JP2841611B2 - Fluorinated surfactant - Google Patents
Fluorinated surfactantInfo
- Publication number
- JP2841611B2 JP2841611B2 JP600890A JP600890A JP2841611B2 JP 2841611 B2 JP2841611 B2 JP 2841611B2 JP 600890 A JP600890 A JP 600890A JP 600890 A JP600890 A JP 600890A JP 2841611 B2 JP2841611 B2 JP 2841611B2
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- JP
- Japan
- Prior art keywords
- resin
- general
- fluorine
- based surfactant
- sample
- 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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- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、汎用樹脂用の界面活性剤に関し、更に詳し
くは、樹脂表面の疎水化に優れたフッ素系界面活性剤に
関する。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant for general-purpose resins, and more particularly, to a fluorine-based surfactant excellent in hydrophobizing a resin surface.
従来技術とその課題 従来より、汎用樹脂にフッ素系界面活性剤を混入して
樹脂表面を疎水化するという考えのもとに、汎用樹脂と
の親和性に優れたフッ素系界面活性剤を得るべく多くの
試みがなされてきている。しかしながら、未だ有効なフ
ッ素系界面活性剤は得られておらず、樹脂表面の疎水化
技術は確立されていないのが現状である。Conventional technology and its problems Conventionally, based on the idea of mixing a general-purpose resin with a fluorine-based surfactant to make the resin surface hydrophobic, to obtain a fluorine-based surfactant with excellent affinity with general-purpose resins Many attempts have been made. However, an effective fluorine-based surfactant has not yet been obtained, and at present, a technique for making the resin surface hydrophobic has not been established.
課題を解決するための手段 本発明は、汎用樹脂表面の疎水化に優れた効果を有す
るフッ素系界面活性剤を提供することを目的とする。Means for Solving the Problems It is an object of the present invention to provide a fluorine-based surfactant having an excellent effect of making a general-purpose resin surface hydrophobic.
本発明者は、上記目的を達成すべく鋭意研究を重ねた
結果、汎用樹脂との親和性が高いN,N−ジメチルアセト
アミドの重合体と考えられるポリ（Ｎ−アセチルエチレ
ンイミン）を親水基に持つフッ素系界面活性剤を開発す
ることに成功し、これを汎用樹脂に混入したときは、そ
の表面を明確に疎水化できることを見出し、本発明を完
成するに至った。The present inventors have conducted intensive studies to achieve the above object, and as a result, poly (N-acetylethyleneimine), which is considered to be a polymer of N, N-dimethylacetamide having a high affinity with general-purpose resins, is used as a hydrophilic group. The present inventors have succeeded in developing a fluorine-based surfactant having the same, and found that when this was mixed into a general-purpose resin, the surface thereof could be clearly hydrophobized, thereby completing the present invention.
即ち、本発明は、一般式 〔式中、Rfは炭素数６〜12のペルフルオロアルキル基
を、Ｘは−OH、−NH2又は−Ｉを表す。また、ｍは平均
値として０〜２の数値を、ｎはｎ＋ｍが平均値として５
〜20となる数値を表す。〕 で示される化合物を有効成分とする汎用樹脂表面疎水化
用のフッ素系界面活性剤に係るものである。また、該フ
ッ素系界面活性剤を汎用樹脂に混入して製膜または成型
する汎用樹脂表面の疎水化方法に係るものである。That is, the present invention relates to the general formula [In the formula, R f represents a perfluoroalkyl group having 6 to 12 carbon atoms, and X represents —OH, —NH 2 or —I. Also, m is a numerical value of 0 to 2 as an average value, and n is n + m as 5 as an average value.
Represents a numerical value of ~ 20. The present invention relates to a fluorine-based surfactant for hydrophobizing the surface of a general-purpose resin, which comprises a compound represented by the formula (1) as an active ingredient. The present invention also relates to a method for hydrophobizing the surface of a general-purpose resin in which a film is formed or molded by mixing the fluorine-based surfactant into a general-purpose resin.
