JP2004143145A - Fluorine-containing surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing surfactant which comprises a compound having an at most 6C short perfluoroalkyl group, is suitable as an additive for enhancing penetrating properties, wetting properties, leveling properties, surface functionalities, and the like, and is used for various coating materials (such as a printing material, a photosensitive material, a photographic material, a paint material, a cleaning agent, an optical material and a releasing agent), molding materials, and the like. <P>SOLUTION: This fluorine-containing surfactant comprises a fluorine-containing compound (A) bearing two to four F(CF<SB>2</SB>)<SB>2m</SB>(CH<SB>2</SB>)<SB>n</SB>SO<SB>2</SB>NR- groups (wherein (m) is 2 or 3; (n) is 0, 1 or 2; and R is an alkyl group) and COOM (wherein M is hydrogen, ammonium or an alkali metal) in one molecule. <P>COPYRIGHT: (C)2004,JPO

Description

尚、本発明がこれら具体例により、なんら限定されないことは勿論である。
【００２１】
前記一般式（１）で表されるフッ素系化合物の製造方法は特に限定されるものではないが、例えば、以下の▲１▼〜▲３▼の方法が挙げられる。
▲１▼下記一般式（２）
Ｆ（ＣＦ_２）_２ｍ（ＣＨ_２）_ｎＳＯ_２Ｘ_１　　　（２）
（式中、ｍは２または３であり、ｎは０〜２の整数であり、Ｘ_１はハロゲンである。）
で示されるパーフルオロアルキルスルホニルハライド（Ｂ）に、アルキルアミンを反応（脱ハロゲン化水素反応）させてパーフルオロアルキルスルホン酸アルキルアミドとした後、ジハロカルボン酸またはジハロカルボン酸塩を反応（脱ハロゲン化水素反応）させる製造方法。
▲２▼前記一般式（２）で示されるパーフルオロアルキルスルホニルハライド（Ｂ）に、アルキルアミンを反応（脱ハロゲン化水素反応）させてパーフルオロアルキルスルホン酸アルキルアミドとした後、ジハロカルボン酸を反応（脱ハロゲン化水素反応）させ、更に中和する製造方法。
▲３▼前記一般式（２）で示されるパーフルオロアルキルスルホニルハライド（Ｂ）に、アルキルアミンを反応（脱ハロゲン化水素反応）させてパーフルオロアルキルスルホン酸アルキルアミドとした後、ジハロカルボン酸エステルを反応（脱ハロゲン化水素反応）させ、更にケン化する製造方法。
【００２２】
まず▲１▼の製造方法について詳細に説明する。
前記一般式（２）で示されるパーフルオロアルキルスルホニルハライド（Ｂ）としては界面活性効果が高く、且つパーフルオロアルキル基中の炭素数が６以下のフッ素系化合物が得られることから、前記一般式（２）中のｍが２または３であり、ｎが０または２であるものが好ましく、具体的には３，３，４，４，５，５，６，６，６−ノナフルオロヘキサンスルホニルクロライド、３，３，４，４，５，５，６，６，６−ノナフルオロヘキサンスルホニルブロミド、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタンスルホニルクロライド、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタンスルホニルブロミド、１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホニルフルオリド、１，１，２，２，３，３，４，４，５，５，６，６，６−トリデカフルオロヘキサン−１−スルホニルフルオリドが挙げられ、これらの中でも３，３，４，４，５，５，６，６，６−ノナフルオロヘキサンスルホニルクロライド、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタンスルホニルクロライド、１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホニルフルオリド、１，１，２，２，３，３，４，４，５，５，６，６，６−トリデカフルオロヘキサン−１−スルホニルフルオリドが特に好ましい。
【００２３】
また、前記一般式（２）で表わされるパーフルオロアルキルスルホニルハライド（Ｂ）に反応させるアルキルアミンとしては、例えば下記一般式（３）
ＲＮＨ_２　　　　　（３）
（式中、Ｒはアルキル基である。）
で示されるアルキルアミン（Ｃ）が挙げられ、界面活性効果が高いフッ素化合物が得られることから、Ｒは炭素数１〜１０のアルキル基が好ましく、炭素数１〜４のアルキル基が特に好ましく、例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン等が挙げられる。メチルアミンまたはエチルアミンを使用する場合は、フリーのアミンガスを使用しても良いが、取り扱いが容易な塩酸塩を使用することが好ましい。
【００２４】
また、アルキルアミンの使用量はパーフルオロアルキルスルホニルハライド（Ｂ）１モルに対し、１．８〜７．０モル、好ましくは２．０〜４．０モルである。また、該反応で副生するハロゲン化水素を除去するために塩基を使用することが好ましく、塩基としては、無機塩基、有機塩基のいずれも使用することができる。無機塩基としては、例えば、水酸化カリウム、水酸化ナトリウム、水酸化リチウム等が挙げられ、有機塩基としては、ピリジン、トリエチルアミン等が挙げられる。塩基の使用量は、使用するアルキルアミン１モルに対し、０．８〜４．０モル、好ましくは０．９〜２．０モルである。該反応は、無溶媒または有機溶媒中で行うことができるが、操作が容易であり、且つ安全性が高いことから有機溶媒中で反応させる方法が好ましい。
【００２５】
前記有機溶媒としては、前記一般式（２）で示される原料のパーフルオロアルキルスルホニルハライド（Ｂ）及びアルキルアミンに対して不活性であり、且つ両者を溶解できるものであれば特に制限されるものではないが、例えば、ジクロロメタン、クロロホルム、１，２−ジクロロエタン等のハロゲン化炭化水素類、ベンゼン、トルエン、キシレン、メシチレン等の芳香族炭化水素類、クロロベンゼン、オルトジクロロベンゼン、パラジクロロベンゼン等のハロゲン化芳香族炭化水素類、ｎ−ペンタン、ｎ−ヘキサン、ｎ−オクタン、シクロヘキサン等の脂肪族炭化水素類、テトラヒドロフラン、ジイソプロピルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル類、酢酸エチル、酢酸ブチル、酢酸プロピル等のエステル類が挙げられ、これらの中でも、ハロゲン化炭化水素類、エーテル類、エステル類が好ましく、エーテル類、エステル類が特に好ましい。また、これらの溶媒は１種類で用いてもよいし、２種以上を混合して使用しても良い。
【００２６】
前記反応の反応条件は、特に制限はないが、反応時間が短く、副生するハロゲン化水素の除去が容易なことから、パーフルオロアルキルスルホニルハライド（Ｂ）またはこれを前記溶媒に溶解したものを、アルキルアミンまたはこれを前記溶媒に溶解したものの中に滴下させる方法が好ましい。反応温度にも制限はないが、脱ハロゲン化水素反応が効率的に起こる条件であれば問題はなく、通常５〜８０℃であり、好ましくは１０〜５０℃である。反応時間にも制限はなく、通常０．５〜１０時間であり、好ましくは、１〜５時間である。反応雰囲気にも制限はないが、使用するアルキルアミンの酸化を抑制するためＮ_２、Ｈｅ、Ａｒ等の不活性ガス雰囲気下が好ましい。
【００２７】
次に、パーフルオロアルキルスルホニルハライド（Ｂ）とアルキルアミンとの反応により得られたパーフルオロアルキルスルホン酸アルキルアミドと、ジハロカルボン酸またはジハロカルボン酸塩との反応について説明する。
【００２８】
ここで用いるジハロカルボン酸としては、例えば下記一般式（４）
（Ｘ_２（ＣＨ_２）_ｏ）（Ｘ_２（ＣＨ_２）_ｐ）ＣＨ（ＣＨ_２）_ｑＣＯＯＨ　　　（４）
（式中、Ｘ_２はハロゲンであり、ｏは１〜１０の整数であり、ｐは０〜１０の整数であり、ｑは０〜１０の整数である。）
で示されるジハロカルボン酸（Ｄ）が挙げられ、ジハロカルボン酸塩としては、例えば下記一般式（５）
（Ｘ_３（ＣＨ_２）_ｏ）（Ｘ_３（ＣＨ_２）_ｐ）ＣＨ（ＣＨ_２）_ｑＣＯＯＭ_１　　　（５）
（式中、Ｘ_３はハロゲンであり、ｏは１〜１０の整数であり、ｐは０〜１０の整数であり、ｑは０〜１０の整数であり、Ｍ_１はアンモニウムまたはアルカリ金属である。）
で示されるジハロカルボン酸塩（Ｅ）が挙げられる。これらの中でも界面活性効果に優れるフッ素系化合物が得られることから、上記一般式（４）、（５）中のｏは１〜４の整数であることが好ましく、１または２であることが特に好ましく、またｐおよびｑは、界面活性効果に優れるフッ素系化合物が得られることから、０〜４の整数であることが好ましく、０〜２の整数であることが特に好ましい。
【００２９】
前記ジハロカルボン酸塩としては、例えばアミン塩として、アンモニア、ジエチルアミン、トリエチルアミン、ｎ−プロピルアミン、ｉｓｏ−プロピルアミン、ｎ−ブチルアミン、ｔｅｒｔ−ブチルアミン、ジ（ｎ−ブチル）アミン、エチレンジアミン、ジエチレンジアミン、モノエタノールアミン、ジエタノールアミン、プロパノールアミン、トルイジン、ピリジン等から誘導されたアミン塩が挙げられ、金属塩としては、アルカリ金属塩が好ましく、Ｌｉ塩、Ｎａ塩、Ｋ塩が挙げられ、これらの中でも実用的な界面活性効果が得られ、且つ、特に製造が容易なことから、アンモニアから誘導されるアミン塩、アルカリ金属塩のＬｉ塩、Ｎａ塩、Ｋ塩が好ましい。
【００３０】
前記ジハロカルボン酸およびジハロカルボン酸塩としては、例えば、２，３−ジクロロ−プロピオニックアシッド、４−クロロ−３−クロロメチル−ブチリックアシッド、３，４−ジクロロ−ブチリックアシッド、３−クロロ−２−クロロメチル−１−プロピオニックアシッド、２，４−ジクロロ−ブチリックアシッド、６−クロロ−４−（２−クロロエチル）−ヘキサノイックアシッド、４，６−ジクロロ−ヘキサノイックアシッド、４−クロロ−２−（２−クロロエチル）ブチリックアシッド、２，３−ジブロモ−プロピオニックアシッド、４−ブロモ−３−ブロモメチル−ブチリックアシッド、３，４−ジブロモ−ブチリックアシッド、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッド、２，４−ジブロモ−ブチリックアシッド、６−ブロモ−４−（２−ブロモエチル）−ヘキサノイックアシッド、４，６−ジブロモ−ヘキサノイックアシッド、４−ブロモ−２−（２−ブロモエチル）ブチリックアシッド等、及びこれらのアミン塩またはアルカリ金属塩が挙げられる。
【００３１】
これらの中でも、２，３−ジクロロ−プロピオニックアシッド、４−クロロ−３−クロロメチル−ブチリックアシッド、３−クロロ−２−クロロメチル−１−プロピオニックアシッド、２，４−ジクロロ−ブチリックアシッド、２，３−ジブロモ−プロピオニックアシッド、４−ブロモ−３−ブロモメチル−ブチリックアシッド、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッド、２，４−ジブロモ−ブチリックアシッド及びこれらのアミン塩またはアルカリ金属塩が好ましく、２，３−ジクロロ−プロピオニックアシッド、３−クロロ−２−クロロメチル−１−プロピオニックアシッド、２，３−ジブロモ−プロピオニックアシッド、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッド、２，３−ジクロロ−プロピオニックアシッドアンモニウム、３−クロロ−２−クロロメチル−１−プロピオニックアシッドアンモニウム、２，３−ジブロモ−プロピオニックアシッドアンモニウム、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドアンモニウム、２，３−ジクロロ−プロピオニックアシッドＬｉ塩、３−クロロ−２−クロロメチル−１−プロピオニックアシッドＬｉ塩、２，３−ジブロモ−プロピオニックアシッドＬｉ塩、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドＬｉ塩、２，３−ジクロロ−プロピオニックアシッドＮａ塩、３−クロロ−２−クロロメチル−１−プロピオニックアシッドＮａ塩、２，３−ジブロモ−プロピオニックアシッドＮａ塩、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドＮａ塩、２，３−ジクロロ−プロピオニックアシッドＫ塩、３−クロロ−２−クロロメチル−１−プロピオニックアシッドＫ塩、２，３−ジブロモ−プロピオニックアシッドＫ塩、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドＫ塩が特に好ましい。
【００３２】
パーフルオロアルキルスルホン酸アルキルアミドの使用量は、ジハロカルボン酸またはジハロカルボン酸塩１モルに対し、１．８〜７．０モルであり、好ましくは２．０〜４．０モルである。この反応はパーフルオロアルキルスルホン酸アルキルアミドの合成反応と同様に脱ハロゲン化水素反応であるため、副生するハロゲン化水素を除去するために前記の塩基を使用することが好ましい。塩基の使用量は、パーフルオロアルキルスルホン酸アルキルアミド１モルに対し、０．８〜４．０モル、好ましくは０．９〜２．０モルである。また、この反応は無溶媒または有機溶媒中で行うことができるが、操作が容易であり、且つ安全性が高いことから有機溶媒中で反応させる方法が好ましい。
