JP4590703B2 - Fluorinated polyether carboxylic acid ester - Google Patents
Fluorinated polyether carboxylic acid ester Download PDFInfo
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- JP4590703B2 JP4590703B2 JP2000262721A JP2000262721A JP4590703B2 JP 4590703 B2 JP4590703 B2 JP 4590703B2 JP 2000262721 A JP2000262721 A JP 2000262721A JP 2000262721 A JP2000262721 A JP 2000262721A JP 4590703 B2 JP4590703 B2 JP 4590703B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、含フッ素ポリエーテルカルボン酸エステルに関する。更に詳しくは、1分子中に2個以上の重合性官能基を有する含フッ素ポリエーテルカルボン酸エステルに関する。
【０００２】
【従来の技術】
特許第2,563,959号公報には、一般式
R1OCH2CFX1(OCF2CFX2)lO(CF2)mO(CFX3CF2O)nCFX4CH2OR2
R1,R2：ビニル基、アリル基、アクリロイル基、メタアクリロイル基
またはエポキシアルキル基
X1〜X4：パーフルオロアルキル基
l,n：0以上の整数
m：2以上の整数
で表される含フッ素エーテル化合物が記載されている。
【０００３】
この化合物は、相当する酸フロライドをメチルエステル化した後還元を行い、得られたアルコールに酸ハライドを反応させるという３つの工程がとられている。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、酸ハライドに直接アルコールを反応させるという１段階の反応によって得られる、1分子中に2個以上の重合性官能基を有する新規な含フッ素ポリエーテルカルボン酸エステルを提供することにある。
【０００５】
【課題を解決するための手段】
かかる本発明の目的は、一般式
R1OCOCF(CF3)[OCF2CF(CF3)]aO(CF2)bO[CF(CF3)CF2O]cCF(CF3)COOR1
〔ここで、R1は一般式 (CH 2 =CR 2 COOCH 2 ) 2 CH- (R 2 は水素原子またはメチル基である)で表わされる基、一般式 (CH 2 =CR 2 COOCH 2 ) 3 CCH 2 - (R 2 は水素原子またはメチル基である)で表わされる基またはグリシジル基であり、a+cは0または28以下の整数であり、bは2以上の整数である〕で表わされる含フッ素ポリエーテルカルボン酸エステルによって達成される。
【０００６】
【発明の実施の形態】
上記含フッ素ポリエーテルカルボン酸エステルは、一般式
XOCCF(CF3)[OCF2CF(CF3)]aO(CF2)bO[CF(CF3)CF2O]cCF(CF3)COX
X：ハロゲン原子
a+c：0または28以下の整数
b：2以上の整数
で表わされるパーフルオロポリエーテルジカルボン酸ジハライドに、一般式R1OHで表わされる水酸基含有化合物を反応させることによって製造される。
【０００７】
この反応の主たる原料物質として用いられるパーフルオロポリエーテルジカルボン酸ジハライドにおいて、ハライド基としては原料合成の容易さからフッ素原子であることが好ましく、またbの値は原料入手の容易さから2〜6であることが好ましい。さらに、a+cの値は28以下が好ましく、製造の容易さからは20以下であることが特に好ましい。a+cの値の調節は、一般的には対応するパーフルオロアルキルジカルボン酸ジフロライドに触媒の存在下でヘキサフルオロプロペンオキシドを反応させ、分布の生じたパーフルオロポリエーテル化合物を蒸留し、希望するa+cの値を有するジカルボン酸ジハライドを取得することによって行われる。
【０００８】
このようなパーフルオロポリエーテルジカルボン酸ジハライドと反応する水酸基含有化合物R1OHのR1基は、ビニル基、アリル基、アクリロイル基、メタクリロイル基等の不飽和二重結合基またはエポキシアルキル基等のエポキシ基などの重合性官能基である。より具体的には、次のような基が例示される。
(CH2=CR2COOCH2)2CH-
(CH2=CR2COOCH2)3CCH2-
R2：水素原子またはメチル基
水酸基含有化合物の具体例としては、グリセリンジアクリレート、グリセリンジメタクリレート、グリセリンモノアクリレートモノメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、2,3-エポキシプロパノール等が挙げられる。
【００１０】
これら両者間の反応は、水酸基含有化合物を約2.0〜3.0倍モル、好ましくは2.0〜2.2倍モル用いる脱ハロゲン化水素縮合反応によって行われる。反応溶媒としては、この反応に不活性なものであれば任意のものを使用し得るが、一般にはジアルキルエーテル、好ましくは沸点が低く、除去の容易なジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン等が用いられる。
【００１１】
