JP2014015551A - Ethylene/tetrafluoroethylene-based copolymer and production method thereof, ethylene/tetrafluoroethylene-based copolymer powder, powder composition, and article - Google Patents
Ethylene/tetrafluoroethylene-based copolymer and production method thereof, ethylene/tetrafluoroethylene-based copolymer powder, powder composition, and article Download PDFInfo
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本発明は、エチレン／テトラフルオロエチレン系共重合体およびその製造方法、エチレン／テトラフルオロエチレン系共重合体粉体、粉体組成物、ならびに物品に関する。 The present invention relates to an ethylene / tetrafluoroethylene copolymer and a method for producing the same, an ethylene / tetrafluoroethylene copolymer powder, a powder composition, and an article.
エチレン／テトラフルオロエチレン系共重合体（以下、「ＥＴＦＥ」と記す。）は、耐熱性、耐薬品性、耐候性、ガスバリア性等に優れる。ＥＴＦＥを成形または塗装して得られた物品は、半導体産業、自動車産業等の種々の分野で使用されている。成形方法としては、押出し成形、射出成形、回転成形等の種々の成形方法が適用される。また、塗装方法としては、静電塗装等の粉体塗装が挙げられる。粉体を使用する回転成形および粉体塗装は、押出し成形、射出成形等の成形方法では製造しにくい異型形状の容器、タンク、配管、継ぎ手等の物品の製造に適する。 An ethylene / tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”) is excellent in heat resistance, chemical resistance, weather resistance, gas barrier properties, and the like. Articles obtained by molding or painting ETFE are used in various fields such as the semiconductor industry and the automobile industry. As the molding method, various molding methods such as extrusion molding, injection molding, and rotational molding are applied. Examples of the coating method include powder coating such as electrostatic coating. Rotational molding and powder coating using powder are suitable for manufacturing articles such as irregularly shaped containers, tanks, pipes, and joints that are difficult to manufacture by a molding method such as extrusion molding or injection molding.
回転成形および粉体塗装に使用されるエチレン／テトラフルオロエチレン系共重合体粉体（以下、「ＥＴＦＥ粉体」と記す。）としては、たとえば、以下に示す粉体が知られている。
テトラフルオロエチレン（以下、「ＴＦＥ」と記す。）に基づく構成単位と、エチレン（以下、「Ｅ」と記す。）に基づく構成単位と、無水イタコン酸または無水シトラコン酸に基づく構成単位と、を特定の比率で有するＥＴＦＥ粉体（特許文献１）。
該ＥＴＦＥ粉体は、被塗装物との接着性に優れ、主にフッ素樹脂の粉体塗装における被塗装物へのプライマー処理に使用される。
For example, the following powders are known as ethylene / tetrafluoroethylene copolymer powders (hereinafter referred to as “ETFE powders”) used for rotational molding and powder coating.
A structural unit based on tetrafluoroethylene (hereinafter referred to as “TFE”), a structural unit based on ethylene (hereinafter referred to as “E”), and a structural unit based on itaconic anhydride or citraconic anhydride. ETFE powder having a specific ratio (Patent Document 1).
The ETFE powder is excellent in adhesion to an object to be coated, and is mainly used for primer treatment on an object to be coated in powder coating of a fluororesin.
近年では、粉体塗装により得られた物品がより厳しい環境下で使用されていることから、特に被塗装物の材質が接着に不利な金属である場合に、ＥＴＦＥと被塗装物との接着性をさらに向上させることが求められている。 In recent years, since articles obtained by powder coating are used in more severe environments, especially when the material of the object to be coated is a metal that is disadvantageous for bonding, the adhesion between ETFE and the object to be coated There is a demand for further improvement.
本発明は、材質が金属である被塗装物の粉体塗装に用いる場合でも、優れた接着性を発現できるＥＴＦＥおよびその製造方法を提供することを目的とする。また、本発明は、材質が金属である被塗装物の粉体塗装に用いる場合でも、優れた接着性を発現できるＥＴＦＥ粉体および粉体組成物、ならびにそれらを粉体塗装した物品を提供することを目的とする。 An object of the present invention is to provide an ETFE that can exhibit excellent adhesion even when used for powder coating of an object to be coated whose material is a metal, and a method for producing the same. The present invention also provides an ETFE powder and a powder composition capable of exhibiting excellent adhesiveness even when used for powder coating of an object to be coated whose material is a metal, and an article obtained by powder coating them. For the purpose.
本発明は、前記課題を解決するために、以下の構成を採用した。
［１］ペルフルオロカーボン類、ヒドロフルオカーボン類およびヒドロフルオロアルキルエーテル類からなる群から選ばれる少なくとも１種の重合媒体を用いた重合により得られ、
下記単量体（ａ）に基づく構成単位（Ａ）と、下記単量体（ｂ）に基づく構成単位（Ｂ）と、下記単量体（ｃ）に基づく構成単位（Ｃ）と、下記連鎖移動剤（ｄ）に基づく末端基（Ｄ）と、を有し、
モル比（Ａ）／（Ｂ）が２０／８０〜８０／２０であり、モル比（Ｃ）／（（Ａ）＋（Ｂ））が０．１／１００〜５／１００であることを特徴とするＥＴＦＥ。
単量体（ａ）：ＴＦＥ。
単量体（ｂ）：Ｅ。
単量体（ｃ）：ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ただし、ＸおよびＹは、それぞれ独立に水素原子またはフッ素原子であり、ｎは２〜１０の整数である。）。
連鎖移動剤（ｄ）：３，３−ジクロロ−１，１，１，２，２−ペンタフルオロプロパン。
［２］前記モル比（Ｃ）／（（Ａ）＋（Ｂ））が０．５／１００〜３．５／１００である、［１］に記載のＥＴＦＥ。
［３］［１］または［２］に記載のＥＴＦＥの平均粒径が０．０１〜１０００μｍの粉体であることを特徴とするＥＴＦＥ粉体。
［４］［３］に記載のＥＴＦＥ粉体と、熱安定剤とを含有することを特徴とする粉体組成物。
［５］前記熱安定剤が、銅化合物、錫化合物、鉄化合物、鉛化合物、チタン化合物およびアルミニウム化合物からなる群から選ばれる少なくとも１種である、［４］に記載の粉体組成物。
［６］［３］に記載のＥＴＦＥ粉体が被塗装物に粉体塗装された物品。
［７］［４］または［５］に記載の粉体組成物が被塗装物に粉体塗装された物品。
［８］ペルフルオロカーボン類、ヒドロフルオカーボン類およびヒドロフルオロアルキルエーテル類からなる群から選ばれる少なくとも１種の重合媒体と、前記連鎖移動剤（ｄ）と、重合開始剤との存在下に、
前記単量体（ａ）と前記単量体（ｂ）と前記単量体（ｃ）とを、モル比（ａ）／（ｂ）を２０／８０〜９９／１、モル比（ｃ）／（（ａ）＋（ｂ））を０．１／１００〜５／１００として共重合することを特徴とするＥＴＦＥの製造方法。
The present invention employs the following configuration in order to solve the above problems.
[1] Obtained by polymerization using at least one polymerization medium selected from the group consisting of perfluorocarbons, hydrofluorocarbons and hydrofluoroalkyl ethers,
Structural unit (A) based on monomer (a) below, Structural unit (B) based on monomer (b) below, Structural unit (C) based on monomer (c) below, A terminal group (D) based on a transfer agent (d),
The molar ratio (A) / (B) is 20/80 to 80/20, and the molar ratio (C) / ((A) + (B)) is 0.1 / 100 to 5/100. ETFE.
Monomer (a): TFE.
Monomer (b): E.
Monomer (c): CH 2 ═CX (CF 2 ) n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10).
Chain transfer agent (d): 3,3-dichloro-1,1,1,2,2-pentafluoropropane.
[2] ETFE according to [1], wherein the molar ratio (C) / ((A) + (B)) is 0.5 / 100 to 3.5 / 100.
[3] An ETFE powder, wherein the ETFE average particle size according to [1] or [2] is a powder having an average particle size of 0.01 to 1000 μm.
[4] A powder composition comprising the ETFE powder according to [3] and a heat stabilizer.
[5] The powder composition according to [4], wherein the thermal stabilizer is at least one selected from the group consisting of a copper compound, a tin compound, an iron compound, a lead compound, a titanium compound, and an aluminum compound.
[6] An article in which the ETFE powder according to [3] is powder-coated on an object to be coated.
[7] An article in which the powder composition according to [4] or [5] is powder-coated on an object to be coated.
[8] In the presence of at least one polymerization medium selected from the group consisting of perfluorocarbons, hydrofluorocarbons and hydrofluoroalkyl ethers, the chain transfer agent (d), and a polymerization initiator,
The monomer (a), the monomer (b), and the monomer (c) are mixed at a molar ratio (a) / (b) of 20/80 to 99/1 and a molar ratio (c) / A method for producing ETFE, wherein ((a) + (b)) is copolymerized at 0.1 / 100 to 5/100.
本発明のＥＴＦＥは、材質が金属である被塗装物の粉体塗装に用いる場合でも、被塗装物との接着性に優れる。
また、本発明のＥＴＦＥ粉体および粉体組成物は、材質が金属である被塗装物の粉体塗装に用いる場合でも、被塗装物との接着性に優れる。
また、本発明の物品は、材質が金属である被塗装物の粉体塗装で得られた場合でも、粉体塗装されたＥＴＦＥ塗膜と被塗装物との接着性に優れる。
また、本発明のＥＴＦＥの製造方法によれば、材質が金属である被塗装物の粉体塗装に用いる場合でも、被塗装物との接着性に優れるＥＴＦＥが得られる。
The ETFE of the present invention is excellent in adhesiveness with the object to be coated even when used for powder coating of the object to be coated whose material is metal.
In addition, the ETFE powder and the powder composition of the present invention are excellent in adhesiveness to the object to be coated even when used for powder coating of the object to be coated whose material is metal.
Further, the article of the present invention is excellent in adhesion between the powder-coated ETFE coating film and the object to be coated, even when obtained by powder coating of the object to be coated whose material is metal.
In addition, according to the ETFE manufacturing method of the present invention, ETFE excellent in adhesiveness to the object to be coated can be obtained even when used for powder coating of the object to be coated whose material is metal.
本明細書における「構成単位」とは、単量体が重合することによって形成された該単量体に基づく単位を意味する。構成単位は、重合反応によって直接形成された単位であってもよく、重合体を処理することによって該単位の一部が別の構造に変換された単位であってもよい。
また、本明細書における「単量体」とは、重合性不飽和結合、すなわち重合反応性の炭素−炭素二重結合を有する化合物を意味する。
The “structural unit” in the present specification means a unit based on the monomer formed by polymerization of the monomer. The structural unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
In addition, the “monomer” in the present specification means a compound having a polymerizable unsaturated bond, that is, a polymerization-reactive carbon-carbon double bond.
＜ＥＴＦＥ＞
本発明のＥＴＦＥは、後述する重合媒体を用いた重合により得られ、後述する単量体（ａ）に基づく構成単位（Ａ）（以下、「単位（Ａ）」と記し、他の構成単位についても同様に示す。）と、単量体（ｂ）に基づく単位（Ｂ）と、単量体（ｃ）に基づく単位（Ｃ）と、連鎖移動剤（ｄ）に基づく末端基（Ｄ）と、を有する。
本発明のＥＴＦＥは、単量体（ｅ）に基づく単位（Ｅ）を有していてもよい。
<ETFE>
The ETFE of the present invention is obtained by polymerization using a polymerization medium, which will be described later. The structural unit (A) based on the monomer (a) described later (hereinafter referred to as “unit (A)”) As well as a unit (B) based on the monomer (b), a unit (C) based on the monomer (c), and a terminal group (D) based on the chain transfer agent (d). Have.
