JP2665961B2 - Coating method - Google Patents
Coating methodInfo
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- JP2665961B2 JP2665961B2 JP63322444A JP32244488A JP2665961B2 JP 2665961 B2 JP2665961 B2 JP 2665961B2 JP 63322444 A JP63322444 A JP 63322444A JP 32244488 A JP32244488 A JP 32244488A JP 2665961 B2 JP2665961 B2 JP 2665961B2
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- film
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- compound
- forming substance
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は揆水揆油性，潤滑性、および防錆性を示す被
膜を形成する方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a method for forming a film exhibiting oil repellency, lubricity, and rust prevention.
従来、揆水揆油性，潤滑性、および防錆性を示す被膜
形成物質としてはフッ素化合物やフッ素樹脂が知られて
いる。Conventionally, fluorine compounds and fluororesins have been known as film-forming substances exhibiting oil repellency, lubricity and rust prevention.
上記フッ素化合物やフッ素樹脂の揆水揆油性はそれ等
の有するパーフルオロアルキル基に存するものである。The oil repellency of the above-mentioned fluorine compounds and fluororesins is due to the perfluoroalkyl groups contained therein.
しかしながら上記フッ素化合物やフッ素樹脂において
はそれら被膜を形成した場合に、それらの有するパーフ
ルオロ基が有効に被膜表面に配向されるとは限らず、パ
ーフルオロアルキル基の優れた揆水揆油性を最大限に利
用するものではなかった。However, in the case of the above-mentioned fluorine compounds and fluororesins, when such a film is formed, the perfluoro group of the film is not always effectively oriented on the film surface, and the excellent repellency of the perfluoroalkyl group is maximized. It was not intended to be used for a limited time.
本発明は上記従来の課題を解決するための手段とし
て、分子鎖の一端にパーフルオロアルキル基を有し、他
端に加水分解可能なシリル基を有する被膜形成物質の溶
液を水面上に展開して被膜を形成する被膜形成方法を提
供するものである。The present invention, as a means for solving the above-mentioned conventional problems, develops a solution of a film-forming substance having a perfluoroalkyl group at one end of a molecular chain and a hydrolyzable silyl group at the other end on a water surface. The present invention provides a method for forming a film by forming a film.
上記本発明に用いられる被膜形成物質は例えば下記の
方法によって合成される。The film-forming substance used in the present invention is synthesized, for example, by the following method.
（１）分子鎖の一端にパーフルオロアルキル基を有し他
端に官能基を有する化合物Ａと、分子鎖の一端に加水分
解可能なシリル基を有し他端に化合物Ａの官能基と反応
可能な官能基を有する化合物Ｂとを反応せしめることに
よって合成する。ここに加水分解可能なシリル基とは下
記の構造を有するものである。(1) Compound A having a perfluoroalkyl group at one end of a molecular chain and a functional group at the other end, and reacting with a functional group of compound A at one end of a molecular chain having a hydrolyzable silyl group at the other end It is synthesized by reacting with a compound B having a possible functional group. Here, the hydrolyzable silyl group has the following structure.
式中Ｒはアルキル基，アリール基，アラルキル基から
選ばれる２価の炭化水素基、Ｘは例えばアルコキシル
基，ハロゲン等の加水分解可能な基、Ｐは1,2,3の整数
である。 In the formula, R is a divalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, X is a hydrolyzable group such as an alkoxyl group and a halogen, and P is an integer of 1,2,3.
また化合物Ａと化合物Ｂとの官能基は例えば第１表の
ような組合わせが適用される。For the functional groups of compound A and compound B, for example, combinations shown in Table 1 are applied.
したがって、本発明に用いられる被膜形成物質は例え
ば下記の構造式１で表わすこと出来るであろう。 Accordingly, the film-forming substance used in the present invention may be represented, for example, by the following structural formula 1.
式中I,m,nは整数、Ｙは第１表に例示するようなエス
テル結合，エーテル結合，アミド結合，ウレタン結合，
尿素結合等である。 In the formula, I, m, n are integers, and Y is an ester bond, an ether bond, an amide bond, a urethane bond, as exemplified in Table 1.
It is a urea bond or the like.
