JP2004098053A - Fluorine-based surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-based surfactant capable of being preferably used as an additive which easily dissolves into various coating material and molding material mainly such as printing material, photosensitive material, photographic material, painting material, detergent, optical material, and mold lubricant, so as to improve their penetrability, wettability, leveling ability, and surface functionality, when used with water-based solvent such as water and/or hydrophilic organic solvent and the like. <P>SOLUTION: The fluorine-based surfactant comprises a fluorine-based compound having in a molecule two F(CF<SB>2</SB>)<SB>2m</SB>(CH<SB>2</SB>)<SB>n</SB>OCO- which are identical with or different from each other (wherein m and n are each an integer of 1 to 12 and they can be identical with or different from each other) and moreover, -SR<SB>1</SB>COOM<SB>1</SB>(wherein R<SB>1</SB>is an alkylene chain, M<SB>1</SB>is a hydrogen atom, an ammonium, or metals) or -OR<SB>2</SB>COOM<SB>2</SB>(wherein R<SB>2</SB>is an alkylene chain, M<SB>2</SB>is an ammonium or metals). <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。
【００１９】
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、１種または２種の下記一般式（２）
Ｆ（ＣＦ２）２ｍ（ＣＨ２）ｎＯＨ　　　（２）
（式中、ｍ、ｎは１〜１２の整数であり、同じでも異なっていてもよい。）
で示されるパーフルオロアルキルアルコール（Ｂ）に、不飽和脂肪族ジカルボン酸を反応させてジエステルとし、更にメルカプトカルボン酸、メルカプトカルボン酸塩、またはメタロキシカルボン酸塩を反応させる製造方法等が挙げられる。
【００２０】
前記不飽和脂肪族ジカルボン酸としては、その構造が特に限定されるものではないが、例えば、下記一般式（３）
ＨＯＯＣ（ＣＨ２）ｏ（Ｘ）Ｃ＝Ｃ（Ｚ）ＣＯＯＨ　　　（３）
（式中、ｏは０〜１２の整数であり、Ｘ、Ｚは水素原子または炭素原子数１〜１２の炭化水素基であり、同じでも異なっていてもよい。）
で示される不飽和脂肪族ジカルボン酸（Ｃ）が挙げられる。
【００２１】
前記製造方法について詳細に説明する。１種または２種の前記一般式（２）で表されるパーフルオロアルキルアルコール（Ｂ）は、優れた界面活性効果が得られ、且つ特に水系溶媒を用いる前述の組成物に対する親和性が得られることから、前記一般式（２）中のｍが２〜３の整数、ｎが１〜４の整数であるものが好ましく、特に３，３，４，４，５，５，６，６，６−ノナフルオロ−１−ヘキサノール、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロ−１−オクタノールが好ましい。
【００２２】
また、前記一般式（３）で表わされる不飽和脂肪族ジカルボン酸（Ｃ）としては、優れた界面活性効果が得られ、且つ特に水系溶媒を用いる前述の組成物に対する親和性が得られ、製造が容易なことから、前記一般式（３）中のｏは０〜４の整数であることが好ましく、特に０〜２の整数が好ましい。Ｘ、Ｚは、水素原子または炭素原子数１〜１２の炭化水素基であり、同じでも異なっていてもよいが、優れた界面活性効果が得られ、且つ特に水系溶媒を用いる前述の組成物に対する親和性が得られることから、水素原子または炭素原子数１〜６のアルキル基が好ましく、特に水素原子または炭素原子数１〜３のアルキル基が好ましく、例えば、フマル酸、マレイン酸、２−エチル−３−メチルー２−ブテンジカルボン酸、２，３−ジメチル−２−ペンテンジカルボン酸、２−メチル−２−ペンテンジカルボン酸、２−ペンテンジカルボン酸、３−エチル−２−ペンテンジカルボン酸、２−エチル−２−ブテンジカルボン酸、２−メチル−２−ブテンジカルボン酸、２，３−ジメチル−２−ブテンジカルボン酸等が挙げられる
【００２３】
前記一般式（２）で表されるパーフルオロアルキルアルコール（Ｂ）の使用量は、１種類のパーフルオロアルキルアルコールを使用する場合は、前記一般式（３）で表される不飽和脂肪族ジカルボン酸（Ｃ）１モルに対し、１．８〜７．０モル使用され、好ましくは２．０〜４．０モル使用される。また、２種類のパーフルオロアルキルアルコールを使用する場合は、不飽和脂肪族ジカルボン酸１分子中の２つのカルボキシル基に２種のパーフルオロアルキルアルコールがそれぞれ反応してジエステルを形成させるために、前記一般式（３）で表される不飽和脂肪族ジカルボン酸（Ｃ）１モルに対し、パーフルオロアルキルアルコール２種をそれぞれ０．８〜１．２モル使用し、好ましくは１．０〜１．１モル使用し、必要に応じて溶媒を用いてエステル化反応を行う。
【００２４】
前記溶媒としては、前記一般式（２）および（３）で表される原料のパーフルオロアルキルアルコール及び不飽和脂肪族ジカルボン酸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が挙げられ、これらの中でも、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が好ましく、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。
【００２５】
一般に、カルボン酸とアルコールの脱水反応によるエステル化反応は平衡反応であり、触媒として、例えば硫酸、塩酸等の鉱酸、メタンスルホン酸、エタンスルホン酸、ベンゼンスルホン酸、ｐ−トルエンスルホン酸等の有機酸、あるいは、三フッ化ホウ素ジエチルエーテル錯体等のルイス酸の存在下で平衡に到達する。この平衡を生成系に移行させるためには、例えば、▲１▼アルコールを過剰に使用する、▲２▼ベンゼンやトルエンを溶媒としてＤｅａｎ−Ｓｔａｒｋ水分離器を用いて、生成する水を共沸蒸留により分離する、▲３▼ソックスレー抽出器に無水硫酸マグネシウムあるいはモレキュラーシーブス等の乾燥剤を入れて溶媒を還流させて脱水を行う方法、▲４▼ジシクロヘキシルカルボジイミド（ＤＣＣ）等の脱水剤を共存させる方法、▲５▼塩化アルミニウムを混合した樹脂を触媒とする方法等が挙げられる。
【００２６】
本発明に係わる、前記一般式（２）および（３）で表されるパーフルオロアルキルアルコールと不飽和脂肪族ジカルボン酸のジエステル化反応は、前述の一般的な手法を用いることによって行うことが出来、ジエステルの収率を挙げる方法としては、製造が容易であることから、▲２▼の手法が好ましい。
【００２７】
前記ジエステル化反応の反応条件は、特に制限はないが、反応操作が容易なことから、前記一般式（２）および（３）で表されるパーフルオロアルキルアルコールと不飽和脂肪族ジカルボン酸を、前記触媒を含む前記溶媒中で一括して反応させる方法が好ましい。反応温度にも制限はないが、脱水反応が効率的に起こる条件であれば問題はなく、通常４０〜２００℃であり、好ましくは７０〜１６０℃である。反応時間にも制限はなく、通常３０分〜２０時間であり、好ましくは、１時間〜１０時間である。反応雰囲気にも制限はないが、空気雰囲気下またはＮ_２、Ｈｅ、Ａｒ等の不活性ガス雰囲気下で行われ、不活性ガス雰囲気下がより好ましい。
【００２８】
次に、得られたジエステル体にメルカプトカルボン酸、メルカプトカルボン酸塩、またはメタロキシカルボン酸塩を反応させる方法について説明する。
【００２９】
ここで使用するメルカプトカルボン酸、メルカプトカルボン酸塩としては、例えば、メルカプト酢酸、メルカプト酢酸・金属塩、２−メルカプトエタン酸、２−メルカプトエタン酸・金属塩、２−メルカプトプロピオン酸、２−メルカプトプロピオン酸・金属塩、２−メルカプトプロピオン酸・アミン塩、３−メルカプトイソブタン酸、３−メルカプトイソブタン酸・金属塩、３−メルカプトイソブタン酸・アミン塩等が挙げられ、メタロキシカルボン酸塩としては、例えば、メタロキシ酢酸・金属塩、メタロキシプロピオン酸・金属塩、メタロキシブタン酸・金属塩等が挙げられ、これらの中でも、２−メルカプトエタン酸、２−メルカプトエタン酸・金属塩、２−メルカプトプロピオン酸、２−メルカプトプロピオン酸・金属塩が好ましい。
【００３０】
前記アミン塩としては、例えば、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、前記金属塩としては例えば、Ｌｉ塩、Ｎａ塩、Ｋ塩、Ｃａ塩、Ｍｇ塩、Ａｌ塩等が挙げられ、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水系溶媒を用いる前述の組成物との親和性が高く、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、Ｌｉ塩、Ｎａ塩、Ｋ塩が好ましく、具体的には、２−メルカプトエタン酸アンモニウム、２−メルカプトエタン酸リチウム、２−メルカプトエタン酸ナトリウム、２−メルカプトエタン酸カリウム、２−メルカプトプロピオン酸アンモニウム、２−メルカプトプロピオン酸リチウム、２−メルカプトプロピオン酸ナトリウム、２−メルカプトプロピオン酸カリウム等が挙げられる
【００３１】
使用するメルカプトカルボン酸、メルカプトカルボン酸塩、メタロキシカルボン酸塩は、前記ジエステル体１モルに対し、０．５〜５．０モル使用され、特に０．８〜１．５モル使用することが好ましい。
【００３２】
前記ジエステル体とメルカプトカルボン酸、メルカプトカルボン酸塩、メタロキシカルボン酸塩とを反応させる方法としては特に制限されるものではないが、反応促進のために反応助剤を用いても良い。
【００３３】
前記反応助剤としては、塩基性物質が好ましく、例えば、水酸化リチウム、水酸化カリウム等の金属水酸化物、炭酸カリウム、炭酸リチウム等の炭酸塩、ナトリウムメチラート、ナトリウムエチラート等のアルカリ金属アルコラート、水素化ナトリウム、水素化カリウム等の金属水素化物、トリエチルアミン、トリ−ｎ−ブチルアミン、ピリジン等のアミン類が挙げられ、特に炭酸ナトリウム、炭酸カリウム、トリエチルアミンが好ましい。反応助剤は、前記ジエステル体１モルに対し、１〜４モル、特に１〜２モル使用することが好ましい。
【００３４】
また、前記反応時には溶媒を使用してもよい。前記溶媒としては、前記ジエステル体と、メルカプトカルボン酸、メルカプトカルボン酸塩、メタロキシカルボン酸塩を溶解できるものであれば特に限定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、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、酢酸エチル、酢酸ブチル等のカルボン酸エステル類、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、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、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、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、１，２−ジクロロエタン等のハロゲン化炭化水素類、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、酢酸エチル、酢酸ブチル等のカルボン酸エステル類、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、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、酢酸エチル、酢酸ブチル等のカルボン酸エステル類、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。
【００３５】
また、反応条件にも特に制限はないが、反応制御が容易である点から、反応温度は通常、０℃〜還流温度であり、２０℃〜６０℃であることが好ましい。反応雰囲気等にも制限はないが、不活性ガス雰囲気下が好ましい。
【００３６】
