JPH032215A - Fluorine-based coating agent - Google Patents
Fluorine-based coating agentInfo
- Publication number
- JPH032215A JPH032215A JP13654989A JP13654989A JPH032215A JP H032215 A JPH032215 A JP H032215A JP 13654989 A JP13654989 A JP 13654989A JP 13654989 A JP13654989 A JP 13654989A JP H032215 A JPH032215 A JP H032215A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- coating agent
- acid dichloride
- based coating
- intrinsic viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000011737 fluorine Substances 0.000 title claims abstract description 30
- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 229920001230 polyarylate Polymers 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 11
- 229930185605 Bisphenol Natural products 0.000 abstract description 8
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- BUQMVYQMVLAYRU-UHFFFAOYSA-N 1,1,2,3-tetrachloropropane Chemical compound ClCC(Cl)C(Cl)Cl BUQMVYQMVLAYRU-UHFFFAOYSA-N 0.000 description 1
- GRSQYISVQKPZCW-UHFFFAOYSA-N 1,1,2-trichloropropane Chemical compound CC(Cl)C(Cl)Cl GRSQYISVQKPZCW-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UDPHJTAYHSSOQB-UHFFFAOYSA-N 1,2,2,3-tetrachloropropane Chemical compound ClCC(Cl)(Cl)CCl UDPHJTAYHSSOQB-UHFFFAOYSA-N 0.000 description 1
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- LQQIOXIIZZGWOR-UHFFFAOYSA-N C1(=C(C(=C(C(=C1F)F)F)C(=O)Cl)OC(=C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)C(=O)Cl Chemical compound C1(=C(C(=C(C(=C1F)F)F)C(=O)Cl)OC(=C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F)F)C(=O)Cl LQQIOXIIZZGWOR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
この発明は、機能性含フツ素ボリアリレートを含有する
フッ素系コーティング剤に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to a fluorine-based coating agent containing a functional fluorine-containing polyarylate.
従来の技術
優れた撥水撥油性、耐薬品性および防汚性等の特性を有
する含フツ素ポリマーを含有するフッ素系コーティング
剤は、繊維、フィルム、シート、プレート、成形品、金
属および木材等の表面改質剤として汎用されているが、
耐熱性、難燃性および耐候性等の点で他のポリマーに比
べて劣り、その改良が要請されている。Conventional technology Fluorine-based coating agents containing fluorine-containing polymers that have excellent properties such as water and oil repellency, chemical resistance, and stain resistance are used for fibers, films, sheets, plates, molded products, metals, wood, etc. It is widely used as a surface modifier for
It is inferior to other polymers in terms of heat resistance, flame retardance, weather resistance, etc., and improvements are required.
発明が解決しようとする課題
この発明は、このような要請に応えて、含フツ素ポリマ
ー固有の特性のほかに、耐熱性や耐候性等の特性ら備え
た被覆層を種々の基体上に形成し得るフッ素系コーティ
ング剤を提供するためになされたしのである。Problems to be Solved by the Invention In response to such demands, the present invention provides a method for forming coating layers on various substrates that have properties such as heat resistance and weather resistance in addition to the properties inherent to fluorine-containing polymers. The purpose of this work was to provide a fluorine-based coating agent that can be used as a coating material.
課題を解決するための手段
即ち本発明は、下記の一般式（Ｄおよび（■）：で表わ
されるパーフルオロアルケニルオキノンカルボン酸ジク
ロリドと一般式（■）：
［式中、ＲｒはパーフルオロアルケニルＭＣ，Ｆ’目ら
しくはＣ，Ｐ、、を示し、ＸはＣ（ＣＨ３）、、ＳＯ２
、Ｃ（ＣＨ３）、、Ｏ，ＣＨｔ、ＣＯまたは単結合を示
し、Ｙは水素原子もしくはハロゲン原子を示ず］で表わ
される構造単位をモル比ｌ：０〜１：１０００で有し、
固有粘度が０１〜２ 、 Ｏｄ（Ｉ／９である含フツ素
ボリアリレートを含有するフッ素系コーティング剤に関
する。Means for solving the problem, that is, the present invention, comprises a perfluoroalkenyl oquinone carboxylic acid dichloride represented by the following general formula (D and (■)): and a general formula (■): [wherein Rr is perfluoroalkenyl] MC, F' eyes indicate C, P, , X is C(CH3),, SO2
, C(CH3), , O, CHt, CO or a single bond, and Y does not represent a hydrogen atom or a halogen atom] in a molar ratio of 1:0 to 1:1000,
The present invention relates to a fluorine-based coating agent containing a fluorine-containing polyarylate having an intrinsic viscosity of 01 to 2 and Od(I/9).