この反応は脱ハロゲン化水素反応であるので、ハロゲン化水素の捕捉剤の存在下で行われることが好ましい。フッ化水素の捕捉剤としてはアルカリ金属フッ化物が一般に用いられ、生じたフッ化水素の保持能力や価格の点からはフッ化ナトリウムが好んで用いられる。それの使用割合は、含フッ素ポリエーテルジカルボン酸ジフロライドに対して約2〜8倍モル、好ましくは2.1〜3.0倍モルの範囲内にある。また、他のハロゲン化水素の場合には、トリアルキルアミン、ピリジン誘導体等が、パーフルオロポリエーテルジカルボン酸ジハライドに対し約2〜6倍モルの割合で用いられ、好ましくはトリエチルアミンが2.0〜3.0倍モルの割合で用いられる。
【００１２】
また、用いられる重合性官能基を有する水酸基含有化合物や生成物の望まない重合を抑制するために、反応系内にフェノチアジン、ハイドロキノン、メトキノン等の重合禁止剤、好ましくはハイドロキノンまたはメトキノンが添加して用いられる。これらの重合禁止剤は、生成が予想される含フッ素ポリエーテルカルボン酸エステルに対し、約0.01〜1重量%の割合で一般に用いられ、生成物が高沸点で蒸留精製などができない場合もあるので、特に好ましくは0.03〜0.1重量%の割合で添加して用いられる。この範囲内での重合禁止剤の添加は、生成物の重合の妨げとなることはない。
【００１３】
反応温度は、約-80℃から用いられる反応溶媒の沸点迄の幅広い選択が可能であるが、原料や生成物の重合を防ぐためには、可能な限り低温であることが望ましく、反応温度の調節のし易さという点からは約-20〜10℃の範囲が特に好ましい。
【００１４】
【発明の効果】
本発明に係る含フッ素ポリエーテルカルボン酸エステルは、1分子中に2個以上の重合性官能基を有し、また1分子中に多数のフッ素原子を有するため、熱的安定性、化学的安定性にすぐれ、その上良好な光学特性や界面活性特性を併せ持っている。
【００１５】
さらに、この生成物は可視光、紫外線、電子線などのエネルギー線の照射による硬化が可能であるので、感光性硬化型のインキ、塗料、電子線硬化型の塗料、紫外線硬化型の接着剤などへの応用が可能である。また、多官能性モノマーであるので、3次元構造での架橋が可能となり、各種樹脂の架橋剤、改質剤等として用い、硬度、強度、耐熱性、耐候性、耐薬品性などの物性の向上や改良を可能とする。
【００１６】
この生成物はまた、分子中のフッ素含量が多いため低屈折率を示しており、このためディスプレイ等の反射防止膜、光ファイバー等のクラッド材として利用することもできる。さらに、界面活性特性を利用して、各種離型用コーティング剤、各種表面コーティング剤、表面改質剤、撥水撥油剤等にも用いることができる。
【００１７】
【実施例】
次に、実施例について本発明を説明する。
【００１８】
実施例１
窒素ガス雰囲気下に、ペンタエリスリトールトリアクリレート71g(0.238モル)をフッ化ナトリウム13g(0.310モル)をけん濁させたジエチルエーテル60ml中に加え、そこにメトキノン0.01gを加えて、氷浴で冷却した。内温を10℃以下に保ちながら、ゆっくりと2,7-ビス(トリフルオロメチル)-3,6-ジオキサオクタンジカルボン酸ジフロライド FOCCF(CF3)O(CF2)2OCF(CF3)COF 52.9g(ガスクロマトグラフィーによる純度95.9%；0.119モル)を滴下した。
【００１９】
滴下終了後氷浴を外し、室温条件下で8時間以上攪拌した後、結晶をロ別したロ液を飽和炭酸水素ナトリウムおよび飽和食塩水の順で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後、減圧下でジエチルエーテルを除去し、常温で高粘度液体である目的物を98.7g(F-NMRによる純度82.3%；収率69.4%)を得た。
【００２０】
この目的物は、H-NMRおよびF-NMRのデーターから、次のような構造式を有するペンタエリスリトールトリアクリレート誘導体であると判断される。
[(CH2=CHCOOCH2)３CCH2OCOCF(CF３)OCF2-]2
H-NMR(CDCl３,TMS)：δ4.28(12H)
4.40(4H)
5.88(2H)
6.14(6H)
6.42(6H)
F-NMR(neat CFCl３)；ppm -82.30(CF３)
-87.35(OCF2)
-131.85(CF)
【００２１】
実施例２
窒素ガス雰囲気下に、2,3-エポキシ-1-プロパノール17.8g(0.240モル)をフッ化ナトリウム14.0g(0.334モル)をけん濁させたジエチルエーテル75ml中に加え、氷浴で冷却した。内温を10℃以下に保ちながら、ゆっくりと2,7-ビス(トリフルオロメチル)-3,6-ジオキサオクタンジカルボン酸ジフロライド FOCCF(CF3)O(CF2)2OCF(CF3)COF 51.9g(ガスクロマトグラフィーによる純度98.5%；0.120モル)を滴下した。
【００２２】
滴下終了後氷浴を外し、室温条件下で8時間以上攪拌した後、結晶をロ別したロ液を飽和炭酸水素ナトリウムおよび飽和食塩水の順で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後、減圧下でジエチルエーテルを除去し、常温で高粘度液体である目的物を49.6g(F-NMRによる純度97.5%；収率75.4%)を得た。
【００２３】
この目的物は、H-NMRおよびF-NMRのデーターから、次のような構造式を有する2,3-エポキシ-1-プロピオニルジエステルであると判断される。
3.26(2H)
4.46(4H)
F-NMR(neat CFCl３)；ppm -81.32(CF3)
-85.80(OCF2)