The ETFE of the present invention may have a unit (E) based on the monomer (e).
［単量体（ａ）］
単量体（ａ）は、ＴＦＥである。本発明のＥＴＦＥが単量体（ａ）に基づく単位（Ａ）を有することで、耐熱性、耐候性、耐薬品性、ガスバリア性、燃料バリア性に優れたＥＴＦＥとなる。
[Monomer (a)]
Monomer (a) is TFE. When the ETFE of the present invention has the unit (A) based on the monomer (a), the ETFE is excellent in heat resistance, weather resistance, chemical resistance, gas barrier properties, and fuel barrier properties.
［単量体（ｂ）］
単量体（ｂ）は、Ｅである。本発明のＥＴＦＥが単量体（ｂ）に基づく単位（Ｂ）を有することで、機械的強度および成形性に優れたＥＴＦＥとなる。
[Monomer (b)]
The monomer (b) is E. When the ETFE of the present invention has a unit (B) based on the monomer (b), it becomes an ETFE excellent in mechanical strength and moldability.
［単量体（ｃ）］
単量体（ｃ）は、ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ただし、ＸおよびＹは、それぞれ独立に水素原子またはフッ素原子であり、ｎは２〜１０の整数である。）で表される単量体である。本発明のＥＴＦＥが単量体（ｃ）に基づく単位（Ｃ）を有することで、クラック等が生じにくく、優れた耐久性を有する塗膜を形成できるＥＴＦＥとなる。
単量体（ｃ）におけるＸは、入手の容易性の点から、水素原子が好ましい。Ｙは、熱安定性の点から、フッ素原子が好ましい。ｎは、ＥＴＦＥの物性の点から、２〜６の整数が好ましく、２〜４の整数が特に好ましい。
単量体（ｃ）の具体例としては、以下の単量体が挙げられる。
[Monomer (c)]
The monomer (c) is represented by CH 2 ═CX (CF 2 ) n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10). Monomer. When the ETFE of the present invention has the unit (C) based on the monomer (c), cracks and the like are hardly generated, and the ETFE can form a coating film having excellent durability.
X in the monomer (c) is preferably a hydrogen atom from the viewpoint of availability. Y is preferably a fluorine atom from the viewpoint of thermal stability. n is preferably an integer of 2 to 6 and particularly preferably an integer of 2 to 4 from the viewpoint of the physical properties of ETFE.
Specific examples of the monomer (c) include the following monomers.
ＣＨ２＝ＣＦ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）３Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）５Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）６Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）７Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）８Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）９Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）１０Ｆ、ＣＨ２＝ＣＦ（ＣＦ２）２Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）３Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）４Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）５Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）６Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）７Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）８Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）９Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）１０Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）３Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）５Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）６Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）７Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）８Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）９Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）１０Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）２Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）３Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）５Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）６Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）７Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）８Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）９Ｈ、ＣＨ２＝ＣＨ（ＣＦ２）１０Ｈ。 CH 2 = CF (CF 2) 2 F, CH 2 = CF (CF 2) 3 F, CH 2 = CF (CF 2) 4 F, CH 2 = CF (CF 2) 5 F, CH 2 = CF (CF 2 ) 6 F, CH 2 = CF (CF 2 ) 7 F, CH 2 = CF (CF 2 ) 8 F, CH 2 = CF (CF 2 ) 9 F, CH 2 = CF (CF 2 ) 10 F, CH 2 = CF (CF 2) 2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2) 5 H, CH 2 = CF (CF 2 ) 6 H, CH 2 = CF (CF 2 ) 7 H, CH 2 = CF (CF 2 ) 8 H, CH 2 = CF (CF 2 ) 9 H, CH 2 = CF (CF 2 ) 10 H, CH 2 = CH (CF 2 ) 2 F, CH 2 = CH (CF 2 ) 3 F, CH 2 = CH (CF 2 ) 4 F, CH 2 = CH (CF 2) 5 F, CH 2 = CH (CF 2) 6 F, CH 2 = CH (CF 2) 7 F, CH 2 = CH (CF 2) 8 F, CH 2 = CH (CF 2) 9 F , CH 2 = CH (CF 2) 10 F, CH 2 = CH (CF 2) 2 H, CH 2 = CH (CF 2) 3 H, CH 2 = CH (CF 2) 4 H, CH 2 = CH ( CF 2) 5 H, CH 2 = CH (CF 2) 6 H, CH 2 = CH (CF 2) 7 H, CH 2 = CH (CF 2) 8 H, CH 2 = CH (CF 2) 9 H, CH 2 = CH (CF 2) 10 H.
単量体（ｃ）としては、ＣＨ２＝ＣＦ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）２Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）２Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）４Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）６Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）６Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）６Ｈ、ＣＨ２＝ＣＦ（ＣＦ２）６Ｈが好ましく、ＣＨ２＝ＣＨ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）６Ｆがより好ましく、ＣＨ２＝ＣＨ（ＣＦ２）２Ｆ、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆが特に好ましい。
単位（Ｃ）は、１種の単量体（ｃ）に基づく１種の構成単位であってもよく、２種以上の単量体（ｃ）に基づく２種以上の構成単位であってもよい。
As the monomer (c), CH 2 ═CF (CF 2 ) 2 F, CH 2 ═CH (CF 2 ) 2 F, CH 2 ═CH (CF 2 ) 2 H, CH 2 ═CF (CF 2 ) 2 H, CH 2 = CF ( CF 2) 4 F, CH 2 = CH (CF 2) 4 F, CH 2 = CH (CF 2) 4 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2 ) 6 F, CH 2 ═CH (CF 2 ) 6 F, CH 2 ═CH (CF 2 ) 6 H, CH 2 ═CF (CF 2 ) 6 H are preferred, and CH 2 ═CH (CF 2 ) 2 F, CH 2 ═CH (CF 2 ) 4 F, CH 2 ═CH (CF 2 ) 6 F are more preferred, CH 2 ═CH (CF 2 ) 2 F, CH 2 ═CH (CF 2 ) 4 F Is particularly preferred.
The unit (C) may be one structural unit based on one monomer (c), or two or more structural units based on two or more monomers (c). Good.
［連鎖移動剤（ｄ）］
連鎖移動剤（ｄ）は、３，３−ジクロロ−１，１，１，２，２−ペンタフルオロプロパン（以下、「Ｒ−２２５ｃａ」と記す。）である。
本発明のＥＴＦＥが連鎖移動剤（ｄ）に基づく末端基（Ｄ）を有することにより、材質が金属の被塗装物に対しても優れた接着性を示す塗膜を形成できる。この理由は必ずしも明確ではないが、以下のように推定される。Ｒ−２２５ｃａ（ＣＨＣｌ２−ＣＦ２−ＣＦ３）は、重合中にラジカルによって水素原子が脱離して連鎖移動を起こし、−ＣＣｌ２−ＣＦ２−ＣＦ３という構造の末端基を形成する。該末端基における−ＣＣｌ２−の部分は、該末端基に隣接する構成単位における炭素原子に結合している水素原子と共に塩化水素として脱離しやすいと考えられる。そのため、金属等の被塗装物に本発明のＥＴＦＥを用いて塗膜を形成した場合でも、該末端基の部分から生じた塩化水素によって被塗装物表面で酸化等の反応が起こり、その結果、被塗装物表面でアンカー効果および新たな化学結合が生じ得るようになることで優れた接着性が得られると考えられる。
なお、本発明のＥＴＦＥの末端基は、連鎖移動剤（ｄ）であるＲ−２２５ｃａに基づく末端基（Ｄ）が主成分であれば、１，３−ジクロロ−１，１，２，２，３−ペンタフルオロプロパン（以下「Ｒ−２２５ｃｂ」と記す。）等の他の連鎖移動剤に基づく末端基が混入していてもよい。本発明のＥＴＦＥの全ての末端基に対する、Ｒ−２２５ｃａに基づく末端基（Ｄ）の割合は、８０モル％以上が好ましく、９０モル％以上がより好ましく、９５モル％以上が特に好ましい。
[Chain transfer agent (d)]
The chain transfer agent (d) is 3,3-dichloro-1,1,1,2,2-pentafluoropropane (hereinafter referred to as “R-225ca”).
When the ETFE of the present invention has an end group (D) based on the chain transfer agent (d), a coating film having excellent adhesion can be formed even on an object to be coated with a metal material. Although this reason is not necessarily clear, it is estimated as follows. R-225ca (CHCl 2 —CF 2 —CF 3 ) forms a terminal group having a structure of —CCl 2 —CF 2 —CF 3 by causing a hydrogen atom to be eliminated by radicals during polymerization to cause chain transfer. It is considered that the —CCl 2 — moiety in the terminal group is likely to be eliminated as hydrogen chloride together with the hydrogen atom bonded to the carbon atom in the structural unit adjacent to the terminal group. Therefore, even when a coating film is formed on the object to be coated such as metal using ETFE of the present invention, a reaction such as oxidation occurs on the surface of the object to be coated due to hydrogen chloride generated from the end group portion. It is considered that an excellent adhesiveness can be obtained when an anchor effect and a new chemical bond can be generated on the surface of the object to be coated.
In addition, if the terminal group (D) based on R-225ca which is a chain transfer agent (d) is a main component, the terminal group of ETFE of the present invention is 1,3-dichloro-1,1,2,2, End groups based on other chain transfer agents such as 3-pentafluoropropane (hereinafter referred to as “R-225cb”) may be mixed therein. The ratio of the terminal group (D) based on R-225ca to all terminal groups of ETFE of the present invention is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
［単量体（ｅ）］
単量体（ｅ）は、単量体（ａ）、単量体（ｂ）および単量体（ｃ）以外の単量体である。単量体（ｅ）としては、たとえば、以下の単量体が挙げられる。
プロピレン、ブテン等の炭化水素系オレフィン（ただし、Ｅを除く。）。
フッ化ビニリデン、フッ化ビニル、トリフルオロエチレン等の不飽和基に水素原子を有するフルオロオレフィン。
クロロトリフルオロエチレン等の不飽和基に水素原子を有しないフルオロオレフィン（ただし、ＴＦＥを除く。）。
ペルフルオロ（プロピルビニルエーテル）等のペルフルオロ（アルキルビニルエーテル）。
アルキルビニルエーテル、（フルオロアルキル）ビニルエーテル、グリシジルビニルエーテル、ヒドロキシブチルビニルエーテル、メチルビニロキシブチルカーボネート等のビニルエーテル。
酢酸ビニル、クロロ酢酸ビニル、ブタン酸ビニル、ピバル酸ビニル、安息香酸ビニル、クロトン酸ビニル等のビニルエステル。
（ポリフルオロアルキル）アクリレート、（ポリフルオロアルキル）メタクリレート等の（メタ）アクリル酸エステル。なお、（メタ）アクリル酸エステルとは、アクリル酸エステルまたはメタクリル酸エステルを示す。
無水イタコン酸、無水シトラコン酸等の酸無水物。
単位（Ｅ）は、１種の単量体（ｅ）に基づく１種の構成単位であってもよく、２種以上の単量体（ｅ）に基づく２種以上の構成単位であってもよい。
[Monomer (e)]
The monomer (e) is a monomer other than the monomer (a), the monomer (b), and the monomer (c). Examples of the monomer (e) include the following monomers.