構造単位（Ｉ）は例えば一般式（■）：（式中、Ｒｆは
前記と同依義である。）（式中、ＸおよびＹは前記と同
意義である。）で表わされるビスフェノール類との縮合
反応によって誘導される。Structural unit (I) is, for example, a bisphenol represented by the general formula (■): (wherein, Rf has the same meaning as above) (wherein, X and Y have the same meaning as above). It is induced by the condensation reaction of
式（ＩＩＩ）で表わされるパーフルオロアルケニルオキ
シジカルボン酸ジクロリドは、例えば特開昭５２−８９
６３０号公報に記載されているｐ−パーフルオロアルケ
ニルオキン安息香酸の製造法に準拠して調製することが
できる。即ち、例えば、５−ヒドロキシイソフタル酸お
よびヘキザフルオロプロペンの二量体もしくは二量体を
過剰のアミンの存在下で反応させることによって生成す
るパーフルオロアルケニルオキシイソフタル酸に、例え
ば塩化チオニルを反応させることによって化合物（Ｉ）
は高収率で得られる。Perfluoroalkenyloxydicarboxylic acid dichloride represented by formula (III) is disclosed in, for example, JP-A-52-89.
It can be prepared according to the method for producing p-perfluoroalkenyl oxynebenzoic acid described in Japanese Patent No. 630. That is, for example, perfluoroalkenyloxyisophthalic acid produced by reacting a dimer or dimer of 5-hydroxyisophthalic acid and hexafluoropropene in the presence of an excess of amine is reacted with, for example, thionyl chloride. Compound (I)
is obtained in high yield.
また、構造単位（ｎ）は例えば一般式（ＩＶ）で表わさ
れる芳香族ジカルボン酸ジクロリド、例えばテレフタル
酸ジクロリドおよび／またはイソフタル酸ジクロリドと
上記一般式（Ｖ）で表わされるビスフェノール類との縮
合反応によって誘導される。Further, the structural unit (n) can be formed by, for example, a condensation reaction between an aromatic dicarboxylic acid dichloride represented by the general formula (IV), such as terephthalic acid dichloride and/or isophthalic acid dichloride, and a bisphenol represented by the above general formula (V). be guided.
本発明に係る含フツ素ボリアリレートは構造単位（Ｉ）
および（ＩＩ）がモル比１：０〜Ｉ：１０００で規則的
もしくは不規則的に配列したポリマー構造を有する。The fluorine-containing polyarylate according to the present invention has a structural unit (I)
and (II) have a polymer structure in which they are regularly or irregularly arranged at a molar ratio of 1:0 to I:1000.
即ち、該含フツ素ボリアリレートは構造単位（Ｉ）と（
ＩＩ）のモル比がｌ二〇の場合には（Ｉ）を繰り返し単
位とする線状ポリマーとなるが、該モル比かそれ以外の
上記範囲内の場合には、式（ＩＩＩ）で表わされるパー
フルオロアルケニルオキシジカルボン酸ツクロリドおよ
び式（■）で表わされる芳香族ジカルボン酸ジクロリド
の種類およびこれらの成分とビスフェノール類との反応
条件等に応じて（Ｉ）と（ｎ）が不規則的に配列したポ
リマーとなる。That is, the fluorine-containing polyarylate has structural units (I) and (
When the molar ratio of II) is 120, it becomes a linear polymer having (I) as a repeating unit, but when the molar ratio is within the above range or other than that, it is represented by formula (III). (I) and (n) are arranged irregularly depending on the type of perfluoroalkenyloxydicarboxylic acid dichloride and the aromatic dicarboxylic acid dichloride represented by the formula (■) and the reaction conditions of these components and bisphenols. It becomes a polymer.
