JP5553333B2 - Water repellent and antifouling ceramics - Google Patents
Water repellent and antifouling ceramics Download PDFInfo
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- JP5553333B2 JP5553333B2 JP2009275066A JP2009275066A JP5553333B2 JP 5553333 B2 JP5553333 B2 JP 5553333B2 JP 2009275066 A JP2009275066 A JP 2009275066A JP 2009275066 A JP2009275066 A JP 2009275066A JP 5553333 B2 JP5553333 B2 JP 5553333B2
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Description
本発明は、食器、タイル、衛生陶器、碍子、ガラス板等の容器、陶磁器、保護材への適用に適した撥水・防汚性セラミックスに関する。 The present invention relates to a water-repellent and antifouling ceramic suitable for application to containers such as tableware, tiles, sanitary ware, insulators, glass plates, ceramics, and protective materials.
セラミックス成形体における素地又は釉薬層表面は親水性表面であり、水に対する吸着力が強く、例えば食器洗浄機においては電気使用量が多く、乾燥に多大なエネルギーを要するという問題があり、また、ご飯粒等による汚れが多いと水や電気の使用量も多くなるという問題がある。また、工業的用途として、アルカリ性や酸性等の腐蝕性物質を含む飛沫に対する保護用途とされる場合があるが、水溶液が水滴となって表面から除去されずに乾燥されると、アルカリ性や酸性等の腐蝕性物質の濃縮によりセラミックス表面が侵されるという問題も生じる。 The surface of the ceramic molded body or the glaze layer surface is a hydrophilic surface and has a strong adsorption power to water. For example, in a dishwasher, there is a problem that a large amount of electricity is used and a lot of energy is required for drying. There is a problem that the amount of water and electricity used increases when there is a lot of dirt due to grains. In addition, as industrial use, it may be used as protection against splashes containing corrosive substances such as alkalinity and acidity, but when the aqueous solution becomes water droplets and is not removed from the surface, it is alkaline or acidic. There is also a problem that the ceramic surface is affected by the concentration of the corrosive substance.
本発明者等は、先に、セラミックス表面にオキシジルコニウム塩や水酸化アルミニウムゾル、水酸化チタンゾル被膜を介して、フッ素系またはシリコン系物質膜を形成して撥水・防汚性を向上させることを提案した（特許文献１、２）が、このような撥水・防汚性物質膜を設けても、水滴が小さいと撥水・防汚性物質膜表面に物理的付着力が働き、例え９０°に傾けたとしても表面から水滴が滑り落ちることはなく、そのため、水切れ性が悪く、乾燥に際してのエネルギーが増大するという問題があることが判明した。このような問題は、水等の飛沫が腐蝕性物質を含んでいるような場合には、特に問題となり、水の蒸発により撥水・防汚性物質膜によっては、その表面が腐蝕されるという問題がある。 The present inventors first improve the water repellency and antifouling properties by forming a fluorine-based or silicon-based material film on the ceramic surface via an oxyzirconium salt, aluminum hydroxide sol, or titanium hydroxide sol film. (Patent Documents 1 and 2), even if such a water-repellent / antifouling substance film is provided, if the water droplets are small, physical adhesion acts on the surface of the water-repellent / antifouling substance film. Even when tilted at 90 °, water droplets do not slide off from the surface, and therefore it has been found that there is a problem that water drainage is poor and energy during drying increases. Such a problem is particularly problematic when water or other droplets contain a corrosive substance, and the surface of the water-repellent / antifouling substance film is corroded by water evaporation. There's a problem.
一方、ご飯茶碗内表面に表面粗さが２０〜３０ミクロンの凹凸を設け、ご飯つぶがくっつきにくくすることが知られている（特許文献３）が、ご飯茶碗等のセラミックス表面は親水性であり、例えば、食器洗浄器等に使用しても乾燥に際して多大な電気エネルギーを要するという問題がある。また、茶碗内表面に小さな半円球突起物を設け、茶碗とご飯粒の接触面積を小さくしてご飯を食べやすくすることも知られている（特許文献４）が、特許文献３と同様に、その表面は親水性であり、乾燥に際しては依然として多大な電気エネルギーを要するという問題があり、また、石膏型を使用して半円球突起物を成型することは困難である。 On the other hand, it is known that the surface roughness of the rice bowl is 20-30 microns and the surface of the ceramic such as rice bowl is hydrophilic. For example, even when used in a dishwasher or the like, there is a problem that a large amount of electric energy is required for drying. In addition, it is also known that a small hemispherical protrusion is provided on the inner surface of the tea bowl to make it easier to eat rice by reducing the contact area between the tea bowl and rice grains (Patent Document 4). The surface thereof is hydrophilic, and there is a problem that a great amount of electric energy is still required for drying, and it is difficult to mold a hemispherical projection using a plaster mold.
本発明は、水切れ性や防汚性に優れ、例えばセラミックス製保護板にあっては表面がアルカリ性や酸性等の腐蝕性物質により汚染されるという問題が少なく、長寿命とでき、また、例えばご飯茶碗等にあっては、使用する水の量や電力量を抑制でき、例えば食器洗浄機が使用される場合にはエネルギー消費量を節約できる撥水・防汚性セラミックスの提供を課題とする。 The present invention is excellent in water drainage and antifouling properties. For example, in a ceramic protective plate, there is little problem that the surface is contaminated with a corrosive substance such as alkali or acid, and it can have a long life. For tea bowls and the like, it is an object to provide water-repellent / antifouling ceramics that can reduce the amount of water and electric power to be used, and can save energy consumption when, for example, a dishwasher is used.
