JP2003310411A - Stainless steel vessel - Google Patents
Stainless steel vesselInfo
- Publication number
- JP2003310411A JP2003310411A JP2002117414A JP2002117414A JP2003310411A JP 2003310411 A JP2003310411 A JP 2003310411A JP 2002117414 A JP2002117414 A JP 2002117414A JP 2002117414 A JP2002117414 A JP 2002117414A JP 2003310411 A JP2003310411 A JP 2003310411A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- hydrophilic film
- hydrophilic
- water
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Table Devices Or Equipment (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、油汚れ等が付着しがた
く、付着しても汚れを容易に除去でき、乾燥時に水滴等
の乾きシミも出にくく、使用時に付着する指紋も目立ち
にくい食器，調理器具等のステンレス鋼製器物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is resistant to oil stains and the like, can easily remove stains even if they adhere, and dry spots such as water droplets do not easily appear during drying, and fingerprints attached during use are not noticeable. It relates to stainless steel utensils such as tableware and cooking utensils.
【０００２】[0002]
【従来の技術】ステンレス鋼製器物は、錆び難く、丈夫
で耐久性に優れているので、学校，病院等における集団
給食用のお椀や皿から調理用器具まで幅広く使用されて
いる。しかし、ステンレス鋼表面が疎水性（換言する
と、親油性）のため、油汚れが付着すると十分に洗浄除
去できない欠点がある。疎水性のステンレス鋼表面は水
をはじく性質があり、ステンレス鋼表面に残存した水滴
が接触角の大きな液滴になる。ステンレス鋼製器物を洗
浄した後に残る液滴には水の他に油分も含まれることが
多く、水分蒸発後に水玉状のシミとなり、美麗なステン
レス鋼表面が醸し出す清潔感が損なわれやすい。付着し
た指紋が目立つことも、ステンレス鋼製器物の欠点であ
る。2. Description of the Related Art Stainless steel utensils are not easily rusted, are durable and have excellent durability, and are therefore widely used in bowls and plates for group lunches in schools, hospitals, etc. to cooking utensils. However, since the stainless steel surface is hydrophobic (in other words, lipophilic), it has a drawback that it cannot be sufficiently washed and removed when oil stains are attached. The hydrophobic stainless steel surface has a property of repelling water, and the water droplets remaining on the stainless steel surface become droplets having a large contact angle. Droplets remaining after washing stainless steel equipment often contain oil as well as water, and become waterdrop-shaped stains after evaporation of water, which tends to impair the cleanliness of a beautiful stainless steel surface. Conspicuous fingerprints attached are also a drawback of stainless steel products.
【０００３】[0003]
【発明が解決しようとする課題】耐油汚れ付着性，付着
した油汚れの除去容易度，水玉状シミによる清潔感の低
下，付着指紋の目立ち易さ等を改善するため、ステンレ
ス鋼表面を親水化することが考えられる。ステンレス鋼
表面の親水化には、界面活性剤，吸水性樹脂，親水性光
触媒の塗布や、ホウロウ引き，セラミックス溶射，シリ
カ膜等の皮膜形成がある。しかし、何れの方法もステン
レス鋼製器物への適用には問題がある。The surface of stainless steel is made hydrophilic in order to improve resistance to oil stains, ease of removing oil stains, deterioration of cleanliness due to polka-dot stains, and conspicuousness of adhered fingerprints. It is possible to do it. Hydrophilization of the surface of stainless steel includes coating with a surfactant, a water-absorbent resin, a hydrophilic photocatalyst, enamelling, ceramic spraying, and silica film formation. However, both methods have problems in application to stainless steel products.
【０００４】界面活性剤をステンレス鋼製器物に塗布す
るとステンレス鋼表面に高い親水性を付与できるが、界
面活性剤自体が水溶性であるため、親水性は短期間で消
失する。吸水性樹脂も、界面活性剤と同様に高い親水性
を付与できるが、アルカリ性洗剤を用いた洗浄によって
容易に劣化する。光触媒で親水性を付与したステンレス
鋼製器物では、光触媒反応を生起させるためブラックラ
イト等の光源を必要とする。そのため、食器洗浄乾燥機
で使用済みステンレス鋼製器物を洗浄する場合、食器洗
浄乾燥機の改造を要求される。ホウロウ引き，セラミッ
クス溶射層，シリカ膜等の皮膜は、何れも加工性が悪い
ことに加え、耐衝撃性に劣る。また、シリカ膜では、ア
ルカリ性洗剤によって劣化する。When a surface-active agent is applied to a stainless steel product, a high hydrophilicity can be imparted to the surface of the stainless steel, but since the surface-active agent itself is water-soluble, the hydrophilicity disappears in a short period of time. The water-absorbent resin can impart high hydrophilicity like the surfactant, but is easily deteriorated by washing with an alkaline detergent. A stainless steel product that has been made hydrophilic with a photocatalyst requires a light source such as a black light to cause a photocatalytic reaction. Therefore, when cleaning used stainless steelware with a dish washer / dryer, it is required to modify the dish washer / dryer. Coatings such as enamelling, ceramic sprayed layers, and silica coatings all have poor workability and inferior impact resistance. Further, the silica film is deteriorated by the alkaline detergent.
