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JP2010053209A - Fluorine-containing copolymer and its usage - Google Patents

Fluorine-containing copolymer and its usage Download PDF

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JP2010053209A
JP2010053209A JP2008217794A JP2008217794A JP2010053209A JP 2010053209 A JP2010053209 A JP 2010053209A JP 2008217794 A JP2008217794 A JP 2008217794A JP 2008217794 A JP2008217794 A JP 2008217794A JP 2010053209 A JP2010053209 A JP 2010053209A
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repeating unit
fluorine
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Junpei Nomura
順平 野村
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing copolymer excellent in heat resistance, chemical resistance, weatherability and stress crack resistance as well as excellent in adhesiveness, and to provide a laminate of the copolymer and a coated article. <P>SOLUTION: The fluorine-containing copolymer contains a repeating unit (a) based on tetrafluoroethylene, a repeating unit (b) based on CF<SB>2</SB>=CFOCF<SB>2</SB>CF<SB>2</SB>CF<SB>3</SB>, a repeating unit (c) based on CF<SB>2</SB>=CFOCF<SB>3</SB>and/or CF<SB>2</SB>=CFOCF<SB>2</SB>CF<SB>3</SB>, and a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group. Based on the total molar amount of the repeating unit (a), repeating unit (b), repeating unit (c) and repeating unit (d), the copolymer contains the repeating unit (a) by from 75 to 99.79 mol%, the repeating unit (b) by from 0.1 to 10.0 mol%, the repeating unit (c) by from 0.1 to 10.0 mol%, and the repeating unit (d) by from 0.01 to 5.0 mol%, and has a volume flow rate of 0.1 to 1,000 mm<SP>3</SP>/sec. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、含フッ素共重合体及びその用途に関する。   The present invention relates to a fluorine-containing copolymer and its use.

ポリテトラフルオロエチレン、テトラフルオロエチレン/ペルフルオロ(アルキルビニルエーテル)共重合体、エチレン/テトラフルオロエチレン共重合体等の含フッ素重合体は、半導体産業や自動車産業等の種々の分野で使用されている。   Fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers, and ethylene / tetrafluoroethylene copolymers are used in various fields such as the semiconductor industry and the automobile industry.

含フッ素重合体は、耐熱性、耐薬品性、耐候性、ガスバリア性等に優れるものの、他材料との接着性が充分でない。例えば、合成樹脂、金属、金属酸化物、ガラス、セラミックス等と接着させるために、含フッ素重合体の表面をコロナ放電処理やナトリウムエッチング処理等を行なった上に、接着剤を塗布して接着させる方法等が用いられる。このような接着方法は、工程が煩雑で、生産性が低く、より簡易な方法で他材料と接着する含フッ素重合体の開発が要請されている。   The fluorine-containing polymer is excellent in heat resistance, chemical resistance, weather resistance, gas barrier properties, and the like, but has insufficient adhesion to other materials. For example, in order to adhere to synthetic resin, metal, metal oxide, glass, ceramics, etc., the surface of the fluoropolymer is subjected to corona discharge treatment, sodium etching treatment, etc., and then applied with an adhesive and adhered. A method or the like is used. Such an adhesion method requires complicated development, low productivity, and development of a fluorine-containing polymer that adheres to other materials by a simpler method.

金属基材の表面に含フッ素重合体の被膜を形成する方法としては、あらかじめサンドブラスト等で表面に凹凸形状を形成し、プライマーを塗布し、その上に含フッ素重合体の粒子を付着させ、ついで含フッ素重合体の融点以上の温度で溶融する方法等が挙げられる。この場合にも、コスト低減、生産性の向上の観点から、プライマーが不要で、金属等との接着性に優れるフッ素系重合体の開発が要請されている。   As a method of forming a fluoropolymer film on the surface of a metal substrate, an uneven shape is formed on the surface in advance by sandblasting or the like, a primer is applied, and the fluoropolymer particles are then adhered to the surface. Examples thereof include a method of melting at a temperature equal to or higher than the melting point of the fluoropolymer. Also in this case, from the viewpoint of cost reduction and productivity improvement, there is a demand for the development of a fluorine-based polymer that does not require a primer and has excellent adhesion to a metal or the like.

近年、塗装ロボット用塗料配管、半導体製造装置用薬液配管、燃料ホース等の材料として、含フッ素重合体とポリアミドとの積層体が検討されている。該用途においては含フッ素重合体の層とポリアミドの層とが強固に接着する必要がある。そこで、含フッ素重合体のチューブの表面を、薬液処理、コロナ放電処理、プラズマ放電処理等の方法により表面処理し、該表面に必要に応じて接着剤を塗布した後、含フッ素重合体チューブの外側にポリアミドを押出し成形し積層して、含フッ素重合体の層とポリアミドの層との接着性を向上する方法等が用いられる。しかし、この方法は、工程が煩雑で、生産性が低いことから、含フッ素重合体の層の表面処理を必要とせずに、層間の接着性に優れる積層体を成形できる含フッ素重合体の開発が要請されている。   In recent years, laminates of fluoropolymers and polyamides have been studied as materials for paint piping for coating robots, chemical piping for semiconductor manufacturing equipment, fuel hoses, and the like. In this application, it is necessary that the fluoropolymer layer and the polyamide layer be firmly bonded. Therefore, the surface of the fluoropolymer tube is subjected to surface treatment by a method such as chemical treatment, corona discharge treatment, plasma discharge treatment, etc., and an adhesive is applied to the surface as necessary. A method of improving the adhesion between the fluoropolymer layer and the polyamide layer by extruding and laminating polyamide on the outside is used. However, since this method is complicated and the productivity is low, development of a fluoropolymer capable of forming a laminate having excellent interlayer adhesion without requiring surface treatment of the fluoropolymer layer is required. Is requested.

そのような含フッ素重合体として、特許文献1には、テトラフルオロエチレンに基づく繰り返し単位/含フッ素モノマーに基づく繰り返し単位/無水イタコン酸に基づく繰り返し単位を含有する共重合体が記載されている。しかし、該テトラフルオロエチレン共重合体は、300℃という高温領域での耐熱性が十分ではなかった。   As such a fluoropolymer, Patent Document 1 describes a copolymer containing a repeating unit based on tetrafluoroethylene / a repeating unit based on a fluorine-containing monomer / a repeating unit based on itaconic anhydride. However, the tetrafluoroethylene copolymer has insufficient heat resistance in a high temperature region of 300 ° C.

特許文献2には、5−ノルボルネン−2,3−ジカルボン酸無水物に基づく繰り返し単位を含有する含フッ素共重合体が開示されている。該含フッ素共重合体は、他材料との接着性は向上するが、柔軟性に乏しく、塗装ロボット用塗料配管、燃料ホース等の材料として耐ストレスクラック性等の機械的強度が充分でなかった。   Patent Document 2 discloses a fluorine-containing copolymer containing a repeating unit based on 5-norbornene-2,3-dicarboxylic acid anhydride. The fluorine-containing copolymer has improved adhesiveness with other materials, but lacks flexibility, and has insufficient mechanical strength such as stress crack resistance as a material for paint piping for paint robots, fuel hoses, etc. .

特開2004−277689号公報Japanese Patent Laid-Open No. 2004-277789 特開2006−152234号公報JP 2006-152234 A

本発明の目的は、上記のような背景のもとに開発が要請されている、耐熱性、耐薬品性、耐侯性、耐ストレスクラック性に優れ、かつ熱可塑性樹脂や基材との接着性に優れる含フッ素共重合体を提供することである。   The object of the present invention is to be developed against the background as described above, and is excellent in heat resistance, chemical resistance, weather resistance, stress crack resistance, and adhesion to thermoplastic resins and substrates. It is to provide a fluorine-containing copolymer having excellent resistance.

