy by a liquid phase reduction method, two or more water-soluble metal compounds that form the alloy and are sources of at least two kinds of metal ions are used. You may use together. Furthermore, in order to produce metal nanoparticles having a composite structure, the deposition of the core material particles and the deposition of the coating layer on the surface of the core material particles may be sequentially performed by a liquid phase reduction method. The metal nanoparticles produced by the liquid phase reduction method are characterized by having a spherical or granular shape, a sharp particle size distribution, and a small particle size.
金属のイオンのもとになる、水溶性の金属化合物としては、例えば、銀の場合は、硝酸銀(I)〔ＡｇＮＯ3〕、メタンスルホン酸銀〔ＣＨ3ＳＯ3Ａｇ〕等が挙げられ、銅の場合は、硝酸銅(II)〔Ｃｕ(ＮＯ3)2〕、硫酸銅(II)五水和物〔ＣｕＳＯ4・５Ｈ2Ｏ〕等が挙げられる。錫の場合は、塩化スズ(IV)五水和物〔ＳｎＣｌ4・５Ｈ2Ｏ〕等が挙げられ、亜鉛の場合は、塩化亜鉛（ＺｎＣｌ2）、硫酸亜鉛七水和物（ＺｎＳＯ4・７Ｈ2Ｏ）、硝酸亜鉛
六水和物〔Ｚｎ（ＮＯ3）2・６Ｈ2Ｏ〕等が挙げられる。白金の場合は、ジニトロジアン
ミン白金(II)（Ｐｔ（ＮＯ3）2（ＮＨ3）2）、ヘキサクロロ白金(IV)酸六水和物（Ｈ2[ＰｔＣｌ6]・６Ｈ2Ｏ）等が挙げられ、パラジウムの場合は、硝酸パラジウム(II)硝酸溶液
〔Ｐｄ(ＮＯ3)2／Ｈ2Ｏ〕、塩化パラジウム(II)溶液〔ＰｄＣｌ2〕等が挙げられる。
Examples of the water-soluble metal compound that is a source of metal ions include silver nitrate (I) [AgNO 3 ], silver methanesulfonate [CH 3 SO 3 Ag], and the like in the case of silver. In this case, copper nitrate (II) [Cu (NO 3 ) 2 ], copper sulfate (II) pentahydrate [CuSO 4 .5H 2 O] and the like can be mentioned. In the case of tin, tin chloride (IV) pentahydrate [SnCl 4 .5H 2 O] and the like are listed. In the case of zinc, zinc chloride (ZnCl 2 ), zinc sulfate heptahydrate (ZnSO 4 .7H) 2 O), zinc nitrate hexahydrate [Zn (NO 3 ) 2 .6H 2 O] and the like. In the case of platinum, dinitrodiammine platinum (II) (Pt (NO 3 ) 2 (NH 3 ) 2 ), hexachloroplatinum (IV) acid hexahydrate (H 2 [PtCl 6 ] · 6H 2 O) and the like can be mentioned. In the case of palladium, palladium (II) nitrate solution [Pd (NO 3 ) 2 / H 2 O], palladium chloride (II) solution [PdCl 2 ] and the like can be mentioned.
ロジウムの場合は、塩化ロジウム（III）三水和物〔ＲｈＣｌ3・３Ｈ2Ｏ〕、硝酸ロ
ジウム（III）溶液〔Ｒｈ(ＮＯ3)3〕等が挙げられ、イリジウムの場合は、塩化イリ
ジウム(III)〔ＩｒＣｌ3〕等が挙げられる。ニッケルの場合は、塩化ニッケル(II)六水和物〔ＮｉＣｌ2・６Ｈ2Ｏ〕、硝酸ニッケル(II)六水和物〔Ｎｉ(ＮＯ3)2・６Ｈ2Ｏ〕等が
挙げられ、鉄の場合は、硝酸鉄(III)六水和物、九水和物（Ｆｅ（ＮＯ3）3・６Ｈ2Ｏ、９Ｈ2Ｏ）、塩化鉄(II)四水和物（ＦｅＣｌ2・４Ｈ2Ｏ）、硫酸鉄(II)七水和物（ＦｅＳＯ4・７Ｈ2Ｏ）、アセチルアセトン鉄(III)（Ｆｅ〔ＣＨ（ＣＯＣＨ3）2〕3）等が挙げられ
る。
In the case of rhodium, rhodium (III) chloride trihydrate [RhCl 3 .3H 2 O], rhodium nitrate (III) solution [Rh (NO 3 ) 3 ] and the like can be mentioned. In the case of iridium, iridium chloride ( III) [IrCl 3 ] and the like. In the case of nickel, nickel (II) chloride hexahydrate [NiCl 2 · 6H 2 O], nickel nitrate (II) hexahydrate [Ni (NO 3 ) 2 · 6H 2 O], and the like can be mentioned. In this case, iron (III) nitrate hexahydrate, nonahydrate (Fe (NO 3 ) 3 · 6H 2 O, 9H 2 O), iron (II) chloride tetrahydrate (FeCl 2 · 4H 2) O), iron (II) sulfate heptahydrate (FeSO 4 .7H 2 O), acetylacetone iron (III) (Fe [CH (COCH 3 ) 2 ] 3 ) and the like.
