JPH0726397A - Substrate material having highly durable and water-repellent composite plated film, its production and ice tray - Google Patents
Substrate material having highly durable and water-repellent composite plated film, its production and ice trayInfo
- Publication number
- JPH0726397A JPH0726397A JP3452794A JP3452794A JPH0726397A JP H0726397 A JPH0726397 A JP H0726397A JP 3452794 A JP3452794 A JP 3452794A JP 3452794 A JP3452794 A JP 3452794A JP H0726397 A JPH0726397 A JP H0726397A
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- Japan
- Prior art keywords
- fine particles
- plating film
- water
- composite plating
- less
- 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.)
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Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、撥水性、潤滑性、離氷
性などに優れたフッ化ピッチ微粒子を共析させた高耐久
性・高撥水性複合メッキ被膜を備えた基板材、その製造
方法およびその様な高耐久性・高撥水性複合メッキ被膜
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 a substrate material provided with a highly durable and highly water-repellent composite plating film in which fluorinated pitch fine particles excellent in water repellency, lubricity and ice releasing property are co-deposited. The present invention relates to a manufacturing method and an ice plate provided with such a highly durable and highly water-repellent composite plating film.
【０００２】[0002]
【従来の技術】一般に、フッ化黒鉛、ポリテトラフルオ
ロエチレン（ＰＴＦＥ）などのフッ素化合物は、自己潤
滑性、低摩擦性、撥水性、非粘着性などに優れている。
この様なフッ素化合物の微粒子を金属とともに析出させ
て、その優れた固有の性質と金属の性質とを併せ持つ複
合メッキ被膜を形成することが行なわれている。2. Description of the Related Art Generally, fluorine compounds such as fluorinated graphite and polytetrafluoroethylene (PTFE) are excellent in self-lubricating property, low friction property, water repellency and non-adhesiveness.
It has been practiced to deposit such fine particles of a fluorine compound together with a metal to form a composite plating film having both the excellent inherent properties and the properties of a metal.
【０００３】本発明者らは、上記の様なフッ素化合物に
代えてフッ化ピッチを使用する場合には、撥水性がより
改善された複合メッキ被膜が得られることを見出した
（特開平４−３２９８９７号公報参照）。しかしなが
ら、この方法により得られる複合メッキ被膜において
も、その表面の撥水性は、最善の状態でも、水による液
滴法での接触角として１００〜１２５度程度であり、満
足すべき撥水性を備えているとはいい難い。The present inventors have found that when a fluoride pitch is used in place of the above-mentioned fluorine compound, a composite plating film having improved water repellency can be obtained (Japanese Patent Laid-Open No. 4-204). 329897). However, even in the composite plating film obtained by this method, the water repellency of the surface is about 100 to 125 degrees as the contact angle in the droplet method with water even in the best state, and it has satisfactory water repellency. It's hard to say.
【０００４】また、特開平４−２８３２６８号公報は、
低分子量のＰＴＦＥ粒子を使用する複合メッキにより、
高撥水性のメッキ被膜を形成することを提案している。
しかしながら、この方法により得られたメッキ被膜は、
高撥水性という特性の再現性に乏しく、また仮に初期撥
水性に優れていたとしても、常温で空気中に放置した場
合には、経時的に撥水性が著しく低下するという欠点が
ある。Further, Japanese Patent Laid-Open No. 4-283268 discloses that
By the composite plating using low molecular weight PTFE particles,
It has been proposed to form a highly water-repellent plating film.
However, the plating film obtained by this method is
Even if the property of high water repellency is poor in reproducibility, and even if the initial water repellency is excellent, there is a drawback that the water repellency significantly decreases with time when left in the air at room temperature.
【０００５】一方、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性を改善するために、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、上
記の様な高度の撥水性、離型性などを有するＰＴＦＥな
どのフッ素系樹脂を金属表面にコ−ティングする方法；
家庭用の冷蔵庫内に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型した
製氷容器を用いる方法なども行なわれている。On the other hand, an ice manufacturing apparatus used for filling ice in fresh fish, fresh foods, etc., usually sprinkles water attached to the surface of an ice making plate whose outer surface has been cooled to a low temperature by an internal refrigerant. It is made into ice by freezing. Conventionally, the surface of an ice making plate is heated or a chemical such as ethylene glycol is mixed in the water to be sprinkled in order to improve the ability of the produced ice to release from the ice making container. . Then, in order to further improve the ice releasing property, a method of coating a fluorine-based resin such as PTFE having the above-mentioned high water repellency and releasability on the metal surface;
For a mobile ice-making container used in a refrigerator for home use, a method of using an ice-making container formed by molding a highly water-repellent resin such as a fluororesin is also used.
【０００６】しかしながら、ＰＴＦＥなどの樹脂コ−テ
ィング層は、フッ素系樹脂の熱伝導率が金属の３００分
の１程度と低いこと、樹脂自体の強度が低いので、耐久
性を得るために膜厚を厚くする必要があることなどの理
由から、製氷板の熱伝達速度を低下させ、製氷効率を著
しく低下させる欠点がある。However, the resin coating layer such as PTFE has a low thermal conductivity of the fluororesin of about 1/300 of that of the metal, and the strength of the resin itself is low. For example, the heat transfer rate of the ice making plate is lowered and the ice making efficiency is remarkably lowered because of the necessity of making the ice thicker.
【０００７】[0007]
【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、撥水性がより
高い複合メッキ被膜およびその製造方法を提供すること
を主な目的とする。Therefore, the main object of the present invention is to provide a composite plating film having excellent durability, lower surface energy and higher water repellency, and a method for producing the same.
【０００８】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。A further object of the present invention is to provide an ice making plate which is more excellent in ice releasing property without lowering the ice making efficiency.
【０００９】[0009]
【課題を解決するための手段】発明者は、上記の様な従
来技術の問題点に鑑みて、鋭意研究を進めた結果、基板
材上にフッ化ピッチ微粒子を分散含有する複合メッキ被
膜を形成させた後、特定の温度で熱処理を行なう場合に
は、驚くべきことに、複合メッキ被膜表面の撥水性（水
の液滴法による）は、１３５度以上となり、測定限界で
あるとされている１４５度を上回る場合もあることを見
出した。SUMMARY OF THE INVENTION The inventors of the present invention have made intensive studies in view of the problems of the prior art as described above, and as a result, formed a composite plating film containing dispersed fluorinated pitch fine particles on a substrate material. When the heat treatment is carried out at a specific temperature after the application, surprisingly, the water repellency of the surface of the composite plating film (by the water droplet method) is 135 degrees or more, which is considered to be the limit of measurement. It has been found that it may exceed 145 degrees.
【００１０】また、製氷板上にこの複合メッキ被膜を形
成する場合には、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。Further, when this composite plating film is formed on an ice making plate, ice releasing property is greatly improved due to its low surface energy shown by high water repellency, and it is derived from its metal component. It has been found that the high thermal conductivity also significantly improves the ice making efficiency.
【００１１】さらに、フッ化ピッチ微粒子とともに、フ
ッ化黒鉛、ＰＴＦＥ、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（ＦＥＰ）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（ＦＥＰ）の少なくとも１種の微粒子を分散含
有する複合メッキ被膜を形成させた後、上記と同様にし
て特定の温度で熱処理を行なう場合には、複合メッキ被
膜表面の撥水性（水の液滴法による）は、１２０度以上
に改善されることを見出した。そして、この様な２種以
上の微粒子を分散含有する複合メッキ被膜を備えた基板
材も、やはり製氷板として優れた性能を発揮することを
見出した。Further, at least one kind of graphite fluoride, PTFE, tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (FEP) is used together with the fluorinated pitch fine particles. When a heat treatment is performed at a specific temperature in the same manner as above after forming a composite plating film containing fine particles dispersed therein, the water repellency (by the water droplet method) of the composite plating film surface is 120 degrees or more. It was found to be improved. It was also found that a substrate material provided with such a composite plating film containing two or more kinds of fine particles dispersed therein also exhibits excellent performance as an ice making plate.
【００１２】即ち、本発明は、下記の複合メッキ被膜を
備えた基板材、その製造方法および製氷板を提供するも
のである； １．平均粒径２μｍ以下のフッ化ピッチ微粒子を分散含
有しており、１５０〜３００℃の温度で熱処理後の水に
よる液滴法での接触角が１３５度以上である高耐久性・
高撥水性複合メッキ被膜を備えた基板材。That is, the present invention provides a substrate material provided with the following composite plating film, a method for producing the same, and an ice plate: Highly durable, containing dispersed fine particles of fluorinated pitch having an average particle size of 2 μm or less, and having a contact angle of 135 degrees or more in a droplet method with water after heat treatment at a temperature of 150 to 300 ° C.
A substrate material with a highly water-repellent composite plating film.
【００１３】２．メッキ液のｐＨにおいてカチオン性を
示す界面活性剤を含み且つ平均粒径２μｍ以下のフッ化
ピッチ微粒子を分散させた電解メッキ液中で基板材表面
にフッ化ピッチ微粒子を共析する複合メッキ被膜を形成
させた後、１５０〜３００℃の温度で複合メッキ被膜を
熱処理することを特徴とする、水による液滴法での接触
角が１３５度以上である高耐久性・高撥水性複合メッキ
被膜の製造方法。2. A composite plating film containing a fluorinated pitch fine particle co-deposited on the surface of a substrate material in an electrolytic plating solution containing a fluorinated pitch fine particle having an average particle size of 2 μm or less and containing a surfactant having a cationic property at the pH of the plating solution. After being formed, the composite plating film is heat-treated at a temperature of 150 to 300 ° C., which is a highly durable and highly water-repellent composite plating film having a contact angle of 135 degrees or more by a water droplet method. Production method.
【００１４】３．平均粒径２μｍ以下のフッ化ピッチ微
粒子を分散含有しており、１５０〜３００℃の温度で熱
処理後の水による液滴法での接触角が１３５度以上であ
る高耐久性・高撥水性複合メッキ被膜を備えた製氷板。3. A highly durable and highly water-repellent composite that contains fluorinated pitch fine particles having an average particle diameter of 2 μm or less in a dispersed state, and has a contact angle of 135 degrees or more in a droplet method with water after heat treatment at a temperature of 150 to 300 ° C. Ice plate with a plated coating.
