JPH09299880A - Water repellent article and manufacture thereof - Google Patents
Water repellent article and manufacture thereofInfo
- Publication number
- JPH09299880A JPH09299880A JP11398396A JP11398396A JPH09299880A JP H09299880 A JPH09299880 A JP H09299880A JP 11398396 A JP11398396 A JP 11398396A JP 11398396 A JP11398396 A JP 11398396A JP H09299880 A JPH09299880 A JP H09299880A
- Authority
- JP
- Japan
- Prior art keywords
- water repellent
- water
- fluoroalkylsilane
- metal
- film
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000005871 repellent Substances 0.000 title claims abstract description 51
- 230000002940 repellent Effects 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000010408 film Substances 0.000 claims abstract description 27
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004703 alkoxides Chemical group 0.000 claims abstract description 4
- 239000000460 chlorine Chemical group 0.000 claims abstract description 4
- 229910052801 chlorine Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 9
- LUDNSFBTTXONSJ-UHFFFAOYSA-N FC(C(F)(F)[Si](Cl)(Cl)Cl)CCCCCCCC(F)(F)F Chemical group FC(C(F)(F)[Si](Cl)(Cl)Cl)CCCCCCCC(F)(F)F LUDNSFBTTXONSJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001343 alkyl silanes Chemical class 0.000 claims 1
- 238000009713 electroplating Methods 0.000 abstract description 7
- 239000002826 coolant Substances 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 organic acid salt Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- JNEGECSXOURYNI-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound FC(F)(F)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl JNEGECSXOURYNI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は撥水性物品、特にテ
トラフルオロエチレンオリゴマーと金属からなる撥水膜
を有する撥水性物品およびその製造法に関する。TECHNICAL FIELD The present invention relates to a water-repellent article, and more particularly to a water-repellent article having a water-repellent film composed of a tetrafluoroethylene oligomer and a metal, and a method for producing the same.
【０００２】[0002]
【従来の技術】鉄、ニッケル、クロムのような金属およ
びそれらの合金は大きな強度と美しい外観を合わせ持つ
ことから，建築，車両等の構造材料としてだけでなく、
最近では内装用の素材としても様々な形で使用されてい
る。2. Description of the Related Art Metals such as iron, nickel and chrome and their alloys have great strength and a beautiful appearance, so that they are not only used as structural materials for construction, vehicles, etc.
Recently, it has been used in various forms as a material for interiors.
【０００３】一般に、金属表面は水分や酸素の存在下で
容易に酸化されるために、強度の低下や外観性能の劣化
を引き起こす。また、金属表面は大きな表面エネルギー
を有することから、汚れが付着し易く落ちにくいという
問題点もある。この様な種々の問題を解決するために、
従来から金属表面に耐水性および／または防汚性の塗膜
をコーティングすることが広く行なわれている。Generally, a metal surface is easily oxidized in the presence of water and oxygen, which causes deterioration of strength and deterioration of appearance performance. Further, since the metal surface has a large surface energy, there is a problem that dirt easily attaches and is hard to remove. In order to solve such various problems,
Conventionally, it has been widely practiced to coat a metal surface with a water-resistant and / or antifouling coating film.
【０００４】しかしながら、これらの塗膜の撥水および
防汚性能は十分とは言えず、さらに塗膜が剥離し易いと
いう欠点があった。However, the water repellency and antifouling performance of these coating films cannot be said to be sufficient, and there is a drawback that the coating films are easily peeled off.
【０００５】一方、特に産業用クーラーにおいては、金
属製フィンや冷媒フロー用金属製パイプに霜が付着する
ために、熱交換率が著しく低下するという問題がある。
従来は一旦運転を停止してから、熱媒で霜を溶かすとい
う、エネルギー的に大変非効率的な方法で対処してい
る。この分野でも、霜が付き難い撥水膜が強く求められ
ている。On the other hand, particularly in an industrial cooler, there is a problem that the heat exchange rate is remarkably reduced because frost adheres to the metal fins and the metal pipes for refrigerant flow.
Conventionally, the operation is stopped once, and then frost is melted by a heat medium, which is an energy-inefficient method. In this field as well, there is a strong demand for a water-repellent film that is resistant to frost.
