JP4677620B2 - Nylon-11 and polyvinylidene fluoride blend film manufacturing method - Google Patents
Nylon-11 and polyvinylidene fluoride blend film manufacturing method Download PDFInfo
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本発明は、ナイロン−１１とポリフッ化ビニリデンのブレンド（以下ナイロン−１１／ポリフッ化ビニリデンブレンドという）から成る多軸結晶配向材料の製造方法に関する。 The present invention relates to a method for producing a multiaxial crystal alignment material comprising a blend of nylon-11 and polyvinylidene fluoride (hereinafter referred to as nylon-11 / polyvinylidene fluoride blend).
従来、ポリフッ化ビニリデンとナイロン12からなり、異方性溶融形態（液晶）を示す成形体でフィブリル化されている、耐薬品性、耐摩耗性、機械的特性に優れた成形体が開示されている。（特許文献１参照）
また、赤外吸収スペクトルのバンドのシフトおよびガラス転移の組成依存性から、ナイロンのアミド基とポリフッ化ビニリデン（以下PVdFという）のCF結合の間に特異的な相互作用があることがわかっている。（非特許文献１参照）
Conventionally, a molded body made of polyvinylidene fluoride and nylon 12 and fibrillated with a molded body exhibiting an anisotropic molten form (liquid crystal) and having excellent chemical resistance, wear resistance, and mechanical properties has been disclosed. Yes. (See Patent Document 1)
In addition, there is a specific interaction between the amide group of nylon and the CF bond between polyvinylidene fluoride (hereinafter referred to as PVdF) from the shift of the band of the infrared absorption spectrum and the composition dependence of the glass transition. . (See Non-Patent Document 1)
本発明は、ナイロン−１１／ポリフッ化ビニリデンブレンドにおいて、圧電性、耐薬品性、耐摩耗性、耐熱性、強度・弾性率などの優れた物理的特性を有するが、一層の力学特性の向上が必要である。ナイロン−１１の配向マトリックス中でPVｄFを結晶化することにより、PVｄFの配向を制御することにより、ナイロン−１１／ポリフッ化ビニリデンブレンドからなる多軸結晶配向材料を作製し、ナイロン−１１／ポリフッ化ビニリデンブレンドの力学特性の向上を図る。 The present invention has excellent physical properties such as piezoelectricity, chemical resistance, abrasion resistance, heat resistance, strength and elastic modulus in the nylon-11 / polyvinylidene fluoride blend, but further improved mechanical properties. is necessary. By controlling the orientation of PVdF by crystallizing PVdF in an orientation matrix of nylon-11, a multiaxial crystal orientation material made of nylon-11 / polyvinylidene fluoride blend was produced, and nylon-11 / polyfluoride was produced. To improve the mechanical properties of vinylidene blends.
ナイロン−１１とPVdF からなるブレンドフィルムでナイロン−１１の分子鎖方向の結晶軸（ｃ軸）とPVdFの分子鎖と垂直方向の結晶軸（ａ軸）が共に延伸方向に配向した多軸結晶配向材料を作製する。
すなわち、本発明は、 ナイロン−１１とポリフッ化ビニリデン（ P V d F） を混練押出機で混練し、その後熱プレスでシート状に成形し、一軸延伸した後、形態を拘束して、ナイロン−１１の融点よりも低く、ポリフッ化ビニリデン（ P V d F） の融点よりも高い温度においてポリフッ化ビニリデン（ P Vｄ F） を融解し、その後８０〜１３５℃ に保温してポリフッ化ビニリデン（ P Vｄ F） を結晶化することにより、ナイロン−１１の分子鎖方向の結晶軸（ｃ軸）とPVdFの分子鎖と垂直方向の結晶軸（ａ軸）が共に延伸方向に配向したことを特徴とする多軸結晶配向材料の製造方法である。
また、本発明においては、ナイロン−１１とPVdFのブレンドフィルムを、ナイロン−１１：ポリフッ化ビニリデン（PVdF）＝４０〜７０：６０〜３０（質量比）ブレンドフィルムとすることが好ましい。
Nylon-11 and PVdF blend film is a multiaxial crystal orientation in which the crystal axis in the molecular chain direction (c-axis) of nylon-11 and the crystal axis in the vertical direction of PVdF molecular chain (a-axis) are both oriented in the stretching direction. Make the material.
That is, according to the present invention, nylon-11 and polyvinylidene fluoride (PV d F) are kneaded with a kneading extruder, then formed into a sheet shape with a hot press, uniaxially stretched, and the form is constrained. Polyvinylidene fluoride (P Vd F) is melted at a temperature lower than the melting point of polyvinylidene fluoride (PV d F) at a temperature higher than the melting point of polyvinylidene fluoride (PV d F) and then kept at 80 to 135 ° C. more crystallizing, multi crystal axes of the molecular chains direction nylon -11 (c axis) and PVdF molecular chain and vertical direction of the crystal axis (a axis), characterized in that oriented in the stretching direction both It is a manufacturing method of an axial crystal orientation material.