（２）分子鎖の一端にパーフルオロアルキル基を有し他
端に官能基を有する化合物Ａと、分子鎖の一端に化合物
Ａの官能基と反応可能な官能基を有し他端に炭素−炭素
二重結合を有する化合物Ｃとを反応させ、次いで化合物
Ｃ部分の炭素−炭素二重結合に加水分解可能なシラン化
合物を反応させる。この場合の化合物Ａと化合物Ｃの官
能 は第１表の組合せと同様なものであり、得られる被
膜形成物質は構造式１と同一の構造を有する。(2) a compound A having a perfluoroalkyl group at one end of a molecular chain and a functional group at the other end, and a carbon atom at one end of the molecular chain having a functional group capable of reacting with the functional group of the compound A The compound C having a carbon double bond is reacted, and then the carbon-carbon double bond of the compound C portion is reacted with a hydrolyzable silane compound. In this case, the functions of the compound A and the compound C are the same as those in the combination in Table 1, and the obtained film-forming substance has the same structure as that of the structural formula 1.
本発明に用いられる被膜形成物質は上記合成方法
（１），（２）によって合成される構造式（１）を有す
る化合物以外に例えば下記の構造式（２），（３）を有
する化合物も本発明に用いられる被膜形成物質に含まれ
る。The film-forming substance used in the present invention includes, for example, compounds having the following structural formulas (2) and (3) in addition to compounds having the structural formula (1) synthesized by the above synthesis methods (1) and (2). It is included in the film-forming substance used in the present invention.
このようにして得られた本発明に用いられる被膜形成
物質を溶剤に溶解させた溶液を水面上に展開して被膜を
形成させる。このような被膜形成方法はラングミュアブ
ロジェット法（LB法）と呼ばれる。LB法によれば得られ
る被膜の揆水揆油性能等が他の被膜形成方法例えばキャ
スト法やスピンコート法に比してより優れたものとな
る。LB法においては本発明の被膜形成物質を例えばメチ
レンクロライド，トリクロロエタン，トリクロロエチレ
ン，アセトン，メチルエチルケトン，ベンゼン，トルエ
ン，酢酸エチル等の有機溶剤に溶解させて溶液とし、該
溶液を水面上に展開して該被膜形成物質の単分子膜を作
成し、該単分子膜を基板上にすくいとる方法である。こ
の場合、該単分子膜を一対の障壁間において圧縮して該
単分子膜表面のパーフルオロ基を最充填密度の状態にす
ることが望ましく、また該単分子膜をつづら折り状に折
り畳ねて膜厚を大としてもよい。 The solution obtained by dissolving the thus-obtained film-forming substance used in the present invention in a solvent is developed on a water surface to form a film. Such a film forming method is called a Langmuir-Blodgett method (LB method). According to the LB method, the resulting film has excellent oil performance and the like, as compared with other film forming methods such as a casting method and a spin coating method. In the LB method, the film-forming substance of the present invention is dissolved in an organic solvent such as methylene chloride, trichloroethane, trichloroethylene, acetone, methyl ethyl ketone, benzene, toluene, and ethyl acetate to form a solution. In this method, a monomolecular film of a film-forming substance is formed, and the monomolecular film is scooped on a substrate. In this case, it is desirable that the monomolecular film is compressed between a pair of barriers to bring perfluoro groups on the surface of the monomolecular film into a state of the highest packing density. The film thickness may be large.
このような本発明の方法によって作成された被膜によ
って被覆された基板が得られるが、該基板としては金
属，プラスチック、あるいは磁気記録担体，光磁気記録
担体等種々なものが対象になる。A substrate coated with the coating prepared by the method of the present invention can be obtained, and the substrate may be a metal, a plastic, or various types such as a magnetic record carrier and a magneto-optical record carrier.
本発明の被膜形成物質の被膜を水面上に形成すると親
水性を有する加水分解可能なシリル基を水面側、即ち被
膜の下側面に配向され、反対にパーフルオロ基は効率よ
く被膜表面側に配向される。そして該加水分解可能なシ
リル基は周囲の水分により加水分解されてシラノール基
となり、更にシラノール基相互によりシラン結合が形成
されることにより本発明に用いられる被膜形成物質は架
橋する。When a film of the film-forming substance of the present invention is formed on a water surface, hydrophilic hydrolyzable silyl groups having hydrophilicity are oriented on the water surface side, that is, on the lower surface of the film, while the perfluoro groups are efficiently oriented on the film surface side. Is done. The hydrolyzable silyl group is hydrolyzed by ambient moisture to form a silanol group, and the silanol group forms a silane bond, whereby the film-forming substance used in the present invention is crosslinked.
したがって本発明においては揆水揆油性に富みかつ機
械的強度の高い被膜が得られ、このような被膜は金属の
防錆膜、磁気記録担体や光磁気記録担体の保護膜，プラ
スチックの潤滑膜等として極めて有用である。Therefore, in the present invention, a film having high oil repellency and high mechanical strength can be obtained, and such a film can be used as a metal rust preventive film, a protective film for a magnetic recording medium or a magneto-optical recording medium, a plastic lubricating film, or the like. Is extremely useful.