【０００６】最近、鄭らはニッケルメッキ浴にテトラフ
ルオロエチレン分散させた液にニッケル基板を浸漬し、
分散電気メッキを行なうことにより、ニッケル基板表面
を撥水化することに成功した（例えば、Ｊ．Ｅｌｅｃｔ
ｒｏａｎａｌ．Ｃｈｅｍ．，２０９ページ，３５３巻，
１９９３年）。この膜は従来に無い優れた初期撥水性能
を有するだけでなく、基板との密着性も良好である。Recently, Zheng et al. Immersed a nickel substrate in a liquid containing tetrafluoroethylene dispersed in a nickel plating bath,
We succeeded in making the nickel substrate surface water repellent by performing distributed electroplating (see, for example, J. Select).
roanal. Chem. , 209 pages, 353 volumes,
1993). This film not only has an excellent initial water repellency that has never been seen, but also has good adhesion to the substrate.
【０００７】しかしながら、この膜は空気中に放置する
と、その撥水性能が著しく低下するという問題点があ
る。However, this film has a problem that its water-repellent performance is remarkably deteriorated when left in the air.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、テトラフル
オロエチレンオリゴマーと金属からなる撥水膜に関する
前述の問題点に鑑みなされたものであって、撥水性能を
安定化して耐久性を向上させるための処理方法を提供す
ることを目的としている。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems relating to a water repellent film composed of a tetrafluoroethylene oligomer and a metal, and stabilizes the water repellent performance to improve the durability. The purpose is to provide a processing method for.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、鋭意研究
の結果、テトラフルオロエチレンオリゴマーと金属から
なる撥水膜表面をフルオロアルキルシランでさらに処理
することにより、撥水性能の時間安定性が著しく向上す
ることを見い出した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the time stability of water repellent performance is improved by further treating the surface of a water repellent film composed of a tetrafluoroethylene oligomer and a metal with a fluoroalkylsilane. Have been found to be significantly improved.
【００１０】まず、本発明の原理について述べる。テト
ラフルオロエチレンオリゴマーとニッケルからなる撥水
膜を表面分析した結果、前記撥水膜表面には多数の凹凸
が存在し、凸部分の主成分がテトラフルオロエチレンオ
リゴマー粒子であるのに対して、凹部分の主成分はニッ
ケルからなることが明らかになった。さらに熱力学的な
考察から、撥水性能の劣化は、ニッケル表面が空気中の
酸素および／または水分により容易に酸化されることに
よることがわかった。酸化されたニッケル部分が親水性
に変化するために、撥水性能が低下するものと考えられ
る。そこで、酸化されたニッケル表面または酸化される
前のニッケル表面にフルオロアルキルシランの薄膜をコ
ーティングすることにより、ニッケル領域と水との相互
作用を弱めることにより、撥水性能の安定性が顕著に向
上したものと考えられる。First, the principle of the present invention will be described. As a result of surface analysis of the water repellent film composed of tetrafluoroethylene oligomer and nickel, there are many irregularities on the surface of the water repellent film. It was revealed that the main component of the part was nickel. Further, from thermodynamic considerations, it was found that the deterioration of the water repellent performance was due to the nickel surface being easily oxidized by oxygen and / or water in the air. It is considered that the water repellent performance is deteriorated because the oxidized nickel portion changes to hydrophilic. Therefore, by coating a thin film of fluoroalkylsilane on the oxidized nickel surface or the nickel surface before being oxidized, the interaction between the nickel region and water is weakened, and the stability of water repellent performance is significantly improved. It is thought that it was done.
【００１１】本発明において、テトラフルオロエチレン
オリゴマーと金属からなる撥水膜が被覆される基材は全
ての金属を用いることができる。In the present invention, all the metals can be used for the substrate coated with the water repellent film composed of the tetrafluoroethylene oligomer and the metal.
【００１２】本発明において、テトラフルオロエチレン
オリゴマーと金属からなる撥水膜の被覆は電気メッキに
よる方法が好ましい。メッキ液としてはニッケルその他
の金属のスルファミン酸その他の有機酸塩、および／ま
たは無機酸塩の溶液にテトラフルオロエチレンオリゴマ
ー、および必要に応じてホウ酸、界面活性剤を添加した
液が用いられる。メッキ液中の上記金属塩とテトラフル
オロエチレンオリゴマーとの割合は重量比で１０：１〜
１０：１０の範囲が好ましい。テトラフルオロエチレン
オリゴマーは平均分子量が５０００〜１５０００の範囲
内例えば約８５００程度のものを好適に使用できる。ま
た撥水膜の金属としては、ニッケル、クロム、アルミニ
ウム、金、銀等を挙げることができる。この撥水膜と金
属基材との接着力を更に大きくする必要がある場合に
は、例えば３２０℃で２時間以上焼成するのが効果的で
ある。In the present invention, the coating of the water repellent film made of a tetrafluoroethylene oligomer and a metal is preferably performed by electroplating. As the plating solution, a solution obtained by adding a tetrafluoroethylene oligomer, and if necessary, boric acid and a surfactant to a solution of sulfamic acid or other organic acid salt of nickel or other metal and / or an inorganic acid salt is used. The ratio of the metal salt to the tetrafluoroethylene oligomer in the plating solution is 10: 1 by weight.