本発明の撥水・防汚性セラミックスは、セラミックス素地が焼成された後、該セラミックス素地表面が撥水物質により撥水処理されたセラミックス焼成成形体であって、前記撥水物質がフッ素樹脂によるコーティング膜、フッ素系またはシリコン系撥水撥油性物質、また、撥水性のジルコニア膜、また、酸化チタン含有の撥水性アルミナ膜の無機撥水膜から選ばれると共に前記セラミックス焼成成形体における表面形状として、底面直径が０．８ｍｍ〜３．４ｍｍの１／１５球状〜１／３球状の多数の凸部がそれぞれの底面円周を接して配列した形状とされるか、または前記多数の凸部が、その底面直径の１／２までの間隔をおいて相互に離間して配列した形状とされたことを特徴とする。 The water-repellent / antifouling ceramic of the present invention is a ceramic fired molded article obtained by firing a ceramic substrate and then subjecting the surface of the ceramic substrate to a water-repellent treatment with a water-repellent material , wherein the water-repellent material is made of a fluororesin. The surface shape of the ceramic fired molded body is selected from a coating film, a fluorine-based or silicon-based water- and oil-repellent substance, a water-repellent zirconia film, and an inorganic water-repellent film of a titanium oxide-containing water-repellent alumina film. The bottom surface diameter is a shape in which a large number of 1/15 spherical to 1/3 spherical projections having a diameter of 0.8 mm to 3.4 mm are arranged in contact with the circumference of each bottom surface, or the multiple projections are , And having a shape of being arranged apart from each other with an interval of up to ½ of the bottom diameter thereof.
前記撥水・防汚性セラミックスが、タイルであることを特徴とする。 The water-repellent / antifouling ceramic is a tile.
前記撥水・防汚性セラミックスが、ご飯茶碗、丼、飯器、またはボウルであり、球状凸部形状を底面直径が１．６ｍｍ〜２．７ｍｍの１／４球状〜１／３球状とすることを特徴とする。 The water-repellent / antifouling ceramic is a rice bowl, rice bowl, rice bowl, or bowl, and the spherical convex shape is a ¼ sphere to ３ sphere with a bottom diameter of 1.6 mm to 2.7 mm. It is characterized by that.
本発明の撥水・防汚性セラミックスは、その表面形状を底面直径が０．８ｍｍ〜３．４ｍｍで、かつ１／１５球〜１／３球状の多数の凸部を配列した形状とすると共にその表面を撥水処理するものであり、これにより形成された曲面と流路により水等の飛沫が移動し、除去できることを見いだしたものである。表面が平坦形状の場合には、小さい水滴では物理的付着力が発生するが、本発明における表面形状とする場合には、その物理的付着力に打ち勝つことができ、除去できることを見いだしたものである。そのため、本発明の撥水・防汚性セラミックスは、水切れ性・防汚性に優れ、また、洗浄・乾燥に際して水量や電力量等のエネルギー消費の少ないセラミックス成形体とできる。 The water repellent / antifouling ceramic of the present invention has a surface shape with a bottom surface diameter of 0.8 mm to 3.4 mm and a large number of projections of 1/15 spheres to 1/3 spheres arranged. The surface is subjected to water repellent treatment, and it has been found that splashes of water and the like can be moved and removed by the curved surface and the flow path formed thereby. In the case where the surface is flat, a physical adhesion force is generated with small water droplets, but in the case of the surface shape in the present invention, it was found that the physical adhesion force can be overcome and removed. is there. Therefore, the water-repellent / antifouling ceramics of the present invention are excellent in water drainage and antifouling properties, and can be formed into a ceramic molded body that consumes less energy such as the amount of water and electric power during washing and drying.
また、セラミックス成形体をご飯茶碗、丼、飯器、またはボウルとする場合には、その表面形状を底面直径が１．６ｍｍ〜２．７ｍｍの１／４球状〜１／３球状の多数の凸部を配列した形状とすると共にその表面を撥水処理することによりご飯等の粘着性物質の付着量を減少でき、汚れ率を低下できるので、食器洗浄機にあって洗浄に使用する水の使用量と共に、洗浄水の付着量を少なくできるので乾燥に際してのエネルギー消費を少なくできる。 In addition, when the ceramic molded body is a rice bowl, bowl, rice bowl, or bowl, the surface shape is a large number of ¼ spheres to 凸 spheres having a bottom diameter of 1.6 mm to 2.7 mm. By using a water-repellent treatment on the surface, the amount of sticky substances such as rice can be reduced and the soiling rate can be reduced by using a water-repellent surface treatment. Along with the amount, the amount of washing water attached can be reduced, so that energy consumption during drying can be reduced.
今後、各種製品の環境負荷に対する消費者の関心が高まり、例えば事業者には、カーボンフットプリント制度に対応すべき製品とすることが求められているが、本発明は、このカーボンフットプリント制度のあり方に関する論点と考え方（経済産業省、２００８年８月４日）で述べられている「使用・維持管理段階」にあたる値を飛躍的に低下させることを可能する技術である。 In the future, consumer interest in the environmental impact of various products will increase. For example, businesses are required to make products that should comply with the carbon footprint system. This is a technology that can drastically reduce the value corresponding to the “use / maintenance and management stage” described in the point of view and concept (METI, August 4, 2008).
本発明におけるセラミックスは、陶磁器やガラス器であり、まず、各種陶土、配合陶土等を石膏型を使用して成型した後、例えば９２０℃で素焼してセラミックス素地体とされる。そして、セラミックス素地体の表面に釉薬層が設けられるか、または設けないで、１３００℃で本焼成され、さらに撥水・防汚性物質が塗布されて撥水・防汚性処理され、撥水・防汚性セラミックス成形体とされる。 The ceramics in the present invention are ceramics or glassware. First, various ceramic clays, blended ceramic clays, and the like are molded using a gypsum mold, and then baked at, for example, 920 ° C. to obtain a ceramic body. Then, the surface of the ceramic base body is provided with or without a glaze layer, and is finally baked at 1300 ° C., further applied with a water-repellent / anti-fouling substance, and subjected to a water / repellent / anti-fouling treatment.・ An antifouling ceramic molded body.