本発明は、テトラフルオロエチレンに基づく繰り返し単位(a)、CF=CFOCFCFCFに基づく繰り返し単位(b)、CF=CFOCF及び/又はCF=CFOCFCFに基づく繰り返し単位(c)、ジカルボン酸無水物基を有する重合性炭化水素モノマーに基づく繰り返し単位(d)を含有し、繰り返し単位(a)、繰り返し単位(b)、繰り返し単位(c)、繰り返し単位(d)の合計モル量に対して、繰り返し単位(a)が75〜99.79モル%であり、繰り返し単位(b)が0.1〜10.0モル%であり、繰り返し単位(c)が0.1〜10.0モル%であり、繰り返し単位(d)が0.01〜5.0モル%であり、容量流速が0.1〜1000mm/秒であることを特徴とする含フッ素共重合体を提供する。 The invention relates to repeating units based on tetrafluoroethylene (a), repeating units based on CF 2 ═CFOCF 2 CF 2 CF 3 (b), CF 2 ═CFOCF 3 and / or CF 2 ═CFOCF 2 CF 3 Unit (c), containing a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic anhydride group, the repeating unit (a), the repeating unit (b), the repeating unit (c), the repeating unit (d ), The repeating unit (a) is 75 to 99.79 mol%, the repeating unit (b) is 0.1 to 10.0 mol%, and the repeating unit (c) is 0. a .1~10.0 mol%, the repeating units (d) is the 0.01 to 5.0 mol%, fluorine-containing, wherein the volume flow rate is 0.1~1000mm 3 / sec To provide a copolymer.

また、本発明は、該含フッ素共重合体の層と該含フッ素共重合体以外の熱可塑性樹脂の層とが直接積層されてなる積層体、及び、該含フッ素共重合体で基材の表面が被覆されてなる被覆物品を提供する。   The present invention also provides a laminate in which a layer of the fluorine-containing copolymer and a layer of a thermoplastic resin other than the fluorine-containing copolymer are directly laminated, and a substrate made of the fluorine-containing copolymer. Provided is a coated article having a surface coated.

本発明の含フッ素共重合体は、樹脂、金属、金属酸化物、ガラス、セラミックス等との接着性に優れ、耐熱性、耐薬品性、耐ストレスクラック性に優れる。   The fluorine-containing copolymer of the present invention is excellent in adhesion to resins, metals, metal oxides, glass, ceramics, etc., and is excellent in heat resistance, chemical resistance, and stress crack resistance.

また、本発明の含フッ素共重合体は、含フッ素重合体以外の熱可塑性樹脂との共押出し成形性に優れる。得られた含フッ素共重合体の層と該熱可塑性樹脂の層とが直接積層されてなる積層体は、層間接着性に優れる。   The fluorine-containing copolymer of the present invention is excellent in coextrusion moldability with a thermoplastic resin other than the fluorine-containing polymer. The laminate obtained by directly laminating the obtained fluorine-containing copolymer layer and the thermoplastic resin layer is excellent in interlayer adhesion.

本発明の含フッ素共重合体は、樹脂、金属、金属酸化物、ガラス、セラミックス等の基材に、プライマーを使用することなく、含フッ素共重合体の被膜を形成でき、基材との接着性に優れる被覆物品を与える。該被覆物品は、耐熱性、耐薬品性、耐食性、耐油性、耐候性、耐磨耗性、潤滑性等に優れる。   The fluorine-containing copolymer of the present invention can form a film of a fluorine-containing copolymer on a substrate such as resin, metal, metal oxide, glass, or ceramic without using a primer, and can adhere to the substrate. A coated article having excellent properties is provided. The coated article is excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance, wear resistance, lubricity, and the like.

本発明の含フッ素共重合体は、テトラフルオロエチレンに基づく繰り返し単位(a)、CF=CFOCFCFCFに基づく繰り返し単位(b)、CF=CFOCF及び/又はCF=CFOCFCFに基づく繰り返し単位(c)、ジカルボン酸無水物基を有する炭化水素モノマーに基づく繰り返し単位(d)を含有する。 The fluorine-containing copolymer of the present invention comprises a repeating unit (a) based on tetrafluoroethylene, a repeating unit (b) based on CF 2 = CFOCF 2 CF 2 CF 3 , CF 2 = CFOCF 3 and / or CF 2 = CFOCF. 2 The repeating unit (c) based on CF 3 and the repeating unit (d) based on a hydrocarbon monomer having a dicarboxylic anhydride group are contained.

以下、CF=CFOCFCFCFをPPVE、CF=CFOCFCFをPEVE、CF=CFOCFをPMVE、という。 Hereinafter, CF 2 = CFOCF 2 CF 2 CF 3 is referred to as PPVE, CF 2 = CFOCF 2 CF 3 as PEVE, and CF 2 = CFOCF 3 as PMVE.

前記、繰り返し単位(a)、繰り返し単位(b)及び繰り返し単位(c)、繰り返し単位(d)の合計モル量に対して、繰り返し単位(a)が75〜99.79モル%であり、繰り返し単位(b)が0.1〜20.0モル%であり、繰り返し単位(c)が0.1〜10.0モル%であり、繰り返し単位(b)が0.1〜10.0モル%である。   The repeating unit (a) is 75 to 99.79 mol% based on the total molar amount of the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d), and the repeating unit The unit (b) is 0.1 to 20.0 mol%, the repeating unit (c) is 0.1 to 10.0 mol%, and the repeating unit (b) is 0.1 to 10.0 mol%. It is.

好ましくは繰り返し単位(a)が85〜98.97モル%、繰り返し単位(b)が0.5〜7モル%であり、繰り返し単位(c)が0.5〜7モル%、繰り返し単位(d)が0.03〜1モル%であり、より好ましくは繰り返し単位(a)が89.5〜97.97モル%、繰り返し単位(b)が1.0〜5モル%であり、繰り返し単位(c)が1.0〜5モル%であり、繰り返し単位(d)が0.03〜0.5モル%である。繰り返し単位(a)、繰り返し単位(b)、繰り返し単位(c)がこの範囲にあると、含フッ素共重合体は、耐熱性、耐薬品性に優れ、成形性や耐ストレスクラック性等の機械物性に優れる。
さらに、繰り返し単位(d)のモル%がこの範囲にあると、含フッ素共重合体は、該フッ素共重合体以外の熱可塑性樹脂や基材との接着性に優れる。
Preferably, the repeating unit (a) is 85 to 98.97 mol%, the repeating unit (b) is 0.5 to 7 mol%, the repeating unit (c) is 0.5 to 7 mol%, and the repeating unit (d ) Is 0.03 to 1 mol%, more preferably the repeating unit (a) is 89.5 to 97.97 mol%, the repeating unit (b) is 1.0 to 5 mol%, and the repeating unit ( c) is 1.0 to 5 mol%, and the repeating unit (d) is 0.03 to 0.5 mol%. When the repeating unit (a), the repeating unit (b), and the repeating unit (c) are within this range, the fluorinated copolymer is excellent in heat resistance and chemical resistance, and has a machineability such as moldability and stress crack resistance. Excellent physical properties.
Furthermore, when the mol% of the repeating unit (d) is in this range, the fluorine-containing copolymer is excellent in adhesiveness with a thermoplastic resin other than the fluorine copolymer or a substrate.

