JP2012177195A - Method for manufacturing cooking tool - Google Patents
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Abstract
Description
本発明は、調理器具の製造方法に関し、特に、調理中に付着した食品の焦げ付き汚れや油汚れを、水拭き程度で簡単に除去することが可能な調理器具を簡単な装置で簡便に製造することが可能な調理器具の製造方法に関するものである。 The present invention relates to a method of manufacturing a cooking utensil, and in particular, a cooking utensil that can easily remove burnt dirt and oil stains of food adhering during cooking with a level of wiping with a simple device. It is related with the manufacturing method of the cooking utensil which can be performed.
従来、焼肉用プレートやオーブン皿等の加熱を要する調理器具においては、食品の焦げ付き汚れを簡単に除去するために、例えば、酸化ジルコニウムを主成分とする薄膜を基体の表面に成膜した調理器具が提案されている（例えば、特許文献１参照）。 2. Description of the Related Art Conventionally, in cooking utensils that require heating, such as grilled meat plates and oven dishes, for example, a cooking utensil in which a thin film mainly composed of zirconium oxide is formed on the surface of a substrate in order to easily remove burnt dirt from foods. Has been proposed (see, for example, Patent Document 1).
しかしながら、上述した従来の調理器具においては、食品の焦げ付き汚れは比較的簡単に除去することができるものの、油汚れについては、水拭き程度の作業では容易に除去することができないという問題点があった。
そこで、食品の焦げ付き汚れはもちろんのこと、油汚れをも簡単に除去することができる調理器具の出現が強く望まれていた。
However, in the above-mentioned conventional cooking utensils, although the burnt dirt of food can be removed relatively easily, the oil dirt cannot be easily removed by a work of wiping with water. It was.
Accordingly, there has been a strong demand for the appearance of cooking utensils that can easily remove oil stains as well as food stains.
本発明は、上記の課題を解決するためになされたものであって、調理中に付着した食品の焦げ付き汚れや油汚れを、水拭き程度で簡単に除去することができる調理器具の製造方法を提供することを目的とする。 The present invention has been made in order to solve the above-described problems, and provides a method for manufacturing a cooking utensil that can easily remove burnt dirt and oil stains of food adhering during cooking with a degree of water wiping. The purpose is to provide.
本発明者等は、上記の課題を解決するために鋭意検討を行った結果、基体の表面のうち、少なくとも、食品に触れる虞のある部分または油汚れが生じる虞のある部分に、ケイ素（Ｓｉ）と、ジルコニウム（Ｚｒ）と、酸素（Ｏ）とを含有し、前記ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、前記ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、前記酸化ケイ素（ＳｉＯ２）の、前記酸化ジルコニウム（ＺｒＯ２）と前記酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である薄膜を成膜すれば、調理中に付着した食品の焦げ付き汚れや油汚れを、水拭き程度で簡単に除去することができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-described problems, the present inventors have found that silicon (Si) is present on at least a portion of the surface of the substrate that may come into contact with food or a portion that may be contaminated with oil. ), Zirconium (Zr), and oxygen (O), when the silicon (Si) is converted into silicon oxide (SiO 2 ) and the zirconium (Zr) is converted into zirconium oxide (ZrO 2 ), respectively. of, the silicon oxide (SiO 2), if a thin film weight percentage is less than 1 wt% or more and 40 wt% relative to the total amount of the zirconium oxide the silicon oxide (ZrO 2) and (SiO 2) The present inventors have found that burnt dirt and oil stains on foods attached during cooking can be easily removed by wiping with water, and the present invention has been completed.
すなわち、本発明の調理器具の製造方法は、ジルコニウムアルコキシド、ジルコニウムアルコキシドの加水分解物、ジルコニウムアルコキシドのキレート化合物及びジルコニウムアルコキシドの加水分解物のキレート化合物の群から選択される１種または２種以上のジルコニウム成分と、ケイ素成分と、溶媒とを含み、前記ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、前記ケイ素成分を酸化ケイ素（ＳｉＯ２）にそれぞれ換算したときの、前記酸化ケイ素の、前記酸化ジルコニウムと前記酸化ケイ素の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である塗布液を、基体の表面の少なくとも一部に塗布して塗布膜を形成し、次いで、この塗布膜を大気中、２００℃以上の温度にて熱処理することを特徴とする。 That is, the method for producing a cooking utensil according to the present invention includes one or more selected from the group consisting of zirconium alkoxide, hydrolyzate of zirconium alkoxide, chelate compound of zirconium alkoxide, and chelate compound of hydrolyzate of zirconium alkoxide. A zirconium component, a silicon component, and a solvent, wherein the zirconium component is converted into zirconium oxide (ZrO 2 ), and the silicon component is converted into silicon oxide (SiO 2 ). And a coating solution having a weight percentage of 1 wt% or more and 40 wt% or less with respect to the total amount of silicon oxide is applied to at least a part of the surface of the substrate to form a coating film. The heat treatment is performed at a temperature of 200 ° C. or higher.
前記ジルコニウムアルコキシドのキレート化合物は、ジルコニウムアルコキシドと、エタノールアミン、β−ジケトン、β−ケト酸エステル及びカルボン酸の群から選択される１種または２種以上の化合物との反応生成物であることが好ましい。
前記ジルコニウムアルコキシドの加水分解物のキレート化合物は、ジルコニウムアルコキシドの加水分解物と、エタノールアミン、β−ジケトン、β−ケト酸エステル及びカルボン酸の群から選択される１種または２種以上の化合物との反応生成物であることが好ましい。
The zirconium alkoxide chelate compound is a reaction product of zirconium alkoxide and one or more compounds selected from the group consisting of ethanolamine, β-diketone, β-keto acid ester and carboxylic acid. preferable.
The zirconium alkoxide hydrolyzate chelate compound includes a zirconium alkoxide hydrolyzate and one or more compounds selected from the group consisting of ethanolamine, β-diketone, β-keto acid ester and carboxylic acid. The reaction product is preferably.
本発明の調理器具の製造方法によれば、基体の表面の少なくとも一部に、ケイ素（Ｓｉ）と、ジルコニウム（Ｚｒ）と、酸素（Ｏ）とを含有し、前記ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、前記ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、前記酸化ケイ素（ＳｉＯ２）の、前記酸化ジルコニウム（ＺｒＯ２）と前記酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である薄膜を成膜した調理器具を、簡単な装置で簡便に製造することができる。 According to the method for manufacturing a cooking utensil of the present invention, silicon (Si), zirconium (Zr), and oxygen (O) are contained in at least a part of the surface of the base, and the silicon (Si) is converted into silicon oxide. a (SiO 2), zirconium oxide the zirconium (Zr) in (ZrO 2), when converted, respectively, said silicon oxide (SiO 2), the zirconium oxide (ZrO 2) and the silicon oxide (SiO 2) A cooking utensil on which a thin film having a weight percentage of 1 wt% or more and 40 wt% or less with respect to the total amount of can be easily manufactured with a simple apparatus.
