JPH0523645A - Method for making surface of heavy metal water repellent and oil repellent - Google Patents
Method for making surface of heavy metal water repellent and oil repellentInfo
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- JPH0523645A JPH0523645A JP20752191A JP20752191A JPH0523645A JP H0523645 A JPH0523645 A JP H0523645A JP 20752191 A JP20752191 A JP 20752191A JP 20752191 A JP20752191 A JP 20752191A JP H0523645 A JPH0523645 A JP H0523645A
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- ring
- heavy metal
- group
- repellent
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- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、重金属表面を撥油性及
び撥水性にする方法、及びそのように処理した表面に関
する。FIELD OF THE INVENTION The present invention relates to a method for rendering heavy metal surfaces oil and water repellent, and surfaces so treated.
【０００２】[0002]
【従来の技術】重金属表面は、一般に親油性が高いこと
で知られていて、油類を比較的良く表面に付着する性質
を有している。このような表面を適当な処理により、加
工を施して撥油性及び撥水性にすることにより、新たな
用途を期待することができる。撥油性及び撥水性を賦与
するものとして、ふっ素樹脂により金属表面を被覆した
工業製品が既に市販されているが、被覆に高度の技術を
要したり、或いは加熱等の強い処理を必要とする場合が
多かった。しかし或る場合には、きわめて緩和な条件で
表面処理することが要求される。BACKGROUND OF THE INVENTION Heavy metal surfaces are generally known for their high lipophilicity and have the property of adhering oils to the surface relatively well. A new application can be expected by subjecting such a surface to an oil-repellent property and a water-repellent property by subjecting it to an appropriate treatment. Industrial products with a metal surface coated with a fluororesin are already on the market as a substance that imparts oil repellency and water repellency, but when advanced technology is required for coating or strong treatment such as heating is required. There were many However, in some cases, surface treatment under extremely mild conditions is required.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、ほと
んど室温で簡便且つ緩和な処理により、重金属表面を撥
油性及び撥水性にする方法を見出すこと、ならびにその
表面を得ることであり、多数の実験を行った結果、以下
に述べる方法により目的を達成することができた。The object of the present invention is to find a method for rendering a heavy metal surface oil-repellent and water-repellent by a simple and mild treatment at almost room temperature, and to obtain such a surface. As a result of carrying out the experiment, the purpose could be achieved by the method described below.
【０００４】[0004]
【課題を解決するための手段】本発明は、下記の一般式
化３又は化４で表される化合物、又はその互変異性形の
チオール化合物、又はその塩を、重金属表面に塗設する
ことによりその表面を撥油性及び撥水性にする方法、及
びそのように処理した表面に関する。According to the present invention, a heavy metal surface is coated with a compound represented by the following general formula 3 or 4, or a tautomeric thiol compound thereof, or a salt thereof. To make the surface oil-repellent and water-repellent according to, and the surface so treated.
【０００５】[0005]
【化３】 [Chemical 3]
【０００６】（但しｎは６〜９の整数、Ｌは単結合又は
２価の結合基、Ｚはチアジアゾリン環、トリアゾリン
環、テトラゾリン環、ジヒドロトリアジン環、テトラヒ
ドロトリアジン環を形成するのに必要な残基を表す。）(Where n is an integer of 6 to 9, L is a single bond or a divalent linking group, Z is a residue necessary to form a thiadiazoline ring, a triazoline ring, a tetrazoline ring, a dihydrotriazine ring or a tetrahydrotriazine ring. Represents a group.)
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（但しｎは６〜９の整数、Ｌは２価の結合
基、Ｒは水素原子、低級アルキル基、低級アルケニル
基、アリール基を表す。）(However, n represents an integer of 6 to 9, L represents a divalent linking group, R represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, or an aryl group.)
