JPH0727457A - Ice making plate - Google Patents
Ice making plateInfo
- Publication number
- JPH0727457A JPH0727457A JP3576694A JP3576694A JPH0727457A JP H0727457 A JPH0727457 A JP H0727457A JP 3576694 A JP3576694 A JP 3576694A JP 3576694 A JP3576694 A JP 3576694A JP H0727457 A JPH0727457 A JP H0727457A
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- ice making
- composite plating
- plating film
- ice
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、基板材表面にフッ素材
料系微粒子を共析させた複合メッキ被膜を備えた製氷板
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ice making plate provided with a composite plating film in which fine particles of a fluorine material are co-deposited on the surface of a substrate material.
【０００２】[0002]
【従来の技術】鮮魚類、生鮮食料品などの氷詰めなどに
用いられる氷の製造装置は、通常内部の冷媒によって外
表面を低温にした製氷板の表面に散水することにより、
付着した水を氷結させて氷とするものである。製造され
た氷の製氷容器からの離氷を促進するために、従来は、
製氷板の表面を加熱したり、或いは散水される水の中に
エチレングリコールなどの薬剤を混入したりしている。
そして、離氷性をさらに一層改善するために、高度の撥
水性、離型性などを有するポリテトラフルオロエチレン
（ＰＴＦＥ）などのフッ素系樹脂を製氷板基板材表面に
被覆する方法；家庭用の冷蔵庫内で用いられる移動式の
製氷容器にあっては、フッ素系樹脂などの撥水性の高い
樹脂を成形した容器を用いるなどの方法が採用されてい
る。2. Description of the Related Art An ice making apparatus used for filling fresh fish, fresh foods, etc. with ice is usually prepared by spraying water on the surface of an ice making plate whose outer surface is cooled by an internal refrigerant.
The water that adheres is frozen to form ice. Conventionally, in order to promote the release of ice from the ice-making container produced,
The surface of the ice making plate is heated, or a chemical such as ethylene glycol is mixed in water to be sprinkled.
Then, in order to further improve the ice releasing property, a method of coating the surface of the ice making plate substrate material with a fluorine-based resin such as polytetrafluoroethylene (PTFE) having a high degree of water repellency and releasability; For a mobile ice making container used in a refrigerator, a method of using a container formed of a highly water-repellent resin such as a fluorine-based resin is adopted.
【０００３】しかしながら、ＰＴＦＥなどの樹脂被覆層
は、フッ素系樹脂の熱伝導率が金属の約１／３００程度
と低いこと、樹脂自体の強度が低いので、耐久性を確保
するために膜厚を大きくする必要があることなどの理由
から、製氷板の熱伝導速度を低下させて、製氷効率を著
しく低下させる欠点がある。また、フッ素系樹脂の成型
品を使用する場合にも、ほぼ同様な問題点が存在する。However, the resin coating layer such as PTFE has a low thermal conductivity of the fluororesin, which is about 1/300 of that of the metal, and the strength of the resin itself is low. There is a drawback that the heat conduction rate of the ice making plate is lowered and the ice making efficiency is remarkably lowered because of the necessity of increasing the size. Also, when using a molded product of a fluororesin, there are almost the same problems.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明は、耐
久性に優れ、表面エネルギーがより低く、撥水性が高い
被覆層を備えた製氷板を提供することを主な目的とす
る。SUMMARY OF THE INVENTION Accordingly, the main object of the present invention is to provide an ice making plate having a coating layer having excellent durability, lower surface energy and high water repellency.
【０００５】さらに、本発明は、製氷効率を低下させる
ことなく、離氷性により優れた製氷板を提供することを
も目的とする。Another object of the present invention is to provide an ice making plate which is excellent in ice releasing property without lowering ice making efficiency.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記のよう
な従来技術の問題点に鑑みて、鋭意研究を重ねた結果、
製氷板基板表面にフッ素系材料の微粒子を分散含有する
複合メッキ被膜を形成させる場合には、高い撥水性によ
り示されるその低表面エネルギーのために離氷性が大幅
に改善され、またその金属成分に由来する高い熱伝導性
のために製氷効率も著しく向上することを見出した。The present inventor has conducted extensive studies in view of the problems of the prior art as described above, and as a result,
When a composite plating film containing fine particles of a fluorine-based material dispersed therein is formed on the surface of an ice making plate substrate, its low surface energy, which is shown by its high water repellency, greatly improves the ice releasing property, and its metal component It was found that the ice-making efficiency is significantly improved due to the high thermal conductivity derived from.
【０００７】則ち、本発明は、下記の製氷板を提供する
ものである； １．基板材表面に平均粒径２μｍ以下のフッ化黒鉛
｛（ＣＦ）n｝微粒子、ポリテトラフルオロエチレン微
粒子、テトラフルオロエチレン−ヘキサフルオロプロピ
レン共重合体微粒子およびテトラフルオロエチレン−パ
ーフルオロアルキルビニルエーテル共重合体微粒子の少
なくとも１種を分散含有する複合メッキ被膜を備えた製
氷板。That is, the present invention provides the following ice making plates: Fluorinated graphite {(CF) n } fine particles having an average particle size of 2 μm or less, polytetrafluoroethylene fine particles, tetrafluoroethylene-hexafluoropropylene copolymer fine particles and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer on the surface of the substrate material. An ice making plate provided with a composite plating film containing at least one kind of fine particles dispersed therein.
【０００８】２．平均粒径２μｍ以下のフッ化黒鉛
｛（ＣＦ）n｝微粒子を分散含有する複合メッキ被膜を
備えた上記項１に記載の製氷板。2. 2. The ice making plate according to item 1 above, which is provided with a composite plating film in which fluorinated graphite {(CF) n } fine particles having an average particle diameter of 2 μm or less are dispersed and contained.
【０００９】３．平均粒径２μｍ以下のポリテトラフル
オロエチレン微粒子を分散含有する複合メッキ被膜を備
えた上記項１に記載の製氷板。3. Item 2. The ice making plate according to Item 1, which is provided with a composite plating film in which polytetrafluoroethylene fine particles having an average particle diameter of 2 µm or less are dispersed and contained.
【００１０】４．平均粒径２μｍ以下のテトラフルオロ
エチレン−ヘキサフルオロプロピレン共重合体微粒子を
分散含有する複合メッキ被膜を備えた上記項１に記載の
製氷板。4. 2. The ice making plate according to item 1 above, which is provided with a composite plating film containing tetrafluoroethylene-hexafluoropropylene copolymer fine particles having an average particle diameter of 2 μm or less dispersed therein.
【００１１】５．平均粒径２μｍ以下のテトラフルオロ
エチレン−パーフルオロアルキルビニルエーテル共重合
体微粒子を分散含有する複合メッキ被膜を備えた上記項
１に記載の製氷板。5. Item 2. The ice making plate according to Item 1, comprising a composite plating film in which fine particles of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer having an average particle diameter of 2 µm or less are dispersed and contained.
【００１２】一般に、フッ化黒鉛、ポリテトラフルオロ
エチレン（以下ＰＴＦＥという）、テトラフルオロエチ
レン−ヘキサフルオロプロピレン共重合体（以下ＦＥＰ
という）、テトラフルオロエチレン−パーフルオロアル
キルビニルエーテル共重合体（以下ＰＦＡという）など
（本願明細書においては、これらをフッ素系材料と総称
する）は、自己潤滑性、低摩擦性、撥水性、非粘着性な
どの性質に優れている。本発明によれば、この様なフッ
素系材料の微粒子を金属とともに製氷板基材表面に電解
析出させて、その固有の優れた性質と金属の性質とを併
せ持つ複合メッキ被膜を形成させることにより、耐久
性、離氷性、製氷効率などに優れた製氷板が得られる。Generally, fluorinated graphite, polytetrafluoroethylene (hereinafter referred to as PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP)
, A tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (hereinafter referred to as PFA), etc. (in the present specification, these are collectively referred to as a fluorine-based material), self-lubricating property, low friction property, water repellency, non- Excellent in properties such as adhesiveness. According to the present invention, such fine particles of a fluorine-based material are electrolytically deposited on the surface of an ice making plate base material together with a metal to form a composite plating film having both its unique excellent properties and metal properties. An ice-making plate having excellent durability, ice releasing property, and ice-making efficiency can be obtained.