本発明のフッ素系界面活性剤の有効成分である上記一
般式（Ｉ）の化合物は、ヨウ化２−ペルフルオロアルキ
ルエチル或いはｐ−トルエンスルホン酸２−ペルフルオ
ロアルキルエチルを開始剤として、２−メチル２−オキ
サゾリンを重合させ、アルカリ処理或いは陰イオン交換
樹脂処理、また必要に応じてアンモニア処理することで
合成される。The compound of the above general formula (I), which is an active ingredient of the fluorosurfactant of the present invention, comprises 2-perfluoroalkylethyl iodide or 2-perfluoroalkylethyl p-toluenesulfonate as an initiator. -It is synthesized by polymerizing oxazoline and treating it with an alkali or an anion exchange resin and, if necessary, with ammonia.
上記重合におけるモノマーと開始剤との仕込みモル比
（モノマー／開始剤）は、特に限定されず、通常１〜５
程度とするのがよい。重合反応は、例えばN,N−ジメチ
ルホルムアミド、アセトニトリルなどの溶媒中で行わ
れ、その使用量は開始剤に対して２〜20重量倍程度とす
るのがよい。重合反応は、オキサゾリン類の公知の重合
方法に準じて行うことができ、例えば80〜110℃程度の
温度で１〜３日間程度保持することにより行われる。生
成物は、必要に応じて、例えばクロロホルム−ジエチル
エーテル混合液、クロロホルム−1,1,2−トリクロロ−
1,2,2−トリフルオロエタン混合液などに溶解させて再
沈殿により精製される。The charged molar ratio of the monomer and the initiator in the above polymerization (monomer / initiator) is not particularly limited, and is usually 1 to 5
It is good to be about. The polymerization reaction is carried out in a solvent such as N, N-dimethylformamide, acetonitrile and the like, and its amount is preferably about 2 to 20 times the weight of the initiator. The polymerization reaction can be carried out according to a known polymerization method for oxazolines, and is carried out, for example, by maintaining the temperature at about 80 to 110 ° C. for about 1 to 3 days. If necessary, the product may be, for example, a chloroform-diethyl ether mixture, chloroform-1,1,2-trichloro-
It is dissolved in a 1,2,2-trifluoroethane mixture or the like and purified by reprecipitation.
このようにして得られる一般式（Ｉ）化合物はその構
造中 の部分はランダム結合よりなる。The compound of general formula (I) thus obtained has the structure Consists of random combinations.
また、本発明のフッ素系界面活性剤は、一般式（Ｉ）
の化合物を有効成分とするものであり、該有効成分以外
に、例えば前記一般式（Ｉ）の化合物の合成時に副生す
る一般式 〔式中、Ｒは水素原子などのフッ素を含まない１価の基
を表す。また、Ｘ、ｍ及びｎは前記と同じ。〕 で示される化合物をモル比で50％程度以下含むものをも
包含する。このような場合であっても、樹脂表面の疎水
化の目的に有効に使用することができる。上記において
一般式（II）の化合物を多量に含有する場合であって
も、分別再沈殿等により精製することで、本発明の目的
を達し得る。Further, the fluorine-based surfactant of the present invention has the general formula (I)
Wherein the compound of the general formula (I) is a by-product during the synthesis of the compound of the general formula (I). [In the formula, R represents a monovalent group containing no fluorine such as a hydrogen atom. X, m and n are the same as above. And a compound containing about 50% or less by mole of the compound represented by the formula (1). Even in such a case, it can be effectively used for the purpose of making the resin surface hydrophobic. Even when the compound of the general formula (II) is contained in a large amount in the above, the object of the present invention can be achieved by purification by fractional reprecipitation or the like.