本発明において「ジカルボン酸無水物基を有する重合性炭化水素モノマー」とは、ジカルボン酸無水物基(−CO−O−CO−)と重合性不飽和基を有する化合物であり、脂肪族ジカルボン酸無水物や炭化水素環を有するジカルボン酸の無水物などが挙げられる。また、この重合性炭化水素モノマーにおける炭素原子に結合した水素原子の一部は、ハロゲン原子、アルキル基、ハロゲン化アルキル基その他の置換基に置換されていてもよい。   In the present invention, the “polymerizable hydrocarbon monomer having a dicarboxylic anhydride group” is a compound having a dicarboxylic anhydride group (—CO—O—CO—) and a polymerizable unsaturated group, and an aliphatic dicarboxylic acid. Examples thereof include anhydrides and anhydrides of dicarboxylic acids having a hydrocarbon ring. In addition, a part of hydrogen atoms bonded to carbon atoms in the polymerizable hydrocarbon monomer may be substituted with a halogen atom, an alkyl group, a halogenated alkyl group or other substituents.

本発明において好ましい上記重合性炭化水素モノマーは、炭化水素環を有するジカルボン酸の無水物である。炭化水素環は炭素原子のみからなる環であり、炭化水素環は、単環、縮合多環、有橋多環、集合多環などのいずれであってもよく、脂環であっても芳香環であってもよい。重合性不飽和基は環を構成する炭素原子間に存在していてもよく、環外の炭素原子と環を構成する炭素原子間又は環外の炭素原子間に存在していてもよい。ジカルボン酸無水物基の2つの結合手はそれぞれ環を構成する炭素原子や環外の炭素原子に結合する。炭化水素環としては単環、縮合多環又は有橋多環の構造を有する脂環が好ましい。さらに、ジカルボン酸無水物基は脂環を構成する2つの炭素原子に結合していることが好ましく、特に脂環を構成しかつ隣接した2つの炭素原子に結合していることが好ましい。   The polymerizable hydrocarbon monomer preferred in the present invention is a dicarboxylic acid anhydride having a hydrocarbon ring. The hydrocarbon ring is a ring composed of only carbon atoms, and the hydrocarbon ring may be any of a monocyclic ring, a condensed polycyclic ring, a bridged polycyclic ring, an aggregated polycyclic ring, an alicyclic ring or an aromatic ring. It may be. The polymerizable unsaturated group may exist between the carbon atoms constituting the ring, or may exist between the carbon atoms constituting the ring and the carbon atoms constituting the ring or between the carbon atoms constituting the ring. The two bonds of the dicarboxylic anhydride group are each bonded to a carbon atom constituting the ring or a carbon atom outside the ring. The hydrocarbon ring is preferably an alicyclic ring having a monocyclic, condensed polycyclic or bridged polycyclic structure. Further, the dicarboxylic anhydride group is preferably bonded to two carbon atoms constituting the alicyclic ring, and particularly preferably bonded to two adjacent carbon atoms constituting the alicyclic ring.

上記ジカルボン酸無水物基を有する重合性環状炭化水素モノマーの具体例としては、5−ノルボルネン−2,3−ジカルボン酸無水物(以下、NAHという。)、下式(1)〜(3)で表される酸無水物等が挙げられる。好ましくは、NAHである。   Specific examples of the polymerizable cyclic hydrocarbon monomer having a dicarboxylic acid anhydride group include 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH), and the following formulas (1) to (3): The acid anhydride etc. which are represented are mentioned. NAH is preferable.

Figure 2010053209
Figure 2010053209

Figure 2010053209
Figure 2010053209

Figure 2010053209
Figure 2010053209

本発明の含フッ素共重合体が、繰り返し単位(a)、繰り返し単位(b)、繰り返し単位(c)、繰り返し単位(d)に加えて、その他のモノマーに基く繰り返し単位(e)を含有することも好ましい。   The fluorine-containing copolymer of the present invention contains a repeating unit (e) based on another monomer in addition to the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d). It is also preferable.

該その他のモノマーとしては、ヘキサフルオロプロピレン(以下、HFPという。)、フッ化ビニル、フッ化ビニリデン(以下、VdFという。)、トリフルオロエチレン、CF=CFORf2SO(Rf2は炭素数1〜10で炭素原子間に酸素原子を含んでもよいペルフルオロアルキレン基、Xはハロゲン原子又は水酸基。)、CF=CFORf2CO(ここで、Rf2は前記と同じ、Xは水素原子又は炭素数1〜3のアルキル基。)、CF=CF(CFOCF=CF(ここで、pは1又は2。)、CH=CX(CF(ここで、X及びXは、互いに独立に水素原子又はフッ素原子、qは2〜10の整数。)、ペルフルオロ(2−メチレン−4−メチル−1,3−ジオキソラン)、ペルフルオロ(2,2−ジメチル−1,3−ジオキソール)、ペルフルオロ(4−メトキシ−1,3−ジオキソール)、エチレン、プロピレン、イソブテン等の炭素数2〜4のオレフィン、酢酸ビニル等のビニルエステル、エチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル等が挙げられる。その他のモノマーは1種単独で用いてもよく、2種以上を併用しれもよい。 Examples of the other monomers include hexafluoropropylene (hereinafter referred to as HFP), vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), trifluoroethylene, CF 2 = CFOR f 2 SO 2 X 1 (R f2 is A perfluoroalkylene group having 1 to 10 carbon atoms and optionally containing an oxygen atom between carbon atoms, X 1 is a halogen atom or a hydroxyl group), CF 2 = CFOR f 2 CO 2 X 2 (where R f2 is the same as above, X 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.), CF 2 = CF (CF 2 ) p OCF═CF 2 (where p is 1 or 2), CH 2 = CX 3 (CF 2 ) Q X 4 (wherein X 3 and X 4 are each independently a hydrogen atom or a fluorine atom, q is an integer of 2 to 10), perfluoro (2-methylene-4-methyl-1, 3-dioxolane), perfluoro (2,2-dimethyl-1,3-dioxole), perfluoro (4-methoxy-1,3-dioxole), ethylene, propylene, isobutene and other olefins having 2 to 4 carbon atoms, vinyl acetate And vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether. Other monomers may be used alone or in combination of two or more.

CH=CX(CFとしては、CH=CH(CFF、CH=CH(CFF、CH=CH(CFF、CH=CF(CFH、CH=CF(CFH等が挙げられる。好ましくは、CH=CH(CFF又はCH=CH(CFFである。
その他のモノマーとして、好ましくは、HFP、VdF、CH=CX(CF、エチレン、プロピレン及び酢酸ビニルからなる群から選ばれる1種以上であり、より好ましくは、HFP、エチレン及びCH=CX(CFからなる群から選ばれる1種以上である。最も好ましくは、HFPである。
As CH 2 = CX 3 (CF 2 ) q X 4 , CH 2 = CH (CF 2 ) 2 F, CH 2 = CH (CF 2 ) 3 F, CH 2 = CH (CF 2 ) 4 F, CH 2 ═CF (CF 2 ) 3 H, CH 2 ═CF (CF 2 ) 4 H, and the like. Preferably, CH 2 ═CH (CF 2 ) 4 F or CH 2 ═CH (CF 2 ) 2 F.
The other monomer is preferably at least one selected from the group consisting of HFP, VdF, CH 2 ═CX 3 (CF 2 ) q X 4 , ethylene, propylene and vinyl acetate, and more preferably HFP, ethylene And CH 2 = CX 3 (CF 2 ) q X 4 is at least one selected from the group consisting of Most preferred is HFP.

本発明の含フッ素共重合体の好ましい具体例としては、TFE/PPVE/PMVE/NAH共重合体、TFE/PPVE/PEVE/NAH共重合体、TFE/HFP/PPVE/PMVE/NAH共重合体、TFE/HFP/PPVE/PEVE/NAH共重合体等が挙げられる。   Preferable specific examples of the fluorine-containing copolymer of the present invention include TFE / PPVE / PMVE / NAH copolymer, TFE / PPVE / PEVE / NAH copolymer, TFE / HFP / PPVE / PMVE / NAH copolymer, Examples include TFE / HFP / PPVE / PEVE / NAH copolymer.