【００１３】本発明における共析複合メッキの形成に
は、製氷板として用いられる金属、樹脂などの基板材の
表面にマトリックス金属を析出させうる公知の無電解メ
ッキ法および電解メッキ法を採用することができる。ま
た、使用するメッキ液についても、公知組成のメッキ液
のいずれをも使用することができる。より具体的には、
例えば、特開昭４９−２７４４３号公報、特開平４−３
２９８９７号公報などに開示されたメッキ手法に準じ
て、フッ素系材料微粒子をメッキ金属塩の水溶液中に分
散させ、基板上にマトリックス金属とともにフッ素系材
料微粒子を共析させて、非金属であるフッ素系材料の固
有の性質とマトリックスである金属の性質とを合わせ持
つ複合メッキ被膜を形成させればよい。To form the eutectoid composite plating in the present invention, a known electroless plating method or electrolytic plating method capable of depositing a matrix metal on the surface of a substrate material such as metal or resin used as an ice making plate is adopted. You can As the plating solution used, any plating solution having a known composition can be used. More specifically,
For example, JP-A-49-27443 and JP-A-4-3
According to the plating method disclosed in Japanese Patent Publication No. 29897, fine particles of a fluorine-based material are dispersed in an aqueous solution of a plating metal salt, and the fine particles of a fluorine-based material are co-deposited with a matrix metal on a substrate to form a non-metal fluorine. It suffices to form a composite plating film having both the inherent properties of the system material and the properties of the metal matrix.
【００１４】本発明で使用するフッ素系材料（フッ化黒
鉛、ＰＴＦＥ，ＦＥＰ、ＰＦＡなど）は、いずれも公知
の物質であり、その原料、製造方法などは特に限定され
ない。The fluorine-based materials (graphite fluoride, PTFE, FEP, PFA, etc.) used in the present invention are all known substances, and their raw materials and manufacturing methods are not particularly limited.
【００１５】本発明においては、フッ素系材料をそれぞ
れ単独で使用しても良く、或いは２種以上を併用しても
良い。以下にフッ素系材料の使用例を例示する。In the present invention, the fluorine-containing materials may be used alone or in combination of two or more kinds. An example of using the fluorine-based material will be illustrated below.
【００１６】（ａ）平均粒径２μｍ以下のフッ化黒鉛、
すなわち（ＣＦ）n（但し，ｎ＞１０００程度である）
で表される化合物の微粒子を単独で使用する。(A) Fluorinated graphite having an average particle size of 2 μm or less,
That is, (CF) n (however, n> 1000)
The fine particles of the compound represented by are used alone.
【００１７】（ｂ）平均粒径２μｍ以下のＰＴＦＥ微粒
子を単独で使用する。(B) The PTFE fine particles having an average particle diameter of 2 μm or less are used alone.
【００１８】（ｃ）平均粒径２μｍ以下のＦＥＰ微粒子
を単独で使用する。(C) FEP fine particles having an average particle size of 2 μm or less are used alone.
【００１９】（ｄ）平均粒径２μｍ以下のＰＦＡ微粒子
を単独で使用する。(D) PFA fine particles having an average particle size of 2 μm or less are used alone.
【００２０】（ｅ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とフッ化黒鉛微粒子とを併用する。この場合の混合割
合は、特に限定されず、任意に選択することができる。(E) PTFE fine particles having an average particle diameter of 2 μm or less and fluorinated graphite fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２１】（ｆ）平均粒径２μｍ以下のフッ化黒鉛微
粒子とＦＥＰ微粒子とを併用する。この場合の混合割合
も、特に限定されず、任意に選択することができる。(F) Fluorinated graphite fine particles having an average particle diameter of 2 μm or less and FEP fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２２】（ｇ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とＦＥＰ微粒子とを併用する。この場合の混合割合
も、特に限定されず、任意に選択することができる。(G) PTFE fine particles having an average particle diameter of 2 μm or less and FEP fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２３】（ｈ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とフッ化黒鉛微粒子とＦＥＰ微粒子とを併用する。こ
の場合の混合割合も、特に限定されず、任意に選択する
ことができる。(H) PTFE fine particles having an average particle diameter of 2 μm or less, fluorinated graphite fine particles and FEP fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２４】（ｉ）平均粒径２μｍ以下のＰＦＡ微粒子
とフッ化黒鉛微粒子とを併用する。この場合の混合割合
も、特に限定されず、任意に選択することができる。(I) PFA fine particles having an average particle diameter of 2 μm or less and fluorinated graphite fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２５】（ｊ）平均粒径２μｍ以下のＰＦＡ微粒子
とＦＴＦＥ微粒子とを併用する。この場合の混合割合
も、特に限定されず、任意に選択することができる。(J) PFA fine particles having an average particle diameter of 2 μm or less and FTFE fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２６】（ｋ）平均粒径２μｍ以下のＰＦＡ微粒子
とＦＥＰ微粒子とを併用する。この場合の混合割合も、
特に限定されず、任意に選択することができる。(K) PFA fine particles having an average particle diameter of 2 μm or less and FEP fine particles are used in combination. In this case, the mixing ratio
It is not particularly limited and can be arbitrarily selected.
【００２７】（ｌ）平均粒径２μｍ以下のＰＦＡ微粒子
とＦＥＰ微粒子とフッ化黒鉛微粒子とを併用する。この
場合の混合割合も、特に限定されず、任意に選択するこ
とができる。(L) PFA fine particles having an average particle diameter of 2 μm or less, FEP fine particles and fluorinated graphite fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２８】（ｍ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とＰＦＡ微粒子とフッ化黒鉛微粒子とを併用する。こ
の場合の混合割合も、特に限定されず、任意に選択する
ことができる。(M) PTFE fine particles having an average particle diameter of 2 μm or less, PFA fine particles and fluorinated graphite fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００２９】（ｎ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とＰＦＡ微粒子とＦＥＰ微粒子とを併用する。この場
合の混合割合も、特に限定されず、任意に選択すること
ができる。(N) PTFE fine particles having an average particle diameter of 2 μm or less, PFA fine particles and FEP fine particles are used in combination. The mixing ratio in this case is not particularly limited and can be arbitrarily selected.
【００３０】（ｏ）平均粒径２μｍ以下のＰＴＦＥ微粒
子とＰＦＡ微粒子とＦＥＰ微粒子とフッ化黒鉛微粒子と
を併用する。この場合の混合割合も、特に限定されず、
任意に選択することができる。(O) PTFE fine particles having an average particle diameter of 2 μm or less, PFA fine particles, FEP fine particles and fluorinated graphite fine particles are used in combination. The mixing ratio in this case is also not particularly limited,
It can be arbitrarily selected.
【００３１】上記のフッ素化合物の使用例中でも、
（ａ）、（ｂ）、（ｃ）、（ｄ）、（ｅ）、（ｆ）、
（ｇ）などがより好ましい。Among the examples of use of the above-mentioned fluorine compounds,
(A), (b), (c), (d), (e), (f),
(G) and the like are more preferable.
【００３２】塩の形態で用いられ、複合メッキ被膜中の
マトリックスとなる金属のメッキ液としては、例えば、
ニッケル、銅、亜鉛、スズ、鉄、鉛、カドミウム、クロ
ム、貴金属類およびそれらの合金を含むメッキ液など何
れも使用することができる。これらのメッキ液は、各種
の組成のものが公知となっており、本発明では、これら
の公知のメッキ液のいずれをも用いることができる。The metal plating solution used in the form of salt and serving as a matrix in the composite plating film is, for example,
Any plating solution containing nickel, copper, zinc, tin, iron, lead, cadmium, chromium, noble metals and alloys thereof can be used. As these plating solutions, those having various compositions are known, and in the present invention, any of these known plating solutions can be used.