Hydrocarbon olefins such as propylene and butene (excluding E).
Fluoroolefin having a hydrogen atom in an unsaturated group such as vinylidene fluoride, vinyl fluoride, trifluoroethylene and the like.
Fluoroolefins that do not have hydrogen atoms in unsaturated groups such as chlorotrifluoroethylene (excluding TFE).
Perfluoro (alkyl vinyl ether) such as perfluoro (propyl vinyl ether).
Vinyl ethers such as alkyl vinyl ethers, (fluoroalkyl) vinyl ethers, glycidyl vinyl ethers, hydroxybutyl vinyl ethers, methylvinyloxybutyl carbonates.
Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butanoate, vinyl pivalate, vinyl benzoate, and vinyl crotonic acid.
(Meth) acrylic acid esters such as (polyfluoroalkyl) acrylate and (polyfluoroalkyl) methacrylate. In addition, (meth) acrylic acid ester shows acrylic acid ester or methacrylic acid ester.
Acid anhydrides such as itaconic anhydride and citraconic anhydride.
The unit (E) may be one type of structural unit based on one type of monomer (e), or may be two or more types of structural units based on two or more types of monomers (e). Good.
単位（Ａ）と単位（Ｂ）のモル比である（Ａ）／（Ｂ）は、２０／８０〜８０／２０であり、４０／６０〜７０／３０が好ましく、５０／５０〜６０／４０がより好ましい。
モル比（Ａ）／（Ｂ）が下限値以上であれば、耐熱性、耐候性、耐薬品性、ガスバリア性、燃料バリア性に優れたＥＴＦＥとなる。モル比（Ａ）／（Ｂ）が上限値以下であれば、機械的強度および成形性に優れたＥＴＦＥとなる。
(A) / (B), which is the molar ratio of the unit (A) to the unit (B), is 20/80 to 80/20, preferably 40/60 to 70/30, and 50/50 to 60/40. Is more preferable.
When the molar ratio (A) / (B) is at least the lower limit, ETFE is excellent in heat resistance, weather resistance, chemical resistance, gas barrier properties, and fuel barrier properties. When the molar ratio (A) / (B) is not more than the upper limit value, ETFE excellent in mechanical strength and moldability is obtained.
単位（Ａ）と単位（Ｂ）の合計に対する単位（Ｃ）のモル比である（Ｃ）／（（Ａ）＋（Ｂ））は、０．１／１００〜５／１００であり、０．５／１００〜５／１００が好ましく、０．５／１００〜３．５／１００がより好ましく、０．７／１００〜３．５／１００が特に好ましい。
モル比（Ｃ）／（（Ａ）＋（Ｂ））が下限値以上であれば、被塗装物に粉体塗装した際に塗膜にクラック等が生じにくく、優れた耐久性が得られる。モル比（Ｃ）／（（Ａ）＋（Ｂ））が上限値以下であれば、結晶性が高くなるため、ＥＴＦＥの融点が充分に高くなり、充分な硬度が得られる。
本発明のＥＴＦＥが単位（Ｅ）を有する場合、すべての単量体に基づく構成単位（１００モル％）に対する単位（Ｅ）の割合は、０．０１〜２０モル％が好ましく、０．０５〜１５モル％がより好ましく、０．１〜１０モル％がさらに好ましく、０．１〜７モル％が特に好ましい。
(C) / ((A) + (B)), which is the molar ratio of the unit (C) to the sum of the unit (A) and the unit (B), is 0.1 / 100 to 5/100. 5/100 to 5/100 is preferable, 0.5 / 100 to 3.5 / 100 is more preferable, and 0.7 / 100 to 3.5 / 100 is particularly preferable.
When the molar ratio (C) / ((A) + (B)) is equal to or greater than the lower limit, cracks or the like hardly occur in the coating film when powder coating is performed on an object to be coated, and excellent durability is obtained. If the molar ratio (C) / ((A) + (B)) is less than or equal to the upper limit value, the crystallinity becomes high, so that the melting point of ETFE becomes sufficiently high and sufficient hardness can be obtained.
When the ETFE of the present invention has the unit (E), the ratio of the unit (E) to the structural unit (100 mol%) based on all monomers is preferably 0.01 to 20 mol%, and 0.05 to 15 mol% is more preferable, 0.1-10 mol% is further more preferable, and 0.1-7 mol% is especially preferable.
本発明において、ＥＴＦＥ中の末端基（Ｄ）の含有量は、１〜１００モル／１０６ｇが好ましく、２〜５０モル／１０６ｇがより好ましく、３〜２０モル／１０６ｇが特に好ましい。前記末端基（Ｄ）の含有量がこの範囲にあると、ＥＴＦＥは被塗装物への接着性に優れる。また、前記末端基（Ｄ）の含有量が下限値以上であれば、ＥＴＦＥの分子量が適切で、ＥＴＦＥの成形が容易であり、またＥＴＦＥ粉体によって充分な平滑性を有する塗膜を形成しやすい。前記末端基（Ｄ）の含有量が上限値以下であれば、ＥＴＦＥの分子量が充分に大きく、ＥＴＦＥは機械的強度に優れる。 In the present invention, the content of the terminal group (D) in ETFE is preferably 1 to 100 mol / 10 6 g, more preferably 2 to 50 mol / 10 6 g, particularly 3 to 20 mol / 10 6 g. preferable. When the content of the terminal group (D) is within this range, ETFE is excellent in adhesion to the object to be coated. Further, if the content of the terminal group (D) is not less than the lower limit, the molecular weight of ETFE is appropriate, ETFE molding is easy, and a coating film having sufficient smoothness is formed by the ETFE powder. Cheap. If the content of the terminal group (D) is not more than the upper limit, the molecular weight of ETFE is sufficiently large, and ETFE is excellent in mechanical strength.
本発明のＥＴＦＥの容量流速（以下、「Ｑ値」と記す。）は、１〜１０００ｍｍ３／秒が好ましく、３〜５００ｍｍ３／秒がより好ましく、５〜３００ｍｍ３／秒が特に好ましい。Ｑ値が下限値以上であれば、ＥＴＦＥを用いた成形が容易になり、またＥＴＦＥ粉体によって充分な平滑性を有する塗膜を形成しやすい。Ｑ値が上限値以下であれば、機械的強度に優れたＥＴＦＥとなる。
なお、前記Ｑ値は、ＥＴＦＥの溶融流動性を表す指標であり、分子量の目安となる。Ｑ値が大きいほど分子量が低く、小さいほど分子量が高いことを示す。本発明におけるＥＴＦＥのＱ値は、島津製作所製フローテスタを用いて、温度２９７℃、荷重７ｋｇの条件で、直径２．１ｍｍ、長さ８ｍｍのオリフィス中にＥＴＦＥを押し出すときの押出し速度である。
The volume flow rate of the ETFE of the present invention (hereinafter, referred to as "Q-value".) Is preferably from 1 to 1000 mm 3 / sec, more preferably 3~500mm 3 / sec, 5~300mm 3 / sec are particularly preferred. When the Q value is equal to or higher than the lower limit, molding using ETFE is facilitated, and a coating film having sufficient smoothness is easily formed by the ETFE powder. If Q value is below an upper limit, it will become ETFE excellent in mechanical strength.
The Q value is an index representing the melt fluidity of ETFE and is a measure of molecular weight. A larger Q value indicates a lower molecular weight, and a smaller Q value indicates a higher molecular weight. The Q value of ETFE in the present invention is an extrusion speed when extruding ETFE into an orifice having a diameter of 2.1 mm and a length of 8 mm under the conditions of a temperature of 297 ° C. and a load of 7 kg using a flow tester manufactured by Shimadzu Corporation.
＜ＥＴＦＥの製造方法＞
本発明のＥＴＦＥの製造方法は、特定の重合媒体と連鎖移動剤（ｄ）と重合開始剤の存在下に、単量体（ａ）、単量体（ｂ）および単量体（ｃ）を必須成分として含み、必要に応じて単量体（ｅ）を含む単量体混合物を共重合する方法である。重合に連鎖移動剤（ｄ）を用いることで、得られるＥＴＦＥに末端基（Ｄ）が導入される。
重合方法としては、ラジカル重合開始剤を用いる重合方法が好ましい。重合形態としては、塊状重合、溶液重合が挙げられ、溶液重合が好ましい。溶液重合の場合、ＥＴＦＥが重合媒体に分散したスラリーが得られる。
<Method of manufacturing ETFE>
In the method for producing ETFE of the present invention, the monomer (a), the monomer (b) and the monomer (c) are prepared in the presence of a specific polymerization medium, a chain transfer agent (d) and a polymerization initiator. This is a method of copolymerizing a monomer mixture containing an essential component and, if necessary, a monomer (e). By using a chain transfer agent (d) for polymerization, a terminal group (D) is introduced into the obtained ETFE.
As the polymerization method, a polymerization method using a radical polymerization initiator is preferred. Examples of the polymerization form include bulk polymerization and solution polymerization, and solution polymerization is preferred. In the case of solution polymerization, a slurry in which ETFE is dispersed in a polymerization medium is obtained.
ラジカル重合開始剤としては、半減期が１０時間である分解温度が０℃〜１００℃のラジカル重合開始剤が好ましく、２０〜９０℃のラジカル重合開始剤がより好ましい。
具体的には、たとえば、アゾ化合物（アゾビスイソブチロニトリル等。）、非フッ素系ジアシルペルオキシド（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。）、ペルオキシジカーボネート（ジイソプロピルペルオキシジカ−ボネート等。）、ペルオキシエステル（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。）、含フッ素ジアシルペルオキシド（（Ｚ（ＣＦ２）ｐＣＯＯ）２（ただし、Ｚは水素原子、フッ素原子または塩素原子であり、ｐは１〜１０の整数である。）で表される化合物等。）、無機過酸化物（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。）等が挙げられる。
The radical polymerization initiator is preferably a radical polymerization initiator having a half-life of 10 hours and a decomposition temperature of 0 ° C. to 100 ° C., more preferably a 20 to 90 ° C. radical polymerization initiator.
Specifically, for example, azo compounds (azobisisobutyronitrile, etc.), non-fluorinated diacyl peroxides (isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, etc.), peroxydicarbonates (diisopropyl peroxy, etc.) Dicarbonate and the like), peroxy ester (tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxyacetate, etc.), fluorine-containing diacyl peroxide ((Z (CF 2 ) p COO) 2 ( However, Z is a hydrogen atom, a fluorine atom, or a chlorine atom, p is an integer of 1-10.), Inorganic peroxides (potassium persulfate, sodium persulfate, ammonium persulfate) Etc.) etc. It is below.
重合媒体は、ペルフルオロカーボン類（以下、「ＰＦＣ」と記す。）、ヒドロフルオカーボン類（以下、「ＨＦＣ」と記す。）およびヒドロフルオロアルキルエーテル類（以下、「ＨＦＥ」と記す。）からなる群から選ばれる少なくとも１種である。これらの重合媒体は、塩素原子を有しておらず、環境保全の側面で優れている。溶液重合の場合の重合媒体は、連鎖移動係数の小さな化合物が好ましい。 The polymerization medium is composed of perfluorocarbons (hereinafter referred to as “PFC”), hydrofluorocarbons (hereinafter referred to as “HFC”), and hydrofluoroalkyl ethers (hereinafter referred to as “HFE”). It is at least one selected from the group. These polymerization media have no chlorine atom and are excellent in terms of environmental conservation. The polymerization medium in the case of solution polymerization is preferably a compound having a small chain transfer coefficient.