【００３３】
前記有機溶媒としては、パーフルオロアルキルスルホン酸アルキルアミドおよびジハロカルボン酸またはジハロカルボン酸塩に対して不活性であり、且つ両者を溶解できるものであれば特に制限されるものではないが、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、ジクロロメタン、クロロホルム、１，２−ジクロロエタン等のハロゲン化炭化水素類、ベンゼン、トルエン、キシレン、メシチレン等の芳香族炭化水素類、クロロベンゼン、オルトジクロロベンゼン、パラジクロロベンゼン等のハロゲン化芳香族炭化水素類、ｎ−ペンタン、ｎ−ヘキサン、ｎ−オクタン、シクロヘキサン等の脂肪族炭化水素類、テトラヒドロフラン、ジイソプロピルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジエチルエーテル等のエーテル類、酢酸エチル、酢酸ブチル、酢酸プロピル等のエステル類、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等が挙げられ、これらの中でも、ケトン類、ハロゲン化炭化水素類、エーテル類、エステル類、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシドが好ましく、ケトン類、エーテル類、エステル類、ジメチルホルムアミド、ジメチルスルホキシドが特に好ましい。また、これらの溶媒は１種類で用いてもよいし、２種以上を混合して使用しても良い。
【００３４】
前記パーフルオロアルキルスルホン酸アルキルアミドとジハロカルボン酸またはジハロカルボン酸塩との反応条件は、特に制限はないが、反応時間が短く、副生するハロゲン化水素の除去が容易なことから、パーフルオロアルキルスルホン酸アルキルアミドまたはこれを前記溶媒に溶解したものを、ジハロカルボン酸またはジハロカルボン酸塩単独、若しくはこれらを前記溶媒に溶解したものの中に滴下させる方法が好ましい。反応温度にも制限はないが、脱ハロゲン化水素反応が効率的に起こる条件であれば問題はなく、通常１０〜１５０℃であり、好ましくは３０〜１００℃である。反応時間にも制限はなく、通常０．５〜１０時間であり、好ましくは、１〜５時間である。反応雰囲気にも制限はないが、Ｎ_２、Ｈｅ、Ａｒ等の不活性ガス雰囲気下が好ましい。
【００３５】
前記製造方法により得られた前記一般式（１）で示されるフッ素系化合物は、用途、目的によっては、未精製で用いることも出来るが、蒸留、溶媒による洗浄、再結晶、各種クロマトグラフィー、吸着剤等により、精製することも可能である。
【００３６】
次に、▲２▼の製造方法について述べる。
前記一般式（２）で示されるパーフルオロアルキルスルホニルハライド（Ｂ）に、アルキルアミンを反応させてパーフルオロアルキルスルホン酸アルキルアミドとし、さらにジハロカルボン酸と反応させる方法は、前述の▲１▼の製造方法と同じである。
【００３７】
前述の手法で得られたパーフルオロアルキルスルホン酸アルキルアミドとジハロカルボン酸との反応物を中和する際の中和剤としては、水酸化リチウム等の水酸化アルカリ金属、塩化リチウム等のハロゲン化アルカリ金属、アンモニア、トリメチルアミン、トリエチルアミン、ピリジン等のアミン類等が挙げられる。これら中和剤の使用量は中和を行う前の化合物１モルに対し、１〜５モル、好ましくは１〜２．５モルである。
【００３８】
前記中和反応時の反応条件としては、特に限定されるものではないが、例えば、反応溶媒として、水単独、あるいは水とメタノール、エタノール、イソプロパノール等のアルコール類との混合溶媒等が挙げられる。また、反応温度は５〜５０℃、特に１０〜３０℃であることが好ましい。
【００３９】
次に、▲３▼の製造方法について述べる。
前記一般式（２）で示されるパーフルオロアルキルスルホニルハライド（Ｂ）に、アルキルアミンを反応させてパーフルオロアルキルスルホン酸アルキルアミドとし、さらにジハロカルボン酸エステルと反応させる方法は、前述の▲１▼の製造方法と同じでジハロカルボン酸またはジハロカルボン酸塩の替わりにジハロカルボン酸エステルを用いればよい。
【００４０】
ここで用いるジハロカルボン酸エステルとしては、例えば下記一般式（６）
（Ｘ_４（ＣＨ_２）_ｏ）（Ｘ_４（ＣＨ_２）_ｐ）ＣＨ（ＣＨ_２）_ｑＣＯＯＲ_１　　　（６）
（式中、Ｘ_４はハロゲンであり、ｏは１〜１０の整数であり、ｐは０〜１０の整数であり、ｑは０〜１０の整数であり、Ｒ_１はアルキル基である。）
で示されるジハロカルボン酸エステル（Ｅ）が挙げられ、界面活性効果に優れるフッ素系化合物が得られることから、ｏは１〜４の整数であることが好ましく、１または２であることが特に好ましく、またｐおよびｑは、界面活性効果に優れるフッ素系化合物が得られることから、０〜４の整数であることが好ましく、０〜２の整数であることが特に好ましく、また、Ｒ_１は炭素数１〜７のアルキル基が好ましく、炭素数１〜４のアルキル基が特に好ましい。
【００４１】
これらの中でも、前記一般式（４）で示されるジハロカルボン酸（Ｄ）のエステルが好ましく、２，３−ジクロロ−プロピオニックアシッドメチルエステル、２，３−ジクロロ−プロピオニックアシッドエチルエステル、３−クロロ−２−クロロメチル−１−プロピオニックアシッドメチルエステル、３−クロロ−２−クロロメチル−１−プロピオニックアシッドエチルエステル、２，３−ジブロモ−プロピオニックアシッドメチルエステル、２，３−ジブロモ−プロピオニックアシッドエチルエステル、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドメチルエステル、３−ブロモ−２−ブロモメチル−１−プロピオニックアシッドエチルエステルが特に好ましい。
【００４２】
パーフルオロアルキルスルホン酸アルキルアミドとジハロカルボン酸エステルとの反応物をケン化する際のケン化剤としては、水酸化リチウム等の水酸化アルカリ金属、塩化リチウム等のハロゲン化アルカリ金属、アンモニア、トリメチルアミン、トリエチルアミン、ピリジン等のアミン類等が挙げられる。これらケン化剤の使用量はケン化を行う前の化合物１モルに対し、１〜５モル、好ましくは１〜２．５モルである。
【００４３】
前記ケン化反応時の反応条件としては、特に限定されるものではないが、例えば、反応溶媒として、水単独、あるいは水とメタノール、エタノール、イソプロパノール等のアルコール類との混合溶媒等が挙げられる。また、反応温度は、１０℃〜還流温度、特に４０〜９０℃であることが好ましい。
【００４４】
前述の３通りの製造方法のうち、ジハロカルボン酸またはジハロカルボン酸塩は有機溶剤に対する溶解性が低くパーフルオロアルキルスルホン酸アルキルアミドとの反応による操作性が低くなり、また、ジハロカルボン酸塩を用いる場合は、パーフルオロアルキルスルホン酸アルキルアミドとの反応により副生するハロゲン化水素とハロゲン化水素キャッチャー（塩基）とにより生成するアミン塩またはハロゲン化アルカリ金属が水溶性のため、水溶解性が比較的高いフッ素系化合物（Ａ）との分離が難しく収率低下を伴うので、効率よくフッ素系化合物（Ａ）を得る方法としては、▲３▼のジハロカルボン酸エステルを用いる方法が好ましい。
【００４５】
本発明のフッ素系界面活性剤は、従来使用されてきたフッ素系界面活性剤と比較し、パーフルオロアルキル基の鎖長が短いものの、水及び／または有機溶媒への溶解性、並びに界面活性効果はほぼ同等であり、用途として特に制限されることはなく、広く使用することができる。また、本発明のフッ素系界面活性剤は、単独で用いても良いが２種類以上のフッ素系化合物（Ａ）を同時に用いても構わない。
【００４６】
本発明のフッ素系界面活性剤を添加剤として使用する組成物としては、例えば、印刷材料、感光性材料、写真材料、塗料、洗浄剤、光学材料、離型剤等の各種コーティング材料や成形材料等が挙げられる。
【００４７】
前記組成物は、溶媒、溶液等であり、溶液の場合、溶媒を必須成分として含有し、溶質として高分子化合物、低分子有機化合物、無機化合物から選ばれる１種類以上の化合物と、必要に応じて、後述する各種添加剤から構成される。
【００４８】
前記溶媒としては、水及び／または各種有機溶媒が挙げられ、例えば、メタノール、エタノ−ル、イソプロピルアルコ−ル、ｎ−ブタノ−ル、ｉｓｏ−ブタノ−ル、ｔｅｒｔ−ブタノ−ル等のアルコ−ル類、アセトン、メチルエチルケトン等の親水性のケトン類、ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン等の極性溶剤、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等の親水性のセロソルブ類、エチレングリコール、プロピレングリコ−ル等の親水性のグリコ−ル類、テトラヒドロフラン、ジオキサン等のエーテル類等が挙げれる。これらの溶媒は、１種類であっても２種類以上の混合溶媒系であっても良い。尚、ここでいう溶媒とは、系中で分散媒として働いているものも溶媒と称する。
【００４９】
前記溶質としては、水及び／または前記有機溶媒に溶解或いは分散するものが好ましく、例えば、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、セルロース、キチン、キトサン等の天然高分子等、ゼラチン等が挙げられる。これらの溶質は、１種類のみを用いても２種類以上を同時に用いても良い。
【００５０】
前記添加剤としては、例えば、シラン系、チタン系、ジルコ−アルミネート系等のカップリング剤、更にフッ素原子含有アルコキシシラン化合物、フッ素原子含有チタンアシレ−ト化合物、フッ素原子含有アルコキシジルコニウム化合物等のフッ素系カップリング剤、シリカ、酸化チタン、酸化亜鉛、酸化アルミニウム、酸化錫、酸化ジルコニウム、酸化カルシウム、炭酸カルシウム、ガラスフィラー等の無機粉末・充填材、高級脂肪酸、ポリ（フッ化ビニリデン）、ポリ（テトラフロロエチレン）、ポリエチレン、アクリルビーズ、カーボン等の有機微粉末、感光剤、増感剤、耐光性向上剤、耐候性向上剤、耐熱性向上剤、導電剤、酸化防止剤、防錆剤、レオロジーコントロール剤、増粘剤、沈降防止剤、消泡剤、防臭剤等の各種充填剤が挙げられる。これらの添加剤は、１種類のみを用いても２種類以上を同時に用いても良い。
【００５１】
また、本発明のフッ素系界面活性剤としては、必要に応じて、その他のフッ素系界面活性剤、シリコン系界面活性剤、炭化水素系界面活性剤等の種々の界面活性剤を自由な組み合わせで併用して前述の各種組成物に適用することもできる。その混合割合としては、特に制限されるものではなく、目的とする界面活性効果のレベル、適応する前述の各種組成物との相溶性等に応じて適宜選択されるものであるが、本発明のフッ素系化合物（Ａ）からなるフッ素系界面活性剤とその他の界面活性剤との重量比として、（フッ素系界面活性剤）／（その他の界面活性剤）が１／９９〜９９／１であることが好ましく、安定した充分な界面活性効果が得られる点から、前記重量比として８０／２０〜１０／９０であることが特に好ましく、５０／５０〜２０／８０であることが最も好ましい。
【００５２】
一般に、フッ素系界面活性剤は炭化水素系界面活性剤と併用することにより、界面活性剤を添加した組成物が接触する材料（例えば、塗布される場合、ガラス、鋼板やプラスチックフィルム、成形される場合には金型）に対する界面張力を低下させる働きが増し、さらには経済的な観点からも有効である。
【００５３】
前記炭化水素系界面活性剤としては、１分子中に親水性基と親油性基とを有する炭化水素系化合物からなり、通常、主に親水性基のイオン性により、アニオン、カチオン、ノニオン、ベタインタイプに分類される。本発明のフッ素系界面活性剤と併用することができる炭化水素系界面活性剤としては、何れのタイプも制限なく使用することができる。代表的なアニオン系界面活性剤としては、スルホン塩、リン酸塩、カルボン酸塩等が挙げられ、具体的には、花王株式会社製エマールシリーズ、ペレックスシリーズ等が例示される。また、カチオン系界面活性剤としては、オキソニウム塩、アンモニウム塩、ホスホニウム塩が挙げられ、具体的には花王株式会社製アセタミンシリーズ、コータミンシリーズが例示される。またノニオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル、ソルビタン脂肪酸エステル等が挙げられ、具体的には、花王株式会社製エマルゲンシリーズ、レオドールシリーズ等が例示される。またベタイン系界面活性剤として、アミノ酸塩、アミンオキシド等が挙げられ、具体的には、花王株式会社製アンヒトールシリーズ等が例示される。
【００５４】
前述の本発明のフッ素系界面活性剤を含む組成物は、種々の加工方法を適用することにより、優れた浸透・濡れ性およびレベリング性等が得られる。加工方法としては特に制限されるものではなく、例えば、グラビアコーター、ナイフコーター、ロールコーター、コンマコーター、スピンコーター、バーコーター、刷毛塗り、デイッピング塗布、スプレー塗布、静電塗装、スクリーン印刷等のコーティング方法・装置、インクジェット法、射出、押し出し、中空、圧縮、反応、真空、ＦＲＰ、熱、ロールシート、カレンダー、２軸延伸フィルム、積層、回転等の各種成形方法、各種金型、スタンパを用いた射出成形等が挙げられる。
【００５５】
また、前述の組成物の用途にも制限はなく、例えば、工業用および家庭用等の接着剤、耐擦傷性、滑り性、非粘着性、撥水撥油性、ガスバリア性、耐熱性、耐光性、耐候性、生理活性、耐水性、防湿性、防汚性、潤滑性等の表面機能性保護膜形成材料、衣料、家具、靴、雑貨等の繊維、人工皮革、合成皮革不織布等の処理剤、紙、フィルム、カード等の各種コーティング剤、自動車、建材、家電、医用材料、ＯＡ機器、電気・電子機器、光学部材、電線・配線材料、各種工業用部品等の成形材料、グリース、各種封止材料、離型剤、防錆剤、防曇剤、防霧剤、ブロッキング防止剤、ＰＳ版等の帯電防止剤、ＬＣＤ、ＬＳＩ、有機ＥＬ、プラズマディスプレイ製造用各種フォトレジスト等の感光性材料、ＬＳＩ製造用反射防止膜剤、ＬＣＤ、ＬＳＩ、有機ＥＬ、プラズマディスプレイ製造用洗浄剤、エッチング剤、剥離剤、現像液、乳剤等の写真材料、自動車、航空機、船舶、建材、家電用等の塗料、染料、洗浄剤、フロアポリッシュ、泡消火薬剤、メッキ浴ミスト防止剤、レンズシート、光ファイバ等の光学材料、または有機化学反応用分散媒等に好適に用いることができる。