本発明の調理器具の製造方法を実施するための最良の形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The best mode for carrying out the method for manufacturing a cooking utensil of the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
本実施形態の調理器具の製造方法により得られた調理器具は、調理器具の本体を構成する基体の表面の少なくとも一部、すなわち、この表面のうち少なくとも食品が触れる虞のある領域または油汚れが生じる虞のある領域に、ケイ素（Ｓｉ）と、ジルコニウム（Ｚｒ）と、酸素（Ｏ）とを含有し、前記ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、前記ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、前記酸化ケイ素（ＳｉＯ２）の、前記酸化ジルコニウム（ＺｒＯ２）と前記酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である薄膜を成膜している。 The cooking utensil obtained by the cooking utensil manufacturing method of the present embodiment has at least a part of the surface of the base that constitutes the main body of the cooking utensil, that is, at least a region of the surface that may be touched by food or oil stains A region that may be formed contains silicon (Si), zirconium (Zr), and oxygen (O), the silicon (Si) is converted into silicon oxide (SiO 2 ), and the zirconium (Zr) is converted into zirconium oxide. a (ZrO 2), when converted respectively, of the silicon oxide (SiO 2), the total amount by weight percent of 1 wt% or more relative and 40 weight of the zirconium oxide the silicon oxide (ZrO 2) and (SiO 2) % Or less is formed.
この調理器具とは、例えば、屋内のキッチンや調理場等の厨房で使用されるフライパン、鍋、調理用プレート、魚焼き用グリルの水入れ皿、焼き網等はもちろんのこと、コンロ天板、コンロ部品、オーブン内部品等、食品の調理に用いられる各種器具及び各種厨房設備の付帯部品を総称したものであり、この各種器具には、グリル、オーブン、トースター等の食品を収容して加熱調理する加熱調理機器の加熱調理室内の天板や内壁面を含む。
この調理器具の材質としては、鋼、ステンレス鋼、アルミニウム、銅等の金属材料、ガラス、ジルコニア等のセラミックス材料、琺瑯等の金属−セラミックス複合材料等、種類を問わない。
This cooking utensil includes, for example, frying pans, pans, cooking plates, fish grilling pans, grills used in kitchens such as indoor kitchens and kitchens, stovetops, It is a collective term for various appliances used for cooking food such as stove parts and oven parts, and accessory parts of various kitchen facilities. These appliances contain food such as grills, ovens, toasters, etc. Includes the top plate and inner wall surface of the cooking chamber of the cooking device.
The material of the cooking utensil is not limited to a metal material such as steel, stainless steel, aluminum, or copper, a ceramic material such as glass or zirconia, or a metal-ceramic composite material such as candy.
この薄膜を成膜する領域としては、少なくとも、食品が触れる虞のある領域または油汚れが生じる虞のある領域とする必要があるが、表面全体に洩れなく上記の薄膜を成膜した構成としてももちろんかまわない。
ここで、薄膜の組成を、ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率を１重量％以上かつ４０重量％以下とした理由は、酸化ケイ素（ＳｉＯ２）の重量百分率が１重量％を下回ると、食品の焦げ付き汚れは水拭き程度で除去できるものの、油汚れは水拭き程度では除去することができないからであり、一方、酸化ケイ素（ＳｉＯ２）の重量百分率が４０重量％を越えると、油汚れは水拭き程度で除去できるものの、食品の焦げ付き汚れは水拭き程度では除去することができないからである。
The region where this thin film is formed must be at least a region where food may be touched or a region where oil stains may occur, but the above thin film may be formed without leaking over the entire surface. Of course it does not matter.
Here, when the composition of the thin film is converted from silicon (Si) to silicon oxide (SiO 2 ) and from zirconium (Zr) to zirconium oxide (ZrO 2 ), zirconium oxide of silicon oxide (SiO 2 ). The reason why the weight percentage of the total amount of (ZrO 2 ) and silicon oxide (SiO 2 ) is 1% by weight or more and 40% by weight or less is that when the weight percentage of silicon oxide (SiO 2 ) is less than 1% by weight, food This is because oily stains cannot be removed with only water wiping, but if the weight percentage of silicon oxide (SiO 2 ) exceeds 40% by weight, oil stains can be removed. This is because, although it can be removed by wiping with water, burnt dirt on food cannot be removed by wiping with water.
ここで、前記重量百分率を１重量％以上かつ２０重量％以下の範囲に限定すると、食品の焦げ付き汚れの除去容易性が特に優れたものとなる。もちろん、油汚れの除去容易性、薄膜の耐水性も良好である。
また、前記重量百分率を２０量％を超えかつ４０重量％以下の範囲に限定すると、油汚れの除去性が特に優れたものとなる。もちろん、食品の焦げ付き汚れの除去容易性、薄膜の耐水性も良好である。
Here, when the weight percentage is limited to the range of 1% by weight or more and 20% by weight or less, the easiness of removing the burnt-on dirt of the food becomes particularly excellent. Of course, oil stains are easily removed and the water resistance of the thin film is also good.
Further, when the weight percentage is limited to the range of more than 20% by weight and 40% by weight or less, the oil stain removal property is particularly excellent. Of course, it is easy to remove burnt dirt from the food and the water resistance of the thin film is good.
この薄膜の組成を撥水性及び親水性の点から考えると、酸化ジルコニウム（ＺｒＯ２）は表面に親水基（−ＯＨ）を有しないので撥水性を示すが、酸化ケイ素（ＳｉＯ２）は、表面に親水基（−ＯＨ）を有するので親水性を示す。したがって、撥水性を示す酸化ジルコニウム（ＺｒＯ２）に、重量百分率が１重量％〜４０重量％となるように酸化ケイ素（ＳｉＯ２）を導入すると、この酸化ケイ素（ＳｉＯ２）含有酸化ジルコニウム（ＺｒＯ２）からなる薄膜は、適度な撥水性と親水性とを兼ね備えたものとなる。 Considering the composition of this thin film from the viewpoint of water repellency and hydrophilicity, zirconium oxide (ZrO 2 ) exhibits water repellency because it does not have a hydrophilic group (—OH) on the surface, but silicon oxide (SiO 2 ) Since it has a hydrophilic group (—OH), it exhibits hydrophilicity. Accordingly, when silicon oxide (SiO 2 ) is introduced into zirconium oxide (ZrO 2 ) exhibiting water repellency so that the weight percentage is 1% by weight to 40% by weight, this silicon oxide (SiO 2 ) -containing zirconium oxide (ZrO 2 ). The thin film made of 2 ) has appropriate water repellency and hydrophilicity.