ＰＦＣとしては、ｎ−ペルフルオロヘキサン、ｎ−ペルフルオロヘプタン、ペルフルオロシクロブタン、ペルフルオロシクロヘキサン、ペルフルオロベンゼン等が挙げられる。
ＨＦＣとしては、ＣＦ３ＣＦＨＣＦ２ＣＦ２ＣＦ３、ＣＦ３（ＣＦ２）４Ｈ、ＣＦ３ＣＦ２ＣＦＨＣＦ２ＣＦ３、ＣＦ３ＣＦＨＣＦＨＣＦ２ＣＦ３、ＣＦ２ＨＣＦＨＣＦ２ＣＦ２ＣＦ３、ＣＦ３（ＣＦ２）５Ｈ、ＣＦ３ＣＨ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ３、ＣＦ３ＣＦ（ＣＦ３）ＣＦＨＣＦ２ＣＦ３、ＣＦ３ＣＦ（ＣＦ３）ＣＦＨＣＦＨＣＦ３、ＣＦ３ＣＨ（ＣＦ３）ＣＦＨＣＦ２ＣＦ３、ＣＦ３ＣＦ２ＣＨ２ＣＨ３、ＣＦ３（ＣＦ２）３ＣＨ２ＣＨ３等が挙げられる。
ＨＦＥとしては、ＣＦ３ＣＨ２ＯＣＦ２ＣＦ２Ｈ、ＣＦ３（ＣＦ３）２ＣＦＣＦ２ＯＣＨ３、ＣＦ３（ＣＦ２）３ＯＣＨ３等が挙げられる。
Examples of PFC include n-perfluorohexane, n-perfluoroheptane, perfluorocyclobutane, perfluorocyclohexane, perfluorobenzene and the like.
As HFC, CF 3 CFHCF 2 CF 2 CF 3 , CF 3 (CF 2 ) 4 H, CF 3 CF 2 CFHCF 2 CF 3 , CF 3 CFHCHFCF 2 CF 3 , CF 2 HCFHCF 2 CF 2 CF 3 , CF 3 ( CF 2 ) 5 H, CF 3 CH (CF 3 ) CF 2 CF 2 CF 3 , CF 3 CF (CF 3 ) CFHCF 2 CF 3 , CF 3 CF (CF 3 ) CFHCFHCCF 3 , CF 3 CH (CF 3 ) CFHCF 2 CF 3 , CF 3 CF 2 CH 2 CH 3 , CF 3 (CF 2 ) 3 CH 2 CH 3 and the like.
Examples of HFE include CF 3 CH 2 OCF 2 CF 2 H, CF 3 (CF 3 ) 2 CFCF 2 OCH 3 , and CF 3 (CF 2 ) 3 OCH 3 .
重合媒体としては、ＨＦＣ、ＨＦＥが好ましく、ＣＦ３（ＣＦ２）５Ｈ、ＣＦ３ＣＨ２ＯＣＦ２ＣＦ２Ｈ、ＣＦ３（ＣＦ２）３ＣＨ２ＣＨ３がより好ましく、ＣＦ３（ＣＦ２）５Ｈ、ＣＦ３ＣＨ２ＯＣＦ２ＣＦ２Ｈが特に好ましい。
重合媒体は、１種を単独で使用してもよく、２種以上を併用してもよい。
As a polymerization medium, HFC and HFE are preferable, CF 3 (CF 2 ) 5 H, CF 3 CH 2 OCF 2 CF 2 H, and CF 3 (CF 2 ) 3 CH 2 CH 3 are more preferable, and CF 3 (CF 2 ) 5 H, CF 3 CH 2 OCF 2 CF 2 H are particularly preferred.
A polymerization medium may be used individually by 1 type, and may use 2 or more types together.
重合媒体の沸点は、３０〜１５０℃が好ましく、３０〜１２０℃がより好ましい。重合媒体の沸点が上限値以下であれば、ＥＴＦＥと重合溶媒との分離が容易になる。重合媒体の沸点が下限値以上であれば、単量体（ａ）と単量体（ｂ）の単量体混合ガスと重合媒体との分離が容易になる
また、重合媒体は、室温で液体であることが好ましい。
The boiling point of the polymerization medium is preferably 30 to 150 ° C, more preferably 30 to 120 ° C. If the boiling point of the polymerization medium is not more than the upper limit, separation of ETFE and the polymerization solvent becomes easy. If the boiling point of the polymerization medium is equal to or higher than the lower limit, it is easy to separate the monomer mixed gas of the monomer (a) and the monomer (b) from the polymerization medium. The polymerization medium is liquid at room temperature. It is preferable that
単量体（ａ）と単量体（ｂ）のモル比（ａ）／（ｂ）は、２０／８０〜９９／１であり、２５／７５〜９８／２が好ましく、８４／１６〜８９／１１がより好ましい。
前記モル比（ａ）／（ｂ）が下限値以上であれば、耐熱性、耐候性、耐薬品性、ガスバリア性、燃料バリア性に優れたＥＴＦＥが得られる。前記モル比（ａ）／（ｂ）が上限値以下であれば、機械的強度および成形性に優れたＥＴＦＥが得られる。
The molar ratio (a) / (b) of the monomer (a) to the monomer (b) is 20/80 to 99/1, preferably 25/75 to 98/2, and 84/16 to 89. / 11 is more preferable.
When the molar ratio (a) / (b) is at least the lower limit value, ETFE excellent in heat resistance, weather resistance, chemical resistance, gas barrier properties and fuel barrier properties can be obtained. When the molar ratio (a) / (b) is not more than the upper limit value, ETFE excellent in mechanical strength and moldability can be obtained.
単量体（ａ）と単量体（ｂ）の合計に対する単量体（ｃ）のモル比（ｃ）／（（ａ）＋（ｂ））は、０．１／１００〜５／１００であり、０．５／１００〜５／１００が好ましく、０．５／１００〜３．５／１００がより好ましく、０．７／１００〜３．５／１００が特に好ましい。
前記モル比（ｃ）／（（ａ）＋（ｂ））が下限値以上であれば、被塗装物に粉体塗装した際に塗膜にクラック等が生じにくく、優れた耐久性を示すＥＴＦＥが得られる。前記モル比（ｃ）／（（ａ）＋（ｂ））が上限値以下であれば、結晶性が高く、融点が充分に高い、充分な硬度を有するＥＴＦＥが得られる。
The molar ratio (c) / ((a) + (b)) of the monomer (c) to the sum of the monomer (a) and the monomer (b) is 0.1 / 100 to 5/100. Yes, 0.5 / 100 to 5/100 is preferable, 0.5 / 100 to 3.5 / 100 is more preferable, and 0.7 / 100 to 3.5 / 100 is particularly preferable.
If the molar ratio (c) / ((a) + (b)) is equal to or greater than the lower limit, ETFE that exhibits excellent durability is resistant to cracks and the like when the powder is coated on an object to be coated. Is obtained. If the molar ratio (c) / ((a) + (b)) is not more than the upper limit value, ETFE having high hardness and sufficiently high melting point can be obtained.
連鎖移動剤（ｄ）の使用量は、すべての単量体の合計（１００質量％）に対して、０．５０〜５．５質量％が好ましく、０．５４〜３質量％がより好ましく、０．５５〜１質量％が特に好ましい。前記連鎖移動剤（ｄ）の使用量が下限値以上であれば、成形が容易で、また粉体塗装において充分な平滑性を有する塗膜を形成できるＥＴＦＥが得られる。前記連鎖移動剤（ｄ）の使用量が上限値以下であれば、機械的強度に優れたＥＴＦＥが得られる。
なお、本発明の製造方法で使用する連鎖移動剤は、連鎖移動剤（ｄ）が主成分であれば、Ｒ−２２５ｃｂ等の他の連鎖移動剤が混入してもよい。使用する全ての連鎖移動剤中の連鎖移動剤（ｄ）の割合は、８０モル％以上が好ましく、９０モル％以上がより好ましく、９５モル％以上が特に好ましい。
The amount of chain transfer agent (d) used is preferably 0.50 to 5.5% by weight, more preferably 0.54 to 3% by weight, based on the total (100% by weight) of all monomers. 0.55-1 mass% is especially preferable. If the amount of the chain transfer agent (d) used is not less than the lower limit, ETFE can be obtained which is easy to mold and can form a coating film having sufficient smoothness in powder coating. If the usage-amount of the said chain transfer agent (d) is below an upper limit, ETFE excellent in mechanical strength will be obtained.
In addition, if the chain transfer agent (d) is a main component, the chain transfer agent used with the manufacturing method of this invention may mix other chain transfer agents, such as R-225cb. The proportion of the chain transfer agent (d) in all the chain transfer agents used is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.
単量体（ｅ）を有する場合、すべての単量体の合計（１００モル％）に対する単量体（ｅ）の割合は、０．０１〜２０モル％が好ましく、０．０５〜１５モル％がより好ましく、０．１〜１０モル％がさらに好ましく、０．１〜７モル％が特に好ましい。 When the monomer (e) is included, the ratio of the monomer (e) to the total (100 mol%) of all the monomers is preferably 0.01 to 20 mol%, and 0.05 to 15 mol%. Is more preferable, 0.1 to 10 mol% is more preferable, and 0.1 to 7 mol% is particularly preferable.
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、０．１〜１０ＭＰａＧ（ゲージ圧）が好ましく、０．５〜３ＭＰａＧ（ゲージ圧）がより好ましい。
重合時間は、１〜３０時間が好ましい。
The polymerization temperature is preferably 0 ° C to 100 ° C, more preferably 20 to 90 ° C.
The polymerization pressure is preferably from 0.1 to 10 MPaG (gauge pressure), more preferably from 0.5 to 3 MPaG (gauge pressure).
The polymerization time is preferably 1 to 30 hours.
本発明のＥＴＦＥの製造方法によれば、特定の重合媒体を用いて、連鎖移動剤（ｄ）の存在下で重合を行うことで、材質が金属である被塗装物の粉体塗装に用いる場合でも、優れた接着性を発現できるＥＴＦＥが得られる。 According to the method for producing ETFE of the present invention, by using a specific polymerization medium and performing polymerization in the presence of a chain transfer agent (d), the material is used for powder coating of an object to be coated. However, ETFE capable of exhibiting excellent adhesiveness can be obtained.
＜ＥＴＦＥ粉体、粉体組成物＞
本発明のＥＴＦＥ粉体は、前述した本発明のＥＴＦＥの粉体であり、平均粒径が０．０１〜１０００μｍのものである。前記平均粒径が下限値未満であると、粉体としての取り扱いが困難となる。前記平均粒径が上限値を超えると、塗膜成形後の表面平滑性に劣る。
ＥＴＦＥ粉体の平均粒径は、静電塗装に使用する場合、０．５〜３００μｍが好ましく、１〜２００μｍがより好ましい。また、ＥＴＦＥ粉体の平均粒径は、回転成形に使用する場合、１〜５００μｍが好ましく、５〜３００μｍがより好ましい。
ＥＴＦＥ粉体の平均粒径は、レーザー回折式粒度分布測定装置により測定される。
前記平均粒径は、たとえば、篩等を用いて分級することで調整できる。
<ETFE powder, powder composition>
The ETFE powder of the present invention is the ETFE powder of the present invention described above, and has an average particle size of 0.01 to 1000 μm. When the average particle size is less than the lower limit, handling as a powder becomes difficult. When the average particle size exceeds the upper limit value, the surface smoothness after forming the coating film is inferior.