【００１５】４．平均粒径２μｍ以下のフッ化ピッチ微
粒子と平均粒径２μｍ以下の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、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およ
びフッ化黒鉛微粒子の少なくとも１種とを分散含有して
おり、１５０〜３５０℃の温度で熱処理後の水による液
滴法での接触角が１２０度以上である高耐久性・高撥水
性複合メッキ被膜を備えた基板材。4. Fluorine pitch fine particles having an average particle diameter of 2 μm or less, polytetrafluoroethylene fine particles having an average particle diameter of 2 μm or less, tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and fluorinated A highly durable and highly water-repellent composite plating film, which contains at least one kind of graphite fine particles dispersed therein and has a contact angle of 120 degrees or more by a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. Substrate material provided.
【００１６】５．メッキ液のｐＨにおいてカチオン性を
示す界面活性剤を含み且つ平均粒径２μｍ以下のフッ化
ピッチ微粒子と平均粒径２μｍ以下のポリテトラフルオ
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、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
粒子およびフッ化黒鉛微粒子の少なくとも１種とを分散
させた電解メッキ液中で基板材表面にフッ化ピッチ微粒
子と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、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およびフッ化黒鉛微粒子の
少なくとも１種とを共析する複合メッキ被膜を形成させ
た後、１５０〜３５０℃の温度で複合メッキ被膜を熱処
理することを特徴とする、水による液滴法での接触角が
１２０度以上である高耐久性・高撥水性複合メッキ被膜
の製造方法。5. Fluoride pitch fine particles having a mean particle size of 2 μm or less, polytetrafluoroethylene fine particles having a mean particle size of 2 μm or less, and tetrafluoroethylene-hexafluoropropylene copolymer fine particles, which contain a surfactant exhibiting cationicity at the pH of the plating solution. Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and at least one kind of fluorinated graphite fine particles are dispersed in an electrolytic plating solution, and fluorinated pitch fine particles, polytetrafluoroethylene fine particles, and tetrafluoroethylene- After forming a composite plating film co-depositing hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and at least one kind of fluorinated graphite fine particles, at a temperature of 150 to 350 ° C. Compound A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 degrees or more by a droplet method using water, characterized by heat-treating the Kicki film.
【００１７】６．平均粒径２μｍ以下のフッ化ピッチ微
粒子と平均粒径２μｍ以下の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、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およ
びフッ化黒鉛微粒子の少なくとも１種とを分散含有して
おり、１５０〜３５０℃の温度で熱処理後の水による液
滴法での接触角が１２０度以上である高耐久性・高撥水
性複合メッキ被膜を備えた製氷板。6. Fluorine pitch fine particles having an average particle diameter of 2 μm or less, polytetrafluoroethylene fine particles having an average particle diameter of 2 μm or less, tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and fluorinated A highly durable and highly water-repellent composite plating film, which contains at least one kind of graphite fine particles dispersed therein and has a contact angle of 120 degrees or more by a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. Prepared ice plate.
【００１８】７．平均粒径２μｍ以下のフッ化ピッチ微
粒子と平均粒径２μｍ以下のポリテトラフルオロエチレ
ン微粒子とを分散含有しており、１５０〜３５０℃の温
度で熱処理後の水による液滴法での接触角が１２０度以
上である高耐久性・高撥水性複合メッキ被膜を備えた基
板材。7. It contains fluorinated pitch fine particles having an average particle diameter of 2 μm or less and polytetrafluoroethylene fine particles having an average particle diameter of 2 μm or less in a dispersed manner, and has a contact angle in a droplet method with water after heat treatment at a temperature of 150 to 350 ° C. A substrate material with a highly durable and highly water repellent composite plating film that is 120 degrees or more.
【００１９】８．メッキ液のｐＨにおいてカチオン性を
示す界面活性剤を含み且つ平均粒径２μｍ以下のフッ化
ピッチ微粒子と平均粒径２μｍ以下のポリテトラフルオ
ロエチレン微粒子とを分散させた電解メッキ液中で基板
材表面にフッ化ピッチ微粒子とポリテトラフルオロエチ
レン微粒子とを共析する複合メッキ被膜を形成させた
後、１５０〜３５０℃の温度で複合メッキ被膜を熱処理
することを特徴とする、水による液滴法での接触角が１
２０度以上である高耐久性・高撥水性複合メッキ被膜の
製造方法。8. Substrate surface in an electrolytic plating solution containing a fluorinated pitch fine particle having an average particle size of 2 μm or less and polytetrafluoroethylene fine particles having an average particle size of 2 μm or less and containing a surfactant exhibiting cationicity at the pH of the plating solution After forming a composite plating film on which co-deposited fluorinated pitch fine particles and polytetrafluoroethylene fine particles are heat-treated, the composite plating film is heat-treated at a temperature of 150 to 350 ° C. by a droplet method using water. Has a contact angle of 1
A method for producing a highly durable and highly water-repellent composite plating film having a temperature of 20 degrees or more.
【００２０】９．平均粒径２μｍ以下のフッ化ピッチ微
粒子と平均粒径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とを分散含有
しており、１５０〜３００℃の温度で熱処理後の水によ
る液滴法での接触角が１２０度以上である高耐久性・高
撥水性複合メッキ被膜を備えた基板材。9. Fine particles of fluorinated pitch having an average particle size of 2 μm or less and tetrafluoroethylene having an average particle size of 2 μm or less
A highly durable and highly water-repellent composite plating film containing hexafluoropropylene copolymer fine particles dispersed therein and having a contact angle of 120 degrees or more by a droplet method with water after heat treatment at a temperature of 150 to 300 ° C. Substrate material with.
【００２１】１０．メッキ液のｐＨにおいてカチオン性
を示す界面活性剤を含み且つ平均粒径２μｍ以下のフッ
化ピッチ微粒子と平均粒径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と
を分散させた電解メッキ液中で基板材表面にフッ化ピッ
チ微粒子と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とを共析する複合メッキ被膜を
形成させた後、１５０〜３００℃の温度で複合メッキ被
膜を熱処理することを特徴とする、水による液滴法での
接触角が１２０度以上である高耐久性・高撥水性複合メ
ッキ被膜の製造方法。10. Electrolytic plating in which fluorinated pitch fine particles having an average particle size of 2 μm or less and tetrafluoroethylene-hexafluoropropylene copolymer fine particles having an average particle size of 2 μm or less and containing a surfactant exhibiting cationicity at the pH of the plating solution are dispersed. After forming a composite plating film in which the fine particles of fluorinated pitch and fine particles of tetrafluoroethylene-hexafluoropropylene copolymer are co-deposited on the surface of the substrate material in a liquid, the composite plating film is heat-treated at a temperature of 150 to 300 ° C. A method for producing a highly durable and highly water-repellent composite plating film, which has a contact angle of 120 degrees or more in a droplet method with water.
【００２２】１１．平均粒径２μｍ以下のフッ化ピッチ
微粒子と平均粒径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
とを分散含有しており、１５０〜３４０℃の温度で熱処
理後の水による液滴法での接触角が１２０度以上である
高耐久性・高撥水性複合メッキ被膜を備えた基板材。11. Liquid containing water containing fine particles of fluorinated pitch having an average particle diameter of 2 μm or less and fine particles of tetrafluoroethylene-perfluoroalkylvinylether copolymer having an average particle diameter of 2 μm or less dispersed therein, after being heat-treated at a temperature of 150 to 340 ° C. A substrate material with a highly durable and highly water-repellent composite plating film that has a contact angle of 120 degrees or more by the drop method.
【００２３】１２．メッキ液のｐＨにおいてカチオン性
を示す界面活性剤を含み且つ平均粒径２μｍ以下のフッ
化ピッチ微粒子と平均粒径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
体微粒子とを分散させた電解メッキ液中で基板材表面に
フッ化ピッチ微粒子と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とを共析
する複合メッキ被膜を形成させた後、１５０〜３４０℃
の温度で複合メッキ被膜を熱処理することを特徴とす
る、水による液滴法での接触角が１２０度以上である高
耐久性・高撥水性複合メッキ被膜の製造方法。12. Electrolysis in which fluorinated pitch fine particles having a mean particle size of 2 μm or less and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles having a mean particle size of 2 μm or less and containing a surfactant exhibiting cationicity at the pH of the plating solution are dispersed. After forming a composite plating film on the surface of the substrate material in the plating solution, in which the fluorinated pitch fine particles and the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles are co-deposited, 150 to 340 ° C.
A method for producing a highly durable and highly water-repellent composite plated coating having a contact angle of 120 degrees or more by a water droplet method, characterized by heat-treating the composite plated coating at a temperature of.
【００２４】本発明で使用するフッ化ピッチは、例え
ば、特開昭６２−２７５１９０号公報に開示されてお
り、ピッチをフッ素ガスを用いてフッ素化することによ
り得られる。The fluorinated pitch used in the present invention is disclosed, for example, in JP-A-62-275190, and can be obtained by fluorinating the pitch with a fluorine gas.
【００２５】一般に、ピッチは、芳香族縮合六員環平面
が積層した層構造を有し、かつ六員環平面を構成する芳
香族がメチレンなどの脂肪族炭化水素基により架橋した
構造を有している。フッ化ピッチの製造原料としては、
石油蒸留残渣、ナフサ熱分解残渣、エチレンボトム油、
石炭液化油、コールタールなどの石油系又は石炭系重質
油を蒸留して沸点２００℃未満の低沸点成分を除去した
ピッチ、さらにこのピッチを熱処理および／または水添
処理したものなどが例示される。より具体的には、フッ
化ピッチの製造原料としてのピッチには、例えば、等方
性ピッチ、メソフェーズピッチ、水素化メソフェーズピ
ッチ、石油系又は石炭系重質油を蒸留して低沸点成分を
除去した後生成するメソフェーズ球体からなるメソカー
ボンマイクロビーズなどが含まれる。In general, the pitch has a layered structure in which fused aromatic six-membered ring planes are laminated, and the aromatic constituting the six-membered ring plane is crosslinked by an aliphatic hydrocarbon group such as methylene. ing. As a raw material for manufacturing fluorinated pitch,
Petroleum distillation residue, naphtha pyrolysis residue, ethylene bottom oil,
Examples include pitches obtained by distilling petroleum-based or coal-based heavy oils such as coal liquefied oil and coal tar to remove low boiling point components having a boiling point of less than 200 ° C., and those obtained by subjecting the pitch to heat treatment and / or hydrogenation treatment. It More specifically, for pitch as a raw material for producing fluorinated pitch, for example, isotropic pitch, mesophase pitch, hydrogenated mesophase pitch, petroleum-based or coal-based heavy oil is distilled to remove low boiling point components. Mesocarbon microbeads composed of mesophase spheres produced after the process are included.