-130.20(CF)
【００２４】
以上の実施例1〜2の生成物の精製は、熱媒を用い、分子蒸留装置内を真空ポンプまたは拡散ポンプを用いて真空とした上で、蒸留装置上部からゆっくりと生成物を滴下し、蒸留回収留分と不揮発性成分とに分け、前者を同様の蒸留操作に再度付すことによって行われた。 [0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fluorine-containing polyether carboxylic acid ester. More specifically, the present invention relates to a fluorine-containing polyether carboxylic acid ester having two or more polymerizable functional groups in one molecule.
[0002]
[Prior art]
Japanese Patent No. 2,563,959 discloses a general formula
R 1 OCH 2 CFX 1 (OCF 2 CFX 2 ) l O (CF 2 ) m O (CFX 3 CF 2 O) n CFX 4 CH 2 OR 2
R 1 and R 2 : Vinyl group, allyl group, acryloyl group, methacryloyl group
Or epoxy alkyl group
X 1 to X 4 : perfluoroalkyl group
l, n: An integer greater than or equal to 0
m: A fluorine-containing ether compound represented by an integer of 2 or more is described.
[0003]
This compound is subjected to three steps: methyl esterification of the corresponding acid fluoride, followed by reduction, and reaction of the acid halide with the resulting alcohol.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel fluorine-containing polyether carboxylic acid ester having two or more polymerizable functional groups in one molecule obtained by a one-step reaction in which an alcohol is directly reacted with an acid halide. It is in.
[0005]
[Means for Solving the Problems]
The object of the present invention is to provide a general formula
R 1 OCOCF (CF 3 ) [OCF 2 CF (CF 3 )] a O (CF 2 ) b O [CF (CF 3 ) CF 2 O] c CF (CF 3 ) COOR 1
(Where R 1 is a group represented by the general formula (CH 2 = CR 2 COOCH 2 ) 2 CH- (R 2 is a hydrogen atom or a methyl group), and a general formula (CH 2 = CR 2 COOCH 2 ) 3 A group represented by CCH 2 − (where R 2 is a hydrogen atom or a methyl group) or a glycidyl group , a + c is 0 or an integer of 28 or less, and b is an integer of 2 or more. Thus it is achieved fluoropolyether carboxylic acid ester.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The fluorine-containing polyether carboxylic acid ester has the general formula
XOCCF (CF 3 ) [OCF 2 CF (CF 3 )] a O (CF 2 ) b O [CF (CF 3 ) CF 2 O] c CF (CF 3 ) COX
X: Halogen atom
a + c: 0 or an integer less than or equal to 28
b: Produced by reacting a perfluoropolyether dicarboxylic acid dihalide represented by an integer of 2 or more with a hydroxyl group-containing compound represented by the general formula R 1 OH.