このような構造を有する含フツ素ボリアリレートの分子
量は通常２０００以上である。The molecular weight of the fluorine-containing polyarylate having such a structure is usually 2,000 or more.
上記の構造を有する含フツ素ボリアリレートの製造方法
は特に限定的ではないが、例えば前記の一般式（ＩＩＩ
）で表わされるパーフルオロアルケニルオキシノカルボ
ン酸ジクロリド、または該パーフルオロアルケニルオキ
シジカルボン酸ジクロリドおよび一般式（ＩＶ）で表わ
される芳香族ジカルボン酸ジクロリドを脱酸剤の存在下
で一般式（Ｖ）で表わされるビスフェノール類と反応さ
せる方法が挙げられる。Although the method for producing the fluorine-containing polyarylate having the above structure is not particularly limited, for example, the above general formula (III
), or the perfluoroalkenyloxydicarboxylic acid dichloride and the aromatic dicarboxylic acid dichloride represented by the general formula (IV) in the presence of a deoxidizer, the perfluoroalkenyloxydicarboxylic acid dichloride represented by the general formula (V) Examples include a method of reacting with the bisphenols shown below.
ビスフェノール類としては次の化合物が例示される。The following compounds are exemplified as bisphenols.
脱酸剤は綜合反応で生成する塩化水素を中和するために
使用するしので、アルカリ金属らしくはアルカリ土類金
属の水酸化物、第三級アミン等が例示されるが、界面重
合法の場合には水酸化ナトリウムや水酸化カリウム等の
アルカリ金属の水酸化物が好適であり、溶液重合法の場
合にはトリエチルアミンやピリジン等の第三級アミンが
好ましい。A deoxidizing agent is used to neutralize hydrogen chloride produced in a synthetic reaction, and examples of alkali metals include alkaline earth metal hydroxides and tertiary amines, but deoxidizing agents are used for interfacial polymerization. In this case, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred, and in the case of solution polymerization, tertiary amines such as triethylamine and pyridine are preferred.
上記の反応は界面重合法によっておこなうのが好ましく
、これによって高重合度の含フツ素ボリアリレートが得
られる。The above reaction is preferably carried out by an interfacial polymerization method, whereby a fluorine-containing polyarylate with a high degree of polymerization can be obtained.
該界面重合法においては、水に不溶性の有機溶媒、例え
ば含ハロゲン溶媒、炭化水素系溶媒、芳香族系溶媒、ケ
トン系溶媒等（特にジクロロメタン、クロロホルム、１
．２−ジクロロエタン等の含塩素溶媒が好ましい）に前
記のパーフルオロアルケニルオキシイソフタル酸ジクロ
リドまたは該パーフルオロアルケニルオキシイソフタル
酸ジクロリドと前記の芳香族ジカルボン酸ジクロリドと
の混合物を溶解させた溶液を前記の脱酸剤の存在下にお
いてビスフェノール類の水溶液と接触さけ、該両名液の
界面において反応をおこなう。In the interfacial polymerization method, water-insoluble organic solvents such as halogen-containing solvents, hydrocarbon solvents, aromatic solvents, ketone solvents, etc. (particularly dichloromethane, chloroform,
．． A solution prepared by dissolving the perfluoroalkenyloxyisophthalic acid dichloride or a mixture of the perfluoroalkenyloxyisophthalic acid dichloride and the aromatic dicarboxylic acid dichloride in a chlorinated solvent such as 2-dichloroethane is preferably used for the desorption process. In the presence of an acid agent, contact with an aqueous solution of bisphenols is avoided, and the reaction takes place at the interface between the two solutions.
この界面重合法においては、第四級アンモニウム塩や界
面活性剤等の反応系に存在させて重合度をさらに高めて
もよい。In this interfacial polymerization method, a quaternary ammonium salt, a surfactant, or the like may be present in the reaction system to further increase the degree of polymerization.