この薄膜の厚みは、０．０１μｍ以上かつ１０μｍ以下であることが好ましい。
この薄膜の厚みが０．０１μｍを下回ると、防汚性の付与（食品の焦げ付き汚れや油汚れの除去容易性）が不充分となるので好ましくなく、一方、厚みが１０μｍを越えると、薄膜の耐衝撃性が低下してクラックが入り易く、また、透明性が低下して調理器具自体の色調等の意匠性が低下するので好ましくない。
The thickness of the thin film is preferably 0.01 μm or more and 10 μm or less.
If the thickness of the thin film is less than 0.01 μm, it is not preferable because the imparting of antifouling properties (easy removal of burnt dirt and oil stains on food) becomes insufficient. On the other hand, if the thickness exceeds 10 μm, the thin film This is not preferable because impact resistance is lowered and cracks are easily generated, and transparency is lowered and design properties such as a color tone of the cooking utensil itself are lowered.
この調理器具は、例えば、次のような方法により製造することができる。
すなわち、ジルコニウムアルコキシド、ジルコニウムアルコキシドの加水分解物、ジルコニウムアルコキシドのキレート化合物、ジルコニウムアルコキシドの加水分解物のキレート化合物の群から選択される１種または２種以上のジルコニウム成分と、ケイ素成分と、溶媒とを含み、前記ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、前記ケイ素成分を酸化ケイ素（ＳｉＯ２）にそれぞれ換算したときの、前記酸化ケイ素の、前記酸化ジルコニウムと前記酸化ケイ素の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である塗布液を、基体の表面の少なくとも一部に塗布して塗布膜を形成し、次いで、この塗布膜を大気中、２００℃以上の温度にて熱処理する。
This cooking utensil can be manufactured, for example, by the following method.
Namely, zirconium alkoxide, hydrolyzate of zirconium alkoxide, chelate compound of zirconium alkoxide, one or more zirconium components selected from the group of chelate compounds of hydrolyzate of zirconium alkoxide, a silicon component, and a solvent When the zirconium component is converted to zirconium oxide (ZrO 2 ) and the silicon component is converted to silicon oxide (SiO 2 ), the weight percentage of the silicon oxide with respect to the total amount of the zirconium oxide and the silicon oxide Is applied to at least a part of the surface of the substrate to form a coating film, and then this coating film is heat-treated at a temperature of 200 ° C. or higher in the atmosphere. To do.
この塗布液においては、上記のジルコニウムアルコキシドとしては、特に制限されるものではないが、例えば、ジルコニウムテトラノルマルブトキシド、ジルコニウムテトラプロポキシドを例示することができる。これらジルコニウムテトラノルマルブトキシドやジルコニウムテトラプロポキシドは、適度な加水分解速度を有し、しかも、取り扱い易いので、膜質が均一な薄膜を成膜することができる。 In the coating solution, the zirconium alkoxide is not particularly limited, and examples thereof include zirconium tetranormal butoxide and zirconium tetrapropoxide. These zirconium tetranormal butoxide and zirconium tetrapropoxide have an appropriate hydrolysis rate and are easy to handle, so that a thin film having a uniform film quality can be formed.
また、ジルコニウムアルコキシドの加水分解物としては、特に制限されるものではないが、例えば、ジルコニウムテトラノルマルブトキシドの加水分解物、ジルコニウムテトラプロポキシドの加水分解物を例示することができる。この加水分解物の加水分解率としては、特に制限はなく、０モル％超〜１００モル％の範囲内のものを使用することができる。 The hydrolyzate of zirconium alkoxide is not particularly limited, and examples thereof include a hydrolyzate of zirconium tetranormal butoxide and a hydrolyzate of zirconium tetrapropoxide. There is no restriction | limiting in particular as a hydrolysis rate of this hydrolyzate, The thing in the range of more than 0 mol%-100 mol% can be used.
これらジルコニウムアルコキシドやジルコニウムアルコキシドの加水分解物は、吸湿性が高く、不安定であり、貯蔵安定性も充分でないので、取り扱う際には、非常に注意を要する。
そこで、取り扱いの容易さの点では、これらジルコニウムアルコキシドやジルコニウムアルコキシドの加水分解物をキレート化したジルコニウムアルコキシドのキレート化合物、ジルコニウムアルコキシドの加水分解物のキレート化合物が好ましい。
These zirconium alkoxides and hydrolysates of zirconium alkoxide have high hygroscopicity, are unstable, and are not sufficiently stable in storage.
Therefore, from the viewpoint of ease of handling, a zirconium alkoxide chelate compound obtained by chelating these zirconium alkoxides or a hydrolyzate of zirconium alkoxide, or a chelate compound of a hydrolyzate of zirconium alkoxide is preferable.
上記のジルコニウムアルコキシドのキレート化合物としては、ジルコニウムアルコキシドと、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のエタノールアミン、アセチルアセトン等のβ−ジケトン、アセト酢酸メチル、アセト酢酸エチル、マロン酸ジエチル、フェノキシ酢酸エチル等のβ−ケト酸エステル、酢酸、乳酸、クエン酸、安息香酸、リンゴ酸等のカルボン酸の群から選択される１種または２種以上の加水分解抑制剤（化合物）との反応生成物を例示することができる。ここで、加水分解抑制剤とは、ジルコニウムアルコキシドとキレート化合物を形成し、このキレート化合物の加水分解反応を抑制する作用を有する化合物のことである。 As the above-mentioned chelate compound of zirconium alkoxide, zirconium alkoxide, ethanolamine such as monoethanolamine, diethanolamine and triethanolamine, β-diketone such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, diethyl malonate, ethyl phenoxyacetate A reaction product with one or more hydrolysis inhibitors (compounds) selected from the group of carboxylic acids such as β-keto acid esters, acetic acid, lactic acid, citric acid, benzoic acid, malic acid, etc. It can be illustrated. Here, the hydrolysis inhibitor is a compound having an action of forming a chelate compound with zirconium alkoxide and suppressing the hydrolysis reaction of the chelate compound.
また、ジルコニウムアルコキシドの加水分解物のキレート化合物としては、ジルコニウムアルコキシドと、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のエタノールアミン、アセチルアセトン等のβ−ジケトン、アセト酢酸メチル、アセト酢酸エチル、マロン酸ジエチル、フェノキシ酢酸エチル等のβ−ケト酸エステル、酢酸、乳酸、クエン酸、安息香酸、リンゴ酸等のカルボン酸の群から選択される１種または２種以上の加水分解抑制剤（化合物）との反応生成物を例示することができる。加水分解抑制剤の定義は、上述した通りである。 Further, as a chelate compound of a hydrolyzate of zirconium alkoxide, zirconium alkoxide, ethanolamine such as monoethanolamine, diethanolamine, and triethanolamine, β-diketone such as acetylacetone, methyl acetoacetate, ethyl acetoacetate, diethyl malonate , One or more hydrolysis inhibitors (compounds) selected from the group of carboxylic acids such as β-keto acid esters such as ethyl phenoxyacetate, acetic acid, lactic acid, citric acid, benzoic acid and malic acid Reaction products can be exemplified. The definition of the hydrolysis inhibitor is as described above.