The range of 10:10 is preferable. As the tetrafluoroethylene oligomer, those having an average molecular weight in the range of 5,000 to 15,000, for example, about 8500 can be preferably used. Examples of the metal of the water repellent film include nickel, chromium, aluminum, gold and silver. When it is necessary to further increase the adhesive force between the water repellent film and the metal base material, it is effective to bake at 320 ° C. for 2 hours or more.
【００１３】本発明で用いるフルオロアルキルシランは
酸化された金属表面と強く結合するものであば、何でも
よい。具体的には、アルコキシドまたは塩素等の官能基
（下記、化学式１のＸ）を有するフルオロアルキルシラ
ンが特に好適に使用される。フルオロアルキル鎖の長さ
は重要なパラメータである。短すぎると、金属領域に十
分な撥水性能を付与することができないからである。従
って、特にｎ＞３以上のものが好適である。The fluoroalkylsilane used in the present invention may be any one as long as it strongly bonds to the oxidized metal surface. Specifically, a fluoroalkylsilane having a functional group such as alkoxide or chlorine (X in the chemical formula 1 below) is particularly preferably used. The length of the fluoroalkyl chain is an important parameter. This is because if it is too short, sufficient water repellent performance cannot be imparted to the metal region. Therefore, it is particularly preferable that n> 3 or more.
【００１４】[0014]
【化１】ＣＦ3（ＣＦ2）n（ＣＨ2）2ＳｉＸ3 （１） （ここで、ｎは３〜１５の整数、Ｘはアルコキシドまた
は塩素基である）Embedded image CF 3 (CF 2 ) n (CH 2 ) 2 SiX 3 (1) (where n is an integer of 3 to 15 and X is an alkoxide or a chlorine group)
【００１５】フルオロアルキルシランの処理方法は、液
相法および気相法を用いることが可能である。しかしな
がら、処理したいニッケルのような金属領域は表面凹凸
の凹部分に相当しており、液相法では処理液が浸透せ
ず、均一に処理し難い場合もある。一方、気相法を用い
ることにより、容易にかつ均一に表面コーティングする
ことができる。この場合、フルオロアルキルシランの蒸
気圧が高い方が好ましく、ｎ＜９のフルオロアルキルシ
ランが好適に使用できる。従って、気相処理では３＜ｎ
＜９の範囲のフルオロアルキルシランを用いることが望
ましい。上記化学式１で表わされる化合物としては、ヘ
プタデカフルオロデシルトリクロロシラン、ヘキサフル
オロデシルトリクロロシラン等を挙げることができる。As the method for treating the fluoroalkylsilane, a liquid phase method and a gas phase method can be used. However, the metal region such as nickel to be treated corresponds to the concave portion of the surface unevenness, and the treatment liquid may not permeate in the liquid phase method, which may make it difficult to perform the treatment uniformly. On the other hand, by using the vapor phase method, the surface can be coated easily and uniformly. In this case, the higher the vapor pressure of the fluoroalkylsilane is, the more preferable the fluoroalkylsilane with n <9 can be used. Therefore, in the gas phase treatment, 3 <n
It is desirable to use fluoroalkylsilanes in the range <9. Examples of the compound represented by the chemical formula 1 include heptadecafluorodecyltrichlorosilane and hexafluorodecyltrichlorosilane.
【００１６】上記気相法の中で減圧ＣＶＤ法が本発明で
好ましく用いられる。減圧ＣＶＤ法自体は、よく知られ
ている方法であり、ＣＶＤ処理時の真空度は、十分な撥
水剤の蒸気圧、例えば５Ｔｏｒｒ以下が得られるように
設定すれば良い。従って、用いる撥水剤の種類によって
異なるが、通常は０．０１〜１０Ｔｏｒｒ、例えば５Ｔ
ｏｒｒ程度で十分である。Among the vapor phase methods, the low pressure CVD method is preferably used in the present invention. The low pressure CVD method itself is a well-known method, and the degree of vacuum during the CVD process may be set so that a sufficient vapor pressure of the water repellent agent, for example, 5 Torr or less can be obtained. Therefore, it is usually 0.01 to 10 Torr, for example, 5T, although it depends on the type of water repellent used.