When used for electrostatic coating, the average particle size of the ETFE powder is preferably 0.5 to 300 μm, more preferably 1 to 200 μm. Further, the average particle diameter of the ETFE powder is preferably 1 to 500 μm, more preferably 5 to 300 μm, when used for rotational molding.
The average particle diameter of the ETFE powder is measured by a laser diffraction particle size distribution measuring device.
The said average particle diameter can be adjusted by classifying using a sieve etc., for example.
本発明のＥＴＦＥ粉体の製造方法としては、たとえば、重合で得られたＥＴＦＥを必要に応じて造粒し、乾燥した後に、ハンマーミル、ターボミル、ジェットミル等の粉砕機で粉砕する方法等が挙げられる。また、溶液重合によりＥＴＦＥを得た場合は、得られたスラリーを直接噴霧して媒体を蒸発除去させる方法を用いてもよい。 Examples of the method for producing the ETFE powder of the present invention include a method in which ETFE obtained by polymerization is granulated as necessary, dried, and then pulverized by a pulverizer such as a hammer mill, a turbo mill, a jet mill, or the like. Can be mentioned. Further, when ETFE is obtained by solution polymerization, a method of directly spraying the obtained slurry and evaporating and removing the medium may be used.
本発明の粉体組成物は、本発明のＥＴＦＥ粉体と熱安定剤とを含有する組成物である。本発明の粉体組成物が熱安定剤を含有することで、熱安定性に優れるうえ、被塗装物との接着性に特に優れた塗膜を形成できる。 The powder composition of the present invention is a composition containing the ETFE powder of the present invention and a heat stabilizer. When the powder composition of the present invention contains a heat stabilizer, it is possible to form a coating film having excellent heat stability and particularly excellent adhesion to an object to be coated.
熱安定剤としては、銅化合物、錫化合物、鉄化合物、鉛化合物、チタン化合物およびアルミニウム化合物からなる群から選ばれる少なくとも１種が好ましい。
熱安定剤の具体例としては、酸化銅、ヨウ化銅、アルミナ、硫酸錫、硫酸ゲルマニウム、塩基性硫酸鉛、亜硫酸錫、燐酸バリウム、ピロリン酸錫等が挙げられる。なかでも、酸化銅、ヨウ化銅、アルミナ、硫酸錫、塩基性硫酸鉛、亜硫酸錫、ピロリン酸錫が好ましく、酸化銅、ヨウ化銅が特に好ましい。
本発明の粉体組成物は、ＥＴＦＥ粉体および熱安定剤に加えて、用途、目的に応じて、各種の添加剤、フィラー、他の合成樹脂粉体等の他の配合剤を含有してもよい。
The heat stabilizer is preferably at least one selected from the group consisting of copper compounds, tin compounds, iron compounds, lead compounds, titanium compounds and aluminum compounds.
Specific examples of the heat stabilizer include copper oxide, copper iodide, alumina, tin sulfate, germanium sulfate, basic lead sulfate, tin sulfite, barium phosphate, tin pyrophosphate and the like. Among these, copper oxide, copper iodide, alumina, tin sulfate, basic lead sulfate, tin sulfite, and tin pyrophosphate are preferable, and copper oxide and copper iodide are particularly preferable.
In addition to the ETFE powder and the heat stabilizer, the powder composition of the present invention contains other additives such as various additives, fillers, and other synthetic resin powders depending on applications and purposes. Also good.
粉体組成物におけるＥＴＦＥ粉体の含有量は、２０質量％以上が好ましく、５０質量％以上がより好ましく、７５質量％以上が特に好ましい。
粉体組成物における熱安定剤の含有量は、１×１０−８〜５質量％が好ましく、１×１０−７〜２質量％がより好ましく、５×１０−７〜１質量％が特に好ましい。
粉体組成物が他の配合剤を含有する場合、粉体組成物中の熱安定剤および他の配合剤を合計した含有量は、８０質量％以下が好ましく、５０質量％以下がより好ましく、２０質量％以下が特に好ましい。
The content of the ETFE powder in the powder composition is preferably 20% by mass or more, more preferably 50% by mass or more, and particularly preferably 75% by mass or more.
The content of the heat stabilizer in the powder composition is preferably 1 × 10 −8 to 5% by mass, more preferably 1 × 10 −7 to 2% by mass, and particularly preferably 5 × 10 −7 to 1% by mass. .
When the powder composition contains other compounding agents, the total content of the heat stabilizer and other compounding agents in the powder composition is preferably 80% by mass or less, more preferably 50% by mass or less, 20 mass% or less is especially preferable.
熱安定剤および他の配合剤の配合方法としては、ミキサーを用いてＥＴＦＥ粉体と混合する方法、または、熱安定剤および他の配合剤をＥＴＦＥ粉体とミキサーで混合してマスターバッチ粉体を製造し、該マスターバッチ粉体とＥＴＦＥ粉体とを混合する方法が好ましい。 As a blending method of the heat stabilizer and other compounding agents, a method of mixing with ETFE powder using a mixer, or a master batch powder by mixing heat stabilizer and other compounding agents with ETFE powder and mixer. Is preferable, and the master batch powder and the ETFE powder are mixed.
本発明のＥＴＦＥ粉体および粉体組成物は、材質が金属である被塗装物の粉体塗装に用いる場合でも、被塗装物への接着性に優れ、塗装作業性にも優れる。また、本発明の粉体組成物は、熱安定性に優れる。そのため、本発明のＥＴＦＥ粉体および粉体組成物は、粉体塗装用として好適に使用できる。また、ＥＴＦＥ、ＴＦＥ／ペルフルオロ（プロピルビニルエーテル）共重合体、ＴＦＥ／ヘキサフルオロプロピレン共重合体、（ポリテトラフルオロエチレン）ＰＴＦＥ等のフッ素樹脂の粉体を粉体塗装する場合のプライマーとしても有用である。本発明のＥＴＦＥ粉体および粉体組成物をプライマーとして用いれば、フッ素樹脂と被塗装物との接着性が優れたものとなる。
また、本発明のＥＴＦＥ粉体および粉体組成物は、公知のＥＴＦＥ粉体と同様の塗装装置を用いてプライマー塗装および粉体塗装が可能なことから、物品の生産性および経済性に優れる。
また、本発明のＥＴＦＥ粉体および粉体組成物は、回転成形等に使用してもよい。
Even when the ETFE powder and the powder composition of the present invention are used for powder coating of an object to be coated whose material is metal, the ETFE powder and the powder composition are excellent in adhesion to the object to be coated and excellent in workability. The powder composition of the present invention is excellent in thermal stability. Therefore, the ETFE powder and powder composition of the present invention can be suitably used for powder coating. It is also useful as a primer for powder coating of fluororesin powders such as ETFE, TFE / perfluoro (propyl vinyl ether) copolymer, TFE / hexafluoropropylene copolymer, (polytetrafluoroethylene) PTFE. is there. When the ETFE powder and the powder composition of the present invention are used as a primer, the adhesiveness between the fluororesin and the object to be coated is excellent.
Moreover, since the ETFE powder and powder composition of the present invention can be applied with primer and powder using a coating apparatus similar to known ETFE powders, they are excellent in product productivity and economy.
Moreover, you may use the ETFE powder and powder composition of this invention for rotational molding etc.
＜物品＞
本発明の物品は、本発明のＥＴＦＥ粉体または粉体組成物が被塗装物に粉体塗装されたものである。本発明の物品には、本発明のＥＴＦＥ粉体または粉体組成物がプライマー塗装される場合等、本発明のＥＴＦＥ粉体または粉体組成物の塗膜上に他の塗膜が設けられた物品も含まれる。
<Article>
The article of the present invention is an article in which the ETFE powder or powder composition of the present invention is powder-coated on an object to be coated. The article of the present invention was provided with another coating film on the coating film of the ETFE powder or powder composition of the present invention, such as when the ETFE powder or powder composition of the present invention was primer-coated. Articles are also included.
被塗装物の材質としては、鉄、ステンレス鋼、アルミニウム、銅、錫、チタン、クロム、ニッケル、亜鉛等の金属、ガラス、セラミックス等の無機物等が挙げられる。なかでも、本発明は、被塗装物の材質が金属の場合により有効であり、被塗装物の材質が鉄、ステンレス鋼、アルミニウムの場合に特に有効である。
本発明における被塗装物の形状としては、パイプ、チューブ、フィルム、板、タンク、ロール、ベッセル、バルブ、エルボー等が挙げられる。
Examples of the material to be coated include metals such as iron, stainless steel, aluminum, copper, tin, titanium, chromium, nickel, and zinc, and inorganic materials such as glass and ceramics. In particular, the present invention is more effective when the material of the object to be coated is metal, and is particularly effective when the material of the object to be coated is iron, stainless steel, or aluminum.
Examples of the shape of the object to be coated in the present invention include pipes, tubes, films, plates, tanks, rolls, vessels, valves, elbows and the like.
物品におけるＥＴＦＥ粉体または粉体組成物を用いて形成された塗膜の厚さは、１μｍ〜１０ｍｍが好ましく、５μｍ〜５ｍｍがより好ましく、１０μｍ〜３ｍｍが特に好ましい。前記塗膜の厚さが下限値以上であれば、被塗装物と塗膜の接着性に優れる。前記塗膜の厚さが上限値以下であれば、被塗装物との充分な接着性が発現される。
本発明のＥＴＦＥ粉体または粉体組成物をプライマー塗装に用いる場合、塗膜の厚さは、１〜５００μｍが好ましく、５〜５００μｍがより好ましく、１０〜５００μｍが特に好ましい。
The thickness of the coating film formed using the ETFE powder or the powder composition in the article is preferably 1 μm to 10 mm, more preferably 5 μm to 5 mm, and particularly preferably 10 μm to 3 mm. If the thickness of the said coating film is more than a lower limit, it will be excellent in the adhesiveness of a to-be-coated object and a coating film. If the thickness of the said coating film is below an upper limit, sufficient adhesiveness with a to-be-coated object will be expressed.
When the ETFE powder or powder composition of the present invention is used for primer coating, the thickness of the coating film is preferably 1 to 500 μm, more preferably 5 to 500 μm, and particularly preferably 10 to 500 μm.
ＥＴＦＥ粉体または粉体組成物の粉体塗装は、公知の方法で行える。たとえば、酸素を含む雰囲気下に２００〜６００℃で被塗装物表面を加熱処理し、ついで、該被塗装物表面をブラスト処理等により粗面化し、該ブラスト処理した被塗装物表面にＥＴＦＥ粉体または粉体組成物を粉体塗装することによって塗膜を形成する方法が挙げられる。
粉体塗装としては、静電塗装等が挙げられる。プライマー塗装は、前記粉体塗装と同様に行える。
Powder coating of ETFE powder or powder composition can be performed by a known method. For example, the surface of the object to be coated is heated at 200 to 600 ° C. in an atmosphere containing oxygen, and then the surface of the object to be coated is roughened by blasting or the like, and the ETFE powder is applied to the surface of the object to be blasted. Or the method of forming a coating film by powder-coating a powder composition is mentioned.