【００２６】フッ化ピッチは、例えば、上記の原料ピッ
チとフッ素とを０〜３５０℃程度で反応させることによ
り得られる。フッ化ピッチの製造方法としては、より具
体的には、次の様な方法が挙げられる。The fluorinated pitch can be obtained, for example, by reacting the above-mentioned raw material pitch with fluorine at about 0 to 350 ° C. More specifically, the method for producing the fluorinated pitch includes the following methods.
【００２７】（１）原料ピッチとフッ素ガスとを０〜３
５０℃程度の温度で直接反応させる方法。(1) The raw material pitch and fluorine gas are 0 to 3
A method of directly reacting at a temperature of about 50 ° C.
【００２８】ピッチとフッ素ガスとを反応させる際の好
ましい温度は、ピッチの軟化点以下の温度である。反応
時のフッ素ガス圧は、特に限定されるものではないが、
一般的に０．０７〜１．５気圧の範囲内にある。この反
応において、フッ素ガスはそのまま用いてもよく、或い
は窒素、ヘリウム、アルゴン、ネオンなどの不活性ガス
で希釈して用いてもよい。The preferred temperature for reacting the pitch with the fluorine gas is a temperature below the softening point of the pitch. The fluorine gas pressure during the reaction is not particularly limited,
It is generally in the range of 0.07 to 1.5 atmospheres. In this reaction, the fluorine gas may be used as it is, or may be diluted with an inert gas such as nitrogen, helium, argon or neon before use.
【００２９】得られたフッ化ピッチは、実質的に炭素原
子およびフッ素原子からなり、Ｆ／Ｃ原子比は、例え
ば、０．５〜１．８程度である。この様なフッ化ピッチ
は、下記（ａ）、（ｂ）、（ｃ）および（ｄ）の特性を
示す。The obtained fluorinated pitch consists essentially of carbon atoms and fluorine atoms, and the F / C atomic ratio is, for example, about 0.5 to 1.8. Such a fluorinated pitch exhibits the following characteristics (a), (b), (c) and (d).
【００３０】（ａ）粉末Ｘ線回折において，２θ＝１３
°付近に最大強度のピークを示し、２θ＝４０°付近に
前記ピークよりも強度の小さいピークを示す。(A) In powder X-ray diffraction, 2θ = 13
A peak of maximum intensity is shown in the vicinity of °, and a peak having a smaller intensity than the above peak is shown in the vicinity of 2θ = 40 °.
【００３１】（ｂ）Ｘ線光電子分光分析において、２９
０．０±１．０ｅＶにＣＦ基に相当するピークおよび２
９２．５±０．９ｅＶ付近にＣＦ2 基に相当するピーク
を示し、ＣＦ基に相当するピークに対するＣＦ2 基に相
当するピークの強さの比が、０．１５〜１．５程度であ
る。(B) In the X-ray photoelectron spectroscopy analysis, 29
Peaks corresponding to CF groups at 0.0 ± 1.0 eV and 2
A peak corresponding to a CF2 group is shown in the vicinity of 92.5 ± 0.9 eV, and a ratio of the intensity of the peak corresponding to a CF2 group to the peak corresponding to a CF group is about 0.15 to 1.5.
【００３２】（ｃ）真空蒸着によって膜を成形すること
ができる。(C) The film can be formed by vacuum vapor deposition.
【００３３】（ｄ）３０℃における水に対する接触角が
１４１°±８°である。(D) The contact angle with water at 30 ° C. is 141 ° ± 8 °.
【００３４】前記（１）のフッ化ピッチは、白色乃至黄
白色もしくは褐色の固体であり、耐水性、耐薬品性に優
れ、非常に安定な化合物である。The above-mentioned fluorinated pitch (1) is a white to yellowish white or brown solid, is a very stable compound having excellent water resistance and chemical resistance.
【００３５】さらに、フッ化ピッチは、透明樹脂状の形
態でも得られる。この様な透明樹脂状のフッ化ピッチ
は、例えば、フッ化ピッチをフッ素ガス含有雰囲気下、
０．１〜３℃／分程度、好ましくは０．５〜１．５℃／
分程度の昇温速度で２５０〜４００℃程度まで昇温し、
所定時間、例えば、１〜１８時間程度、好ましくは６〜
１２時間程度反応させることにより得られる。得られた
透明樹脂状のフッ化ピッチは、例えば、次のような特性
を示す。Further, the fluorinated pitch can also be obtained in the form of a transparent resin. Such a transparent resin-like fluorinated pitch, for example, fluorinated pitch in a fluorine gas-containing atmosphere,
0.1 to 3 ° C./minute, preferably 0.5 to 1.5 ° C./minute
The temperature is raised to about 250 to 400 ° C. at a heating rate of about a minute,
Predetermined time, for example, about 1 to 18 hours, preferably 6 to
It is obtained by reacting for about 12 hours. The obtained transparent resin-like fluorinated pitch exhibits the following characteristics, for example.
【００３６】Ｆ／Ｃ：１．５〜１．７ 光透過率（２５０〜９００ｎｍ）：９０％以上 分子量：１５００〜２０００ 軟化点：１５０〜２５０℃ 本発明においては、さらに、上記のフッ化ピッチ微粒子
の少なくとも一部（最大限９０％程度まで）を平均粒径
２μｍ以下のＰＴＦＥ微粒子、ＦＥＰ微粒子、ＰＦＡ微
粒子およびフッ化黒鉛微粒子の少なくとも１種により代
替することができる。この場合には、撥水性は若干低下
するものの、代替物を適宜選択することにより、耐久
性、摺動性、防汚性、耐焦げ付き性などが向上するとい
う利点が得られる。フッ化ピッチ微粒子の一部をこれら
の材料で代替する場合にも、その粒径、複合メッキ被膜
中での微粒子としての配合量、複合メッキ被膜の形成方
法などに実質的な変わりはないので、以下においては特
に必要でない限り、フッ化ピッチ微粒子を代表例として
説明する。F / C: 1.5 to 1.7 Light transmittance (250 to 900 nm): 90% or more Molecular weight: 1500 to 2000 Softening point: 150 to 250 ° C. In the present invention, the above fluorinated pitch is further used. At least a part (up to about 90% at maximum) of the fine particles can be replaced with at least one of PTFE fine particles having an average particle diameter of 2 μm or less, FEP fine particles, PFA fine particles and fluorinated graphite fine particles. In this case, although the water repellency will be slightly lowered, there is an advantage that durability, slidability, antifouling property, scorching resistance and the like are improved by appropriately selecting a substitute. Even when a part of the fluorinated pitch fine particles is replaced with these materials, there is substantially no change in the particle size, the amount of fine particles mixed in the composite plating film, the method of forming the composite plating film, etc. Hereinafter, unless otherwise necessary, fluorinated pitch fine particles will be described as a typical example.
【００３７】本発明における共析複合メッキの形成に
は、製氷板などとして用いられる金属などの基板材の表
面にマトリックス金属を析出させ得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、各種の公知の組成の
メッキ液のいずれをも使用できる。より具体的には、例
えば、特開昭４９−２７４４３号公報、特開願４−３２
９８９７号公報などに開示されているメッキ手法に準じ
て、フッ化ピッチ微粒子をメッキ金属塩の水溶液中に分
散させ、基板板上にマトリックス金属とともにフッ化ピ
ッチ微粒子を共析させて、非金属であるフッ化炭素化合
物の固有の性質とマトリックスである金属の性質とを併
せ持った複合メッキ被膜を形成させれば良い。In forming the eutectoid composite plating in the present invention, it is possible to adopt a known electroless plating method or electrolytic plating method capable of depositing a matrix metal on the surface of a substrate material such as a metal used as an ice making plate or the like. it can. As the plating solution used, any plating solution having various known compositions can be used. More specifically, for example, JP-A-49-27443 and JP-A-4-32
In accordance with the plating technique disclosed in Japanese Patent Publication No. 9897, fine particles of fluorinated pitch are dispersed in an aqueous solution of a plating metal salt, and the fine particles of fluorinated pitch are co-deposited with a matrix metal on a substrate plate to obtain a non-metal. It suffices to form a composite plating film having both the unique properties of a fluorocarbon compound and the properties of a metal that is a matrix.
【００３８】メッキ浴中では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など何れも使用す
ることができる。これら金属を含むメッキ液は、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 used in the plating bath in the form of a salt and serving as a matrix in the composite plating film is, for example, nickel, copper, zinc, tin, iron, lead, cadmium,
Any of chromium, precious metals and alloys thereof can be used. The plating solutions containing these metals are known to have various compositions, and any of these known plating solutions can be used in the present invention.
【００３９】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
るフッ化ピッチ微粒子の粒径は、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、基板材の材
質、用途および形状、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
ッ化ピッチ微粒子の粒径は、この複合メッキ被膜の厚さ
をも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化ピッチ微
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
フッ化ピッチ微粒子の添加量は、特に限定されないが、
通常２００ｇ／ｌ程度以下、好ましくは１〜１００ｇ／
ｌ程度である。フッ化ピッチ微粒子の一部をＰＴＦＥ微
粒子などで代替する場合にも、その全体としての添加量
は、同じである。In the present invention, the particle diameter of the fluorinated pitch fine particles 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 total particle size of the 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 material, application and shape of the substrate material, the type of matrix metal, etc., but is usually about 1 to 50 μm. Therefore, the particle diameter of the fluorinated pitch fine particles 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 fluorinated pitch fine particles in the composite plating solution and the composite plating film, it is desirable that coarse particles of 30 μm or more are not included. The addition amount of fluorinated pitch fine particles in the composite plating solution is not particularly limited,
Usually about 200 g / l or less, preferably 1 to 100 g / l
It is about 1. Even when a part of the fluorinated pitch fine particles is replaced with PTFE fine particles or the like, the total addition amount is the same.
【００４０】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、メッキ被膜と基板材との密着性を考慮すれば、
複合メッキ被膜中の共析物（フッ化ピッチ微粒子）の体
積分率は、６０％が限度である。一方、フッ化ピッチ微
粒子の体積分率が低すぎる場合には、撥水性の改善が十
分に行なわれない。従って、本発明においては、複合メ
ッキ被膜中のフッ化ピッチ微粒子の体積分率は、通常２
５〜５０％程度、より好ましくは３５〜４５％程度とす
る。この共析物の量的な数値は、フッ化ピッチ微粒子と
他の微粒子との混合物を使用する場合についても、同様
である。In general, in a composite plating film composed of a metal and an eutectoid, the larger the volume fraction of eutectoid, the lower the adhesion between the plating layer and the substrate. Also in the present invention, considering the adhesion between the plating film and the substrate material,
The volume fraction of the eutectoid (fluoride pitch fine particles) in the composite plating film is limited to 60%. On the other hand, if the volume fraction of the fluorinated pitch fine particles is too low, the water repellency is not sufficiently improved. Therefore, in the present invention, the volume fraction of fluorinated pitch fine particles in the composite plating film is usually 2
It is about 5 to 50%, more preferably about 35 to 45%. The numerical value of this eutectoid is the same in the case of using a mixture of fluorinated pitch fine particles and other fine particles.