【０００５】[0005]
【課題を解決するための手段】本発明は、このような問
題を解消すべく案出されたものであり、特定組成の親水
性皮膜をステンレス鋼表面に設けることにより、油汚れ
が付着しがたく、付着しても油汚れが容易に除去され、
洗浄後に水玉状のシミが残らず、付着した指紋も目立ち
がたいステンレス鋼製器物を提供することを目的とす
る。本発明のステンレス鋼製器物は、その目的を達成す
るため、化学式ＬｉaＮａbＫc(ＳｉＯm)x(ＺｒＯn)y(Ｈ
2Ｏ)z〔ａ，ｂ，ｃ，ｚ：任意数，ｍ，ｎ：１〜４の自
然数，ｘ＋ｙ＝１〕で表される親水性皮膜が基材・ステ
ンレス鋼の表面に設けられていることを特徴とする。The present invention has been devised to solve such problems, and by providing a hydrophilic film of a specific composition on the surface of stainless steel, oil stains are prevented from adhering to it. The oil stains can be easily removed even if you stick it,
It is an object of the present invention to provide a stainless steel product which does not have polka-dot-like stains after cleaning and has a conspicuous fingerprint. In order to achieve the object, the stainless steel product of the present invention has a chemical formula of Li a Na b K c (SiO m ) x (ZrO n ) y (H
2 O) z [a, b, c, z: arbitrary number, m, n: natural number of 1 to 4, x + y = 1] is provided on the surface of the base material / stainless steel with a hydrophilic film. It is characterized by
【０００６】親水性皮膜は、アルミニウムイオン又はア
ルカリ土類金属，Ｚｎ，Ｃｕから選ばれた１種又は２種
以上の二価金属イオンを含んでも良い。アルミニウムイ
オン又は二価金属イオンを含む親水性皮膜では、更にポ
リアクリル酸又はアクリル酸モノマーを含む共重合体を
配合することが好ましい。親水性皮膜の形成に先立ち、
基材・ステンレス鋼をＲｚ：０.１〜１０μｍの表面粗さ
に改質することが好ましい。The hydrophilic film may contain one or more divalent metal ions selected from aluminum ions or alkaline earth metals, Zn and Cu. In the hydrophilic film containing aluminum ions or divalent metal ions, it is preferable to further blend a copolymer containing polyacrylic acid or an acrylic acid monomer. Prior to forming the hydrophilic film,
It is preferable to modify the substrate / stainless steel to have a surface roughness of Rz: 0.1 to 10 μm.
【０００７】[0007]
【実施の形態】本発明者等は、油汚れ付着，付着した油
汚れの除去容易性，水玉状シミの発現，付着指紋の目立
ち易さに及ぼすステンレス鋼表面及び親水性皮膜の影響
について種々調査・検討した。その結果，器物内外面を
構成するステンレス鋼表面に特定された親水性皮膜を設
けると油汚れが付着しがたく、付着しても容易に油汚れ
を除去でき、洗浄後に水分が蒸発した状態でも水玉状の
シミがつかず、付着指紋も目立ちがたい表面に改質でき
ることを見出した。BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have conducted various investigations on the effects of stainless steel surface and hydrophilic film on the adhesion of oil stains, the ease with which oil stains can be removed, the appearance of polka-dot stains, and the noticeability of adhered fingerprints. ·investigated. As a result, when the specified hydrophilic film is provided on the stainless steel surface that constitutes the inner and outer surfaces of the container, oil stains do not easily adhere to it, and even if it adheres, oil stains can be easily removed, and even if the water content has evaporated after cleaning. It was found that polka-dot-like stains do not occur and the surface of the attached fingerprint can be modified to be inconspicuous.
【０００８】基材・ステンレス鋼は、鋼種に特段の制約
が加わるものでなく、オーステナイト系，フェライト
系，マルテンサイト系，二相系等、何れのステンレス鋼
も使用できる。親水性皮膜の形成に先立ち、基材・ステ
ンレス鋼には研磨，脱脂，酸洗等の前処理が適宜施され
る。場合によっては、リン酸塩処理，クロメート処理，
Ｃｒフリーの化成処理等の塗装前処理を施しても良い。The base material / stainless steel is not particularly limited in steel type, and any stainless steel such as austenitic, ferritic, martensitic, and duplex stainless steel can be used. Prior to forming the hydrophilic film, the substrate / stainless steel is appropriately subjected to pretreatment such as polishing, degreasing, and pickling. In some cases, phosphate treatment, chromate treatment,
Pre-painting treatment such as Cr-free chemical conversion treatment may be performed.