本発明の含フッ素共重合体の融点は、150〜320℃が好ましく、200〜310℃がより好ましい。この範囲にあると熱可塑性樹脂との溶融共押出し成形性に優れる。融点は、繰り返し単位(a)、繰り返し単位(b)繰り返し単位(c)、及び繰り返し単位(d)の含有割合を前記範囲内で適宜選定して調節することが好ましい。   150-320 degreeC is preferable and, as for melting | fusing point of the fluorine-containing copolymer of this invention, 200-310 degreeC is more preferable. Within this range, the melt coextrusion moldability with the thermoplastic resin is excellent. The melting point is preferably adjusted by appropriately selecting the content ratio of the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d) within the above range.

本発明の含フッ素共重合体の高分子末端基として、エステル基、カーボネート基、水酸基、カルボキシル基、カルボニルフルオリド基、酸無水物残基等の接着性官能基を有すると、熱可塑性樹脂や基材との接着性に優れるので好ましい。該接着性官能基を有する高分子末端基は、含フッ素共重合体の製造時に、ラジカル重合開始剤、連鎖移動剤等を適宜選定することにより導入することが好ましい。   When the fluorine-containing copolymer of the present invention has an adhesive functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group, or an acid anhydride residue as a polymer terminal group, a thermoplastic resin or Since it is excellent in adhesiveness with a substrate, it is preferable. The polymer end group having an adhesive functional group is preferably introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, etc. during the production of the fluorine-containing copolymer.

本発明の含フッ素共重合体の380℃における容量流速(以下、Q値という。)は、0.1〜1000mm/秒である。Q値は、含フッ素共重合体の溶融流動性を表す指標であり、分子量の目安となる。Q値が大きいと分子量が低く、小さいと分子量が高いことを示す。本発明におけるQ値は、島津製作所製フローテスタを用いて、含フッ素共重合体の融点より50℃高い温度において、荷重7kg下に直径2.1mm、長さ8mmのオリフィス中に押出すときの含フッ素共重合体の押出し速度である。Q値が小さすぎると押出し成形が困難となり、大きすぎると含フッ素共重合体の耐ストレスクラック性が充分でない。本発明の含フッ素共重合体のQ値は5〜500mm/秒が好ましく、10〜200mm/秒がより好ましい。 The volume flow rate (hereinafter referred to as Q value) at 380 ° C. of the fluorinated copolymer of the present invention is 0.1 to 1000 mm 3 / sec. The Q value is an index representing the melt fluidity of the fluorinated copolymer and is a measure of the molecular weight. A large Q value indicates a low molecular weight, and a small Q value indicates a high molecular weight. The Q value in the present invention is the value when extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the fluorine-containing copolymer using a flow tester manufactured by Shimadzu Corporation. This is the extrusion rate of the fluorinated copolymer. When the Q value is too small, extrusion molding becomes difficult. When the Q value is too large, the stress crack resistance of the fluorine-containing copolymer is not sufficient. Q value of the fluorocopolymer of the present invention is preferably from 5 to 500 mm 3 / sec, 10 to 200 mm 3 / sec is more preferable.

本発明における含フッ素共重合体のMIT折り曲げ寿命は100万回以上である。ここ
で、MIT折り曲げ寿命とは、ASTM D2176に準じて実施される折り曲げ試験に
おいて、試料が破断するまでの折り曲げ回数である。この値が大きいほど、耐ストレスク
ラック性に優れることを示す。好ましくは200万回以上、より好ましくは300万回以上である。
The MIT bending life of the fluorine-containing copolymer in the present invention is 1 million times or more. Here, the MIT bending life is the number of bendings until the sample breaks in a bending test performed in accordance with ASTM D2176. It shows that it is excellent in stress crack resistance, so that this value is large. Preferably it is 2 million times or more, More preferably, it is 3 million times or more.

本発明の含フッ素共重合体の製造方法は特に制限はなく、ラジカル重合開始剤を用いるラジカル重合法が用いられる。重合方法としては、塊状重合、フッ化炭化水素、フッ化炭化水素エーテル、塩化炭化水素、フッ化塩化炭化水素、アルコール、炭化水素等の有機溶媒を使用する溶液重合、水性媒体及び必要に応じて適当な有機溶剤を使用する懸濁重合、水性媒体及び乳化剤を使用する乳化重合が挙げられ、特に溶液重合が好ましい。   The method for producing the fluorine-containing copolymer of the present invention is not particularly limited, and a radical polymerization method using a radical polymerization initiator is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, fluorinated hydrocarbon ethers, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols, hydrocarbons, aqueous media, and as required. Examples thereof include suspension polymerization using an appropriate organic solvent, and emulsion polymerization using an aqueous medium and an emulsifier, and solution polymerization is particularly preferable.

ラジカル重合開始剤としては、その半減期が10時間である温度が0℃〜100℃が好ましく、20〜90℃がより好ましい。その具体例としては、アゾビスイソブチロニトリル等のアゾ化合物、イソブチリルペルオキシド、オクタノイルペルオキシド、ベンゾイルペルオキシド、ラウロイルペルオキシド等の非フッ素系ジアシルペルオキシド、ジイソプロピルペルオキシジカーボネート、ジ−n−プロピルペルオキシジカーボネート等のペルオキシジカーボネート、tert−ブチルペルオキシピバレート、tert−ブチルペルオキシイソブチレート、tert−ブチルペルオキシアセテート等のペルオキシエステル、(Z(CFCOO)(ここで、Zは水素原子、フッ素原子又は塩素原子であり、rは1〜10の整数である。)で表される化合物等の含フッ素ジアシルペルオキシド、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の無機過酸化物等が挙げられる。 As the radical polymerization initiator, the temperature at which the half-life is 10 hours is preferably 0 ° C to 100 ° C, more preferably 20 to 90 ° C. Specific examples thereof include azo compounds such as azobisisobutyronitrile, non-fluorine diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxy. peroxydicarbonate such dicarbonate, tert- butyl peroxypivalate, tert- butylperoxy isobutyrate, peroxy esters such as tert- butylperoxy acetate, 2 (where (Z (CF 2) r COO ), Z is hydrogen An atom, a fluorine atom, or a chlorine atom, and r is an integer of 1 to 10.) Fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc. Peroxides and the like.

本発明において、含フッ素共重合体のQ値を制御するために、連鎖移動剤を使用することも好ましい。連鎖移動剤としては、メタノール、エタノール等のアルコール、1,3−ジクロロ−1,1,2,2,3−ペンタフルオロプロパン、1,1−ジクロロ−1−フルオロエタン等のクロロフルオロハイドロカーボン、ペンタン、ヘキサン、シクロヘキサン等のハイドロカーボンが挙げられる。含フッ素共重合体の高分子末端に接着性官能基を導入するための連鎖移動剤としては、酢酸、無水酢酸、酢酸メチル、エチレングリコール、プロピレングリコール等が挙げられる。   In the present invention, it is also preferable to use a chain transfer agent in order to control the Q value of the fluorine-containing copolymer. Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed. Examples of the chain transfer agent for introducing an adhesive functional group to the polymer terminal of the fluorinated copolymer include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

本発明において重合条件は特に限定されず、重合温度は0〜100℃が好ましく、20〜90℃がより好ましい。重合圧力は0.1〜10MPaが好ましく、0.5〜3MPaがより好ましい。重合時間は1〜30時間が好ましい。   In the present invention, the polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.