【０００９】本発明に用いる化合物は、一般式で示され
るように、炭素数６〜９のパーフルオロアルキル基を有
するものであり、これが撥油性及び撥水性を発現する基
であるが、パーフルオロアルキル基の炭素数が５以下で
は作用が弱く、又、炭素数が１０以上では高価になり実
用上の価値は減少する。パーフルオロアルキル基の末端
はＣＦ3 −基であるが、このことは本発明の目的に特に
重要であり、末端基のふっ素原子１個を水素で置換し
た。例えばＣＨＦ2 −基では効果が弱くなる。The compound used in the present invention has a perfluoroalkyl group having 6 to 9 carbon atoms as represented by the general formula, and this is a group which exhibits oil repellency and water repellency. When the number of carbon atoms in the alkyl group is 5 or less, the action is weak, and when the number of carbon atoms is 10 or more, the cost becomes high and the practical value decreases. Terminal perfluoroalkyl groups CF 3 - is a radical, but this is particularly important for the purposes of the present invention, one fluorine atom of the terminal groups was substituted with hydrogen. For example, the effect becomes weaker with a CHF 2 — group.
【００１０】本発明の化合物の構造の１部であるチオン
基は、緩和な条件で重金属表面に極めて強固に吸着ない
し化学結合を起す性質を有している。この基は、中性な
いし弱アルカリ性では解離してアニオンとなり、水溶性
を示すようになる。一方、本発明の化合物は疎水性のパ
ーフルオロアルキル基も有するので、このような条件の
もとでは両親媒性となり、強い界面活性を示す。The thione group, which is part of the structure of the compound of the present invention, has the property of adsorbing or chemically bonding to the heavy metal surface extremely strongly under mild conditions. When neutral or weakly alkaline, this group dissociates into an anion and becomes water-soluble. On the other hand, since the compound of the present invention also has a hydrophobic perfluoroalkyl group, it becomes amphiphilic under such conditions and exhibits strong surface activity.
【００１１】従って本発明の化合物は、中性ないし弱ア
ルカリ性水溶液にして、又はメタノールその他の有機溶
媒の溶液にして、浸漬、塗布、噴霧などの操作により、
容易に、簡便に、且つ緻密に重金属表面に塗設すること
が可能であり、これを単に乾燥するだけで、パーフルオ
ロアルキル基で密に強固に被覆した撥油性及び撥水性の
表面を得ることができる。この場合、パーフルオロアル
キル基を有する分子の界面活性作用と、重金属表面に対
する強い結合基の存在とが、上記の処理を効果的にして
いると思われる。Therefore, the compound of the present invention is made into a neutral to weakly alkaline aqueous solution or a solution of an organic solvent such as methanol and the like, and is subjected to operations such as dipping, coating and spraying.
It is possible to easily, conveniently, and precisely coat a heavy metal surface, and by simply drying this, an oil-repellent and water-repellent surface densely and firmly coated with a perfluoroalkyl group can be obtained. You can In this case, it seems that the surface-active action of the molecule having a perfluoroalkyl group and the presence of a strong bonding group to the surface of the heavy metal make the above treatment effective.
【００１２】従って本発明の対象となる重金属は、銀、
銅、鉄、ニッケル、コバルト、その他の本発明のチオン
化合物と強い親和性を示す重金属である。Therefore, the heavy metal to which the present invention is applied is silver,
It is a heavy metal having a strong affinity with copper, iron, nickel, cobalt and other thione compounds of the present invention.
【００１３】このようにして得た重金属表面は、撥油性
及び撥水性を示すだけでなく、ふっ素化合物の特徴であ
る滑り性、剥離性向上や腐食防止等にも効果を発揮する
ものと考えられる。It is considered that the thus-obtained heavy metal surface exhibits not only oil repellency and water repellency, but also exerts effects such as improvement in slidability, peelability, and corrosion prevention, which are characteristics of fluorine compounds. ..
【００１４】以下に本発明の化合物の具体例を示すが、
本発明はこれに限定されるものではない。Specific examples of the compound of the present invention are shown below.
The present invention is not limited to this.