還元剤としては、液相の反応系中で、金属のイオンを還元して、金属ナノ粒子として析出させることができる種々の還元剤が、いずれも使用可能である。前記還元剤としては、例えば、水素化ホウ素ナトリウム、次亜リン酸ナトリウム、ヒドラジン、遷移金属のイオン（三価のチタンイオン、二価のコバルトイオン等）が挙げられる。ただし、析出させる金属ナノ粒子の、粒度分布の９０％累積径Ｄ90を、先に説明した１５０ｎｍ以下の範囲内でも、できるだけ小さくするためには、金属のイオンの還元、析出速度を遅くするのが有効であり、還元、析出速度を遅くするためには、できるだけ還元力の弱い還元剤を、選択して使用することが好ましい。 As the reducing agent, any of various reducing agents capable of reducing metal ions in a liquid phase reaction system and precipitating them as metal nanoparticles can be used. Examples of the reducing agent include sodium borohydride, sodium hypophosphite, hydrazine, and transition metal ions (trivalent titanium ions, divalent cobalt ions, and the like). However, in order to make the 90% cumulative diameter D 90 of the particle size distribution of the metal nanoparticles to be deposited as small as possible even within the range of 150 nm or less as described above, the reduction of metal ions and the deposition rate are slowed down. Is effective, and in order to slow down the reduction and precipitation rate, it is preferable to select and use a reducing agent having a reducing power as weak as possible.
還元力の弱い還元剤としては、例えば、メタノール、エタノール、２−プロパノール等のアルコールや、あるいはアスコルビン酸等が挙げられる他、エチレングリコール、グルタチオン、有機酸類（クエン酸、リンゴ酸、酒石酸等）、還元性糖類（グルコース、ガラクトース、マンノース、フルクトース、スクロース、マルトース、ラフィノース、スタキ
オース等）、および糖アルコール類（ソルビトール等）等が挙げられ、中でも、還元性糖類や、その誘導体としての糖アルコール類が好ましい。
Examples of the reducing agent having a weak reducing power include alcohols such as methanol, ethanol and 2-propanol, ascorbic acid, and the like, as well as ethylene glycol, glutathione, organic acids (citric acid, malic acid, tartaric acid, etc.), Reducing sugars (glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose, etc.) and sugar alcohols (sorbitol, etc.). Among them, reducing sugars and sugar alcohols as derivatives thereof preferable.
分散剤としては、親水性基を有し、水に対して良好な溶解性を有すると共に、析出した金属ナノ粒子を、水中に良好に分散させることができる種々の分散剤が使用できる。前記分散剤は、反応系中で、析出した金属ナノ粒子の表面を被覆して、前記金属ナノ粒子の凝集を防止し、分散を維持する働きをする。金属ナノ粒子を析出させた液相の反応系は、前記反応系から金属ナノ粒子を分離せずに、不純物のみを除去した液相の状態のままで、窯業表面処理剤を調製するための出発原料として使用することができる。その際に、分散剤は、不純物の除去工程では殆ど除去されずに残存して、調製された窯業表面処理剤中で、先に説明したように、金属ナノ粒子の表面を被覆して、凝集を防止すると共に、分散を維持する分散剤として機能し続けることができる。 As the dispersant, various dispersants having a hydrophilic group and having good solubility in water and capable of dispersing the deposited metal nanoparticles in water can be used. In the reaction system, the dispersant functions to coat the surface of the deposited metal nanoparticles, prevent aggregation of the metal nanoparticles, and maintain dispersion. The liquid phase reaction system in which the metal nanoparticles are deposited is a starting point for preparing a ceramic surface treatment agent in a liquid phase state in which only impurities are removed without separating the metal nanoparticles from the reaction system. Can be used as a raw material. At that time, the dispersant remains almost removed in the impurity removal step, and in the prepared ceramic surface treatment agent, as described above, the surface of the metal nanoparticles is coated and agglomerated. And can continue to function as a dispersant for maintaining dispersion.
分散剤は、数平均分子量Ｍｎが１０００〜８０００００、特に２０００〜３０００００であるのが好ましい。数平均分子量Ｍｎが前記範囲未満では、前記分散剤による、金属ナノ粒子の凝集を防止して、分散を維持する効果が十分に得られないおそれがある。また、前記範囲を超える場合には、窯業表面処理剤の粘度が高くなりすぎて、素地表面への塗布等の際の取り扱いが容易でなくなるおそれがある。分散剤に導入する親水性基としては、オキシ基（−Ｏ−）、ヒドロキシ基（−ＯＨ）、カルボキシ基（−ＣＯＯＨ）等の含酸素官能基や、アミノ基（−ＮＨ2）、イミノ基（＞ＮＨ）、アンモニウム基（−ＮＨ4 +）等
の含窒素官能基、スルファニル基（−ＳＨ）、スルファンジイル基（−Ｓ−）等の含硫黄官能基等が挙げられる。分散剤は、前記親水性基を、１種単独で有していてもよいし、２種以上を有していてもよい。
The dispersant preferably has a number average molecular weight Mn of 1000 to 800000, particularly 2000 to 300000. If the number average molecular weight Mn is less than the above range, there is a possibility that the effect of maintaining the dispersion by preventing aggregation of the metal nanoparticles by the dispersant may not be obtained. Moreover, when the said range is exceeded, there exists a possibility that the handling at the time of the application | coating to a base material surface etc. may become easy because the viscosity of a ceramics surface treatment agent becomes too high. Examples of the hydrophilic group to be introduced into the dispersant include oxygen-containing functional groups such as an oxy group (—O—), a hydroxy group (—OH), and a carboxy group (—COOH), an amino group (—NH 2 ), and an imino group. (> NH), nitrogen-containing functional groups such as ammonium group (-NH 4 + ), sulfur-containing functional groups such as sulfanyl group (-SH), sulfanediyl group (-S-), and the like. The dispersing agent may have the said hydrophilic group individually by 1 type, and may have 2 or more types.