【００３３】本発明において、複合メッキ被膜を形成す
るためのメッキ液（以下複合メッキ液という）に添加す
るフッ素系材料微粒子の粒径は、特に限定されるもので
はないが、複合メッキ被膜全体の膜厚よりも大きい場合
には、摩擦によりメッキ面から粒子が脱落するので、メ
ッキ被膜厚よりも小さい微粒子を使用することが望まし
い。本発明による複合メッキ被膜の厚さは、製氷板の大
きさおよび材質、マトリックス金属の種類などにより異
なるが、通常１〜５０μｍ程度である。従って、フッ素
系材料微粒子の粒径は、この複合メッキ被膜の厚さを考
慮して定めれば良いが、通常平均２μｍ程度であり、平
均１μｍ以下のものがより好ましい。また、複合メッキ
液中および複合メッキ被膜中でのフッ素系材料微粒子の
分散の均一性を確保するために、３０μｍ以上の粗大粒
子を含まないことが望ましい。複合メッキ液中のフッ素
系材料微粒子の添加量は、特に限定されないが、通常２
００ｇ／ｌ程度以下、好ましくは１〜１００ｇ／ｌ程度
である。In the present invention, the particle diameter of the fine particles of the fluorine-based material added to the plating solution for forming the composite plating film (hereinafter referred to as the composite plating solution) is not particularly limited, but the particle size of the entire composite plating film is not limited. When the thickness is larger than the film thickness, particles fall off from the plated surface due to friction, so it is desirable to use fine particles smaller than the film thickness to be plated. The thickness of the composite plating film according to the present invention varies depending on the size and material of the ice making plate, the type of matrix metal, etc., but is usually about 1 to 50 μm. Therefore, the particle size of the fine particles of the fluorine-based material may be determined in consideration of the thickness of the composite plating film, but is usually about 2 μm on average and more preferably 1 μm or less on average. Further, in order to ensure the uniformity of dispersion of the fluorine-based material fine particles in the composite plating solution and the composite plating film, it is desirable not to include coarse particles of 30 μm or more. The amount of the fluorine-based material particles added to the composite plating solution is not particularly limited, but is usually 2
It is about 100 g / l or less, preferably about 1 to 100 g / l.
【００３４】一般に、金属と共析物とからなる複合メッ
キ被膜においては、共析物の体積分率が大きくなるほ
ど、メッキ層と基材との密着性は低下する。本発明にお
いても、メッキ被膜と製氷板基材との密着性を考慮すれ
ば、複合メッキ被膜中の共析物（フッ素系材料微粒子）
の体積分率は、６０％が限度である。一方、フッ素系材
料微粒子の体積分率が低すぎる場合には、撥水性、潤滑
性、離氷性などの改善が十分に行なわれない。従って、
本発明においては、複合メッキ被膜中のフッ素系材料微
粒子の体積分率は、通常２５〜５０％程度、より好まし
くは３５〜４５％程度とする。In general, in a composite plating film composed of a metal and an eutectoid, the larger the volume fraction of the eutectoid, the lower the adhesion between the plating layer and the substrate. Also in the present invention, if the adhesion between the plated coating and the ice making plate substrate is taken into consideration, the eutectoid (fluorine-based material fine particles) in the composite plated coating
The volume fraction of is limited to 60%. On the other hand, if the volume fraction of the fine particles of the fluorine-based material is too low, the water repellency, lubricity, and ice releasing property are not sufficiently improved. Therefore,
In the present invention, the volume fraction of the fine particles of the fluorine-based material in the composite plating film is usually about 25 to 50%, more preferably about 35 to 45%.
【００３５】本発明においては、製氷板基材としては、
銅、ステンレス鋼、一般鋼、アルミニウム、アルミニウ
ム合金などの金属、ＡＢＳ（アクリロニトリル・ブタジ
エン・スチレン共重合体）、ＰＴＦＥなどの樹脂などが
用いられる。これらの中では、熱伝導性の高い金属が好
ましく、銅、アルミニウム、アルミニウム合金などがよ
り好ましい。In the present invention, the ice making plate base material is
Metals such as copper, stainless steel, general steel, aluminum and aluminum alloys, resins such as ABS (acrylonitrile / butadiene / styrene copolymer) and PTFE are used. Among these, metals having high thermal conductivity are preferable, and copper, aluminum, aluminum alloys and the like are more preferable.
【００３６】本発明においては、製氷板基材の材質、製
氷板の使用環境、目的とする氷の製造速度、形状などに
よりマトリックス金属および／またはフッ素系材料の種
類を選択することができる。例えば、製氷板に優れた耐
熱性、耐食性などが要求される場合には、マトリックス
金属としてニッケルを使用し、フッ素系材料としてフッ
化黒鉛、ＰＴＦＥ或いはこれらの混合系を用いることが
好ましい。また、高度の撥水性が求められる場合には、
フッ素系材料としてＦＥＰ、ＰＴＦＥ或いはこれらの混
合系を使用することが好ましい。さらに、特に良好な離
型性が要求される場合には、ＰＴＦＥ、ＰＦＡ、ＦＥＰ
或いはこれらの混合系を使用することが好ましい。さら
にまた、特に優れた耐傷付き性が必要とされる場合に
は、フッ化黒鉛或いはフッ化黒鉛含有混合物を使用する
ことが好ましい。In the present invention, the type of the matrix metal and / or the fluorine-based material can be selected according to the material of the ice making plate base material, the environment in which the ice making plate is used, the desired ice production rate, the shape, and the like. For example, when excellent heat resistance and corrosion resistance are required for the ice making plate, it is preferable to use nickel as the matrix metal and use fluorinated graphite, PTFE or a mixed system thereof as the fluorine-based material. Also, when high water repellency is required,
It is preferable to use FEP, PTFE or a mixture thereof as the fluorine-based material. Furthermore, when particularly good mold releasability is required, PTFE, PFA, FEP
Alternatively, it is preferable to use a mixed system of these. Furthermore, it is preferable to use fluorinated graphite or a fluorinated graphite-containing mixture when particularly excellent scratch resistance is required.
【００３７】本発明による複合メッキ被膜を形成させる
ための複合メッキ液では、撥水性が非常に高いフッ素系
材料をメッキ液中に均一に分散させ且つ完全に濡れた状
態とする必要があるので、界面活性剤を用いる。界面活
性剤としては、例えば、水溶性のカチオン系、非イオン
系およびメッキ液のｐＨ値においてカチオン性を示す両
性界面活性剤を用いることができる。この場合、カチオ
ン系界面活性剤としては、第４級アンモニウム塩、第２
および３アミン類などが挙げられ、非イオン系界面活性
剤としては、ポリエチレンイミン系、エステル系のもの
などが挙げられ、両性界面活性剤としては、カルボン酸
系、スルホン系のものなどが挙げられる。特に、分子中
にＣ−Ｆ結合を有するフッ素系界面活性剤を用いること
が好ましい。In the composite plating solution for forming the composite plating film according to the present invention, it is necessary to uniformly disperse the fluorine-containing material having extremely high water repellency in the plating solution and keep it completely wet. Use a surfactant. As the surfactant, for example, a water-soluble cationic or nonionic amphoteric surfactant exhibiting a cationic property at the pH value of the plating solution can be used. In this case, as the cationic surfactant, a quaternary ammonium salt, a second
Examples of the nonionic surfactant include polyethyleneimine-based and ester-based surfactants, and amphoteric surfactants include carboxylic-acid-based and sulfone-based surfactants. . In particular, it is preferable to use a fluorochemical surfactant having a C—F bond in the molecule.
【００３８】メッキ液中への界面活性剤の添加量は、フ
ッ素系材料１ｇに対し、通常１〜１００ｍｇ程度であ
り、より好ましくは１〜５０ｍｇ程度である。The amount of the surfactant added to the plating solution is usually about 1 to 100 mg, more preferably about 1 to 50 mg, based on 1 g of the fluorine-containing material.
【００３９】本発明においては、上記の複合メッキ液に
一次光沢剤、二次光沢剤などの公知の添加剤をさらに配
合することができる。In the present invention, known additives such as a primary brightener and a secondary brightener can be further added to the above composite plating solution.