【００５６】
【実施例】
次に本発明をより詳細に説明するために、実施例、試験例及び比較試験例を掲げる。
【００５７】
実施例１
▲１▼スルホン酸アルキルアミドの合成
攪拌装置、滴下管および還流冷却器を付した１０００ｍｌの四ツ口フラスコに、メチルアミン塩酸塩５４ｇ（０．８モル）、トリエチルアミン１２１．４ｇ（１．２モル）および酢酸エチル２５０ｇを仕込み、更に、滴下管に１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホニルフロリド１２０．８ｇ（０．４モル）を入れた。窒素雰囲気下、２５℃で攪拌しながら、２０分かけて、１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホニルフロリドを滴下した。滴下終了後、更に３時間２５℃で攪拌した。攪拌終了後、固形分をろ過によって取り除いた後、ろ液を蒸留して溶媒を取り除き、更に温度を上げて蒸留を行い、留分として、１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホン酸メチルアミド［スルホン酸アルキルアミド（１−▲１▼）］１１０．５ｇを得た。
【００５８】
▲２▼エステルの合成
攪拌装置および還流冷却器を付した５００ｍｌの四ツ口フラスコに、▲１▼で得られたスルホン酸アルキルアミド（１−▲１▼）５４ｇ（０．１７２モル）、炭酸水素ナトリウム１４．４ｇ（０．１７２モル）、アセトン８０ｇ及びイオン交換水５０ｇを仕込み、更に、滴下管にアセトン４０ｇに溶解させた２，３−ジブロモ−プロピオン酸エチルエステル２２．２ｇ（０．０８５モル）を入れた。フラスコ内を６０℃に加温した後、１５分かけて滴下管より２，３−ジブロモ−プロピオン酸エチルエステルのアセトン溶液を滴下した。更に窒素雰囲気下、６０℃で４時間攪拌した。攪拌終了後、室温に冷却し、反応液にイオン交換水１００ｇおよび酢酸エチル２００ｇを加えた。有機層を分離した後、蒸留によって溶媒を取り除き、更に蒸留を行い、留分として、２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸エチルエステル［エステル（１−▲２▼）］５５ｇを得た。
【００５９】
▲３▼ケン化反応
攪拌装置および還流冷却器を付した３００ｍｌの四ツ口フラスコに、エステル（１−▲２▼）４８ｇ（０．０６６モル）、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）、イソプロパノール６０ｇおよびイオン交換水４０ｇを加えた後、６０℃で１時間攪拌しケン化反応を行った。次いで、減圧下で溶媒を留去し乾燥することにより、フッ素系化合物（１−▲３▼）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸リチウム塩４６．６ｇを得た。
【００６０】
実施例２
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、水酸化ナトリウム２．６ｇ（０．０６６モル）を用いた以外は実施例１と同様にして、フッ素系化合物（２−▲３▼）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸ナトリウム塩４６．５ｇを得た。
【００６１】
実施例３
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、水酸化カリウム３．７ｇ（０．０６６モル）を用いた以外は実施例１と同様にして、フッ素系化合物（３−▲３▼）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸カリウム塩４９ｇを得た。
【００６２】
実施例４
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、２５重量％アンモニア水９ｇ（０．１３２モル）を用いた以外は実施例１と同様にして、フッ素系化合物（４−▲３▼）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸アンモニウム塩４７ｇを得た。
【００６３】
実施例５
▲２▼エステルの合成において、２，３−ジブロモ−プロピオン酸エチルエステル２２．２ｇ（０．０８５モル）の代わりに、３−クロロ−２−クロロメチル−プロピオン酸エチルエステル２３．３ｇ（０．０８５モル）を用いた以外は実施例１−▲１▼、１−▲２▼と同様にして、３−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−２−｛［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］メチル｝−プロピオン酸エチルエステル［エステル（５−▲２▼）］５８．６ｇを得た。次いで、▲３▼ケン化反応において、エステル（１−▲２▼）４８ｇ（０．０６６モル）の代わりに、エステル（５−▲２▼）４７．８ｇ（０．０６６モル）を用いた以外は実施例１−▲３▼と同様にして、フッ素系化合物（５−▲３▼）３−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−２−｛［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］メチル｝−プロピオン酸リチウム塩４５．９ｇを得た。
【００６４】
実施例６
▲１▼スルホン酸アルキルアミドの合成
１，１，２，２，３，３，４，４，４−ノナフルオロブタン−１−スルホニルフロリド１２０．８ｇ（０．４モル）の代わりに１，１，２，２，３，３，４，４，５，５，６，６，６−トリデカフルオロヘキサン−１−スルホニルフロリド１６０．８ｇ（０．４モル）用いた以外は実施例１−▲１▼と同様にして、１，１，２，２，３，３，４，４，５，５，６，６，６−トリデカフルオロヘキサン−１−スルホン酸メチルアミド［スルホン酸アルキルアミド（６−▲１▼）］１５９．５ｇを得た。
【００６５】
▲２▼エステルの合成
スルホン酸アルキルアミド（１−▲１▼）５４ｇ（０．１７２モル）の代わりにスルホン酸アルキルアミド（６−▲１▼）７１．１ｇ（０．１７２モル）を用いた以外は実施例１−▲２▼と同様にして２，３−ビス−［メチル−（トリデカフルオロヘキサン−１−スルホニル）−アミノ］−プロピオン酸エチルエステル［エステル（６−▲２▼）］７５．５ｇを得た。
【００６６】
▲３▼ケン化反応
エステル（１−▲２▼）４８ｇ（０．０６６モル）の代わりに、エステル（６−▲２▼）６０．１ｇ（０．０６６モル）を用いた以外は実施例１−▲３▼と同様にしてフッ素系化合物（６−▲３▼）２，３−ビス−［メチル−（トリデカフルオロヘキサン−１−スルホニル）−アミノ］−プロピオン酸リチウム塩５８．２ｇを得た。
【００６７】
実施例７
▲１▼スルホン酸アルキルアミドの合成
攪拌装置、滴下管および還流冷却器を付した１０００ｍｌの四ツ口フラスコに、メチルアミン塩酸塩５４ｇ（０．８モル）、トリエチルアミン１２１．４ｇ（１．２モル）および酢酸エチル１５０ｇを仕込み、更に、滴下管に酢酸エチル１５０ｇに溶解させた３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−スルホニルクロライド１３９．８ｇ（０．４モル）を入れた。窒素雰囲気下、２５℃で攪拌しながら、２０分かけて、３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−スルホニルクロライドの酢酸エチル溶液を滴下した。滴下終了後、更に２時間攪拌した。攪拌終了後、固形分をろ過によって取り除いた後、ろ液を蒸留して溶媒を取り除き、更に温度を上げて蒸留を行い、留分として、３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−１−スルホニックアシッドメチルアミド［スルホン酸アルキルアミド（７−▲１▼）］１３０．３ｇを得た。
【００６８】
▲２▼エステルの合成
攪拌装置および還流冷却器を付した５００ｍｌの四ツ口フラスコに、▲１▼で得られたスルホン酸アルキルアミド（７−▲１▼）５８．７ｇ（０．１７２モル）、炭酸水素ナトリウム１４．４ｇ（０．１７２モル）、アセトン８０ｇ及びイオン交換水５０ｇを仕込み、更に、滴下管に、アセトン４０ｇに溶解させた２，３−ジブロモ−プロピオン酸エチルエステル２２．２ｇ（０．０８５モル）を入れた。フラスコを５０℃に加温した後、１５分かけて２，３−ジブロモ−プロピオン酸エチルエステルのアセトン溶液を滴下管より滴下し、更に窒素雰囲気下、５０℃で２時間攪拌した。攪拌終了後、室温に冷却し、反応液にイオン交換水１００ｇおよび酢酸エチル２００ｇを加えた。有機層を分離した後、蒸留によって溶媒を取り除き、更に蒸留を行い留分として、２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドエチルエステル［エステル（７−▲２▼）］６２．４ｇを得た。
【００６９】
▲３▼ケン化反応
攪拌装置および還流冷却器を付した３００ｍｌの四ツ口フラスコに、エステル（７−▲２▼）５０．６ｇ（０．０６６モル）、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）、イソプロパノール６０ｇおよびイオン交換水４０ｇを加えた後、６０℃で１時間攪拌しケン化反応を行った。次いで、減圧下で溶媒を留去し乾燥することにより、フッ素系化合物（７−▲３▼）２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，６−ノナフルオロ−ヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドリチウム塩４８．２ｇを得た。
【００７０】
実施例８
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、水酸化ナトリウム２．６ｇ（０．０６６モル）を用いた以外は実施例７と同様にして、フッ素系化合物（８−▲３▼）２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドナトリウム塩４８．７ｇを得た。
【００７１】
実施例９
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、水酸化カリウム３．７ｇ（０．０６６モル）を用いた以外は実施例７と同様にして、フッ素系化合物（８−▲３▼）２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドカリウム塩５０．３ｇを得た。
【００７２】
実施例１０
▲３▼ケン化反応において、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）の代わりに、２５重量％アンモニア水９ｇ（０．１３２モル）を用いた以外は実施例７と同様にして、フッ素系化合物（１０−▲３▼）２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，６−ノナフルオロ−ヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドアンモニウム塩４８．９ｇを得た。
【００７３】
実施例１１
▲２▼エステルの合成において、２，３−ジブロモ−プロピオン酸エチルエステル２２．２ｇ（０．０８５モル）の代わりに、３−クロロ−２−クロロメチル−プロピオン酸エチルエステル２３．３ｇ（０．０８５モル）を用いた以外は実施例１−▲１▼、１−▲２▼と同様にして、２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン−１−スルホニル）−アミノ］−プロピオニックアシッドエチルエステル［エステル（１１−▲２▼）］６０．７ｇを得た。次いで、▲３▼ケン化反応において、エステル（１−▲２▼）４８ｇ（０．０６６モル）の代わりに、エステル（１１−▲２▼）４７．８ｇ（０．０６６モル）を用いた以外は実施例１−▲３▼と同様にして、フッ素系化合物（１１−▲３▼）２，３−ビス−［メチル−（３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン−１−スルホニル）−アミノ］−プロピオニックアシッドリチウム塩４６．２ｇを得た。
【００７４】
実施例１２
▲１▼スルホン酸アルキルアミドの合成
３，３，４，４，５，５，６，６，６−ノナフルオロヘキサン−スルホニルクロライド１３９．８ｇ（０．４ｍｏｌ）の代わりに３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン−スルホニルクロライド１７９．８ｇ（０．４モル）を用いた以外は実施例７−▲１▼と同様にして、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクタン−１−スルホニックアシッドエチルアミド［スルホン酸アルキルアミド（１２−▲１▼）］１７４．６ｇを得た。
【００７５】
▲２▼エステルの合成
スルホン酸アルキルアミド（７−▲１▼）５８．７ｇ（０．１７２モル）の代わりにスルホン酸アルキルアミド（１２−▲１▼）７５．９ｇ（０．１７２モル）を用いた以外は実施例７−▲２▼と同様にして、２，３−ビス−　［メチル−（トリデカフルオロヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドエチルエステル［エステル（１２−▲２▼）］８０．１ｇを得た。
【００７６】
▲３▼ケン化反応