好適な分散剤としては、例えば、ポバール（ポリビニルアルコール）、ポリエチレンオキシド、ポリプロピレンオキシド、ポリエチレンイミン、ポリビニルピロリドン、ポリアルカンチオール、マレイン酸系共重合体等が挙げられる。分散剤は、水、または水溶性有機溶媒に溶解した溶液の状態で、反応系に添加することもできる。分散剤の添加量は、前記分散剤が、窯業表面処理剤中で、金属ナノ粒子の表面を被覆して、その凝集を防止する分散剤として、引き続いて使用される場合、前記窯業表面処理剤中での、分散剤の、金属ナノ粒子の量に対する百分率で表される含有率は１〜２０重量％、特に８〜１５重量％であるのが好ましい。分散剤の含有率が、前記範囲未満では、分散剤による、反応系中、および窯業表面処理剤中で、金属ナノ粒子の表面を被覆して、その凝集を防止する効果が十分に得られないおそれがある。 Suitable dispersants include, for example, poval (polyvinyl alcohol), polyethylene oxide, polypropylene oxide, polyethyleneimine, polyvinyl pyrrolidone, polyalkanethiol, maleic acid copolymer and the like. The dispersant can also be added to the reaction system in the state of water or a solution dissolved in a water-soluble organic solvent. The amount of the dispersant added is such that when the dispersant is subsequently used as a dispersant for coating the surface of the metal nanoparticles in the ceramic surface treatment agent and preventing its aggregation, the ceramic surface treatment agent is used. The content of the dispersant, expressed as a percentage of the amount of metal nanoparticles, is preferably 1 to 20% by weight, more preferably 8 to 15% by weight. If the content of the dispersant is less than the above range, the effect of preventing the aggregation by covering the surface of the metal nanoparticles in the reaction system and in the ceramic surface treatment agent by the dispersant cannot be obtained sufficiently. There is a fear.
また、例えば、窯業表面処理剤が釉薬である場合に、分散剤の含有率が、前記範囲を超えると、焼成時に、過剰の分散剤が、釉薬中に含まれる釉薬成分の焼結を阻害して、形成される釉薬層の緻密性を低下させるおそれがある。また、下絵具の場合は、形成される下絵の緻密性や、釉薬層に対する密着性等を低下させるおそれがある。金属ナノ粒子の、粒度分布の９０％累積径Ｄ90を調整するには、金属化合物、分散剤、還元剤の種類と配合割合とを調整すると共に、金属化合物を還元反応させる際に、かく拌速度、温度、時間、ｐＨ等を調整すればよい。例えば、反応系のｐＨは、できるだけ９０％累積径Ｄ90の小さい金属ナノ粒子を形成することを考慮すると、７〜１３であるのが好ましい。反応系のｐＨを、前記範囲に調整するためには、ｐＨ調整剤が使用される。ｐＨ調整剤としては、調整するｐＨ値に応じて、硝酸等の種々の酸や、アンモニア等の種々のアルカリが挙げられる。 In addition, for example, when the ceramic surface treatment agent is a glaze, if the content of the dispersant exceeds the above range, an excessive dispersant inhibits sintering of the glaze component contained in the glaze during firing. Therefore, there is a possibility that the denseness of the formed glaze layer may be reduced. Moreover, in the case of a lower paint, there exists a possibility that the closeness of the formed rough sketch, the adhesiveness with respect to a glaze layer, etc. may be reduced. In order to adjust the 90% cumulative diameter D 90 of the particle size distribution of the metal nanoparticles, the types and blending ratios of the metal compound, the dispersant, and the reducing agent are adjusted, and the metal compound is stirred when the reduction reaction is performed. The speed, temperature, time, pH, etc. may be adjusted. For example, the pH of the reaction system is preferably 7 to 13 in consideration of forming metal nanoparticles having a 90% cumulative diameter D90 as small as possible. In order to adjust the pH of the reaction system to the above range, a pH adjusting agent is used. Examples of the pH adjuster include various acids such as nitric acid and various alkalis such as ammonia, depending on the pH value to be adjusted.