【００４０】本発明において、複合メッキ被膜を形成す
るに際しては、フッ素系材料微粒子を均一に分散させる
ために、複合メッキ液を撹拌しつつメッキ操作を行なう
ことが好ましい。撹拌方法は特に限定されず、通常の機
械的撹拌手段、例えばスクリュ−撹拌、マグネチックス
タ−ラ−による撹拌などの方法を採用することができ
る。In the present invention, when forming the composite plating film, it is preferable to perform the plating operation while stirring the composite plating solution in order to uniformly disperse the fine particles of the fluorine-based material. The stirring method is not particularly limited, and an ordinary mechanical stirring means such as a screw stirring, a stirring by a magnetic stirrer, or the like can be adopted.
【００４１】メッキ条件は、製氷板基材の材質、使用す
る複合メッキ液の種類などに応じて適宜決定すればよ
く、一般に通常の複合メッキ法の場合と同様の液温、ｐ
Ｈ値、電流密度などを採用すれば良い。The plating conditions may be appropriately determined according to the material of the ice making plate base material, the type of the composite plating solution used, and the like, and generally the same solution temperature and p as in the case of the normal composite plating method.
The H value, the current density, etc. may be adopted.
【００４２】なお、本発明における複合メッキ被膜は、
必ずしも製氷板基材上に直接形成する必要はなく、銅、
アルミニウムなどの金属或いは樹脂からなる基材上に公
知の下地メッキ層（例えば、ニッケルメッキ、銅メッキ
など）を形成した後、複合メッキ被膜を形成しても良
い。The composite plating film of the present invention is
It is not always necessary to form directly on the ice making plate base material, but copper,
A composite plating film may be formed after forming a known base plating layer (for example, nickel plating, copper plating, etc.) on a base material made of a metal such as aluminum or a resin.
【００４３】本発明において、フッ素系材料としてＰＴ
ＦＥおよび／またはＦＥＰを使用する場合には、上記の
様にして基材上に形成した複合メッキ被膜を１５０〜３
５０℃で熱処理することが好ましい。この熱処理によ
り、複合メッキ被膜の耐久性および表面撥水性が著しく
改善される。この熱処理により、撥水性が著しく改善さ
れる理由は、明確ではないが、複合メッキ被膜自体の熱
的改質、界面活性剤の除去（熱分解、蒸発、昇華などに
よる）による濡れ性の低下もその一因をなしているもの
と推考される。熱処理時間は、特に限定されるものでは
ないが、通常１０〜３０分間程度行なえば良い。熱処理
温度が１５０℃未満である場合には、十分な処理効果を
得るために処理時間を長くする必要があり、一方、３５
０℃を上回る場合には、メッキ被膜が劣化するおそれが
ある。In the present invention, PT is used as the fluorine-based material.
When FE and / or FEP is used, the composite plating film formed on the substrate as described above is used in an amount of 150 to 3
It is preferable to perform heat treatment at 50 ° C. This heat treatment significantly improves the durability and surface water repellency of the composite plated coating. Although it is not clear why the water repellency is significantly improved by this heat treatment, the wettability is also deteriorated due to thermal modification of the composite plating film itself and removal of the surfactant (by thermal decomposition, evaporation, sublimation, etc.). It is thought that this is one of the reasons. Although the heat treatment time is not particularly limited, it is usually 10 to 30 minutes. If the heat treatment temperature is lower than 150 ° C., it is necessary to lengthen the treatment time in order to obtain a sufficient treatment effect.
If the temperature exceeds 0 ° C, the plating film may deteriorate.
【００４４】[0044]
【発明の効果】本発明により製氷板基材上に形成された
複合メッキ被膜は、非金属であるフッ素化合物の固有の
性質とマトリックス金属の固有の性質とを兼ね備えてい
る。EFFECTS OF THE INVENTION The composite plating film formed on the ice making plate substrate according to the present invention has both the unique properties of the non-metal fluorine compound and the unique properties of the matrix metal.
【００４５】より具体的には、この複合メッキ被膜は、
先ず、フッ素系材料に由来する高度の潤滑性、耐摩耗性
などを有し、さらに特に優れた耐久性、撥水性などを発
揮する。More specifically, the composite plating film is
First, it has a high degree of lubricity and wear resistance derived from a fluorine-based material, and exhibits particularly excellent durability and water repellency.
【００４６】この複合メッキ被膜は、さらに、マトリッ
クス金属に由来する高硬度、高強度、高熱伝導性などを
備え、且つ基材に対する優れた密着性を発揮する。従っ
て、例えばＰＴＦＥなどのフッ素系樹脂の被膜或いはフ
ッ素樹脂成型品に比べて、本発明による複合メッキ被膜
は、強度に優れ、傷付き難く、基材からも剥離しにく
く、熱伝導性および耐久性にも優れている。The composite plating film further has high hardness, high strength, high thermal conductivity, etc. derived from the matrix metal, and exhibits excellent adhesion to the substrate. Therefore, as compared with, for example, a fluororesin coating such as PTFE or a fluororesin molded product, the composite plating coating according to the present invention has excellent strength, is less likely to be scratched, is less likely to be peeled from the base material, and has thermal conductivity and durability. Is also excellent.
【００４７】その結果、本発明の製氷板を使用する場合
には、離氷性および製氷効率が大幅に改善され、製氷容
器の耐久性が向上する。As a result, when the ice making plate of the present invention is used, the ice releasing property and the ice making efficiency are greatly improved, and the durability of the ice making container is improved.
【００４８】[0048]
【実施例】以下に実施例および比較例を示し、本発明の
特徴とするところをより一層明確にする。EXAMPLES Examples and comparative examples will be shown below to further clarify the features of the present invention.
【００４９】なお、物性の測定は、下記の方法により行
った。The physical properties were measured by the following methods.
【００５０】（１）接触角 ＦＡＣＥ接触角計（協和界面科学（株）製、“ＣＡ−Ａ
型”）を用いて、液滴法により、水の接触角を測定し
た。(1) Contact angle FACE contact angle meter (Kyowa Interface Science Co., Ltd., "CA-A")
The contact angle of water was measured by the sessile drop method.
【００５１】（２）密着力（ＪＩＳ Ｋ５４００） サンプルに１ｃｍ2当たり１００個のごばん目を入れ、
下記の各条件下に放置した後、常温に戻し、セロファン
粘着テープにより、圧着剥離試験を行った。(2) Adhesion (JIS K5400) 100 pieces per 1 cm 2 are put in the sample,
After standing under each of the following conditions, the temperature was returned to room temperature, and a pressure-bonding peeling test was performed using a cellophane adhesive tape.
【００５２】（ａ）２５０℃で２時間放置 （ｂ）−１０℃で２時間放置 （ｃ）（２００℃で１時間→−１０℃で１時間）×１０
サイクル 密着力を示す結果において、“１００／１００”とある
のは、剥離がなかったことを示し、“５０／１００”と
あるのは、ごばん目の半数が剥離したことを示す。(A) Leave at 250 ° C. for 2 hours (b) Leave at -10 ° C. for 2 hours (c) (200 ° C. for 1 hour → -10 ° C. for 1 hour) × 10
In the results showing the cycle adhesion, "100/100" means that there was no peeling, and "50/100" means that half of the eyes were peeled.
【００５３】（３）衝撃変形試験（ＪＩＳ Ｋ５４０
０） ２０℃でデュポン方式により衝撃試験を行って変形させ
た部分の塗面の損傷を確認した。(3) Impact deformation test (JIS K540
0) An impact test was performed at 20 ° C. by the DuPont method to confirm the damage on the coated surface of the deformed portion.
【００５４】おもり ：５００ｇ 落下高さ：５００ｍｍ （４）離氷性試験 複合メッキサンプル板の表面（３０ｍｍ×５０ｍｍ）上
に注射器で１ｃｃの蒸留水を静かに滴下し、直径２．１
ｃｍの水滴を形成させ、−２０℃の製氷室に３時間静置
して水滴を氷結させた。次いで、メッキ被膜サンプル板
を製氷室からすばやく取り出し、１７℃の恒温室内に垂
直に静置し、氷滴の落下（滑落）開始までの時間を測定
した。Weight: 500 g Drop height: 500 mm (4) Ice release test 1 cc of distilled water was gently dropped by a syringe onto the surface (30 mm x 50 mm) of the composite plating sample plate, and the diameter was 2.1.