エステル（７−▲２▼）５０．６ｇ（０．０６６モル）の代わりに、エステル（１２−▲２▼）６３．８ｇ（０．０６６モル）を用いた以外は実施例７−▲３▼と同様にしてフッ素系化合物（１２−▲３▼）２，３−ビス−［メチル−（トリデカフルオロヘキサン−１−スルホニル）−アミノ］−プロピオニックアシッドリチウム塩６２．２ｇを得た。
【００７７】
実施例１３
攪拌装置および還流冷却器を付した５００ｍｌの四ツ口フラスコに、実施例１で得られたスルホン酸アルキルアミド（１−▲１▼）５４ｇ（０．１７２ｍｏｌ）、炭酸水素ナトリウム１４．４ｇ（０．１７２ｍｏｌ）、アセトン１１０ｇ及びイオン交換水５０ｇを仕込み、更に、滴下管にイオン交換水６０ｇに溶解させた２，３−ジブロモ−プロピオン酸リチウム塩２０．２ｇ（０．０８５モル）を入れた。フラスコ内を６０℃に加温した後、２０分かけて滴下管より２，３−ジブロモ−プロピオン酸リチウム塩水溶液を滴下した。更に窒素雰囲気下、６０℃で４時間攪拌した。攪拌終了後、反応液を濃縮し、送風により乾固させた。得られた固体をイオン交換水３０ｇで洗浄した後、乾燥させることによりフッ素系化合物（１３）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸リチウム塩４６．４ｇを得た。
【００７８】
実施例１４
▲１▼カルボン酸の合成
攪拌装置および還流冷却器を付した５００ｍｌの四ツ口フラスコに、▲１▼で得られたスルホン酸アルキルアミド（１−▲１▼）５４ｇ（０．１７２モル）、炭酸水素ナトリウム１４．４ｇ（０．１７２モル）、アセトン１１０ｇ及びイオン交換水９０ｇを仕込み、更に、滴下管にイオン交換水６０ｇに溶解させた２，３−ジブロモ−プロピオン酸１９．６ｇ（０．０８５モル）を入れた。フラスコ内を６０℃加温した後、２０分かけて滴下管より２，３−ジブロモ−プロピオン酸水溶液を滴下した。更に窒素雰囲気下、６０℃で４時間攪拌した。攪拌終了後、反応液を濃縮し、送風により乾固させた。得られた固体をイオン交換水３０ｇで洗浄した後、乾燥させることにより２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸［カルボン酸−１５］５６．９ｇを得た。
▲２▼中和反応
攪拌装置および還流冷却器を付した３００ｍｌの四ツ口フラスコに、カルボン酸−１５　４５ｇ（０．０６６モル）、水酸化リチウム・一水和物２．８ｇ（０．０６６モル）、イソプロパノール６０ｇおよびイオン交換水４０ｇを加えた後、６０℃で１時間攪拌した。反応終了後、減圧下で溶媒を留去し乾燥することにより、フッ素系化合物（１４）２，３−ビス−［メチル−（ノナフルオロブタン−１−スルホニル）−アミノ］−プロピオン酸リチウム塩４５．４ｇを得た。
【００７９】
試験例１〜１４および比較試験例１
実施例１〜１４で得られたフッ素系化合物からなるフッ素系界面活性剤の水溶解度と表面張力を以下の方法で測定し試験例１〜１４として表１及び表２に示す。
【００８０】
試験方法
水溶解度：２５℃においてイオン交換水で攪拌、目視で濁りのないクリアーな状態を完溶とした。（単位：重量％）
表面張力：自動表面張力計ＣＢＰＶ−Ｚ（協和界面化学株式会社製）を用いて、ウィルヘルミー白金プレート法にて、２０℃における各濃度（イオン交換水溶液）での表面張力を測定した。（単位：ｍＮ／ｍ）
【００８１】
また、比較試験例１として、大日本インキ化学工業株式会社製のメガファックＦ−１２０（Ｃ_８Ｆ_１７ＳＯ_２Ｎ（ＣＨ_２ＣＨ_２ＣＨ_３）ＣＨ_２ＣＯＯＫ）の水溶解度並びに水溶液での表面張力を測定した。その結果を表１、表２に示す。
【００８２】
【表１】

【００８３】
【表２】

【００８４】
本発明のフッ素系化合物からなるフッ素系界面活性剤を用いた試験例１〜１４では、化合物中のパーフルオロアルキル基の炭素数が６以下と短いものでありながら、従来使用されてきた炭素数８のパーフルオロアルキル基を持つ化合物からなる比較例１のフッ素系界面活性剤と、水への溶解度並びに表面張力低下作用がほぼ同様の性能であることを確認した。
【００８５】
試験例１５、１６、比較試験例２、３
実施例１で得られたフッ素系化合物１−▲３▼及び従来品のメガファックＦ−１２０を用いて、メタノール（試験例１５、比較試験例２）、及びイオン交換水／メタノール＝１／１（重量比）混合溶媒（試験例１６、比較試験例３）における溶解度、並びに表面張力を測定した。これらの結果を表３に示す。
【００８６】
【表３】

【００８７】
本発明のフッ素系化合物からなるフッ素界面活性剤は、水のみならず、親水性有機溶剤に対しても従来品とほぼ同様の界面活性効果を発現しうることを確認した。
【００８８】
試験例１７、１８
実施例１で得られたフッ素系化合物（１−▲３▼）を用いて、炭化水素系界面活性剤との併用効果を確認した。フッ素系化合物（１−▲３▼）と炭化水素系界面活性剤（ポリオキシエチレンオレイルエーテル：花王株式会社製エマルゲン４３０）との混合物の０．００１重量％水溶液における表面張力を測定し、試験例１７、１８として結果を表４に示す。
【００８９】
【表４】

【００９０】
本発明のフッ素系化合物からなるフッ素系界面活性剤は、その他の界面活性剤との併用においても優れた界面活性効果を発現することを確認した。
【００９１】
【発明の効果】
本発明によれば、主に印刷材料、感光性材料、写真材料、塗料、洗浄剤、光学材料、離型剤等の各種コーティング材料や成形材料等に使用され、浸透・濡れ性、レベリング性、表面機能性等を高めるための添加剤として好適に用いることができ、且つ一般的に安全性が高いと認識されている化合物中のパーフルオロアルキル基の炭素数が６以下の短い化合物からなるフッ素系界面活性剤を提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is mainly soluble in various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, mold release agents, etc., easily penetrates and wets, leveling properties, The present invention relates to a fluorine-based surfactant that can be suitably used as an additive for enhancing surface functionality and the like.
[0002]
[Prior art]
Fluorosurfactants are additives that have a high surface tension lowering ability and achieve excellent penetration / wetting properties, leveling properties, surface functionality, etc. when mixed with coating compositions and molding compositions. There have been proposed various fluorine-based surfactants.
[0003]
Generally, a fluorine-based surfactant has an affinity for a perfluoroalkyl (Rf) group for realizing a surface tension lowering function and various compositions such as a coating material and a molding material using the activator as an additive. It is composed of a compound having an amphiphilic group contributing to the property in the same molecule.
[0004]
For example, C ₈ F ₁₇ SO ₂ N (R) (CH ₂ ) _n A compound represented by COOM (wherein R is hydrogen or an alkyl group having 1 to 12 carbon atoms, n is an integer of 1 to 4, and M is H, Na, K, or Li), It has excellent surface active effects and water solubility, and has been widely used for plating and various coating applications (for example, see Patent Document 1).
[0005]
However, in recent years, fluorinated compounds having a perfluoroalkyl group having 7 or more carbon atoms cause inhibition of intercellular communication which is thought to contribute to carcinogenicity in in vitro tests using cell lines. In addition, this inhibition is determined not by the functional group but by the length of the fluorinated carbon chain, and it has been found that the longer the fluorinated carbon chain, the higher the inhibitory power (see, for example, Non-Patent Document 1). The use of fluorine-based surfactants consisting of
[0006]
On the other hand, in general, a fluorine-based surfactant comprising a compound having a small number of carbon atoms in a perfluoroalkyl group does not have a sufficient surface-active effect. Therefore, it has a surfactant effect equal to or higher than that of the conventionally used fluorine-based surfactant, and generally has a perfluoroalkyl group in a compound that is recognized as having high safety, because the number of carbon atoms is short. There is a strong demand for such fluorine-based surfactants.
[0007]
[Patent Document 1]
U.S. Pat. No. 2,809,990 (pages 1-3)
[Non-patent document 1]
Brad L. UPAM, Nestor D. DEOCAMPO, Beth WURL and James E.A. TROSKO "Inhibition of Gap Junctional Intercellular Communication by Perfluorinated Fatty Acids is Dependent on the International Union of the United States of the Republic of the United States." 78, p491-495 (Pages 1-3, Figure 5)
[0008]
[Problems to be solved by the invention]
In view of the above circumstances, the object of the present invention is mainly used for various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, release agents, Fluorinated surfactant which can be suitably used as an additive for enhancing penetration / wetting properties, leveling properties, surface functionality, etc., and which comprises a short compound having a perfluoroalkyl group having 6 or less carbon atoms in the compound. Is to provide.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, the number of carbon atoms of the perfluoroalkyl group in the fluorine-based compound having the following specific structure is as short as 6 or less. The present inventors have found that such a fluorine-based surfactant does not impair the surfactant effect of the conventional fluorine-based surfactant, and completed the present invention.