【００４１】本発明においては、基板材としては、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、ＰＴＦＥなどの樹脂類、炭素プレート、
黒鉛プレートなどの炭素材などが用いられる。本発明に
よる基板材を調理器具用の部材（例えば天板など）とし
て用いる場合には、熱伝導性が高く、耐熱温度の高い炭
素材および金属が好ましい。また、製氷板の基板材とし
て用いる場合には、熱伝導率の高い金属が好ましく、銅
板、アルミニウム板、アルミニウム合金板などがさらに
好ましい。In the present invention, the substrate material is copper,
Metals such as stainless steel, general steel, aluminum and aluminum alloys, resins such as PTFE, carbon plates,
A carbon material such as a graphite plate is used. When the substrate material according to the present invention is used as a member for cooking utensils (for example, a top plate), carbon materials and metals having high thermal conductivity and high heat resistance are preferable. When used as a substrate material for an ice making plate, a metal having a high thermal conductivity is preferable, and a copper plate, an aluminum plate, an aluminum alloy plate and the like are more preferable.
【００４２】本発明の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化ピッチ
微粒子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、ポリオキシエチレン系、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 of the present invention, it is necessary to uniformly disperse the fluorinated pitch fine particles having extremely high water repellency in the plating solution and keep them completely wet. , Using 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, examples of the cationic surfactant include quaternary ammonium salts, secondary and tertiary amines, and examples of the nonionic surfactant include polyoxyethylene-based, polyethyleneimine-based, and ester-based surfactants. Examples of the amphoteric surfactant 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.
【００４３】メッキ液中への界面活性剤の添加量は、フ
ッ化ピッチ微粒子１ｇに対し、通常１〜１００ｍｇ程度
の範囲内であり、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 in the range of about 1 to 100 mg, more preferably about 1 to 50 mg, per 1 g of the fluorinated pitch fine particles.
【００４４】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、メッキ被膜着色のための顔料
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 brightening agent, a secondary brightening agent and a pigment for coloring a plated coating can be further added to the above composite plating solution.
【００４５】本発明方法により複合メッキ被膜を形成す
るに際しては、フッ化ピッチ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。When forming the composite plating film by the method of the present invention, it is preferable to perform the plating operation while stirring the composite plating solution in order to uniformly disperse the fine pitch fluoride particles. 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.
【００４６】メッキ条件は、基板材の材質、使用する複
合メッキ液の種類などに応じて、一般に通常の複合メッ
キ法において採用されていると同様の範囲の液温、ｐＨ
値、電流密度などから選択すればよい。The plating conditions depend on the material of the substrate material, the type of the composite plating solution used, and the like, and the same range of liquid temperature and pH as that used in the general composite plating method.
It may be selected from a value, a current density and the like.
【００４７】なお、本発明における複合メッキ被膜は、
必ずしも基板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、樹脂類、炭素材などからなる基板
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 substrate material, but a known undercoating layer (for example, nickel plating, on a substrate material made of a metal such as copper or aluminum, a resin, a carbon material, or the like,
The composite plating film may be formed after the copper plating etc. is formed.
【００４８】本発明においては、上記の様にして基板材
上に形成した複合メッキ被膜を１５０〜３５０℃の温度
範囲内で熱処理することを必須とする。この範囲内で熱
処理温度の上限を若干低めとすることが好ましい場合も
ある。例えば、フッ化ピッチを単独で使用する場合或い
はフッ化ピッチとＦＥＰとを併用する場合には、熱処理
温度を３００℃以下で行うことが好ましい。また、フッ
化ピッチとＰＦＡとを併用する場合には、熱処理温度を
３４０℃以下で行うことが好ましい。In the present invention, it is essential to heat-treat the composite plating film formed on the substrate material as described above within a temperature range of 150 to 350 ° C. In some cases, it may be preferable to lower the upper limit of the heat treatment temperature within this range. For example, when fluorinated pitch is used alone or when fluorinated pitch and FEP are used together, it is preferable to perform the heat treatment at a temperature of 300 ° C. or lower. Further, when the fluorinated pitch and PFA are used in combination, the heat treatment temperature is preferably 340 ° C. or lower.
【００４９】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、フッ化ピッチ微
粒子を単独で共析させる場合には、水による液滴法での
接触角が１３５度以上にも達し、場合によってはこの方
法による測定限界であるとされている１４５度を超える
こともある。また、フッ化ピッチと他の微粒子を併用す
る場合には、水による液滴法での接触角が１２０度以上
に改善される。この熱処理により、複合メッキ被膜の撥
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、３５０℃を上回る場合には、メッキ被
膜が劣化するおそれがある。By this heat treatment, the durability and surface water repellency of the composite plating film are remarkably improved, and when the fluorinated pitch fine particles are co-deposited alone, the contact angle by the droplet method with water becomes 135 degrees or more. In some cases, it may exceed 145 degrees, which is considered to be the limit of measurement by this method. Further, when the fluorinated pitch and other fine particles are used in combination, the contact angle by the droplet method using water is improved to 120 degrees or more. Although it is not clear why this heat treatment significantly improves the water repellency of the composite plating film, wetting due to thermal modification of the composite plating film itself and removal of surfactants (due to thermal decomposition, evaporation, sublimation, etc.) It is speculated that the decrease in sex is one of the causes. Although the heat treatment time is not particularly limited, it is usually 10 to 30 minutes. When 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, while when it exceeds 350 ° C., the plating film may deteriorate.
【００５０】本発明においては、基板材の用途などに応
じて、共析成分を選択することができる。例えば、高い
耐熱性が要求される場合には、フッ化ピッチとＰＴＦＥ
との混合系が好適であり、高い撥水性が要求される場合
には、フッ化ピッチ単独或いはフッ化ピッチとＰＴＦＥ
および／またはＦＥＰとの混合系（フッ化ピッチ含有量
を高めたもの）が好適である。さらに、防汚性、耐焦げ
付き性、離氷性、摺動性などを高めるためには、フッ化
ピッチとＰＴＦＥおよび／またはＦＥＰとの混合系（Ｐ
ＴＦＥおよび／またはＦＥＰの含有量を高めたもの）が
好適である。In the present invention, the eutectoid component can be selected depending on the use of the substrate material and the like. For example, when high heat resistance is required, fluoride pitch and PTFE
A mixed system with is preferable, and when high water repellency is required, fluorinated pitch alone or fluorinated pitch and PTFE
And / or a mixed system with FEP (having a high fluorinated pitch content) is preferable. Further, in order to improve antifouling property, scorching resistance, ice releasing property, slidability, etc., a mixed system (P of PTFE and FEP and / or FEP) is used.
Higher content of TFE and / or FEP) is preferred.
【００５１】[0051]
【発明の効果】本発明により基板材上に形成された複合
メッキ被膜は、非金属であるフッ化ピッチの固有の性質
とマトリックス金属の固有の性質とを兼ね備えている。
より具体的には、この複合メッキ被膜は、先ず、フッ化
ピッチ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および撥水性を発揮する。The composite plating film formed on the substrate material according to the present invention has both the unique properties of the non-metal fluoride pitch and the unique properties of the matrix metal.
More specifically, this composite plating film first has a high degree of lubricity derived from fluorinated pitch, wear resistance, etc.,
Furthermore, it exhibits particularly excellent durability and water repellency.
【００５２】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、高電
気伝導性などを備え、且つ基板材に対する優れた密着性
を発揮する。従って、ＰＴＦＥなどのフッ素系樹脂のコ
−ティング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、
基板材からも分離し難く、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, high electrical conductivity, etc. derived from the matrix metal and exhibits excellent adhesion to the substrate material. Therefore, the composite plating film according to the present invention has excellent strength and is less likely to be scratched, as compared with a coating film of a fluororesin such as PTFE or a molded fluororesin product.
It is also difficult to separate from the substrate material and has excellent thermal conductivity and durability.
【００５３】また、フッ化ピッチ微粒子とＰＴＦＥなど
の他の微粒子とを併用する場合にも撥水性は若干低下す
るものの、耐久性は改善され、その他の点では、上記に
類似する効果が得られる。Also, when the fluorinated pitch fine particles and other fine particles such as PTFE are used in combination, the water repellency is slightly reduced, but the durability is improved, and in other respects, the similar effects to the above can be obtained. .
【００５４】その結果、本発明による複合メッキ被膜を
有する基板材により製氷板を形成する場合には、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 an ice making plate is formed from the substrate material having the composite plating film according to the present invention, the ice releasing property and the ice making efficiency are greatly improved, and the durability of the ice making container is improved.
【００５５】また、本発明による複合メッキ被膜を有す
る基板材は、撥水性或いは撥水性とともにその他の種々
の優れた特性を利用して、製氷板以外にも、広い範囲の
用途における材料として有用である。これら用途の若干
を例示すれば、以下の通りである： −撥油性、防汚性、耐熱焦げ付き性…食器洗い機の内
面、洗濯機水槽内面、レンジフード、換気扇、テーブル
コンロ天板、テーブルコンロ汁受け皿、オーブン皿、焼
き肉用鉄板、ロストル、ジンギスカン鍋、フライパン、
ごとく、焼き網、ガスコンロ、オーブン、電子レンジ、
炊飯器、バーベキューコンロ、ホットプレート、鍋、オ
ーブントースター、電気ポット、電磁誘導ヒーター、シ
ステムキッチン天板、流し台（シンク）、水栓、混合水
栓、ガス管内外面コートなど。特に、フッ化ピッチ微粒
子とＰＴＦＥなどの他の微粒子とを併せて分散させた場
合に、防汚性、耐熱焦げ付き性などの点でより優れた結
果が得られる。Further, the substrate material having the composite plating film according to the present invention is useful as a material in a wide range of applications other than the ice making plate by utilizing water repellency or various other excellent properties together with the water repellency. is there. Some examples of these applications are as follows: -Oil repellency, antifouling property, heat-resistant charcoal-dishwasher inner surface, washing machine water tank inner surface, range hood, ventilation fan, table cooktop, table cooker juice. Saucer, oven dish, iron plate for roast meat, roastle, Genghis Khan pot, frying pan,
Like, grill, gas stove, oven, microwave,
Rice cookers, barbecue stoves, hot plates, pots, oven toasters, electric kettles, electromagnetic induction heaters, system kitchen tops, sinks, faucets, mixed faucets, gas pipe interior and exterior coats, etc. In particular, when fluorinated pitch fine particles and other fine particles such as PTFE are dispersed together, more excellent results can be obtained in terms of antifouling property, heat-resistant scorching property, and the like.