本発明のフッ素系界面活性剤を樹脂表面の疎水化に用
いるときは、樹脂の製膜時或いは成型時に、樹脂に対し
て0.01〜２重量％程度、より好ましくは0.05〜0.2重量
％混入して使用すればよい。また、予め樹脂のペレット
の中に配合して使用してもよい。When the fluorinated surfactant of the present invention is used for hydrophobizing the resin surface, it is mixed with the resin at about 0.01 to 2% by weight, more preferably 0.05 to 0.2% by weight, at the time of forming or molding the resin. Just use it. Moreover, you may mix | blend and use in resin pellets beforehand.
本発明のフッ素系界面活性剤は、ポリ塩化ビニル樹
脂、ポリメタクリル酸メチル樹脂、ポリ酢酸ビニル樹
脂、ポリ塩化ビニリデン樹脂、ポリアクリロニトリル樹
脂等の汎用樹脂に広く使用され得るが、殊にポリ塩化ビ
ニル樹脂、ポリメタクリル酸メチル樹脂に対して有効で
ある。The fluorinated surfactant of the present invention can be widely used for general-purpose resins such as polyvinyl chloride resin, polymethyl methacrylate resin, polyvinyl acetate resin, polyvinylidene chloride resin, and polyacrylonitrile resin. It is effective for resin and polymethyl methacrylate resin.
発明の効果 本発明のフッ素系界面活性剤を用いることにより、汎
用樹脂表面を効果的に疎水化することができ、樹脂表面
の水に対する接触角でいえば、樹脂の種類にもよるが約
10度もしくはそれ以上大きくすることができる。Effect of the Invention By using the fluorosurfactant of the present invention, it is possible to effectively hydrophobize a general-purpose resin surface, and in terms of the contact angle of the resin surface with water, it depends on the type of the resin.
Can be as large as 10 degrees or more.
実施例 以下に実施例を示し、本発明の特徴とするところをよ
り一層明確にする。Examples Examples are given below to further clarify features of the present invention.
実施例１ 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカ
フルオロ−１−ヨードデカン（開始剤）172.2g（0.3モ
ル）を窒素気流下でN,N−ジメチルホルムアミド（DMF）
300mlに加熱溶解し、80℃に保ち、そこへ２−メチル−
２−オキサゾリン76.8g（0.9モル）をDMF300mlに溶かし
た溶液を終夜かけて滴下した。滴下終了後引き続き80℃
で37時間加熱した後、室温まで放冷した。析出した開始
剤の結晶を吸引ろ過で除き、ろ液から溶媒等を減圧下留
去した。残渣をクロロホルム90mlに溶かし、1,1,2−ト
リクロロ−1,2,2−トリフルオロエタン（Ｒ−113）600m
lを少しずつ加えて生成物を再沈殿させた。沈殿をエタ
ノール600mlに溶かし、OH型陰イオン交換樹脂300mlを詰
めたカラムに通した。流出液から溶媒を留去して、残渣
（95.4g）のヨウ素分析をしたところ、0.49％（重量）
であった。このうち67gをエタノール600mlに溶かし、28
％アンモニア水溶液16.4gとシュウ酸（２水和物）1.4g
を加えて終夜撹拌した。沈殿をろ過で除去して、ろ液を
OH型陰イオン交換樹脂300mlを詰めたカラムに通した。
流出液から溶媒を留去して、残渣（65.2g）のヨウ素分
析をしたところ、0.009％（重量）であった。フッ素分
析値は14.66％（重量）であった。このうち5.8gをクロ
ロホルム10mlに溶かし、Ｒ−113 10mlを加えて分別再沈
殿をした。さらにクロロホルム10mlとＲ−113 10mlの混
合物を加え、振りまぜて静置して、上澄み（母液）を分
離して溶媒を減圧下留去した。。残渣（1.83g）のフッ
素分析をしたところ、23.26％（重量）であった。Example 1 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-iododecane (initiator) 172.2 g (0.3 mol) in a nitrogen stream under N, N-dimethylformamide (DMF)
Heat and dissolve in 300 ml, keep at 80 ° C, and add 2-methyl-
A solution prepared by dissolving 76.8 g (0.9 mol) of 2-oxazoline in 300 ml of DMF was added dropwise over night. 80 ° C after dropping
And then allowed to cool to room temperature. The precipitated initiator crystals were removed by suction filtration, and the solvent and the like were distilled off from the filtrate under reduced pressure. The residue was dissolved in 90 ml of chloroform, and 1,1,2-trichloro-1,2,2-trifluoroethane (R-113) 600 m
l was added portionwise to reprecipitate the product. The precipitate was dissolved in 600 ml of ethanol and passed through a column packed with 300 ml of an OH type anion exchange resin. The solvent was distilled off from the effluent, and the residue (95.4 g) was analyzed for iodine.