図１は、撥水・防汚性セラミックスの断面を説明するための図で、図２（ａ）（ｂ）におけるＸ−Ｙでの断面図である。本発明の撥水・防汚性セラミックスは、石膏型を使用し、または彫り等により成型された後、素焼してセラミックス素地体１とされる。石膏型を使用した成型に際しては、図１におけるセラミックス素地体１として示すように、直方体素地表面として多数の凸部が配列した構造となるように成型される。 FIG. 1 is a view for explaining a cross section of a water-repellent / antifouling ceramic, and is a cross-sectional view taken along line XY in FIGS. 2 (a) and 2 (b). The water-repellent / antifouling ceramic of the present invention is formed into a ceramic body 1 by using a gypsum mold or molding it by engraving or the like and then baking it. At the time of molding using a plaster mold, as shown as a ceramic base body 1 in FIG. 1, it is molded so as to have a structure in which a large number of convex portions are arranged as a rectangular parallelepiped base body surface.
表面における球状凸部形状として、底面直径としては焼成前では１ｍｍ〜４ｍｍから選ばれ、凸部形状としては１／１５球〜１／３球状から選ばれる多数の凸部が配列するように成型するとよい。得られる成型体には、釉薬層２がディッピング等により膜厚０．１ｍｍ〜０．５ｍｍで設けられるか、または設けないで、本焼成される。なお、焼成後、後述するように、撥水・防汚性膜が設けられる。 As the spherical convex shape on the surface, the bottom diameter is selected from 1 mm to 4 mm before firing, and the convex shape is molded so that a large number of convex portions selected from 1/15 sphere to 1/3 sphere are arranged. Good. In the obtained molded body, the glaze layer 2 is provided with a film thickness of 0.1 mm to 0.5 mm by dipping or the like, or is fired without being provided. In addition, after baking, a water-repellent / antifouling film is provided as described later.
焼成前では、成型体における底面直径が１ｍｍ〜４ｍｍである場合、成型材料における組成や収縮性から、焼成後、釉薬層含め、底面直径が０．８ｍｍ〜３．４ｍｍの凸部とされる。凸部形状としては、図１に１／３球を例として示すように、底面直径と球形状を同一のものとする多数の凸部にされるとよい。また、底面直径、または球形状を相違する複数種類の凸部形状を組合せた配列となるように成形してもよい。 Before firing, when the bottom surface diameter of the molded body is 1 mm to 4 mm, the bottom surface diameter including the glaze layer is a convex part having a bottom surface diameter of 0.8 mm to 3.4 mm after firing due to the composition and shrinkage of the molding material. As the convex shape, as shown in FIG. 1 as an example of a 1/3 sphere, it is preferable that the convex shape be a large number of convex portions having the same bottom diameter and spherical shape. Moreover, you may shape | mold so that it may become the arrangement | sequence which combined multiple types of convex part shape from which a bottom face diameter or a spherical shape differs.
図１に示すように、多数の凸部がそれぞれの底面円周を接して配列した形状となるように成型され、焼成されたものである。なお、本発明にあっては、「１／ｎ球状凸部」（ｎ＝３〜１５）とは、焼成後にあって、直径を０．９〜３．６ｍｍとする球体の直径において、１／ｎの位置で輪切りにして形成される１／ｎ球体を意味し、また、「底面直径」とは、その１／ｎ球体における「円形底面の直径」を意味する。図１において、凸部における底面直径は（Ｌ）で示される。なお、１／２球状凸部においては、球の「直径」と１／２球における「底面直径」とが一致する。 As shown in FIG. 1, a large number of convex portions are molded and fired so as to have a shape in which the bottom surface circumferences are in contact with each other. In the present invention, the term “1 / n spherical projection” (n = 3 to 15) means that after firing, the diameter of a sphere having a diameter of 0.9 to 3.6 mm is 1 / n. The 1 / n sphere formed by slicing at the position of n means the “bottom diameter” means the “diameter of the circular bottom surface” in the 1 / n sphere. In FIG. 1, the bottom surface diameter of the convex portion is indicated by (L). In the ½ spherical convex portion, the “diameter” of the sphere and the “bottom diameter” of the ½ sphere coincide.
焼成後での球状凸部における底面直径が０．８ｍｍ未満、また、底面直径が３．４ｍｍより大きい場合、かつ、１／１５球未満の凸部形状（例えば１／２０球状）であると、撥水・防汚性セラミックス表面において水滴の付着力に打ち勝つ力が弱くなり、流路が形成されず、水滴の除去性が低下するので好ましくない。また、１／３球より大きい凸部形状（例えば１／２球（半球））であると、石膏型等を利用した成型性が困難となる。 When the bottom surface diameter of the spherical convex portion after firing is less than 0.8 mm, the bottom surface diameter is larger than 3.4 mm, and the convex shape is less than 1/15 sphere (for example, 1/20 spherical) The water repellent / antifouling ceramic surface is not preferable because the strength to overcome the adhesion of water droplets is weakened, the flow path is not formed, and the water droplet removability is reduced. Further, if the convex shape is larger than 1/3 sphere (for example, 1/2 sphere (hemisphere)), moldability using a plaster mold or the like becomes difficult.