この加水分解抑制剤の、ジルコニウムアルコキシドまたはジルコニウムアルコキシドの加水分解物に対する割合は、このジルコニウムアルコキシドまたはジルコニウムアルコキシドの加水分解物に含まれるジルコニウム（Ｚｒ）の０．５モル倍〜４モル倍、好ましくは１モル倍〜３モル倍が好ましい。
割合が０．５モル倍よりも少ないと、塗布液の安定性が不充分なものとなるからであり、一方、４モル倍を超えると、熱処理した後においても加水分解抑制剤が薄膜中に残留し、その結果、薄膜の硬度が低下するからである。
The ratio of this hydrolysis inhibitor to zirconium alkoxide or the hydrolyzate of zirconium alkoxide is 0.5 mol times to 4 mol times of zirconium (Zr) contained in this zirconium alkoxide or zirconium alkoxide hydrolyzate, preferably 1 mol times-3 mol times are preferable.
If the ratio is less than 0.5 mol times, the stability of the coating solution becomes insufficient. On the other hand, if the proportion exceeds 4 mol times, the hydrolysis inhibitor remains in the thin film even after heat treatment. This is because the hardness of the thin film decreases as a result.
これらジルコニウムアルコキシドのキレート化合物、ジルコニウムアルコキシドの加水分解物のキレート化合物としては、ジルコニウムアルコキシドまたはジルコニウムアルコキシドの加水分解物を溶媒中に溶解し、さらに加水分解抑制剤を添加し、得られた溶媒中にてキレート化反応を生じさせたものであってもよい。 As the chelate compound of these zirconium alkoxides and the hydrolyzate of zirconium alkoxides, the zirconium alkoxide or the hydrolyzate of zirconium alkoxide is dissolved in a solvent, and further, a hydrolysis inhibitor is added to the resulting solvent. Thus, a chelation reaction may be caused.
上記のケイ素成分としては、熱処理により酸化ケイ素となり得るケイ素化合物であれば特に制限はないが、例えば、コロイダルシリカ、ケイ素アルコキシド、ケイ素アルコキシドの加水分解物を例示することができる。この加水分解物の加水分解率としては、特に制限はなく、０モル％超〜１００モル％の範囲内のものを使用することができる。 The silicon component is not particularly limited as long as it is a silicon compound that can be converted into silicon oxide by heat treatment, and examples thereof include colloidal silica, silicon alkoxide, and hydrolyzate of silicon alkoxide. There is no restriction | limiting in particular as a hydrolysis rate of this hydrolyzate, The thing in the range of more than 0 mol%-100 mol% can be used.
上記の溶媒としては、上述したジルコニウム成分及びケイ素成分を溶解または分散させることのできる溶媒であれば、特に制限なく用いることができ、例えば、水、メタノール、エタノール、２−プロパノール、１−ブタノール等の低級アルコールが好適である。特に、溶媒として水を用いる場合、アルコキシドの加水分解量以上の量の水を含有させると、塗布液の安定性が低下するので好ましくない。 As said solvent, if it can melt | dissolve or disperse | distribute the zirconium component and silicon component which were mentioned above, it can use without a restriction | limiting especially, For example, water, methanol, ethanol, 2-propanol, 1-butanol, etc. The lower alcohols are preferred. In particular, when water is used as the solvent, it is not preferable to add water in an amount equal to or greater than the hydrolysis amount of the alkoxide because the stability of the coating solution is lowered.
ここで、ジルコニウム成分としてジルコニウムアルコキシドおよび／またはジルコニウムアルコキシドの加水分解物を用いる場合、あるいは、ケイ素成分としてシリコンアルコキシドおよび／またはシリコンアルコキシドの加水分解物を用いる場合には、このジルコニウム成分またはケイ素成分の加水分解反応を制御する触媒を添加してもよい。
この触媒としては、塩酸、硝酸等の無機酸、クエン酸、酢酸等の有機酸等を例示することができる。また、この触媒の添加量は、通常、塗布液中のジルコニウム成分及びケイ素成分の合計量に対して０．０１〜１０重量％程度が好ましい。なお、触媒の過剰の添加は、熱処理の際に熱処理炉を腐食する虞があるので好ましくない。
Here, when zirconium alkoxide and / or zirconium alkoxide hydrolyzate is used as the zirconium component, or when silicon alkoxide and / or silicon alkoxide hydrolyzate is used as the silicon component, the zirconium component or silicon component A catalyst for controlling the hydrolysis reaction may be added.
Examples of the catalyst include inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as citric acid and acetic acid. Moreover, the addition amount of this catalyst is usually preferably about 0.01 to 10% by weight with respect to the total amount of zirconium component and silicon component in the coating solution. An excessive addition of the catalyst is not preferable because it may corrode the heat treatment furnace during the heat treatment.
この点、ジルコニウム成分としてジルコニウムアルコキシドのキレート化合物またはジルコニウムアルコキシドの加水分解物のキレート化合物を用い、ケイ素成分としてコロイダルシリカを用いると、加水分解反応を制御する触媒である酸を添加する必要がなく、したがって、熱処理の際に熱処理炉を腐食する虞がないので好ましい。 In this regard, when a zirconium alkoxide chelate compound or a zirconium alkoxide hydrolyzate chelate compound is used as the zirconium component and colloidal silica is used as the silicon component, there is no need to add an acid which is a catalyst for controlling the hydrolysis reaction. Therefore, it is preferable because there is no possibility of corroding the heat treatment furnace during the heat treatment.
この塗布液においては、ジルコニウム成分とケイ素成分の合計の含有率は、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）にそれぞれ換算したときの、酸化ジルコニウムと酸化ケイ素の合計の含有率が１重量％以上かつ１０重量％以下であることが好ましい。
合計の含有率が１重量％を下回ると、所定の膜厚の薄膜を形成することが困難となり、一方、合計の含有率が１０重量％を超えると、所定の膜厚を超えて薄膜が白化したり、剥離する原因となるので好ましくない。
In this coating solution, the total content of the zirconium component and the silicon component is as follows: zirconium oxide and silicon oxide when the zirconium component is converted to zirconium oxide (ZrO 2 ) and the silicon component is converted to silicon oxide (SiO 2 ). The total content of is preferably 1% by weight or more and 10% by weight or less.
If the total content is less than 1% by weight, it is difficult to form a thin film having a predetermined film thickness. On the other hand, if the total content exceeds 10% by weight, the thin film exceeds the predetermined film thickness and is white. This is not preferable because it may cause discoloration or peeling.