A water droplet of cm was formed, and the water droplet was left to stand in an ice making chamber at -20 ° C for 3 hours to freeze the water droplet. Then, the plated film sample plate was quickly taken out from the ice making chamber, and was left standing vertically in a constant temperature room at 17 ° C., and the time until the start of ice drop (sliding) was measured.
【００５５】実施例１メッキ液の調製 フッ化黒鉛微粒子（平均粒径１μｍ以下、旭硝子（株）
製）５重量％を下記の組成を有するニッケル電解浴に添
加した。なお、界面活性剤（商標“メガファックＦ１５
０”、大日本インキ化学（株）製、第３級パ−フルオロ
アンモニウム塩（Ｃ8 Ｆ17ＳＯ2 ＮＨ（ＣＨ2 ）3 Ｎ+
（ＣＨ3 ）3 ・Ｃｌ- ））をフッ化黒鉛１ｇに対し４
０．０ｍｇの割合で添加した。Example 1 Preparation of plating solution Fluorinated graphite fine particles (average particle size 1 μm or less, Asahi Glass Co., Ltd.)
5% by weight) was added to a nickel electrolytic bath having the following composition. In addition, a surfactant (trademark "Megafuck F15
0 ″, manufactured by Dainippon Ink and Chemicals, Inc., tertiary perfluoroammonium salt (C 8 F 17 SO 2 NH (CH 2 ) 3 N +
(CH 3 ) 3 · Cl − )) 4 for 1 g of fluorinated graphite
Added at a rate of 0.0 mg.
【００５６】スルファミン酸ニッケル電解浴組成 スルファミン酸ニッケル ３５０ｇ／ｌ 塩化ニッケル ４５ｇ／ｌ ほう酸 ４０ｇ／ｌ負極として用いたサンプル 平板状のステンレス鋼板（ＳＵＳ３０４、３０ｍｍ×５
０ｍｍ×０．５ｍｍ）を用いた。 Nickel Sulfamate Electrolytic Bath Composition Nickel Sulfamate 350 g / l Nickel Chloride 45 g / l Boric Acid 40 g / l Sample Flat Stainless Steel Plate Used as Negative Electrode (SUS304, 30 mm × 5)
0 mm × 0.5 mm) was used.
【００５７】メッキ法 次いで、上記のステンレス鋼板を負極として、下記の組
成を有するウッド浴を用いて、液温２５℃、電流密度１
０Ａ／ｄｍ2の条件下に膜厚１〜３μｍの下地ニッケル
メッキ層を形成させた。 Plating Method Next, using the above-mentioned stainless steel plate as a negative electrode and a wood bath having the following composition, a liquid temperature of 25 ° C. and a current density of 1
A base nickel plating layer having a film thickness of 1 to 3 μm was formed under the condition of 0 A / dm 2 .
【００５８】塩化ニッケル ２４５ｇ／ｌ 塩酸 １２０ｇ／ｌ 次いで、上記の下地ニッケルメッキ層を備えたステンレ
ス鋼板を液温４５±５℃、ｐＨ３．８〜４．２、電流密
度３Ａ／ｄｍ2の条件でスクリュー撹拌しつつ、膜厚が
１０μｍとなるまで電解メッキを行って、ニッケル−フ
ッ化黒鉛複合メッキ被膜を形成させた。Nickel chloride 245 g / l Hydrochloric acid 120 g / l Then, the stainless steel plate provided with the above-mentioned underlying nickel plating layer was subjected to the conditions of a liquid temperature of 45 ± 5 ° C., a pH of 3.8 to 4.2, and a current density of 3 A / dm 2 . While stirring with a screw, electroplating was performed until the film thickness reached 10 μm to form a nickel-fluorinated graphite composite plating film.
【００５９】得られたニッケル−フッ化黒鉛複合メッキ
被膜を有するステンレス鋼板を熱風循環式乾燥炉中で、
３５０℃で３０分間加熱した後、常温で室内放置１時間
後に、ＦＡＣＥ接触角計を用いて液適法により、水の接
触角を測定し、その撥水性を調べた。The stainless steel plate having the nickel-fluorinated graphite composite plating film thus obtained was placed in a hot air circulation type drying oven.
After being heated at 350 ° C. for 30 minutes and left at room temperature for 1 hour, the contact angle of water was measured by a liquid suiting method using a FACE contact angle meter, and its water repellency was examined.
【００６０】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００６１】結果を表１に示す。なお、表１には、実施
例２〜１１および比較例１〜２の結果を併せて示す。The results are shown in Table 1. In addition, Table 1 also shows the results of Examples 2 to 11 and Comparative Examples 1 and 2.
【００６２】実施例２ ＰＴＦＥ微粒子（粒子径２μｍ以下、ダイキン工業
（株）製）５重量％を使用し、且つＰＴＦＥ１ｇに対し
界面活性剤（商標“メガファックＦ１５０”、大日本イ
ンキ化学（株）製）を３０．０ｍｇの割合で添加したメ
ッキ液を使用する以外は実施例１と同様にして、実施例
１と同様にして予めニッケル下地メッキ層を形成したス
テンレス鋼板に対して、ニッケル−ＰＴＦＥ複合メッキ
被膜を形成させた。Example 2 5% by weight of PTFE fine particles (particle diameter 2 μm or less, manufactured by Daikin Industries, Ltd.) was used, and 1 g of PTFE was used as a surfactant (trademark “Megafuck F150”, Dainippon Ink and Chemicals, Inc.). Manufactured in the same manner as in Example 1 except that a plating solution added with 30.0 mg was used for nickel-PTFE with respect to a stainless steel plate on which a nickel underplating layer was previously formed in the same manner as in Example 1. A composite plating film was formed.
【００６３】得られたニッケル−ＰＴＦＥ複合メッキ被
膜を有するステンレス鋼板を熱風循環式乾燥炉中で、３
５０℃で３０分間加熱した後、常温で室内放置１時間後
に、ＦＡＣＥ接触角計を用いて液適法により、水の接触
角を測定し、その撥水性を調べた。The stainless steel plate having the nickel-PTFE composite plating film thus obtained was placed in a hot-air circulation type drying oven for 3 days.
After heating at 50 ° C. for 30 minutes and leaving it at room temperature for 1 hour, the contact angle of water was measured by a liquid suiting method using a FACE contact angle meter to examine its water repellency.
【００６４】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００６５】実施例３ まず、実施例１と同様にしてステンレス鋼板に対して下
地メッキ被膜を形成させた後、下記の材料を主成分と
し、ＰＴＦＥ微粒子（粒子径０．３μｍ以下、ダイキン
工業（株）製）１重量％を使用し、且つＰＴＦＥ１ｇに
対し界面活性剤（商標“メガファックＦ１５０”、大日
本インキ化学（株）製）を３０．０ｍｇの割合で添加し
たメッキ液を使用して、無電解ニッケル−ＰＴＦＥ複合
メッキ被膜を形成させた。Example 3 First, a base plating film was formed on a stainless steel sheet in the same manner as in Example 1, and then the following materials were used as main components and PTFE fine particles (particle diameter 0.3 μm or less, Daikin Industries ( 1% by weight, and a plating solution in which a surfactant (trademark "Megafuck F150", manufactured by Dainippon Ink and Chemicals, Inc.) was added at a ratio of 30.0 mg to 1 g of PTFE. , An electroless nickel-PTFE composite plating film was formed.