【００１５】本発明の化合物の具体例：Specific examples of compounds of the present invention:
【００１６】[0016]
【化５】 [Chemical 5]
【００１７】[0017]
【化６】 [Chemical 6]
【００１８】[0018]
【化７】 [Chemical 7]
【００１９】[0019]
【化８】 [Chemical 8]
【００２０】[0020]
【化９】 [Chemical 9]
【００２１】[0021]
【化１０】 [Chemical 10]
【００２２】[0022]
【化１１】 [Chemical 11]
【００２３】[0023]
【化１２】 [Chemical 12]
【００２４】[0024]
【化１３】 [Chemical 13]
【００２５】[0025]
【化１４】 [Chemical 14]
【００２６】[0026]
【化１５】 [Chemical 15]
【００２７】[0027]
【化１６】 [Chemical 16]
【００２８】[0028]
【化１７】 [Chemical 17]
【００２９】[0029]
【化１８】 [Chemical 18]
【００３０】[0030]
【化１９】 [Chemical 19]
【００３１】[0031]
【化２０】 [Chemical 20]
【００３２】［合成例］ 合成例１ ５−パーフルオロヘキシル−１，３，４−３
Ｈ−チアジアゾリン−２−チオン（化５）の合成。 １−パーフルオロヘプタノイル−ジオチカルバジン酸カ
リウム１１ｇを濃硫酸５５ml中にかきまぜながら１５℃
以下で加え、加え終って同温に５時間かきまぜ、１夜室
温に放置後、水２７５ｇ上にあけて析晶を濾取、水洗。
得られる結晶を０．１Ｎ−ＮａＯＨに一旦溶解後、１Ｎ
−ＨＣｌを加えて析晶させ、これを濾取し、ｎ−ヘキサ
ンから再結晶。m.p.１１３〜１１４℃、収量６．１ｇ。
ＭＳ（ｍ／ｚ）４３６、ＩＲ（ＫＢｒ）３２５０cm
-1（ＮＨ）、 1Ｈ−ＮＭＲ（アセトン−ｄ6 ）δ：１
４．１（br.s，ＮＨ）。Synthesis Example Synthesis Example 1 5-perfluorohexyl-1,3,4-3
Synthesis of H-thiadiazoline-2-thione (Chemical formula 5). While stirring 11 g of potassium 1-perfluoroheptanoyl-dithiocarbadate in 55 ml of concentrated sulfuric acid at 15 ° C.
After the addition below, after the addition, the mixture was stirred at the same temperature for 5 hours and left overnight at room temperature, then poured onto 275 g of water and the precipitated crystals were collected by filtration and washed with water.
The obtained crystals are once dissolved in 0.1N-NaOH and then 1N
-HCl was added to cause crystallization, which was collected by filtration and recrystallized from n-hexane. mp 113-114 ° C, yield 6.1 g.
MS (m / z) 436, IR (KBr) 3250 cm
-1 (NH), 1 H-NMR (acetone-d 6 ) δ: 1
4.1 (br.s, NH).
【００３３】合成例２ ５−パーフルオロオクチル−
１，３，４−３Ｈ−チアジアゾリン−２−チオン（化
７）の合成。 パーフルオロノナノイル−ジチオカルバジン酸カリウム
１１ｇを濃硫酸５５ml中に５〜１５℃で加え、以後合成
例１と同様に処理し、得られる結晶をトルエンから再結
晶。m.p.１４０〜１４０．５℃、収量６．９ｇ。ＭＳ
（ｍ／ｚ）５３６、ＩＲ（ＫＢｒ）３２５０cm-1（Ｎ
Ｈ）、 1Ｈ−ＮＭＲ（アセトン−ｄ6 ）δ：１４．１
（br.s，ＮＨ）。Synthesis Example 2 5-Perfluorooctyl-
Synthesis of 1,3,4-3H-thiadiazoline-2-thione (Chemical formula 7). 11 g of potassium perfluorononanoyl-dithiocarbazate was added to 55 ml of concentrated sulfuric acid at 5 to 15 ° C., and then the same treatment as in Synthesis Example 1 was performed, and the obtained crystals were recrystallized from toluene. mp 140-140.5 ° C, yield 6.9g. MS
(M / z) 536, IR (KBr) 3250 cm -1 (N
H), 1 H-NMR (acetone-d 6 ) δ: 14.1
(Br.s, NH).