（合成例）1. CF3（CF2）７（CH2）2OCONH（CH2）3Si（OCH2CH3）３ 被膜形成物質（１）の合成 攪拌機，温度計，還流冷却機を取り付けた100mlのガ
ラス製反応器中に式CF3（CF2）7CH2CH2OHで表わされる
フルオロアルコール5.03g（10.8m mol）と、式Ｏ＝Ｃ＝
Ｎ−CH2CH2CH2Si（OCH2CH3）３で表わされるシリルイソ
シアネート2.72g（11.0m mol）と、ベンゼン50mlを仕込
み、窒素気流下70℃にて20時間反応させた。反応終了
後、反応液中の低沸分を70℃/10-2mmHgの条件で除去し
たところ7.6gの無色透明のやや粘稠な液体が得られた。
赤外吸収スペクト分析、該磁気共鳴スペクトル分析、元
素分析の結果から目的とする被膜形成物質（１）である
ことが確認された。(Synthesis example) 1. Synthesis of CF 3 (CF 2 ) 7 (CH 2 ) 2 OCONH (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 film forming substance (1) Attach a stirrer, thermometer, and reflux cooler In a 100 ml glass reactor, 5.03 g (10.8 mmol) of a fluoroalcohol represented by the formula CF 3 (CF 2 ) 7 CH 2 CH 2 OH and the formula O = C =
Silyl isocyanate 2.72 g (11.0 m mol) represented by N-CH 2 CH 2 CH 2 Si (OCH 2 CH 3) 3, were charged benzene 50 ml, it was reacted for 20 hours under a nitrogen stream 70 ° C.. After the completion of the reaction, low boiling components in the reaction solution were removed at 70 ° C./10 −2 mmHg to obtain 7.6 g of a colorless, transparent, slightly viscous liquid.
From the results of infrared absorption spectrum analysis, magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the substance was the target film-forming substance (1).
（合成例）2. 被膜形成物質の別途合成 攪拌機、温度計、還流冷却機を取り浸けた100mlのガ
ラス製反応器中に、式CF3（CF2）7CH2CH2OHで表わされ
るフルオロアルコール5.12g（11.0m mol）と式Ｏ＝Ｃ＝
Ｎ−CH2CH＝CH2で表わされるアリルイソシアネート1.25
g（15.0m mol）と、ベンゼン50mlを仕込み、窒素気流下
70℃にて20時間反応させた。反応終了後反応液中の低沸
分を減圧除去したところ6.1gの無色透明のやや粘稠な液
体が得られら。赤外吸収スペクトル分析、該磁気共鳴ス
ペクトル分析、元素分析の結果から式CF3（CF2）７（CH
2）2OCONHCH2CH＝CH2で表される化合物（ａ）であるこ
とが確認された。(Synthesis example) 2. Separate synthesis of film-forming substance In a 100 ml glass reactor soaked with a stirrer, thermometer, and reflux condenser, the fluorocarbon represented by the formula CF 3 (CF 2 ) 7 CH 2 CH 2 OH 5.12 g (11.0 mmol) of alcohol and formula O = C =
Allyl isocyanate represented by N-CH 2 CH = CH 2 1.25
g (15.0 mmol) and 50 ml of benzene, under a nitrogen stream
The reaction was performed at 70 ° C. for 20 hours. After the completion of the reaction, low-boiling components in the reaction solution were removed under reduced pressure to obtain 6.1 g of a colorless, transparent, slightly viscous liquid. From the results of the infrared absorption spectrum analysis, the magnetic resonance spectrum analysis, and the elemental analysis, the formula CF 3 (CF 2 ) 7 (CH
2 ) 2 OCONHCH 2 CH = Compound (a) represented by CH 2 was confirmed.
次に上記化合物（ａ）5.00g（9.1m mol）と、ベンゼ
ン50mlと塩化白金酸を0.0003g含むイソプロパノール溶
液0.5mlと、トリエトキシシランHSi（OCH2CH3）31.9g
（11.6m mol）を窒素気流下にて仕込み90℃いて12時間
反応させた。反応終了後、反応液中の低沸分を減圧除去
したところ6.3gの淡黒色のやや粘稠な液体が得られた。
赤外吸収スペクトル分析、該磁気共鳴スペクトル分析、
元素分析の結果から目的とする被膜形成物質（１）であ
ることが確認された。Next, 5.00 g (9.1 mmol) of the compound (a), 0.5 ml of an isopropanol solution containing 50 ml of benzene and 0.0003 g of chloroplatinic acid, and 1.9 g of triethoxysilane HSi (OCH 2 CH 3 ) 3
(11.6 mmol) was charged under a nitrogen stream and reacted at 90 ° C. for 12 hours. After completion of the reaction, low boiling components in the reaction solution were removed under reduced pressure to obtain 6.3 g of a light black, slightly viscous liquid.