次いで、上記の塗布液を、調理器具の本体を構成する基体の表面の少なくとも一部、すなわち、少なくとも、食品が触れる虞のある領域または油汚れが生じる虞のある領域に、塗布する。塗布方法としては特に制限はなく、スプレー法、ディップ法、刷毛塗り法等が適用できる。塗布に当たっては、塗布膜の厚みを、熱処理後の膜厚が０．０１μｍ〜１０μｍの範囲になるように調製することが好ましい。 Next, the above-described coating liquid is applied to at least a part of the surface of the base constituting the main body of the cooking utensil, that is, at least a region where food may be touched or a region where oil stains may occur. There is no restriction | limiting in particular as an application | coating method, A spray method, a dip method, a brush coating method etc. are applicable. In coating, the thickness of the coating film is preferably adjusted so that the film thickness after the heat treatment is in the range of 0.01 μm to 10 μm.
このようにして得られた塗布膜を、大気中、２００℃以上、より好ましくは４００℃以上、さらに好ましくは５００℃以上の温度にて熱処理する。
熱処理温度が２００℃を下回ると、得られた薄膜の膜強度が低下するので好ましくない。なお、熱処理温度が高すぎると、基体が変形する虞があるため、熱処理温度を調理器具を構成する基体の材質に応じて調整する。熱処理時の雰囲気は特に制限されず、通常、大気雰囲気中で行う。
The coating film thus obtained is heat-treated in the atmosphere at a temperature of 200 ° C. or higher, more preferably 400 ° C. or higher, and even more preferably 500 ° C. or higher.
When the heat treatment temperature is lower than 200 ° C., the film strength of the obtained thin film decreases, which is not preferable. In addition, since there exists a possibility that a base | substrate may deform | transform if heat processing temperature is too high, heat processing temperature is adjusted according to the material of the base | substrate which comprises a cooking appliance. The atmosphere during the heat treatment is not particularly limited, and is usually performed in an air atmosphere.
このようにして得られた薄膜は、下記の（１）〜（４）のいずれかの組成を有している。
（１）ケイ素（Ｓｉ）原子とジルコニウム（Ｚｒ）原子が酸素（Ｏ）原子を介して結合した下記式（１）
(1) The following formula (1) in which a silicon (Si) atom and a zirconium (Zr) atom are bonded via an oxygen (O) atom
（２）ジルコニウム（Ｚｒ）原子同士が酸素（Ｏ）原子を介して結合した下記式（２）
（３）ケイ素酸化物微粒子とジルコニウム酸化物微粒子が互いに分散している無機物質。
（４）上記の（１）〜（３）のいずれか１種または２種以上の無機物質が混在した状態のもの。
(3) An inorganic substance in which silicon oxide fine particles and zirconium oxide fine particles are dispersed with each other.
(4) Any one of the above (1) to (3) in which one or more inorganic substances are mixed.
以上説明したように、本実施形態の調理器具によれば、基体の表面の少なくとも一部に、ケイ素（Ｓｉ）と、ジルコニウム（Ｚｒ）と、酸素（Ｏ）とを含有し、ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である薄膜を成膜したので、水拭き程度で、食品の焦げ付き汚れはもちろんのこと、油汚れも簡単に除去することができる。
また、上記の薄膜は、高屈折率材料である酸化ジルコニウム（ＺｒＯ２）を主成分としたので、屈折率が大きく、深みのある反射が得られ、見た目にも美しく、意匠性も向上したものとなる。
As described above, according to the cooking utensil of this embodiment, silicon (Si), zirconium (Zr), and oxygen (O) are contained in at least a part of the surface of the base, and silicon (Si). Of silicon oxide (SiO 2 ) and zirconium oxide (Zr) into zirconium oxide (ZrO 2 ), respectively, of silicon oxide (SiO 2 ), zirconium oxide (ZrO 2 ) and silicon oxide (SiO 2 ) Since a thin film having a weight percentage of 1% by weight or more and 40% by weight or less with respect to the total amount is formed, it is possible to easily remove oil stains as well as scorching stains on food with a water wipe.
In addition, the above-mentioned thin film is mainly composed of zirconium oxide (ZrO 2 ), which is a high refractive index material, so that it has a large refractive index, a deep reflection, is beautiful in appearance, and has improved design. It becomes.
本実施形態の調理器具の製造方法によれば、ジルコニウムアルコキシド、ジルコニウムアルコキシドの加水分解物、ジルコニウムアルコキシドのキレート化合物、ジルコニウムアルコキシドの加水分解物のキレート化合物の群から選択される１種または２種以上のジルコニウム成分と、ケイ素成分と、溶媒とを含み、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）にそれぞれ換算したときの、酸化ケイ素の、酸化ジルコニウムと酸化ケイ素の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である塗布液を、基体の表面の少なくとも一部に塗布して塗布膜を形成し、次いで、この塗布膜を大気中、２００℃以上の温度にて熱処理するので、本実施形態の調理器具を、簡単な装置で簡便に製造することができる。 According to the method for producing a cooking utensil of this embodiment, one or more selected from the group consisting of zirconium alkoxide, hydrolyzate of zirconium alkoxide, chelate compound of zirconium alkoxide, and chelate compound of hydrolyzate of zirconium alkoxide. Zirconium oxide and silicon oxide when the zirconium component is converted to zirconium oxide (ZrO 2 ) and the silicon component is converted to silicon oxide (SiO 2 ). A coating solution having a weight percentage with respect to the total amount of 1 to 40% by weight is applied to at least a part of the surface of the substrate to form a coating film, and then the coating film is 200 ° C. in the atmosphere. Since it heat-processes at the above temperature, the cooking utensil of this embodiment is a simple apparatus. It can be easily manufactured.
以下、実施例及び比較例により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。
「実施例１」
ジルコニウムテトラブトキシド６重量部、アセト酢酸エチル３重量部、２−プロパノール９０．９重量部を室温（２５℃）下で３０分混合し、ジルコニウムテトラブトキシドとアセト酢酸エチルとのキレート化合物を生成させた。次いで、この溶液にテトラメトキシシラン０．１重量部を添加し、塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は２重量％であった。
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples.
"Example 1"
6 parts by weight of zirconium tetrabutoxide, 3 parts by weight of ethyl acetoacetate, and 90.9 parts by weight of 2-propanol were mixed at room temperature (25 ° C.) for 30 minutes to form a chelate compound of zirconium tetrabutoxide and ethyl acetoacetate. . Next, 0.1 part by weight of tetramethoxysilane was added to this solution to obtain a coating solution.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 2% by weight.