[0007]
In the perfluoropolyether dicarboxylic acid dihalide used as the main raw material of this reaction, the halide group is preferably a fluorine atom because of the ease of raw material synthesis, and the value of b is 2 to 6 because of the availability of the raw material. It is preferable that Further, the value of a + c is preferably 28 or less, and particularly preferably 20 or less for ease of production. Adjustment of the value of a + c is generally achieved by reacting the corresponding perfluoroalkyldicarboxylic acid difluoride with hexafluoropropene oxide in the presence of a catalyst and distilling the perfluoropolyether compound with the desired distribution. This is done by obtaining a dicarboxylic acid dihalide having a value of a + c.
[0008]
The R 1 group of the hydroxyl group-containing compound R 1 OH that reacts with such a perfluoropolyether dicarboxylic acid dihalide is an unsaturated double bond group such as a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, or an epoxyalkyl group. It is a polymerizable functional group such as an epoxy group. More specifically, the following groups are exemplified .
( CH 2 = CR 2 COOCH 2 ) 2 CH-
(CH 2 = CR 2 COOCH 2 ) 3 CCH 2-
R 2 : hydrogen atom or methyl group
Specific examples of the hydroxyl group-containing compound include glycerol diacrylate , glycerol dimethacrylate, glycerol monoacrylate monomethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and 2,3-epoxypropanol.
[0010]
The reaction between them is carried out by a dehydrohalogen condensation reaction using a hydroxyl group-containing compound in an amount of about 2.0 to 3.0 times mol, preferably 2.0 to 2.2 times mol. Any reaction solvent can be used as long as it is inert to this reaction. Generally, dialkyl ethers, preferably diethyl ether, diisopropyl ether, tetrahydrofuran, etc., having a low boiling point and easy to remove are used. .
[0011]
Since this reaction is a dehydrohalogenation reaction, it is preferably carried out in the presence of a hydrogen halide scavenger. Alkali metal fluoride is generally used as the scavenger for hydrogen fluoride, and sodium fluoride is preferably used from the viewpoint of the ability to retain the generated hydrogen fluoride and the cost. The use ratio thereof is about 2 to 8 times mol, preferably 2.1 to 3.0 times mol for the fluorine-containing polyether dicarboxylic acid difluoride. In the case of other hydrogen halides, trialkylamines, pyridine derivatives and the like are used in a ratio of about 2 to 6 times moles with respect to perfluoropolyether dicarboxylic acid dihalide, preferably triethylamine is 2.0 to 3.0 times. Used in molar proportions.
[0012]
In addition, in order to suppress unwanted polymerization of the hydroxyl group-containing compound or product having a polymerizable functional group used, a polymerization inhibitor such as phenothiazine, hydroquinone, or methoquinone, preferably hydroquinone or methoquinone is added to the reaction system. Used. These polymerization inhibitors are generally used at a ratio of about 0.01 to 1% by weight with respect to the fluorine-containing polyether carboxylic acid ester expected to be produced, and the product has a high boiling point and may not be purified by distillation. Particularly preferably, it is added and used at a ratio of 0.03 to 0.1% by weight. Addition of the polymerization inhibitor within this range does not hinder the polymerization of the product.
[0013]
The reaction temperature can be selected widely from about -80 ° C to the boiling point of the reaction solvent used. However, in order to prevent polymerization of raw materials and products, it is desirable that the temperature be as low as possible. A range of about −20 to 10 ° C. is particularly preferable from the viewpoint of ease of treatment.
[0014]
【The invention's effect】
The fluorine-containing polyether carboxylic acid ester according to the present invention has two or more polymerizable functional groups in one molecule and also has a large number of fluorine atoms in one molecule, so that it has thermal stability and chemical stability. In addition, it has excellent optical properties and surface active properties.
[0015]
Furthermore, this product can be cured by irradiation with energy rays such as visible light, ultraviolet rays, and electron beams, so photosensitive curable inks, paints, electron beam curable paints, ultraviolet curable adhesives, etc. Application to is possible. In addition, since it is a polyfunctional monomer, it can be cross-linked in a three-dimensional structure and used as a cross-linking agent, modifier, etc. for various resins and has physical properties such as hardness, strength, heat resistance, weather resistance, and chemical resistance. Improve and improve.
[0016]
This product also exhibits a low refractive index because of the high fluorine content in the molecule, and can therefore be used as an antireflection film for displays and the like, and a cladding material for optical fibers and the like. Furthermore, it can be used for various release coating agents, various surface coating agents, surface modifiers, water- and oil-repellent agents and the like by utilizing surface active properties.
[0017]
【Example】
Next, the present invention will be described with reference to examples.