Infrared absorption spectrum analysis, the magnetic resonance spectrum analysis,
From the result of elemental analysis, it was confirmed that the substance was the target film-forming substance (1).
（合成例）3. CF3（CF2）５（CH2）2O（CH2）3Si（OCH2CH3）３ 被膜形成物質（２）の合成 攪拌機，温度計，還流冷却機を取り付けた100mlのガ
ラス製反応器中に、式CF3（CF2）5CH2CH2OHで表わされ
るフルオロアルコール5.12g（14.1m mol）と、無水テト
ラヒドロキシフラン50mlと、金属ナトリウムワイヤー0.
3g（13.5m mol）を窒素気流下にて仕込み、24時間還流
させた。金属ナトリウムが完全に消失していることを確
認した後、溶媒を除去し、生成固体をドライボックス中
でろ別し、真空乾燥した。(Synthesis example) 3. Synthesis of CF 3 (CF 2 ) 5 (CH 2 ) 2 O (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 film forming substance (2) A stirrer, thermometer, and reflux condenser were installed. In a 100 ml glass reactor, 5.12 g (14.1 mmol) of a fluoroalcohol represented by the formula CF 3 (CF 2 ) 5 CH 2 CH 2 OH, 50 ml of anhydrous tetrahydroxyfuran, and 0.
3 g (13.5 mmol) was charged under a nitrogen stream and refluxed for 24 hours. After confirming that the metallic sodium had completely disappeared, the solvent was removed, and the resulting solid was filtered off in a dry box and dried in vacuo.
次に攪拌機、温度計、滴下ロート、還流冷却機を取り
付けた200mlのガラス製反応器中に、式CF3（CF3）5CH2C
H2ONaで表わされる上記生成物4.3g（11.1m mol）と、ヘ
キサフルオロパラキシレン100mlを仕込み、窒素気流下
塩化アリル（CH2＝CHCH2Cl）3.5g（46m mol）を含む無
水テトラヒドロキシフラン溶液50mlを１時間で滴下し、
滴下終了後120℃にて24時間攪拌した。反応終了反応液
中の低沸分を70℃/10-2mmHgの条件で除去したところ5.2
gの淡黄色透明のやや粘稠な液体が得られた。赤外吸収
スペクトル分析、核磁気共鳴スペクトル分析、元素分析
の結果から式CF3（CF2）５（CH2）2OCH2CH＝CH2で表わ
される化合物（ｂ）であることが確認された。Next, in a 200 ml glass reactor equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, the formula CF 3 (CF 3 ) 5 CH 2 C was added.
4.3 g (11.1 mmol) of the above product represented by H 2 ONa and 100 ml of hexafluoroparaxylene were charged, and anhydrous tetrahydroxyl containing 3.5 g (46 mmol) of allyl chloride (CH 2 CHCHCH 2 Cl) under a nitrogen stream. 50 ml of a furan solution is dropped in one hour,
After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 24 hours. When the low boiling components in the reaction solution at the end of the reaction were removed under the conditions of 70 ° C / 10 -2 mmHg, 5.2
g of a pale yellow transparent, slightly viscous liquid was obtained. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the compound (b) was represented by the formula CF 3 (CF 2 ) 5 (CH 2 ) 2 OCH 2 CH = CH 2 . .
次に攪拌機、温度計、還流冷却機械を取り付けた100m
lのガラス製反応器に、上記化合物（ｂ）4.1g（10.0m m
ol）と、ベンゼン30mlと、塩化白金酸を0.0003gを含む
イソプロパノール溶液0.5mlと、トリエトキシシランHSi
（OCH2CH3）31.9g（11.6m mol）を窒素気流下にて仕込
み、80℃にて12時間反応させた。反応終了後反応液中の
低沸分を減圧除去したところ5.3gの淡黒色のやや粘稠な
液体が得られた。赤外吸収スペクトル分析、核磁気共鳴
スペクトル分析、元素分析の結果から目的とする上記被
膜形成物質（２）であることが確認される。Next, 100m equipped with a stirrer, thermometer and reflux cooling machine
l of the compound (b) 4.1 g (10.0 mm
ol), 30 ml of benzene, 0.5 ml of an isopropanol solution containing 0.0003 g of chloroplatinic acid, and triethoxysilane HSi
(OCH 2 CH 3 ) 3 1.9 g (11.6 mmol) was charged under a nitrogen stream and reacted at 80 ° C. for 12 hours. After the completion of the reaction, low-boiling components in the reaction solution were removed under reduced pressure to obtain 5.3 g of a pale black, slightly viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it is confirmed that the substance is the target film-forming substance (2).