前述の製造方法により得られた前記一般式（１）で表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、必要に応じて中和反応、ケン化反応にそのまま進むことも可能である。また、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。
【００３７】
また、前記一般式（１）で示されるフッ素系化合物の製法として、前記一般式（２）で表されるパーフルオロアルキルアルコールと前記一般式（３）で表される不飽和脂肪族ジカルボン酸との反応により生成するジエステル体に、メルカプトカルボン酸またはメルカプトカルボン酸エステルを反応させ、中和またはケン化せしめる方法でも良い。
【００３８】
ここで用いるメルカプトカルボン酸またはメルカプトカルボン酸エステルとしては、特に限定されるものではないが、例えば、メルカプト酢酸、メルカプト酢酸エステル、２−メルカプトエタン酸、２−メルカプトエタン酸エステル、２−メルカプトプロピオン酸、２−メルカプトプロピオン酸エステル、３−メルカプトイソブタン酸、３−メルカプトイソブタン酸エステル等が挙げられ、これらの中でも２−メルカプトエタン酸、２−メルカプトエタン酸エステル、２−メルカプトプロピオン酸、２−メルカプトプロピオン酸エステルが好ましい。
【００３９】
また、中和剤、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。これら中和剤、ケン化剤はフッ素系化合物１モルに対し、１〜５モル、好ましくは１〜２．５モル使用することが好ましい。
【００４０】
前記中和、並びに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、中和反応の場合は、５℃〜５０℃、特に１０℃〜３０℃であることが好ましい。また、ケン化反応の場合は、１０℃〜還流温度、特に４０℃〜９０℃であることが好ましい。
【００４１】
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。
【００４２】
本発明のフッ素系界面活性剤は、特に水単独、メタノール、イソプロピルアルコール、アセトン、メチルエチルケトン、ジメチルホルムアミド等の水と１％以上、好ましくは１０％以上混合可能な親水性有機溶媒単独、水と有機溶媒の混合溶媒を含む組成物、その中でも水単独または水を１０％以上含む水と有機溶媒の混合溶媒を含む組成物において、その親和性が高いことから、添加量の許容範囲が広く、用途に応じて優れた界面活性効果を発現させ得ることができる。
【００４３】
前述の本発明のフッ素系界面活性剤を添加剤として使用する前述の組成物としては、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。
【００４４】
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。
【００４５】
前記溶媒としては、水、親水性の有機溶媒が挙げられ、親水性の有機溶媒としては例えば、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、ジオキサン等の親水性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。
【００４６】
前述の親水性の有機溶媒以外の、水と混和しにくい溶媒は、前記親水性の有機溶媒と併用し、２成分以上の混合溶媒として使用することが好ましい。
【００４７】
前記溶質としては、前記親水性の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。
【００４８】
前記以外の親水性の有機溶媒に溶解或いは分散しにくい溶質は、水と混和しにくい溶媒と、前述の親水性の有機溶媒を併用した混合溶媒を用いて使用することが好ましい。
【００４９】
前記添加剤としては、親水性のものが好ましいが、その使用量が極少量である場合が多いことより、水溶解度が低いものでも使用でき、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（テトラフルオロエチレン）、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。
【００５０】
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。
【００５１】
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。
【００５２】
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。
【００５３】
本発明のフッ素系界面活性剤を含む前述の組成物は、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。
【００５４】
また、前述の組成物の用途にも制限はなく、種々の用途に使用できるが、特に、水単独または水と有機溶媒混合系等の親水性が高い溶媒系組成物中で用いる場合に優れた界面活性効果を発揮し、例えば、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用いられ、浸透・濡れ性、レベリング性等のコーティング・モールディング適正を向上させることが可能である。
【００５５】
本発明のフッ素系界面活性剤は、前述の親水性の有機溶媒や溶質以外の一般的に使用されている溶媒、溶質に対する親和性も高く、表面偏析性にも優れ、従来のフッ素系界面活性剤の持つ界面活性効果を損なわないものであるため、前述の親水性の組成物並びに用途に限定されるものではなく、従来より一般的に有機溶剤系で使用される場合が多い用途、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等としても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▼ジエステル体の合成
攪拌装置、Ｄｅａｒｎ−Ｓｔａｒｋ水分離器および還流冷却器を付した３００ｍｌの四ツ口フラスコに、マレイン酸２０ｇ（１７２ｍｍｏｌ）、３，３，４，４，５，５，６，６，６−ノナフルオロ−１−ヘキサノール９９．８ｇ（３７８ｍｍｏｌ）、硫酸０．５ｇ（５ｍｍｏｌ）およびトルエン５０ｇを加えた後、１３０℃の油浴中で３時間加熱攪拌した。Ｄｅａｒｎ−Ｓｔａｒｋ水分離器により、理論量の水（６．２ｍｌ）の留出を確認し反応を止めた。反応終了後、９０℃に冷却し、溶媒および過剰に用いたアルコールを減圧下で留去した後、乾燥することにより、２−ブテンジカルボン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［ジエステル体（１−▲１▼）］１０４．６ｇを得た。
【００５８】
▲２▼親水性基の導入
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、▲１▼で得られたジエステル体（１−▲１▼）１０４．６ｇ（１７２ｍｍｏｌ）、２−メルカプトエタン酸１６ｇ（１７４ｍｍｏｌ）、トリエチルアミン１９．１ｇ（１８９ｍｍｏｌ）および酢酸エチル２５０ｇを加えた後、２００℃で３時間攪拌した。反応終了後、反応液に、５重量％塩酸水溶液１００ｇを加え、過剰のトリエチルアミンを除去した。有機層と水層を分離し、有機層を５重量％塩酸水溶液１００ｇで洗浄した。有機層を分離した後、減圧下で溶媒を留去し乾燥することにより、２−カルボキシメチルスルファニ酸ルスクシン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［置換基含有ジエステル体（１−▲２▼）］１２０ｇを得た。
【００５９】
▲３▼中和・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、置換基含有ジエステル体（１−▲２▼）１２０ｇ（１７２ｍｍｏｌ）、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）、イソプロパノール１７０ｇおよびイオン交換水１２０ｇを加えた後、２０℃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、目的のフッ素系化合物（１−▲３▼）２−カルボキシメチルスルファニルスクシン酸リチウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２１．５ｇを得た。
【００６０】
実施例２
▲３▼中和・ケン化反応において、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）の代わりに、水酸化カリウム９．７ｇ（１７２ｍｍｏｌ）を用いた以外は実施例１と同様にして、目的のフッ素系化合物（２−▲３▼）２−カルボキシメチルスルファニルスクシン酸カリウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２７ｇを得た。
【００６１】
実施例３
▲３▼中和・ケン化反応において、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）の代わりに、水酸化ナトリウム６．９ｇ（１７２ｍｍｏｌ）を用いた以外は実施例１と同様にして、目的のフッ素系化合物（３−▲３▼）２−カルボキシメチルスルファニルスクシン酸ナトリウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２４．２ｇを得た。
【００６２】
実施例４
▲３▼中和・ケン化反応において、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）の代わりに、２５重量％アンモニア水１７．６ｇ（２５８ｍｍｏｌ）を用いた以外は実施例１と同様にして、目的のフッ素系化合物（４−▲３▼）２−カルボキシメチルスルファニルスクシン酸アンモニウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２３．４ｇを得た。
【００６３】
実施例５
▲２▼親水性基の導入において、２−メルカプトエタン酸１６ｇ（１７４ｍｍｏｌ）の代わりに、２−メルカプトプロピオン酸１８．５ｇ（１７４ｍｍｏｌ）を用いた以外は実施例１−▲１▼、１−▲２▼と同様にして、２−（２−カルボキシエチルスルファニル）スクシン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［置換基含有ジエステル体（５−▲２▼）］１２１．６ｇを得た。次いで、▲３▼中和・ケン化反応において、置換基含有ジエステル体（１−▲２▼）１２０ｇ（１７２ｍｍｏｌ）の代わりに、置換基含有ジエステル体（５−▲２▼）１２１．６ｇ（１７０ｍｍｏｌ）を用いた以外は実施例１−▲３▼と同様にして、目的のフッ素系化合物（５−▲３▼）２−（２−カルボキシエチルスルファニル）スクシン酸リチウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２２．４ｇを得た。
【００６４】
実施例６
▲２▼親水性基の導入において、２−メルカプトエタン酸１６ｇ（１７４ｍｍｏｌ）の代わりに、２−リチウムオキシエタン酸リチウム１５．３ｇ（１７４ｍｍｏｌ）を用い、▲３▼中和・ケン化反応を行わなかった以外は実施例１と同様にして、目的のフッ素系化合物（６−▲２▼）２−カルボキシメトキシスクシン酸リチウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１１８．７ｇを得た。
【００６５】
実施例７
▲１▼ジエステル体の合成
マレイン酸２０ｇ（１７２ｍｍｏｌ）の代わりにシス−２−ペンテンジカルボン酸２２．４ｇ（１７２ｍｍｏｌ）用いた以外は実施例１−▲１▼と同様にして、ジエステル体（７−▲１▼）２−ペンテンジカルボン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［ジエステル体（７−▲１▼）］１０７ｇを得た。
【００６６】
▲２▼親水性基の導入
ジエステル体（１−▲１▼）１０４．６ｇ（１７２ｍｍｏｌ）の代わりにジエステル体（７−▲１▼）１０７ｇ（１７２ｍｍｏｌ）を用いた以外は実施例１−▲２▼と同様にして３−カルボキシメチルスルファニルペンタンジカルボン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［置換基含有ジエステル体（７−▲２▼）］１２１．７ｇを得た。
【００６７】
▲３▼中和・ケン化反応
置換基含有ジエステル体（１−▲２▼）１２０ｇ（１７２ｍｍｏｌ）の代わりに、置換基含有ジエステル体（７−▲２▼）１２１．７ｇ（１７０．４ｍｍｏｌ）を用いた以外は実施例１−▲３▼と同様にして目的のフッ素系化合物（７−▲３▼）３−カルボキシメチルスルファニルペンタンジカルボン酸リチウムビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル１２２．７ｇを得た。
【００６８】
実施例８
▲１▼ジエステル体の合成
攪拌装置、Ｄｅａｒｎ−Ｓｔａｒｋ水分離器および還流冷却器を付した３００ｍｌの四ツ口フラスコに、マレイン酸２０ｇ（１７２ｍｍｏｌ）、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロ−１−オクタノール１３７．６ｇ（３７８ｍｍｏｌ）、硫酸０．５ｇ（５ｍｍｏｌ）およびトルエン１００ｇを加えた後、１４０℃の油浴中で４時間加熱攪拌した。Ｄｅａｒｎ−Ｓｔａｒｋ水分離器により、理論量の水（６．２ｍｌ）の留出を確認し反応を止めた。反応終了後、９０℃に冷却し、溶媒および過剰に用いたアルコールを減圧下で留去した後、乾燥することにより、２−ブテンジカルボン酸ビス−（３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチル）エステル［ジエステル体（８−▲１▼）］１３９ｇを得た。