【０００９】親水性皮膜は、化学式ＬｉaＮａbＫc(Ｓｉ
Ｏm)x(ＺｒＯn)y(Ｈ2Ｏ)z〔ａ，ｂ，ｃ，ｚ：任意数，
ｍ，ｎ：１〜４の自然数，ｘ＋ｙ＝１〕で特定される皮
膜である。式中、Ｈ2Ｏは、単なる液体の水ではなく、
水和反応で皮膜に固定されている結晶水等である。当該
化学式で表される複合酸化物は、通常非晶質であり、ア
ルカリ性洗剤に対して優れた耐久性を示す。Ｌｉ，Ｎ
ａ，Ｋ等のアルカリ金属イオン及びＨ2Ｏで外部の水分
子が引き付けられるため、親水性皮膜が優れた親水性を
発現する。The hydrophilic film has a chemical formula of Li a Na b K c (Si
O m ) x (ZrO n ) y (H 2 O) z [a, b, c, z: any number,
m, n: a natural number of 1 to 4, x + y = 1]. In the formula, H 2 O is not just liquid water,
It is water of crystallization and the like fixed to the film by hydration reaction. The complex oxide represented by the chemical formula is usually amorphous and exhibits excellent durability against alkaline detergents. Li, N
Since external water molecules are attracted by the alkali metal ions such as a and K and H 2 O, the hydrophilic film exhibits excellent hydrophilicity.
【００１０】親水性皮膜は、好ましくは液体状の塗料を
ステンレス鋼表面に塗布し焼き付けることによって形成
される。液体状の塗料は、各成分の原料を溶液又は液体
に分散することにより調製される。化学式を構成するＳ
ｉＯmに対応する酸化ケイ素原料には、各種ケイ酸アル
カリの水溶液，コロイダルシリカ（シリカゾル），ケイ
酸エチルに代表される各種ケイ酸アルコキシド等が好適
である。アルコキシドを酸化ケイ素原料に使用する場
合、水及び触媒（酸又はアルカリ）の存在下でアルコキ
シドを一旦加水分解して得られたゾルとして使用する
と、良質の親水性皮膜が形成される。皮膜全体に占める
酸化ケイ素の割合が１質量％以上になると、皮膜に十分
な親水性が付与される。しかし、９０質量％を超える酸
化ケイ素では、皮膜の耐アルカリ性が低下する。The hydrophilic coating is preferably formed by applying a liquid coating material to the surface of stainless steel and baking it. Liquid paints are prepared by dispersing the raw materials of the components in a solution or liquid. S composing the chemical formula
As a silicon oxide raw material corresponding to iO m , various alkali silicate aqueous solutions, colloidal silica (silica sol), and various silicic acid alkoxides represented by ethyl silicate are suitable. When an alkoxide is used as a silicon oxide raw material, a good quality hydrophilic film is formed when it is used as a sol obtained by once hydrolyzing the alkoxide in the presence of water and a catalyst (acid or alkali). When the proportion of silicon oxide in the entire coating is 1% by mass or more, sufficient hydrophilicity is imparted to the coating. However, if the silicon oxide content exceeds 90% by mass, the alkali resistance of the film will be reduced.
【００１１】化学式を構成するＺｒＯnに対応する酸化
ジルコニウム原料には、オキシ塩化ジルコニウム又はオ
キシ硝酸ジルコニウムの水溶液，ジルコニウムテトラブ
トキシド等のアルコキシドの加水分解物，ジルコニアゾ
ル等がある。皮膜全体に占める酸化ジルコニウムの割合
が１質量％以上で、皮膜の耐アルカリ性が向上する。し
かし、９０質量％を超える過剰量の酸化ジルコニウムが
含まれると、皮膜の親水性が低下する。The zirconium oxide raw material corresponding to ZrO n constituting the chemical formula includes an aqueous solution of zirconium oxychloride or zirconium oxynitrate, a hydrolyzate of an alkoxide such as zirconium tetrabutoxide, and zirconia sol. When the proportion of zirconium oxide in the entire coating is 1% by mass or more, the alkali resistance of the coating is improved. However, if an excess amount of zirconium oxide exceeding 90% by mass is contained, the hydrophilicity of the film will decrease.
【００１２】化学式を構成するＬｉaＮａbＫcに対応す
るＬｉ，Ｎａ，Ｋ等のアルカリ金属イオンは、硝酸塩，
塩化物，有機酸塩等の水溶性塩類として供給される。こ
れらの塩は、水溶性である限り特段の制約なく使用され
る。皮膜全体に占めるアルカリ金属イオンの割合が０.
１質量％以上で、十分な親水性が皮膜に付与される。し
かし、アルカリ金属イオンの割合が１０質量％を超える
と、親水性皮膜の耐アルカリ性が低下する。化学式を構
成するＨ2Ｏは、容易に蒸発する液体の水ではなく、化
学的な水和反応によって結合した結晶水等である。Ｈ2
Ｏは、各成分原料の水溶液，アルコキシドの加水分解に
用いた水，空気中の水分等から供給される。皮膜全体に
占めるＨ2Ｏの割合は、１〜７０質量％の範囲が好まし
い。Alkali metal ions such as Li, Na and K corresponding to Li a Na b K c constituting the chemical formula are nitrates,
Supplied as water-soluble salts such as chlorides and organic acid salts. These salts are used without particular restrictions as long as they are water-soluble. The proportion of alkali metal ions in the entire coating is 0.