Orr level is sufficient.
【００１７】テトラフルオロエチレンオリゴマーと金属
からなる撥水膜表面（基材）とフルオロアルキルシラン
との反応を促進するためには、基材を加熱しながら減圧
ＣＶＤ法によりフルオロアルキルシランを付着させるこ
とが好ましく、加熱温度は４０〜１００℃、例えば８０
℃程度で十分である。このフルオロアルキルシラン薄膜
の厚みは好ましくは約０．５ｎｍ〜１００ｎｍ、より好
ましくは５〜３０ｎｍである。In order to promote the reaction between the surface (base material) of the water repellent film made of tetrafluoroethylene oligomer and metal and the fluoroalkylsilane, the fluoroalkylsilane is attached by the low pressure CVD method while heating the base material. Is preferred, and the heating temperature is 40 to 100 ° C., for example 80.
C is enough. The thickness of this fluoroalkylsilane thin film is preferably about 0.5 nm to 100 nm, more preferably 5 to 30 nm.
【００１８】[0018]
【発明の実施の形態】以下、実施例に基づいて本発明を
詳細に説明するが、本発明はかかる実施例にのみに限定
されるものではない。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to such Examples.
【００１９】１４０ｇのスルファミン酸ニッケル，１８
ｇの塩化ニッケル，および１６ｇのホウ酸を４００ｍＬ
の蒸留水に加え、攪拌しながら５０℃で約２時間加熱す
ることにより、緑色の均一溶液を得た（ニッケルメッキ
溶液）。カチオン性界面活性剤５．０５ｇに蒸留水５０
０ｍＬを加え、６０℃で３時間攪拌することにより薄黄
色の均一溶液を得た（界面活性剤溶液）。テトラフルオ
ロエチレンオリゴマー（ＴＦＥＯ、分子量 ８５００）
５５ｇに界面活性剤溶液５５ｍＬを添加し、ホモジナイ
ザーを用いて１１５０ｒｐｍの速度で約５分間攪拌した
（オリゴマー分散液）。140 g of nickel sulfamate, 18
400 mL of g nickel chloride and 16 g boric acid
Was added to the distilled water and heated at 50 ° C. for about 2 hours with stirring to obtain a green uniform solution (nickel plating solution). Distilled water 50 to 5.05g of cationic surfactant
0 mL was added and the mixture was stirred at 60 ° C. for 3 hours to obtain a light yellow uniform solution (surfactant solution). Tetrafluoroethylene oligomer (TFEO, molecular weight 8500)
55 mL of a surfactant solution was added to 55 g, and the mixture was stirred using a homogenizer at a speed of 1150 rpm for about 5 minutes (oligomer dispersion liquid).
【００２０】このオリゴマー分散液にニッケルメッキ溶
液を１５０ｍＬ加えて攪拌した。さらに、この液に残り
のニッケルメッキ溶液４５０ｍＬを加えてから十分に攪
拌することにより、撥水膜用分散電気メッキ液を調製し
た。To this oligomer dispersion, 150 mL of nickel plating solution was added and stirred. Furthermore, 450 mL of the remaining nickel plating solution was added to this solution, and the mixture was sufficiently stirred to prepare a dispersed electroplating solution for a water repellent film.
【００２１】分散電気メッキに用いた装置を図１に示
す。恒温槽９のウォーターバス５中で４５℃に保温され
たメッキ浴槽８（７．５ｃｍ×８ｃｍ×１０ｃｍ）に分
散電気メッキ液４を入れ、磁気攪拌子７による攪拌を続
けた。陰極２および陽極３として、それぞれニッケル基
板（有効面積＝５ｃｍ×７ｃｍ）を準備し、これを予め
アセトンに１０分間浸漬して脱脂したものを更に１０％
塩酸水溶液に２秒間浸漬後、乾燥させたものを用いた。
北斗電工製ポテンシオガルバノスタット（ＨＡ５０１）
を直流電源１として、２Ａ／ｄｍ2 の電流密度で４０分
間通電したところ、メッキされた撥水膜の厚みは約３０
μｍであった。サンプルをメッキ浴から取り出し、エタ
ノールで洗浄してから乾燥させた。The apparatus used for distributed electroplating is shown in FIG. The dispersed electroplating solution 4 was placed in the plating bath 8 (7.5 cm × 8 cm × 10 cm) kept at 45 ° C. in the water bath 5 of the constant temperature bath 9, and stirring by the magnetic stirrer 7 was continued. A nickel substrate (effective area = 5 cm × 7 cm) was prepared as each of the cathode 2 and the anode 3, and this was further immersed in acetone for 10 minutes to be degreased, and further 10%
It was used after being dipped in a hydrochloric acid aqueous solution for 2 seconds and then dried.