（合成例）4. CF3（CF2）５（CH2）2COO（CH2）3Si（OCH2CH3）３ 被膜形成物質（３）の合成 攪拌機、温度計、還流冷却機を取り付けた100mlのガ
ラス製反応器中に、式CF3（CF2）5CH2CH2COOHで表わさ
れるフルオロガルボン酸5.02g（12.8m mol）と、塩化チ
オニル50mlと、ジメチルホルムアミド10mlを仕込み、12
0℃にて８時間還流させた。反応終了後反応液中の低沸
分を70℃/10-2mmHgの条件で除去したところ4.9gの淡黄
色透明のかなり粘稠な液体が得られた。赤外吸収スペク
トル分析、該磁気共鳴スペクトル分析、元素分析の結果
から式CF3（CF2）５（CH2）2COClで表わされる化合物
（Ｃ）であることが確認された。(Synthesis example) 4. Synthesis of CF 3 (CF 2 ) 5 (CH 2 ) 2 COO (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 film forming substance (3) A stirrer, thermometer, and reflux condenser were installed. A 100 ml glass reactor was charged with 5.02 g (12.8 mmol) of fluorogarbonic acid represented by the formula CF 3 (CF 2 ) 5 CH 2 CH 2 COOH, 50 ml of thionyl chloride, and 10 ml of dimethylformamide. 12
Reflux at 0 ° C. for 8 hours. After the completion of the reaction, low boiling components in the reaction solution were removed under the condition of 70 ° C./10 −2 mmHg, to obtain 4.9 g of a pale yellow, transparent and viscous liquid. From the results of infrared absorption spectrum analysis, magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the compound (C) was represented by the formula CF 3 (CF 2 ) 5 (CH 2 ) 2 COCl.
次に攪拌機、還流冷却器を取り付けた100mlのガラス
製反応器中に、上記生成物（Ｃ）4.2g（10.2m mol）
と、アリルアルコール（CH2＝CHCH2OH）1.3g（22.4m mo
l）と、2,6−ジ−ｔ−ブチルピリジン2.3g（12.0m mo
l）と、ヘキサフルオロパラキシレン50mlを仕込み、室
温で12時間攪拌した。反応終了後、水を加えて固体を完
全に溶かし、エーテルで抽出し、70℃/10-2mmHgの条件
で減圧除去したところ4.3gの茶褐色の粘稠な液体が得ら
れた。赤外吸収スペクトル分析、該磁気共鳴スペクトル
分析、元素分析の経過から式CF3（CF2）５（CH2）2COOC
H2CH＝CH2で表わされる化合物（ｄ）であることが確認
された。Next, 4.2 g (10.2 mmol) of the above product (C) was placed in a 100 ml glass reactor equipped with a stirrer and a reflux condenser.
And, allyl alcohol (CH 2 = CHCH 2 OH) 1.3g (22.4m mo
l) and 2.3 g of 2,6-di-t-butylpyridine (12.0 mmol
l) and 50 ml of hexafluoroparaxylene were charged and stirred at room temperature for 12 hours. After completion of the reaction, water was added to completely dissolve the solid, extracted with ether, and removed under reduced pressure at 70 ° C./10 −2 mmHg to obtain 4.3 g of a brown viscous liquid. From the course of the infrared absorption spectrum analysis, the magnetic resonance spectrum analysis, and the elemental analysis, the formula CF 3 (CF 2 ) 5 (CH 2 ) 2 COOC
It was confirmed that H 2 CH was a compound (d) represented by CH 2 .