[0010]
That is, the present invention provides 2 to 4 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR- (where m is 2 or 3, n is an integer of 0 to 2 and R is an alkyl group), and -COOM (where M is hydrogen, ammonium or an alkali metal) The present invention provides a fluorine-based surfactant comprising a fluorine-containing compound having the formula (1):
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The surfactant effect according to the present invention includes various surfactant effects, for example, wettability, permeability, anti-repellent property, leveling property, uniformity / homogeneity of a coating film, and surface modification in coating and molding applications. And the like.
[0012]
The fluorine-based surfactant of the present invention contains 2 to 4 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR- (where m is 2 or 3; n is an integer of 0 to 2; R is an alkyl group) and -COOM (where M is hydrogen, ammonium or an alkali metal). ), And the structure is not particularly limited.
[0013]
F (CF) in the fluorine compound (A) ₂ ) _2m (CH ₂ ) _n SO ₂ NR- is an indispensable segment for obtaining excellent surface active effects. The chain length of the group is appropriately selected depending on the application when used as a surfactant, the composition of a composition such as a coating material or a molding material mixed with the additive as an additive, the level of a desired surfactant effect, and the like. However, when m is 1, the resulting fluorine-based compound has insufficient surface active effect, and when m is 4 or more, the number of fluorinated carbon atoms in the perfluoroalkyl group becomes 8 or more. Therefore, it is necessary to set the number to 2 or 3 because it is concerned about safety. When n is 3 or more, a practical surface-active effect cannot be obtained, and therefore it is essential that n be an integer of 0 to 2.
[0014]
Further, -COOM (where M is hydrogen, ammonium or an alkali metal) of the fluorine-based compound (A) is a hydrophilic group, and M in the group is hydrogen of a carboxylic acid or a carboxylic acid amine salt. It represents an alkali metal of ammonium or a carboxylic acid alkali metal salt, for example, as a hydrophilic group, -COOH, -COONH ₄ , -COOLi, -COONa, and -COOK.
[0015]
As the fluorine-based compound (A), F (CF) ₂ ) _2m (CH ₂ ) _n SO ₂ Those having two NR- in one molecule are preferable, and examples thereof include those represented by the following general formula (1).
｛F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR (CH ₂ ) _o ｝ ｛F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR (CH ₂ ) _p ｝ CH (CH ₂ ) _q COOM (1) (wherein, m is 2 or 3, n is an integer of 0 to 2, o is an integer of 1 to 10, p is an integer of 0 to 10, and q is 0 to 0. An integer of 10, R is an alkyl group, and M is hydrogen, ammonium or an alkali metal.)
[0016]
Among these, n in the general formula (1) is preferably 0 or 2 from the viewpoint that a fluorine-based compound having a practical surfactant effect can be obtained and the production is easy. R is a substituent of the amide nitrogen, and is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, since a fluorine-based compound having a practical surface-active effect can be obtained.
[0017]
In the general formula (1), o is preferably an integer of 1 to 4, and is preferably an integer of 1 to 4 because a fluorine-based compound having excellent surface active effect and affinity with various compositions to be added can be obtained. Or 2 is particularly preferred. p and q are preferably integers of 0 to 4 and are integers of 0 to 2 since a fluorine-based compound having excellent surface active effects and affinity with various compositions to be added is obtained. Is particularly preferred.
[0018]
In the general formula (1), -COOM (where M is hydrogen, ammonium or an alkali metal) is a hydrophilic group, and examples of the ammonium include ammonia, diethylamine, triethylamine, and n-propylamine. , Iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine, propanolamine, toluidine, ammonium derived from pyridine and the like. Examples of the metal include Li, Na, K, and Rb. Among them, a fluorine-based compound having a practical surface-active effect can be obtained and the production is easy, so that NH ₄ , Li, Na and K are preferred, and Li, Na and K are particularly preferred.
[0019]
Specific examples of the fluorine-based compound used for the fluorine-based surfactant of the present invention include the following compounds.
[0020]
Embedded image

The present invention is, of course, not limited by these specific examples.
[0021]
The method for producing the fluorine-based compound represented by the general formula (1) is not particularly limited, and examples thereof include the following methods (1) to (3).
(1) The following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (2)
Wherein m is 2 or 3, n is an integer of 0 to 2, and X ₁ Is halogen. )
Is reacted with a perfluoroalkylsulfonyl halide (B) represented by the formula (1) to react with an alkylamine (dehydrohalogenation reaction) to form a perfluoroalkylsulfonic acid alkylamide, and then reacted with a dihalocarboxylic acid or a dihalocarboxylic acid salt (dehydrohalogenation). Reaction).
{Circle around (2)} A perfluoroalkylsulfonyl halide (B) represented by the general formula (2) is reacted with an alkylamine (dehydrohalogenation reaction) to give a perfluoroalkylsulfonic acid alkylamide, and then a dihalocarboxylic acid is reacted. (Dehydrohalogenation reaction), followed by neutralization.
{Circle around (3)} A perfluoroalkylsulfonyl halide (B) represented by the general formula (2) is reacted with an alkylamine (dehydrohalogenation reaction) to give a perfluoroalkylsulfonic acid alkylamide, and then a dihalocarboxylic acid ester is added. A production method of reacting (dehydrohalogenation reaction) and further saponifying.
[0022]
First, the manufacturing method (1) will be described in detail.
As the perfluoroalkylsulfonyl halide (B) represented by the general formula (2), a fluorine-based compound having a high surface active effect and having 6 or less carbon atoms in the perfluoroalkyl group can be obtained. It is preferable that m in (2) is 2 or 3, and n is 0 or 2, and specifically, 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl Chloride, 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl bromide, 3,3,4,4,5,5,6,6,7,7,8,8, 8-tridecafluorooctanesulfonyl chloride, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanesulfonyl bromide, 1,1,2,2 3,3,4,4,4-nonafluorobuta -1-sulfonyl fluoride, 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride. 3,3,4,4,5,5,6,6,6-nonafluorohexanesulfonyl chloride, 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctanesulfonyl chloride, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride, 1,1,2,2,3,3,4,4 , 5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride are particularly preferred.
[0023]
Examples of the alkylamine reacted with the perfluoroalkylsulfonyl halide (B) represented by the general formula (2) include, for example, the following general formula (3)
RNH ₂ (3)
(In the formula, R is an alkyl group.)
R is preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, since a fluorine compound having a high surface active effect can be obtained. For example, methylamine, ethylamine, propylamine, butylamine and the like can be mentioned. When methylamine or ethylamine is used, a free amine gas may be used, but it is preferable to use a hydrochloride salt which is easy to handle.
[0024]
The amount of the alkylamine to be used is 1.8 to 7.0 mol, preferably 2.0 to 4.0 mol, per 1 mol of the perfluoroalkylsulfonyl halide (B). In addition, a base is preferably used to remove hydrogen halide by-produced in the reaction, and as the base, any of an inorganic base and an organic base can be used. Examples of the inorganic base include potassium hydroxide, sodium hydroxide, and lithium hydroxide. Examples of the organic base include pyridine and triethylamine. The amount of the base to be used is 0.8 to 4.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of the alkylamine used. The reaction can be performed without a solvent or in an organic solvent, but a method in which the reaction is performed in an organic solvent is preferable because the operation is easy and the safety is high.
[0025]
The organic solvent is not particularly limited as long as it is inert to the raw material perfluoroalkylsulfonyl halide (B) and the alkylamine represented by the general formula (2) and can dissolve both. However, for example, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and the like, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, and halogenated hydrocarbons such as chlorobenzene, orthodichlorobenzene and paradichlorobenzene Aromatic hydrocarbons, aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane, cyclohexane, ethers such as tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethyl acetate, acetic acid Chill, esters such as propyl acetate. Among these, halogenated hydrocarbons, ethers, esters are preferable, ethers, esters are particularly preferred. These solvents may be used singly or as a mixture of two or more.
[0026]
The reaction conditions for the reaction are not particularly limited. However, since the reaction time is short and the by-product hydrogen halide is easily removed, perfluoroalkylsulfonyl halide (B) or a solution obtained by dissolving the same in the solvent is used. , An alkylamine or a method in which it is dropped into a solution obtained by dissolving the same in the solvent. The reaction temperature is not limited, but there is no problem if the dehydrohalogenation reaction occurs efficiently, and it is usually 5 to 80 ° C, preferably 10 to 50 ° C. The reaction time is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. There is no limitation on the reaction atmosphere, but N is used to suppress oxidation of the alkylamine used. ₂ In an atmosphere of an inert gas such as He, Ar, or the like.
[0027]
Next, the reaction of the perfluoroalkylsulfonyl halide (B) with the alkylamine obtained by the reaction of the alkylamine with the dihalocarboxylic acid or dihalocarboxylate will be described.
[0028]
As the dihalocarboxylic acid used here, for example, the following general formula (4)
(X ₂ (CH ₂ ) _o ) (X ₂ (CH ₂ ) _p ) CH (CH ₂ ) _q COOH (4)
(Where X ₂ Is a halogen, o is an integer of 1 to 10, p is an integer of 0 to 10, and q is an integer of 0 to 10. )
And a dihalocarboxylic acid salt represented by the following general formula (5):
(X ₃ (CH ₂ ) _o ) (X ₃ (CH ₂ ) _p ) CH (CH ₂ ) _q COOM ₁ (5)
(Where X ₃ Is a halogen, o is an integer of 1 to 10, p is an integer of 0 to 10, q is an integer of 0 to 10, M ₁ Is ammonium or an alkali metal. )
And a dihalocarboxylate (E) represented by the formula: Of these, o in the above general formulas (4) and (5) is preferably an integer of 1 to 4, and particularly preferably 1 or 2, since a fluorine-based compound having an excellent surfactant effect can be obtained. Preferably, p and q are each an integer of 0 to 4, and particularly preferably 0 to 2 in order to obtain a fluorine-based compound having an excellent surfactant effect.
[0029]
Examples of the dihalocarboxylate include amine salts such as ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, and monoamine. Examples thereof include amine salts derived from ethanolamine, diethanolamine, propanolamine, toluidine, pyridine, and the like. As the metal salt, an alkali metal salt is preferable, and a Li salt, a Na salt, and a K salt are preferable. Amine salts derived from ammonia, and Li salts, Na salts, and K salts of alkali metal salts are preferred because of their excellent surface active effects and particularly easy production.
[0030]
Examples of the dihalocarboxylic acid and dihalocarboxylic acid salt include, for example, 2,3-dichloro-propionic acid, 4-chloro-3-chloromethyl-butylic acid, 3,4-dichloro-butylic acid, and 3-chloro-acid. 2-chloromethyl-1-propionic acid, 2,4-dichloro-butylic acid, 6-chloro-4- (2-chloroethyl) -hexanoic acid, 4,6-dichloro-hexanoic acid, 4-chloro-2- (2-chloroethyl) butyric acid, 2,3-dibromo-propionic acid, 4-bromo-3-bromomethyl-butyric acid, 3,4-dibromo-butyric acid, 3- Bromo-2-bromomethyl-1-propionic acid, 2,4-dibromo-butylic acid , 6-bromo-4- (2-bromoethyl) -hexanoic acid, 4,6-dibromo-hexanoic acid, 4-bromo-2- (2-bromoethyl) butyric acid, and the like, and the like. Amine salts or alkali metal salts are mentioned.
[0031]
Among these, 2,3-dichloro-propionic acid, 4-chloro-3-chloromethyl-butylic acid, 3-chloro-2-chloromethyl-1-propionic acid, 2,4-dichloro-acid Butyric acid, 2,3-dibromo-propionic acid, 4-bromo-3-bromomethyl-butyric acid, 3-bromo-2-bromomethyl-1-propionic acid, 2,4-dibromo-butyric Acids and their amine salts or alkali metal salts are preferred, and 2,3-dichloro-propionic acid, 3-chloro-2-chloromethyl-1-propionic acid, and 2,3-dibromo-propionic acid are preferred. , 3-bromo-2-bromomethyl-1-propionic acid, 2,3-dichloro-propionic Acid ammonium, 3-chloro-2-chloromethyl-1-propionic acid ammonium, 2,3-dibromo-propionic acid ammonium, 3-bromo-2-bromomethyl-1-propionic acid ammonium, 2 , 3-Dichloro-propionic acid Li salt, 3-chloro-2-chloromethyl-1-propionic acid Li salt, 2,3-dibromo-propionic acid Li salt, 3-bromo-2-bromomethyl -1-propionic acid Li salt, 2,3-dichloro-propionic acid Na salt, 3-chloro-2-chloromethyl-1-propionic acid Na salt, 2,3-dibromo-propionic Acid Na salt, 3-bromo-2-bromomethyl-1-propionic acid N Salt, 2,3-dichloro-propionic acid K salt, 3-chloro-2-chloromethyl-1-propionic acid K salt, 2,3-dibromo-propionic acid K salt, 3-bromo- 2-bromomethyl-1-propionic acid K salt is particularly preferred.