【００５６】−結露防止性…浴室内装など。-Prevention of dew condensation: Bathroom interior and the like.
【００５７】−撥水性および防汚性…浴槽 −熱伝導性…排気トップ、熱交換器フィン部、炭素繊維
表面コート、炭素材コート、ＬＮＧ気化器蒸発板、コピ
ーローラーなど。-Water repellency and antifouling property-Bath-Heat conductivity-Exhaust top, heat exchanger fins, carbon fiber surface coat, carbon material coat, LNG vaporizer evaporation plate, copy roller, etc.
【００５８】−離型性…金型など。-Releasability: Mold and the like.
【００５９】−撥水性および離氷性…航空機およびヘリ
コプター用部品、 −摺動性…ガスバルブ内面コートなど。特に、フッ化ピ
ッチ微粒子とＰＴＦＥなどの他の微粒子とを併せて分散
させた場合に、その効果の改善が著しい。-Water repellency and ice-free property: parts for aircraft and helicopters, -sliding property: gas valve inner surface coating, etc. In particular, when fluorinated pitch fine particles and other fine particles such as PTFE are dispersed together, the effect is remarkably improved.
【００６０】[0060]
【実施例】以下に参考例（フッ化ピッチ微粒子の製造
例）、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 Reference examples (production examples of fluorinated pitch fine particles), examples and comparative examples are shown below to further clarify the features of the present invention.
【００６１】参考例１ 軟化点１００℃、キノリン不溶分０．２重量％、ベンゼ
ン不溶分３０重量％のコールタールピッチに２倍量の水
素化アントラセン油を添加し、４３０℃で９０分間加熱
した後、減圧下３００℃で水素化アントラセン油を除去
して、還元ピッチを得た。Reference Example 1 A double amount of hydrogenated anthracene oil was added to coal tar pitch having a softening point of 100 ° C., a quinoline insoluble content of 0.2% by weight and a benzene insoluble content of 30% by weight, and heated at 430 ° C. for 90 minutes. Then, the hydrogenated anthracene oil was removed at 300 ° C. under reduced pressure to obtain reduced pitch.
【００６２】次いで、得られた還元ピッチに窒素ガスを
導入して低分子量成分を除去し、４５０℃で５時間熱重
合し、軟化点３００℃、キノリン不溶分６０重量％、ベ
ンゼン不溶分９８重量％、メソフェーズ含有量９０重量
％以上のメソフェーズピッチを得た。Then, nitrogen gas was introduced into the obtained reduced pitch to remove low molecular weight components, and thermal polymerization was carried out at 450 ° C. for 5 hours to give a softening point of 300 ° C., quinoline insoluble matter 60% by weight, benzene insoluble matter 98% by weight. %, A mesophase pitch having a mesophase content of 90% by weight or more was obtained.
【００６３】得られたメソフェーズピッチ５０ｇを粉砕
し、ニッケル製反応容器に仕込み、系内を真空排気し、
アルゴンガスで満たした後、フッ素２０％およびアルゴ
ン８０％の混合ガスを７０℃で平均流速６５０ｃｃ／分
の速度で流通させ、２０時間反応させたところ、フッ化
ピッチ粒子１４４ｇが得られた。元素分析の結果、その
組成式は、ＣＦ1.38であり、またその平均粒径は１０μ
ｍであった。50 g of the obtained mesophase pitch was crushed, charged into a reaction vessel made of nickel, the system was evacuated,
After being filled with argon gas, a mixed gas of 20% fluorine and 80% argon was passed through at 70 ° C. at an average flow rate of 650 cc / min and reacted for 20 hours to obtain 144 g of fluorinated pitch particles. As a result of elemental analysis, its composition formula was CF 1.38 , and its average particle size was 10 μm.
It was m.
【００６４】実施例１ 参考例１で得たフッ化ピッチの微粉砕粒子（平均粒径
１．３μｍ）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、界面活性剤として第３級パ−フ
ルオロアンモニウム塩｛商標“メガファックＦ−１５
０”、大日本インキ化学（株）製、（Ｃ8Ｆ17ＳＯ2ＮＨ
（ＣＨ2 ）3 Ｎ+ （ＣＨ3 ）3 ・Ｃｌ- ）｝をフッ化ピ
ッチ１ｇに対し３０．０ｍｇの割合で添加した。Example 1 5% by weight of finely ground particles of fluorinated pitch (average particle size 1.3 μm) obtained in Reference Example 1 were added to a nickel electrolytic bath having the following composition. As a surfactant, a tertiary perfluoroammonium salt {Trademark "MegaFac F-15
0 ", manufactured by Dainippon Ink and Chemicals, Inc. (C 8 F 17 SO 2 NH
(CH 2 ) 3 N + (CH 3 ) 3 · Cl − )} was added at a ratio of 30.0 mg to 1 g of fluorinated pitch.
【００６５】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 次いで、０．５ｍｍ×３ｃｍ×５ｃｍのニッケル板およ
び銅板をそれぞれ正極および負極として、液温４５±５
℃、ｐＨ４．２、電流密度３または５A／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−フッ化ピッチ複合メッキ被膜
を形成させた。Nickel Sulfamate Electrolyte Bath Composition Nickel Sulfamate 350 g / l Nickel Chloride 45 g / l Boric Acid 40 g / l Then, a nickel plate and a copper plate of 0.5 mm × 3 cm × 5 cm were used as the positive electrode and the negative electrode, respectively, and the liquid temperature was 45 ± 5.
Under conditions of ℃, pH 4.2, current density 3 or 5 A / dm 2 ,
Electrolytic plating was performed while stirring with a screw until the film thickness reached 10 μm to form a nickel-fluoride pitch composite plating film.
【００６６】得られたニッケル−フッ化ピッチ複合メッ
キ被膜を有する銅板を真空乾燥した後、２５０℃で３０
分間加熱し、その表面（３ｃｍ×５ｃｍ）について、常
温で室内放置１時間後および３ケ月後に、ＦＡＣＥ接触
角計（“ＣＡ−Ａ型”、協和界面科学（株）製）を用い
て液滴法により、水の接触角の測定を行い、その撥水性
を調べた。結果を表１に示す。なお、表１には、実施例
２〜６および比較例１〜７の結果を併せて示す。但し、
実施例２と４および比較例２以外の比較例については、
熱処理後１時間の結果のみを示す。The copper plate having the nickel-fluoride pitch composite plating film thus obtained was vacuum dried and then heated at 250 ° C. for 30 minutes.
After heating for 1 minute and leaving the surface (3 cm x 5 cm) indoors at room temperature for 1 hour and 3 months, droplets were applied using a FACE contact angle meter ("CA-A type", manufactured by Kyowa Interface Science Co., Ltd.). The contact angle of water was measured by the method to examine its water repellency. The results are shown in Table 1. In addition, Table 1 also shows the results of Examples 2 to 6 and Comparative Examples 1 to 7. However,
For Comparative Examples other than Examples 2 and 4 and Comparative Example 2,
Only the results 1 hour after the heat treatment are shown.
【００６７】比較例１ メッキ被膜の真空乾燥および熱処理を行なわない以外は
実施例１と同様にして銅板上にニッケル−フッ化ピッチ
複合メッキ被膜を形成した。Comparative Example 1 A nickel-fluoride pitch composite plating film was formed on a copper plate in the same manner as in Example 1 except that the vacuum drying and heat treatment of the plating film were not performed.
【００６８】比較例２ 平均粒径４μｍのテトラフルオロエチレンオリゴマー粒
子（セントラル硝子（株）製）を用いて下記の組成を有
するニッケル電解浴を調製し、下記の条件で０．１ｍｍ
×３０ｍｍ×３０ｍｍの銅板に複合メッキ被膜（膜厚１
０μｍ）を形成した。Comparative Example 2 A nickel electrolytic bath having the following composition was prepared by using tetrafluoroethylene oligomer particles having an average particle size of 4 μm (manufactured by Central Glass Co., Ltd.), and 0.1 mm was prepared under the following conditions.
Composite plating film (thickness 1
0 μm) was formed.
【００６９】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 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） ０．５ｇ／ｌメッキ条件 ｐＨ ３．７ 温度 ４３℃ 陰極電流密度 ５Ａ／ｄｍ2 陽極 ニッケル板 撹拌 超音波 時間 １０分間 実施例２ 下記の組成を有するウッド浴を用いて、液温２５℃、電
流密度１０A／dm2 の条件下に膜厚が２μｍとなるまで
０．５ｍｍ×３ｃｍ×５ｃｍのステンレス鋼（ＳＵＳ３
０４）に対しニッケルメッキ処理を行なった。 Nickel Electrolyte Bath Composition Nickel Sulfamate 350 g / l Nickel Chloride 45 g / l Boric Acid 40 g / l Surfactant (Trademark "Megafuck F-150", Dainippon Ink and Chemicals, Inc.) 0.5 g / l Plating Conditions pH 3.7 Temperature 43 ° C. Cathode current density 5 A / dm 2 Anode nickel plate Stirring ultrasonic wave time 10 minutes Example 2 Using a wood bath having the following composition, liquid temperature 25 ° C., current density 10 A / dm 2 0.5 mm × 3 cm × 5 cm stainless steel (SUS3 until the film thickness reaches 2 μm under the conditions
04) was nickel-plated.
【００７０】ウッド浴組成 塩化ニッケル ２４５ｇ／ｌ 塩酸 １２０ｇ／ｌ 次いで、上記のニッケルメッキステンレス鋼を負極とす
る以外は実施例１と同様にして、ニッケルメッキステン
レス鋼にニッケル−フッ化ピッチ複合メッキ被膜を形成
し、熱処理し、被膜の撥水性を調べた。 Wood bath composition Nickel chloride 245 g / l Hydrochloric acid 120 g / l Then, nickel-plated stainless steel was coated with nickel-fluoride pitch composite plating film in the same manner as in Example 1 except that the above nickel-plated stainless steel was used as the negative electrode. Was formed and heat treated to examine the water repellency of the coating.