次いで、この塗布液を、結晶化ガラス製のコンロ天板（いわゆるガラストップ）上に塗布量（固形分換算）が３ｇ／ｍ２となるようにスプレー塗装し、大気雰囲気中、５００℃にて２０分間、熱処理して、コンロ天板上に薄膜を成膜し、実施例１の調理器具を得た。
この薄膜の厚みは１μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
Next, this coating solution is spray-coated on a stove top plate (so-called glass top) made of crystallized glass so that the coating amount (in terms of solid content) is 3 g / m 2, and at 500 ° C. in an air atmosphere. Heat processing was performed for 20 minutes, and the thin film was formed on the stove top plate, and the cooking utensil of Example 1 was obtained.
The thickness of this thin film was 1 μm, and the surface of the stove top plate was more glossy than before the thin film was formed, showing a beautiful surface.
次いで、この調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を評価した。評価結果を表１に示す。
なお、評価項目及び評価方法は次のとおりである。
（１）焦げ付き汚れの除去容易性
調理器具（結晶化ガラス製のコンロ天板）の表面に醤油を１０ｍｌ滴下し、大気中、３００℃にて１時間加熱し、醤油を焦げ付かせた。次いで、水を含ませた布を用いてこの焦げ付きを水拭きし、除去の容易性を評価した。
◎；極めて良好
○；良好
×；不良
Subsequently, the antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil were evaluated. The evaluation results are shown in Table 1.
The evaluation items and evaluation methods are as follows.
(1) Ease of removing burnt dirt 10 ml of soy sauce was dropped on the surface of a cooking utensil (crystallized glass stove top) and heated in the atmosphere at 300 ° C. for 1 hour to burn the soy sauce. Next, the burn was wiped with a cloth soaked with water, and the ease of removal was evaluated.
◎; Extremely good ○; Good ×; Poor
（２）油汚れの除去容易性
調理器具（結晶化ガラス製のコンロ天板）の表面に廃てんぷら油１ｍｌを滴下し、水を含ませた布切れでこの廃てんぷら油を水拭きし、「べたつき残り」を指先で確認し、除去の容易性を評価した。
◎；極めて良好
○；良好
×；不良
(2) Easy removal of oil stains 1 ml of waste tempura oil is dropped on the surface of a cooking utensil (crystallized glass stove top), and the waste tempura oil is wiped with a piece of cloth soaked in water. The “sticky residue” was confirmed with a fingertip, and the ease of removal was evaluated.
◎; Extremely good ○; Good ×; Poor
（３）耐水性
調理器具（結晶化ガラス製のコンロ天板）を、水道水を沸騰させた沸騰水中に２４時間浸漬した後、薄膜を指先で擦り、薄膜の剥離状況を評価した。
◎；極めて良好
○；良好
×；不良
(3) Water resistance A cooking utensil (a stovetop made of crystallized glass) was immersed in boiling water in which tap water was boiled for 24 hours, and then the thin film was rubbed with a fingertip to evaluate the peeling state of the thin film.
◎; Extremely good ○; Good ×; Poor
「実施例２」
２−プロパノールを９０．４重量部に、テトラメトキシシランを０．６重量部に変更した他は、実施例１に準じて実施例２の塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は１０重量％であった。
"Example 2"
A coating solution of Example 2 was obtained according to Example 1 except that 2-propanol was changed to 90.4 parts by weight and tetramethoxysilane was changed to 0.6 parts by weight.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 10% by weight.
次いで、この塗布液を用いて、実施例１に準じて実施例２の調理器具を得た。
この薄膜の厚みは１μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
この実施例２の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
Subsequently, the cooking utensil of Example 2 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm, and the surface of the stove top plate was more glossy than before the thin film was formed, showing a beautiful surface.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Example 2 were evaluated according to Example 1. The evaluation results are shown in Table 1.
「実施例３」
２−プロパノールを８９．９重量部に、テトラメトキシシランを１．１重量部に変更した他は、実施例１に準じて実施例３の塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は１８重量％であった。
"Example 3"
A coating solution of Example 3 was obtained according to Example 1 except that 2-propanol was changed to 89.9 parts by weight and tetramethoxysilane was changed to 1.1 parts by weight.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 18% by weight.
次いで、この塗布液を用いて、実施例１に準じて実施例３の調理器具を得た。
この薄膜の厚みは１μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
この実施例３の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
Subsequently, the cooking utensil of Example 3 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm, and the surface of the stove top plate was more glossy than before the thin film was formed, showing a beautiful surface.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Example 3 were evaluated according to Example 1. The evaluation results are shown in Table 1.
「実施例４」
ジルコニウムテトラブトキシドを２．３重量部に、アセト酢酸エチルを１．２重量部に、２−プロパノールを９６．０重量部に、テトラメトキシシランを０．５重量部に変更した他は、実施例１に準じて実施例４の塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は２５重量％であった。
Example 4
Examples were changed except that zirconium tetrabutoxide was changed to 2.3 parts by weight, ethyl acetoacetate to 1.2 parts by weight, 2-propanol to 96.0 parts by weight, and tetramethoxysilane to 0.5 parts by weight. The coating solution of Example 4 was obtained according to 1.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 25% by weight.
次いで、この塗布液を用いて、実施例１に準じて実施例４の調理器具を得た。
この薄膜の厚みは１μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
この実施例４の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
Subsequently, the cooking utensil of Example 4 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm, and the surface of the stove top plate was more glossy than before the thin film was formed, showing a beautiful surface.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Example 4 were evaluated according to Example 1. The evaluation results are shown in Table 1.
「実施例５」
ジルコニウムテトラブトキシドを２．０重量部に、アセト酢酸エチルを１．０重量部に、２−プロパノールを９６．３重量部に、テトラメトキシシランを０．７重量部に変更した他は、実施例１に準じて実施例５の塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は３５重量％であった。
"Example 5"
Examples were changed to 2.0 parts by weight of zirconium tetrabutoxide, 1.0 part by weight of ethyl acetoacetate, 96.3 parts by weight of 2-propanol, and 0.7 parts by weight of tetramethoxysilane. The coating solution of Example 5 was obtained according to 1.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 35% by weight.
次いで、この塗布液を用いて、実施例１に準じて実施例５の調理器具を得た。
この薄膜の厚みは１μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
この実施例５の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
Subsequently, the cooking utensil of Example 5 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm, and the surface of the stove top plate was more glossy than before the thin film was formed, showing a beautiful surface.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Example 5 and water resistance were evaluated according to Example 1. The evaluation results are shown in Table 1.
「比較例１」
ジルコニウムテトラブトキシド６重量部、２−プロパノール９３重量部、６０重量％の硝酸１重量部を混合して、塗布液を得た。
次いで、この塗布液を用いて、実施例１に準じて比較例１の調理器具を得た。
この薄膜の厚みは１μｍであった。
この比較例１の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
“Comparative Example 1”
A coating solution was obtained by mixing 6 parts by weight of zirconium tetrabutoxide, 93 parts by weight of 2-propanol, and 1 part by weight of 60% by weight nitric acid.