第四級アンモニウム塩としてはテトラエチルアンモニウ
ムクロリド、テトラエチルアンモニウムプロミド、テト
ラプロピルアンモニウムクロリド、テトラプロピルアン
モニウムプロミド、テトラブチルアンモニウムクロリド
、テトラブチルアンモニウムプロミド等が例示される。Examples of the quaternary ammonium salt include tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
また、界面活性剤としては各種の中性界面活性剤が使用
できるが、ポリオキシエチレンノニルフェニルエーテル
、ポリオキシエチレンアルキルエーテル、ポリオキシエ
チレンパーフルオロアルキルエーテル等が好適である。Further, as the surfactant, various neutral surfactants can be used, and polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene perfluoroalkyl ether, etc. are suitable.
上記の様にして製造される含フツ素ボリアリレートの固
有粘度は０．１〜２．０ｄｉ２／９、好ましくは０２〜
ｌ 、 ５ ｄ（Ｉ／９である（本明細書において、固
有粘度とは、１，１，２，２．−テトラクロルエタン溶
媒中、３０．０℃で測定した値を意味する）。The intrinsic viscosity of the fluorine-containing polyarylate produced as described above is 0.1 to 2.0 di2/9, preferably 02 to 2.0 di2/9.
l, 5d (I/9 (in this specification, intrinsic viscosity means a value measured at 30.0°C in a 1,1,2,2.-tetrachloroethane solvent).
固有粘度が０ 、 ｌ ｄ（Ｉ／９以下の場合には、形
成される被覆層の機械的強度や耐熱性が低下し、２．０
ｄ（ｌ／９以上になると粘度が高過ぎて、一般にコーテ
ィング処理が困難となる。When the intrinsic viscosity is 0, 1 d (I/9 or less, the mechanical strength and heat resistance of the formed coating layer decreases, and 2.0
d(l/9 or more, the viscosity is too high and coating treatment is generally difficult.
含フツ素ボリアリレートの濃度は通常０．１〜ｌＯ重量
％、好ましくは０．２〜５重量％であり、０．１ｍｍ％
以下の場合には、被処理表面上に形成される被覆層が薄
過ぎて含フツ素ボリアリレートの諸特性か充分に発揮さ
れず、１０重量％以上の場合には、コーティング剤の粘
度が高くなり過ぎてコーティング処理が困難になるだけ
でなく、不経済である。The concentration of the fluorine-containing polyarylate is usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight, and 0.1 mm%
In the following cases, the coating layer formed on the surface to be treated is too thin to fully exhibit the properties of the fluorine-containing polyarylate, and in the case of 10% by weight or more, the viscosity of the coating agent is high. If the coating becomes too large, the coating process is not only difficult but also uneconomical.
本発明によるフッ素系コーティング剤の溶剤は特に限定
的ではないが、以下に例示する含ハロゲン溶剤が好適で
ある。The solvent for the fluorine-based coating agent according to the present invention is not particularly limited, but the halogen-containing solvents listed below are suitable.
塩化メチレン、クロロホルム、１．１−ジクロロエタン
、１．２−ジクロロエタン、１，１．１−トリクロロエ
タン、！、１．２−トリクロロエタン、１．１，１．２
−テトラクロロエタン、１，１，２．２テトラクロロエ
タン、１，１．２−トリクロロプロパン、１，２．３−
トリクロロプロパン、１，１゜１．２−テトラクロロプ
ロパン、１，１，２．３−テトラクロロプロパン、１，
２，２．３−テトラクロロプロパン、１，１．１−トリ
クロロ−２，２，２−トリフルオロエタン、１，１．２
−トリクロロ−１゜２．２−）リフルオロエタン、ｌ、
２−ジフルオロ−１，１，２，２−テトラクロロエタン
。Methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane,! , 1.2-trichloroethane, 1.1,1.2
-tetrachloroethane, 1,1,2.2tetrachloroethane, 1,1.2-trichloropropane, 1,2.3-
Trichloropropane, 1,1゜1.2-tetrachloropropane, 1,1,2.3-tetrachloropropane, 1,
2,2.3-tetrachloropropane, 1,1.1-trichloro-2,2,2-trifluoroethane, 1,1.2
-trichloro-1゜2.2-)lifluoroethane, l,
2-difluoro-1,1,2,2-tetrachloroethane.
上記の溶剤は２種以上適宜併用してもよい。Two or more of the above solvents may be used in combination as appropriate.