【００７１】実施例３ 参考例１で得たフッ化ピッチの微粉砕粒子（平均粒径
１．３μｍ）１．２５重量％およびＦＥＰ微粒子（平均
粒径０．２〜０．３μｍ；ダイキン工業（株）製）５重
量％を実施例１で使用したと同様なニッケルメッキ浴に
分散させた。この際、フッ化ピッチ１ｇおよびＰＴＦＥ
１ｇに対しては、界面活性剤（商標“メガファックF-15
0”、大日本インキ化学（株）製）をそれぞれ３０ｍｇ
および６５ｍｇの割合で予め混合しておいた。Example 3 1.25% by weight of finely pulverized fluorinated pitch particles (average particle size 1.3 μm) obtained in Reference Example 1 and FEP fine particles (average particle size 0.2 to 0.3 μm; Daikin Industries ( 5% by weight) was dispersed in a nickel plating bath similar to that used in Example 1. At this time, 1 g of fluorinated pitch and PTFE
For 1 g, the surfactant (trademark “MegaFac F-15
0 ", manufactured by Dainippon Ink and Chemicals, Inc., 30 mg each
And 65 mg premixed.
【００７２】次いで、実施例２と同様にして予め膜厚２
μｍのニッケルメッキ被膜を形成した０．５ｍｍ×３ｃ
ｍ×５ｃｍのステンレス鋼板を負極とし、ニッケル板を
正極として、液温４５±５℃、ｐＨ３．８〜４．２、電
流密度３または５A／dm2 の条件で、膜厚が１０μｍと
なるまで電解メッキを行って、ニッケル−フッ化ピッチ
−ＦＥＰ複合メッキ被膜を形成させた。Then, in the same manner as in Example 2, the film thickness 2 was previously set.
0.5mm × 3c with nickel plating film of μm
A stainless steel plate of m × 5 cm is used as a negative electrode, a nickel plate is used as a positive electrode, and the film thickness is 10 μm under the conditions of a liquid temperature of 45 ± 5 ° C., a pH of 3.8 to 4.2, and a current density of 3 or 5 A / dm 2. Electrolytic plating was performed to form a nickel-fluoride pitch-FEP composite plating film.
【００７３】得られたニッケル−フッ化ピッチ−ＦＥＰ
複合メッキ被膜を有するステンレス鋼板を熱風乾燥機に
より２５０℃で３０分間加熱する以外は実施例１と同様
に処理して、被膜の撥水性を測定した。Obtained Nickel-Fluoride Pitch-FEP
The water repellency of the coating was measured by treating in the same manner as in Example 1 except that the stainless steel plate having the composite plated coating was heated at 250 ° C. for 30 minutes with a hot air dryer.
【００７４】実施例４ 参考例１で得たフッ化ピッチの微粉砕粒子（平均粒径
１．３μｍ）５重量％および低分子量ＰＴＦＥの微粒子
（平均粒径約０．５μｍ；商標“セフラルルーブＶ”、
セントラル硝子（株）製）１．２５重量％を実施例１で
使用したと同様なニッケルメッキ浴に分散させた。この
際、フッ化ピッチ１ｇおよびＰＴＦＥ１ｇに対しては、
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）をそれぞれ３０ｍｇおよび６５ｍｇの
割合で予め混合しておいた。Example 4 5% by weight of finely pulverized fluorinated pitch particles (average particle size 1.3 μm) obtained in Reference Example 1 and fine particles of low molecular weight PTFE (average particle size about 0.5 μm; trademark “Sefraral Lube V”) ,
1.25% by weight of Central Glass Co., Ltd. was dispersed in the same nickel plating bath as that used in Example 1. At this time, for 1 g of fluorinated pitch and 1 g of PTFE,
Surfactants (trademark "Megafuck F-150", manufactured by Dainippon Ink and Chemicals, Inc.) were mixed in advance at a ratio of 30 mg and 65 mg, respectively.
【００７５】得られたニッケルメッキ浴を用いて、実施
例２と同様にして予め膜厚２μｍのニッケルメッキ被膜
を形成したステンレス鋼板に実施例３と同様にしてニッ
ケル−フッ化ピッチ−ＰＴＦＥ複合メッキ被膜を形成さ
せた後、熱風乾燥機により２５０℃で３０分間加熱する
以外は実施例１と同様に処理して、被膜の撥水性を測定
した。Using the obtained nickel plating bath, a nickel-fluoride pitch-PTFE composite plating was performed in the same manner as in Example 3 on a stainless steel plate on which a nickel plating film having a film thickness of 2 μm was previously formed in the same manner as in Example 2. After forming the coating, the same treatment as in Example 1 was performed except that the coating was heated at 250 ° C. for 30 minutes with a hot air dryer, and the water repellency of the coating was measured.
【００７６】実施例５ 参考例１で得たフッ化ピッチの微粒子（平均粒径１．３
μｍ）１．２５重量％およびＰＴＦＥ微粒子（粒径２μ
ｍ以下、ダイキン工業（株）製）５重量％を使用し、且
つフッ化ピッチ１ｇおよびＰＴＦＥ１ｇに対して界面活
性剤（商標“メガファックF-150”、大日本インキ化学
（株）製）をそれぞれ３０ｍｇおよび３０ｍｇの割合で
添加したメッキ浴を使用する以外は実施例１と同様にし
て、実施例２と同様にして予め膜厚２μｍのニッケルメ
ッキ被膜を形成したステンレス鋼板上にフッ化ピッチ−
ＰＴＦＥ複合メッキ被膜を形成させた。Example 5 Fine particles of fluorinated pitch obtained in Reference Example 1 (average particle size 1.3
μm) 1.25 wt% and PTFE fine particles (particle size 2 μm
m or less, 5% by weight of Daikin Industries, Ltd., and a surfactant (trademark “Megafuck F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) for 1 g of fluorinated pitch and 1 g of PTFE. In the same manner as in Example 2 except that the plating baths added in the proportions of 30 mg and 30 mg, respectively, were used, in the same manner as in Example 2, a fluorinated pitch was formed on a stainless steel plate on which a nickel-plated coating having a film thickness of 2 μm had been previously formed.
A PTFE composite plating film was formed.
【００７７】得られたニッケル−フッ化ピッチ−ＰＴＦ
Ｅ複合メッキ被膜を有するステンレス鋼板を熱風乾燥器
により２５０℃で３０分間加熱する以外は実施例１と同
様に処理して、被膜の撥水性を測定した。Obtained nickel-fluoride pitch-PTF
The water repellency of the coating was measured in the same manner as in Example 1 except that the stainless steel plate having the E composite plated coating was heated at 250 ° C. for 30 minutes with a hot air dryer.
【００７８】実施例６ 参考例１で得たフッ化ピッチの微粒子（平均粒径１．３
μｍ）１．２５重量％およびＰＦＡ微粒子（粒径２μｍ
以下、ダイキン工業（株）製）５重量％を使用し、且つ
フッ化ピッチ１ｇおよびＰＦＡ１ｇに対して界面活性剤
（商標“メガファックF-150”、大日本インキ化学
（株）製）をそれぞれ３０ｍｇおよび３０ｍｇの割合で
添加したメッキ浴を使用する以外は実施例１と同様にし
て、実施例２と同様にして予め膜厚２μｍのニッケルメ
ッキ被膜を形成したステンレス鋼板上にフッ化ピッチ−
ＰＦＡ複合メッキ被膜を形成させた。Example 6 Fine particles of fluorinated pitch obtained in Reference Example 1 (average particle size 1.3
μm) 1.25 wt% and PFA fine particles (particle size 2 μm
Hereinafter, 5% by weight of Daikin Industries, Ltd. is used, and a surfactant (trademark “Megafuck F-150”, manufactured by Dainippon Ink and Chemicals, Inc.) is used for 1 g of fluorinated pitch and 1 g of PFA. In the same manner as in Example 2 except that the plating bath added at a ratio of 30 mg and 30 mg was used, in the same manner as in Example 2, a fluorinated pitch was formed on a stainless steel plate on which a nickel plating film having a film thickness of 2 μm was previously formed.
A PFA composite plating film was formed.
【００７９】得られたニッケル−フッ化ピッチ−ＰＦＡ
複合メッキ被膜を有するステンレス鋼板を熱風乾燥器に
より２５０℃で３０分間加熱する以外は実施例１と同様
に処理して、被膜の撥水性を測定した。Obtained Nickel-Fluoride Pitch-PFA
The water repellency of the coating was measured by treating in the same manner as in Example 1 except that the stainless steel plate having the composite plated coating was heated at 250 ° C. for 30 minutes with a hot air dryer.
【００８０】比較例３ 参考例１で得たフッ化ピッチの粉末（平均粒径１０μ
ｍ）を使用する以外は実施例１と同様にしてニッケル−
フッ化ピッチ複合メッキ被膜を有する銅板を得た後、熱
処理し、その撥水性を調べた。Comparative Example 3 Fluoride pitch powder obtained in Reference Example 1 (average particle size 10 μm
nickel) in the same manner as in Example 1 except that m) is used.
After obtaining a copper plate having a fluorinated pitch composite plating film, it was heat-treated and its water repellency was examined.
【００８１】比較例４ フッ化ピッチ微粒子に代えて平均粒径１μｍのフッ化黒
鉛微粒子を使用する以外は実施例１と同様にしてニッケ
ル−フッ化黒鉛複合メッキ被膜を有する銅板を得た後、
熱処理し、その撥水性を調べた。但し、フッ化黒鉛１ｇ
に対し界面活性剤の添加量を４０ｍｇとした。Comparative Example 4 A copper plate having a nickel-fluorinated graphite composite plating film was obtained in the same manner as in Example 1 except that fluorinated graphite fine particles having an average particle size of 1 μm were used in place of the fluorinated pitch fine particles.
It was heat-treated and its water repellency was examined. However, 1g of fluorinated graphite
On the other hand, the amount of the surfactant added was 40 mg.
【００８２】比較例５ フッ化ピッチ微粒子に代えて平均粒径３．５μｍのＰＴ
ＦＥを使用する以外は実施例１と同様にしてニッケル−
ＰＴＦＥ複合メッキ被膜を有する銅板を得た後、熱処理
し、その撥水性を調べた。但し、ＰＴＦＥ１ｇに対し界
面活性剤の添加量を４．５ｍｇとした。Comparative Example 5 PT having an average particle size of 3.5 μm was used in place of the fluorinated pitch fine particles.
Nickel-in the same manner as in Example 1 except that FE was used.
After obtaining a copper plate having a PTFE composite plating film, it was heat-treated and its water repellency was examined. However, the amount of the surfactant added was 4.5 mg per 1 g of PTFE.
【００８３】比較例６ フッ化ピッチを使用しない以外は実施例１と同様にして
銅板に対するニッケルメッキ被膜を形成させた。Comparative Example 6 A nickel plating film was formed on a copper plate in the same manner as in Example 1 except that fluorinated pitch was not used.