液相の反応系中に析出させた金属ナノ粒子は、ロ別、洗浄、乾燥、解砕等の工程を経て、一旦、粉末状とした後、水と分散剤と、さらに必要に応じて、水溶性の有機溶媒とを所定の割合で配合して、窯業表面処理剤を調製してもよいが、先に説明したように、金属ナ
ノ粒子を析出させた液相の反応系を出発原料として用いて、窯業表面処理剤を調製するのが好ましい。すなわち、金属ナノ粒子を析出させた後の、前記金属ナノ粒子と、金属ナノ粒子の表面を被覆する分散剤と、反応に使用した水とを含む液相の反応系から、限外ろ過、遠心分離、水洗、電気透析等の処理を行って、不純物を除去すると共に、必要に応じて、濃縮して水を除去するか、逆に水を加えることで、金属ナノ粒子の濃度を調整した後、窯業表面処理剤を構成する他の成分を、所定の割合で配合することによって、窯業表面処理剤が調製される。この方法では、金属ナノ粒子の凝集による、粗大で不定形な粒子の発生を防止することができる。
The metal nanoparticles precipitated in the liquid phase reaction system are subjected to steps such as separation, washing, drying, crushing, etc., once powdered, then water and a dispersant, and if necessary, A ceramic surface treatment agent may be prepared by blending with a water-soluble organic solvent at a predetermined ratio, but as described above, a liquid phase reaction system in which metal nanoparticles are precipitated is used as a starting material. It is preferable to prepare a ceramic surface treatment agent. That is, from the reaction system of the liquid phase containing the metal nanoparticles after the metal nanoparticles are deposited, the dispersant covering the surface of the metal nanoparticles, and the water used for the reaction, ultrafiltration, centrifugation After adjusting the concentration of the metal nanoparticles by removing the impurities by performing treatments such as separation, washing, electrodialysis, etc., and if necessary, concentrating to remove the water or adding water. The ceramic surface treatment agent is prepared by blending other components constituting the ceramic surface treatment agent at a predetermined ratio. According to this method, generation of coarse and irregular particles due to aggregation of metal nanoparticles can be prevented.
窯業表面処理剤を構成する他の成分としては、前記窯業表面処理剤の粘度や蒸気圧を調整するための、水溶性の有機溶媒等が挙げられる。水溶性の有機溶媒としては、水溶性である種々の有機溶媒が使用可能である。その具体例としては、メタノール、エタノール、２−プロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のグリコールエーテル類等が挙げられる。水溶性の有機溶媒の添加量は、金属ナノ粒子１００重量部あたり、３０〜９００重量部であるのが好ましい。添加量が、前記範囲未満では、有機溶媒を添加することによる、分散液の粘度や蒸気圧を調整する効果が十分に得られないおそれがある。また、前記範囲を超える場合には、水による、分散剤を十分に膨潤させて、前記分散剤で被覆された金属ナノ粒子を、窯業表面処理剤中に、凝集を生じさせることなく、良好に分散させる効果が阻害されるおそれがある。 Examples of the other components constituting the ceramic surface treatment agent include water-soluble organic solvents for adjusting the viscosity and vapor pressure of the ceramic surface treatment agent. As the water-soluble organic solvent, various organic solvents that are water-soluble can be used. Specific examples thereof include alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and the like. The addition amount of the water-soluble organic solvent is preferably 30 to 900 parts by weight per 100 parts by weight of the metal nanoparticles. If the addition amount is less than the above range, the effect of adjusting the viscosity or vapor pressure of the dispersion by adding the organic solvent may not be sufficiently obtained. In addition, when the above range is exceeded, the water-based dispersant is sufficiently swollen so that the metal nanoparticles coated with the dispersant are satisfactorily produced without causing aggregation in the ceramic surface treatment agent. The effect of dispersing may be hindered.
前記分散液は、調製後、２４時間、経過した時点での金属ナノ粒子の沈降量が、前記金属ナノ粒子の総量の０．１重量％以下であるのが好ましい。沈降量が、前記範囲を超える場合には、金属ナノ粒子が沈降を生じやすくなる。そのため、前記分散液を用いて窯業表面処理剤を調製した場合、前記窯業表面処理剤を焼成して形成される表面に露出する金属ナノ粒子の割合が少なくなって、抗菌性金属の利用効率が低下したり、外観が悪くなったりするおそれがある。これに対し、金属ナノ粒子の沈降量が、前記範囲内であれば、前記金属ナノ粒子の、コロイド分散の安定性を向上して、窯業表面処理剤中に、より一層、均一にコロイド分散させて、沈降等を防止することができる。そのため、前記窯業表面処理剤を焼成して形成される表面に露出する金属ナノ粒子の割合を多くして、前記金属ナノ粒子を構成する抗菌性金属の利用効率を、より一層、向上したり、その外観を良好なものとしたりすることが可能となる。沈降量を調整するためには、金属ナノ粒子の粒子径や、分散剤の被覆量を調整すればよい。一般的には、金属ナノ粒子の粒子径を小さくするほど、また分散剤の被覆量を多くするほど、沈降量を、小さくすることができる。 In the dispersion, it is preferable that the amount of sedimentation of the metal nanoparticles at the time when 24 hours have elapsed after preparation is 0.1% by weight or less of the total amount of the metal nanoparticles. When the amount of sedimentation exceeds the above range, the metal nanoparticles tend to sediment. Therefore, when a ceramic surface treatment agent is prepared using the dispersion, the proportion of metal nanoparticles exposed on the surface formed by firing the ceramic surface treatment agent is reduced, and the use efficiency of the antibacterial metal is reduced. There is a risk that it may deteriorate or the appearance may deteriorate. On the other hand, if the amount of sedimentation of the metal nanoparticles is within the above range, the stability of the colloidal dispersion of the metal nanoparticles is improved, and the colloidal dispersion is further uniformly dispersed in the ceramic surface treatment agent. Thus, sedimentation and the like can be prevented. Therefore, by increasing the proportion of metal nanoparticles exposed on the surface formed by firing the ceramic surface treatment agent, the utilization efficiency of the antibacterial metal constituting the metal nanoparticles is further improved, It becomes possible to make the appearance good. In order to adjust the sedimentation amount, the particle diameter of the metal nanoparticles and the coating amount of the dispersant may be adjusted. In general, the amount of sedimentation can be reduced as the particle size of the metal nanoparticles is reduced and the amount of coating of the dispersant is increased.