本発明によるフッ素コーティング剤に熱分解防止剤（例
えば、亜リン酸、トリアリール亜リン酸エステル等）、
酸化防止剤（例えば、２．６−シーｔブチル−４−エチ
ルフェノール、２，２°−メヂレンービス（４−メチル
−６−ｔ−ブチルフェノール）および紫外線吸収剤（例
えば、ベンゾフェノン、ベンゾトリアゾール等）を適宜
配合して被覆層の耐熱性や耐候性等をさらに高めてもよ
い。In the fluorine coating agent according to the present invention, a thermal decomposition inhibitor (for example, phosphorous acid, triaryl phosphite, etc.),
Antioxidants (e.g., 2,6-sheet-t-butyl-4-ethylphenol, 2,2°-methylene bis(4-methyl-6-t-butylphenol) and ultraviolet absorbers (e.g., benzophenone, benzotriazole, etc.) The heat resistance, weather resistance, etc. of the coating layer may be further improved by appropriately blending them.
本発明によるコーティング剤の被覆方法としては例えば
噴霧法、浸漬法、ロールコーティング法、刷毛塗法等が
挙げられる。Examples of methods for applying the coating agent according to the present invention include spraying, dipping, roll coating, and brush coating.
本発明によるコーティング剤の適用対象は特に限定的で
はないが、各種の繊維、フィルム、シート、プレート、
種々の形態を有する成形品、金属、木材等が例示される
。The coating agent according to the present invention can be applied to various types of fibers, films, sheets, plates, etc., but is not particularly limited.
Molded products having various shapes, metal, wood, etc. are exemplified.
この場合、コーティング剤と被コーテイング面との密着
性を向上さけるために、アンダーコーティング剤、例え
ば、変性樹脂（変性ＰＥＴ、変性ナイロン等）、エラス
トマー、オリゴマー等を用いて被コーテイング面を予め
前処理してもよい。In this case, in order to avoid improving the adhesion between the coating agent and the surface to be coated, the surface to be coated is pretreated using an undercoating agent, for example, a modified resin (modified PET, modified nylon, etc.), elastomer, oligomer, etc. You may.
以下、本発明を実施例によって説明する。Hereinafter, the present invention will be explained by examples.
実施例１
パーフルオロノネニルオキシイソフタル酸ジクロリド６
４．９９をクロロホルム１５００ｉ（に溶解させた溶液
およびビスフェノールＡ２２．８９を２当ｍの水酸化ナ
トリウム水溶液１５００ｍ（に溶解させた溶液を臭化テ
トラブチルアンモニウム０゜５９の存在下において、界
面重合法により約２５°Ｃで約１００分間反応させるこ
とによって含フツ素ボリアリレート（Ｉ）（固有粘度：
０．３５）を調製した。Example 1 Perfluorononenyloxyisophthalic acid dichloride 6
A solution of 4.99 dissolved in 1500 m of chloroform and a solution of bisphenol A22.89 dissolved in 1500 m of a 2 equim sodium hydroxide aqueous solution were subjected to interfacial polymerization in the presence of 0.59 m of tetrabutylammonium bromide. By reacting at about 25°C for about 100 minutes, fluorine-containing polyarylate (I) (intrinsic viscosity:
0.35) was prepared.
含フツ素ボリアリレート（Ｉ）の１％の濃度でクロロホ
ルムに溶解させることによってフッ素系コーティング剤
（Ｉ）を調製した。A fluorine-based coating agent (I) was prepared by dissolving fluorine-containing polyarylate (I) in chloroform at a concentration of 1%.
コーティング剤（Ｉ）をＰＥＴフィルム「ルミラー」（
東し株式会社製：膜厚２５０μｍ）上にパーコーターを
用いて塗布して被覆層（Ｉ）を形成さ口“た。Coating agent (I) is applied to PET film “Lumirror” (
A coating layer (I) was formed by coating the coating layer (manufactured by Toshi Co., Ltd., film thickness: 250 μm) using a percoater.
被覆層（Ｉ）の厚さは０．２μｍで、水に体する接触角
は１０５．０℃であった。The thickness of the coating layer (I) was 0.2 μm, and the contact angle with water was 105.0°C.