重合中のジカルボン酸無水物基を有する重合性炭化水素モノマーの濃度は、全モノマーに対して0.01〜5モル%が好ましく、0.05〜3モル%がより好ましく、0.05〜1モル%が最も好ましい。ジカルボン酸無水物基を有する重合性炭化水素モノマーの濃度が高すぎると、重合速度が低下する傾向となる。前記範囲にあると製造時の重合速度が低下せず、かつ、含フッ素共重合体は接着性に優れる。重合中、ジカルボン酸無水物基を有する重合性炭化水素モノマーが重合で消費されるに従って、消費された量を連続的又は断続的に重合槽内に供給し、ジカルボン酸無水物基を有する重合性炭化水素モノマーの濃度をこの範囲に維持することが好ましい。   The concentration of the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group during the polymerization is preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%, more preferably 0.05 to 1 with respect to the total monomers. Mole% is most preferred. When the concentration of the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group is too high, the polymerization rate tends to decrease. Within the above range, the polymerization rate during production does not decrease, and the fluorinated copolymer is excellent in adhesiveness. During the polymerization, as the polymerizable hydrocarbon monomer having a dicarboxylic anhydride group is consumed in the polymerization, the consumed amount is continuously or intermittently supplied into the polymerization tank, and the polymerization property having the dicarboxylic anhydride group is obtained. It is preferred to maintain the concentration of the hydrocarbon monomer within this range.

本発明の積層体は、含フッ素共重合体の層と該フッ素共重合体以外の熱可塑性樹脂の層とが直接積層されてなる。含フッ素共重合体と該熱可塑性樹脂との積層は、溶融成形法を用いることが好ましく、共押出し成形法が生産性に優れるのでより好ましい。共押出し成形法は、フィルム、チューブ等の形状の2層以上の積層体を得る方法である。2機以上の押出機の吐出口から出てくる溶融物は、溶融状態で接触しつつダイを通り積層体に成形される。共押出し成形のために、含フッ素共重合体と該熱可塑性樹脂とは、互いに近い成形温度を有することが好ましい。押出し温度は、含フッ素共重合体及び該熱可塑性樹脂の融点及び分解温度等の観点より決定される。スクリュー温度は100〜400℃が好ましく、ダイ温度は150〜400℃が好ましい。スクリュー回転数は特に限定されないが10〜200回転/分が好ましい。含フッ素共重合体の押出し機内の滞留時間は1〜20分が好ましい。   The laminate of the present invention is obtained by directly laminating a fluorine-containing copolymer layer and a thermoplastic resin layer other than the fluorine copolymer. The lamination of the fluorine-containing copolymer and the thermoplastic resin is preferably performed by a melt molding method, and the co-extrusion molding method is more preferable because it is excellent in productivity. The coextrusion molding method is a method for obtaining a laminate of two or more layers in the shape of a film, a tube or the like. The melt coming out from the discharge ports of two or more extruders passes through the die while being in contact in the molten state, and is formed into a laminate. For coextrusion molding, the fluorinated copolymer and the thermoplastic resin preferably have molding temperatures close to each other. The extrusion temperature is determined from the viewpoints of the melting point and decomposition temperature of the fluorine-containing copolymer and the thermoplastic resin. The screw temperature is preferably 100 to 400 ° C, and the die temperature is preferably 150 to 400 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. The residence time of the fluorine-containing copolymer in the extruder is preferably 1 to 20 minutes.

本発明の積層体における、含フッ素共重合体以外の熱可塑性樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等のポリエステル類、ポリアミド6、ポリアミド66、ポリアミド46、ポリアミド11、ポリアミド12、ポリアミドMXD6(半芳香族系ポリアミド)等のポリアミド類、ポリエチレン、ポリプロピレン等のポリオレフィン類、ポリ酢酸ビニル、ポリ(エチレン/酢酸ビニル)、ポリビニルアルコール、ポリ(エチレン/ビニルアルコール)、ポリスチレン、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリオキシメチレン、ポリフェニレンスルフィド、ポリフェニレンエーテル、ポリカーボネート、ポリアミドイミド、ポリエーテルイミド、ポリスルホン、ポリアリレエート等が挙げられる。   Examples of the thermoplastic resin other than the fluorine-containing copolymer in the laminate of the present invention include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, polyamide 6, polyamide 66, polyamide 46, and polyamide. 11. Polyamides such as polyamide 12, polyamide MXD6 (semi-aromatic polyamide), polyolefins such as polyethylene and polypropylene, polyvinyl acetate, poly (ethylene / vinyl acetate), polyvinyl alcohol, poly (ethylene / vinyl alcohol), Polystyrene, polyvinylidene chloride, polyacrylonitrile, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyamideimide, polyetherimide Polysulfone, Poriarireeto, and the like.

本発明の被覆物品は、含フッ素共重合体で基材の表面が被覆されてなる。基材としては、前記含フッ素重合体以外の熱可塑性樹脂等の有機材料、鉄、ステンレス鋼、銅、黄銅、アルミニウム、ニッケル、マグネシウム合金、チタン等の金属材料、ガラス、セラミックス等の無機材料が挙げられる。
該基材を被覆する方法としては、静電粉体成形法、回転成形法、溶射成形法、流動浸漬法、ディスパージョン法、溶媒キャスト法等が採用できる。
The coated article of the present invention is formed by coating the surface of a substrate with a fluorine-containing copolymer. Examples of the base material include organic materials such as thermoplastic resins other than the fluorine-containing polymer, metal materials such as iron, stainless steel, copper, brass, aluminum, nickel, magnesium alloy, and titanium, and inorganic materials such as glass and ceramics. Can be mentioned.
As a method for coating the substrate, an electrostatic powder molding method, a rotational molding method, a thermal spray molding method, a fluidized immersion method, a dispersion method, a solvent casting method, or the like can be employed.

静電粉体成形法では、含フッ素共重合体の粉末に負の高電圧を印加して帯電させ、基材表面に付着させ、ついで付着した含フッ素共重合体をその融点以上分解点以下の温度で5分〜1時間、加熱して溶融させ、基材表面に一定の厚さの含フッ素共重合体の被膜を形成させることが好ましい。
回転成形法では、缶状や筒状の基材の内部に含フッ素共重合体の粉末を挿入し、基材を回転させながら含フッ素共重合体の融点以上分解点以下の温度に5分〜1時間、基材を加熱して含フッ素共重合体を溶融させ、基材の内面に均一な厚さの含フッ素共重合体の被膜を形成させることが好ましい。
In the electrostatic powder molding method, a negative high voltage is applied to the powder of the fluorine-containing copolymer to be charged and adhered to the surface of the substrate, and then the adhered fluorine-containing copolymer is not lower than its melting point and not higher than the decomposition point. It is preferable to heat and melt at a temperature for 5 minutes to 1 hour to form a fluorine-containing copolymer film having a certain thickness on the surface of the substrate.
In the rotational molding method, the fluorine-containing copolymer powder is inserted into the inside of a can-like or cylindrical substrate, and the temperature of the melting point of the fluorine-containing copolymer is not lower than the decomposition point while rotating the substrate. It is preferable to heat the substrate for 1 hour to melt the fluorine-containing copolymer and form a film of the fluorine-containing copolymer having a uniform thickness on the inner surface of the substrate.

溶射成形法では、予熱した基材に粉末溶射器を用い、半融解状態の含フッ素共重合体を吹き付けることによって、基材表面に含フッ素共重合体の被膜を形成させることが好ましい。
流動浸漬法では、含フッ素共重合体の粉末を、底が通気性の多孔板である容器に入れ、多孔板より気体を送ることにより粉末を流動化させ、この流動層中に含フッ素共重合体の融点以上分解点以下に加熱した基材を1分以上1時間以下浸漬することにより、基材表面に均一な含フッ素共重合体の被膜を形成させることが好ましい。
In the thermal spray molding method, it is preferable to form a coating film of the fluorinated copolymer on the surface of the substrate by spraying a semi-molten fluorinated copolymer onto a preheated substrate.
In the fluidized immersion method, the powder of the fluorinated copolymer is placed in a container having a gas-permeable porous plate at the bottom, and the powder is fluidized by sending gas from the porous plate. It is preferable to form a uniform fluorine-containing copolymer film on the substrate surface by immersing the substrate heated to the melting point or more and the decomposition point or less of the coalescence for 1 minute or more and 1 hour or less.