《抗菌性窯業製品の製造方法》
本発明の、抗菌性窯業製品の製造方法は、窯業製品の表面に、前記本発明の窯業表面処理剤を塗布した後、８００〜１６００℃で焼成する工程を含むことを特徴とするものである。具体的には、例えば、本発明の窯業表面処理剤を釉薬として使用して、窯業製品の素地の表面や、前記表面に形成した釉薬層の表面に塗布したり、前記窯業表面処理剤を下絵具として使用して、窯業製品の素地の表面に形成した釉薬層の表面に下絵を描いたりした後、前記温度範囲で焼成することによって、その表面に、平均粒子径２００ｎｍ以下の金属ナノ粒子が存在する本発明の抗菌性窯業製品が製造される。
《Method for manufacturing antibacterial ceramic products》
The method for producing an antibacterial ceramic product according to the present invention includes a step of baking at 800 to 1600 ° C. after applying the ceramic surface treatment agent of the present invention to the surface of the ceramic product. . Specifically, for example, the ceramic surface treatment agent of the present invention is used as a glaze and applied to the surface of a ceramic product substrate or the surface of a glaze layer formed on the surface, or the ceramic surface treatment agent is applied as a glaze. Use as a paint, draw a sketch on the surface of the glaze layer formed on the surface of the ceramic product substrate, and then baked in the temperature range, the metal nanoparticles with an average particle diameter of 200 nm or less on the surface An existing antibacterial ceramic product of the present invention is produced.
焼成の温度が８００〜１６００℃に限定されるのは、下記の理由による。すなわち、焼成の温度が前記範囲未満では、例えば、窯業表面処理剤が釉薬である場合に、釉薬成分を十分に焼結させることができないため、形成される釉薬層の緻密性が低下するおそれがある。また、下絵具の場合は、形成される下絵の緻密性や、釉薬層に対する密着性等が低下するおそれがある。一方、焼成の温度が前記範囲を超える場合には、釉薬層や下絵具の表面に露出した金属ナノ粒子が、焼成の熱によって揮発して、失われてしまいやすくなる。
そのため、釉薬層の表面に露出する抗菌性金属の割合が少なくなって、その利用効率が低下してしまい、十分な抗菌性が得られないおそれがある。なお、焼成の温度は、釉薬成分、顔料等の種類にも依存するが、前記範囲内でも１０００〜１６００℃、特に１１５０〜１３００℃程度であるのが好ましい。焼成は、大気雰囲気中で行っても良いし、釉薬や下絵具の種類によっては、還元性雰囲気中等の、適宜の焼成雰囲気中で行なっても良い。また焼成の時間は、前記温度範囲での焼成の場合、製造される窯業製品の表面に形成される金属ナノ粒子の平均粒子径を２００ｎｍ以下として、良好な抗菌性を付与することを考慮すると、２０分〜３０時間であるのが好ましい。
The firing temperature is limited to 800-1600 ° C. for the following reason. That is, when the firing temperature is less than the above range, for example, when the ceramic surface treatment agent is a glaze, the glaze component cannot be sufficiently sintered, so that the denseness of the formed glaze layer may be reduced. is there. Moreover, in the case of a lower paint, there exists a possibility that the denseness of the formed background sketch, the adhesiveness with respect to a glaze layer, etc. may fall. On the other hand, when the firing temperature exceeds the above range, the metal nanoparticles exposed on the surface of the glaze layer and the lower paint are volatilized by the heat of firing and are easily lost.
Therefore, the ratio of the antibacterial metal exposed on the surface of the glaze layer is reduced, the utilization efficiency thereof is lowered, and sufficient antibacterial properties may not be obtained. The firing temperature depends on the type of glaze component, pigment, etc., but it is preferably in the range of 1000 to 1600 ° C., particularly about 1150 to 1300 ° C. Firing may be performed in an air atmosphere, or may be performed in an appropriate firing atmosphere, such as in a reducing atmosphere, depending on the type of glaze or underlying paint. In addition, in the case of firing in the above temperature range, the firing time is set so that the average particle diameter of the metal nanoparticles formed on the surface of the manufactured ceramic product is 200 nm or less, and imparting good antibacterial properties, It is preferably 20 minutes to 30 hours.
《抗菌性窯業製品》
前記の製造方法等によって製造することができる、本発明の抗菌性窯業製品は、表面に、少なくとも銀を含む、平均粒子径２００ｎｍ以下の金属ナノ粒子が存在していることを特徴とするものである。表面に存在する金属ナノ粒子の平均粒子径が２００ｎｍ以下に限定されるのは、下記の理由による。すなわち、平均粒子径が、前記範囲内であれば、金属ナノ粒子を形成する抗菌性金属の利用効率を向上して、抗菌性金属の使用量に見合う十分な抗菌性を得ることができる。そのため、抗菌性金属の使用量を少なくして、例えば、釉薬層や下絵が所定の色目にならなかったり、窯業製品のコストアップに繋がったりするのを、確実に防止することが可能となる。
<Antimicrobial ceramic products>
The antibacterial ceramic product of the present invention, which can be manufactured by the above-described manufacturing method, is characterized in that metal nanoparticles containing at least silver and having an average particle diameter of 200 nm or less are present on the surface. is there. The reason why the average particle diameter of the metal nanoparticles present on the surface is limited to 200 nm or less is as follows. That is, if the average particle diameter is within the above range, the utilization efficiency of the antibacterial metal forming the metal nanoparticles can be improved, and sufficient antibacterial properties commensurate with the amount of the antibacterial metal used can be obtained. For this reason, the amount of the antibacterial metal used can be reduced, and for example, it is possible to reliably prevent the glaze layer and the background from becoming a predetermined color or increasing the cost of the ceramic product.