【００３４】合成例３ ５−パーフルオロノナノイルア
ミノ−１，３，４−３Ｈ−チアジアゾリン−２−チオン
（化８）の合成。 ５−アミノ−１，３，４−３Ｈ−チアジアゾリン−２−
チオン０．６ｇを乾燥ＴＨＦ１８mlに溶解し、これに塩
化パーフルオロノナノイル４．３５ｇを滴下する。次に
外部から氷冷しながらトリエチルアミン１．２mlを滴下
する。滴下終了後同温で５分間、更に室温で３．５時間
撹拌する。１夜放置後更に室温で６時間撹拌し、これを
水３００ml中に加え、析晶を濾取。これを１Ｎ−ＮａＯ
Ｈに一旦溶かし、１Ｎ−ＨＣｌでｐＨ２にして再び沈殿
させ、沈殿物を集めて、アセトニトリルから再結晶。m.
p.１９８〜２０６℃、収量１．０ｇ。ＭＳ（ｍ／ｚ）５
７９、ＩＲ（ＫＢｒ）（cm-1）：３１７０，３０９０
（ＮＨ）、１７３０（Ｃ＝０）、 1Ｈ−ＮＭＲ（アセト
ン−ｄ6 ）δ：１３．０（s,ヘテロ環ＮＨ）、ＵＶ（エ
タノール）λmax/nm：３２８，２８３，２２５。Synthesis Example 3 Synthesis of 5-perfluorononanoylamino-1,3,4-3H-thiadiazoline-2-thione (Chemical formula 8) 5-amino-1,3,4-3H-thiadiazoline-2-
0.6 g of thione is dissolved in 18 ml of dry THF, and 4.35 g of perfluorononanoyl chloride is added dropwise thereto. Next, 1.2 ml of triethylamine is added dropwise from the outside while cooling with ice. After completion of dropping, the mixture is stirred at the same temperature for 5 minutes and further at room temperature for 3.5 hours. After standing overnight, the mixture was further stirred at room temperature for 6 hours, added to 300 ml of water, and the precipitated crystals were collected by filtration. This is 1N-NaO
Once dissolved in H, adjusted to pH 2 with 1N-HCl to precipitate again, the precipitates were collected and recrystallized from acetonitrile. m.
p. 198-206 ° C, yield 1.0 g. MS (m / z) 5
79, IR (KBr) (cm -1 ): 3170, 3090
(NH), 1730 (C = 0), 1 H-NMR (acetone-d 6 ) δ: 13.0 (s, heterocycle NH), UV (ethanol) λmax / nm: 328, 283, 225.
【００３５】合成例４ １−（３´−パーフルオロノナ
ノイルアミノ）フェニル−テトラゾリン−５−チオン
（化１１）の合成 １−（３´−アミノ）フェニル−テトラゾリン−５−チ
オン０．９８ｇと乾燥ＴＨＦ２５mlを混合し、４〜５℃
を保って塩化パーフルオロノナノイル１．２ｇのＴＨＦ
１０ml溶液を滴下し、滴下終了後ほぼ同温に４時間２０
分撹拌し、析晶を濾去し、濾液を蒸発乾固する。得られ
る固形物を０．５Ｎ−ＨＣｌ、次に８０℃のトルエンで
洗い、不溶物を０．２Ｎ−ＮａＯＨに一旦溶かし、１Ｎ
−ＨＣｌを加えて析晶させ、これを濾取後アセトニトリ
ルから再結晶。収量１．２６ｇ、m.p.１６２〜１６３℃
（分解）、ＭＳ（ｍ／ｚ）６４０（Ｍ＋１）、ＩＲ（Ｋ
Ｂｒ）（cm-1）：３３００，３０８０（ＮＨ）、１７０
０（Ｃ＝０）、 1Ｈ−ＮＭＲ（アセトン−ｄ6 ）δ：１
０．７（br,s，ＣＯ−ＮＨ）。Synthesis Example 4 Synthesis of 1- (3'-perfluorononanoylamino) phenyl-tetrazoline-5-thione (Chemical Formula 11) 1- (3'-amino) phenyl-tetrazoline-5-thione (0.98 g) Mix 25 ml of dry THF and mix at 4-5 ℃
Keep Perfluorononanoyl Chloride 1.2g THF
Add 10 ml of solution dropwise, and at the same temperature for 4 hours 20
The mixture is stirred for minutes, the precipitated crystals are filtered off, and the filtrate is evaporated to dryness. The obtained solid matter was washed with 0.5N-HCl and then with toluene at 80 ° C, and the insoluble matter was once dissolved in 0.2N-NaOH.