[0032]
The amount of the perfluoroalkylsulfonic acid alkylamide to be used is 1.8 to 7.0 mol, preferably 2.0 to 4.0 mol, per 1 mol of the dihalocarboxylic acid or dihalocarboxylic acid salt. Since this reaction is a dehydrohalogenation reaction similarly to the synthesis reaction of perfluoroalkylsulfonic acid alkylamide, it is preferable to use the above-described base to remove by-product hydrogen halide. The amount of the base to be used is 0.8 to 4.0 mol, preferably 0.9 to 2.0 mol, per 1 mol of the perfluoroalkylsulfonic acid alkylamide. In addition, this reaction can be carried out without a solvent or in an organic solvent, but a method in which the reaction is carried out in an organic solvent is preferable because the operation is easy and the safety is high.
[0033]
The organic solvent is not particularly limited as long as it is inert to perfluoroalkylsulfonic acid alkylamide and dihalocarboxylic acid or dihalocarboxylic acid salt, and can dissolve both of them. Ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, chlorobenzene, orthodichlorobenzene and paradichlorobenzene Halogenated aromatic hydrocarbons such as n-pentane, n-hexane, n-octane, cyclohexane and other aliphatic hydrocarbons, tetrahydrofuran, diisopropyl ether, ethylene glycol diethyl ether, diethyl Ethers such as ethylene glycol diethyl ether, esters such as ethyl acetate, butyl acetate and propyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. Among these, ketones, halogenated hydrocarbons and ethers , Esters, dimethylformamide, dimethylacetamide and dimethylsulfoxide are preferred, and ketones, ethers, esters, dimethylformamide and dimethylsulfoxide are particularly preferred. These solvents may be used singly or as a mixture of two or more.
[0034]
The reaction conditions of the perfluoroalkylsulfonic acid alkylamide with the dihalocarboxylic acid or dihalocarboxylic acid salt are not particularly limited, but the reaction time is short, and the removal of by-produced hydrogen halide is easy. It is preferable to drop the acid alkylamide or a solution obtained by dissolving the same in the above-mentioned solvent into a dihalocarboxylic acid or a dihalocarboxylic acid salt alone or a solution obtained by dissolving the same in the solvent. The reaction temperature is not limited, but there is no problem if the dehydrohalogenation reaction occurs efficiently, and it is usually 10 to 150 ° C, preferably 30 to 100 ° C. The reaction time is not limited, and is usually 0.5 to 10 hours, preferably 1 to 5 hours. The reaction atmosphere is not limited. ₂ In an atmosphere of an inert gas such as He, Ar, or the like.
[0035]
The fluorine-based compound represented by the general formula (1) obtained by the above-mentioned production method can be used in an unpurified state depending on the use and purpose. However, distillation, washing with a solvent, recrystallization, various types of chromatography, and adsorption It is also possible to purify with an agent or the like.
[0036]
Next, the method (2) will be described.
The method of reacting a perfluoroalkylsulfonyl halide (B) represented by the general formula (2) with an alkylamine to form a perfluoroalkylsulfonic acid alkylamide and further reacting with a dihalocarboxylic acid is described in the above-mentioned (1). Same as the method.
[0037]
Examples of the neutralizing agent for neutralizing the reaction product of the perfluoroalkylsulfonic acid alkylamide and dihalocarboxylic acid obtained by the above-mentioned method include alkali metal hydroxides such as lithium hydroxide and alkali halides such as lithium chloride. Examples thereof include metals, ammonia, amines such as trimethylamine, triethylamine, and pyridine. The amount of the neutralizing agent to be used is 1 to 5 mol, preferably 1 to 2.5 mol, per 1 mol of the compound before neutralization.
[0038]
The reaction conditions for the neutralization reaction are not particularly limited, and examples of the reaction solvent include water alone or a mixed solvent of water and an alcohol such as methanol, ethanol, or isopropanol. Further, the reaction temperature is preferably 5 to 50C, particularly preferably 10 to 30C.
[0039]
Next, the method (3) will be described.
The method of reacting a perfluoroalkylsulfonyl halide (B) represented by the general formula (2) with an alkylamine to form a perfluoroalkylsulfonic acid alkylamide and further reacting with a dihalocarboxylic acid ester is described in the above-mentioned (1). In the same manner as in the production method, a dihalocarboxylic acid ester may be used instead of dihalocarboxylic acid or dihalocarboxylic acid salt.
[0040]
As the dihalocarboxylic acid ester used here, for example, the following general formula (6)
(X ₄ (CH ₂ ) _o ) (X ₄ (CH ₂ ) _p ) CH (CH ₂ ) _q COOR ₁ (6)
(Where X ₄ Is a halogen, o is an integer of 1 to 10, p is an integer of 0 to 10, q is an integer of 0 to 10, R ₁ Is an alkyl group. )
O is preferably an integer of 1 to 4, and is particularly preferably 1 or 2, since a dihalocarboxylic acid ester (E) represented by Further, p and q are preferably integers of 0 to 4, particularly preferably integers of 0 to 2, since a fluorine-based compound excellent in surface active effect can be obtained. ₁ Is preferably an alkyl group having 1 to 7 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.
[0041]
Of these, esters of the dihalocarboxylic acid (D) represented by the general formula (4) are preferable, and 2,3-dichloro-propionic acid methyl ester, 2,3-dichloro-propionic acid ethyl ester, and 3 -Chloro-2-chloromethyl-1-propionic acid methyl ester, 3-chloro-2-chloromethyl-1-propionic acid ethyl ester, 2,3-dibromo-propionic acid methyl ester, 2, 3-Dibromo-propionic acid ethyl ester, 3-bromo-2-bromomethyl-1-propionic acid methyl ester, 3-bromo-2-bromomethyl-1-propionic acid ethyl ester are particularly preferred.
[0042]
As a saponifying agent when saponifying a reaction product of a perfluoroalkylsulfonic acid alkylamide and a dihalocarboxylic acid ester, an alkali metal hydroxide such as lithium hydroxide, an alkali metal halide such as lithium chloride, ammonia, trimethylamine, Examples include amines such as triethylamine and pyridine. The amount of the saponifying agent to be used is 1 to 5 mol, preferably 1 to 2.5 mol, per 1 mol of the compound before the saponification.
[0043]
The reaction conditions for the saponification reaction are not particularly limited, and examples of the reaction solvent include water alone or a mixed solvent of water and an alcohol such as methanol, ethanol, or isopropanol. Further, the reaction temperature is preferably from 10C to reflux temperature, particularly preferably from 40C to 90C.
[0044]
Among the above three production methods, dihalocarboxylic acid or dihalocarboxylic acid salt has low solubility in an organic solvent and low operability by reaction with perfluoroalkylsulfonic acid alkylamide, and when dihalocarboxylic acid salt is used, The water solubility is relatively high because the amine salt or the alkali metal halide formed by the hydrogen halide and the hydrogen halide catcher (base) by-produced by the reaction with the perfluoroalkylsulfonic acid alkylamide is water-soluble. Since it is difficult to separate from the fluorine-based compound (A) and the yield is reduced, the method of using a dihalocarboxylic acid ester of (3) is preferable as a method of efficiently obtaining the fluorine-based compound (A).
[0045]
The fluorosurfactant of the present invention has a shorter perfluoroalkyl group chain length than conventionally used fluorosurfactants, but has solubility in water and / or an organic solvent and a surfactant effect. Are almost the same, and are not particularly limited in use, and can be widely used. The fluorine-based surfactant of the present invention may be used alone, or two or more fluorine-based compounds (A) may be used simultaneously.
[0046]
Examples of the composition using the fluorosurfactant of the present invention as an additive include, for example, various coating materials and molding materials such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, and release agents. And the like.
[0047]
The composition is a solvent, a solution or the like. In the case of a solution, the solvent contains a solvent as an essential component, and as a solute, a high molecular compound, a low molecular organic compound, at least one compound selected from inorganic compounds, and, if necessary, And various additives described below.
[0048]
Examples of the solvent include water and / or various organic solvents, for example, alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol and tert-butanol. , Hydrophilic solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, hydrophilic cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethylene glycol, propylene glycol And hydrophilic ethers such as tetrahydrofuran and dioxane. These solvents may be a single solvent or a mixed solvent of two or more solvents. In addition, the solvent used here as a dispersion medium in the system is also referred to as a solvent.
[0049]
As the solute, those dissolved or dispersed in water and / or the organic solvent are preferable. For example, acrylic polymers, urethane resins, epoxy resins, polyimide resins, polyamide resins, cellulose, chitin, natural polymers such as chitosan, and the like, Gelatin and the like can be mentioned. These solutes may be used alone or in combination of two or more.
[0050]
Examples of the additive include coupling agents such as silane-based, titanium-based, and zircon-aluminate-based compounds, and fluorine atoms such as fluorine-containing alkoxysilane compounds, fluorine-containing titanium acylate compounds, and fluorine-containing alkoxyzirconium compounds. -Based coupling agents, inorganic powders and fillers such as silica, titanium oxide, zinc oxide, aluminum oxide, tin oxide, zirconium oxide, calcium oxide, calcium carbonate, glass filler, higher fatty acids, poly (vinylidene fluoride), poly ( Organic fine powders such as tetrafluoroethylene), polyethylene, acrylic beads, carbon, etc., photosensitizers, sensitizers, light resistance improvers, weather resistance improvers, heat resistance improvers, conductive agents, antioxidants, rust inhibitors, Various fillers such as rheology control agents, thickeners, anti-settling agents, defoamers and deodorants It is below. These additives may be used alone or in combination of two or more.
[0051]
Further, as the fluorine-based surfactant of the present invention, if necessary, other fluorine-based surfactants, silicon-based surfactants, various surfactants such as hydrocarbon-based surfactants in a free combination. It can be used in combination with the various compositions described above. The mixing ratio is not particularly limited, and is appropriately selected depending on the level of the intended surface active effect, compatibility with the various compositions to be applied, and the like. As a weight ratio of the fluorine-based surfactant composed of the fluorine-based compound (A) to the other surfactant, (fluorine-based surfactant) / (other surfactant) is 1/99 to 99/1. The weight ratio is particularly preferably from 80/20 to 10/90, and most preferably from 50/50 to 20/80, from the viewpoint that a stable and sufficient surface active effect is obtained.
[0052]
In general, a fluorine-based surfactant is used in combination with a hydrocarbon-based surfactant to form a material (for example, glass, steel plate, plastic film, or the like, when applied) in contact with the composition to which the surfactant is added. In this case, the function of lowering the interfacial tension with respect to the mold is increased, and this is also effective from an economic viewpoint.
[0053]
The hydrocarbon-based surfactant comprises a hydrocarbon-based compound having a hydrophilic group and a lipophilic group in one molecule, and is usually an anion, a cation, a nonion, a betaine mainly due to the ionicity of the hydrophilic group. Classified into types. As the hydrocarbon-based surfactant that can be used in combination with the fluorine-based surfactant of the present invention, any type can be used without limitation. Representative anionic surfactants include sulfone salts, phosphate salts, carboxylate salts, and the like, and specific examples thereof include Emar series and Perex series manufactured by Kao Corporation. Examples of the cationic surfactant include oxonium salts, ammonium salts, and phosphonium salts, and specific examples thereof include acetamine series and coatamine series manufactured by Kao Corporation. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, sorbitan fatty acid ester and the like, and specific examples thereof include Emulgen series and Rheodol series manufactured by Kao Corporation. Examples of the betaine-based surfactant include amino acid salts and amine oxides, and specific examples include Amphitol series manufactured by Kao Corporation.