なお、前記平均粒子径は、さらに良好な抗菌性を得ることを考慮すると、前記範囲内でも０．５〜１００ｎｍ、特に０．５〜５０ｎｍであるのが好ましい。平均粒子径は、直接観察法による粒子径から判定することができる。具体的には、例えば、観察倍率一万倍以上の高分解能ＳＥＭ（走査型電子顕微鏡）等を用いて、抗菌性窯業製品の表面を観察して求めた、少なくとも１０個の金属ナノ粒子の粒子径から、その平均値を求めて、平均粒子径とすることができる。 The average particle diameter is preferably 0.5 to 100 nm, particularly preferably 0.5 to 50 nm even within the above range, in consideration of obtaining better antibacterial properties. The average particle diameter can be determined from the particle diameter obtained by the direct observation method. Specifically, for example, particles of at least 10 metal nanoparticles obtained by observing the surface of an antibacterial ceramic product using a high-resolution SEM (scanning electron microscope) having an observation magnification of 10,000 times or more. The average value can be obtained from the diameter to obtain the average particle diameter.
〈銀ナノ粒子分散液の合成〉
金属化合物としての硝酸銀(I)を純水に溶解し、アンモニア水を加えて液のｐＨを１０
に調整し、次いで、分散剤としてのマレイン酸系共重合体〔日本化成(株)製のクロバックス（登録商標）４００−２１Ｓ、分子量：９０００、酸価：１００ｍｇＫＯＨ／ｇ〕を加えて溶解させた後、還元剤としてのエチレングリコールを純水に溶解した溶液を添加して、液相の反応系を調製した。反応系における各成分の濃度は、硝酸銀(I)：２５ｇ／リッ
トル、マレイン酸系共重合体：２０ｇ／リットル、還元剤：１２０ｇ／リットルとした。
<Synthesis of silver nanoparticle dispersion>
Silver (I) nitrate as a metal compound is dissolved in pure water, and aqueous ammonia is added to adjust the pH of the solution to 10.
Then, a maleic acid copolymer (Crobacs (registered trademark) 400-21S manufactured by Nippon Kasei Co., Ltd., molecular weight: 9000, acid value: 100 mgKOH / g) as a dispersant is added and dissolved. After that, a solution in which ethylene glycol as a reducing agent was dissolved in pure water was added to prepare a liquid phase reaction system. The concentration of each component in the reaction system was silver (I) nitrate: 25 g / liter, maleic acid copolymer: 20 g / liter, reducing agent: 120 g / liter.
前記反応系を、かく拌速度１００ｒｐｍでかく拌しながら８５℃で１８０分間、反応させて、銀ナノ粒子を析出させた後、限外ろ過処理により、純水で希釈を繰り返して不純物を除去して、前記銀ナノ粒子がコロイド分散した分散液を得た。前記分散液における、銀ナノ粒子の、粒度分布の９０％累積径Ｄ90を、レーザードップラー法を応用した粒度分布測定装置〔日機装(株)製のナノトラック（登録商標）ＵＰＡ−ＥＸ１５０〕を用いて測定した、前記銀ナノ粒子の粒度分布から求めたところ４５ｎｍであった。また、銀ナノ粒子の組成を、誘導結合高周波プラズマ発光分析装置〔(株)リガク製のＣＩＲＯＳ−１２０〕を用いて測定したところ、銀の含有率が１００％であった。 After reacting the reaction system at 85 ° C. for 180 minutes while stirring at a stirring speed of 100 rpm to precipitate silver nanoparticles, the impurities are removed by repeated dilution with pure water by ultrafiltration treatment. A dispersion liquid in which the silver nanoparticles were colloidally dispersed was obtained. The 90% cumulative diameter D 90 of the particle size distribution of the silver nanoparticles in the dispersion was measured using a particle size distribution measuring device [Nanotrack (registered trademark) UPA-EX150 manufactured by Nikkiso Co., Ltd.] using a laser Doppler method. It was 45 nm when calculated | required from the particle size distribution of the said silver nanoparticle measured. Moreover, when the composition of the silver nanoparticles was measured using an inductively coupled high-frequency plasma emission spectrometer [CIROS-120 manufactured by Rigaku Corporation], the silver content was 100%.
また、分散液における固形分濃度は１０重量％、銀ナノ粒子１００重量部あたりの分散剤の量は９重量部であった。また、前記分散液１０００ｇをガラス容器に採取し、前記ガラス容器を、ポリプロピレン製の樹脂キャップによって密栓した状態で、２５℃に保持された恒温槽中で２４時間、静置した後、スポイトで上澄みを取り除いて、ガラス容器の底に沈降した沈降物を採取し、１０５℃で３時間、乾燥させて精密天秤で秤量したところ、沈降量は、銀ナノ粒子の総量の０．０３重量％であることが確認された。 Further, the solid content concentration in the dispersion was 10% by weight, and the amount of the dispersant per 100 parts by weight of the silver nanoparticles was 9 parts by weight. Further, 1000 g of the dispersion liquid was collected in a glass container, and the glass container was allowed to stand in a thermostatic bath maintained at 25 ° C. for 24 hours in a state where the glass container was tightly sealed with a polypropylene resin cap. The sediment settled on the bottom of the glass container was collected, dried at 105 ° C. for 3 hours, and weighed with a precision balance. The sedimentation amount was 0.03% by weight of the total amount of silver nanoparticles. It was confirmed.