-HCl was added to cause crystallization, which was collected by filtration and recrystallized from acetonitrile. Yield 1.26g, mp 162-163 ° C
(Decomposition), MS (m / z) 640 (M + 1), IR (K
Br) (cm -1 ): 3300, 3080 (NH), 170
0 (C = 0), 1 H-NMR (acetone-d 6 ) δ: 1
0.7 (br, s, CO-NH).
【００３６】合成例５ １−パーフルオロノナノイル−
チオセミカルバジド（化１７）の合成 チオセミカルバジド粉末５．０ｇを乾燥ＴＨＦ２５mlと
混合し、−７〜−１２℃を保って塩化パーフルオロノナ
ノイル１０．５５ｇを滴下。滴下終り同温に２時間かき
まぜ、１夜室温に放置後析出物を濾去し、濾液を蒸発乾
固して得られる粉末をエーテル及び水で洗い、アセトニ
トリルから再結晶。m.p.１５５．５〜１５７℃（分
解）、収量３．７ｇ、ＭＳ（ｍ／ｚ）５３８（Ｍ＋
１）、ＩＲ（ＫＢｒ）（cm-1）：３２８０，３１８０
（ＮＨ）、１７４３（Ｃ＝０）、 1Ｈ−ＮＭＲ（ＤＭＳ
Ｏ−ｄ6 ）δ：７．９（２Ｈ，br.s，ＮＨ2 ），９．８
５（１Ｈ，ｓ，ＮＨ），１１．４２（１Ｈ，br.s，Ｎ
Ｈ）。Synthesis Example 5 1-Perfluorononanoyl-
Synthesis of thiosemicarbazide (Chemical Formula 17) 5.0 g of thiosemicarbazide powder was mixed with 25 ml of dry THF, and 10.55 g of perfluorononanoyl chloride was added dropwise while maintaining -7 to -12 ° C. After the dropwise addition, the mixture was stirred at the same temperature for 2 hours and left overnight at room temperature, the precipitate was filtered off, the filtrate was evaporated to dryness, and the powder obtained was washed with ether and water and recrystallized from acetonitrile. mp 155.5-157 ° C. (decomposition), yield 3.7 g, MS (m / z) 538 (M +
1), IR (KBr) (cm -1 ): 3280, 3180
(NH), 1743 (C = 0), 1 H-NMR (DMS
O-d 6 ) δ: 7.9 (2H, br.s, NH 2 ), 9.8
5 (1H, s, NH), 11.42 (1H, br.s, N
H).
【００３７】合成例６ ６−（１´Ｈ，１´Ｈ−パーフ
ルオロオクチル）アミノ−テトラヒドロ−１，３，５−
１Ｈ，３Ｈ−トリアジン−２，４−ジチオン（化１５）
の合成 ４，６−ジクロロ−２−（１´Ｈ，１´Ｈ−パーフルオ
ロオクチル）アミノ−１，３，５−トリアジン２．３９
ｇをＤＭＦ１０mlに溶かし、外部から氷塩冷却下に撹拌
しながらＮａＳＨ粉末０．９０ｇを加える。加え終り同
温に２時間撹拌。（この間にＤＭＦ５mlを追加）。反応
液を水４００ml中に加え、１Ｎ−ＨＣｌを加えてｐＨ２
に調節して析晶を濾取。これを一旦１Ｎ−ＮａＯＨに溶
かし、塩酸を加えて析晶させ、これを濾取してアセトニ
トリルから再結晶。収量１．４２ｇ、m.p.２３５〜２４
１℃（分解）、ＭＳ（ｍ／ｚ）５４２、 1Ｈ−ＮＭＲ
（ＤＭＳＯ−ｄ6 ）δ：４．３３（２Ｈ，ｔ，Ｃ
Ｈ2 ），７．６２（１Ｈ，ｓ，ＮＨ），１３．１１（１
Ｈ，ｓ，ヘテロ環ＮＨ）Synthesis Example 6 6- (1'H, 1'H-perfluorooctyl) amino-tetrahydro-1,3,5-
1H, 3H-triazine-2,4-dithione
Synthesis of 4,6-dichloro-2- (1'H, 1'H-perfluorooctyl) amino-1,3,5-triazine 2.39
g was dissolved in 10 ml of DMF, and 0.90 g of NaSH powder was added from the outside with stirring under ice-salt cooling. After the addition, stir at the same temperature for 2 hours. (Add 5 ml of DMF in the meantime). The reaction solution was added to 400 ml of water and 1N-HCl was added to adjust the pH to 2
After adjusting to, the crystal is collected by filtration. This was once dissolved in 1N-NaOH, hydrochloric acid was added to crystallize, this was filtered and recrystallized from acetonitrile. Yield 1.42g, mp 235-24
1 ° C. (decomposition), MS (m / z) 542, 1 H-NMR
(DMSO-d 6 ) δ: 4.33 (2H, t, C