次に攪拌機、温度計、還流冷却機を取り付けた100ml
のガラス製反応器中に、上記化合物（ｄ）3.2g（7.4m m
ol）と、ベンゼン30mlと、塩化白金酸を0.0003g含むイ
ソプロパノール溶液0.5mlと、トリエトキシシランHSi
（OCH2CH3）31.9g（11.6m mol）を窒素気流下にて仕込
み、80℃にて12時間反応させた。反応終了後反応液中の
低沸分を減圧除去し4.3gの淡黒色のやや粘稠な液体を得
た。赤外吸収スペクトル分析、核磁気共鳴スペクトル分
析、元素分析の結果から目的とする上記被膜形成物質
（３）てあることが確認された。Next, 100ml equipped with a stirrer, thermometer, reflux condenser
3.2 g (7.4 mm) of the above compound (d) in a glass reactor
ol), 30 ml of benzene, 0.5 ml of an isopropanol solution containing 0.0003 g of chloroplatinic acid, and triethoxysilane HSi
(OCH 2 CH 3 ) 3 1.9 g (11.6 mmol) was charged under a nitrogen stream and reacted at 80 ° C. for 12 hours. After completion of the reaction, low-boiling components in the reaction solution were removed under reduced pressure to obtain 4.3 g of a pale black, slightly viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the desired film-forming substance (3) was obtained.
（合成例）5. CF3（CH2）５（CH2）OCO（CH2）3Si（OCH2CH3）３ 被膜形成物質（４）の合成 攪拌機、温度計、還流冷却機械を取り付けた100mlの
ガラス製反応器中に式CF3（CF2）5CH2CH2OHで表わされ
るフロオロアルコール5.06g（13.9m mol）と、別途合成
したビニル酢酸塩化物CH2＝CHCH2COCl1.5g（17.4m mo
l）と、2.6−ジｔ−ブチルピリジン2.8g（14.6m mol）
とヘキサフルオロパラキシレン50mlを仕込み室温で12時
間攪拌した。反応終了後水を加えて固体を完全に溶か
し、エーテルで抽出し70℃/10-2mmHgの条件で低沸分を
除去し7.3gの茶褐色の粘稠な液状物を得た。赤外吸収ス
ペクトル分析、核磁気共鳴スペクトル分析、元素分析の
結果から式CF3（CF2）５（CH2）2COOCH2CH＝CH2で表さ
れる生成物（ｅ）であることが確認された。(Synthesis example) 5. Synthesis of CF 3 (CH 2 ) 5 (CH 2 ) OCO (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 film forming substance (4) A stirrer, a thermometer, and a reflux cooling machine were attached. formula CF 3 into a glass reactor of 100ml (CF 2) 5 CH 2 fluoroalkyl alcohol 5.06g represented by CH 2 OH and (13.9 m mol), vinyl acetate chloride was separately synthesized CH 2 = CHCH 2 COCl1. 5g (17.4m mo
l) and 2.8 g (14.6 mmol) of 2.6-di-t-butylpyridine
And 50 ml of hexafluoroparaxylene were charged and stirred at room temperature for 12 hours. After completion of the reaction, water was added to completely dissolve the solid, extracted with ether, and low boiling components were removed at 70 ° C./10 −2 mmHg to obtain 7.3 g of a brown viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the product (e) was represented by the formula CF 3 (CF 2 ) 5 (CH 2 ) 2 COOCH 2 CH = CH 2 Was done.
次に攪拌機、温度計、還流冷却機を取り付けた100ml
のガラス製反応器中に上記化合物（ｅ）3.0g（6.9m mo
l）と、ベンゼン30mlと、塩化白金酸を0.0003g含むイソ
プロパノール溶液0.5mlと、トリエトキシシランHSi（OC
H2CH3）31.9g（11.6m mol）を窒素気流下にて仕込み80
℃にて12時間反応させた。反応終了後反応液中の低沸分
を減圧除去し3.6gの淡黒色のやや粘稠な液体を得た。赤
外吸収スペクトル分析、核磁気共鳴スペクトル分析、元
素分析の結果から目的とする上記被膜形成物質（４）で
あることが確認された。Next, 100ml equipped with a stirrer, thermometer, reflux condenser
3.0 g (6.9 mmol) of the above compound (e) in a glass reactor
l), benzene 30 ml, isopropanol solution 0.5 ml containing 0.0003 g of chloroplatinic acid, and triethoxysilane HSi (OC
H 2 CH 3 ) 3 Charge 1.9 g (11.6 mmol) under a nitrogen stream 80
Reaction was performed at 12 ° C. for 12 hours. After completion of the reaction, low-boiling components in the reaction solution were removed under reduced pressure to obtain 3.6 g of a pale black, slightly viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the target film-forming substance (4) was intended.
（合成例）6. CF3（CF2）５（CH2）2CONH（CH2）3Si（OCH2CH3）３ 被膜形成物質（５）の合成 攪拌機、温度計、還流冷却機を取り付けた100mlのガ
ラス製反応器中に、合成例４で合成した化合物（ｅ）5.