【００６６】無電解ニッケル複合メッキ浴組成 硫酸ニッケル六水塩 ２０ｇ／ｌ クエン酸ナトリウム ８ｇ／ｌ マロン酸ナトリウム ２０ｇ／ｌ 次亜リン酸ナトリウム ２０ｇ／ｌ 上記で得た下地ニッケルメッキ層を備えたステンレス鋼
板を無電解ニッケル複合メッキ浴に液温９０±２℃、ｐ
Ｈ４．９〜５．２の条件でスクリュー撹拌しつつ、膜厚
が１０μｍとなるまで１時間かけて無電解メッキを行っ
て、無電解ニッケル−ＰＴＦＥ複合メッキ被膜を形成さ
せた。 Electroless nickel composite plating bath composition Nickel sulfate hexahydrate 20 g / l Sodium citrate 8 g / l Sodium malonate 20 g / l Sodium hypophosphite 20 g / l Stainless steel with the nickel plating layer obtained above Steel plate in electroless nickel composite plating bath, liquid temperature 90 ± 2 ℃, p
While stirring with a screw under the conditions of H4.9 to 5.2, electroless plating was performed for 1 hour until the film thickness became 10 μm to form an electroless nickel-PTFE composite plating film.
【００６７】得られた無電解ニッケル−ＰＴＦＥ複合メ
ッキ被膜を有するステンレス鋼板を熱風循環式乾燥炉中
で、３５０℃で３０分間加熱した後、常温で室内放置１
時間後に、ＦＡＣＥ接触角計を用いて液適法により、水
の接触角を測定し、その撥水性を調べた。The obtained stainless steel sheet having the electroless nickel-PTFE composite plating film was heated at 350 ° C. for 30 minutes in a hot-air circulation type drying furnace and then left indoors at room temperature 1
After a lapse of time, the contact angle of water was measured by a liquid suiting method using a FACE contact angle meter to examine its water repellency.
【００６８】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００６９】実施例４ ＦＥＰ微粒子（粒子径０．２〜０．３μｍ、ダイキン工
業（株）製）５重量％を使用し、且つＦＥＰ１ｇに対し
界面活性剤（商標“メガファックＦ１５０”、大日本イ
ンキ化学（株）製）を６５．０ｍｇの割合で添加したメ
ッキ液を使用する以外は実施例１と同様にして、実施例
１と同様にして予めニッケル下地メッキ層を形成したス
テンレス鋼板に対して、ニッケル−ＦＥＰ複合メッキ被
膜を形成させた。Example 4 5% by weight of FEP fine particles (particle size: 0.2 to 0.3 μm, manufactured by Daikin Industries, Ltd.) was used, and 1 g of FEP was mixed with a surfactant (trademark “Megafuck F150”, Dainippon Dainippon). Ink Kagaku Co., Ltd.) was used in the same manner as in Example 1 except that a plating solution containing 65.0 mg was added to a stainless steel plate on which a nickel-underlying plating layer was previously formed. To form a nickel-FEP composite plating film.
【００７０】得られたニッケル−ＦＥＰ複合メッキ被膜
を有するステンレス鋼板を熱風循環式乾燥炉中で、２５
０℃で３０分間加熱した後、常温で室内放置１時間後
に、ＦＡＣＥ接触角計を用いて液適法により、水の接触
角を測定し、その撥水性を調べた。The obtained stainless steel plate having the nickel-FEP composite plating film was placed in a hot-air circulation type drying oven for 25 hours.
After heating at 0 ° C. for 30 minutes, after leaving it for 1 hour at room temperature in a room, the contact angle of water was measured by a liquid suiting method using a FACE contact angle meter, and its water repellency was examined.
【００７１】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００７２】実施例５ フッ化黒鉛微粒子（粒子径１μｍ以下、旭硝子（株）
製）１．２５重量％、ＰＴＦＥ微粒子（粒子径２μｍ以
下、ダイキン工業（株）製）２．５重量％およびＦＥＰ
微粒子（粒子径０．２〜０．３μｍ、ダイキン工業
（株）製）２．５重量％を使用し、且つ界面活性剤（商
標“メガファックＦ１５０”、大日本インキ化学（株）
製）をフッ化黒鉛１ｇに対し４０．０ｍｇ、ＰＴＦＥ１
ｇに対し３０．０ｍｇおよびＦＥＰ１ｇに対し６５．０
ｍｇの割合で添加したメッキ液を使用する以外は実施例
１と同様にして、実施例１と同様にして予めニッケル下
地メッキ層を形成したステンレス鋼板に対して、ニッケ
ル−フッ化黒鉛−ＰＴＦＥ−ＦＥＰ複合メッキ被膜を形
成させた。Example 5 Graphite fluorinated fine particles (particle size 1 μm or less, Asahi Glass Co., Ltd.)
1.25% by weight, PTFE fine particles (particle diameter 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.5% by weight and FEP
2.5% by weight of fine particles (particle diameter 0.2 to 0.3 μm, manufactured by Daikin Industries, Ltd.) are used, and a surfactant (trademark “Megafuck F150”, Dainippon Ink and Chemicals, Inc.) is used.
40.0 mg per 1 g of fluorinated graphite, PTFE1
30.0 mg / g and 65.0 / g FEP
In the same manner as in Example 1 except that the plating liquid added in the proportion of mg was used, nickel-fluorinated graphite-PTFE- An FEP composite plating film was formed.
【００７３】得られたニッケル−フッ化黒鉛−ＰＴＦＥ
−ＦＥＰ複合メッキ被膜を有するステンレス鋼板を熱風
循環式乾燥炉中で、３５０℃で３０分間加熱した後、常
温で室内放置１時間後に、ＦＡＣＥ接触角計を用いて液
適法により、水の接触角を測定し、その撥水性を調べ
た。Obtained nickel-fluorinated graphite-PTFE
-A stainless steel plate having a FEP composite plating film is heated in a hot-air circulation type drying oven at 350 ° C for 30 minutes, and then left indoors at room temperature for 1 hour, and then a contact angle of water is measured by a liquid method using a FACE contact angle meter. Was measured and its water repellency was investigated.
【００７４】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００７５】実施例６ フッ化黒鉛微粒子（粒子径１μｍ以下、旭硝子（株）
製）１．２５重量％およびＰＴＦＥ微粒子（粒子径２μ
ｍ以下、ダイキン工業（株）製）５重量％を使用し、且
つ界面活性剤（商標“メガファックＦ１５０”、大日本
インキ化学（株）製）をフッ化黒鉛１ｇに対し４０．０
ｍｇおよびＰＴＦＥ１ｇに対し３０．０ｍｇの割合で添
加したメッキ液を使用する以外は実施例１と同様にし
て、実施例１と同様にして予めニッケル下地メッキ層を
形成したステンレス鋼板に対して、ニッケル−フッ化黒
鉛−ＰＴＦＥ複合メッキ被膜を形成させた。Example 6 Fluorinated graphite fine particles (particle diameter 1 μm or less, Asahi Glass Co., Ltd.)
1.25 wt% and PTFE fine particles (particle diameter 2μ
m or less, 5% by weight of Daikin Industries, Ltd., and a surfactant (trademark “Megafuck F150”, manufactured by Dainippon Ink and Chemicals, Inc.) of 40.0% per 1 g of fluorinated graphite.
In the same manner as in Example 1 except that a plating solution added at a ratio of 30.0 mg to 1 mg of PTFE and PTFE was used, nickel was added to a stainless steel plate on which a nickel underplating layer was previously formed in the same manner as in Example 1. -A fluorinated graphite-PTFE composite plating film was formed.
【００７６】得られたニッケル−フッ化黒鉛−ＰＴＦＥ
複合メッキ被膜を有するステンレス鋼板を熱風循環式乾
燥炉中で、３５０℃で３０分間加熱した後、常温で室内
放置１時間後に、ＦＡＣＥ接触角計を用いて液適法によ
り、水の接触角を測定し、その撥水性を調べた。Obtained nickel-fluorinated graphite-PTFE
A stainless steel plate with a composite coating is heated in a hot-air circulation type drying oven at 350 ° C for 30 minutes and then left indoors at room temperature for 1 hour, and then the contact angle of water is measured by a liquid method using a FACE contact angle meter. Then, the water repellency was examined.