【００６９】
▲２▼親水性基の導入
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、ジエステル体（８−▲１▼）１３９ｇ（１７２ｍｍｏｌ）、２−メルカプトエタン酸１６ｇ（１７４ｍｍｏｌ）、トリエチルアミン１９．１ｇ（１８９ｍｍｏｌ）および酢酸エチル２５０ｇを加えた後、２００℃で４時間攪拌した。反応終了後、反応液に、５重量％塩酸水溶液１００ｇを加え、過剰のトリエチルアミンを除去した。有機層と水層を分離し、有機層を５重量％塩酸水溶液１００ｇで洗浄した。有機層を分離した後、減圧下で溶媒を留去し乾燥することにより、２−カルボキシメチルスルファニルスクシン酸ビス−（３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチル）エステル［置換基含有ジエステル体（８−▲２▼）］１５４．９ｇを得た。
【００７０】
▲３▼中和・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、置換基含有ジエステル体（８−▲２▼）１５４．９ｇ（１７２ｍｍｏｌ）、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）、イソプロパノール２００ｇおよびイオン交換水１５０ｇを加えた後、２０℃で３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、目的のフッ素系化合物（８−▲３▼）２−カルボキシメチルスルファニルスクシン酸リチウムビス−（３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチル）エステル１５５．９ｇを得た。
【００７１】
実施例９
▲１▼ジエステル体の合成
攪拌装置、Ｄｅａｒｎ−Ｓｔａｒｋ水分離器および還流冷却器を付した３００ｍｌの四ツ口フラスコに、シス−２−メチル−２−ブテン２２．４ｇ（１７２ｍｍｏｌ）、３，３，４，４，５，５，６，６，６−ノナフルオロ−１−ヘキサノール９９．８ｇ（３７８ｍｍｏｌ）、硫酸０．５ｇ（５ｍｍｏｌ）およびトルエン１００ｇを加えた後、１４０℃の油浴中で４時間加熱攪拌した。Ｄｅａｒｎ−Ｓｔａｒｋ水分離器により、理論量の水（６．２ｍｌ）の留出を確認し反応を止めた。反応終了後、９０℃に冷却し、溶媒および過剰に用いたアルコールを減圧下で留去した後、乾燥することにより、２−メチルスクシン酸ビス−（３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル）エステル［ジエステル体（９−▲１▼）］１０７ｇを得た。
【００７２】
▲２▼親水性基の導入
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、ジエステル体（９−▲１▼）１０７ｇ（１７２ｍｍｏｌ）、２−メルカプトエタン酸１６ｇ（１７４ｍｍｏｌ）、トリエチルアミン１９．１ｇ（１８９ｍｍｏｌ）および酢酸エチル２５０ｇを加えた後、２００℃で４時間攪拌した。反応終了後、反応液に、５重量％塩酸水溶液１００ｇを加え、過剰のトリエチルアミンを除去した。有機層と水層を分離し、有機層を５重量％塩酸水溶液１００ｇで洗浄した。有機層を分離した後、減圧下で溶媒を留去し乾燥することにより、２−カルボキシメチルスルファニル−３−メチルスルシン酸ビス−（３，３，４，４，５，５，６，６，７，７，７−ノナフルオロヘキシル）エステル［置換基含有ジエステル体（９−▲２▼）］１２２．９ｇを得た。
【００７３】
▲３▼中和・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、置換基含有ジエステル体（９−▲２▼）１２２．９ｇ（１７２ｍｍｏｌ）、水酸化リチウム・一水和物７．２ｇ（１７２ｍｍｏｌ）、イソプロパノール１９０ｇおよびイオン交換水１４０ｇを加えた後、３０℃で４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、目的のフッ素系化合物（９−▲３▼）２−カルボキシメチルスルファニル−３−メチルスルシン酸リチウムビス−（３，３，４，４，５，５，６，６，７，７，７−ノナフルオロヘキシル）エステル１２３．９ｇを得た。
【００７４】
試験例１〜９、比較試験例１
実施例１〜９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１〜９として表１及び表２に示す。
【００７５】
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）
【００７６】
また、比較試験例１として、クラリアントジャパン株式会社のＦｌｕｏｗｅｔ製品のカタログに記載されているＦｌｕｏｗｅｔ　ＳＢ（ブチルグリコール／水混合溶媒の３０重量％溶液）を１２０℃で溶剤を完全に留去した後、上記の方法で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。
【００７７】
【表２】

【００７８】
【表３】

【００７９】
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１〜９では、水への溶解度が高く、且つ表面張力低下作用にも優れていることを確認した。
【００８０】
試験例１０、１１
実施例１で得られたフッ素系化合物１−▲３▼を用いて、メタノール（試験例１０）、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１１）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。
【表４】

【００８１】
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溶解度が高く、且つ水単独使用時と同様に優れた界面活性効果を発現しうることを確認した。
【００８２】
試験例１２、１３
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）　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１２、１３として結果を表４に示す。
【００８３】
【表５】

【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。
【００８５】
【発明の効果】
本発明によれば、水、及び／または親水性有機溶媒等の水系溶媒を用いて使用される、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容易に溶解し、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るフッ素系界面活性剤を提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to various types of printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, release agents, etc., which are used by using water and / or an aqueous solvent such as a hydrophilic organic solvent. The present invention relates to a fluorine-based surfactant which easily dissolves in a coating material, a molding material, and the like, and can be suitably used as an additive for enhancing permeation / wetting property, leveling property, 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]
Among conventionally known fluorine-based surfactants, there is a fluorine-based surfactant composed of a compound having two Rf groups in the same molecule (for example, Non-Patent Document 1). Fluowet SB “RfCH2CH2OOCCH (SO3Na) CH2COOCH2CH2Rf” described in the above-mentioned patent documents is composed of a compound having two Rf groups in one molecule, so that the surface transferability of the Rf group is high, and the water and oil repellency is high. Excellent in antifouling, low friction, lubricity, non-adhesiveness, releasability, and moisture resistance, surface modifier, solder flux spread inhibitor, mold release agent, moisture-proof coating agent for electronic components It can be used in various applications such as solid lubricants, water and oil repellents for clothing and paper, but the rate of surface tension reduction is not at a satisfactory level and its solubility in water is low, so its addition Because the amount is limited, polymerization emulsifiers using aqueous solvents, leveling agents such as photographic emulsions or photoresist sensitizers, paints, inks, floor waxes, etc. Leveling agent to the coating solution of the substrate in the coating sector, the pigments dispersion stabilizer or the like has a problem that surface activity is not fully functional. For example, when a fluorine-based surfactant is used as a silver halide light-sensitive material, if the solubility of the activator in water is low, the activator is eluted in a developing solution during a development process, whereby The developer easily foams, and bubbles accumulate on the liquid surface of the developer, causing a problem that when the photosensitive material enters the developer, the bubbles adhere to the surface of the photosensitive material to cause foamy development unevenness. . In recent years, from the viewpoint of protection of the global environment, the solvent used in the industrial field tends to shift from an organic solvent system to an aqueous system, and the development of a fluorine-based surfactant having high affinity for water has been demanded.
[0005]