ディスパージョン法では、含フッ素共重合体の微粉末を水又は溶剤に浮遊、又は液に懸濁させて、これを基材に噴射して、水又は溶剤を蒸発させて均一な粉末の堆積層を形成させる。ついで、含フッ素共重合体の融点以上分解点以下に1分〜1時間加熱し溶融させ、基材表面に含フッ素共重合体の被膜を形成させることが好ましい。   In the dispersion method, a fine powder of a fluorine-containing copolymer is suspended in water or a solvent, or suspended in a liquid, and sprayed onto a substrate to evaporate the water or the solvent, thereby depositing a uniform powder. To form. Next, it is preferable to heat and melt for 1 minute to 1 hour below the melting point and below the decomposition point of the fluorine-containing copolymer to form a film of the fluorine-containing copolymer on the substrate surface.

含フッ素共重合体を溶媒に溶解できる場合には、キャスティング、浸漬等により基材の表面に塗布して、含フッ素共重合体の被膜を形成することも好ましい。
前記基材の表面は、接着性を向上するために前処理されることも好ましい。前処理方法としては、サンドブラスト処理、リン酸塩処理、塩酸処理、硫酸処理等が挙げられる。
When the fluorine-containing copolymer can be dissolved in a solvent, it is also preferable to form a film of the fluorine-containing copolymer by coating it on the surface of the substrate by casting, dipping or the like.
It is also preferable that the surface of the substrate is pretreated in order to improve adhesion. Examples of the pretreatment method include sandblast treatment, phosphate treatment, hydrochloric acid treatment, and sulfuric acid treatment.

以下に実施例1〜4及び比較例1〜4を挙げて本発明を説明するが、本発明はこれらに限定されない。なお、接着強度、耐ストレスクラック性能、及びNAHの含有量は下記の方法によって測定した。   EXAMPLES Although Examples 1-4 and Comparative Examples 1-4 are given below and this invention is demonstrated, this invention is not limited to these. The adhesive strength, stress crack resistance, and NAH content were measured by the following methods.

[接着強度(単位:N/cm)]
100μmの厚さの含フッ素共重合体のフィルムと、100μmの厚さのポリアミド12(宇部興産株式会社製3030JLX、以下PA12という。)のフィルム、銅箔又はアルミ箔とを重ね合せ、ヒートシーラー(富士インパルス社製)を用いて、加熱レベル9(到達温度280℃)の設定で溶融接着させた。得られた積層フィルムを縦10cm横1cmの短冊状に切断し、試験片を作成した。引張試験機を用いて該試験片の剥離強度を測定し、接着強度とした。
[Adhesive strength (unit: N / cm)]
A 100 μm-thick fluorine-containing copolymer film and a 100 μm-thick polyamide 12 (Ube Industries, Ltd., 3030JLX, hereinafter referred to as PA12) film, a copper foil or an aluminum foil are overlaid, and a heat sealer ( Using Fuji Impulse Co., Ltd., melt bonding was performed at a setting of a heating level 9 (attainment temperature 280 ° C.). The obtained laminated film was cut into strips having a length of 10 cm and a width of 1 cm to prepare test pieces. The peel strength of the test piece was measured using a tensile tester to obtain the adhesive strength.

同様に、100μmの厚さの含フッ素共重合体のフィルムと、厚さ20μmの銅箔(福田金属箔粉工業社製電解銅箔SV)との接着強度、厚さ100μmのアルミ箔(東海アルミ箔社製硬質アルミ箔)との接着強度、を測定した。   Similarly, the adhesive strength between a 100 μm-thick fluorine-containing copolymer film and a 20 μm-thick copper foil (electrolytic copper foil SV manufactured by Fukuda Metal Foil Powder Co., Ltd.), a 100 μm-thick aluminum foil (Tokai Aluminum) The adhesive strength with a hard aluminum foil manufactured by Foil Co., Ltd. was measured.

[耐ストレスクラック性試験(MIT折り曲げ寿命)]
含フッ素共重合体を340℃で圧縮成形して得た厚さ0.220〜0.236μmのフィルムを幅12.5mmの短冊状に打ち抜いて測定試料を得た。ASTM D2176に準じて、荷重1.25kg、折り曲げ角度±135度、室温で折り曲げ試験機MIT−D(東洋精機製作社製)を用いて測定試料の折り曲げ試験を行った。破断するまでの折り曲げ回数をMIT折り曲げ寿命とした。この値が大きいほど、耐ストレスクラック性に優れることを示す。
[Stress crack resistance test (MIT bending life)]
A film having a thickness of 0.220 to 0.236 μm obtained by compression molding the fluorine-containing copolymer at 340 ° C. was punched into a strip having a width of 12.5 mm to obtain a measurement sample. In accordance with ASTM D2176, a bending test of the measurement sample was performed using a bending tester MIT-D (manufactured by Toyo Seiki Seisakusho) at a load of 1.25 kg, a bending angle of ± 135 degrees, and room temperature. The number of folds until rupture was defined as the MIT fold life. It shows that it is excellent in stress crack resistance, so that this value is large.

[NAHに基づく繰り返し単位の含有量(単位:モル%)]
100μmの含フッ素共重合体のフィルムを用いて、赤外吸収スペクトルを測定した。赤外吸収スペクトルにおけるNAHの吸収ピークは1778cm−1に現れるのでそのピークの吸光度を測定した。NAHのモル吸光係数1340l・mol−1・cm−1を用いてNAHに基づく繰り返し単位の含有量を算出した。
[Content of repeating unit based on NAH (unit: mol%)]
An infrared absorption spectrum was measured using a 100 μm fluorine-containing copolymer film. Since the absorption peak of NAH in the infrared absorption spectrum appears at 1778 cm −1 , the absorbance of the peak was measured. The content of repeating units based on NAH was calculated using a molar extinction coefficient of NAH of 1340 l · mol −1 · cm −1 .

[PMVE、PEVE、PPVE、HFPに基づく繰り返し単位の含有量(単位:モル%)]
旭硝子研究報告40(1)、75(1990)に記載の方法に準じて、溶融NMR分析して算出した。
[Content of repeating unit based on PMVE, PEVE, PPVE, HFP (unit: mol%)]
In accordance with the method described in Asahi Glass Research Report 40 (1), 75 (1990), it was calculated by melt NMR analysis.

[実施例1(TFE/PPVE/PMVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、1,1,2,2,−テトラフルオロエチル−2,2,2,−トリフルオロエチルエーテル(旭硝子社製AE−3000、以下、AE−3000という。)の1131g、PPVEの35g、PMVEの22g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの155gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFEを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始5.6時間後、TFEの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Example 1 (TFE / PPVE / PMVE / NAH copolymer)]
The polymerization tank with a stirrer having an internal volume of 1.2 L was degassed, and 1,1,2,2, -tetrafluoroethyl-2,2,2, -trifluoroethyl ether (AE-3000 manufactured by Asahi Glass Co., Ltd. AE-3000), 1131 g of PPVE, 35 g of PPVE, 22 g of PMVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 155 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体1のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体1の45gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体1の共重合組成は、TFEに基づく繰り返し単位/PPVEに基づく繰り返し単位/PMVEに基づく繰り返し単位/NAHに基づく繰り返し単位=95.8/2.0/2.1/0.1(モル%)であった。融点は285℃、Q値は28mm/秒であった。MIT折り曲げ寿命は220万回であり、耐ストレスクラック性に優れることがわかった。含フッ素共重合体1のフィルムと、PA12のフィルムとの接着強度は14.1N/cmであり、銅箔との接着強度は10.5N/cmであり、アルミ箔との接着強度は9.3N/cmであり、いずれも接着性に優れることがわかった。得られた含フッ素共重合体1の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 1 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 45 g of fluorinated copolymer 1.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 1 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on PMVE / repeating unit based on NAH = 95 0.8 / 2.0 / 2.1 / 0.1 (mol%). The melting point was 285 ° C., and the Q value was 28 mm 3 / sec. The MIT bending life was 2.2 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 1 film and the PA12 film is 14.1 N / cm, the adhesive strength with the copper foil is 10.5 N / cm, and the adhesive strength with the aluminum foil is 9. 3 N / cm, both of which were found to be excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 1 are shown in Table 1.