そして、底面直径が３．４ｍｍで１／１５球形状の場合には、凸部間での深さは０．２ｍｍ程度であり、水滴の流路を形成でき、本発明の範囲である。 When the bottom diameter is 3.4 mm and a 1/15 spherical shape, the depth between the convex portions is about 0.2 mm, and a water droplet channel can be formed, which is within the scope of the present invention.
また、頂点間距離（図１における「ｌ」）は、図１、および図４における配置にあっては、０．８ｍｍ〜３．４ｍｍである。 Further, the distance between the vertices (“l” in FIG. 1) is 0.8 mm to 3.4 mm in the arrangement in FIGS. 1 and 4.
また、図３の配置では多数の凸部が、図１、および図４における配置にあって、その底面直径の１／２までの間隔（図３での「ｍ」）をおいて相互に離間して配列した形状とするものであるが、底面直径の１／２を超える間隔をおいて相互に離間した配列とすると平坦部が多くなり、水滴の付着力に打ち勝つ力が弱くなり、流路が形成されず、水滴の除去性に問題となる。なお、図３の配置においては、凸部間にあって谷部を平坦状に図示するが、谷部を凹状とし、水滴の流路を形成してもよい。また、図３における配置では、底面直径が０．８ｍｍの場合には、垂直・水平方向で隣接する頂点間距離は０．８ｍｍ〜１．２ｍｍであり、また、底面直径が３．４ｍｍの場合には、３．４ｍｍ〜５．１ｍｍ程度である。 Further, in the arrangement of FIG. 3, a large number of convex portions are arranged in the arrangements of FIG. 1 and FIG. 4, and are separated from each other with an interval (“m” in FIG. 3) up to ½ of the bottom diameter. However, if the arrangement is separated from each other with an interval exceeding the half of the bottom diameter, the flat portions will increase, and the force to overcome the adhesion of water drops will be weakened. Is not formed, which causes a problem in water droplet removal. In the arrangement of FIG. 3, the valley is illustrated as being flat between the convex portions, but the valley may be concave to form a water droplet flow path. Further, in the arrangement in FIG. 3, when the bottom diameter is 0.8 mm, the distance between adjacent vertices in the vertical and horizontal directions is 0.8 mm to 1.2 mm, and the bottom diameter is 3.4 mm. Is about 3.4 mm to 5.1 mm.
本発明においては図１、図３、図４に示すように、焼成後における凸部間での深さとしては、０．１ｍｍ〜１．３ｍｍとするとよく、水滴の流路が形成され、水の除去性に優れるものである。 In the present invention, as shown in FIGS. 1, 3, and 4, the depth between the protrusions after firing may be 0.1 mm to 1.3 mm, and a water droplet flow path is formed. It has excellent removability.
図２は、図１、図４における撥水・防汚性セラミックス成形体を上面から見た図（平面図）で、（ａ）は凸部配列として水平垂直方向において平行に凸部が配列された状態である。この配列のＸ−Ｙ方向での断面は図１に示されるものに相当する。また、この配列の対角線方向における谷部にあっては、図３の配置のごとく、平坦状であっても、また、凸部間にあって、凹状に形成されてもよい。また、図２（ｂ）に示すごとく、ずらして配列したものでもよく、より凸部の配置密度の高い状態とできる。 FIG. 2 is a view (plan view) of the water-repellent / antifouling ceramic molded body in FIGS. 1 and 4 as viewed from above (plan view). FIG. It is in the state. The cross section in the XY direction of this arrangement corresponds to that shown in FIG. In addition, the valleys in the diagonal direction of this array may be flat as shown in FIG. 3 or may be concave between the convex portions. Moreover, as shown in FIG.2 (b), it may be shifted and it can be in the state where the arrangement density of a convex part is higher.
また、図３における撥水・防汚性セラミックス成形体においては、水平垂直方向において平行に凸部が配列された状態において、一定間隔おいて配列したものとすればよく、水滴の付着力に打ち勝つ力を付与できる。また、図２（ｂ）のごとく、隣接する相互の凸部を一定間隔をおいて配列したものとすると、より平坦部が少なくなり、水滴の付着力に打ち勝つ力が強く、また、流路が形成され、水滴の移動性に優れるものとなり、乾燥時間等を短縮できる。 Further, in the water repellent / antifouling ceramic molded body in FIG. 3, it is sufficient that the convex portions are arranged in parallel in the horizontal and vertical directions, and they are arranged at regular intervals, and the adhesion force of water droplets is overcome. Can give power. In addition, as shown in FIG. 2B, if the adjacent convex portions are arranged at regular intervals, the flat portion is reduced, the force to overcome the adhesion of water droplets is strong, and the flow path is It is formed and has excellent water droplet mobility, and the drying time and the like can be shortened.
次に、本発明の撥水・防汚性セラミックス成形体をご飯茶碗、丼、飯器、またはボウルとする場合について説明する。ご飯茶碗とする場合には、ご飯茶碗の内面にあって焼成前で底面直径としては２ｍｍ〜３ｍｍ、焼成後で底面直径が１．７ｍｍ〜２．３ｍｍで、１／４球〜１／３球状から選ばれる多数の凸部が配列するように成型するとよく、図１、図３に示した凸状部の配列とするとよい。図４に示すものでは、ご飯等の粘着性物質の接触を少なくできず、好ましくない。ご飯茶碗の場合、凸部形状における底面直径が１．７ｍｍ〜２．３ｍｍで、その形状が１／４球状〜１／３球状とするとよく、これにより飯つぶと茶碗内面との接触面積を少なくでき、ご飯による汚れの少ないものとできるので、洗浄水の使用量を減少させることができる。 Next, the case where the water repellent / antifouling ceramic molded body of the present invention is used as a rice bowl, bowl, rice bowl, or bowl will be described. In the case of a rice bowl, it is on the inner surface of the rice bowl and has a bottom diameter of 2 mm to 3 mm before baking, and a bottom diameter of 1.7 mm to 2.3 mm after baking. It is good to shape | mold so that many convex parts chosen from may be arranged, and it is good to set it as the arrangement | sequence of the convex-shaped part shown in FIG. 1, FIG. The thing shown in FIG. 4 is not preferable because it cannot reduce the contact of sticky substances such as rice. In the case of rice bowls, the bottom diameter of the convex shape is 1.7 mm to 2.3 mm, and the shape is preferably ¼ sphere to １ ／ sphere, which reduces the contact area between the rice crumb and the inner surface of the bowl. It is possible to reduce the amount of washing water used because it is less contaminated with rice.