【００８４】比較例７ ニッケルメッキ被膜を形成しない銅板について撥水性を
測定した。Comparative Example 7 Water repellency was measured on a copper plate on which no nickel plating film was formed.
【００８５】[0085]
【表１】 [Table 1]
【００８６】表１に示す結果から、本発明によるフッ化
ピッチ共析複合メッキ被膜が極めて優れた撥水性を備え
ていることが明らかである。From the results shown in Table 1, it is apparent that the fluorinated pitch eutectoid composite plating film of the present invention has extremely excellent water repellency.
【００８７】実施例７ 実施例１で得られた２種のニッケル−フッ化ピッチ複合
メッキ被覆銅板の表面（３ｃｍ×５ｃｍ）上に注射器で
１ｃｃの蒸留水を静かに滴下し、直径２．１ｃｍ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、メッキ被覆銅板を製氷室から素早
く取出し、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。結果を表２に示
す。なお、表２には、実施例８〜１０および比較例８〜
９の結果をも併せて示す。Example 7 1 cc of distilled water was gently dropped with a syringe onto the surface (3 cm × 5 cm) of the two nickel-fluoride pitch composite plating-coated copper plates obtained in Example 1, and the diameter was 2.1 cm. Water droplets were formed and allowed to stand in an ice making chamber at -20 ° C for 3 hours to freeze the water droplets. Then, the plated copper plate was quickly taken out of 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. The results are shown in Table 2. In addition, in Table 2, Examples 8-10 and Comparative Examples 8-.
The results of 9 are also shown.
【００８８】実施例８ 実施例３で得られた２種の複合メッキ銅板を用いて実施
例７と同様の実験を行った。Example 8 An experiment similar to that of Example 7 was conducted using the two kinds of composite plated copper plates obtained in Example 3.
【００８９】実施例９ 実施例５で得られた２種の複合メッキ銅板を用いて実施
例７と同様の実験を行った。Example 9 An experiment similar to that of Example 7 was conducted using the two kinds of composite plated copper plates obtained in Example 5.
【００９０】実施例１０ 実施例６で得られた２種の複合メッキ鋼板を用いて実施
例７と同様の実験を行った。Example 10 The same experiment as in Example 7 was conducted using the two kinds of composite plated steel sheets obtained in Example 6.
【００９１】比較例８ 比較例６で得たニッケルメッキ銅板について実施例７と
同様にして離氷性試験を行なった。Comparative Example 8 The ice releasing test was conducted on the nickel-plated copper plate obtained in Comparative Example 6 in the same manner as in Example 7.
【００９２】比較例９ 比較例７と同様なニッケルメッキ被膜を有しない銅板に
ついて実施例７と同様にして離氷性試験を行なった。Comparative Example 9 An ice releasing test was conducted in the same manner as in Example 7 on a copper plate having no nickel plating film as in Comparative Example 7.
【００９３】[0093]
【表２】 [Table 2]
【００９４】第２表に示す結果から、本発明によるフッ
化ピッチ微粒子含有共析複合メッキ被膜が極めて優れた
離氷性を備えていることが明らかである。From the results shown in Table 2, it is clear that the eutectoid composite plating film containing fluorinated pitch fine particles according to the present invention has extremely excellent ice releasing property.
【００９５】実施例１１ ０．５ｍｍ×３ｃｍ×５ｃｍの鋼板を負極として使用す
る以外は実施例１と同様にして電解メッキを行ない、ニ
ッケル−フッ化ピッチ複合メッキ被覆を有する鋼板を作
成した後、実施例１と同様にして熱処理し、接触角の測
定を行なった。この場合にも、実施例１と同様の優れた
撥水性および耐久性が得られた。Example 11 After electrolytic plating was conducted in the same manner as in Example 1 except that a 0.5 mm × 3 cm × 5 cm steel plate was used as the negative electrode, a steel plate having a nickel-fluoride pitch composite plating coating was prepared. It heat-processed like Example 1 and measured the contact angle. Also in this case, excellent water repellency and durability similar to those in Example 1 were obtained.
【００９６】実施例１２ 参考例１で得たフッ化ピッチの微粒子（平均粒径１．３
μｍ）１．２５重量％、ＰＴＦＥ微粒子（粒径２μｍ以
下、ダイキン工業（株）製）２．５重量％およびＦＥＰ
微粒子（粒径０．２〜０．３μｍ、ダイキン工業（株）
製）２．５重量％を使用し、且つフッ化ピッチ１ｇ、Ｐ
ＴＦＥ１ｇおよびＦＥＰ１ｇに対して界面活性剤（商標
“メガファックF-150”、大日本インキ化学（株）製）
をそれぞれ３０ｍｇ、３０ｍｇおよび６５ｍｇの割合で
添加したメッキ浴を使用する以外は実施例１と同様にし
て、実施例２と同様にして予め膜厚２μｍのニッケルメ
ッキ被膜を形成したステンレス鋼板上にフッ化ピッチ−
ＰＴＦＥ−ＦＥＰ複合メッキ被膜を形成させた。Example 12 Fine particles of fluorinated pitch obtained in Reference Example 1 (average particle size 1.3
μm) 1.25% by weight, PTFE fine particles (particle size 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.5% by weight and FEP
Fine particles (particle size 0.2 to 0.3 μm, Daikin Industries, Ltd.)
2.5% by weight, and 1g of fluorinated pitch, P
Surfactant (Trademark "Megafuck F-150", manufactured by Dainippon Ink and Chemicals, Inc.) for 1 g of TFE and 1 g of FEP
Was used in the same manner as in Example 1 except that the plating baths containing 30 mg, 30 mg, and 65 mg were added, respectively. Pitch-
A PTFE-FEP composite plating film was formed.
【００９７】得られたニッケル−フッ化ピッチ−ＰＴＦ
Ｅ−ＦＥＰ複合メッキ被膜を有するステンレス鋼板を熱
風乾燥器により２５０℃で３０分間加熱する以外は実施
例１と同様に処理して、被膜の撥水性を測定した。Obtained Nickel-Fluoride Pitch-PTF
The water repellency of the coating was measured in the same manner as in Example 1 except that the stainless steel plate having the E-FEP composite plated coating was heated at 250 ° C. for 30 minutes with a hot air dryer.
【００９８】この場合にも、実施例１と同様の優れた撥
水性および耐久性が得られた。Also in this case, excellent water repellency and durability similar to those of Example 1 were obtained.
【００９９】実施例１３ 参考例１で得たフッ化ピッチの微粒子（平均粒径１．３
μｍ）１．２５重量％、ＰＴＦＥ微粒子（粒径２μｍ以
下、ダイキン工業（株）製）２．５重量％およびＰＦＡ
微粒子（粒径２μｍ以下、ダイキン工業（株）製）２．
５重量％を使用し、且つフッ化ピッチ１ｇ、ＰＴＦＥ１
ｇおよびＰＦＡ１ｇに対して界面活性剤（商標“メガフ
ァックF-150”、大日本インキ化学（株）製）をそれぞ
れ３０ｍｇ、３０ｍｇおよび３０ｍｇの割合で添加した
メッキ浴を使用する以外は実施例１と同様にして、実施
例２と同様にして予め膜厚２μｍのニッケルメッキ被膜
を形成したステンレス鋼板上にフッ化ピッチ−ＰＴＦＥ
−ＰＦＡ複合メッキ被膜を形成させた。Example 13 Fine particles of fluorinated pitch obtained in Reference Example 1 (average particle size 1.3
μm) 1.25% by weight, PTFE fine particles (particle size 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.5% by weight and PFA
Fine particles (particle diameter 2 μm or less, manufactured by Daikin Industries, Ltd.) 2.
5% by weight and 1g of fluorinated pitch, PTFE1
Example 1 except that a plating bath in which a surfactant (trademark "Megafuck F-150", manufactured by Dainippon Ink and Chemicals, Inc.) was added at a ratio of 30 mg, 30 mg and 30 mg to 1 g of PFA and 1 g of PFA, respectively. In the same manner as in Example 2, fluoride pitch-PTFE was formed on a stainless steel plate on which a nickel-plated coating having a film thickness of 2 μm was formed in advance.
-A PFA composite plating film was formed.
【０１００】得られたニッケル−フッ化ピッチ−ＰＴＦ
Ｅ−ＰＦＡ複合メッキ被膜を有するステンレス鋼板を熱
風乾燥器により２５０℃で３０分間加熱する以外は実施
例１と同様に処理して、被膜の撥水性を測定した。Obtained Nickel-Fluoride Pitch-PTF
The water repellency of the coating was measured in the same manner as in Example 1 except that the stainless steel plate having the E-PFA composite plated coating was heated at 250 ° C. for 30 minutes with a hot air dryer.
【０１０１】この場合にも、実施例１と同様の優れた撥
水性および耐久性が得られた。Also in this case, excellent water repellency and durability similar to those of Example 1 were obtained.
Claims (12)
を分散含有しており、１５０〜３００℃の温度で熱処理
後の水による液滴法での接触角が１３５度以上である高
耐久性・高撥水性複合メッキ被膜を備えた基板材。1. High durability, in which fine particles of fluorinated pitch having an average particle diameter of 2 μm or less are dispersed and contained, and a contact angle by a droplet method with water after heat treatment at a temperature of 150 to 300 ° C. is 135 degrees or more. -A substrate material with a highly water-repellent composite plating film.
界面活性剤を含み且つ平均粒径２μｍ以下のフッ化ピッ
チ微粒子を分散させた電解メッキ液中で基板材表面にフ
ッ化ピッチ微粒子を共析する複合メッキ被膜を形成させ
た後、１５０〜３００℃の温度で複合メッキ被膜を熱処
理することを特徴とする、水による液滴法での接触角が
１３５度以上である高耐久性・高撥水性複合メッキ被膜
の製造方法。2. Co-deposition of fluorinated pitch fine particles on the surface of a substrate material in an electrolytic plating solution containing a fluorinated pitch fine particle having an average particle size of 2 μm or less, which contains a surfactant exhibiting a cationic property at the pH of the plating solution. Which is characterized by heat-treating the composite plating film at a temperature of 150 to 300 ° C., which has a high contact resistance of 135 degrees or more by the water-drop method and is highly durable and highly repellent. A method for producing an aqueous composite plating film.
を分散含有しており、１５０〜３００℃の温度で熱処理
後の水による液滴法での接触角が１３５度以上である高
耐久性・高撥水性複合メッキ被膜を備えた製氷板。3. High durability in which fine particles of fluorinated pitch having an average particle diameter of 2 μm or less are dispersed and contained, and a contact angle by a droplet method with water after heat treatment at a temperature of 150 to 300 ° C. is 135 degrees or more. -Ice plate with a highly water-repellent composite plating film.