Met. Dissolve 67 g of this in 600 ml of ethanol,
1% aqueous ammonia solution 16.4g and oxalic acid (dihydrate) 1.4g
Was added and stirred overnight. The precipitate is removed by filtration and the filtrate is
The solution was passed through a column packed with 300 ml of an OH type anion exchange resin.
The solvent was distilled off from the effluent, and the residue (65.2 g) was analyzed for iodine. As a result, it was 0.009% (by weight). The fluorine analysis value was 14.66% (weight). Of these, 5.8 g was dissolved in 10 ml of chloroform, and 10 ml of R-113 was added for fractional reprecipitation. Further, a mixture of 10 ml of chloroform and 10 ml of R-113 was added, shaken and allowed to stand, the supernatant (mother liquor) was separated, and the solvent was distilled off under reduced pressure. . The residue (1.83 g) was analyzed for fluorine, and found to be 23.26% (by weight).
得られたフッ素系界面活性剤の組成（フッ素分析、ア
ミノ基分析、水酸基分析による）を下記に示す。The composition (based on fluorine analysis, amino group analysis, and hydroxyl group analysis) of the obtained fluorine-based surfactant is shown below.
末端NH2率＝７モル％、アセチル基の脱落はランダムで
ある。〕 以下の試験例は、試料として上記実施例１で得たフッ
素系界面活性剤を用いて樹脂表面の疎水化を試みたもの
である。 Terminal NH 2 ratio = 7 mol%, dropout of acetyl groups is random. In the following test examples, an attempt was made to make the resin surface hydrophobic by using the fluorine-based surfactant obtained in Example 1 as a sample.
また、ここで樹脂として使用したポリ塩化ビニル（粉
末）の平均重合度は1100、ポリメタクリル酸メチル（粉
末）の平均重合度は6000である。The average degree of polymerization of polyvinyl chloride (powder) used here as resin is 1100, and the average degree of polymerization of polymethyl methacrylate (powder) is 6000.
試験例１ 0.1gのポリ塩化ビニルを9.9gのテトラヒドロフランに
溶解し、試料の10％エタノール溶液0.02mlを加えて、振
り混ぜた（0.2重量％試料／樹脂）。この溶液を、ポリ
エチレンテレフタレート（PET）フィルムを敷いたポリ
メチルペンテン（PMP）シャーレ（85φ）に入れてか
ら、ドライヤーで溶媒を徐々に蒸発させた（簡略法）。
溶媒がほぼ蒸発した後、乾燥器にいれて一日乾燥した。
生成したフィルムを取り出して、水でよく洗って、両面
の接触角（水）を４回ずつ測定した。平均値は、表（空
気接触面）128±３°、裏（PET接触面）100±３°であ
った。Test Example 1 0.1 g of polyvinyl chloride was dissolved in 9.9 g of tetrahydrofuran, 0.02 ml of a 10% ethanol solution of a sample was added, and the mixture was shaken (0.2% by weight of sample / resin). This solution was put in a polymethylpentene (PMP) petri dish (85φ) covered with a polyethylene terephthalate (PET) film, and then the solvent was gradually evaporated with a drier (simplified method).