When it is 1% by mass or more, sufficient hydrophilicity is imparted to the film. However, if the proportion of alkali metal ions exceeds 10% by mass, the alkali resistance of the hydrophilic film is reduced. The H 2 O that constitutes the chemical formula is not water that easily evaporates, but water of crystallization that is bound by a chemical hydration reaction. H 2
O is supplied from an aqueous solution of each component raw material, water used for hydrolysis of alkoxide, moisture in air, and the like. The proportion of H 2 O in the entire coating is preferably in the range of 1 to 70 mass%.
【００１３】親水性皮膜にアルミニウムイオンが含まれ
ると、皮膜の耐久性，強度が向上する。アルミニウムイ
オンによる性質改善効果は、０.１質量％以上で顕著に
なる。アルミニウムイオンの原料には、硝酸塩，塩化物
等の水溶性塩類やアルミニウムイソプロポキシドに代表
されるアルコキシドの加水分解物，アルミナゾル等があ
る。アルミニウムイオンに代え又はアルミニウムイオン
と共に、Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｃｕ，Ｚｎ等の二価
金属イオンを０.１〜１０質量％含ませることによって
も皮膜の耐久性，強度が向上する。二価金属イオンによ
り皮膜の耐久性，高度が向上することは、酸化ケイ素，
酸化ジルコニウム等の複合酸化物とアルカリ金属イオン
及びＨ2Ｏからなるネットワーク構造が二価金属イオン
によって架橋されることに拠るものと推察される。二価
金属イオンは、硝酸塩，塩化物等の水溶性塩類として供
給される。When the hydrophilic film contains aluminum ions, the durability and strength of the film are improved. The effect of improving properties by aluminum ions becomes remarkable at 0.1% by mass or more. Examples of the raw material of aluminum ions include water-soluble salts such as nitrates and chlorides, hydrolysates of alkoxides represented by aluminum isopropoxide, and alumina sol. The durability and strength of the coating are also improved by containing divalent metal ions such as Mg, Ca, Sr, Ba, Cu, and Zn in an amount of 0.1 to 10 mass% instead of or together with aluminum ions. The improvement of the durability and altitude of the film due to the divalent metal ion is due to the fact that silicon oxide,
It is presumed that this is due to the fact that a network structure composed of a complex oxide such as zirconium oxide, an alkali metal ion and H 2 O is crosslinked by a divalent metal ion. Divalent metal ions are supplied as water-soluble salts such as nitrates and chlorides.
【００１４】ポリアクリル酸又はアクリル酸モノマーを
含む共重合体を親水性皮膜に配合すると、基材・ステン
レス鋼に対する親水性皮膜の接着性が向上する。接着性
の向上は、アクリル酸ポリマーがステンレス鋼表面／無
機質皮膜との界面に介在して親和性を向上させる結果と
考えられる。接着性改善効果は、ポリアクリル酸又はア
クリル酸モノマーを含む共重合体の配合量１質量％以上
でみられる。しかし、１０質量％を超える配合量では、
親水性の低下が認められる。When a copolymer containing polyacrylic acid or an acrylic acid monomer is blended in the hydrophilic film, the adhesion of the hydrophilic film to the substrate / stainless steel is improved. It is considered that the improved adhesiveness is a result of the acrylic acid polymer intervening at the interface between the surface of the stainless steel and the inorganic film to improve the affinity. The effect of improving the adhesiveness is observed when the blending amount of the copolymer containing polyacrylic acid or acrylic acid monomer is 1% by mass or more. However, if the blending amount exceeds 10% by mass,
A decrease in hydrophilicity is observed.
【００１５】各成分原料は、所定の割合になるように予
め秤量しておき、好ましくは塗布し易いように各種有機
溶媒を用いて親水性コーティング液として用意する。溶
媒は、水以外に、水と相溶するアルコール類，ケトン類
等の有機溶媒が好ましい。親水性コーティング液の調製
に際しては、沈殿，相分離等が生じないように酸又はア
ルカリ添加でｐＨ調整し、水分量を調整することが好ま
しい。親水性コーティング液の固形分濃度は、特に本発
明に制約を加えるものではないが、０.１〜１０質量％
の範囲が好ましい。The raw materials for each component are weighed in advance so as to have a predetermined ratio, and preferably prepared as a hydrophilic coating liquid using various organic solvents so as to facilitate coating. In addition to water, the solvent is preferably an organic solvent compatible with water, such as alcohols and ketones. When preparing the hydrophilic coating liquid, it is preferable to adjust the pH by adding an acid or an alkali so as to prevent precipitation, phase separation and the like, and to adjust the water content. The solid content concentration of the hydrophilic coating liquid is not particularly limited to the present invention, but is 0.1 to 10% by mass.
Is preferred.
【００１６】親水性コーティング液は、ロールコート
法，カーテンフローコート法，スプレー法，浸漬法等で
ステンレス鋼表面に塗布される。塗布後、焼付け，冷却
することにより目標とする親水性皮膜が形成される。過
酷な加工が予想される形状のステンレス鋼製器物では、
製品形状に基材・ステンレス鋼を成型加工した後で浸漬
法，スプレー法等で親水性コーティング液がステンレス
鋼表面に塗布される。親水性コーティング液の塗布・焼
付けを繰り返すことにより、親水性皮膜を厚膜化でき
る。The hydrophilic coating liquid is applied to the stainless steel surface by a roll coating method, a curtain flow coating method, a spraying method, a dipping method or the like. After coating, baking and cooling form a target hydrophilic film. For stainless steel instruments with shapes that are expected to undergo severe processing,
After forming the base material and stainless steel into the product shape, the hydrophilic coating liquid is applied to the stainless steel surface by dipping, spraying, or the like. The hydrophilic coating can be thickened by repeating the application and baking of the hydrophilic coating liquid.