2g（12.6m mol）と、アリルアミンCH2＝CHCH2NH21.5g
（26.3m mol）と2,6−ジｔ−ブチルピリジン2.8g（14.6
m mol）とヘキサフルオロパラキシレン50mlを仕込み、
室温で12時間攪拌した。反応終了後水を加えて固体を完
全に溶かし、エーテルで抽出し70℃/10-2mmHgの条件で
低沸分を除去し5.3gの淡黄色の粘稠な液状物を得た。赤
外吸収スペクトル分析、核磁気共鳴スペクトル分析、元
素分析の結果から式CF3（CF2）５（CH2）2CONHCH2CH＝C
H2で表わされる化合物（ｆ）であることが確認された。(Synthesis example) 6. Synthesis of CF 3 (CF 2 ) 5 (CH 2 ) 2 CONH (CH 2 ) 3 Si (OCH 2 CH 3 ) 3 film-forming substance (5) A stirrer, thermometer, and reflux condenser were installed. Compound (e) synthesized in Synthesis Example 4 in a 100 ml glass reactor.
2 g (12.6 mmol) and allylamine CH 2 = CHCH 2 NH 2 1.5 g
(26.3 mmol) and 2.8 g of 2,6-di-tert-butylpyridine (14.6
mmol) and 50 ml of hexafluoroparaxylene,
Stirred at room temperature for 12 hours. After completion of the reaction, water was added to completely dissolve the solid, extracted with ether, and low boiling components were removed at 70 ° C./10 −2 mmHg to obtain 5.3 g of a pale yellow viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, the formula CF 3 (CF 2 ) 5 (CH 2 ) 2 CONHCH 2 CH = C
The compound (f) represented by H 2 was confirmed.
次に攪拌機、温度計、還流冷却機を取り付けた100ml
のガラス製反応器中に上記化合物（ｆ）2.2g（5.1m mo
l）と、ベンゼン30mlと、塩化白金酸を0.0003g含むイソ
プロパノール溶液0.5mlと、トリエトキシシランHSi（OC
H2CH3）31.9g（11.6m mol）を窒素気流下にて仕込み80
℃にて12時間反応させた。反応終了後反応液中の低沸分
を減圧除去し3.3gの淡黒色のやや粘稠な液体を得た。赤
外吸収スペクトル分析、核磁気共鳴スペクトル分析、元
素分析の結果から目的とする上記被膜形成物質（５）で
あることが確認された。Next, 100ml equipped with a stirrer, thermometer, reflux condenser
2.2 g (5.1 mmol) of the above compound (f) in a glass reactor
l), benzene 30 ml, isopropanol solution 0.5 ml containing 0.0003 g of chloroplatinic acid, and triethoxysilane HSi (OC
H 2 CH 3 ) 3 Charge 1.9 g (11.6 mmol) under a nitrogen stream 80
Reaction was performed at 12 ° C. for 12 hours. After completion of the reaction, low boiling components in the reaction solution were removed under reduced pressure to obtain 3.3 g of a slightly black, slightly viscous liquid. From the results of infrared absorption spectrum analysis, nuclear magnetic resonance spectrum analysis, and elemental analysis, it was confirmed that the target film-forming substance (5) was intended.
実施例1. 合成例１〜６で得られた被膜形成物質（１）〜（５）
を50mg秤量し、0.5mg/mlのクロロホルム溶液にする。こ
れをLB法において20℃、pH2の水面上に展開したときの
表面圧−一分子当りの面積の関係（Ｆ−Ａ曲線）を測定
した結果を第１図に示す。これより被膜形成物質（１）
〜（５）について一分子当りの分子占有面積はフルオロ
アルキル鎖の断面積と同じ30A2になる。Example 1. Film-forming substances (1) to (5) obtained in Synthesis Examples 1 to 6
Is weighed to make a 0.5 mg / ml chloroform solution. FIG. 1 shows the result of measuring the relationship between surface pressure and area per molecule (FA curve) when this was developed on a water surface at 20 ° C. and pH 2 by the LB method. From this film-forming substance (1)
Regarding (5), the molecular occupied area per molecule is 30 A 2 which is the same as the cross-sectional area of the fluoroalkyl chain.
次いで水面上に展開した上記被膜形成物質（１）〜
（５）を表面圧45mN/mで粗面度0.05μｍのアルミ基板上
に単分子膜を移しとり110℃で加熱重合させたものの薄
膜の水との接触角および臨界表面張力を測定した。その
結果は第２表に示される。Next, the above-mentioned film-forming substances (1) to-
(5) The monomolecular film was transferred onto an aluminum substrate having a surface pressure of 45 mN / m and a roughness of 0.05 μm, and was subjected to heat polymerization at 110 ° C., but the contact angle with water and the critical surface tension of the thin film were measured. The results are shown in Table 2.