Examples of the powder coating include electrostatic coating. Primer coating can be performed in the same manner as the powder coating.
本発明のＥＴＦＥ粉体または粉体組成物を粉体塗装した物品は、被塗装物の材質が金属である場合でも、被塗装物と塗膜の接着性に優れる。また、本発明の粉体組成物を粉体塗装した物品は、本発明のＥＴＦＥ粉体を粉体塗装した物品に比べて、塗膜と被塗装物との接着性がさらに優れる。この理由は必ずしも明確ではないが、以下のように推定される。
熱安定剤によってＥＴＦＥの熱安定性がより良好になることで、塗装工程における塗膜の劣化および収縮が防止されるため、被塗装物と塗膜の接着性が高まると考えられる。また、高温でのＥＴＦＥの安定性が向上することから、高温で被塗装物上に塗膜を形成でき、このことでさらに接着性が向上すると考えられる。
An article coated with the ETFE powder or powder composition of the present invention is excellent in adhesion between the object to be coated and the coating film even when the material of the object to be coated is a metal. Further, an article coated with the powder composition of the present invention is more excellent in adhesion between the coating film and the article to be coated than an article coated with the ETFE powder of the present invention. Although this reason is not necessarily clear, it is estimated as follows.
Since the thermal stability of ETFE is improved by the heat stabilizer, the deterioration and shrinkage of the coating film in the coating process are prevented, so that it is considered that the adhesion between the object to be coated and the coating film is increased. In addition, since the stability of ETFE at high temperature is improved, a coating film can be formed on an object to be coated at high temperature, and this is considered to further improve the adhesiveness.
以上説明した本発明の物品は、ＥＴＦＥ粉体または粉体組成物により形成した塗膜と被塗装物の接着性に優れる。また、本発明の物品は、耐薬品性、耐蝕性、耐油性、耐熱性、耐候性、非粘着性、撥水性等の特性に優れ、これらの特性の耐久性にも優れる。 The article of the present invention described above is excellent in adhesion between a coating film formed from ETFE powder or a powder composition and an object to be coated. In addition, the article of the present invention is excellent in properties such as chemical resistance, corrosion resistance, oil resistance, heat resistance, weather resistance, non-adhesiveness, water repellency and the like, and is excellent in durability of these properties.
以下、実施例によって本発明を詳細に説明するが、本発明は以下の記載によっては限定されない。例１〜５は実施例であり、例６〜７は比較例である。
接着性評価、ならびにＥＴＦＥの融点、Ｑ値および共重合組成（モル％）等の測定方法は、以下に示すとおりである。
［接着性評価］
各例で得られた物品の長手方向の端部において、ステンレス鋼板と、形成された塗膜との間にカッターナイフで切り込みを入れ、端から１０ｍｍの部分を剥離した。剥離した部分の塗膜を引張り試験機のチャックに固定し、部分的に剥離した側の端から５０ｍｍの位置まで、塗膜をステンレス鋼板から９０度剥離した。剥離試験は、引張り速度を５０ｍｍ／分として５回行い、それぞれの剥離時の最大荷重の平均値を剥離強度（単位：Ｎ／１０ｍｍ）とした。剥離強度が大きいほど、接着性に優れる。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description. Examples 1 to 5 are examples, and examples 6 to 7 are comparative examples.
Adhesive evaluation and measuring methods such as melting point, Q value and copolymer composition (mol%) of ETFE are as follows.
[Adhesion evaluation]
At the end in the longitudinal direction of the article obtained in each example, a notch was cut between the stainless steel plate and the formed coating film with a cutter knife, and a 10 mm portion from the end was peeled off. The peeled portion of the coating film was fixed to a chuck of a tensile tester, and the coating film was peeled from the stainless steel plate by 90 degrees from the end of the partially peeled side to a position of 50 mm. The peel test was performed five times at a tensile speed of 50 mm / min, and the average value of the maximum load at each peel was defined as the peel strength (unit: N / 10 mm). The greater the peel strength, the better the adhesion.
［融点（℃）］
ＥＴＦＥの融点は、走査型示差熱分析器（セイコーインスツルメンツ社製、ＤＳＣ２２０ＣＵ）を用いて、空気雰囲気下、１０℃／分で３００℃まで加熱した際の吸熱ピークから求めた。
[Melting point (° C)]
The melting point of ETFE was obtained from an endothermic peak when heated to 300 ° C. at 10 ° C./min in an air atmosphere using a scanning differential thermal analyzer (DSC220CU, manufactured by Seiko Instruments Inc.).
［Ｑ値］
島津製作所社製のフローテスタを用いて、温度２９７℃、荷重７ｋｇの条件で、直径２．１ｍｍ、長さ８ｍｍのオリフィス中に押し出すときのＥＴＦＥの押出し速度（ｍｍ３／秒）をＱ値とした。
[Q value]
Using a flow tester manufactured by Shimadzu Corporation, the extrusion rate of ETFE (mm 3 / sec) when extruding into an orifice with a diameter of 2.1 mm and a length of 8 mm under the conditions of a temperature of 297 ° C. and a load of 7 kg is Q value did.
［共重合組成（モル％）］
ＥＴＦＥの共重合組成は、全フッ素量測定および溶融１９Ｆ−ＮＭＲ測定の結果から算出した。
[Copolymerization composition (mol%)]
The copolymerization composition of ETFE was calculated from the results of total fluorine measurement and melt 19 F-NMR measurement.
［高分子鎖末端基の分析］
ＴＯＦＭＳを用いて、高分子鎖末端基を分析した。
[Analysis of polymer chain end groups]
The polymer chain end groups were analyzed using TOFMS.
［平均粒径］
ＥＴＦＥ粉体の平均粒径は、レーザー回折式粒度分布測定装置により測定した。
[Average particle size]
The average particle size of the ETFE powder was measured with a laser diffraction particle size distribution measuring device.
［例１］
内容積が１．３リットルの撹拌機付き重合槽を脱気し、重合媒体であるＣＦ３（ＣＦ２）５Ｈ（以下、「ＨＦＣ−１」と記す。）の１３３６．５ｇ、連鎖移動剤（ｄ）であるＲ−２２５ｃａ（旭硝子社製ＡＫ２２５ｃａ）の２２．４ｇ、および単量体（ｃ）であるＣＨ２＝ＣＨ（ＣＦ２）４Ｆの７．５９ｇを仕込み、単量体（ａ）であるＴＦＥの１６５ｇと、単量体（ｂ）であるＥの９．８ｇを圧入し、重合槽内を６６℃に昇温した。重合槽内の圧力は１．５２ＭＰａＧ（ゲージ圧）を示した。重合開始剤であるｔｅｒｔ−ブチルペルオキシピバレートの濃度を１質量％としたＨＦＣ−１溶液の１０．６ｍＬを仕込み、重合を開始させた。重合中、前記圧力を保持するように組成ＴＦＥ／Ｅ＝５４／４６（モル比）の単量体混合ガスを連続的に仕込んだ。また、前記単量体混合ガスに対して１．４モル％となるように、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆを連続的に仕込んだ。重合開始から３時間後、単量体混合ガスの１００ｇを仕込んだ時点で、重合槽内の温度を３０℃まで降下させるとともに、０ＭＰａＧまでパージし、スラリー状のＥＴＦＥ−１を得た。スラリー状のＥＴＦＥ−１をガラスフィルターで吸引ろ過し、１５０℃で１５時間乾燥することにより、１０２ｇのＥＴＦＥ−１を得た。
ＥＴＦＥ−１の融点は２６０．４℃、Ｑ値は１３ｍｍ３／秒であった。また、共重合組成は、ＴＦＥに基づく構成単位／Ｅに基づく構成単位／ＣＨ２＝ＣＨ（ＣＦ２）４Ｆに基づく構成単位＝５２．９／４５．６／１．５（モル％）であった。ＥＴＦＥ−１の高分子鎖
末端基の構造は、−ＣＣｌ２−ＣＦ２−ＣＦ３であった。
該ＥＴＦＥ−１をターボミルにより粉砕し、平均粒径８０μｍのＥＴＦＥ粉体−１を得た。
[Example 1]
A polymerization tank equipped with a stirrer having an internal volume of 1.3 liters was degassed, and 1336.5 g of a polymerization medium CF 3 (CF 2 ) 5 H (hereinafter referred to as “HFC-1”), a chain transfer agent (D) 22.4 g of R-225ca (Asahi Glass Co., Ltd. AK225ca) and 7.59 g of monomer (c) CH 2 ═CH (CF 2 ) 4 F were charged, and monomer (a 165 g of TFE which is) and 9.8 g of E which is the monomer (b) were press-fitted, and the temperature in the polymerization tank was raised to 66 ° C. The pressure in the polymerization tank was 1.52 MPaG (gauge pressure). 10.6 mL of HFC-1 solution with a concentration of tert-butyl peroxypivalate as a polymerization initiator of 1% by mass was charged to initiate polymerization. During the polymerization, a monomer mixed gas having a composition TFE / E = 54/46 (molar ratio) was continuously charged so as to maintain the pressure. Further, CH 2 ═CH (CF 2 ) 4 F was continuously charged so as to be 1.4 mol% with respect to the monomer mixed gas. Three hours after the start of polymerization, when 100 g of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to 30 ° C. and purged to 0 MPaG to obtain slurry-like ETFE-1. Slurry ETFE-1 was suction filtered with a glass filter and dried at 150 ° C. for 15 hours to obtain 102 g of ETFE-1.
The melting point of ETFE-1 was 260.4 ° C., and the Q value was 13 mm 3 / sec. The copolymer composition is TFE-based structural unit / E-based structural unit / CH 2 ═CH (CF 2 ) 4 F-based structural unit = 52.9 / 45.6 / 1.5 (mol%). there were. The structure of the polymer chain end group of ETFE-1 was —CCl 2 —CF 2 —CF 3 .
The ETFE-1 was pulverized by a turbo mill to obtain ETFE powder-1 having an average particle size of 80 μm.
縦５０ｍｍ、横１００ｍｍ、厚さ２ｍｍのステンレス鋼板（ＳＵＳ３０４）の表面をブラスト処理した後、エアーガンでブラスト粉を除去し、該ステンレス鋼板をエタノールに３０分間浸漬した。その後、空気中で４００℃、１時間加熱処理して被塗装物−１を得た。
粉体スプレーガンを用いて、印加電圧−６０ｋＶで被塗装物−１の表面全体にＥＴＦＥ粉体−１を吹き付け、オーブンにて３００℃で１０分焼成した。この作業を複数回繰り返し、ＥＴＦＥ粉体−１の塗膜の厚さが０．９８ｍｍの物品−１を得た。
After blasting the surface of a stainless steel plate (SUS304) having a length of 50 mm, a width of 100 mm, and a thickness of 2 mm, the blast powder was removed with an air gun, and the stainless steel plate was immersed in ethanol for 30 minutes. Then, it heat-processed in air at 400 degreeC for 1 hour, and to-be-coated object-1 was obtained.
Using a powder spray gun, ETFE powder-1 was sprayed on the entire surface of the object 1 to be coated at an applied voltage of −60 kV, and baked in an oven at 300 ° C. for 10 minutes. This operation was repeated a plurality of times to obtain an article 1 having a coating thickness of ETFE powder-1 of 0.98 mm.