Hokuto Denko Potentio Galvanostat (HA501)
When a current density of 2 A / dm 2 was applied for 40 minutes as a DC power source 1, the thickness of the plated water-repellent film was about 30.
μm. The sample was removed from the plating bath, washed with ethanol and dried.
【００２２】この方法に従って、４枚の撥水性ニッケル
基板を作製した。さらに、その内２枚を８０℃に保温し
た真空チャンバー内にセットし、約１０Ｔｏｒｒに減圧
した。５０μＬのヘキサフルオロデシルトリクロロシラ
ン（ＨＦＴＳ）を注射器で真空チャンバー内に導入し
た。系を閉じて、８０℃で３０分間加熱した。過剰のＨ
ＦＴＳを除去するために、さらに真空ポンプで真空引き
しながら、１００℃に昇温して３０分間加熱を続けた。
撥水性ニッケル基板表面のヘキサフルオロデシルトリク
ロロシラン薄膜の厚みは約１５ｎｍであった。According to this method, four water-repellent nickel substrates were prepared. Further, two of them were set in a vacuum chamber kept at 80 ° C., and the pressure was reduced to about 10 Torr. 50 μL of hexafluorodecyltrichlorosilane (HFTS) was introduced into the vacuum chamber with a syringe. The system was closed and heated at 80 ° C. for 30 minutes. Excess H
In order to remove FTS, the temperature was raised to 100 ° C. and heating was continued for 30 minutes while further vacuuming with a vacuum pump.
The thickness of the hexafluorodecyltrichlorosilane thin film on the surface of the water repellent nickel substrate was about 15 nm.
【００２３】撥水処理のみを施したサンプル（比較例）
をＡ１，Ａ２とする。さらにＨＦＴＳ処理したサンプル
（実施例）をＢ１，Ｂ２とする。比較例サンプルおよび
実施例サンプルの水に対する接触角の経時変化を図２で
それぞれデータ１１（●）および１２（▲）に示す。但
し、データ１１，１２はぞれぞれＡ１，Ａ２およびＢ
１，Ｂ２の平均値を表わしている。Samples subjected only to water repellent treatment (comparative example)
Are A1 and A2. Further, samples (Example) subjected to HFTS are designated as B1 and B2. FIG. 2 shows data 11 () and 12 (▲) of the contact angle of water of the comparative example sample and the example sample with water, respectively. However, the data 11 and 12 are A1, A2 and B respectively.
1 represents the average value of B2.
【００２４】これより、実施例（Ｂ１，Ｂ２）および比
較例（Ａ１，Ａ２）の初期接触角はともに１４０°を超
えており、良好な撥水性能が得られていることがわか
る。しかしながら、室内放置時間と共に比較例（Ａ１，
Ａ２）の接触角は急激に低下し室内放置時間４日で接触
角は約１２０°と低くなっている。これに対して、実施
例（Ｂ１，Ｂ２）サンプルでは、室内放置時間が１０日
でも接触角は約１３５°と高く、室内放置時間が増加し
ても接触角は初期接触角と殆ど変化せず、経時変化が非
常に小さくなっている。From this, it can be seen that the initial contact angles of Examples (B1 and B2) and Comparative Examples (A1 and A2) both exceeded 140 °, and good water repellency was obtained. However, with the time left indoors, a comparative example (A1,
The contact angle of A2) sharply decreases, and the contact angle is as low as about 120 ° after being left indoors for 4 days. On the other hand, in the samples of Examples (B1 and B2), the contact angle was as high as about 135 ° even when the indoor exposure time was 10 days, and the contact angle hardly changed from the initial contact angle even when the indoor exposure time was increased. , The change over time is very small.