第２表によれば各試料の臨界表面張力はテフロン表面
の18dyn/cmよりも小さくなり、パーフルオロ基が有効に
表面に配向されていることが認められる。 According to Table 2, the critical surface tension of each sample was smaller than 18 dyn / cm on the Teflon surface, and it was confirmed that the perfluoro group was effectively oriented on the surface.
第１図は本発明の実施例における表面圧−一分子当りの
面積の関係（Ｆ−Ａ曲線）の測定結果を示すグラフであ
る。FIG. 1 is a graph showing the results of measurement of the relationship between surface pressure and area per molecule (FA curve) in Examples of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 左右田 義浩 愛知県名古屋市瑞穂区二野町８番３号 ナトコペイント株式会社研究所内 (72)発明者 畑 宏則 愛知県名古屋市瑞穂区二野町８番３号 ナトコペイント株式会社研究所内 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshihiro Sokita 8-3 Ninocho, Mizuho-ku, Nagoya-shi, Aichi Pref. Inside the laboratory of Natco Paint Co., Ltd. (72) Inventor Hironori Hata 8 Ninocho, Mizuho-ku, Nagoya-shi, Aichi No. 3 Inside the laboratory of Natco Paint Co., Ltd.
Claims (2)
有し、他端に加水分解可能なシリル基を有する被膜形成
物質の溶液を水面上に展開して被膜を形成することを特
徴とする被膜形成方法。1. A film is formed by spreading a solution of a film-forming substance having a perfluoroalkyl group at one end of a molecular chain and a hydrolyzable silyl group at the other end on a water surface. Coating method.
圧縮することを特徴とする「特許請求の範囲第１項」に
記載の被膜形成方法。2. The method according to claim 1, wherein the coating developed on the water surface is compressed between barriers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63322444A JP2665961B2 (en) | 1988-12-20 | 1988-12-20 | Coating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63322444A JP2665961B2 (en) | 1988-12-20 | 1988-12-20 | Coating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02169067A JPH02169067A (en) | 1990-06-29 |
| JP2665961B2 true JP2665961B2 (en) | 1997-10-22 |
Family
ID=18143739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63322444A Expired - Lifetime JP2665961B2 (en) | 1988-12-20 | 1988-12-20 | Coating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2665961B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2921197B2 (en) * | 1991-09-03 | 1999-07-19 | 松下電器産業株式会社 | Water / oil repellent coating material and method for producing the same |
| JP4061656B2 (en) * | 1993-12-28 | 2008-03-19 | ダイキン工業株式会社 | Coating composition and painted product |
| FR2777567B1 (en) * | 1998-04-15 | 2000-06-23 | Oreal | FLUORO-SILICONE COMPOUNDS IN THE OIL FORM AND THEIR USE IN COSMETICS |
| TW591097B (en) * | 1998-12-10 | 2004-06-11 | Toray Industries | Optical articles and the preparation of optical articles |
| JP4757474B2 (en) * | 2004-10-15 | 2011-08-24 | 日本曹達株式会社 | Organic thin film formation method |
| US7745653B2 (en) * | 2007-03-08 | 2010-06-29 | 3M Innovative Properties Company | Fluorochemical compounds having pendent silyl groups |
| US8058463B2 (en) | 2007-12-04 | 2011-11-15 | E. I. Du Pont De Nemours And Compnay | Fluorosilanes |
| WO2009087981A1 (en) * | 2008-01-11 | 2009-07-16 | Kri Inc. | Polymerizable compound and method for producing the same |
| JP2011147890A (en) * | 2010-01-22 | 2011-08-04 | Seiko Epson Corp | Method for forming thin film and method for producing functional material |
| CN102643303A (en) * | 2012-04-13 | 2012-08-22 | 阜新恒通氟化学有限公司 | Preparation method of fluoride anti-fingerprint agent |
| CN105801618A (en) * | 2016-05-04 | 2016-07-27 | 厦门建霖工业有限公司 | Preparation method of fluorine-containing super-hydro-oleophobic agent |
| CN105968131A (en) * | 2016-05-04 | 2016-09-28 | 厦门建霖工业有限公司 | Fluorine-containing super hydrophobic and oleophobic agent and application thereof |
-
1988
- 1988-12-20 JP JP63322444A patent/JP2665961B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02169067A (en) | 1990-06-29 |
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