On the other hand, when a fluorine-based surfactant is used as an additive in compositions for various coatings and molding materials by applying the surface tension lowering function of the compound, in order to express a sufficient function with a small amount, It is necessary to increase the Rf chain length, but in this case, there is a phenomenon that the affinity for the composition is necessarily reduced. This phenomenon is remarkable when the composition uses water, a hydrophilic organic solvent, a mixed solvent of a hydrophilic organic solvent and water, or the like. Therefore, in order to obtain a fluorine-based surfactant having a high affinity for water, the design of the amphiphilic group in the fluorine-based compound used for the surfactant is extremely important.
[0006]
[Non-patent document 1]
Clariant Japan Co., Ltd. homepage, [online], searched on July 10, 2002, Internet <URL: http: // www. Clariant. co. jp / tlp / 07. html>
[0007]
[Problems to be solved by the invention]
In view of the circumstances as described above, an object of the present invention is to provide a printing material, a photosensitive material, a photographic material, a paint, and a cleaning agent, which are used using water and / or an aqueous solvent such as a hydrophilic organic solvent. Fluorine-based interface that easily dissolves in various coating materials such as optical materials and release agents, molding materials, etc., and can be suitably used as an additive for enhancing permeation / wetting properties, leveling properties, surface functionality, etc. It is to provide an activator.
[0008]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, two identical or different F (CF ₂ ) _2m (CH ₂ ) _n OCO- (wherein, m and n are integers of 1 to 12 and may be the same or different), and -SR. ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. The present inventors have found that a fluorine-based surfactant composed of a fluorine-containing compound having the formula (1) has high solubility in water and does not impair the surface-active effect, thereby completing the present invention.
[0009]
That is, the present invention provides two identical or different F (CF ₂ ) _2m (CH ₂ ) _n OCO- (wherein, m and n are integers of 1 to 12 and may be the same or different), and -SR. ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. The present invention provides a fluorine-based surfactant comprising a fluorine-containing compound having the formula (1).
[0010]
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.
[0011]
The fluorine-based surfactant of the present invention contains two identical or different F (CF ₂ ) _2m (CH ₂ ) _n OCO- (wherein, m and n are integers of 1 to 12 and may be the same or different), and -SR. ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. ), And the structure is not particularly limited.
[0012]
Two F (CF) in the fluorine compound (A) ₂ ) _2m (CH ₂ ) _n The OCO- (wherein, m and n are an integer of 1 to 12 and may be the same or different) groups are indispensable segments for obtaining excellent surface active effects. The chain length of the group is appropriately selected depending on the use when used as a surfactant, the composition of a composition such as a coating material or a molding material, which is mixed with the surfactant as an additive, the intended level of performance, and the like. Things.
[0013]
Further, -SR of the fluorine-based compound (A) ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. ) Is a hydrophilic group, in which R ₁ And R ₂ The structure and chain length of the polymer are not particularly limited, and are used in the case of being used as a surfactant, the composition of a composition such as a coating material or a molding material in which this is mixed as an additive, and a desired level of performance. Although it is appropriately selected depending on the conditions, an alkylene chain having 1 to 5 carbon atoms is preferable, and an alkylene chain having 1 to 3 carbon atoms is particularly preferable. Also, M ₁ And M ₂ Represents a hydrogen atom of a carboxylic acid, ammonium of a carboxylic acid amine salt, or a metal of a carboxylic acid metal salt.
[0014]
The structure of the fluorine-based compound (A) is not particularly limited, and examples thereof include compounds represented by the following general formula (1).
F (CF2) 2m (CH2) nOCO (CH2) oC (X) (Y) CH (Z) COO (CH2) n (CF2) 2mF (1)
(In the formula, m, n, and o are integers of 1 to 12, and may be the same or different. X and Z are a hydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms, and are the same or different. Y is -SR ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. ). )
[0015]
Among these, F (CF) in the general formula (1) ₂ ) _2m (CH ₂ ) _n M in the OCO- group is preferably an integer of 2 to 3 from the viewpoint of obtaining an excellent surface-active effect and achieving compatibility with the above-mentioned composition using an aqueous solvent. Further, n is preferably an integer of 1 to 4, and n is preferably an integer of 1 to 2, since a practical surfactant effect is obtained, the affinity with the above-described composition is high, and the production is easy. preferable.
[0016]
Further, o in the general formula (1) is preferably an integer of 0 to 4 from the viewpoint of excellent surface active effect and affinity with various compositions to be added and easy production. Integers of 2 to 2 are particularly preferred.
[0017]
Further, Y in the general formula (1) is a hydrophilic group, and -SR ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Represents a hydrogen atom, ammonium, or a metal. ) Or -OR ₂ COOM ₂ (Where R ₂ Is an alkylene chain, M ₂ Represents ammonium or metals. M in) ₁ And M ₂ Are amines such as ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, Examples include ammonium derived from diethanolamine, propanolamine, toluidine, pyridine, and the like. Examples of the metals include Li, Na, K, Ca, Mg, and Al. Since the obtained and particularly high affinity with the above-mentioned composition using an aqueous solvent and easy production, -SR ₁ COOM ₁ (Where R ₁ Is an alkylene chain, M ₁ Is a hydrogen atom, -NH ₄ Or metal. Is preferred.