【００１７】ステンレス鋼表面に塗布された親水性コー
ティング液は、強度のある親水性皮膜を十分成長させる
ため１００℃以上の温度で焼き付けることが好ましい。
しかし、３００℃を超える高温焼付けは、ステンレス鋼
表面に酸化皮膜が生成してテンパーカラーが発現し、器
物として不適切な外観になる虞がある。親水性皮膜は、
１μｍ以下の膜厚でステンレス鋼表面に形成することが
好ましい。厚すぎる親水性皮膜では、ステンレス鋼板を
器物形状に成形加工する際に基材・ステンレス鋼から剥
離する虞がある。親水性コーティング液の焼付けは、１
００〜３００℃の温度域で実施することが好ましい。The hydrophilic coating liquid applied to the surface of stainless steel is preferably baked at a temperature of 100 ° C. or higher in order to sufficiently grow a strong hydrophilic film.
However, high temperature baking exceeding 300 ° C. may generate an oxide film on the surface of stainless steel and develop a temper color, which may result in an unsuitable appearance as a container. The hydrophilic film is
It is preferably formed on the surface of stainless steel with a film thickness of 1 μm or less. If the hydrophilic coating is too thick, it may be peeled from the base material / stainless steel when the stainless steel sheet is formed into a container shape. Baking of hydrophilic coating liquid is 1
It is preferably carried out in the temperature range of 00 to 300 ° C.
【００１８】親水性皮膜の形成に先立って、基材・ステ
ンレス鋼をＲｚ：０.１〜１０μｍの表面粗さに調質し
ても良い。Ｒｚ：０.１〜１０μｍの表面粗さは、ステ
ンレス鋼製器物に付着した指紋を目立たなくする上で有
効である。Ｒｚ：０.１μｍ未満の表面粗さでは、ステ
ンレス鋼製器物の表面光沢が増し、付着した指紋が強調
される。逆にＲｚ：１０μｍを超える表面粗さでは、プ
レス成形性が低下し、器物使用時に付着した澱粉等を洗
浄除去しがたくなる。素材・ステンレス鋼板又は器物形
状に成形した基材・ステンレス鋼板に研磨，ブラスト処
理等を施すことにより表面粗さをＲｚ：０.１〜１０μ
ｍに調整できるが、目方向のない電解研磨，ショットブ
ラスト等の表面仕上げが好ましい。Prior to the formation of the hydrophilic film, the substrate / stainless steel may be conditioned to have a surface roughness of Rz: 0.1 to 10 μm. The surface roughness of Rz: 0.1 to 10 μm is effective in making fingerprints attached to the stainless steel product inconspicuous. Rz: When the surface roughness is less than 0.1 μm, the surface gloss of the stainless steel product is increased and the attached fingerprint is emphasized. On the other hand, when the surface roughness Rz is more than 10 μm, the press formability is deteriorated, and it becomes difficult to wash and remove the starch and the like adhering to the container during use. The surface roughness of the material / stainless steel plate or the base material / stainless steel plate formed into a container shape is Rz: 0.1 to 10μ by polishing and blasting.
Although it can be adjusted to m, surface finishing such as electropolishing and shot blasting with no grain direction is preferable.
【００１９】[0019]
【実施例】テトラエトキシシラン：１０ｇにエタノー
ル：８０ｇ，ブトキシエタノール：９ｇ，１質量％硝酸
水溶液：１ｇを加え、６０℃で２４時間攪拌しながら加
水分解することによりシリカゾル液Ａを得た。また、オ
キシ硝酸ジルコニウム：１ｇ，硝酸アルミニウム：０.
１ｇ，硝酸亜鉛：０.１ｇ，硝酸リチウム：１ｇ及びポ
リアクリル酸：１ｇを水に溶解し、水溶液Ｂ：１００ｇ
を得た。Example To 10 g of tetraethoxysilane, 80 g of ethanol, 9 g of butoxyethanol and 1 g of a 1% by mass nitric acid aqueous solution were added and hydrolyzed at 60 ° C. for 24 hours while stirring to obtain a silica sol solution A. Further, zirconium oxynitrate: 1 g, aluminum nitrate: 0.0
1 g, zinc nitrate: 0.1 g, lithium nitrate: 1 g and polyacrylic acid: 1 g are dissolved in water to prepare an aqueous solution B: 100 g.