[0018]
Example 1
Under a nitrogen gas atmosphere, 71 g (0.238 mol) of pentaerythritol triacrylate was added to 60 ml of diethyl ether in which 13 g (0.310 mol) of sodium fluoride was suspended, and 0.01 g of methoquinone was added thereto, followed by cooling in an ice bath. . Slowly maintain 2,7-bis (trifluoromethyl) -3,6-dioxaoctanedicarboxylic acid difluoride FOCCF (CF 3 ) O (CF 2 ) 2 OCF (CF 3 ) COF while keeping the internal temperature below 10 ° C 52.9 g (purity 95.9% by gas chromatography; 0.119 mol) was added dropwise.
[0019]
After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred for 8 hours or more at room temperature. After the organic layer was dried over anhydrous magnesium sulfate, diethyl ether was removed under reduced pressure to obtain 98.7 g (purity 82.3% by F-NMR; yield 69.4%) of a target product which was a high-viscosity liquid at room temperature.
[0020]
This target product is judged to be a pentaerythritol triacrylate derivative having the following structural formula from H-NMR and F-NMR data.
[(CH 2 = CHCOOCH 2 ) 3 CCH 2 OCOCF (CF 3 ) OCF 2- ] 2
H-NMR (CDCl 3 , TMS): δ 4.28 (12H)
4.40 (4H)
5.88 (2H)
6.14 (6H)
6.42 (6H)
F-NMR (neat CFCl 3 ); ppm -82.30 (CF 3 )
-87.35 (OCF 2 )
-131.85 (CF)
[0021]
Example 2
Under a nitrogen gas atmosphere, 17.8 g (0.240 mol) of 2,3-epoxy-1-propanol was added to 75 ml of diethyl ether in which 14.0 g (0.334 mol) of sodium fluoride was suspended and cooled in an ice bath. Slowly maintain 2,7-bis (trifluoromethyl) -3,6-dioxaoctanedicarboxylic acid difluoride FOCCF (CF 3 ) O (CF 2 ) 2 OCF (CF 3 ) COF while keeping the internal temperature below 10 ° C 51.9 g (purity 98.5% by gas chromatography; 0.120 mol) was added dropwise.
[0022]
After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred for 8 hours or more at room temperature. After the organic layer was dried over anhydrous magnesium sulfate, diethyl ether was removed under reduced pressure to obtain 49.6 g (purity: 97.5% by F-NMR; yield: 75.4%) of the target compound which was a high-viscosity liquid at room temperature.
[0023]
This target product is judged to be 2,3-epoxy-1-propionyl diester having the following structural formula from H-NMR and F-NMR data.
3.26 (2H)
4.46 (4H)
F-NMR (neat CFCl 3 ); ppm -81.32 (CF 3 )
-85.80 (OCF 2 )
-130.20 (CF)
[0024]
For purification of the products of Examples 1 and 2 above, the heating medium is used and the molecular distillation apparatus is evacuated using a vacuum pump or a diffusion pump, and then the product is slowly dropped from the upper part of the distillation apparatus. It was carried out by dividing the distillation-recovered fraction and the non-volatile component, and subjecting the former to the same distillation operation again.
Claims (4)
R1OCOCF(CF3)[OCF2CF(CF3)]aO(CF2)bO[CF(CF3)CF2O]cCF(CF3)COOR1
〔ここで、R1は一般式 (CH 2 =CR 2 COOCH 2 ) 2 CH- (R 2 は水素原子またはメチル基である)で表わされる基、一般式 (CH 2 =CR 2 COOCH 2 ) 3 CCH 2 - (R 2 は水素原子またはメチル基である)で表わされる基またはグリシジル基であり、a+cは0または28以下の整数であり、bは2以上の整数である〕で表わされる含フッ素ポリエーテルカルボン酸エステル。General formula
R 1 OCOCF (CF 3 ) [OCF 2 CF (CF 3 )] a O (CF 2 ) b O [CF (CF 3 ) CF 2 O] c CF (CF 3 ) COOR 1
( Where R 1 is a group represented by the general formula (CH 2 = CR 2 COOCH 2 ) 2 CH- (R 2 is a hydrogen atom or a methyl group), and a general formula (CH 2 = CR 2 COOCH 2 ) 3 CCH 2 - (R 2 is hydrogen atom or a methyl group) is a group or a glycidyl group represented by, a + c is 0 or 28 an integer, b is represented by a is] an integer of 2 or more Fluorine-containing polyether carboxylic acid ester.