ご飯茶碗は、一般には逆円錐形状の内表面とされるが、内表面において凸状部を単一ドットで成型しようとすると、茶碗の縁部近傍と底部（中心部）近傍とでは単一ドットでの展開が難しい。そのため、茶碗縁部近傍と茶碗底部近傍とおいて、凸部形状として底面直径が例えば焼成後１．８ｍｍ、２．３ｍｍとするものから、また、頂点間距離が１．８ｍｍ、２．３ｍｍ、２．８ｍｍ、３．３ｍｍとするものの中から適宜選択して組合せるとよい。 In general, rice bowls have an inverted conical inner surface, but if you try to mold the convex part with a single dot on the inner surface, there will be a single dot near the edge and the bottom (center) of the bowl. Difficult to deploy in Therefore, in the vicinity of the edge of the tea bowl and the vicinity of the bottom of the bowl, the bottom diameter is, for example, 1.8 mm, 2.3 mm after baking, and the distance between the apexes is 1.8 mm, 2.3 mm, 2 .8 mm and 3.3 mm may be appropriately selected and combined.
特に、ご飯茶碗の縁部近傍にあっては、底面直径を２ｍｍ、頂点間距離を２．５ｍｍとして成型した後、焼成後底面直径が１．８ｍｍ、頂点間距離が２．３ｍｍとし、また、茶碗の底部近傍にあっては、底面直径を２ｍｍ、頂点間距離を２ｍｍとして成型した後、焼成後にあっては底面直径が１．８ｍｍ、頂点間距離が１．８ｍｍとする組合せとするとよく、ご飯等の粘着性物質による汚れ残り率が少なく、好ましいことがわかった。 In particular, in the vicinity of the edge of the rice bowl, after molding with a bottom diameter of 2 mm and a distance between vertices of 2.5 mm, the bottom diameter after firing is 1.8 mm and a distance between the vertices is 2.3 mm. In the vicinity of the bottom of the tea bowl, after molding with a bottom diameter of 2 mm and a distance between vertices of 2 mm, after baking, the bottom diameter is 1.8 mm and the distance between the vertices is 1.8 mm. It was found that the rate of remaining dirt due to sticky substances such as rice was small and preferable.
本発明の撥水・防汚性セラミックス成形体における釉薬としては、珪灰石釉、石灰釉、亜鉛釉、灰釉等を例示され、釉薬層としては、素焼きしたセラミックス成形体にディッピング法、スプレー法等により施釉し、本焼成後の平均膜厚が０．１〜０．５ｍｍの釉薬層とされる。 Examples of the glaze in the water-repellent / antifouling ceramic molded body of the present invention include wollastonite, lime, zinc, and ash, and the glaze layer includes a dipping method, a spray method, etc. The glaze layer has an average film thickness of 0.1 to 0.5 mm after the main baking.
また、焼成後のセラミックス素地表面、または釉薬層表面には撥水・防汚性物質により撥水・防汚性処理が施される。撥水・防汚性物質としてはフッ素樹脂によるコーティング膜が例示され、例えば商品名Ｘ−２４−７８９０（信越化学（株）製）等が例示され、セラミックス成形体面にディッピングにより塗布され、撥水・防汚性膜を形成するものである。 In addition, the surface of the ceramic base or the glaze layer after firing is subjected to a water-repellent / antifouling treatment with a water-repellent / antifouling substance. Examples of the water repellent / antifouling substance include a coating film made of a fluororesin, for example, trade name X-24-7890 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.・ It forms an antifouling film.
また、フッ素系またはシリコン系撥水撥油性物質が例示され、CF3(CH2)2Si(OCH3)3、CF3(CF2)5(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2SiCH3(OCH3)2 、CF3(CF2)3(CH2)2Si(OCH3)3、CF3(CF2)7(CH2)2SiCl3等の炭素数が１〜２０のパーフルオロアルキル基を含むシラン化合物またはその加水分解した縮合体、その他、ノニオン系フッソ系界面活性剤、パーフルオロ安息香酸、Ｎ−〔３−（トリメトキシシリル）プロピル〕−Ｎ−ｎ−プロピルパーフルオロオクチルスルホンアミド、ポリジメチルシロキサン等が挙げられる。これらの撥水・防汚性物質は、セラミックス上にジルコニア膜、または、アルミナ膜を介して塗布形成した後、乾燥、または焼成し、撥水撥油性層が成膜される。 Further, fluorine-based or silicon-based water and oil repellent materials are exemplified, and CF 3 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCH 3 (OCH 3 ) 2 , CF 3 (CF 2 ) 3 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 and other silane compounds containing a perfluoroalkyl group having 1 to 20 carbon atoms, hydrolyzed condensates thereof, and other nonionic compounds Examples thereof include a fluorosurfactant, perfluorobenzoic acid, N- [3- (trimethoxysilyl) propyl] -Nn-propyl perfluorooctylsulfonamide, polydimethylsiloxane, and the like. These water-repellent / antifouling substances are applied and formed on ceramics via a zirconia film or an alumina film, and then dried or fired to form a water- and oil-repellent layer.