[0018]
Specific examples of the fluorine-based compound used for the fluorine-based surfactant of the present invention include the following compounds.
[Table 1]

The present invention is, of course, not limited by these specific examples.
[0019]
The method for producing the fluorine-based compound represented by the general formula (1) is not particularly limited. For example, one or two of the following general formulas (2)
F (CF2) 2m (CH2) nOH (2)
(In the formula, m and n are integers of 1 to 12, and may be the same or different.)
A perfluoroalkyl alcohol (B) represented by the formula (I) is reacted with an unsaturated aliphatic dicarboxylic acid to form a diester, and further reacted with a mercaptocarboxylic acid, a mercaptocarboxylate, or a metaloxycarboxylate. .
[0020]
Although the structure of the unsaturated aliphatic dicarboxylic acid is not particularly limited, for example, the following general formula (3)
HOOC (CH2) o (X) C = C (Z) COOH (3)
(In the formula, o is an integer of 0 to 12, X and Z are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different.)
And an unsaturated aliphatic dicarboxylic acid (C) represented by
[0021]
The manufacturing method will be described in detail. One or two kinds of the perfluoroalkyl alcohols (B) represented by the general formula (2) have an excellent surface active effect, and particularly have an affinity for the above-described composition using an aqueous solvent. From the above, it is preferable that m in the general formula (2) is an integer of 2 to 3 and n is an integer of 1 to 4, and particularly 3,3,4,4,5,5,6,6,6. -Nonafluoro-1-hexanol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol are preferred.
[0022]
In addition, as the unsaturated aliphatic dicarboxylic acid (C) represented by the general formula (3), an excellent surface active effect can be obtained, and particularly, an affinity for the above-mentioned composition using an aqueous solvent can be obtained. In the general formula (3), o is preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 2 in the general formula (3). X and Z are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different, but provide an excellent surface active effect, and particularly to the above-mentioned composition using an aqueous solvent. From the viewpoint of obtaining affinity, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is particularly preferable. For example, fumaric acid, maleic acid, 2-ethyl -3-methyl-2-butenedicarboxylic acid, 2,3-dimethyl-2-pentenedicarboxylic acid, 2-methyl-2-pentenedicarboxylic acid, 2-pentenedicarboxylic acid, 3-ethyl-2-pentenedicarboxylic acid, 2- Ethyl-2-butenedicarboxylic acid, 2-methyl-2-butenedicarboxylic acid, 2,3-dimethyl-2-butenedicarboxylic acid and the like can be mentioned.
[0023]
When one kind of perfluoroalkyl alcohol is used, the amount of the perfluoroalkyl alcohol (B) represented by the general formula (2) may be less than the amount of the unsaturated aliphatic dicarboxylic acid represented by the general formula (3). It is used in an amount of 1.8 to 7.0 mol, preferably 2.0 to 4.0 mol, per 1 mol of the acid (C). When two kinds of perfluoroalkyl alcohols are used, two kinds of perfluoroalkyl alcohols react with two carboxyl groups in one molecule of the unsaturated aliphatic dicarboxylic acid to form diesters. Two moles of the perfluoroalkyl alcohol are used in an amount of 0.8 to 1.2 moles, preferably 1.0 to 1.0 moles, per mole of the unsaturated aliphatic dicarboxylic acid (C) represented by the general formula (3). One mole is used, and an esterification reaction is carried out using a solvent if necessary.
[0024]
As the solvent, any solvent can be used as long as it is inert to the raw material perfluoroalkyl alcohol and unsaturated aliphatic dicarboxylic acid represented by the general formulas (2) and (3) and can dissolve both. Although not limited, for example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, and aromatics such as benzene, toluene, xylene and mesitylene Hydrocarbons, halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene, and paradichlorobenzene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane, and cyclohexane; tetrahydrofuran, diisopropyl ether; ethylene glycol Diethyl ether Ethers such as diethylene glycol diethyl ether; and among them, halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; chlorobenzene; Preferred are halogenated aromatic hydrocarbons such as dichlorobenzene and paradichlorobenzene, and aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane and cyclohexane, and halogens such as dichloromethane, chloroform and 1,2-dichloroethane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene are particularly preferred. These solvents may be used singly or as a mixture of two or more.
[0025]
In general, the esterification reaction by the dehydration reaction of carboxylic acid and alcohol is an equilibrium reaction. As a catalyst, for example, sulfuric acid, a mineral acid such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc. Equilibrium is reached in the presence of organic acids or Lewis acids such as boron trifluoride diethyl etherate complex. In order to transfer this equilibrium to the production system, for example, (1) excessive use of alcohol, (2) azeotropic distillation of generated water using a Dean-Stark water separator using benzene or toluene as a solvent. (3) a method in which a drying agent such as anhydrous magnesium sulfate or molecular sieves is put into a Soxhlet extractor and the solvent is refluxed to perform dehydration; And (5) a method using a resin mixed with aluminum chloride as a catalyst.
[0026]
The diesterification reaction between the perfluoroalkyl alcohol represented by the general formulas (2) and (3) and the unsaturated aliphatic dicarboxylic acid according to the present invention can be performed by using the above-mentioned general method. As a method for increasing the yield of the diester, the method (2) is preferable because the production is easy.
[0027]
The reaction conditions for the diesterification reaction are not particularly limited. However, since the reaction operation is easy, the perfluoroalkyl alcohol represented by the general formulas (2) and (3) and the unsaturated aliphatic dicarboxylic acid are used. A method of reacting all at once in the solvent containing the catalyst is preferable. The reaction temperature is not limited, but there is no problem as long as the dehydration reaction occurs efficiently, and it is usually 40 to 200 ° C, preferably 70 to 160 ° C. The reaction time is not limited, and is usually 30 minutes to 20 hours, preferably 1 hour to 10 hours. There is no limitation on the reaction atmosphere, but under an air atmosphere or N ₂ , He, Ar, etc., and more preferably under an inert gas atmosphere.
[0028]
Next, a method of reacting the obtained diester with mercaptocarboxylic acid, mercaptocarboxylate, or metaloxycarboxylate will be described.
[0029]
Examples of the mercaptocarboxylic acid and mercaptocarboxylate used herein include, for example, mercaptoacetic acid, mercaptoacetic acid / metal salt, 2-mercaptoethane acid, 2-mercaptoethane acid / metal salt, 2-mercaptopropionic acid, and 2-mercapto acid Propionic acid / metal salt, 2-mercaptopropionic acid / amine salt, 3-mercaptoisobutanoic acid, 3-mercaptoisobutanoic acid / metal salt, 3-mercaptoisobutanoic acid / amine salt, and the like. For example, metaloxyacetic acid / metal salt, metaloxypropionic acid / metal salt, metaloxybutanoic acid / metal salt, etc., among these, 2-mercaptoethane acid, 2-mercaptoethane acid / metal salt, Mercaptopropionic acid and 2-mercaptopropionic acid / metal salts are preferred. .
[0030]
Examples of the amine salt include ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine. , Propanolamine, toluidine, amine salts derived from pyridine and the like. Examples of the metal salt include Li salt, Na salt, K salt, Ca salt, Mg salt, Al salt and the like. Since a practical surfactant effect is obtained and the affinity with the above-described composition using an aqueous solvent is particularly high and the production is easy, amine salts, Li salts, Na salts, and K salts derived from ammonia are used. Preferably, specifically, ammonium 2-mercaptoethaneate, 2-mer Lithium Putoetan acid, sodium 2-mercapto ethane acid, potassium 2-mercapto ethane acid, 2-mercaptopropionic acid ammonium, 2-mercapto lithium propionate, 2-mercapto sodium propionate, and potassium 2-mercaptopropionic acid
[0031]
The mercaptocarboxylic acid, mercaptocarboxylate, or metaloxycarboxylate used is used in an amount of 0.5 to 5.0 mol, preferably 0.8 to 1.5 mol, per 1 mol of the diester. preferable.
[0032]
The method for reacting the diester with a mercaptocarboxylic acid, a mercaptocarboxylate, or a metaloxycarboxylate is not particularly limited, but a reaction aid may be used to promote the reaction.
[0033]
As the reaction aid, a basic substance is preferable, for example, a metal hydroxide such as lithium hydroxide and potassium hydroxide, a carbonate such as potassium carbonate and lithium carbonate, an alkali metal such as sodium methylate and sodium ethylate. Examples thereof include metal hydrides such as alcoholates, sodium hydride, and potassium hydride, and amines such as triethylamine, tri-n-butylamine, and pyridine. Particularly, sodium carbonate, potassium carbonate, and triethylamine are preferable. The reaction assistant is preferably used in an amount of 1 to 4 mol, particularly 1 to 2 mol, per 1 mol of the diester compound.