[実施例2(TFE/PPVE/PEVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの35g、PEVEの29g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの160gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFEを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始5.6時間後、TFEの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Example 2 (TFE / PPVE / PEVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 35 g of PPVE, 29 g of PEVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 160 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体2のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体2の46gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体2の共重合組成は、TFEに基づく繰り返し単位/PPVEに基づく繰り返し単位/PEVEに基づく繰り返し単位/NAHに基づく繰り返し単位=95.6/2.1/2.2/0.1(モル%)であった。融点は287℃、Q値は30mm/秒であった。MIT折り曲げ寿命は230万回であり、耐ストレスクラック性に優れることがわかった。含フッ素共重合体2のフィルムと、ポリアミド12のフィルムとの接着強度は13.2N/cmであり、銅箔との接着強度は9.5N/cmであり、アルミ箔との接着強度は9.9N/cmであり、いずれも接着性に優れることがわかった。得られた含フッ素共重合体2の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 2 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 2.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 2 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on PEVE / repeating unit based on NAH = 95 0.6 / 2.1 / 2.2 / 0.1 (mol%). The melting point was 287 ° C., and the Q value was 30 mm 3 / sec. The MIT bending life was 2.3 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 2 film and the polyamide 12 film is 13.2 N / cm, the adhesive strength with the copper foil is 9.5 N / cm, and the adhesive strength with the aluminum foil is 9 It was found to be excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 2 are shown in Table 1.

[比較例1(TFE/PPVE共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの40g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの169gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFEを連続的に仕込んだ。重合開始5時間後、TFEの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Comparative Example 1 (TFE / PPVE copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 40 g of PPVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 169 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. After 5 hours from the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体3のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体3の45gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体3の共重合組成は、TFEに基づく繰り返し単位/PPVEに基づく繰り返し単位=98.0/2.0(モル%)であった。融点は300℃、Q値は20mm/秒であった。MIT折り曲げ寿命は50万回であった。含フッ素共重合体3のフィルムは、PA12のフィルム、銅箔、アルミ箔のいずれとも全く接着しなかった。得られた含フッ素共重合体3の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 3 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 45 g of fluorinated copolymer 3.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 3 was a repeating unit based on TFE / repeating unit based on PPVE = 98.0 / 2.0 (mol%). It was. The melting point was 300 ° C., and the Q value was 20 mm 3 / sec. The MIT bending life was 500,000 times. The film of fluorine-containing copolymer 3 did not adhere to any of PA12 film, copper foil, and aluminum foil. The physical properties of the resulting fluorinated copolymer 3 are shown in Table 1.

[比較例2(TFE/PPVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの40g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの169gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFEを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始5.5時間後、TFEの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Comparative Example 2 (TFE / PPVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 40 g of PPVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 169 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.5 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体4のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体4の46gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体4の共重合組成は、TFEに基づく繰り返し単位/PPVEに基づく繰り返し単位/NAHに基づく繰り返し単位=97.9/2.0/0.1(モル%)であった。融点は300℃、Q値は23mm/秒であった。MIT折り曲げ寿命は30万回であった。含フッ素共重合体4のフィルムと、PA12のフィルムとの接着強度は13.5N/cmであり、銅箔との接着強度は9.5N/cmであり、アルミ箔との接着強度は8.4N/cmであり、いずれも接着性に優れることがわかった。得られた含フッ素共重合体の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 4 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 4.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 4 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on NAH = 97.9 / 2.0. /0.1 (mol%). The melting point was 300 ° C., and the Q value was 23 mm 3 / sec. The MIT bending life was 300,000 times. The adhesive strength between the fluorine-containing copolymer 4 film and the PA12 film is 13.5 N / cm, the adhesive strength with the copper foil is 9.5 N / cm, and the adhesive strength with the aluminum foil is 8. 4 N / cm, both of which were found to be excellent in adhesiveness. Table 1 shows the physical properties of the obtained fluorinated copolymer.

[実施例3(TFE/HFP/PPVE/PMVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの15g、PMVEの10g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの25g、HFPの300gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFE/HFP=91/9(モル比)の混合ガスを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始6.1時間後、TFE/HFP=91/9(モル比)の混合ガスの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Example 3 (TFE / HFP / PPVE / PMVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, 10 g of PMVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.1 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体5のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体5の47gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体5の共重合組成は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/PPVEに基づく繰り返し単位/PMVEに基づく繰り返し単位/NAHに基づく繰り返し単位=88.1/8.1/1.6/2.1/0.1(モル%)であった。融点は246℃、Q値は56mm/秒であった。MIT折り曲げ寿命は200万回であり、耐ストレスクラック性に優れることがわかった。含フッ素共重合体5のフィルムと、PA12のフィルムとの接着強度は14.1N/cmであり、銅箔との接着強度は12.1N/cmであり、アルミ箔との接着強度は12.5N/cmであり、いずれも接着性に優れることがわかった。得られた含フッ素共重合体5の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 5 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 47 g of fluorinated copolymer 5.
From the results of the melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 5 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on PMVE / NAH The repeating unit based on the formula was 88.1 / 8.1 / 1.6 / 2.1 / 0.1 (mol%). The melting point was 246 ° C., and the Q value was 56 mm 3 / sec. The MIT bending life was 2 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 5 film and the PA12 film is 14.1 N / cm, the adhesive strength with the copper foil is 12.1 N / cm, and the adhesive strength with the aluminum foil is 12.1. It was 5 N / cm, and it was found that both were excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 5 are shown in Table 1.

[実施例4(TFE/HFP/PPVE/PEVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの15g、PEVEの12.5g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの25g、HFPの300gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFE/HFP=91/9(モル比)の混合ガスを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始6.3時間後、TFE/HFP=91/9(モル比)の混合ガスの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Example 4 (TFE / HFP / PPVE / PEVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated, and charged with 1131 g of AE-3000, 15 g of PPVE, 12.5 g of PEVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.3 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体6のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体6の46gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体6の共重合組成は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/PPVEに基づく繰り返し単位/PEVEに基づく繰り返し単位/NAHに基づく繰り返し単位=88.2/8.0/1.7/2.0/0.1(モル%)であった。融点は245℃、Q値は56mm/秒であった。MIT折り曲げ寿命は210万回であり、耐ストレスクラック性に優れることがわかった。含フッ素共重合体6のフィルムと、PA12のフィルムとの接着強度は13.6N/cmであり、銅箔との接着強度は11.9N/cmであり、アルミ箔との接着強度は13.7N/cmであり、いずれも接着性に優れることがわかった。得られた共重合体の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 6 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 6.
From the results of the melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 6 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on PEVE / NAH The repeating unit based on the formula was 88.2 / 8.0 / 1.7 / 2.0 / 0.1 (mol%). The melting point was 245 ° C., and the Q value was 56 mm 3 / sec. The MIT bending life was 2.1 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 6 film and the PA12 film is 13.6 N / cm, the adhesive strength with the copper foil is 11.9 N / cm, and the adhesive strength with the aluminum foil is 13. 7 N / cm, both of which were found to be excellent in adhesiveness. The physical properties of the obtained copolymer are shown in Table 1.