After the solvent was almost evaporated, it was placed in a dryer and dried for a day.
The formed film was taken out, washed well with water, and the contact angles (water) on both sides were measured four times. The average value was 128 ± 3 ° for the front (air contact surface) and 100 ± 3 ° for the back (PET contact surface).
試験例２ 試験例１と同様の試験を、試料配合比２重量％試料／
樹脂として行った。得た樹脂フィルムの接触角（水）
は、表（空気接触面）86±２°、裏（PET接触面）91±
２°であった。Test Example 2 The same test as in Test Example 1 was carried out except that the sample mixture ratio was 2% by weight of the sample /
Performed as resin. Contact angle of obtained resin film (water)
Is 86 ± 2 ° for front (air contact surface) and 91 ± for back (PET contact surface)
2 °.
比較例１ 試料のフッ素系界面活性剤を加えなかった以外は、試
験例１と同様にして樹脂フィルムを得、接触角（水）を
測定した。その結果、表（空気接触面）81±４°、裏
（PET接触面）81±３°であった。Comparative Example 1 A resin film was obtained and the contact angle (water) was measured in the same manner as in Test Example 1 except that the fluorine-based surfactant of the sample was not added. As a result, the front (air contact surface) was 81 ± 4 ° and the back (PET contact surface) was 81 ± 3 °.
試験例３ 0.2gのポリ塩化ビニルを3.8gのテトラヒドロフランに
溶解し、試料の10％エタノール溶液0.02mlを加えて、振
り混ぜた（0.1重量％試料／樹脂）。この溶液を、気体
を流せるデシケータ中のPETフィルムを敷いたPMPシャー
レに入れて、室温で窒素を３〜５時間流して溶媒を徐々
に蒸発させた（防湿法）。その後、デシケータから取り
出して、乾燥器にいれて一日乾燥した。生成したフィル
ムを取り出して、水でよく洗って、両面の接触角（水）
を４回ずつ測定した。平均値は、表（空気接触面）82°
±１、裏（PET接触面）83°±２であった。Test Example 3 0.2 g of polyvinyl chloride was dissolved in 3.8 g of tetrahydrofuran, 0.02 ml of a 10% ethanol solution of a sample was added, and the mixture was shaken (0.1% by weight of sample / resin). This solution was placed in a PMP petri dish covered with a PET film in a desiccator through which gas can flow, and nitrogen was flowed at room temperature for 3 to 5 hours to gradually evaporate the solvent (moisture proof method). Then, it was taken out of the desiccator and placed in a drier to dry for one day. Take out the formed film, wash well with water, contact angle on both sides (water)
Was measured four times. The average value is 82 ° in the table (air contact surface)
± 1 and back (PET contact surface) 83 ° ± 2.
比較例２ 試料のフッ素系界面活性剤を加えなかった以外は、試
験例３と同様にして樹脂フィルムを得、接触角（水）を
測定した。その結果、表（空気接触面）75±３°、裏
（PET接触面）79±３°であった。Comparative Example 2 A resin film was obtained and the contact angle (water) was measured in the same manner as in Test Example 3 except that the fluorine-based surfactant of the sample was not added. As a result, the front surface (air contact surface) was 75 ± 3 ° and the back surface (PET contact surface) was 79 ± 3 °.