実施例２〜１０
実施例１の手順に準拠し、表−１の配合処方によって含
フツ素ボリアリレート（２）〜（ｌＯ）を調製し、これ
らのポリマーを１％の濃度でクロロホルムに溶解させる
ことによってそれぞれフッ素系コーティング剤（２）〜
（Ｉ０）を調製した。Examples 2 to 10 Based on the procedure of Example 1, fluorine-containing polyarylates (2) to (lO) were prepared according to the formulation shown in Table 1, and these polymers were dissolved in chloroform at a concentration of 1%. Depending on the respective fluorine-based coating agent (2) ~
(I0) was prepared.
コーティング剤（２）〜（Ｉ０）を表−２に示す基材樹
脂フィルム上にバーコーターを用いて塗布することによ
ってそれぞれ被覆層（２）〜（Ｉ０）を杉成させた。Coating layers (2) to (I0) were formed by applying coating agents (2) to (I0) on the base resin film shown in Table 2 using a bar coater, respectively.
これらの被覆層（２）〜（Ｉ０）の厚さおよび水に対す
る接触ｌ１ｆ１（度）を表−２に示す。Table 2 shows the thickness of these coating layers (2) to (I0) and the contact l1f1 (degrees) with water.
発明の効果
本発明によるフッ素系コーティング剤は含フツ素ポリマ
ー固有の特性のほかに、耐熱性や耐候性等のボリアリレ
ートの特性ら兼有する被覆層を種々の基体上に形成させ
るので、フッ素系コーティング剤の利用分野を大幅に拡
大する。Effects of the Invention The fluorine-based coating agent according to the present invention forms coating layers on various substrates that have not only the properties inherent to fluorine-containing polymers but also the properties of polyarylates such as heat resistance and weather resistance. Significantly expand the range of applications for coating agents.
Claims (1)
＿１もしくはＣ＿８Ｆ＿１＿７を示し、ＸはＣ（ＣＦ＿
３）＿２、ＳＯ＿２、Ｃ（ＣＨ＿３）＿２、Ｏ、ＣＨ＿
２、ＣＯまたは単結合を示し、Ｙは水素原子もしくはハ
ロゲン原子を示す］で表わされる構造単位をモル比１：
０〜１：１０００で有し、固有粘度が０．１〜２．０ｄ
ｌ／ｇである含フッ素ポリアリレートを含有するフッ素
系コーティング剤。[Claims] 1. The following general formulas (I) and (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...( II) [Wherein, Rf is a perfluoroalkenyl group C_6F_1
_1 or C_8F_1_7, X is C(CF_
3)_2, SO_2, C(CH_3)_2, O, CH_
2, CO or a single bond, and Y represents a hydrogen atom or a halogen atom] in a molar ratio of 1:
It has a ratio of 0 to 1:1000, and an intrinsic viscosity of 0.1 to 2.0 d.
A fluorine-based coating agent containing a fluorine-containing polyarylate of l/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1136549A JP2711280B2 (en) | 1989-05-30 | 1989-05-30 | Fluorine coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1136549A JP2711280B2 (en) | 1989-05-30 | 1989-05-30 | Fluorine coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH032215A true JPH032215A (en) | 1991-01-08 |
| JP2711280B2 JP2711280B2 (en) | 1998-02-10 |
Family
ID=15177813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1136549A Expired - Fee Related JP2711280B2 (en) | 1989-05-30 | 1989-05-30 | Fluorine coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2711280B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031740A (en) * | 2006-07-28 | 2008-02-14 | Raiteku:Kk | Guard fence against collapsed sediment |
| JP2009242712A (en) * | 2008-03-31 | 2009-10-22 | Unitika Ltd | Polyarylate and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6444747A (en) * | 1987-08-12 | 1989-02-17 | Neos Kk | Fluorine-containing polyallylate composite body |
-
1989
- 1989-05-30 JP JP1136549A patent/JP2711280B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6444747A (en) * | 1987-08-12 | 1989-02-17 | Neos Kk | Fluorine-containing polyallylate composite body |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031740A (en) * | 2006-07-28 | 2008-02-14 | Raiteku:Kk | Guard fence against collapsed sediment |
| JP2009242712A (en) * | 2008-03-31 | 2009-10-22 | Unitika Ltd | Polyarylate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2711280B2 (en) | 1998-02-10 |
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