また、撥水・防汚性処理として撥水性のジルコニア膜、また、酸化チタン含有の撥水性アルミナ膜などの無機撥水膜も挙げられる。
以下、本発明を実施例により詳細に説明する。
Examples of the water / oil-repellent treatment include water-repellent zirconia films and inorganic water-repellent films such as titanium oxide-containing water-repellent alumina films.
Hereinafter, the present invention will be described in detail with reference to examples.
（実施例１）
天草撰上陶土を使用し、図１、図２（ａ）に示すように、タイル（７．２ｃｍ×７．２ｃｍ、厚さ０．６ｃｍ）形状の素地部分に底面直径が２ｍｍの１／３球状凸部が、頂点間距離水平垂直方向２ｍｍで、平行列で配置するように石膏型を使用して成型し、素焼温度９２０℃でセラミックス素地１を作成する。ついで、珪灰石釉を使用して釉薬層２をディッピングにより厚さ０．１ｍｍで形成し、１３００℃で本焼成を行った。その後、フッ素樹脂（商品名Ｘ−２４−７８９０（信越化学（株）製））を塗布して撥水・防汚性膜を形成し、本発明のセラミックス成形体とした。
Example 1
As shown in Fig. 1 and Fig. 2 (a), 1/3 of the base diameter of the tile (7.2cm x 7.2cm, thickness 0.6cm) is used as the base diameter of 2mm. A spherical base is formed using a plaster mold so that the spherical protrusions are arranged in parallel rows with a vertex-to-vertex distance of 2 mm in the vertical direction, and the ceramic substrate 1 is created at a firing temperature of 920 ° C. Subsequently, the glaze layer 2 was formed with a thickness of 0.1 mm by dipping using a wollastonite casket and subjected to main firing at 1300 ° C. Thereafter, a fluororesin (trade name: X-24-7890 (manufactured by Shin-Etsu Chemical Co., Ltd.)) was applied to form a water-repellent / antifouling film to obtain a ceramic molded body of the present invention.
得られたセラミックス成形体は、タイル（６．５ｃｍ×６．５ｃｍ、厚さ０．５ｃｍ）形状の素地部分に底面直径が１．８ｍｍの１／３球状凸部が、頂点間距離水平垂直方向１．８ｍｍで配置した形状のものであり、また、凸部間における最深部での深さは０．５ｍｍであった。
（実施例２）
実施例１において、凸部形状を底面直径が４ｍｍの１／３球状凸部が、頂点間距離水平垂直方向４ｍｍで、平行列で配置するように石膏型を使用して成型した以外は、実施例１と同様に焼成して本発明のセラミックス成形体とした。
The obtained ceramic molded body has a tile (6.5 cm × 6.5 cm, thickness 0.5 cm) base portion having a 1/3 spherical convex portion with a bottom surface diameter of 1.8 mm, a vertex distance, a horizontal vertical direction The shape was arranged at 1.8 mm, and the depth at the deepest portion between the convex portions was 0.5 mm.
(Example 2)
In Example 1, except that the convex shape was formed using a gypsum mold so that the 1/3 spherical convex portion having a bottom surface diameter of 4 mm was arranged in parallel rows at a distance between apexes of 4 mm in the horizontal and vertical directions. It fired like Example 1 and it was set as the ceramic molded object of this invention.
得られたセラミックス成形体は、タイル（６．５ｃｍ×６．５ｃｍ、厚さ０．５ｃｍ）形状の素地部分に底面直径が３．６ｍｍの１／３球状凸部が、頂点間距離水平垂直方向３．６ｍｍで配置した形状のものであり、また、凸部間における最深部での深さは１．１ｍｍであった。 The obtained ceramic molded body has a tile (6.5 cm × 6.5 cm, thickness 0.5 cm) base portion having a 1/3 spherical convex portion with a bottom diameter of 3.6 mm, a vertex-to-vertex distance, a horizontal vertical direction It was the thing arrange | positioned at 3.6 mm, and the depth in the deepest part between convex parts was 1.1 mm.
（実施例３）
実施例１において、図３に示すように、凸部形状として、底面直径が２ｍｍの１／３球状凸部が、頂点間距離を水平垂直方向で２．５ｍｍ（凸部間距離ｍ＝０．５ｍｍ）として配置したものであり、図２（ａ）同様に、平行列で配置するように石膏型を使用して成型した以外は、実施例１と同様に、焼成して本発明のセラミックス成形体とした。
(Example 3)
In Example 1, as shown in FIG. 3, a 1/3 spherical convex portion having a bottom surface diameter of 2 mm as the convex shape has a distance between vertices of 2.5 mm in the horizontal and vertical directions (distance between convex portions m = 0. 5 mm), and the ceramic molding of the present invention by firing as in Example 1 except that the gypsum mold was molded so as to be arranged in parallel rows as in FIG. The body.
得られたセラミックス成形体は、タイル（６．５ｃｍ×６．５ｃｍ、厚さ０．５ｃｍ）形状の素地部分に底面直径が１．８ｍｍの１／３球状凸部が、頂点間距離水平垂直方向２．３ｍｍで配置した形状のものであり、また、凸部間における最深部での深さは０．４ｍｍであった。 The obtained ceramic molded body has a tile (6.5 cm × 6.5 cm, thickness 0.5 cm) base portion having a 1/3 spherical convex portion with a bottom surface diameter of 1.8 mm, a vertex distance, a horizontal vertical direction It was the shape arrange | positioned by 2.3 mm, and the depth in the deepest part between convex parts was 0.4 mm.