［例２］
縦５０ｍｍ、横１００ｍｍ、厚さ２ｍｍのステンレス鋼板（ＳＳ４００）の表面をブラスト処理した後、エアーガンでブラスト粉を除去し、該ステンレス鋼板をエタノールに３０分間浸漬した。その後、空気中で４００℃、１時間加熱処理して被塗装物−２を得た。
被塗装物−１の代わりに被塗装物−２を使用した以外は、例１と同様にして、ＥＴＦＥ粉体−１の塗膜の厚さが１．００ｍｍの物品−２を得た。
[Example 2]
After blasting the surface of a stainless steel plate (SS400) having a length of 50 mm, a width of 100 mm, and a thickness of 2 mm, the blast powder was removed with an air gun, and the stainless steel plate was immersed in ethanol for 30 minutes. Then, it heat-processed in air at 400 degreeC for 1 hour, and to-be-coated article-2 was obtained.
Article-2 having a coating film thickness of ETFE powder-1 of 1.00 mm was obtained in the same manner as in Example 1 except that the object-2 was used instead of the object-1.
［例３］
例１で得たＥＴＦＥ粉体−１の１００部に対して、平均粒径０．７６μｍ、比表面積１１．２ｍ２／ｇの酸化銅粉末の１．３部をブレンダーにより均一に混合して粉体組成物−１を得た。また、ＥＴＦＥ粉体−１の１００部に対して、粉体組成物−１の０．１部をブレンダーにより均一に混合して粉体組成物−２を得た。
ＥＴＦＥ粉体−１の代わりに粉体組成物−２を使用した以外は、例１と同様にして粉体組成物−２の塗膜を形成した。さらに該塗膜の表面に、ＥＴＦＥ粉体−２（旭硝子社製、フルオンＥＴＦＥ Ｚ−８８２０Ｘ）を使用した以外は、例１と同様にしてＥＴＦＥ粉体−２の塗膜を形成して物品−３を得た。
物品−３における粉体組成物−２の塗膜の厚さは０．２０ｍｍ、粉体組成物−２の塗膜とＥＴＦＥ粉体−２の塗膜を合計した厚さは１．１４ｍｍであった。
[Example 3]
To 100 parts of ETFE powder-1 obtained in Example 1, 1.3 parts of copper oxide powder having an average particle size of 0.76 μm and a specific surface area of 11.2 m 2 / g were uniformly mixed with a blender to obtain a powder. Body composition-1 was obtained. Further, 0.1 part of the powder composition-1 was uniformly mixed with 100 parts of the ETFE powder-1 by a blender to obtain a powder composition-2.
A coating film of the powder composition-2 was formed in the same manner as in Example 1 except that the powder composition-2 was used instead of the ETFE powder-1. Further, an ETFE powder-2 coating film was formed in the same manner as in Example 1 except that ETFE powder-2 (manufactured by Asahi Glass Co., Ltd., Fullon ETFE Z-8820X) was used on the surface of the coating film. 3 was obtained.
The thickness of the coating film of the powder composition-2 in the article-3 was 0.20 mm, and the total thickness of the coating film of the powder composition-2 and the coating film of the ETFE powder-2 was 1.14 mm. It was.
［例４］
被塗装物−１の代わりに被塗装物−２を使用し、ＥＴＦＥ粉体−１の代わりに粉体組成物−２を使用した以外は、例１と同様にして粉体組成物−２の塗膜を形成した。さらに該塗膜の表面に、ＥＴＦＥ粉体−２（旭硝子社製、フルオンＥＴＦＥ Ｚ−８８２０Ｘ）を使用した以外は、例１と同様にしてＥＴＦＥ粉体−２の塗膜を形成して物品−４を得た。
物品−４における粉体組成物−２の塗膜の厚さは０．２０ｍｍ、粉体組成物−２の塗膜とＥＴＦＥ粉体−２の塗膜を合計した厚さは１．１４ｍｍであった。
[Example 4]
The powder composition-2 was prepared in the same manner as in Example 1, except that the object-2 was used instead of the object-1 and the powder composition-2 was used instead of the ETFE powder-1. A coating film was formed. Further, an ETFE powder-2 coating film was formed in the same manner as in Example 1 except that ETFE powder-2 (manufactured by Asahi Glass Co., Ltd., Fullon ETFE Z-8820X) was used on the surface of the coating film. 4 was obtained.
The thickness of the coating film of the powder composition-2 in the article-4 was 0.20 mm, and the total thickness of the coating film of the powder composition-2 and the coating film of the ETFE powder-2 was 1.14 mm. It was.
［例５］
内容積が１．３リットルの撹拌機付き重合槽を脱気し、重合媒体であるＨＦＣ−１の１３３５．２ｇ、連鎖移動剤（ｄ）である旭硝子社製ＡＫ−２２５Ａ（Ｒ−２２５ｃａとＲ−２２５ｃｂの質量比が９５：５）の２３．６ｇ、および単量体（ｃ）であるＣＨ２＝ＣＨ（ＣＦ２）４Ｆの７．５９ｇを仕込み、単量体（ａ）であるＴＦＥの１６５ｇと、単量体（ｂ）であるＥの９．８ｇを圧入し、重合槽内を６６℃に昇温した。重合槽内の圧力は１．５１ＭＰａＧ（ゲージ圧）を示した。重合開始剤であるｔｅｒｔ−ブチルペルオキシピバレートの濃度を１質量％としたＨＦＣ−１溶液の１０．６ｍＬを仕込み、重合を開始させた。重合中、前記圧力を保持するように組成ＴＦＥ／Ｅ＝５４／４６（モル比）の単量体混合ガスを連続的に仕込んだ。また、前記単量体混合ガスに対して１．４モル％となるように、ＣＨ２＝ＣＨ（ＣＦ２）４Ｆを連続的に仕込んだ。重合開始から３時間後、単量体混合ガスの１００ｇを仕込んだ時点で、重合槽内の温度を３０℃まで降下させるとともに、０ＭＰａＧまでパージし、スラリー状のＥＴＦＥ−３を得た。スラリー状のＥＴＦＥ−３をガラスフィルターで吸引ろ過し、１５０℃で１５時間乾燥することにより、９９ｇのＥＴＦＥ−３を得た。
ＥＴＦＥ−３の融点は２６０．４℃、Ｑ値は１３ｍｍ３／秒であった。また、共重合組成は、ＴＦＥに基づく構成単位／Ｅに基づく構成単位／ＣＨ２＝ＣＨ（ＣＦ２）４Ｆに基づく構成単位＝５３．１／４５．５／１．４（モル％）であった。ＥＴＦＥ−３の高分子鎖末端基の構造は、−ＣＣｌ２−ＣＦ２−ＣＦ３であった。
該ＥＴＦＥ−３をターボミルにより粉砕し、平均粒径８０μｍのＥＴＦＥ粉体−３を得た。
ＥＴＦＥ粉体−１の代わりにＥＴＦＥ粉体−３を使用した以外は、例１と同様にして、ＥＴＦＥ粉体−３の塗膜の厚さが０．９５ｍｍの物品−５を得た。
[Example 5]
A polymerization tank equipped with a stirrer having an internal volume of 1.3 liters was degassed, 1335.2 g of HFC-1 as a polymerization medium, and AK-225A (R-225ca and R manufactured by Asahi Glass Co., Ltd.) as a chain transfer agent (d). 23.6 g of a mass ratio of -225cb of 95: 5) and 7.59 g of CH 2 ═CH (CF 2 ) 4 F which is the monomer (c) are charged, and TFE which is the monomer (a) And 9.8 g of E as the monomer (b) were injected, and the temperature in the polymerization tank was raised to 66 ° C. The pressure in the polymerization tank was 1.51 MPaG (gauge pressure). 10.6 mL of HFC-1 solution with a concentration of tert-butyl peroxypivalate as a polymerization initiator of 1% by mass was charged to initiate polymerization. During the polymerization, a monomer mixed gas having a composition TFE / E = 54/46 (molar ratio) was continuously charged so as to maintain the pressure. Further, CH 2 ═CH (CF 2 ) 4 F was continuously charged so as to be 1.4 mol% with respect to the monomer mixed gas. Three hours after the start of polymerization, when 100 g of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to 30 ° C. and purged to 0 MPaG to obtain slurry-like ETFE-3. Slurry ETFE-3 was suction filtered with a glass filter and dried at 150 ° C. for 15 hours to obtain 99 g of ETFE-3.
The melting point of ETFE-3 was 260.4 ° C., and the Q value was 13 mm 3 / sec. The copolymer composition is TFE-based structural unit / E-based structural unit / CH 2 ═CH (CF 2 ) 4 F-based structural unit = 53.1 / 45.5 / 1.4 (mol%). there were. The structure of the polymer chain end group of ETFE-3 was —CCl 2 —CF 2 —CF 3 .
The ETFE-3 was pulverized by a turbo mill to obtain ETFE powder-3 having an average particle size of 80 μm.
Except that ETFE powder-3 was used instead of ETFE powder-1, an article-5 having a coating thickness of ETFE powder-3 of 0.95 mm was obtained in the same manner as in Example 1.
［例６］
内容積が１．３リットルの撹拌機付き重合槽を脱気し、重合媒体であるＨＦＣ−１の９３４．２ｇ、連鎖移動剤であるＲ−２２５ｃｂ（旭硝子社製ＡＫ２２５ｃｂ）の２８７．０ｇ、および単量体（ｃ）であるＣＨ２＝ＣＨ（ＣＦ２）４Ｆの７．５９ｇを仕込み、単量体（ａ）であるＴＦＥの１６５ｇ、単量体（ｂ）であるＥの９．８ｇを圧入し、重合槽内を６６℃に昇温した。圧力は１．４９ＭＰａＧ（ゲージ圧）を示した。重合開始剤であるｔｅｒｔ−ブチルペルオキシピバレートの濃度を１質量％としたＨＦＣ−１溶液の７．７ｍＬを仕込み、重合を開始させた。重合中、前記圧力を保持するように組成ＴＦＥ／Ｅ＝５４／４６（モル比）の単量体混合ガスを連続的に仕込み、前記単量体混合ガスに対して１．４モル％となるようにＣＨ２＝ＣＨ（ＣＦ２）４Ｆを連続的に仕込んだ。重合開始から３時間後、単量体混合ガスの１００ｇを仕込んだ時点で、重合槽内の温度を３０℃まで降下させるとともに、０ＭＰａＧまでパージし、スラリー状のＥＴＦＥ−４を得た。
得られたスラリー状のＥＴＦＥ−４をガラスフィルターで吸引ろ過し、１５０℃で１５時間乾燥することにより、９７ｇのＥＴＦＥ−４を得た。
ＥＴＦＥ−４の融点は２５８．１℃、Ｑ値は１０．２ｍｍ３／秒であった。また、共重合組成は、ＴＦＥに基づく構成単位／Ｅに基づく構成単位／ＣＨ２＝ＣＨ（ＣＦ２）４Ｆに基づく構成単位＝５３．０／４５．６／１．４（モル％）であった。ＥＴＦＥ−４の高分子鎖末端基の構造は、−ＣＦＣｌ−ＣＦ２−ＣＦ２Ｃｌであった。該ＥＴＦＥ−４をターボミルにより粉砕し、平均粒径３０μｍのＥＴＦＥ粉体−４を得た。
ＥＴＦＥ粉体−１の代わりにＥＴＦＥ粉体−４を使用した以外は、例１と同様にして、ＥＴＦＥ粉体−４の塗膜の厚さが０．８９ｍｍの物品−６を得た。
[Example 6]
Degas the polymerization tank with a stirrer having an internal volume of 1.3 liters, 934.2 g of HFC-1 as a polymerization medium, 287.0 g of R-225cb (AK225cb manufactured by Asahi Glass Co., Ltd.) as a chain transfer agent, and 7.59 g of monomer (c) CH 2 ═CH (CF 2 ) 4 F was charged, 165 g of TFE as monomer (a), and 9.8 g of E as monomer (b). The inside of the polymerization tank was heated to 66 ° C. The pressure was 1.49 MPaG (gauge pressure). 7.7 mL of an HFC-1 solution with a concentration of tert-butyl peroxypivalate, which is a polymerization initiator, having a concentration of 1% by mass was charged to initiate polymerization. During the polymerization, a monomer mixed gas having the composition TFE / E = 54/46 (molar ratio) is continuously charged so as to maintain the pressure, and becomes 1.4 mol% with respect to the monomer mixed gas. Thus, CH 2 ═CH (CF 2 ) 4 F was continuously charged. Three hours after the start of polymerization, when 100 g of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to 30 ° C. and purged to 0 MPaG to obtain slurry-like ETFE-4.