Got
【００２０】シリカゾル液Ａ，水溶液Ｂそれぞれ５０ｇ
を混合し、硝酸でｐＨ１に調整した親水性コーティング
液Ｉを調整した。親水性コーティング液Ｉは固形分濃度
が約５質量％であり、２００℃に加熱したときの化学組
成（親水性皮膜の組成に相当）はＳｉＯ2：５８質量
％，ＺｒＯ2：１１質量％，Ａｌ2Ｏ3：０.４質量％，Ｚ
ｎＯ2：０.８質量％，Ｌｉ2Ｏ：４質量％，Ｈ2Ｏ：７質
量％，ポリアクリル酸：１９質量％であった。加熱後の
化学組成に含まれるＨ2Ｏは、２００℃加熱でも蒸発し
ないことから水和反応によって固定化された水と考えら
れる。50 g each of silica sol liquid A and aqueous solution B
Was mixed, and a hydrophilic coating liquid I adjusted to pH 1 with nitric acid was prepared. The hydrophilic coating liquid I has a solid content concentration of about 5 mass%, and the chemical composition (corresponding to the composition of the hydrophilic film) when heated to 200 ° C. is SiO 2 : 58 mass%, ZrO 2 : 11 mass%, al 2 O 3: 0.4 wt%, Z
nO 2 was 0.8% by mass, Li 2 O was 4% by mass, H 2 O was 7% by mass, and polyacrylic acid was 19% by mass. Since H 2 O contained in the chemical composition after heating does not evaporate even when heated at 200 ° C., it is considered to be water immobilized by the hydration reaction.
【００２１】〔スプーンへの適用〕板厚１.２ｍｍのＳ
ＵＳ４３０ステンレス鋼板を成形加工し、機械研磨する
ことによりスプーンを作製した。スプーンを５％ＮａＯ
Ｈ水溶液で１時間脱脂・洗浄し、蒸留水で濯ぎ、自然乾
燥した。乾燥後のスプーンを温度２３℃の親水性コーテ
ィング液Ｉに浸漬し、引き上げ速度１ｍｍ／秒で親水性
コーティング液Ｉから引き上げた。次いで、スプーンを
加熱炉に装入し、大気雰囲気下で２５０℃×２分加熱
し、スプーン表面に膜厚０.２μｍの親水性皮膜を形成
した。親水性皮膜が形成されたスプーンの対水接触角は
１９度であり、親水性皮膜のないスプーンの対水接触角
７２度に比較すると、親水性皮膜によって親水性が付与
されていることが判る。親水性皮膜が設けられたスプー
ンに付着した油汚れは、洗剤を用いる必要なく水洗だけ
で容易に除去できた。[Application to spoon] S having a plate thickness of 1.2 mm
A US430 stainless steel plate was formed and mechanically polished to prepare a spoon. Spoon 5% NaO
It was degreased and washed with an aqueous H solution for 1 hour, rinsed with distilled water, and naturally dried. The dried spoon was dipped in the hydrophilic coating liquid I at a temperature of 23 ° C. and pulled out from the hydrophilic coating liquid I at a pulling rate of 1 mm / sec. Then, the spoon was placed in a heating furnace and heated in an air atmosphere at 250 ° C. for 2 minutes to form a hydrophilic film having a thickness of 0.2 μm on the surface of the spoon. The spoon having a hydrophilic film has a water contact angle of 19 degrees, and compared to the spoon having no hydrophilic film having a water contact angle of 72 degrees, it can be seen that the hydrophilic film imparts hydrophilicity. . The oil stains attached to the spoon provided with the hydrophilic film could be easily removed only by washing with water without using a detergent.
【００２２】〔お椀への適用〕板厚０.３ｍｍのＳＵＳ
３０４ステンレス鋼板をプレス加工し、お椀を作製し
た。一部のお椀については、＃８０ヘアライン研磨，＃
２４０ヘアライン研磨，電解研磨，ショットブラスト，
エッチング仕上げ等を内外面に施した。更に一部のお椀
については、１０％ＮａＯＨ水溶液で３０分脱脂・洗浄
し、水洗，乾燥した後、親水性コーティング液Ｉをスプ
レーした。本例では、2-プロパノールを用い親水性コー
ティング液Ｉを重量比で３倍に希釈した液を用意し、お
椀１００ｃｍ2当り０.１ｇの割合でスプレーした。スプ
レー後、加熱炉に装入したお椀を大気雰囲気下２００℃
×１分加熱することにより、お椀の表面に親水性皮膜を
形成した。[Application to bowl] SUS with a plate thickness of 0.3 mm
A 304 stainless steel plate was pressed to produce a bowl. For some bowls, # 80 hairline polishing, #
240 hairline polishing, electrolytic polishing, shot blasting,
Etching finish etc. were applied to the inner and outer surfaces. Further, some of the bowls were degreased / washed with a 10% NaOH aqueous solution for 30 minutes, washed with water, dried, and then sprayed with the hydrophilic coating liquid I. In this example, a solution prepared by diluting the hydrophilic coating solution I with 2-propanol three times by weight was prepared and sprayed at a rate of 0.1 g per 100 cm 2 of the bowl. After spraying, the bowl placed in the heating furnace is heated to 200 ° C in the atmosphere.
By heating for 1 minute, a hydrophilic film was formed on the surface of the bowl.