【００７７】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００７８】実施例７ ＰＴＦＥ微粒子（粒子径２μｍ以下、ダイキン工業
（株）製）２．５重量％およびＦＥＰ微粒子（粒子径
０．２〜０．３μｍ、ダイキン工業（株）製）２．５重
量％を使用し、且つ界面活性剤（商標“メガファックＦ
１５０”、大日本インキ化学（株）製）をＰＴＦＥ１ｇ
に対し３０．０ｍｇおよびＦＥＰ１ｇに対し６５．０ｍ
ｇの割合で添加したメッキ液を使用する以外は実施例１
と同様にして、実施例１と同様にして予めニッケル下地
メッキ層を形成したステンレス鋼板に対して、ニッケル
−ＰＴＦＥ−ＦＥＰ複合メッキ被膜を形成させた。Example 7 2.5% by weight of PTFE fine particles (particle diameter 2 μm or less, manufactured by Daikin Industries, Ltd.) and 2.5% FEP fine particles (particle diameter 0.2 to 0.3 μm, manufactured by Daikin Industries, Ltd.) 2.5 % By weight and a surfactant (trademark “MegaFac F
150 ", made by Dainippon Ink and Chemicals, Inc., PTFE 1g
For 30.0 mg and FEP for 1 g 65.0 m
Example 1 except that the plating solution added in the proportion of g was used.
In the same manner as in Example 1, a nickel-PTFE-FEP composite plating film was formed on a stainless steel plate on which a nickel undercoating layer had been previously formed in the same manner as in Example 1.
【００７９】得られたニッケル−ＰＴＦＥ−ＦＥＰ複合
メッキ被膜を有するステンレス鋼板を熱風循環式乾燥炉
中で、２５０℃で３０分間加熱した後、常温で室内放置
１時間後に、ＦＡＣＥ接触角計を用いて液適法により、
水の接触角を測定し、その撥水性を調べた。The obtained stainless steel plate having the nickel-PTFE-FEP composite plating film was heated at 250 ° C. for 30 minutes in a hot-air circulation type drying furnace, and then left at room temperature for 1 hour and then, using a FACE contact angle meter. By the appropriate method
The contact angle of water was measured and its water repellency was investigated.
【００８０】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００８１】実施例８ フッ化黒鉛微粒子（粒子径１μｍ以下、旭硝子（株）
製）１．２５重量％およびＦＥＰ微粒子（粒子径０．２
〜０．３μｍ、ダイキン工業（株）製）５重量％を使用
し、且つ界面活性剤（商標“メガファックＦ１５０”、
大日本インキ化学（株）製）をフッ化黒鉛１ｇに対し４
０．０ｍｇおよびＦＥＰ１ｇに対し６５．０ｍｇの割合
で添加したメッキ液を使用する以外は実施例１と同様に
して、実施例１と同様にして予めニッケル下地メッキ層
を形成したステンレス鋼板に対して、ニッケル−フッ化
黒鉛−ＦＥＰ複合メッキ被膜を形成させた。Example 8 Fluorinated graphite fine particles (particle diameter 1 μm or less, Asahi Glass Co., Ltd.)
1.25 wt% and FEP fine particles (particle size 0.2)
.About.0.3 .mu.m, 5% by weight of Daikin Industries, Ltd., and a surfactant (trademark "Megafuck F150",
Dainippon Ink and Chemicals Inc.) 4 for 1 g of fluorinated graphite
In the same manner as in Example 1 except that the plating solution added in a ratio of 0.0 mg and 65.0 mg to 1 g of FEP was used, in the same manner as in Example 1, with respect to a stainless steel plate on which a nickel underplating layer was previously formed. , Nickel-fluorinated graphite-FEP composite plating film was formed.
【００８２】得られたニッケル−フッ化黒鉛−ＦＥＰ複
合メッキ被膜を有するステンレス鋼板を熱風循環式乾燥
炉中で、３５０℃で３０分間加熱した後、常温で室内放
置１時間後に、ＦＡＣＥ接触角計を用いて液適法によ
り、水の接触角を測定し、その撥水性を調べた。The obtained stainless steel plate having the nickel-fluorinated graphite-FEP composite plating film was heated at 350 ° C. for 30 minutes in a hot-air circulation type drying furnace, and then left at room temperature for 1 hour, and then the FACE contact angle meter. Was used to measure the contact angle of water by a liquid method, and its water repellency was investigated.
【００８３】次いで、密着力試験、衝撃変形試験および
離氷性試験を行った。Then, an adhesion test, an impact deformation test and an ice releasing test were conducted.
【００８４】実施例９ ＰＦＡ微粒子（粒子径２μｍ以下、ダイキン工業（株）
製）５重量％を使用し、且つ界面活性剤（商標“メガフ
ァックＦ１５０”、大日本インキ化学（株）製）をＰＦ
Ａ１ｇに対し３０．０ｍｇの割合で添加したメッキ液を
使用する以外は実施例１と同様にして、実施例１と同様
にして予めニッケル下地メッキ層を形成したステンレス
鋼板に対して、ニッケル−ＰＦＡ複合メッキ被膜を形成
させた。Example 9 PFA fine particles (particle size: 2 μm or less, Daikin Industries, Ltd.)
5% by weight, and a surfactant (trademark "Megafuck F150", manufactured by Dainippon Ink and Chemicals, Inc.) PF
Nickel-PFA was added to a stainless steel plate on which a nickel underplating layer was previously formed in the same manner as in Example 1 except that the plating solution added in a ratio of 30.0 mg to A1 g was used. A composite plating film was formed.
【００８５】得られたニッケル−ＰＦＡ複合メッキ被膜
を有するステンレス鋼板を熱風循環式乾燥炉中で、３４
０℃で３０分間加熱した後、常温で室内放置１時間後
に、ＦＡＣＥ接触角計を用いて液適法により、水の接触
角を測定し、その撥水性を調べた。The obtained stainless steel plate having a nickel-PFA composite plating film was placed in a hot air circulation type drying oven for 34 seconds.
After heating at 0 ° C. for 30 minutes, after leaving it for 1 hour at room temperature in a room, the contact angle of water was measured by a liquid suiting method using a FACE contact angle meter, and its water repellency was examined.
【００８６】次いで、密着力試験を行った。Next, an adhesion test was conducted.
【００８７】実施例１０ フッ化黒鉛微粒子（粒子径１μｍ以下、旭硝子（株）
製）１．２５重量％およびＰＦＡ微粒子（粒子径２μｍ
以下、ダイキン工業（株）製）５重量％を使用し、且つ
界面活性剤（商標“メガファックＦ１５０”、大日本イ
ンキ化学（株）製）をフッ化黒鉛１ｇに対し４０．０ｍ
ｇおよびＰＦＡ１ｇに対し３０．０ｇの割合で添加した
メッキ液を使用する以外は実施例１と同様にして、実施
例１と同様にして予めニッケル下地メッキ層を形成した
ステンレス鋼板に対して、ニッケル−フッ化黒鉛−ＰＦ
Ａ複合メッキ被膜を形成させた。Example 10 Fluorinated graphite fine particles (particle diameter 1 μm or less, Asahi Glass Co., Ltd.)
1.25 wt% and PFA fine particles (particle diameter 2 μm)
Hereafter, 5% by weight of Daikin Industries, Ltd. is used, and a surfactant (trademark “Megafuck F150”, manufactured by Dainippon Ink and Chemicals, Inc.) is used in an amount of 40.0 m per 1 g of fluorinated graphite.
g and nickel in the same manner as in Example 1 except that a plating solution added at a ratio of 30.0 g to 1 g of PFA was used in the same manner as in Example 1 except that a nickel underplating layer was previously formed. -Fluorinated graphite-PF
A composite plating film was formed.
【００８８】得られたニッケル−フッ化黒鉛−ＰＦＡ複
合メッキ被膜を有するステンレス鋼板を熱風循環式乾燥
炉中で、３４０℃で３０分間加熱した後、常温で室内放
置１時間後に、ＦＡＣＥ接触角計を用いて液適法によ
り、水の接触角を測定し、その撥水性を調べた。The obtained stainless steel plate having the nickel-fluorinated graphite-PFA composite plating film was heated at 340 ° C. for 30 minutes in a hot-air circulation type drying furnace, and then left at room temperature for 1 hour, and then the FACE contact angle meter. Was used to measure the contact angle of water by a liquid method, and its water repellency was investigated.