[比較例3(TFE/HFP/PPVE共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの15g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの25g、HFPの300gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFE/HFP=91/9(モル比)の混合ガスを連続的に仕込んだ。重合開始6時間後、TFE/HFP=91/9(モル比)の混合ガスの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Comparative Example 3 (TFE / HFP / PPVE copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. Six hours after the start of the polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the polymerization tank internal temperature was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体7のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体7の46gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体7の共重合組成は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/PPVEに基づく繰り返し単位=90.5/8.0/1.5(モル%)であった。融点は262℃、Q値は50mm/秒であった。MIT折り曲げ寿命は25万回であった。含フッ素共重合体7のフィルムは、PA12のフィルム、銅箔、アルミ箔のいずれとも全く接着しなかった。得られた含フッ素共重合体の物性を表1に示す。
The slurry of the obtained fluorinated copolymer 7 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 7.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 7 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE = 90.5 / 8.0 /1.5 (mol%). The melting point was 262 ° C., and the Q value was 50 mm 3 / sec. The MIT bending life was 250,000 times. The film of fluorine-containing copolymer 7 did not adhere to any of PA12 film, copper foil, and aluminum foil. Table 1 shows the physical properties of the obtained fluorinated copolymer.

[比較例4(TFE/HFP/PPVE/NAH共重合体)]
内容積が1.2Lの撹拌機付き重合槽を脱気し、AE−3000の1131g、PPVEの15g、メタノールの5gを仕込んだ。ついで重合槽内を50℃に昇温し、TFEの25g、HFPの300gを仕込んで圧力を0.99MPa/Gまで昇圧した。重合開始剤溶液として(ペルフルオロブチリル)ペルオキシドの0.1質量%AE−3000溶液の1cmを仕込み、重合を開始させ、以後10分毎に該重合開始剤溶液の1cmを仕込んだ。また、重合中圧力が0.99MPa/Gを保持するようにTFE/HFP=91/9(モル比)の混合ガスを連続的に仕込んだ。また、重合中に仕込むTFEのモル数に対して0.2モル%に相当する量のNAHの0.3質量%AE−3000溶液を連続的に仕込んだ。重合開始6.1時間後、TFE/HFP=91/9(モル比)の混合ガスの50gを仕込んだ時点で、重合槽内温を室温まで降温するとともに常圧までパージした。
[Comparative Example 4 (TFE / HFP / PPVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm 3 of the peroxide and the polymerization was started and charged with 1 cm 3 of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.1 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

得られた含フッ素共重合体8のスラリをガラスフィルターで濾過して溶媒を分離した後150℃で15時間乾燥することにより、含フッ素共重合体8の46gを得た。
溶融NMR分析及び赤外吸収スペクトル分析の結果から、含フッ素共重合体8の共重合組成は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/PPVEに基づく繰り返し単位/NAHに基づく繰り返し単位=90.2/8.1/1.6/0.1(モル%)であった。融点は260℃、Q値は55mm/秒であった。MIT折り曲げ寿命は15万回であった。含フッ素共重合体8のフィルムと、PA12のフィルムとの接着強度は14.0N/cmであり、銅箔との接着強度は10.2N/cmであり、アルミ箔との接着強度は12.5N/cmであり、いずれも接着性に優れることがわかった。得られた含フッ素共重合体の物性を表1に示す。
46 g of the fluorinated copolymer 8 was obtained by filtering the slurry of the obtained fluorinated copolymer 8 through a glass filter and separating the solvent, followed by drying at 150 ° C. for 15 hours.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 8 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on NAH = 90 2 / 8.1 / 1.6 / 0.1 (mol%). The melting point was 260 ° C., and the Q value was 55 mm 3 / sec. The MIT bending life was 150,000 times. The adhesive strength between the fluorine-containing copolymer 8 film and the PA12 film is 14.0 N / cm, the adhesive strength with the copper foil is 10.2 N / cm, and the adhesive strength with the aluminum foil is 12. It was 5 N / cm, and it was found that both were excellent in adhesiveness. Table 1 shows the physical properties of the obtained fluorinated copolymer.

Figure 2010053209
Figure 2010053209

本発明の含フッ素共重合体及び積層体は、耐熱性、耐薬品性、耐食性、耐油性、耐候性等に優れ且つ、耐ストレスクラック性に優れることから、塗装ロボット用塗料配管、半導体製造装置用薬液配管、自動車用燃料用ホース、産業用ホース、食品用ホース、耐候性積層フィルム、耐候性積層シート、IC基板、接着材等の用途に適する。   The fluorine-containing copolymer and laminate of the present invention are excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance and the like, and are excellent in stress crack resistance. Suitable for chemical liquid piping, automotive fuel hoses, industrial hoses, food hoses, weather resistant laminated films, weather resistant laminated sheets, IC substrates, adhesives, etc.

また、本発明の被覆物品は、耐熱性、耐薬品性、耐食性、耐油性、耐候性、耐磨耗性、潤滑性等に優れることから、食品用、医療用、半導体用、化学プラント用等の反応器、容器、配管等、薬液輸送用タンクローリー、飛散防止ガラス板、飛散防止ガラスビン、耐磨耗性セラミックス部品等の用途に適する。   Further, the coated article of the present invention is excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance, abrasion resistance, lubricity, etc., so it is used for food, medical use, semiconductor use, chemical plant use, etc. Suitable for applications such as reactors, containers, pipes, tank trucks for transporting chemicals, shatterproof glass plates, shatterproof glass bottles, and wear-resistant ceramic parts.

Claims (4)

テトラフルオロエチレンに基づく繰り返し単位(a)、CF=CFOCFCFCFに基づく繰り返し単位(b)、CF=CFOCF及び/又はCF=CFOCFCFに基づく繰り返し単位(c)、ジカルボン酸無水物基を有する重合性炭化水素モノマーに基づく繰り返し単位(d)を含有し、繰り返し単位(a)、繰り返し単位(b)、繰り返し単位(c)、繰り返し単位(d)の合計モル量に対して、繰り返し単位(a)が75〜99.79モル%であり、繰り返し単位(b)が0.1〜10.0モル%であり、繰り返し単位(c)が0.1〜10.0モル%であり、繰り返し単位(d)が0.01〜5.0モル%であり、容量流速が0.1〜1000mm/秒であることを特徴とする含フッ素共重合体。 Repeating units based on tetrafluoroethylene (a), repeating units based on CF 2 = CFOCF 2 CF 2 CF 3 (b), CF 2 = CFOCF 3 and / or CF 2 = CFOCF repeating units based on 2 CF 3 (c) , Containing a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic anhydride group, the total mole of the repeating unit (a), the repeating unit (b), the repeating unit (c) and the repeating unit (d). The repeating unit (a) is 75 to 99.79 mol%, the repeating unit (b) is 0.1 to 10.0 mol%, and the repeating unit (c) is 0.1 to 10% with respect to the amount. 2.0 the mole%, a repeating unit (d) is 0.01 to 5.0 mol%, the fluorine-containing copolymer, wherein the volume flow rate is 0.1~1000mm 3 / sec 前記ジカルボン酸無水物基を有する重合性炭化水素モノマーが、5−ノルボルネン−2,3−ジカルボン酸無水物である請求項1に記載の含フッ素共重合体。   The fluorine-containing copolymer according to claim 1, wherein the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group is 5-norbornene-2,3-dicarboxylic acid anhydride. 請求項1又は2に記載の含フッ素共重合体の層と該含フッ素共重合体以外の熱可塑性樹脂の層とが直接積層されてなる積層体。   A laminate comprising the fluorine-containing copolymer layer according to claim 1 and a thermoplastic resin layer other than the fluorine-containing copolymer directly laminated. 請求項1又は2に記載の含フッ素共重合体で基材の表面が被覆されてなる被覆物品。   A coated article obtained by coating the surface of a substrate with the fluorine-containing copolymer according to claim 1.
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