Subsequently, the cooking utensil of Comparative Example 1 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Comparative Example 1 were evaluated according to Example 1. The evaluation results are shown in Table 1.
「比較例２」
ジルコニウムテトラブトキシドを１．７重量部に、アセト酢酸エチルを０．８重量部に、２−プロパノールを９６．６重量部に、テトラメトキシシランを０．９重量部に変更した他は、実施例１に準じて比較例２の塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は４５重量％であった。
"Comparative Example 2"
Except that zirconium tetrabutoxide was changed to 1.7 parts by weight, ethyl acetoacetate to 0.8 parts by weight, 2-propanol to 96.6 parts by weight, and tetramethoxysilane to 0.9 parts by weight. The coating liquid of Comparative Example 2 was obtained according to 1.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 45% by weight.
次いで、この塗布液を用いて、実施例１に準じて比較例２の調理器具を得た。
この薄膜の厚みは１μｍであった。
この比較例２の調理器具の防汚性（食品の焦げ付き汚れや油汚れの除去容易性）及び耐水性を実施例１に準じて評価した。評価結果を表１に示す。
Subsequently, the cooking utensil of Comparative Example 2 was obtained according to Example 1 using this coating solution.
The thickness of this thin film was 1 μm.
The antifouling property (easy removal of burnt food and oil stains) and water resistance of the cooking utensil of Comparative Example 2 were evaluated according to Example 1. The evaluation results are shown in Table 1.
表１によれば、実施例１〜３では、食品の焦げ付き汚れの除去容易性が特に優れており、また、油汚れの除去容易性、薄膜の耐水性も良好なものであった。
また、実施例４、５では、油汚れの除去性が特に優れており、食品の焦げ付き汚れ、薄膜の耐水性も良好なものであった。
これに対して、比較例１では、食品の焦げ付き汚れの除去容易性は良好であるものの、油汚れの除去容易性、薄膜の耐水性は共に不良であった。また、比較例２では、油汚れの除去容易性、薄膜の耐水性は優れているものの、食品の焦げ付き汚れの除去容易性が不良であった。
したがって、食品の焦げ付き汚れの除去容易性、油汚れの除去容易性、薄膜の耐水性のいずれも良好なのは、薄膜中のＳｉＯ２量が１重量％〜４０重量％の範囲であることが分かった。
According to Table 1, in Examples 1 to 3, the ease of removal of burnt-on stains of food was particularly excellent, and the ease of removal of oil stains and the water resistance of the thin film were also good.
Further, in Examples 4 and 5, the oil stain removability was particularly excellent, and the food burnt stain and the water resistance of the thin film were also good.
On the other hand, in Comparative Example 1, although the easy removal of burnt-on stains of food was good, both the easy removal of oil stains and the water resistance of the thin film were poor. Further, in Comparative Example 2, although the oil stains were easily removed and the water resistance of the thin film was excellent, the easy removal of the burnt-on stains of food was poor.
Therefore, it was found that the SiO 2 content in the thin film was in the range of 1% by weight to 40% by weight, with good removal of burnt dirt, easy removal of oil dirt, and water resistance of the thin film. .
「実施例６」
ジルコニウムテトラブトキシド１０重量部、アセチルアセトン５重量部、２−プロパノール８４．５重量部を混合し、ジルコニウムテトラブトキシドとアセチルアセトンとのキレート化合物を生成させた。次いで、この溶液にテトラメトキシシラン０．５重量部を添加し、塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は７．２重量％であった。
"Example 6"
10 parts by weight of zirconium tetrabutoxide, 5 parts by weight of acetylacetone, and 84.5 parts by weight of 2-propanol were mixed to form a chelate compound of zirconium tetrabutoxide and acetylacetone. Next, 0.5 part by weight of tetramethoxysilane was added to this solution to obtain a coating solution.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 7.2% by weight.
次いで、この塗布液を、結晶化ガラス製のコンロ天板上に塗布量（固形分換算）が１．５ｇ／ｍ２となるようにスプレー塗装し、大気雰囲気中、６００℃にて１０分間、熱処理して、コンロ天板上に薄膜を成膜し、実施例６の調理器具を得た。
この薄膜の厚みは０．５μｍであり、コンロ天板の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
Next, this coating solution is spray-coated on a stovetop made of crystallized glass so that the coating amount (in terms of solid content) is 1.5 g / m 2, and in an air atmosphere at 600 ° C. for 10 minutes. A thin film was formed on the stove top by heat treatment, and the cooking utensil of Example 6 was obtained.
The thickness of this thin film was 0.5 μm, and the surface of the stove top was more glossy than before the thin film was formed, and showed a beautiful surface.
「実施例７」
ジルコニウムテトラアセチルアセトネート１５重量部、３０重量％のコロイダルシリカを含む２−プロパノール分散液０．５重量部、ブチル−β−オキシエチルエーテル（ブチルセロソルブ）８４．５重量部を混合し、塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は４重量％であった。
"Example 7"
15 parts by weight of zirconium tetraacetylacetonate, 0.5 parts by weight of a 2-propanol dispersion containing 30% by weight of colloidal silica, and 84.5 parts by weight of butyl-β-oxyethyl ether (butyl cellosolve) are mixed, and the coating solution is prepared. Obtained.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 4% by weight.
次いで、この塗布液を、琺瑯製オーブン皿上に塗布量（固形分換算）が０．３ｇ／ｍ２となるようにディップ塗装し、大気雰囲気中、５００℃にて３０分間、熱処理して、オーブン皿上に薄膜を成膜し、実施例７の調理器具を得た。
この薄膜の厚みは０．１μｍであり、琺瑯製オーブン皿の表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
Next, the coating solution is dip-coated on a smoked oven dish so that the coating amount (in terms of solid content) is 0.3 g / m 2, and heat-treated at 500 ° C. for 30 minutes in an air atmosphere. A thin film was formed on an oven dish to obtain the cooking utensil of Example 7.
The thickness of this thin film was 0.1 μm, and the surface of the smoked oven dish was more glossy than before the thin film was formed, showing a beautiful surface.
「実施例８」
ジルコニウムテトラブトキシド１０重量部、アセチルアセトン５重量部、２−プロパノール８４重量部を混合し、ジルコニウムテトラブトキシドとアセチルアセトンとのキレート化合物を生成させた。次いで、この溶液にテトラエトキシシラン１重量部を添加し、塗布液を得た。
この塗布液における、ジルコニウム成分を酸化ジルコニウム（ＺｒＯ２）に、ケイ素成分を酸化ケイ素（ＳｉＯ２）に、それぞれ換算したときの、酸化ケイ素（ＳｉＯ２）の、酸化ジルコニウム（ＺｒＯ２）と酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率は８．６重量％であった。
"Example 8"
10 parts by weight of zirconium tetrabutoxide, 5 parts by weight of acetylacetone and 84 parts by weight of 2-propanol were mixed to produce a chelate compound of zirconium tetrabutoxide and acetylacetone. Next, 1 part by weight of tetraethoxysilane was added to this solution to obtain a coating solution.