と平均粒径２μｍ以下の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、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およびフ
ッ化黒鉛微粒子の少なくとも１種とを分散含有してお
り、１５０〜３５０℃の温度で熱処理後の水による液滴
法での接触角が１２０度以上である高耐久性・高撥水性
複合メッキ被膜を備えた基板材。4. A fluorinated pitch fine particle having an average particle diameter of 2 μm or less, a polytetrafluoroethylene fine particle having an average particle diameter of 2 μm or less, a tetrafluoroethylene-hexafluoropropylene copolymer fine particle, and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer weight. At least one kind of coalesced fine particles and fluorinated graphite fine particles are dispersed and contained, and the contact angle by the droplet method with water after heat treatment at a temperature of 150 to 350 ° C. is 120 degrees or more. A substrate material with an aqueous composite plating film.
界面活性剤を含み且つ平均粒径２μｍ以下のフッ化ピッ
チ微粒子と平均粒径２μｍ以下の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、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
およびフッ化黒鉛微粒子の少なくとも１種とを分散させ
た電解メッキ液中で基板材表面にフッ化ピッチ微粒子と
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、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およびフッ化黒鉛微粒子の少なく
とも１種とを共析する複合メッキ被膜を形成させた後、
１５０〜３５０℃の温度で複合メッキ被膜を熱処理する
ことを特徴とする、水による液滴法での接触角が１２０
度以上である高耐久性・高撥水性複合メッキ被膜の製造
方法。5. A fluorinated pitch fine particle having an average particle size of 2 μm or less, a polytetrafluoroethylene fine particle having an average particle size of 2 μm or less, and tetrafluoroethylene-hexafluoropropylene, which contains a surfactant exhibiting a cationic property at a pH of a plating solution. Fluoride pitch fine particles and polytetrafluoroethylene fine particles on the surface of the substrate material in an electrolytic plating solution in which at least one of copolymer fine particles, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and fluorinated graphite fine particles are dispersed. , Tetrafluoroethylene-hexafluoropropylene copolymer fine particles, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles and at least one kind of fluorinated graphite fine particles, after forming a composite plating film,
The contact angle in the droplet method using water is 120, which is characterized in that the composite plating film is heat-treated at a temperature of 150 to 350 ° C.
A method for producing a highly durable and highly water-repellent composite plating film that is more than 100 degrees.
と平均粒径２μｍ以下の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、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およびフ
ッ化黒鉛微粒子の少なくとも１種とを分散含有してお
り、１５０〜３５０℃の温度で熱処理後の水による液滴
法での接触角が１２０度以上である高耐久性・高撥水性
複合メッキ被膜を備えた製氷板。6. A fluorinated pitch fine particle having an average particle diameter of 2 μm or less, a polytetrafluoroethylene fine particle having an average particle diameter of 2 μm or less, a tetrafluoroethylene-hexafluoropropylene copolymer fine particle, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer weight. At least one kind of coalesced fine particles and fluorinated graphite fine particles are dispersed and contained, and the contact angle by the droplet method with water after heat treatment at a temperature of 150 to 350 ° C. is 120 degrees or more. An ice plate with an aqueous composite plating film.
と平均粒径２μｍ以下のポリテトラフルオロエチレン微
粒子とを分散含有しており、１５０〜３５０℃の温度で
熱処理後の水による液滴法での接触角が１２０度以上で
ある高耐久性・高撥水性複合メッキ被膜を備えた基板
材。7. A droplet method using water, which comprises dispersed fine particles of fluorinated pitch having an average particle diameter of 2 μm or less and fine particles of polytetrafluoroethylene having an average particle diameter of 2 μm or less, and which has been heat-treated at a temperature of 150 to 350 ° C. with water. A substrate material with a highly durable and highly water-repellent composite plating film with a contact angle of 120 degrees or more.
界面活性剤を含み且つ平均粒径２μｍ以下のフッ化ピッ
チ微粒子と平均粒径２μｍ以下のポリテトラフルオロエ
チレン微粒子とを分散させた電解メッキ液中で基板材表
面にフッ化ピッチ微粒子とポリテトラフルオロエチレン
微粒子とを共析する複合メッキ被膜を形成させた後、１
５０〜３５０℃の温度で複合メッキ被膜を熱処理するこ
とを特徴とする、水による液滴法での接触角が１２０度
以上である高耐久性・高撥水性複合メッキ被膜の製造方
法。8. An electroplating solution in which fluorinated pitch fine particles having an average particle size of 2 .mu.m or less and polytetrafluoroethylene fine particles having an average particle size of 2 .mu.m or less are dispersed, containing a surfactant exhibiting a cationic property at the pH of the plating solution. After forming a composite plating film in which the fluorinated pitch fine particles and polytetrafluoroethylene fine particles are co-deposited on the surface of the substrate material,
A method for producing a highly durable and highly water-repellent composite plating film, which comprises subjecting the composite plating film to a heat treatment at a temperature of 50 to 350 ° C., which has a contact angle of 120 degrees or more by a water droplet method.
と平均粒径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とを分散含有して
おり、１５０〜３００℃の温度で熱処理後の水による液
滴法での接触角が１２０度以上である高耐久性・高撥水
性複合メッキ被膜を備えた基板材。9. A fluorinated pitch fine particle having an average particle diameter of 2 μm or less and a tetrafluoroethylene-hexafluoropropylene copolymer fine particle having an average particle diameter of 2 μm or less are dispersed and contained, and after heat treatment at a temperature of 150 to 300 ° C. A substrate material provided with a highly durable and highly water-repellent composite plating film having a contact angle of 120 degrees or more by the water droplet method.
す界面活性剤を含み且つ平均粒径２μｍ以下のフッ化ピ
ッチ微粒子と平均粒径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とを分
散させた電解メッキ液中で基板材表面にフッ化ピッチ微
粒子と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とを共析する複合メッキ被膜を形成
させた後、１５０〜３００℃の温度で複合メッキ被膜を
熱処理することを特徴とする、水による液滴法での接触
角が１２０度以上である高耐久性・高撥水性複合メッキ
被膜の製造方法。10. Fluorinated pitch fine particles having a mean particle size of 2 μm or less and tetrafluoroethylene-hexafluoropropylene copolymer fine particles having a mean particle size of 2 μm or less and containing a surfactant exhibiting a cationic property at the pH of the plating solution. After forming a composite plating film in which the fluorinated pitch fine particles and the tetrafluoroethylene-hexafluoropropylene copolymer fine particles are co-deposited on the surface of the substrate material in the dispersed electrolytic plating solution, the composite is coated at a temperature of 150 to 300 ° C. A method for producing a highly durable and highly water-repellent composite plating film having a contact angle of 120 degrees or more by a water drop method, characterized by heat-treating the plating film.
子と平均粒径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とを
分散含有しており、１５０〜３４０℃の温度で熱処理後
の水による液滴法での接触角が１２０度以上である高耐
久性・高撥水性複合メッキ被膜を備えた基板材。11. A fluorinated pitch fine particle having an average particle diameter of 2 μm or less and a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particle having an average particle diameter of 2 μm or less are dispersed and contained, and heat treatment is performed at a temperature of 150 to 340 ° C. Substrate material provided with a highly durable and highly water-repellent composite plating film, which has a contact angle of 120 degrees or more by a later water droplet method.
す界面活性剤を含み且つ平均粒径２μｍ以下のフッ化ピ
ッチ微粒子と平均粒径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
粒子とを分散させた電解メッキ液中で基板材表面にフッ
化ピッチ微粒子と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とを共析する
複合メッキ被膜を形成させた後、１５０〜３４０℃の温
度で複合メッキ被膜を熱処理することを特徴とする、水
による液滴法での接触角が１２０度以上である高耐久性
・高撥水性複合メッキ被膜の製造方法。12. Fluoride pitch fine particles having a mean particle size of 2 μm or less and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles having a mean particle size of 2 μm or less and containing a surfactant exhibiting cationicity at the pH of the plating solution. After forming a composite plating film in which the fluorinated pitch fine particles and the tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fine particles are co-deposited on the surface of the substrate material in the electrolytic plating solution in which is dispersed, a temperature of 150 to 340 ° C. A method for producing a highly durable and highly water-repellent composite plating film, wherein the contact angle by the droplet method with water is 120 degrees or more, which is characterized in that the composite plating film is heat-treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03452794A JP3306606B2 (en) | 1993-05-14 | 1994-03-04 | Substrate provided with highly durable and highly water-repellent composite plating film, method for producing the same, and ice plate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5-113309 | 1993-05-14 | ||
| JP11330993 | 1993-05-14 | ||
| JP03452794A JP3306606B2 (en) | 1993-05-14 | 1994-03-04 | Substrate provided with highly durable and highly water-repellent composite plating film, method for producing the same, and ice plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0726397A true JPH0726397A (en) | 1995-01-27 |
| JP3306606B2 JP3306606B2 (en) | 2002-07-24 |
Family
ID=26373347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03452794A Expired - Lifetime JP3306606B2 (en) | 1993-05-14 | 1994-03-04 | Substrate provided with highly durable and highly water-repellent composite plating film, method for producing the same, and ice plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3306606B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1564314A1 (en) * | 2002-11-01 | 2005-08-17 | Shinshu University | Metal plating structure and method for production thereof |
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| KR20180118592A (en) * | 2016-10-31 | 2018-10-31 | 한국생산기술연구원 | Hard PTFE coating layer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3521240B2 (en) | 1996-06-21 | 2004-04-19 | 大阪瓦斯株式会社 | Colored composite plating solution, colored composite plating method, and colored composite plating film |
-
1994
- 1994-03-04 JP JP03452794A patent/JP3306606B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1564314A1 (en) * | 2002-11-01 | 2005-08-17 | Shinshu University | Metal plating structure and method for production thereof |
| EP1564314A4 (en) * | 2002-11-01 | 2006-07-12 | Univ Shinshu | Metal plating structure and method for production thereof |
| JP2007009333A (en) * | 2006-10-23 | 2007-01-18 | Shinshu Univ | Plated structure and method of manufacturing the same |
| JP4599565B2 (en) * | 2006-10-23 | 2010-12-15 | 国立大学法人信州大学 | Electrolytic plating method and electrolytic plating solution |
| KR20180118592A (en) * | 2016-10-31 | 2018-10-31 | 한국생산기술연구원 | Hard PTFE coating layer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3306606B2 (en) | 2002-07-24 |
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