XOCCF(CFXOCCF (CF 3Three )[OCF) [OCF 22 CF(CFCF (CF 3Three )])] aa O(CFO (CF 22 )) bb O[CF(CFO [CF (CF 3Three )CFCF 22 O]O] cc CF(CFCF (CF 3Three )COXCOX
(ここで、Xはハロゲン原子であり、a+cは0または28以下の整数であり、bは2以上の整数である)で表わされるパーフルオロポリエーテルジカルボン酸ジハライドに、一般式 R(Wherein X is a halogen atom, a + c is an integer of 0 or 28 or less, and b is an integer of 2 or more), a perfluoropolyether dicarboxylic acid dihalide represented by the general formula R 11 OH〔ここで、ROH (where R 11 は一般式 (CHIs the general formula (CH 22 =CR= CR 22 COOCHCOOCH 22 )) 22 CH- (RCH- (R 22 は水素原子またはメチル基である)で表わされる基、一般式 (CHIs a hydrogen atom or a methyl group), a general formula (CH 22 =CR= CR 22 COOCHCOOCH 22 )) 3Three CCHCCH 22 - (R-(R 22 は水素原子またはメチル基である)で表わされる基またはグリシジル基である〕で表わされる水酸基含有化合物を反応させることを特徴とする請求項１記載の含フッ素ポリエーテルカルボン酸エステルの製造法。Is a hydrogen atom or a methyl group), or a glycidyl group] is reacted. 2. The process for producing a fluorinated polyether carboxylic acid ester according to claim 1, wherein
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| US6496637B2 (en) * | 2000-12-21 | 2002-12-17 | Corning Incorporated | Low optical loss polymers |
| JP4285238B2 (en) * | 2001-09-11 | 2009-06-24 | ダイキン工業株式会社 | Fluorine-containing unsaturated compound, fluorine-containing polymer, and curable composition using them |
| DE602005016710D1 (en) | 2004-11-25 | 2009-10-29 | Unimatec Co Ltd | NEW FLUOR CONTAINING POLYETHEREPHOSPHONATE COMPOUNDS AND A PROCESS FOR THEIR PREPARATION |
| JP5071612B2 (en) * | 2005-01-27 | 2012-11-14 | 信越化学工業株式会社 | Fluorine-containing curable composition |
| EP3037455B1 (en) * | 2013-08-23 | 2018-10-31 | Daikin Industries, Ltd. | Method for separating carboxylic acid compound containing perfluoro(poly)ether group |
| US11220649B2 (en) | 2017-01-26 | 2022-01-11 | Showa Denko K.K. | Fluorine-containing ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
| US11767483B2 (en) | 2018-09-12 | 2023-09-26 | Resonac Corporation | Fluorine-containing ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
| US11820953B2 (en) | 2019-03-12 | 2023-11-21 | Resonac Corporation | Fluorine-containing ether compound, lubricant for magnetic recording medium and magnetic recording medium |
| US11879109B2 (en) | 2019-09-18 | 2024-01-23 | Resonac Corporation | Fluorine-containing ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
| CN114845989A (en) | 2019-12-26 | 2022-08-02 | 昭和电工株式会社 | Fluorinated ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
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| JPH01131135A (en) * | 1987-11-16 | 1989-05-24 | Asahi Chem Ind Co Ltd | Perfluropolyether diacrylate |
| JPH01278507A (en) * | 1988-04-28 | 1989-11-08 | Asahi Chem Ind Co Ltd | Oxygen permeable resin composition |
| JPH0328819A (en) * | 1989-06-27 | 1991-02-07 | Asahi Chem Ind Co Ltd | Contact lens material |
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| JPH0725876B2 (en) * | 1987-04-24 | 1995-03-22 | 株式会社トクヤマ | Polyfluoropolyether |
| JP2563959B2 (en) * | 1988-02-25 | 1996-12-18 | 株式会社トクヤマ | Fluorine-containing ether compound and method for producing the same |
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| JPH01131135A (en) * | 1987-11-16 | 1989-05-24 | Asahi Chem Ind Co Ltd | Perfluropolyether diacrylate |
| JPH01278507A (en) * | 1988-04-28 | 1989-11-08 | Asahi Chem Ind Co Ltd | Oxygen permeable resin composition |
| JPH0328819A (en) * | 1989-06-27 | 1991-02-07 | Asahi Chem Ind Co Ltd | Contact lens material |
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