【００８９】次いで、密着力試験を行った。Next, an adhesion test was conducted.
【００９０】実施例１１ ＰＴＦＥ微粒子（粒子径２μｍ以下、ダイキン工業
（株）製）２．５重量％およびＰＦＡ微粒子（粒子径２
μｍ以下、ダイキン工業（株）製）２．５重量％を使用
し、且つ界面活性剤（商標“メガファックＦ１５０”、
大日本インキ化学（株）製）をＰＴＦＥ１ｇに対し３
０．０ｍｇおよびＰＦＡ１ｇに対し３０．０ｇの割合で
添加したメッキ液を使用する以外は実施例１と同様にし
て、実施例１と同様にして予めニッケル下地メッキ層を
形成したステンレス鋼板に対して、ニッケル−ＰＴＦＥ
−ＰＦＡ複合メッキ被膜を形成させた。Example 11 2.5% by weight of PTFE fine particles (particle diameter 2 μm or less, manufactured by Daikin Industries, Ltd.) and PFA fine particles (particle diameter 2
μm or less, 2.5% by weight of Daikin Industries, Ltd., and a surfactant (trademark “MegaFac F150”,
Dainippon Ink and Chemicals Inc.) 3 for 1 g of PTFE
In the same manner as in Example 1 except that a plating solution added in an amount of 0.0 mg and 30.0 g per 1 g of PFA was used, in the same manner as in Example 1, with respect to a stainless steel plate on which a nickel underplating layer was previously formed. , Nickel-PTFE
-A PFA composite plating film was formed.
【００９１】得られたニッケル−ＰＴＦＥ−ＰＦＡ複合
メッキ被膜を有するステンレス鋼板を熱風循環式乾燥炉
中で、３５０℃で３０分間加熱した後、常温で室内放置
１時間後に、ＦＡＣＥ接触角計を用いて液適法により、
水の接触角を測定し、その撥水性を調べた。The obtained stainless steel plate having the nickel-PTFE-PFA composite plating film was heated at 350 ° C. for 30 minutes in a hot air circulation type drying furnace, and then left at room temperature for 1 hour, and then, using a FACE contact angle meter. By the appropriate method
The contact angle of water was measured and its water repellency was investigated.
【００９２】次いで、密着力試験を行った。Then, an adhesion test was conducted.
【００９３】比較例１ フッ化黒鉛を使用しない以外は実施例１と同様にしてス
テンレス鋼板に対してニッケルメッキ被膜を形成させ
た。Comparative Example 1 A nickel-plated film was formed on a stainless steel plate in the same manner as in Example 1 except that fluorinated graphite was not used.
【００９４】得られたニッケルメッキ被膜を有するステ
ンレス鋼板を熱風循環式乾燥炉中で、１５０℃で３０分
間加熱した後、常温で室内放置１時間後に、ＦＡＣＥ接
触角計を用いて液適法により、水の接触角を測定し、そ
の撥水性を調べた。The obtained stainless steel plate having a nickel-plated coating was heated in a hot-air circulation type drying oven at 150 ° C. for 30 minutes and then left at room temperature for 1 hour, and then, after an hour of indoor exposure, by a liquid proper method using a FACE contact angle meter. The contact angle of water was measured and its water repellency was investigated.
【００９５】次いで、離氷性試験を行った。Next, an ice releasing test was conducted.
【００９６】比較例２ 従来製氷板として使用されてきたと同様な銅板（３０ｍ
ｍ×５０ｍｍ）を熱風循環式乾燥炉中で、１５０℃で３
０分間加熱した後、常温で室内放置１時間後に、ＦＡＣ
Ｅ接触角計を用いて液適法により、水の接触角を測定
し、その撥水性を調べた。Comparative Example 2 A copper plate (30 m) similar to that used as a conventional ice plate
m × 50 mm) in a hot air circulation type drying oven at 150 ° C. for 3
After heating for 0 minutes, leave it at room temperature for 1 hour and then use FAC.
The contact angle of water was measured by an appropriate method using an E contact angle meter, and its water repellency was examined.
【００９７】次いで、離氷性試験を行った。Next, an ice releasing test was conducted.
【００９８】[0098]
【表１】 [Table 1]
【００９９】表１に示す結果から、本発明によるフッ素
系材料微粒子共析複合メッキ被膜が極めて優れた撥水
性、密着性、耐衝撃変形性、耐磨耗性などを備えている
ことが明らかである。From the results shown in Table 1, it is clear that the fluorine-based material fine particle eutectoid composite plating film according to the present invention has extremely excellent water repellency, adhesion, impact deformation resistance, abrasion resistance and the like. is there.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ２５Ｄ 15/02 Ｈ Ｆ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C25D 15/02 HF
Claims (5)
黒鉛｛（ＣＦ）n｝微粒子、ポリテトラフルオロエチレ
ン微粒子、テトラフルオロエチレン−ヘキサフルオロプ
ロピレン共重合体微粒子およびテトラフルオロエチレン
−パーフルオロアルキルビニルエーテル共重合体微粒子
の少なくとも１種を分散含有する複合メッキ被膜を備え
た製氷板。1. A fluorinated graphite {(CF) n } fine particle having an average particle size of 2 μm or less, polytetrafluoroethylene fine particle, tetrafluoroethylene-hexafluoropropylene copolymer fine particle and tetrafluoroethylene-perfluoro on the surface of a substrate material. An ice plate provided with a composite plating film containing at least one kind of fine particles of an alkyl vinyl ether copolymer.
Ｆ）n｝微粒子を分散含有する複合メッキ被膜を備えた
請求項１に記載の製氷板。2. A fluorinated graphite having an average particle size of 2 μm or less {(C
The ice-making plate according to claim 1, comprising a composite plating film containing F) n } fine particles dispersed therein.
エチレン微粒子を分散含有する複合メッキ被膜を備えた
請求項１に記載の製氷板。3. The ice making plate according to claim 1, comprising a composite plating film containing dispersed polytetrafluoroethylene fine particles having an average particle diameter of 2 μm or less.
レン−ヘキサフルオロプロピレン共重合体微粒子を分散
含有する複合メッキ被膜を備えた請求項１に記載の製氷
板。4. The ice making plate according to claim 1, further comprising a composite plating film containing dispersed tetrafluoroethylene-hexafluoropropylene copolymer fine particles having an average particle diameter of 2 μm or less.
レン−パーフルオロアルキルビニルエーテル共重合体微
粒子を分散含有する複合メッキ被膜を備えた請求項１に
記載の製氷板。5. The ice making plate according to claim 1, further comprising a composite plating film containing dispersed tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles having an average particle diameter of 2 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3576694A JPH0727457A (en) | 1993-05-14 | 1994-03-07 | Ice making plate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11330993 | 1993-05-14 | ||
| JP5-113309 | 1993-05-14 | ||
| JP3576694A JPH0727457A (en) | 1993-05-14 | 1994-03-07 | Ice making plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0727457A true JPH0727457A (en) | 1995-01-27 |
Family
ID=26374767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3576694A Pending JPH0727457A (en) | 1993-05-14 | 1994-03-07 | Ice making plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0727457A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005300023A (en) * | 2004-04-12 | 2005-10-27 | Hoshizaki Electric Co Ltd | Ice-making compartment and manufacturing method thereof |
| WO2006059495A1 (en) * | 2004-12-01 | 2006-06-08 | Sharp Kabushiki Kaisha | Ice making device |
-
1994
- 1994-03-07 JP JP3576694A patent/JPH0727457A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005300023A (en) * | 2004-04-12 | 2005-10-27 | Hoshizaki Electric Co Ltd | Ice-making compartment and manufacturing method thereof |
| WO2006059495A1 (en) * | 2004-12-01 | 2006-06-08 | Sharp Kabushiki Kaisha | Ice making device |
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