【００２５】[0025]
【発明の効果】以上説明したように、テトラフルオロエ
チレンオリゴマーおよび金属からなる撥水膜に、フルオ
ロアルキルシラン処理を施すことにより、撥水性能の時
間安定性を著しく向上させることができる。従って、本
処理方法は金属の腐食防止、霜、氷、雪の付着防止、防
汚処理等の目的に好適に使用することができる。As described above, by applying a fluoroalkylsilane treatment to a water repellent film made of a tetrafluoroethylene oligomer and a metal, the time stability of the water repellent performance can be remarkably improved. Therefore, the present treatment method can be suitably used for the purpose of preventing corrosion of metal, preventing adhesion of frost, ice and snow, antifouling treatment and the like.
【図１】本発明の撥水物品を作製するための装置を示す
概略側面図。FIG. 1 is a schematic side view showing an apparatus for producing a water repellent article of the present invention.
【図２】本発明の撥水物品の接触角の時間安定性を示す
グラフ。FIG. 2 is a graph showing the time stability of the contact angle of the water repellent article of the present invention.
１ 電源（ポテンシオガルバノスタット） ２ 陰極 ３ 陽極 ４ 分散電気メッキ溶液 ５ ウォーターバス ６ 撥水膜 ７ 磁気攪拌子 ８ メッキ浴槽 ９ 恒温槽 1 Power supply (potentio galvanostat) 2 Cathode 3 Anode 4 Dispersed electroplating solution 5 Water bath 6 Water repellent film 7 Magnetic stirrer 8 Plating bath 9 Constant temperature bath
Claims (6)
属からなる撥水膜を有する撥水性物品において、前記撥
水膜の上に更にフルオロアルキルシランの薄膜が設けら
れていることを特徴とする撥水性物品。1. A water-repellent article having a water-repellent film composed of a tetrafluoroethylene oligomer and a metal, wherein a thin film of fluoroalkylsilane is further provided on the water-repellent film.
０．５ｎｍ〜１００ｎｍの厚みを有する請求項１記載の
撥水性物品。2. The water repellent article according to claim 1, wherein the thin film of fluoroalkylsilane has a thickness of 0.5 nm to 100 nm.
化学式（１）で表わされる化合物である請求項１または
２記載の撥水性物品。 【化１】ＣＦ3（ＣＦ2）n（ＣＨ2）2ＳｉＸ3 （１） （ここで、ｎは３〜１５の整数、Ｘはアルコキシドまた
は塩素基である）3. The water repellent article according to claim 1, wherein the fluoroalkylsilane is a compound represented by the following chemical formula (1). Embedded image CF 3 (CF 2 ) n (CH 2 ) 2 SiX 3 (1) (where n is an integer of 3 to 15 and X is an alkoxide or a chlorine group)
サフルオロデシルトリクロロシランである請求項３記載
の撥水性物品。4. The water repellent article according to claim 3, wherein the fluoroalkylsilane is hexafluorodecyltrichlorosilane.
のいずれかに記載の撥水性物品。5. The method according to claim 1, wherein the metal is nickel.
The water repellent article according to any one of 1.
オリゴマーを分散させたメッキ液の浴に基材を浸漬して
メッキを行なう撥水性物品の製造方法において、その撥
水性物品表面に減圧ＣＶＤ法によりフルオロアルキルシ
ランの薄膜を被覆させることを特徴とする撥水性物品の
製造方法。6. A method for producing a water-repellent article, which comprises plating a substrate by immersing a substrate in a bath of a plating solution in which a tetrafluoroethylene oligomer is dispersed in a metal plating solution. A method for producing a water-repellent article, which comprises coating a thin film of alkylsilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11398396A JPH09299880A (en) | 1996-05-08 | 1996-05-08 | Water repellent article and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11398396A JPH09299880A (en) | 1996-05-08 | 1996-05-08 | Water repellent article and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09299880A true JPH09299880A (en) | 1997-11-25 |
Family
ID=14626127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11398396A Pending JPH09299880A (en) | 1996-05-08 | 1996-05-08 | Water repellent article and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09299880A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0947478A1 (en) * | 1998-02-13 | 1999-10-06 | Central Glass Company, Limited | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
-
1996
- 1996-05-08 JP JP11398396A patent/JPH09299880A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0947478A1 (en) * | 1998-02-13 | 1999-10-06 | Central Glass Company, Limited | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
| US6235833B1 (en) | 1998-02-13 | 2001-05-22 | Central Glass Company, Limited | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
| US6461670B2 (en) | 1998-02-13 | 2002-10-08 | Central Glass Company, Ltd. | Water-repellent solution and method of forming water-repellent film on substrate by using the solution |
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