[0054]
By applying various processing methods to the composition containing the above-mentioned fluorine-based surfactant of the present invention, excellent penetration / wetting properties and leveling properties can be obtained. The processing method is not particularly limited. For example, coating such as gravure coater, knife coater, roll coater, comma coater, spin coater, bar coater, brush coating, dipping coating, spray coating, electrostatic coating, screen printing, etc. Method / Apparatus, Ink jet method, Injection, Extrusion, Hollow, Compression, Reaction, Vacuum, FRP, Heat, Roll sheet, Calender, Biaxially stretched film, Lamination, Rotation, etc. Various molding methods, Various dies, Stampers Injection molding and the like can be mentioned.
[0055]
There is no limitation on the use of the above-mentioned composition. For example, adhesives for industrial use and home use, scratch resistance, slipperiness, non-adhesion, water / oil repellency, gas barrier properties, heat resistance, light resistance Surface-functional protective film forming materials such as, weather resistance, physiological activity, water resistance, moisture resistance, antifouling properties, lubricity, etc., fabrics for clothing, furniture, shoes, sundries, etc. , Paper, film, various coating agents such as cards, automobiles, building materials, home appliances, medical materials, office automation equipment, electrical and electronic equipment, optical members, electric wires and wiring materials, molding materials for various industrial parts, grease, various seals Anti-blocking materials, release agents, anti-rust agents, anti-fog agents, anti-fog agents, anti-blocking agents, anti-static agents such as PS plates, photosensitive materials such as LCDs, LSIs, organic EL, and various photoresists for plasma display manufacturing , Anti-reflective coating agent for LSI production, LCD, L I, Organic EL, Detergents for plasma display manufacturing, etchants, release agents, photographic materials such as developers and emulsions, paints for automobiles, aircraft, ships, building materials, home appliances, etc., dyes, detergents, floor polish, foam It can be suitably used as a fire extinguishing agent, a plating bath mist inhibitor, an optical material such as a lens sheet and an optical fiber, or a dispersion medium for an organic chemical reaction.
[0056]
【Example】
Next, in order to explain the present invention in more detail, Examples, Test Examples and Comparative Test Examples will be given.
[0057]
Example 1
(1) Synthesis of sulfonic acid alkylamide
In a 1000 ml four-necked flask equipped with a stirrer, a dropping tube and a reflux condenser, 54 g (0.8 mol) of methylamine hydrochloride, 121.4 g (1.2 mol) of triethylamine and 250 g of ethyl acetate were charged. Then, 120.8 g (0.4 mol) of 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was put into the dropping tube. In a nitrogen atmosphere, 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride was added dropwise over 20 minutes while stirring at 25 ° C. After completion of the dropwise addition, the mixture was further stirred at 25 ° C. for 3 hours. After completion of the stirring, the solid content was removed by filtration, then the filtrate was distilled to remove the solvent, and the temperature was further increased to carry out distillation. As a fraction, 1,1,2,2,3,3,4,4 110.5 g of 4,4-nonafluorobutane-1-sulfonic acid methylamide [sulfonic acid alkylamide (1- (1))] was obtained.
[0058]
(2) Synthesis of ester
In a 500 ml four-necked flask equipped with a stirrer and a reflux condenser, 54 g (0.172 mol) of the sulfonic acid alkylamide (1- (1)) obtained in (1) and 14.4 g of sodium hydrogencarbonate ( 0.172 mol), 80 g of acetone and 50 g of ion-exchanged water, and 22.2 g (0.085 mol) of 2,3-dibromo-propionic acid ethyl ester dissolved in 40 g of acetone were charged into a dropping tube. After heating the inside of the flask to 60 ° C., an acetone solution of 2,3-dibromo-propionic acid ethyl ester was dropped from the dropping tube over 15 minutes. Further, the mixture was stirred at 60 ° C. for 4 hours under a nitrogen atmosphere. After completion of the stirring, the mixture was cooled to room temperature, and 100 g of ion-exchanged water and 200 g of ethyl acetate were added to the reaction solution. After separating the organic layer, the solvent was removed by distillation, distillation was further performed, and as a fraction, ethyl 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionic acid [ester (1- (2))] 55 g was obtained.
[0059]
(3) Saponification reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 48 g (0.066 mol) of ester (1- (2)) and 2.8 g (0.066 mol) of lithium hydroxide monohydrate were placed. After adding 60 g of isopropanol and 40 g of ion-exchanged water, the mixture was stirred at 60 ° C. for 1 hour to carry out a saponification reaction. Then, the solvent is distilled off under reduced pressure and the residue is dried to obtain a fluorine compound (1- (3)) 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -lithium propionate. 46.6 g of salt were obtained.
[0060]
Example 2
{Circle around (3)} Example 1 was repeated except that 2.6 g (0.066 mol) of sodium hydroxide was used in place of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. In the same manner, 46.5 g of sodium salt of a fluorine compound (2- (3)) 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionic acid was obtained.
[0061]
Example 3
{Circle around (3)} The same procedures as in Example 1 were carried out except that 3.7 g (0.066 mol) of potassium hydroxide was used instead of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. Similarly, 49 g of potassium fluoride compound (3- (3)) 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionate was obtained.
[0062]
Example 4
{Circle around (3)} Example 1 was repeated except that 9 g (0.132 mol) of 25% by weight aqueous ammonia was used in place of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. Similarly, 47 g of a fluorine-based compound (4- (3)) ammonium salt of 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionic acid were obtained.
[0063]
Example 5
{Circle around (2)} In the synthesis of the ester, instead of 22.2 g (0.085 mol) of ethyl 2,3-dibromo-propionate, 23.3 g of ethyl 3-chloro-2-chloromethyl-propionate (0.03 mol). 0-85 mol), except that 3- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -2-{[methyl- 58.6 g of (nonafluorobutane-1-sulfonyl) -amino] methyl} -propionic acid ethyl ester [ester (5- ▲ 2)] was obtained. Next, in (3) saponification reaction, 47.8 g (0.066 mol) of ester (5- (2)) was used instead of 48 g (0.066 mol) of ester (1- (2)). Is a fluorine-based compound (5- (3)) 3- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -2-{[methyl- (nonafluoro) 45.9 g of lithium salt of butane-1-sulfonyl) -amino] methyl} -propionate were obtained.
[0064]
Example 6
(1) Synthesis of sulfonic acid alkylamide
1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonyl fluoride Instead of 120.8 g (0.4 mol), 1,1,2,2,3,3 , 4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride 160.8 g (0.4 mol) was used in the same manner as in Example 1- (1). 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonic acid methylamide [sulfonic acid alkylamide (6- ▲ 1)] 159 0.5 g was obtained.
[0065]
(2) Synthesis of ester
Example 1 was repeated except that 71.1 g (0.172 mol) of sulfonic acid alkylamide (6- (1)) was used in place of 54 g (0.172 mol) of sulfonic acid alkylamide (1- (1)). In the same manner as in (2), 75.5 g of 2,3-bis- [methyl- (tridecafluorohexane-1-sulfonyl) -amino] -propionic acid ethyl ester [ester (6- (2))] was obtained. .
[0066]
(3) Saponification reaction
Same as Example 1- (3) except that 60.1 g (0.066 mol) of ester (6- (2)) was used instead of 48 g (0.066 mol) of ester (1- (2)) Thus, 58.2 g of lithium compound (6-６−3) 2,3-bis- [methyl- (tridecafluorohexane-1-sulfonyl) -amino] -propionate lithium salt was obtained.
[0067]
Example 7
(1) Synthesis of sulfonic acid alkylamide
In a 1000 ml four-necked flask equipped with a stirrer, a dropping tube and a reflux condenser, 54 g (0.8 mol) of methylamine hydrochloride, 121.4 g (1.2 mol) of triethylamine and 150 g of ethyl acetate were further charged. Then, 139.8 g (0.4 mol) of 3,3,4,4,5,5,6,6,6-nonafluorohexane-sulfonyl chloride dissolved in 150 g of ethyl acetate was placed in a dropping tube. Under stirring in a nitrogen atmosphere at 25 ° C, a solution of 3,3,4,4,5,5,6,6,6-nonafluorohexane-sulfonyl chloride in ethyl acetate was added dropwise over 20 minutes. After the addition, the mixture was further stirred for 2 hours. After completion of the stirring, the solid content was removed by filtration, the filtrate was distilled to remove the solvent, the temperature was further increased, and distillation was carried out. As a fraction, 3,3,4,4,5,5,6 130.3 g of 6,6-nonafluorohexane-1-sulfonic acid methylamide [sulfonic acid alkylamide (7-1)] was obtained.
[0068]
(2) Synthesis of ester
13. In a 500 ml four-necked flask equipped with a stirrer and a reflux condenser, 58.7 g (0.172 mol) of the sulfonic acid alkylamide (7-1) obtained in (1) and sodium hydrogencarbonate (14). 4 g (0.172 mol), 80 g of acetone and 50 g of ion-exchanged water were charged, and 22.2 g (0.085 mol) of 2,3-dibromo-propionic acid ethyl ester dissolved in 40 g of acetone was further added to a dropping tube. I put it. After the flask was heated to 50 ° C, an acetone solution of 2,3-dibromo-propionic acid ethyl ester was added dropwise from a dropping tube over 15 minutes, and the mixture was further stirred at 50 ° C under a nitrogen atmosphere for 2 hours. After completion of the stirring, the mixture was cooled to room temperature, and 100 g of ion-exchanged water and 200 g of ethyl acetate were added to the reaction solution. After separating the organic layer, the solvent was removed by distillation, and further distillation was performed to obtain 2,3-bis- [methyl- (3,3,4,4,5,5,6,6,6-nonazone) as a fraction. 62.4 g of fluorohexane-1-sulfonyl) -amino] -propionic acid ethyl ester [ester (7- [2])] were obtained.
[0069]
(3) Saponification reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 50.6 g (0.066 mol) of ester (7- (2)) and 2.8 g (0.066 mol) of lithium hydroxide monohydrate were added. Mol), 60 g of isopropanol and 40 g of ion-exchanged water, followed by stirring at 60 ° C. for 1 hour to carry out a saponification reaction. Next, the solvent was distilled off under reduced pressure and dried to obtain a fluorine compound (7- [3]) 2,3-bis- [methyl- (3,3,4,4,5,5,6,6). , 6-Nonafluoro-hexane-1-sulfonyl) -amino] -propionic acid lithium salt (48.2 g) was obtained.
[0070]
Example 8
{Circle around (3)} Example 7 was repeated except that 2.6 g (0.066 mol) of sodium hydroxide was used instead of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. Similarly, a fluorine compound (8-3) 2,3-bis- [methyl- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -Amino] -propionic acid sodium salt (48.7 g) was obtained.
[0071]
Example 9
{Circle around (3)} Example 7 was repeated except that 3.7 g (0.066 mol) of potassium hydroxide was used in place of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. Similarly, a fluorine compound (8-3) 2,3-bis- [methyl- (3,3,4,4,5,5,6,6,6-nonafluorohexane-1-sulfonyl) -Amino] -propionic acid potassium salt (50.3 g) was obtained.
[0072]
Example 10
{Circle around (3)} Example 7 was repeated except that 9 g (0.132 mol) of 25% by weight aqueous ammonia was used in place of 2.8 g (0.066 mol) of lithium hydroxide monohydrate in the saponification reaction. Similarly, a fluorine compound (10- {3}) 2,3-bis- [methyl- (3,3,4,4,5,5,6,6,6-nonafluoro-hexane-1-sulfonyl) -Amino] -propionic acid ammonium salt (48.9 g) was obtained.
[0073]
Example 11
{Circle around (2)} In the synthesis of the ester, instead of 22.2 g (0.085 mol) of ethyl 2,3-dibromo-propionate, 23.3 g of ethyl 3-chloro-2-chloromethyl-propionate (0.03 mol). 085 mol), except that 2,3-bis- [methyl- (3,3,4,4,5,5,6,6) was used in the same manner as in Examples 1- (1) and 1- (2). There was obtained 60.7 g of 6,7,7,8,8,8-tridecafluorooctane-1-sulfonyl) -amino] -propionic acid ethyl ester [ester (11- {2})]. Then, in (3) saponification reaction, 47.8 g (0.066 mol) of ester (11- (2)) was used instead of 48 g (0.066 mol) of ester (1- (2)). In the same manner as in Example 1- (3), the fluorine-based compound (11- (3)) 2,3-bis- [methyl- (3,3,4,4,5,5,6,6,7) , 7,8,8,8-Tridecafluorooctane-1-sulfonyl) -amino] -propionic acid lithium salt 46.2 g were obtained.