H 2 ), 7.62 (1H, s, NH), 13.11 (1
H, s, heterocycle NH)
【００３８】[0038]
実施例１ 本発明の化合物又は比較用の化合物のメタノール溶液
（濃度５ｍmol/ｌ）をノンウブンフアブリック（大日本
スクリーン製造株式会社製 商品名ソフパッド）に含ま
せて、重金属表面を軽く２回拭き、乾燥後そのまま、又
は更に流水で１０分間洗って乾燥後に、接触角測定に供
した。接触角の測定は、ｎ−ヘキサデカン、あまに油及
び水の３種類の液体について、協和科学株式会社製 接
触角計ＣＡ−Ｄ型を用いて室温で行った。重金属の表面
としては、ゼラチンを下引したポリエチレンテレフタレ
ートフィルム上に無電解メッキ法で作成した銀膜を用い
た。測定結果を表１に示す。ただし表中の比較化合物は
次の通りである。Example 1 A methanol solution of a compound of the present invention or a compound for comparison (concentration: 5 mmol / l) was included in a non-woven fabric (trade name: Sofpad, manufactured by Dainippon Screen Mfg. Co., Ltd.), and the heavy metal surface was lightly twice. After wiping and drying, it was used as it was, or further washed with running water for 10 minutes and dried, and then subjected to contact angle measurement. The contact angle was measured at room temperature for three types of liquids, n-hexadecane, linseed oil and water, using a contact angle meter CA-D type manufactured by Kyowa Scientific Co., Ltd. As the surface of the heavy metal, a silver film prepared by an electroless plating method on a polyethylene terephthalate film with a gelatin subbing was used. The measurement results are shown in Table 1. However, the comparative compounds in the table are as follows.
【００３９】比較化合物（本発明外）：Comparative compound (outside the invention):
【００４０】[0040]
【化２１】 [Chemical 21]
【００４１】[0041]
【化２２】 [Chemical formula 22]
【００４２】[0042]
【化２３】 [Chemical formula 23]
【００４３】[0043]
【化２４】 [Chemical formula 24]
【００４４】[0044]
【表１】 [Table 1]
【００４５】表からわかるように、本発明の化合物は銀
膜表面を撥油性及び撥水性にするのに対し、パーフルオ
ロアルキル基の短いものや、吸着能の強いチオン基を欠
く化合物では、いずれも効果が劣る。As can be seen from the table, the compounds of the present invention make the surface of the silver film oil-repellent and water-repellent, whereas the compounds having a short perfluoroalkyl group or compounds lacking a strong adsorbing thione group are Is less effective.
【００４６】実施例２ 実施例１に準拠して、銀膜の代りにステンレスＳＡＳ１
８−８箔粘着シート（新日鉄株式会社製 商品名助つ
人）の清浄なステンレス表面を用いて測定を行った。結
果を表２に示す。Example 2 In accordance with Example 1, stainless steel SAS1 was used instead of the silver film.
The measurement was carried out using a clean stainless steel surface of an 8-8 foil adhesive sheet (product name assistant manufactured by Nippon Steel Co., Ltd.). The results are shown in Table 2.
【００４７】[0047]
【表２】 [Table 2]
【００４８】表からわかるように、本発明の効果は明瞭
である。As can be seen from the table, the effect of the present invention is clear.
【００４９】実施例３ 実施例１に準拠して、清浄な銅板表面を用いて測定を行
った。結果を表３に示す。Example 3 In accordance with Example 1, measurement was carried out using a clean copper plate surface. The results are shown in Table 3.