The obtained slurry ETFE-4 was suction filtered with a glass filter and dried at 150 ° C. for 15 hours to obtain 97 g of ETFE-4.
The melting point of ETFE-4 was 258.1 ° C., and the Q value was 10.2 mm 3 / sec. The copolymer composition is TFE-based structural unit / E-based structural unit / CH 2 ═CH (CF 2 ) 4 F-based structural unit = 53.0 / 45.6 / 1.4 (mol%). there were. The structure of the polymer chain end group of ETFE-4 was —CFCl—CF 2 —CF 2 Cl. The ETFE-4 was pulverized by a turbo mill to obtain ETFE powder-4 having an average particle size of 30 μm.
Except for using ETFE powder-4 instead of ETFE powder-1, an article-6 was obtained in the same manner as in Example 1 in which the coating thickness of ETFE powder-4 was 0.89 mm.
［例７］
被塗装物−１の代わりに被塗装物−２を使用し、ＥＴＦＥ粉体−１の代わりにＥＴＦＥ粉体−４を使用した以外は、例１と同様にして、ＥＴＦＥ粉体−４の塗膜の厚さが１．００ｍｍの物品−７を得た。
[Example 7]
Applying ETFE powder-4 in the same manner as in Example 1 except that the object-2 was used instead of the object-1 and ETFE powder-4 was used instead of the ETFE powder-1. Article 7 having a film thickness of 1.00 mm was obtained.
例１〜７の物品−１〜物品−７についての接着性評価を表１に示す。表１における「粉体組成物−２／ＥＴＦＥ粉体−２」は、粉体組成物−２による塗膜上にＥＴＦＥ粉体−２による塗膜を形成したことを示す。 Table 1 shows the adhesive evaluation of Articles 1 to 7 of Examples 1 to 7. “Powder composition-2 / ETFE powder-2” in Table 1 indicates that a coating film made of ETFE powder-2 was formed on a coating film made of powder composition-2.
表１に示すように、本発明のＥＴＦＥ粉体または粉体組成物を使用した例１〜４では、連鎖移動剤としてＲ−２２５ｃｂを使用して得たＥＴＦＥ粉体を使用した例６および例７に比べて、剥離強度が高く、金属製の被塗装物に対して優れた接着性を有する塗膜が形成された。また、例５では、ほんの少量のＲ−２２５ｃｂが混入しているＲ−２２５ｃａを主成分とする連鎖移動剤を使用したが、Ｒ−２２５ｃｂによる悪影響はなく、剥離強度の高い、金属製の被塗装物に対して良好な接着性を有する塗膜が形成できた。 As shown in Table 1, in Examples 1 to 4 using the ETFE powder or powder composition of the present invention, Examples 6 and Examples using ETFE powder obtained using R-225cb as a chain transfer agent. Compared to 7, the peel strength was high, and a coating film having excellent adhesion to a metal object was formed. In Example 5, a chain transfer agent mainly composed of R-225ca mixed with a small amount of R-225cb was used. However, there was no adverse effect due to R-225cb, and the metal coating with high peel strength was used. A coating film having good adhesion to the coated product could be formed.
Claims (8)
下記単量体（ａ）に基づく構成単位（Ａ）と、下記単量体（ｂ）に基づく構成単位（Ｂ）と、下記単量体（ｃ）に基づく構成単位（Ｃ）と、下記連鎖移動剤（ｄ）に基づく末端基（Ｄ）と、を有し、
モル比（Ａ）／（Ｂ）が２０／８０〜８０／２０であり、モル比（Ｃ）／（（Ａ）＋（Ｂ））が０．１／１００〜５／１００であることを特徴とするエチレン／テトラフルオロエチレン系共重合体。
単量体（ａ）：テトラフルオロエチレン。
単量体（ｂ）：エチレン。
単量体（ｃ）：ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ただし、ＸおよびＹは、それぞれ独立に水素原子またはフッ素原子であり、ｎは２〜１０の整数である。）。
連鎖移動剤（ｄ）：３，３−ジクロロ−１，１，１，２，２−ペンタフルオロプロパン。 Obtained by polymerization using at least one polymerization medium selected from the group consisting of perfluorocarbons, hydrofluorocarbons and hydrofluoroalkyl ethers,
Structural unit (A) based on monomer (a) below, Structural unit (B) based on monomer (b) below, Structural unit (C) based on monomer (c) below, A terminal group (D) based on a transfer agent (d),
The molar ratio (A) / (B) is 20/80 to 80/20, and the molar ratio (C) / ((A) + (B)) is 0.1 / 100 to 5/100. An ethylene / tetrafluoroethylene copolymer.
Monomer (a): Tetrafluoroethylene.
Monomer (b): ethylene.
Monomer (c): CH 2 ═CX (CF 2 ) n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10).
Chain transfer agent (d): 3,3-dichloro-1,1,1,2,2-pentafluoropropane.
下記単量体（ａ）と下記単量体（ｂ）と下記単量体（ｃ）とを、モル比（ａ）／（ｂ）を２０／８０〜９９／１、モル比（ｃ）／（（ａ）＋（ｂ））を０．１／１００〜５／１００として共重合することを特徴とするエチレン／テトラフルオロエチレン系共重合体の製造方法。
単量体（ａ）：テトラフルオロエチレン。
単量体（ｂ）：エチレン。
単量体（ｃ）：ＣＨ２＝ＣＸ（ＣＦ２）ｎＹ（ただし、ＸおよびＹは、それぞれ独立に水素原子またはフッ素原子であり、ｎは２〜１０の整数である。）。
連鎖移動剤（ｄ）：３，３−ジクロロ−１，１，１，２，２−ペンタフルオロプロパン。 In the presence of at least one polymerization medium selected from the group consisting of perfluorocarbons, hydrofluorocarbons, and hydrofluoroalkyl ethers, the following chain transfer agent (d), and a polymerization initiator:
The following monomer (a), the following monomer (b), and the following monomer (c) have a molar ratio (a) / (b) of 20/80 to 99/1, a molar ratio (c) / A method for producing an ethylene / tetrafluoroethylene copolymer, wherein ((a) + (b)) is copolymerized at 0.1 / 100 to 5/100.
Monomer (a): Tetrafluoroethylene.
Monomer (b): ethylene.
Monomer (c): CH 2 ═CX (CF 2 ) n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10).
Chain transfer agent (d): 3,3-dichloro-1,1,1,2,2-pentafluoropropane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015198986A1 (en) * | 2014-06-24 | 2015-12-30 | 旭硝子株式会社 | Ethylene/tetrafluoroethylene copolymer, method for producing same, powder coating, and molded article |
| JP2016044231A (en) * | 2014-08-22 | 2016-04-04 | 旭硝子株式会社 | Fluorine-containing copolymer, powder composed of fluorine-containing copolymer, fluorine-containing copolymer composition and coated article containing powder |
| WO2017018354A1 (en) * | 2015-07-28 | 2017-02-02 | 旭硝子株式会社 | Fluorine-containing copolymer composition and molded article |
| JP2017177464A (en) * | 2016-03-29 | 2017-10-05 | マツダ株式会社 | Method of joining metal member and resin member, and metal member used in the method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053261A (en) * | 2001-08-10 | 2003-02-25 | Daikin Ind Ltd | Method for producing fluororesin coating film, fluororesin coating film and processed article |
| JP2005029704A (en) * | 2003-07-07 | 2005-02-03 | Asahi Glass Co Ltd | Fluorine-containing copolymer and method for producing granulated substance thereof |
| JP2006206637A (en) * | 2005-01-25 | 2006-08-10 | Asahi Glass Co Ltd | Ethylene/tetrafluoroethylene-based copolymer powder and article coated with the same |
| JP2011225677A (en) * | 2010-04-16 | 2011-11-10 | Asahi Glass Co Ltd | Manufacturing method for fluorine-containing copolymer powder, and porous fluorine-containing copolymer powder |
-
2012
- 2012-07-10 JP JP2012154688A patent/JP2014015551A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053261A (en) * | 2001-08-10 | 2003-02-25 | Daikin Ind Ltd | Method for producing fluororesin coating film, fluororesin coating film and processed article |
| JP2005029704A (en) * | 2003-07-07 | 2005-02-03 | Asahi Glass Co Ltd | Fluorine-containing copolymer and method for producing granulated substance thereof |
| JP2006206637A (en) * | 2005-01-25 | 2006-08-10 | Asahi Glass Co Ltd | Ethylene/tetrafluoroethylene-based copolymer powder and article coated with the same |
| JP2011225677A (en) * | 2010-04-16 | 2011-11-10 | Asahi Glass Co Ltd | Manufacturing method for fluorine-containing copolymer powder, and porous fluorine-containing copolymer powder |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015198986A1 (en) * | 2014-06-24 | 2015-12-30 | 旭硝子株式会社 | Ethylene/tetrafluoroethylene copolymer, method for producing same, powder coating, and molded article |
| CN106459233A (en) * | 2014-06-24 | 2017-02-22 | 旭硝子株式会社 | Ethylene/tetrafluoroethylene copolymer, method for producing same, powder coating, and molded article |
| JPWO2015198986A1 (en) * | 2014-06-24 | 2017-06-01 | 旭硝子株式会社 | Ethylene / tetrafluoroethylene copolymer, process for producing the same, powder coating material, and molded article |
| EP3162815A4 (en) * | 2014-06-24 | 2018-01-03 | Asahi Glass Company, Limited | Ethylene/tetrafluoroethylene copolymer, method for producing same, powder coating, and molded article |
| JP2016044231A (en) * | 2014-08-22 | 2016-04-04 | 旭硝子株式会社 | Fluorine-containing copolymer, powder composed of fluorine-containing copolymer, fluorine-containing copolymer composition and coated article containing powder |
| WO2017018354A1 (en) * | 2015-07-28 | 2017-02-02 | 旭硝子株式会社 | Fluorine-containing copolymer composition and molded article |
| JP2017177464A (en) * | 2016-03-29 | 2017-10-05 | マツダ株式会社 | Method of joining metal member and resin member, and metal member used in the method |
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