[0034]
In the reaction, a solvent may be used. The solvent is not particularly limited as long as it can dissolve the diester and mercaptocarboxylic acid, mercaptocarboxylate, and metaloxycarboxylate.Examples include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, halogenated aromatic hydrocarbons such as chlorobenzene, orthodichlorobenzene and paradichlorobenzene, n-pentane, n-hexane and n-octane , Aliphatic hydrocarbons such as cyclohexane, carboxylic esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and isopropanol, tetrahydrofuran, diisopropyl ether and ethylene glycol diethyl ether Ethers such as diethylene glycol diethyl ether, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like, among them, acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, halogenated hydrocarbons such as 1,2-dichloroethane, Alcohols such as methanol, ethanol and isopropanol, carboxylic esters such as ethyl acetate and butyl acetate, dimethylformamide, dimethylacetamide and dimethyl sulfoxide are preferred, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and butyl acetate Particularly preferred are carboxylic esters such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide. These solvents may be used singly or as a mixture of two or more.
[0035]
The reaction conditions are not particularly limited, but the reaction temperature is usually 0 ° C. to reflux temperature, preferably 20 ° C. to 60 ° C., from the viewpoint of easy reaction control. The reaction atmosphere and the like are not limited, but are preferably in an inert gas atmosphere.
[0036]
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, but may be used for a neutralization reaction and a saponification reaction as necessary. It is also possible to proceed as it is. Further, purification can be performed by distillation, washing with a solvent, recrystallization, various types of chromatography, an adsorbent, or the like.
[0037]
As a method for producing the fluorine-based compound represented by the general formula (1), a perfluoroalkyl alcohol represented by the general formula (2) and an unsaturated aliphatic dicarboxylic acid represented by the general formula (3) are used. May be reacted with mercaptocarboxylic acid or a mercaptocarboxylic acid ester to form a diester, and neutralized or saponified.
[0038]
The mercaptocarboxylic acid or mercaptocarboxylic acid ester used here is not particularly limited, but, for example, mercaptoacetic acid, mercaptoacetic acid ester, 2-mercaptoethaneic acid, 2-mercaptoethaneic acid ester, 2-mercaptopropionic acid , 2-mercaptopropionic acid ester, 3-mercaptoisobutanoic acid ester, 3-mercaptoisobutanoic acid ester and the like. Propionates are preferred.
[0039]
Examples of the neutralizer and saponifier include alkali metal hydroxides such as lithium hydroxide, alkali metal halides such as lithium chloride, and amines such as ammonia, trimethylamine, triethylamine, and pyridine. These neutralizing agents and saponifying agents are preferably used in an amount of 1 to 5 mol, preferably 1 to 2.5 mol, per 1 mol of the fluorine compound.
[0040]
The neutralization, and the reaction conditions at the time of the saponification reaction is not particularly limited, for example, as a reaction solvent, water alone or a mixed solvent of water and alcohols such as methanol, ethanol, isopropanol and the like. Is mentioned. The reaction temperature is preferably 5 ° C to 50 ° C, particularly preferably 10 ° C to 30 ° C in the case of the neutralization reaction. In the case of a saponification reaction, the temperature is preferably from 10 ° C to reflux temperature, particularly preferably from 40 ° C to 90 ° C.
[0041]
The fluorinated surfactant of the present invention may be used alone, or two or more fluorinated compounds (A) may be used simultaneously.
[0042]
The fluorinated surfactant of the present invention is preferably a hydrophilic organic solvent alone which can be mixed with water alone, such as methanol, isopropyl alcohol, acetone, methyl ethyl ketone, and dimethylformamide in an amount of 1% or more, preferably 10% or more. In a composition containing a mixed solvent of solvents, in particular, a composition containing water alone or a mixed solvent of water and an organic solvent containing 10% or more of water, since the affinity is high, the allowable range of the addition amount is wide, and , An excellent surfactant effect can be exhibited.
[0043]
Examples of the above-mentioned composition using the above-mentioned fluorine-containing surfactant of the present invention as an additive include various coatings such as printing materials, photosensitive materials, photographic materials, paints, cleaning agents, optical materials, and release agents. Materials and molding materials.
[0044]
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.
[0045]
Examples of the solvent include water and hydrophilic organic solvents. Examples of the hydrophilic organic solvent include methanol, ethanol, isopropyl alcohol, n-butanol, iso-butanol, and tert- Alcohols such as butanol, hydrophilic ketones such as acetone and methyl ethyl ketone, polar solvents such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, and hydrophilic cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve And hydrophilic glycols such as ethylene glycol and 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.
[0046]
A solvent that is hardly miscible with water, other than the above-mentioned hydrophilic organic solvent, is preferably used in combination with the hydrophilic organic solvent and used as a mixed solvent of two or more components.
[0047]
As the solute, those which dissolve or disperse in the hydrophilic organic solvent are preferable, for example, acrylic resin, urethane resin, epoxy resin, polyimide resin, polyamide resin, cellulose, chitin, natural polymers such as chitosan, gelatin, etc. And the like. These solutes may be used alone or in combination of two or more.
[0048]
Solutes that are difficult to dissolve or disperse in a hydrophilic organic solvent other than those described above are preferably used using a mixed solvent in which a solvent that is hardly miscible with water and the aforementioned hydrophilic organic solvent are used in combination.
[0049]
As the additives, hydrophilic ones are preferable, but since the amount of use is often very small, even those having low water solubility can be used, for example, silane-based, titanium-based, and zirco-aluminate-based additives. Coupling agents such as, further fluorine-containing alkoxysilane compounds, fluorine-containing titanium acylate compounds, fluorine-containing coupling agents such as fluorine-containing alkoxyzirconium compounds, silica, titanium oxide, zinc oxide, aluminum oxide, tin oxide, Inorganic powders and fillers such as zirconium oxide, calcium oxide, calcium carbonate, glass filler, etc., organic fine powders such as higher fatty acids, poly (vinylidene fluoride), poly (tetrafluoroethylene), polyethylene, acrylic beads, carbon, etc., photosensitizer , Sensitizer, light resistance improver, weather resistance improver, heat resistance improver, Conductive agents, antioxidants, rust inhibitors, rheology control agents, thickeners, anti-settling agents, antifoaming agents, include various fillers, such as deodorants. These additives may be used alone or in combination of two or more.
[0050]
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.
[0051]
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.
[0052]
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.
[0053]
By applying various processing methods to the above-described composition containing the fluorine-containing surfactant of the present invention, excellent permeation / 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.
[0054]
The use of the above-mentioned composition is not limited, and can be used for various uses.In particular, it is excellent when used in a highly hydrophilic solvent-based composition such as water alone or a mixture of water and an organic solvent. Demonstrates surface active effect, for example, antistatic agent such as PS plate, LCD, LSI, organic EL, photosensitive material such as various photoresists for plasma display manufacturing, anti-reflective coating agent for LSI manufacturing, LCD, LSI, organic Photographic materials such as EL, detergents for plasma display manufacturing, etching agents, release agents, developing solutions, emulsions, paints for automobiles, aircraft, ships, building materials, home appliances, dyes, detergents, floor polish, foam fire extinguishing agents, It is used as 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. It is possible to improve the grayed proper.
[0055]
The fluorine-based surfactant of the present invention has a high affinity for commonly used solvents other than the above-mentioned hydrophilic organic solvents and solutes, solutes, excellent surface segregation properties, and conventional fluorine-based surfactants. Because it does not impair the surface active effect of the agent, it is not limited to the above-mentioned hydrophilic composition and use, and is often used conventionally in an organic solvent system in general, for example, Industrial and household adhesives, abrasion resistance, slip resistance, non-adhesion, water and oil repellency, gas barrier properties, heat resistance, light resistance, weather resistance, physiological activity, water resistance, moisture resistance, stain resistance , Surface functional protective film forming materials such as lubricity, textiles for clothing, furniture, shoes, sundries, etc., treatment agents for artificial leather, synthetic leather nonwoven fabric, etc., various coating agents for paper, film, card, etc., automobiles, building materials, Home appliances, medical materials, office automation equipment, electric / electronic equipment Suitable for use as optical materials, electric wires and wiring materials, molding materials for various industrial parts, grease, various sealing materials, release agents, rust inhibitors, antifogging agents, antifog agents, antiblocking agents, etc. be able to.