また、セラミックス成形体を、ご飯茶碗（焼成後の内面直径１１．８ｃｍ、深さ３．８ｃｍ）として成形した。 Moreover, the ceramic molded body was molded as a rice bowl (inner diameter after firing 11.8 cm, depth 3.8 cm).
（実施例４）
天草撰上陶土を使用し、図４、図２（ａ）に示すように、タイル（７．２ｃｍ×７．２ｃｍ、厚さ０．６ｃｍ）形状の素地部分に底面直径が１ｍｍの１／１５球状凸部が、頂部間距離水平垂直方向１ｍｍで、平行列で配置するように素地表面を直接彫ることにより成型し、素焼温度９２０℃でセラミックス素地１を作成した後、１３００℃で本焼成を行った。その後、フッ素樹脂（商品名Ｘ−２４−７８９０（信越化学（株）製））を塗布して撥水・防汚性膜を形成し、本発明のセラミックス成形体とした。
Example 4
As shown in Fig. 4 and Fig. 2 (a), using Amakusa-bamboo clay, 1/15 with a bottom diameter of 1mm on the base of the tile (7.2cm x 7.2cm, thickness 0.6cm) The spherical convex part is formed by directly carving the surface of the base so as to be arranged in parallel rows with a horizontal distance between the tops of 1 mm in the horizontal direction. went. Thereafter, a fluororesin (trade name: X-24-7890 (manufactured by Shin-Etsu Chemical Co., Ltd.)) was applied to form a water-repellent / antifouling film to obtain a ceramic molded body of the present invention.
得られたセラミックス成形体は、タイル（６．５ｃｍ×６．５ｃｍ、厚さ０．５ｃｍ）形状の素地部分に底面直径が０．９ｍｍの１／１５球状凸部が、頂点間距離が水平垂直方向で０．９ｍｍとするものであり、また、頂点間における最深部での深さは０．１ｍｍであった。 The obtained ceramic molded body has a tile (6.5 cm × 6.5 cm, thickness 0.5 cm) base portion having a 1/15 spherical convex portion with a bottom surface diameter of 0.9 mm and a vertex-to-vertex distance of horizontal and vertical. The depth was 0.9 mm in the direction, and the depth at the deepest part between the apexes was 0.1 mm.
（比較例１）
実施例１において、凸部形成、および撥水・防汚性処理を行わない以外は、実施例１と同様にしてセラミックス成形体とした。
(Comparative Example 1)
In Example 1, a ceramic molded body was obtained in the same manner as in Example 1 except that the convex portion formation and the water repellency / antifouling treatment were not performed.
（比較例２）
実施例１において、凸部形成を行わない以外は、実施例１と同様にしてセラミックス成形体とした。
(Comparative Example 2)
In Example 1, a ceramic molded body was obtained in the same manner as in Example 1 except that the convex portion was not formed.
（比較例３）
比較例２において、セラミックス素地上に、ジルコニア薄膜を介してフッ素樹脂（商品名Ｘ−２４−７８９０（信越化学（株）製））をディップ法により塗布し、３００℃で焼成して、焼成後膜厚０．２μｍの撥水撥油膜を形成した以外は、比較例２と同様にしてセラミックス成形体とした。
(Comparative Example 3)
In Comparative Example 2, a fluororesin (trade name X-24-7890 (manufactured by Shin-Etsu Chemical Co., Ltd.)) was applied to the ceramic substrate via a zirconia thin film by a dip method, fired at 300 ° C., and after firing A ceramic molded body was obtained in the same manner as in Comparative Example 2 except that a water- and oil-repellent film having a thickness of 0.2 μm was formed.
（比較例４）
実施例３において、撥水・防汚性処理を行わない以外は、実施例３と同様にしてセラミックス成形体とした。
(Comparative Example 4)
In Example 3, a ceramic molded body was obtained in the same manner as in Example 3 except that the water repellency / antifouling treatment was not performed.
また、セラミックス成形体を、ご飯茶碗（焼成後の内面直径１１．８ｃｍ、深さ３．８ｃｍ）として成形した。 Moreover, the ceramic molded body was molded as a rice bowl (inner diameter after firing 11.8 cm, depth 3.8 cm).
（比較例５）
実施例３において、凸部形状を底面直径が２ｍｍの１／３球状凸部が、頂点間距離水平垂直方向４ｍｍで、図２（ａ）同様に、平行列で配置するように石膏型を使用して成型した以外は、実施例３と同様に焼成してセラミックス成形体とした。
(Comparative Example 5)
In Example 3, a gypsum mold is used so that the convex shape is a 1/3 spherical convex portion having a bottom surface diameter of 2 mm, and the intervertex distance is 4 mm in the horizontal and vertical directions, as in FIG. 2A. Except for molding, a ceramic molded body was fired in the same manner as in Example 3.
得られたセラミックス成形体は、タイル（６．５ｃｍ×６．５ｃｍ、厚さ０．５ｃｍ）形状の素地部分に底面直径が１．８ｍｍの１／３球状凸部が、頂点間距離水平垂直方向３．６ｍｍで配置した形状のものであり、また、凸部間における最深部での深さは０．４ｍｍであった。 The obtained ceramic molded body has a tile (6.5 cm × 6.5 cm, thickness 0.5 cm) base portion having a 1/3 spherical convex portion with a bottom surface diameter of 1.8 mm, a vertex distance, a horizontal vertical direction The shape was arranged at 3.6 mm, and the depth at the deepest portion between the convex portions was 0.4 mm.