試験例７ 0.2gのポリメタクリル酸メチルを6.5gのアセトンに溶
解し、試料の10％エタノール溶液0.02mlを加えて、振り
混ぜた（0.1重量％試料／樹脂）。この溶液を、気体を
流せるデシケータ中のPMPシャーレに入れて、室温で窒
素を３〜５時間流して溶媒を徐々に蒸発させた（防湿
法）。その後、デシケータから取り出して、乾燥器にい
れて一日乾燥した。生成したフィルムを取り出して、水
でよく洗って、両面の接触角（水）を４回ずつ測定し
た。平均値は、表（空気接触面）71°±３、裏（PEP接
触面）65°±２。Test Example 7 0.2 g of polymethyl methacrylate was dissolved in 6.5 g of acetone, 0.02 ml of a 10% ethanol solution of a sample was added, and the mixture was shaken (0.1% by weight of sample / resin). This solution was placed in a PMP petri dish in a desiccator through which gas could flow, and nitrogen was flowed at room temperature for 3 to 5 hours to gradually evaporate the solvent (moisture proof method). Then, it was taken out of the desiccator and placed in a drier to dry for one day. The formed film was taken out, washed well with water, and the contact angles (water) on both sides were measured four times. The average value is 71 ° ± 3 for the front (air contact surface) and 65 ° ± 2 for the back (PEP contact surface).
比較例３ 試料のフッ素系界面活性剤を加えなかった以外は、試
験例７と同様にして樹脂フィルムを得、接触角（水）を
測定した。その結果、表（空気接触面）59±４°、裏
（PET接触面）62±４°であった。Comparative Example 3 A resin film was obtained and the contact angle (water) was measured in the same manner as in Test Example 7 except that the fluorine-based surfactant of the sample was not added. As a result, the front surface (air contact surface) was 59 ± 4 ° and the back surface (PET contact surface) was 62 ± 4 °.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08G 73/02 C08L 79/02,101/00 C09K 3/18 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C08G 73/02 C08L 79 / 02,101 / 00 C09K 3/18 CA (STN) REGISTRY (STN)
Claims (2)
を、Ｘは−OH、−NH2又は−Ｉを表す。また、ｍは平均
値として０〜２の数値を、ｎはｎ＋ｍが平均値として５
〜20となる数値を表す。〕 で示される化合物を有効成分とする汎用樹脂表面疎水化
用のフッ素系界面活性剤。(1) General formula [In the formula, R f represents a perfluoroalkyl group having 6 to 12 carbon atoms, and X represents —OH, —NH 2 or —I. Also, m is a numerical value of 0 to 2 as an average value, and n is n + m as 5 as an average value.
Represents a numerical value of ~ 20. ] A fluorinated surfactant for making the surface of a general-purpose resin hydrophobic, comprising a compound represented by the following formula:
用樹脂に混入して製膜または成型する汎用樹脂表面の疎
水化方法。2. A method for hydrophobizing the surface of a general-purpose resin, wherein the fluorine-containing surfactant according to claim 1 is mixed into a general-purpose resin to form or form a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP600890A JP2841611B2 (en) | 1990-01-11 | 1990-01-11 | Fluorinated surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP600890A JP2841611B2 (en) | 1990-01-11 | 1990-01-11 | Fluorinated surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03210332A JPH03210332A (en) | 1991-09-13 |
| JP2841611B2 true JP2841611B2 (en) | 1998-12-24 |
Family
ID=11626698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP600890A Expired - Fee Related JP2841611B2 (en) | 1990-01-11 | 1990-01-11 | Fluorinated surfactant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2841611B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170010317A (en) | 2014-07-04 | 2017-01-26 | 후지필름 가부시키가이샤 | Composition for fabricating optically functional layer, method for manufacturing optical film including optically functional layer, and optical film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2935403B1 (en) | 2012-12-19 | 2018-05-16 | 3M Innovative Properties Company | Reactive polyoxazolines having a perfluorinated group |
| JP6305429B2 (en) * | 2012-12-19 | 2018-04-04 | スリーエム イノベイティブ プロパティズ カンパニー | Polyoxazoline copolymer |
-
1990
- 1990-01-11 JP JP600890A patent/JP2841611B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170010317A (en) | 2014-07-04 | 2017-01-26 | 후지필름 가부시키가이샤 | Composition for fabricating optically functional layer, method for manufacturing optical film including optically functional layer, and optical film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03210332A (en) | 1991-09-13 |
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