〈窯業表面処理剤の調製〉
釉薬成分としての、３５．５８重量部の長石と、１３．５重量部の石灰と、９．７重量部の粘土と、４０．２重量部の珪砂とを、１００重量部の水と共に混合し、遠心ボールミルで粉砕してスラリー化した。次いで、このスラリーに、固形分の総量中の銀ナノ粒子の割合が０．０２重量％となるように、先に調製した銀ナノ粒子の分散液を加え、混合して、窯業表面処理剤としての釉薬を調製した。前記釉薬について、ＴＧ−ＭＡＳＳ分析を行って求めた分散剤の含有量と、ＩＣＰ分析を行って求めた銀の含有量とから、分散剤の、金属ナノ粒子の量に対する百分率で表される含有率を求めたところ３．３重量％であった。
<Preparation of ceramics surface treatment agent>
As a glaze component, 35.58 parts by weight of feldspar, 13.5 parts by weight of lime, 9.7 parts by weight of clay and 40.2 parts by weight of silica sand are mixed together with 100 parts by weight of water. The slurry was pulverized with a centrifugal ball mill. Next, the silver nanoparticle dispersion prepared earlier is added to this slurry so that the ratio of silver nanoparticles in the total amount of solids is 0.02% by weight, and mixed to obtain a ceramic surface treatment agent. A glaze was prepared. About the said glaze, the content represented by the percentage with respect to the quantity of a metal nanoparticle of a dispersing agent from content of the dispersing agent calculated | required by performing TG-MASS analysis, and content of silver calculated | required by performing ICP analysis The rate was determined to be 3.3% by weight.
〈抗菌性窯業製品の製造〉
先に調製した釉薬を、タイル素地の表面に吹き付け塗布し、乾燥させた後、電気炉を用いて、大気雰囲気中で１２００℃に加熱して３０分間、焼成して、釉薬層を有する抗菌性窯業製品のサンプルを製造した。そして、前記サンプルの、釉薬層の表面を、高分解能ＳＥＭ（走査型電子顕微鏡）を用いて撮影して画像データを得、前記画像データを画像解析して、画像データ中に写された全ての銀ナノ粒子の、個々の粒子径を求めると共に、その平均値を、平均粒子径として算出したところ３０ｎｍであった。
<Manufacture of antibacterial ceramic products>
The glaze prepared above is spray-coated on the surface of the tile substrate, dried, then heated to 1200 ° C. in an air atmosphere and baked for 30 minutes using an electric furnace to have antibacterial properties having a glaze layer Samples of ceramic products were manufactured. Then, the surface of the glaze layer of the sample is photographed using a high resolution SEM (scanning electron microscope) to obtain image data, the image data is subjected to image analysis, and all the images captured in the image data are captured. While calculating | requiring each particle diameter of a silver nanoparticle and calculating the average value as an average particle diameter, it was 30 nm.
〈抗菌性評価〉
前記サンプルの、釉薬層の表面に、黄色ブドウ球菌の菌液１ミリリットルを滴下した後、滅菌ポリエチレンフィルムを載置して２５℃で２４時間、静置した後、式(1)：
<Antimicrobial evaluation>
After dripping 1 ml of the staphylococcus aureus solution on the surface of the glaze layer of the sample, a sterilized polyethylene film was placed and allowed to stand at 25 ° C. for 24 hours, and then the formula (1):
実施例１に記載の方法に準拠して、表１に示すように、銀ナノ粒子の、粒度分布の９０％累積径Ｄ90が異なる５種の銀ナノ粒子分散液を調製し、前記銀ナノ粒子分散液を用いて、実施例１と同条件で釉薬を調製して抗菌性窯業製品を製造した後、滅菌率を求めて、抗菌性を評価した。結果を表１に示す。 In accordance with the method described in Example 1, as shown in Table 1, the silver nanoparticles, the 90% cumulative diameter D 90 of five different silver nanoparticle dispersion of the particle size distribution were prepared, the silver nano A glaze was prepared using the particle dispersion under the same conditions as in Example 1 to produce an antibacterial ceramic product, and then the sterilization rate was determined to evaluate the antibacterial properties. The results are shown in Table 1.
表１より、釉薬中での、銀ナノ粒子の、粒度分布の９０％累積径Ｄ90を１５０ｎｍ以下
としたとき、抗菌性窯業製品の表面に形成される銀ナノ粒子の平均粒子径を２００ｎｍ以下として、良好な抗菌性を付与できることが確認された。また、表１の試料Ｎｏ．２−３で製造した抗菌性窯業製品の表面を、走査型電子顕微鏡で観察したところ、図１に示すように、前記表面に、微細な銀ナノ粒子が形成されているのが確認された。
From Table 1, when the 90% cumulative diameter D 90 of the particle size distribution of silver nanoparticles in the glaze is 150 nm or less, the average particle diameter of the silver nanoparticles formed on the surface of the antibacterial ceramic product is 200 nm or less. As a result, it was confirmed that good antibacterial properties can be imparted. In addition, sample No. When the surface of the antibacterial ceramic product manufactured in 2-3 was observed with a scanning electron microscope, it was confirmed that fine silver nanoparticles were formed on the surface as shown in FIG.