実施例１〜実施例４で得たセラミックス成形体について、その表面に注射器を使用して１０μｌ（ミクロンリットル）の水滴を落下させたところ、接触角は１３０．６°であった。また、その表面に２μｌ（ミクロンリットル）の水滴を付着させる実験を行ったところ、水滴の球面の凸部が成形体表面に付け、針を遠ざけても水滴は針から離れることなく、接地させても注射針の先端にすぐ戻ってしまうという現象が生じ、見掛けの付着力が低下し、水滴が付きにくいことがわかった。また、連続的に２μｌの水滴を落下させたところ、水滴が球面の凸部より低くなった谷部に移動し、この谷部は隣接するところと連続になっており、傾斜させると低い方に移動し、この谷部で移動するうち他の水滴と一緒になって、質量が増し、滑り落ちるようになった。また、この現象は少しの振動で、より顕著になった。 When a 10 μl (micron liter) water droplet was dropped on the surface of the ceramic molded bodies obtained in Examples 1 to 4 using a syringe, the contact angle was 130.6 °. In addition, when an experiment was carried out to attach a 2 μl (micron liter) water droplet to the surface, a spherical convex portion of the water droplet was attached to the surface of the molded product, and even if the needle was moved away, the water droplet did not leave the needle and was grounded. However, it was found that the phenomenon of immediately returning to the tip of the injection needle occurred, the apparent adhesion was reduced, and water droplets were difficult to adhere. In addition, when 2 μl of water droplets are continuously dropped, the water droplets move to a valley that is lower than the convex portion of the spherical surface, and this valley is continuous with the adjacent portion, and when tilted, the lower one As it moved and moved in this valley, it increased in mass with other water droplets and began to slide down. This phenomenon became more prominent with a little vibration.
これに対して、比較例１のものは、その表面が親水性のため、うすく濡れ広がり、水玉状にもならなかった。また、比較例２のものは、その表面に注射器を使用して１０μｌ（ミクロンリットル）の水滴を落下させたところ、接触角は１３１．９°であり、また、その表面に２μｌの水滴を付着させる実験を行ったところ、水滴の球面の凸部が成形体表面に付き、針を遠ざけると針から離れ、表面で水滴となった。このセラミックス成形体を傾け、９０°としても水滴はセラミックス成形体を滑り落ちることはなかった。 On the other hand, since the surface of Comparative Example 1 was hydrophilic, it was slightly wet and spread, and did not become polka dots. In the case of Comparative Example 2, when a 10 μl (micron liter) water droplet was dropped on the surface using a syringe, the contact angle was 131.9 °, and 2 μl of water droplet adhered to the surface. As a result of the experiment, the spherical convex portion of the water droplet was attached to the surface of the molded body, and when the needle was moved away from the needle, it was separated from the needle and became a water droplet on the surface. Even when this ceramic molded body was tilted to 90 °, water droplets did not slide down the ceramic molded body.
また、実施例１と比較例２で得たタイル状のセラミックス成型体におけるそれぞれの撥水・防汚処理面に水を噴霧した後、９０°に傾斜し、その表面を観察したところ、実施例１のセラミックス成型体にあっては、その表面に水滴は認められなかったが、比較例２のものは、表面に微小な水滴が多数付着した状態であった。 Moreover, after spraying water on each water-repellent / antifouling treated surface in the tile-shaped ceramic molded body obtained in Example 1 and Comparative Example 2, the surface was inclined at 90 ° and the surface was observed. In the ceramic molded body of No. 1, water droplets were not observed on the surface, but in the case of Comparative Example 2, many fine water droplets adhered to the surface.
また、実施例４のものを除き、実施例１〜３、比較例１〜５で得られたセラミックス成形体に、標準水量で炊いた米飯を厚さ１ｃｍとなるように載せ、１．２ｇ／ｃｍ2 の重りを載せ、１時間放置した後、裏返し、ご飯つぶと重りを取り除き、４時間放置した。その後、家庭用食器洗浄器を使用し、洗剤なしのモードで洗浄後、ポビドンヨード５倍希釈液を使用して染色し、画像処理により汚れ残り面積率（％）を算出した。下記の表１、表２に汚れ残り面積率（％）を示す。また、図５に、洗浄前の実施例３で得た碗について同様の試験を実施した汚れ状況の写真を示し、図６に洗浄前の比較例４で得た碗の同様の汚れ状況の写真を示す。 Moreover, except the thing of Example 4, it puts in the ceramic molded body obtained in Examples 1-3 and Comparative Examples 1-5 so that the cooked rice cooked with the standard amount of water may become thickness 1cm, and 1.2g / A weight of cm 2 was placed and allowed to stand for 1 hour, then turned over, the rice crushing and the weight were removed, and left for 4 hours. Thereafter, using a household dishwasher, after washing in a mode without detergent, dyeing was performed using a 5-fold dilution of povidone iodine, and the remaining area ratio (%) of dirt was calculated by image processing. Tables 1 and 2 below show the remaining area ratio (%) of dirt. Also, FIG. 5 shows a photograph of the dirt situation in which the same test was performed on the soot obtained in Example 3 before washing, and FIG. 6 shows a photograph of the same dirt situation of the soot obtained in Comparative Example 4 before washing. Indicates.
表から、実施例１〜実施例３で示すものは、ご飯粒による汚れを低下させることがわかる。 From the table, it can be seen that those shown in Examples 1 to 3 reduce the stain caused by the rice grains.
本発明は、アルカリ性や酸性等の腐蝕性物質を含む飛沫に対するセラミックス製保護板やご飯茶碗等に利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be used for ceramic protective plates, rice bowls, and the like against splashes containing corrosive substances such as alkali and acid.
１はセラミックス素地体、２は釉薬層 1 is ceramic body, 2 is glaze layer
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