[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 diester compound
20 g (172 mmol) of maleic acid, 3,3,4,4,5,5,6,6,6-nonafluoro were placed in a 300 ml four-necked flask equipped with a stirrer, a Dean-Stark water separator and a reflux condenser. After 99.8 g (378 mmol) of -1-hexanol, 0.5 g (5 mmol) of sulfuric acid and 50 g of toluene were added, the mixture was heated and stirred in a 130 ° C. oil bath for 3 hours. The reaction was stopped by confirming the distillation of the theoretical amount of water (6.2 ml) by a Dean-Stark water separator. After completion of the reaction, the mixture was cooled to 90 ° C., the solvent and excess alcohol used were distilled off under reduced pressure, and the residue was dried to obtain bis- (3,3,4,4,5,5,2-butenedicarboxylic acid). , 6,6,6-Nonafluorohexyl) ester [the diester (1- (1))] was obtained in an amount of 104.6 g.
[0058]
(2) Introduction of hydrophilic group
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 104.6 g (172 mmol) of the diester compound (1- (1)) obtained in (1), 16 g (174 mmol) of 2-mercaptoethanic acid, After adding 19.1 g (189 mmol) of triethylamine and 250 g of ethyl acetate, the mixture was stirred at 200 ° C. for 3 hours. After completion of the reaction, 100 g of a 5% by weight aqueous hydrochloric acid solution was added to the reaction solution to remove excess triethylamine. The organic layer and the aqueous layer were separated, and the organic layer was washed with 100 g of a 5% by weight aqueous hydrochloric acid solution. After the organic layer was separated, the solvent was distilled off under reduced pressure and the residue was dried to give bis- (3,3,4,4,5,5,6,6,6-6-carboxymethylsulfanilic acid succinate. Nonafluorohexyl) ester [substituent-containing diester (1- (2))] (120 g) was obtained.
[0059]
(3) Neutralization and saponification reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 120 g (172 mmol) of a diester derivative having a substituent (1- (2)), 7.2 g (172 mmol) of lithium hydroxide monohydrate, and isopropanol After adding 170 g and ion-exchanged water 120 g, the mixture was stirred at 20 ° C. for 1 hour. After completion of the reaction, the solvent is distilled off under reduced pressure and the residue is dried, whereby lithium bis- (3,3,4,4,5) of the desired fluorine compound (1- (3)) 2-carboxymethylsulfanylsuccinate is obtained. (12,5,6,6,6-Nonafluorohexyl) ester was obtained.
[0060]
Example 2
{Circle around (3)} In the neutralization / saponification reaction, in the same manner as in Example 1 except that 9.7 g (172 mmol) of potassium hydroxide was used instead of 7.2 g (172 mmol) of lithium hydroxide / monohydrate. 127 g of potassium bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester of the desired fluorine compound (2- (3)) 2-carboxymethylsulfanylsuccinate Obtained.
[0061]
Example 3
{Circle around (3)} In the neutralization / saponification reaction, in the same manner as in Example 1 except that 6.9 g (172 mmol) of sodium hydroxide was used instead of 7.2 g (172 mmol) of lithium hydroxide / monohydrate. , The desired fluorine-based compound (3- {3}) sodium 2-carboxymethylsulfanylsuccinate bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester 2 g were obtained.
[0062]
Example 4
{Circle around (3)} Same as Example 1 except that in the neutralization / saponification reaction, 17.6 g (258 mmol) of 25 wt% aqueous ammonia was used instead of 7.2 g (172 mmol) of lithium hydroxide monohydrate. To obtain the desired fluorine compound (4- (3)) 2-carboxymethylsulfanyl ammonium bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester 123.4 g were obtained.
[0063]
Example 5
(2) Examples 1- (1) and 1- (1) except that 18.5 g (174 mmol) of 2-mercaptopropionic acid was used instead of 16 g (174 mmol) of 2-mercaptoethanic acid in the introduction of the hydrophilic group. 2- (2-carboxyethylsulfanyl) succinic acid bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester [substituent-containing diester compound] (5- (2))] 121.6 g was obtained. Next, in the neutralization / saponification reaction of (3), instead of 120 g (172 mmol) of the diester compound having a substituent (1- (2)), 121.6 g (170 mmol) of a diester compound having a substituent (5- (2)) was used. ) Was used in the same manner as in Example 1- (3), except that the desired fluorine-containing compound (5- (3)) 2- (2-carboxyethylsulfanyl) lithium bis- (3,3,4) was used. , 4,5,5,6,6,6-Nonafluorohexyl) ester 122.4 g was obtained.
[0064]
Example 6
{Circle around (2)} In introducing a hydrophilic group, 15.3 g (174 mmol) of lithium 2-lithium oxyethanoate is used instead of 16 g (174 mmol) of 2-mercaptoethanic acid, and [3] a neutralization / saponification reaction is performed. In the same manner as in Example 1 except that there was no such compound, the target fluorine-based compound (6- ▲ 2) lithium bis- (3,3,4,4,5,5,6,6) -2-carboxymethoxysuccinate was used. , 6-Nonafluorohexyl) ester was obtained.
[0065]
Example 7
(1) Synthesis of diester compound
In the same manner as in Example 1- (1), except that 22.4 g (172 mmol) of cis-2-pentenedicarboxylic acid was used instead of 20 g (172 mmol) of maleic acid, the diester (7- (1)) 2-pentene was used. 107 g of dicarboxylic acid bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester [diester (7-1)] was obtained.
[0066]
(2) Introduction of hydrophilic group
3-Carboxy was prepared in the same manner as in Example 1- (2), except that 107 g (172 mmol) of the diester (7-1) was used instead of 104.6 g (172 mmol) of the diester (1- (1)). 121.7 g of bis- (3,3,4,4,5,5,6,6,6-nonafluorohexyl) ester of methylsulfanylpentanedicarboxylic acid [substituent-containing diester (7- [2])] was obtained. Was.
[0067]
(3) Neutralization and saponification reaction
Example 1- ▲ except that 121.7 g (170.4 mmol) of the substituent-containing diester (7- ▲ 2) was used instead of 120 g (172 mmol) of the substituent-containing diester (1- ▲ 2). In the same manner as in 3), the desired fluorine compound (7- (3)) 3-carboxymethylsulfanylpentanedicarboxylate lithium bis- (3,3,4,4,5,5,6,6,6-nonafluoro) 122.7 g of hexyl) ester were obtained.
[0068]
Example 8
(1) Synthesis of diester compound
In a 300 ml four-necked flask equipped with a stirrer, a Dean-Stark water separator and a reflux condenser, 20 g (172 mmol) of maleic acid, 3,3,4,4,5,5,6,6,7,7 were added. After adding 13,7.6 g (378 mmol) of sulfuric acid, 8,8,8-tridecafluoro-1-octanol, 0.5 g (5 mmol) of sulfuric acid and 100 g of toluene, the mixture was heated and stirred in a 140 ° C. oil bath for 4 hours. The reaction was stopped by confirming the distillation of the theoretical amount of water (6.2 ml) by a Dean-Stark water separator. After completion of the reaction, the mixture was cooled to 90 ° C., the solvent and excess alcohol used were distilled off under reduced pressure, and the residue was dried to obtain bis- (3,3,4,4,5,5,2-butenedicarboxylic acid). , 6,6,7,7,8,8,8-Tridecafluorooctyl) ester [diester (8- (1)]] was obtained.
[0069]
(2) Introduction of hydrophilic group
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 139 g (172 mmol) of the diester compound (8- (1)), 16 g (174 mmol) of 2-mercaptoethanic acid, 19.1 g (189 mmol) of triethylamine and acetic acid After adding 250 g of ethyl, the mixture was stirred at 200 ° C. for 4 hours. After completion of the reaction, 100 g of a 5% by weight aqueous hydrochloric acid solution was added to the reaction solution to remove excess triethylamine. The organic layer and the aqueous layer were separated, and the organic layer was washed with 100 g of a 5% by weight aqueous hydrochloric acid solution. After separating the organic layer, the solvent was distilled off under reduced pressure and dried to obtain bis- (3,3,4,4,5,5,6,6,7,7,2-carboxymethylsulfanylsuccinate. , 8,8,8-Tridecafluorooctyl) ester [substituent-containing diester (8- (2))] was obtained in an amount of 154.9 g.
[0070]
(3) Neutralization and saponification reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 154.9 g (172 mmol) of the diester derivative (8- (2)) having a substituent and 7.2 g (172 mmol) of lithium hydroxide monohydrate were placed. After adding 200 g of isopropanol and 150 g of ion-exchanged water, the mixture was stirred at 20 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was dried to obtain the desired fluorine-based compound (8- [3]) 2-carboxymethylsulfanyl lithium bis- (3,3,4,4,5). , 5,6,6,7,7,8,8,8-Tridecafluorooctyl) ester were obtained in an amount of 155.9 g.