【００５０】[0050]
【表３】 [Table 3]
【００５１】[0051]
【発明の効果】本発明は、一般式化３及び化４で示され
てる特定の化合物を用いることにより、重金属表面を緩
和な条件で、撥油性及び撥水性にする方法、及びそのよ
うにして得られる重金属表面を提供する。INDUSTRIAL APPLICABILITY The present invention provides a method for rendering a heavy metal surface oil-repellent and water-repellent under mild conditions by using the specific compounds represented by the general formulas 3 and 4, and thus, The resulting heavy metal surface is provided.
Claims (1)
オン化合物、又はその互変異性形のチオール化合物、又
はその塩を、重金属表面に塗設することにより、その表
面を撥油性及び撥水性にする方法。 【化１】 （但しｎは６〜９の整数、Ｌは単結合又は２価の結合
基、Ｚはチアジアゾリン環、トリアゾリン環、テトラゾ
リン環、ジヒドロトリアジン環、テトラヒドロトリアジ
ン環を形成するのに必要な残基を表す。） 【化２】 （但しｎは６〜９の整数、Ｌは２価の結合基、Ｒは水素
原子、低級アルキル基、低級アルケニル基、アリール基
を表す。）What is claimed is: 1. A thione compound represented by the following general formula 1 or 2, or a thiol compound in its tautomeric form, or a salt thereof is applied to the surface of a heavy metal. , A method of rendering its surface oil-repellent and water-repellent. [Chemical 1] (However, n represents an integer of 6 to 9, L represents a single bond or a divalent bonding group, Z represents a residue necessary for forming a thiadiazoline ring, a triazoline ring, a tetrazoline ring, a dihydrotriazine ring, or a tetrahydrotriazine ring. .) [Chemical formula 2] (However, n represents an integer of 6 to 9, L represents a divalent bonding group, R represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, or an aryl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20752191A JPH0523645A (en) | 1991-07-23 | 1991-07-23 | Method for making surface of heavy metal water repellent and oil repellent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20752191A JPH0523645A (en) | 1991-07-23 | 1991-07-23 | Method for making surface of heavy metal water repellent and oil repellent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0523645A true JPH0523645A (en) | 1993-02-02 |
Family
ID=16541101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20752191A Pending JPH0523645A (en) | 1991-07-23 | 1991-07-23 | Method for making surface of heavy metal water repellent and oil repellent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0523645A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2291439A (en) * | 1994-07-19 | 1996-01-24 | Secr Defence | Oil and water repellent treatments |
| WO1997027059A1 (en) * | 1996-01-23 | 1997-07-31 | Seiko Epson Corporation | Ink jet printer head, method of manufacturing the same, and ink |
| US5734920A (en) * | 1993-06-28 | 1998-03-31 | Nippondenso Co., Ltd. | Input/output processing IC |
| US6011135A (en) * | 1997-08-27 | 2000-01-04 | Iwate University | Triazine thiol derivative having a perfluoro group, method for producing same and use of same |
| WO2021131691A1 (en) * | 2019-12-26 | 2021-07-01 | 日本ペイントホールディングス株式会社 | Coating material composition, coated metal material, and method for coating metal material |
-
1991
- 1991-07-23 JP JP20752191A patent/JPH0523645A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5734920A (en) * | 1993-06-28 | 1998-03-31 | Nippondenso Co., Ltd. | Input/output processing IC |
| GB2291439A (en) * | 1994-07-19 | 1996-01-24 | Secr Defence | Oil and water repellent treatments |
| WO1997027059A1 (en) * | 1996-01-23 | 1997-07-31 | Seiko Epson Corporation | Ink jet printer head, method of manufacturing the same, and ink |
| EP0829357A1 (en) * | 1996-01-23 | 1998-03-18 | Seiko Epson Corporation | Ink jet printer head, method of manufacturing the same, and ink |
| EP0829357A4 (en) * | 1996-01-23 | 1999-04-07 | Seiko Epson Corp | Ink jet printer head, method of manufacturing the same, and ink |
| US6074040A (en) * | 1996-01-23 | 2000-06-13 | Seiko Epson Corporation | Ink jet printer head, its manufacturing method and ink |
| US6011135A (en) * | 1997-08-27 | 2000-01-04 | Iwate University | Triazine thiol derivative having a perfluoro group, method for producing same and use of same |
| WO2021131691A1 (en) * | 2019-12-26 | 2021-07-01 | 日本ペイントホールディングス株式会社 | Coating material composition, coated metal material, and method for coating metal material |
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