In this coating solution, a zirconium component of zirconium oxide (ZrO 2), silicon oxide and silicon component (SiO 2), when converted, respectively, of silicon oxide (SiO 2), oxide and zirconium oxide (ZrO 2), silicon The weight percentage with respect to the total amount of (SiO 2 ) was 8.6% by weight.
次いで、この塗布液を、セラミック製焼肉プレート上に塗布量（固形分換算）が１．５ｇ／ｍ２となるようにディップ塗装し、大気雰囲気中、７００℃にて５０分間、熱処理して、この焼肉プレート上に薄膜を成膜し、実施例８の調理器具を得た。
この薄膜の厚みは０．５μｍであり、焼肉プレートの表面は、薄膜の成膜前よりも光沢が増し、美しい表面を示した。
Next, this coating solution is dip-coated on a ceramic grilled meat plate so that the coating amount (in terms of solid content) is 1.5 g / m 2, and heat-treated at 700 ° C. for 50 minutes in an air atmosphere, A thin film was formed on the grilled meat plate to obtain the cooking utensil of Example 8.
The thickness of the thin film was 0.5 μm, and the surface of the yakiniku plate was more glossy than before the thin film was formed, showing a beautiful surface.
実施例６〜８それぞれの調理器具の表面に卵白を塗りつけ、大気雰囲気中、３５０℃にて１時間加熱し、焦げ付かせた。次いで、水を含ませた布を用いてこの焦げ付きを水拭きしたところ、簡単に拭き取ることができた。
また、実施例６〜８それぞれの調理器具の表面に廃てんぷら油を滴下し、水を含ませた布切れでこの廃てんぷら油を水拭きしたところ、簡単に拭き取ることができた。
Examples 6 to 8 Egg white was applied to the surface of each cooking utensil and heated in an air atmosphere at 350 ° C. for 1 hour to burn it. Next, when this burn was wiped with a cloth soaked with water, it could be easily wiped off.
Moreover, when waste tempura oil was dripped on the surface of each cooking appliance of Examples 6-8, and this waste tempura oil was wiped off with a piece of cloth soaked in water, it could be easily wiped off.
本発明の調理器具は、基体の表面の少なくとも一部に、ケイ素（Ｓｉ）と、ジルコニウム（Ｚｒ）と、酸素（Ｏ）とを含有し、前記ケイ素（Ｓｉ）を酸化ケイ素（ＳｉＯ２）に、前記ジルコニウム（Ｚｒ）を酸化ジルコニウム（ＺｒＯ２）に、それぞれ換算したときの、前記酸化ケイ素（ＳｉＯ２）の、前記酸化ジルコニウム（ＺｒＯ２）と前記酸化ケイ素（ＳｉＯ２）の合計量に対する重量百分率が１重量％以上かつ４０重量％以下である薄膜を成膜したことにより、調理中に付着した食品の焦げ付き汚れや油汚れを水拭き程度で簡単に除去することができたものであるから、食品の調理に用いられる調理器具や各種厨房設備の付帯部品はもちろんのこと、この調理器具以外の防汚性が要求される各種部材や各種部品等に対しても適用可能であり、その工業的意義は極めて大きいものである。 The cooking utensil of the present invention contains silicon (Si), zirconium (Zr), and oxygen (O) in at least a part of the surface of the base, and the silicon (Si) is converted into silicon oxide (SiO 2 ). The weight of the silicon oxide (SiO 2 ) with respect to the total amount of the zirconium oxide (ZrO 2 ) and the silicon oxide (SiO 2 ) when the zirconium (Zr) is converted into zirconium oxide (ZrO 2 ), respectively. By depositing a thin film with a percentage of 1% by weight or more and 40% by weight or less, it is possible to easily remove the burnt-on dirt and oily dirt on the food adhering during cooking with a water wipe. It is suitable not only for cooking utensils used for cooking food and accessory parts of various kitchen facilities, but also for various components and parts that require antifouling properties other than these cooking utensils. It can be used and its industrial significance is extremely large.
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| JP5435395B2 (en) * | 2008-02-06 | 2014-03-05 | 日本電気硝子株式会社 | Method for manufacturing glass article |
| JP2012021739A (en) * | 2010-07-16 | 2012-02-02 | Panasonic Corp | Cooking device |
| CN108758754B (en) * | 2018-08-28 | 2024-10-18 | 杭州老板电器股份有限公司 | Oil filtering device, manufacturing method and range hood |
| US11802086B2 (en) | 2018-09-13 | 2023-10-31 | Sumitomo Osaka Cement Co., Ltd. | Anti-fouling coating film, glass ceramic product, coating material for forming anti-fouling coating film, and method for producing glass ceramic product |
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| JPH04310586A (en) * | 1991-04-03 | 1992-11-02 | Sekisui Chem Co Ltd | Production of zircon-based coating composition and zircon-based oxide-coated graphite compact |
| JP2002302637A (en) * | 2001-01-30 | 2002-10-18 | Sumitomo Osaka Cement Co Ltd | Hydrophilic coated film-forming composition, process for preparing composite material using this and composite material |
| JP2004307897A (en) * | 2003-04-03 | 2004-11-04 | Nippon Steel Corp | Surface-treated metal having silica-zirconia film, and method of manufacturing the same |
| JP2005281443A (en) * | 2004-03-29 | 2005-10-13 | Sumitomo Osaka Cement Co Ltd | Hydrophilic membrane and its formation method |
| JP2005325440A (en) * | 2004-04-16 | 2005-11-24 | Nippon Steel Corp | Surface-treated metal and method for producing the same |
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|---|---|---|---|---|
| JPH04310586A (en) * | 1991-04-03 | 1992-11-02 | Sekisui Chem Co Ltd | Production of zircon-based coating composition and zircon-based oxide-coated graphite compact |
| JP2002302637A (en) * | 2001-01-30 | 2002-10-18 | Sumitomo Osaka Cement Co Ltd | Hydrophilic coated film-forming composition, process for preparing composite material using this and composite material |
| JP2004307897A (en) * | 2003-04-03 | 2004-11-04 | Nippon Steel Corp | Surface-treated metal having silica-zirconia film, and method of manufacturing the same |
| JP2005281443A (en) * | 2004-03-29 | 2005-10-13 | Sumitomo Osaka Cement Co Ltd | Hydrophilic membrane and its formation method |
| JP2005325440A (en) * | 2004-04-16 | 2005-11-24 | Nippon Steel Corp | Surface-treated metal and method for producing the same |
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| JP5403094B2 (en) | 2014-01-29 |
| JP2008209104A (en) | 2008-09-11 |
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