【００２３】各椀の表面粗さをJIS B0601に準拠して測
定すると共に、油汚れ除去性，乾きシミ防止性，指紋視
認性，澱粉除去性を調査した。油汚れ除去性は、青色絵
の具を溶かし込んだサラダ油をお椀内面に塗布し、４０
℃の温水に漬け込み、１分間超音波洗浄した後でお椀内
面を目視観察することにより評価した。乾きシミ防止性
は、水道水で洗浄したお椀を温風乾燥機内にうつ伏せ状
にセットし、４０℃に３時間放置した後、お椀表面を目
視観察することにより評価した。指紋視認性は、お椀の
内外面に指紋を付着させ、付着指紋の目立ち易さを官能
評価した。澱粉除去性は、ご飯粒が潰れるまで擦り付け
たお椀内面をスポンジを用いて水洗し乾燥させた後、ヨ
ウ素溶液を塗布し呈色反応の有無で評価した。The surface roughness of each bowl was measured according to JIS B0601, and the oil stain removability, dry stain prevention, fingerprint visibility, and starch removability were investigated. To remove oil stains, apply salad oil with blue paint dissolved on the inner surface of the bowl to
It was evaluated by visually observing the inner surface of the bowl after soaking in warm water at ℃ for 1 minute and ultrasonic cleaning. The anti-dry stain property was evaluated by visually observing the surface of the bowl after setting the bowl washed with tap water in a warm air dryer in a prone position and leaving it at 40 ° C. for 3 hours. For fingerprint visibility, fingerprints were adhered to the inner and outer surfaces of the bowl, and a sensory evaluation of the conspicuousness of the adhered fingerprints was performed. The starch removability was evaluated based on the presence or absence of color reaction after the inner surface of the bowl, which had been rubbed until the rice grains were crushed, was washed with water using a sponge and dried, and then an iodine solution was applied.
【００２４】表１の調査結果にみられるように、親水性
皮膜を設けたお椀は、無被覆のお椀と比較して何れも優
れた親水性，油汚れ除去性を示し、乾きシミも検出され
ず、指紋も見えにくかった。なかでも、表面粗さＲｚ：
０.１μｍ以上で無方向性の表面仕上げを施したお椀で
は、付着指紋が極めて見え難かった。また、表面粗さを
Ｒｚ：１０μｍ以下に規制することにより、お椀表面に
こびりついた澱粉も容易に除去できた。しかも、親水性
皮膜によって金属特有の臭いの発散が抑えられているの
で、嗜好性の高い飲食物の食器として好適であった。As can be seen from the results of the survey in Table 1, the bowls provided with a hydrophilic coating exhibited excellent hydrophilicity and oil stain removability in comparison with the uncoated bowls, and dry spots were also detected. The fingerprints were hard to see. Among them, the surface roughness Rz:
With a bowl having a non-directional surface finish of 0.1 μm or more, it was extremely difficult to see the attached fingerprints. Further, by controlling the surface roughness to Rz: 10 μm or less, the starch stuck to the bowl surface could be easily removed. Moreover, since the hydrophilic film suppresses the emission of the odor peculiar to metal, it was suitable as a tableware for food and drink with a high taste.
【００２５】 [0025]
【００２６】[0026]
【発明の効果】以上に説明したように、本発明のステン
レス鋼製器物は、化学式ＬｉaＮａbＫ c(ＳｉＯm)x(Ｚｒ
Ｏn)y(Ｈ2Ｏ)zで特定される親水性皮膜を基材・ステンレ
ス鋼の表面に設けているので、油汚れが付着し難く、付
着しても油汚れを容易に除去でき、乾燥後にも水玉状の
シミが残らず、取り扱い時の指紋も目立ち難い。そのた
め、ステンレス鋼本来の美麗で清潔感のある表面が活か
され、金属臭も親水性皮膜で抑制されることから、清潔
な食器，調理器具等として重宝される。As described above, the stainless steel of the present invention is used.
The less steel equipment has the chemical formula LiaNabK c(SiOm)x(Zr
On)y(H2O)zThe hydrophilic film specified by
Since it is provided on the surface of stainless steel, it does not easily get oil stains
Oil stains can be easily removed even when worn, and even after drying
No stains remain, and fingerprints during handling are inconspicuous. That
Therefore, the beautiful and clean surface of stainless steel is utilized.
The metallic odor is also suppressed by the hydrophilic film, so it is clean.