実施例１に記載の方法に準拠して、銀ナノ粒子の、粒度分布の９０％累積径Ｄ90が８０ｎｍ、沈降量が、銀ナノ粒子の総量の０．０６重量％である銀ナノ粒子分散液を調製し、前記銀ナノ粒子分散液を用いて、分散剤の含有率が１．２重量％の釉薬を調製した後、前記釉薬を用いて、表２に示す焼成条件としたこと以外は実施例１と同様にして抗菌性窯業製品を製造し、滅菌率を求めて、抗菌性を評価した。結果を表２に示す。 In accordance with the method described in Example 1, the silver nanoparticles, 90% cumulative diameter D 90 of 80nm particle size distribution, sedimentation volume, silver nanoparticle dispersion is 0.06% by weight of the total amount of silver nanoparticles A liquid was prepared, and after using the silver nanoparticle dispersion liquid to prepare a glaze having a dispersant content of 1.2% by weight, the glaze was used except for the firing conditions shown in Table 2. An antibacterial ceramic product was produced in the same manner as in Example 1, the sterilization rate was determined, and the antibacterial property was evaluated. The results are shown in Table 2.
表２より、焼成の温度を８００〜１６００℃、時間を３０時間以下としたとき、抗菌性窯業製品の表面に形成される銀ナノ粒子の平均粒子径を２００ｎｍ以下として、良好な抗菌性を付与できることが確認された。なお、試料３−６の抗菌性窯業製品は、表面を観察しても銀ナノ粒子が観察されず、高温での焼成によって揮発して、失われてしまったことが確認された。 From Table 2, when the firing temperature is 800 to 1600 ° C. and the time is 30 hours or less, the average particle diameter of silver nanoparticles formed on the surface of the antibacterial ceramic product is 200 nm or less, and good antibacterial properties are imparted. It was confirmed that it was possible. In addition, it was confirmed that the antibacterial ceramic product of Sample 3-6 was lost due to volatilization by baking at a high temperature without observing silver nanoparticles even when the surface was observed.
実施例１に記載の方法に準拠して、銀ナノ粒子の、粒度分布の９０％累積径Ｄ90が３３ｎｍである銀ナノ粒子分散液を調製し、前記銀ナノ粒子分散液を用いて、表３に示すように、分散剤の含有率が異なる３種の釉薬を調製した後、前記釉薬を用いて、実施例１と同条件で抗菌性窯業製品を製造し、滅菌率を求めて、抗菌性を評価した。また、製造された抗菌性窯業製品の外観を観察した。結果を表３に示す。 In accordance with the method described in Example 1, the silver nanoparticles, 90% cumulative diameter D 90 of the particle size distribution is prepared silver nanoparticle dispersion is 33 nm, by using the silver nanoparticle dispersion, Table 3, after preparing three types of glazes with different dispersant contents, an antibacterial ceramic product was manufactured under the same conditions as in Example 1 using the glaze, and the sterilization rate was determined. Sex was evaluated. In addition, the appearance of the manufactured antibacterial ceramic products was observed. The results are shown in Table 3.
表３より、分散剤の含有率は、抗菌性窯業製品の外観を考慮すると１〜２０重量％であるのが好ましいことが確認された。 From Table 3, it was confirmed that the content of the dispersant is preferably 1 to 20% by weight in consideration of the appearance of the antibacterial ceramic product.
実施例１に記載の方法に準拠して、表４に示すように、銀または銀とパラジウムの合金からなる金属ナノ粒子を含み、前記金属ナノ粒子の、粒度分布の９０％累積径Ｄ90が３５〜４０ｎｍである金属ナノ粒子分散液を調製し、前記銀ナノ粒子分散液を用いて、分散剤の含有率が１２．５〜１５．０重量％の釉薬を調製した後、前記釉薬を用いて、実施例１と同条件で抗菌性窯業製品を製造し、滅菌率を求めて、抗菌性を評価した。分散剤としては、ポリアクリル酸（分子量５０００）を用いた。結果を表４に示す。 In accordance with the method described in Example 1, as shown in Table 4, metal nanoparticles composed of silver or an alloy of silver and palladium are included, and the 90% cumulative diameter D 90 of the particle size distribution of the metal nanoparticles is A metal nanoparticle dispersion liquid of 35 to 40 nm is prepared, and after using the silver nanoparticle dispersion liquid to prepare a glaze having a dispersant content of 12.5 to 15.0% by weight, the glaze is used. An antibacterial ceramic product was manufactured under the same conditions as in Example 1, the sterilization rate was determined, and the antibacterial property was evaluated. As the dispersant, polyacrylic acid (molecular weight 5000) was used. The results are shown in Table 4.
表４より、合金からなる金属ナノ粒子の場合、銀の含有割合は、合金の総量中の５０重量％以上、特に８０重量％以上であるのが好ましいことが確認された。 From Table 4, in the case of metal nanoparticles made of an alloy, it was confirmed that the silver content was preferably 50% by weight or more, particularly preferably 80% by weight or more, based on the total amount of the alloy.
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