[0074]
Example 12
(1) Synthesis of sulfonic acid alkylamide
Instead of 3,3,4,4,5,5,6,6,6-nonafluorohexane-sulfonyl chloride, 139.8 g (0.4 mol), 3,3,4,4,5,5,6,6 , 7,7,8,8,8-Tridecafluorooctane-sulfonyl chloride in the same manner as in Example 7- (1), except that 179.8 g (0.4 mol) was used. 17,4.6 g of 4,5,5,6,6,7,7,8,8,8-tridecafluorooctane-1-sulfonic acid ethylamide [alkyl sulfonic acid (12- (1)]] was obtained. Was.
[0075]
(2) Synthesis of ester
Example 7 except that 55.9 g (0.172 mol) of sulfonic acid alkylamide (12- (1)) was used in place of 58.7 g (0.172 mol) of sulfonic acid alkylamide (7-1). 2,3-Bis- [methyl- (tridecafluorohexane-1-sulfonyl) -amino] -propionic acid ethyl ester [ester (12- [2])] 80 in the same manner as 7- [2] .1 g were obtained.
[0076]
(3) Saponification reaction
Example 7- (3) except that 63.8 g (0.066 mol) of the ester (12- (2)) was used instead of 50.6 g (0.066 mol) of the ester (7- (2)). In the same manner as in the above, 62.2 g of a lithium compound (12-III) 2,3-bis- [methyl- (tridecafluorohexane-1-sulfonyl) -amino] -propionic acid lithium salt was obtained.
[0077]
Example 13
In a 500 ml four-necked flask equipped with a stirrer and a reflux condenser, 54 g (0.172 mol) of the sulfonic acid alkylamide (1- (1)) obtained in Example 1 and 14.4 g (0. .172 mol), 110 g of acetone and 50 g of ion-exchanged water, and further, 20.2 g (0.085 mol) of lithium 2,3-dibromo-propionate dissolved in 60 g of ion-exchanged water was placed in a dropping tube. After heating the inside of the flask to 60 ° C., an aqueous solution of lithium 2,3-dibromo-propionate was dropped from the dropping tube over 20 minutes. Further, the mixture was stirred at 60 ° C. for 4 hours under a nitrogen atmosphere. After completion of the stirring, the reaction solution was concentrated and dried by blowing air. The obtained solid is washed with 30 g of ion-exchanged water and then dried to obtain a fluorine compound (13) lithium salt of 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionate. 46.4 g were obtained.
[0078]
Example 14
(1) Synthesis of carboxylic acid
In a 500 ml four-necked flask equipped with a stirrer and a reflux condenser, 54 g (0.172 mol) of the sulfonic acid alkylamide (1- (1)) obtained in (1) and 14.4 g of sodium hydrogencarbonate ( 0.172 mol), 110 g of acetone and 90 g of ion-exchanged water were charged, and further, 19.6 g (0.085 mol) of 2,3-dibromo-propionic acid dissolved in 60 g of ion-exchanged water was added to the dropping tube. After heating the inside of the flask at 60 ° C., a 2,3-dibromo-propionic acid aqueous solution was dropped from the dropping tube over 20 minutes. Further, the mixture was stirred at 60 ° C. for 4 hours under a nitrogen atmosphere. After completion of the stirring, the reaction solution was concentrated and dried by blowing air. The obtained solid was washed with 30 g of ion-exchanged water and then dried to obtain 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionic acid [carboxylic acid-15]. 9 g were obtained.
(2) Neutralization reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 45 g (0.066 mol) of carboxylic acid-15, 2.8 g (0.066 mol) of lithium hydroxide monohydrate, 60 g of isopropanol and After adding 40 g of ion-exchanged water, the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure and dried to obtain a fluorine-based compound (14), lithium 2,3-bis- [methyl- (nonafluorobutane-1-sulfonyl) -amino] -propionate 45 0.4 g was obtained.
[0079]
Test Examples 1 to 14 and Comparative Test Example 1
The water solubility and surface tension of the fluorine-based surfactant comprising the fluorine-based compound obtained in Examples 1 to 14 were measured by the following methods, and are shown in Tables 1 and 2 as Test Examples 1 to 14.
[0080]
Test method
Water solubility: Stirred with ion-exchanged water at 25 ° C., and a clear state free from visual turbidity was defined as complete dissolution. (Unit: wt%)
Surface tension: The surface tension at each concentration (ion exchange aqueous solution) at 20 ° C. was measured by Wilhelmy platinum plate method using an automatic surface tensiometer CBPV-Z (manufactured by Kyowa Interface Chemical Co., Ltd.). (Unit: mN / m)
[0081]
Also, as Comparative Test Example 1, Megafac F-120 (C ₈ F ₁₇ SO ₂ N (CH ₂ CH ₂ CH ₃ ) CH ₂ COOK) and the surface tension in an aqueous solution were measured. The results are shown in Tables 1 and 2.
[0082]
[Table 1]

[0083]
[Table 2]

[0084]
In Test Examples 1 to 14 using the fluorine-based surfactant composed of the fluorine-based compound of the present invention, the carbon number of the perfluoroalkyl group in the compound was as short as 6 or less, but the carbon number conventionally used was It was confirmed that the solubility in water and the effect of lowering the surface tension were almost the same as those of the fluorine-based surfactant of Comparative Example 1 comprising a compound having a perfluoroalkyl group of 8.
[0085]
Test Examples 15 and 16, Comparative Test Examples 2 and 3
Methanol (Test Example 15, Comparative Test Example 2) and ion-exchanged water / methanol = 1/1 using the fluorine compound 1- (3) obtained in Example 1 and Megafac F-120 as a conventional product. (Weight Ratio) The solubility and the surface tension in the mixed solvent (Test Example 16 and Comparative Test Example 3) were measured. Table 3 shows the results.
[0086]
[Table 3]

[0087]
It was confirmed that the fluorine surfactant comprising the fluorine-based compound of the present invention can exert almost the same surfactant effect as a conventional product on not only water but also a hydrophilic organic solvent.
[0088]
Test Examples 17, 18
Using the fluorine compound (1- (3)) obtained in Example 1, the effect of using the compound with a hydrocarbon surfactant was confirmed. Surface tension in a 0.001% by weight aqueous solution of a mixture of a fluorine compound (1- (3)) and a hydrocarbon surfactant (polyoxyethylene oleyl ether: Emulgen 430 manufactured by Kao Corporation) was measured, and a test example was used. Table 4 shows the results as 17 and 18.
[0089]
[Table 4]

[0090]
It was confirmed that the fluorine-based surfactant comprising the fluorine-based compound of the present invention exhibited an excellent surfactant effect even when used in combination with other surfactants.
[0091]
【The invention's effect】
According to the present invention, mainly used for printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, various coating materials and molding materials such as release agents, penetration and wettability, leveling properties, Fluorine consisting of a short compound having a perfluoroalkyl group of 6 or less carbon atoms in a compound that can be suitably used as an additive for enhancing surface functionality and the like and is generally recognized as having high safety. A system surfactant can be provided.

Claims (9)

2 to 4 F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR— in one molecule, wherein m is 2 or 3, n is an integer of 0 to 2, and R is an alkyl group. ) And -COOM (wherein M is hydrogen, ammonium or an alkali metal), comprising a fluorine-based compound (A). The fluorine compound (A) has the following general formula (1)
｛F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR (CH ₂ ) _o ｝ ｛F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ NR (CH ₂ ) _p ｝ CH (CH ₂ ) _q COOM ( 1) (wherein, m is 2 or 3, n is an integer of 0 to 2, o is an integer of 1 to 10, p is an integer of 0 to 10, and q is 0 to 10 Is an integer, R is an alkyl group, and M is hydrogen, ammonium or an alkali metal.)
The fluorine-based surfactant according to claim 1, which is a fluorine-based compound represented by the formula: The fluorine compound (A) has the following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (2)
(In the formula, m and n are the same as described above, and X ₁ is a halogen.)
3. A perfluoroalkylsulfonyl halide (B) represented by the formula (1), which is a fluorine-based compound obtained by reacting an alkylamine with a perfluoroalkylsulfonic acid alkylamide and then reacting with a dihalocarboxylic acid or a dihalocarboxylic acid salt. The fluorinated surfactant according to the above. The fluorine compound (A) has the following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (2)
(In the formula, m and n are the same as described above, and X ₁ is a halogen.)
To the perfluoroalkylsulfonyl halide (B) represented by the following general formula (3)
RNH ₂ (3)
(In the formula, R is an alkyl group.)
Is reacted to give a perfluoroalkylsulfonic acid alkylamide, and then reacted with the following general formula (4)
_{(X 2 (CH 2) o} ) (X 2 (CH 2) p) CH (CH 2) q COOH (4)
(In the formula, X ₂ is a halogen, and o, p, and q are the same as described above.)
Or a dihalocarboxylic acid (D) represented by the following general formula (5)
_{(X 3 (CH 2) o} ) (X 3 (CH 2) p) CH (CH 2) q COOM 1 (5)
(In the formula, X ₃ is a halogen, o, p, and q are the same as described above, and M ₁ is ammonium or an alkali metal.)
The fluorine-based surfactant according to claim 2, which is a fluorine-based compound obtained by reacting a dihalocarboxylate (E) represented by the following formula: The fluorine compound (A) has the following general formula (2)
F (CF ₂ ) _2m (CH ₂ ) _n SO ₂ X ₁ (2)
(In the formula, m and n are the same as described above, and X ₁ is a halogen.)
To the perfluoroalkylsulfonyl halide (B) represented by the following general formula (3)
RNH ₂ (3)
(In the formula, R is an alkyl group.)
After reacting an alkylamine (C) represented by the formula (1) to give a perfluoroalkylsulfonic acid alkylamide,
The following general formula (4)
_{(X 2 (CH 2) o} ) (X 2 (CH 2) p) CH (CH 2) q COOH (4)
(In the formula, X ₂ is a halogen, and o, p, and q are the same as described above.)
A compound obtained by reacting with a dihalocarboxylic acid (D) represented by
After forming a perfluoroalkylsulfonic acid alkylamide, the following general formula (6)
(X ₄ (CH ₂ ) _o ) (X ₄ (CH ₂ ) _p ) CH (CH ₂ ) _q COOR ₁ (6)
(In the formula, X ₄ is a halogen, o, p, and q are the same as described above, and R ₁ is an alkyl group.)
The fluorine-based surfactant according to claim 2, which is a compound obtained by reacting a dihalocarboxylic acid ester (E) represented by the formula (1) and then saponifying the compound. In the general formula (1), n is 0 or 2, o is an integer of 1 to 4, p is an integer of 0 to 4, q is an integer of 0 to 4, M is H, NH _4, Li, fluorosurfactants according to claim 2, wherein the Na or K. And n is 0 or 2 in the general formula (2), X ₁ is fluorine when n is 0, n is a fluorine-based surfactant according to claim 3, wherein the chlorine or bromine in the case of 2 . In the above general formula (2), n is 0 or 2, X ₁ is fluorine when n is 0, chlorine or bromine when n is 2, and R 1 in the above general formula (3) Is an alkyl group having 1 to 4 carbon atoms, o in the above general formulas (4) and (5) is an integer of 1 to 4, p is an integer of 0 to 4, and q is 0 to 4. The fluorinated surfactant according to claim ₄ , which is an integer, and M ₁ in the general formula (5) is NH ₄ , Li, Na, or K. In the above general formula (2), n is 0 or 2, X ₁ is fluorine when n is 0, chlorine or bromine when n is 2, and R 1 in the above general formula (3) Is an alkyl group having 1 to 4 carbon atoms, o in the above general formulas (4) and (6) is an integer of 1 to 4, p is an integer of 0 to 4, and q is 0 to 4. The fluorosurfactant according to claim 5, which is an integer.