It is useful as a tableware and cooking utensils.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 深見 泰民 東京都千代田区丸の内三丁目４番１号 日 新製鋼株式会社内 (72)発明者 茂 啓二郎 東京都千代田区六番町６番地28 住友大阪 セメント株式会社内 Ｆターム(参考） 3B001 AA00 CC40 4D075 CA37 DA11 DB04 DC38 DC41 EA07 EB01 EB22 4K044 AA03 AB05 BA13 BA14 BA19 BA21 BB03 BC09 CA07 CA53 CA62 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Fumin Taimin 3-4-1, Marunouchi, Chiyoda-ku, Tokyo Within Shin Steel Co., Ltd. (72) Inventor Keijiro Shige 28 Sumitomo Osaka, 6-6 Rokubancho, Chiyoda-ku, Tokyo Inside Cement Co., Ltd. F-term (reference) 3B001 AA00 CC40 4D075 CA37 DA11 DB04 DC38 DC41 EA07 EB01 EB22 4K044 AA03 AB05 BA13 BA14 BA19 BA21 BB03 BC09 CA07 CA53 CA62
Claims (4)
n)y(Ｈ2Ｏ)z〔ａ，ｂ，ｃ，ｚ：任意数，ｍ，ｎ：１〜
４の自然数，ｘ＋ｙ＝１〕で表される親水性皮膜が基材
・ステンレス鋼の表面に設けられていることを特徴とす
るステンレス鋼製器物。1. A chemical formula of Li a Na b K c (SiO m ) x (ZrO
n ) y (H 2 O) z [a, b, c, z: any number, m, n: 1 to
4 is a natural number, x + y = 1], and a hydrophilic coating is provided on the surface of the base material / stainless steel.
ルカリ土類金属，Ｚｎ，Ｃｕから選ばれた１種又は２種
以上の二価金属イオンを含む請求項１記載のステンレス
鋼製器物。2. The stainless steel container according to claim 1, wherein the hydrophilic film contains aluminum ions or one or more divalent metal ions selected from alkaline earth metals, Zn and Cu.
クリル酸モノマーを含む共重合体を含有している請求項
２記載のステンレス鋼製器物。3. The stainless steel container according to claim 2, wherein the hydrophilic film further contains a copolymer containing polyacrylic acid or an acrylic acid monomer.
０.１〜１０μｍである請求項１〜３何れかに記載のス
テンレス鋼製器物。4. The surface roughness of the base material / stainless steel is Rz:
It is 0.1-10 micrometers, The stainless steelware in any one of Claims 1-3.
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|---|---|---|---|
| JP2002117414A JP4131534B2 (en) | 2002-04-19 | 2002-04-19 | Stainless steel fixtures |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002117414A JP4131534B2 (en) | 2002-04-19 | 2002-04-19 | Stainless steel fixtures |
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| Publication Number | Publication Date |
|---|---|
| JP2003310411A true JP2003310411A (en) | 2003-11-05 |
| JP4131534B2 JP4131534B2 (en) | 2008-08-13 |
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|---|---|---|---|
| JP2002117414A Expired - Lifetime JP4131534B2 (en) | 2002-04-19 | 2002-04-19 | Stainless steel fixtures |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007046097A (en) * | 2005-08-09 | 2007-02-22 | Nisshin Steel Co Ltd | Surface treated stainless steel sheet having excellent adhesion durability |
| JP2008231551A (en) * | 2007-03-23 | 2008-10-02 | Nisshin Steel Co Ltd | Stainless steel product excellent in temper coloring resistance and method for manufacturing the same |
| WO2010140571A1 (en) * | 2009-06-03 | 2010-12-09 | 株式会社神戸製鋼所 | Titanium plate and process for producing titanium plate |
| JP2014088531A (en) * | 2012-10-31 | 2014-05-15 | Sumitomo Osaka Cement Co Ltd | Hydrophilic film, hydrophilic film coated article, coating liquid for forming hydrophilic film and method for producing hydrophilic film |
| JP5854168B2 (en) * | 2013-02-27 | 2016-02-09 | 住友大阪セメント株式会社 | Porous article and method for producing the same |
| WO2017056845A1 (en) * | 2015-09-28 | 2017-04-06 | 住友大阪セメント株式会社 | Method for manufacturing dishwasher/dryer |
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2002
- 2002-04-19 JP JP2002117414A patent/JP4131534B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007046097A (en) * | 2005-08-09 | 2007-02-22 | Nisshin Steel Co Ltd | Surface treated stainless steel sheet having excellent adhesion durability |
| JP4579789B2 (en) * | 2005-08-09 | 2010-11-10 | 日新製鋼株式会社 | Surface-treated stainless steel sheet with excellent adhesion durability |
| JP2008231551A (en) * | 2007-03-23 | 2008-10-02 | Nisshin Steel Co Ltd | Stainless steel product excellent in temper coloring resistance and method for manufacturing the same |
| WO2010140571A1 (en) * | 2009-06-03 | 2010-12-09 | 株式会社神戸製鋼所 | Titanium plate and process for producing titanium plate |
| JP2010280938A (en) * | 2009-06-03 | 2010-12-16 | Kobe Steel Ltd | Titanium sheet and method of manufacturing the same |
| JP2014088531A (en) * | 2012-10-31 | 2014-05-15 | Sumitomo Osaka Cement Co Ltd | Hydrophilic film, hydrophilic film coated article, coating liquid for forming hydrophilic film and method for producing hydrophilic film |
| JP5854168B2 (en) * | 2013-02-27 | 2016-02-09 | 住友大阪セメント株式会社 | Porous article and method for producing the same |
| WO2017056845A1 (en) * | 2015-09-28 | 2017-04-06 | 住友大阪セメント株式会社 | Method for manufacturing dishwasher/dryer |
| CN108135433A (en) * | 2015-09-28 | 2018-06-08 | 住友大阪水泥股份有限公司 | The manufacturing method of dish ware washing drier |
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