[0071]
Example 9
(1) Synthesis of diester compound
In a 300 ml four-necked flask equipped with a stirrer, a Dean-Stark water separator and a reflux condenser, 22.4 g (172 mmol) of cis-2-methyl-2-butene, 3,3,4,4,5, After 99.8 g (378 mmol) of 5,6,6,6-nonafluoro-1-hexanol, 0.5 g (5 mmol) of sulfuric acid and 100 g of toluene were added, the mixture was heated and stirred in a 140 ° C. oil bath for 4 hours. The reaction was stopped by confirming the distillation of the theoretical amount of water (6.2 ml) by a Dean-Stark water separator. After completion of the reaction, the reaction mixture was cooled to 90 ° C., and the solvent and excess alcohol were distilled off under reduced pressure, followed by drying to obtain bis- (3,3,4,4,5,5,2-methylsuccinate). 107 g of 6,6,6-nonafluorohexyl) ester [a diester derivative (9-1-1)] was obtained.
[0072]
(2) Introduction of hydrophilic group
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 107 g (172 mmol) of the diester compound (9-1), 16 g (174 mmol) of 2-mercaptoethanic acid, 19.1 g (189 mmol) of triethylamine and acetic acid After adding 250 g of ethyl, the mixture was stirred at 200 ° C. for 4 hours. After completion of the reaction, 100 g of a 5% by weight aqueous hydrochloric acid solution was added to the reaction solution to remove excess triethylamine. The organic layer and the aqueous layer were separated, and the organic layer was washed with 100 g of a 5% by weight aqueous hydrochloric acid solution. After the organic layer was separated, the solvent was distilled off under reduced pressure and the residue was dried, whereby bis- (3,3,4,4,5,5,6,6,6,7-carboxymethylsulfanyl-3-methylsulfinate was obtained. , 7,7-Nonafluorohexyl) ester [substituent-containing diester (9- {2})] was obtained in an amount of 122.9 g.
[0073]
(3) Neutralization and saponification reaction
In a 300 ml four-necked flask equipped with a stirrer and a reflux condenser, 122.9 g (172 mmol) of a diester derivative having a substituent (9- (2)) and 7.2 g (172 mmol) of lithium hydroxide monohydrate. After adding 190 g of isopropanol and 140 g of ion-exchanged water, the mixture was stirred at 30 ° C. for 4 hours. After completion of the reaction, the solvent is distilled off under reduced pressure and the residue is dried to obtain the desired fluorine-based compound (9- [3]) 2-carboxymethylsulfanyl-3-methyllithium bis- (3,3,4,4). , 5,5,6,6,7,7,7-Nonafluorohexyl) ester were obtained.
[0074]
Test Examples 1 to 9, 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 9 were measured by the following methods, and are shown in Tables 1 and 2 as Test Examples 1 to 9.
[0075]
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)
[0076]
Further, as Comparative Test Example 1, Fluowet SB (30% by weight solution of a butyl glycol / water mixed solvent) described in a catalog of Fluowet products of Clariant Japan Co., Ltd. was completely distilled off the solvent at 120 ° C. The solubility in water and the surface tension in the aqueous solution were measured by the methods described above. The results are shown in Tables 1 and 2.
[0077]
[Table 2]

[0078]
[Table 3]

[0079]
In Test Examples 1 to 9 using the fluorine-based surfactant comprising the fluorine-based compound of the present invention, it was confirmed that the solubility in water was high and the surface tension-reducing action was excellent.
[0080]
Test Examples 10 and 11
Using the fluorine-based compound 1- (3) obtained in Example 1, the solubility in methanol (Test Example 10) and a mixed solvent of ion-exchanged water / methanol = 1/1 (weight ratio) (Test Example 11), In addition, the surface tension was measured. Table 3 shows the results.
[Table 4]

[0081]
The fluorine surfactant comprising the fluorine-based compound of the present invention has high solubility not only in water but also in a hydrophilic organic solvent, and can exhibit excellent surface active effects as in the case of using water alone. confirmed.
[0082]
Test Examples 12 and 13
Using the fluorine compound (1- (3)) obtained in Example 1, the effect of using the compound with a hydrocarbon surfactant was confirmed. Test Example 12 The surface tension of a mixture of a fluorine-based compound (1- (3)) and a hydrocarbon-based surfactant (polyoxyethylene oleyl ether: Emulgen 430 manufactured by Kao Corporation) in a 0.001% by weight aqueous solution was measured. , 13 are shown in Table 4.
[0083]
[Table 5]

[0084]
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.
[0085]
【The invention's effect】
According to the present invention, mainly a printing material, a photosensitive material, a photographic material, a paint, a cleaning agent, an optical material, a release agent, and the like, which are used by using water and / or an aqueous solvent such as a hydrophilic organic solvent. It is possible to provide a fluorine-based surfactant which can be easily dissolved in various coating materials and molding materials, and can be suitably used as an additive for enhancing permeation / wetting property, leveling property, surface functionality and the like.

Claims (7)

In one molecule, two identical or different F (CF ₂ ) _2m (CH ₂ ) _n OCO- (where m and n are integers of 1 to 12 and may be the same or different). And —SR ₁ COOM ₁ (wherein, R ₁ represents an alkylene chain, M ₁ represents a hydrogen atom, ammonium, or a metal), or —OR ₂ COOM ₂ (where R ₂ represents an alkylene chain) chains, M ₂ is a fluorine-based surface active agent characterized by comprising a fluorine-based compound (a) having a show.) ammonium or metals. The fluorine compound (A) has the following general formula (1)
F (CF2) 2m (CH2) nOCO (CH2) oC (X) (Y) CH (Z) COO (CH2) n (CF2) 2mF (1)
(In the formula, m, n, and o are integers of 1 to 12, and may be the same or different. X and Z are a hydrogen atom or a hydrocarbon group of 1 to 12 carbon atoms, and are the same or different. Y is -SR ₁ COOM ₁ (wherein, R ₁ represents an alkylene chain, M ₁ represents a hydrogen atom, ammonium, or metals), or -OR ₂ COOM ₂ (where R _{2 represents} is an alkylene chain, M ₂ represents an ammonium or metals.).)
The fluorine-based surfactant according to claim 1, which is a fluorine-based compound represented by the formula: In the general formula (1), m is an integer of 2 to 3, n is an integer of 1 to 4, o is an integer of 0 to 4, X and Z are hydrogen atoms, Y is -SR ₁ COOM ₁ , and M ₁ Is a hydrogen atom, —NH ₄ , or a metal. The fluorine compound (A) has the following general formula (2)
F (CF2) 2m (CH2) nOH (2)
(In the formula, m and n are integers of 1 to 12, and may be the same or different.)
The unsaturated aliphatic dicarboxylic acid is reacted with one or two kinds of perfluoroalkyl alcohols (B) represented by the following formula to form a diester, and further reacted with a mercaptocarboxylic acid, a mercaptocarboxylate or a metaloxycarboxylate. The fluorinated surfactant according to claim 1, which is a fluorinated compound obtained by the reaction. The fluorine compound (A) has the following general formula (2)
F (CF2) 2m (CH2) nOH (2)
(In the formula, m and n are integers of 1 to 12, and may be the same or different.)
One or two kinds of perfluoroalkyl alcohols (B) represented by the following general formula (3)
HOOC (CH2) o (X) C = C (Z) COOH (3)
(In the formula, o is an integer of 0 to 12, X and Z are a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and may be the same or different.)
Is a fluorine-based compound obtained by reacting an unsaturated aliphatic dicarboxylic acid (C) represented by the formula (1) to form a diester, and further reacting a mercaptocarboxylic acid, a mercaptocarboxylic acid salt, or a metaloxycarboxylic acid salt. 2. The fluorine-based surfactant according to 2. M in the general formula (2) is an integer of 2 to 3, n is an integer of 1 to 4, o in the general formula (3) is an integer of 0 to 4, X and Z are hydrogen atoms, 4. The fluorine-based surfactant according to claim 3, wherein the mercaptocarboxylic acid, mercaptocarboxylic acid salt or metaloxycarboxylic acid salt is a mercaptocarboxylic acid, a mercaptocarboxylic acid metal salt, or a mercaptocarboxylic acid ammonium salt. After reacting one or two compounds represented by the general formula (2) with a compound represented by the general formula (3) to form a diester, and further reacting with a mercaptocarboxylic acid or a mercaptocarboxylic acid ester, The fluorinated surfactant according to claim 4, 5 or 6, which is neutralized or saponified.