In the present invention, the nylon-11 and PVdF blend film is preferably a nylon-11: polyvinylidene fluoride (PVdF) = 40-70: 60-30 (mass ratio) blend film.
本発明の多軸結晶配向材料の製造方法は、ナイロン−１１の配向マトリックス中でPVｄFを結晶化することにより、PVｄFの配向を制御することにより、PVｄFの優れた物理的特性（耐薬品性、耐摩耗性、圧電性）などを維持したまま、機械的特性の向上を効率よく作り出すことができた。 The method for producing a multiaxial crystal alignment material of the present invention is characterized by controlling the orientation of PVdF by crystallizing PVdF in a nylon-11 alignment matrix, thereby improving the excellent physical properties (chemical resistance, While maintaining the wear resistance, piezoelectricity, etc., the mechanical properties could be improved efficiently.
本発明において用いるナイロン−１１（ポリウンデカンアミド）とポリフッ化ビニリデン（ＰＶｄＦ）からなるブレンドは、どのような配合割合のものでも良いが、ナイロン−１１（ポリウンデカンアミド）：ポリフッ化ビニリデン＝３０〜８０：７０〜２０（質量比）、より好ましくはナイロン−１１（ポリウンデカンアミド）：ポリフッ化ビニリデン＝４０〜７０：６０〜３０（質量比）のものが良い。
例えば、典型的な一例を示せば、ナイロン−１１とPVdFの粉末を混合して（混合質量比：ナイロン-11/PVdF＝4/6〜7/3）、混練押出機に導入し、溶融状態で混練して押し出す。入り口、シリンダー、ダイスの温度はそれぞれ、150 − 180 ℃、160 − 190 ℃、195 − 225 ℃（好ましくは、それぞれ160 −170 ℃、170 − 180 ℃、205 − 215 ℃）である。その後、熱プレスで215 ℃において溶融してシート状に成形する。さらに、 20 〜180℃、好ましくは120〜150 ℃において、２倍以上（好ましくは３倍以上）に一軸延伸する。その後、形態を拘束して、ナイロン−１１の融点よりも低く、PVdＦの融点よりも高い温度（好ましくは165〜175 ℃）においてPVｄFを融解した後、80〜135℃（好ましくは110〜125℃）においてPVｄFを結晶化することが必要である。
The blend of nylon-11 (polyundecanamide) and polyvinylidene fluoride (PVdF) used in the present invention may have any blending ratio, but nylon-11 (polyundecanamide): polyvinylidene fluoride = 30 to 80: 70-20 (mass ratio), more preferably nylon-11 (polyundecanamide): polyvinylidene fluoride = 40-70: 60-30 (mass ratio) is preferable.
For example, if a typical example is shown, nylon-11 and PVdF powder are mixed (mixing mass ratio: nylon-11 / PVdF = 4/6 to 7/3), introduced into a kneading extruder, and melted. Knead and extrude. The temperatures of the inlet, the cylinder, and the die are 150 to 180 ° C, 160 to 190 ° C, and 195 to 225 ° C (preferably 160 to 170 ° C, 170 to 180 ° C, and 205 to 215 ° C, respectively). Thereafter, it is melted at 215 ° C. by a hot press and formed into a sheet. Furthermore, it is uniaxially stretched at 20 to 180 ° C., preferably 120 to 150 ° C., twice or more (preferably 3 times or more). Then, after constraining the form and melting PVdF at a temperature lower than the melting point of nylon-11 and higher than the melting point of PVdF (preferably 165 to 175 ° C), 80 to 135 ° C (preferably 110 to 125 ° C) ) To crystallize PVdF.
本発明について実施例を用いてさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
ナイロン−１１とPVdFの粉末を混合して（混合比：ナイロン-11/PVdF＝5/5）、混練押出機に導入し、溶融状態で混練して押し出す。入り口、シリンダー、ダイスの温度はそれぞれ、165℃、185℃、210℃である。その後、熱プレスで215℃において溶融してシート状に成形する。さらに、145℃において、 4倍に一軸延伸する。その後、形態を拘束して、170℃においてPVｄFを5分間融解した後、120℃においてPVｄFを結晶化した。
フルオレセインで染色して共焦点レーザスキャン顕微鏡観察を行うと、直径 2〜10μm、長さ 10〜50μmのPVdFのドメインがナイロンの配向マトリックス中に配列しているのが観測される。広角X線回折によると、ナイロンについては分子鎖方向の結晶軸（結晶c軸）が延伸方向に配向しているのに対し、PVdFについては、分子鎖と垂直方向の結晶軸である結晶ａ軸が延伸方向に配向し、多軸結晶配向構造が形成されているのが確認できる。（図２ｄ）
引っ張り試験、動的粘弾性測定によると、破断強度140MPa、破断伸度32.5％、動的貯蔵弾性率 2.1GPaであった。（図３）
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Nylon-11 and PVdF powder are mixed (mixing ratio: nylon-11 / PVdF = 5/5), introduced into a kneading extruder, kneaded in a molten state and extruded. The temperatures of the inlet, cylinder, and die are 165 ° C, 185 ° C, and 210 ° C, respectively. Thereafter, it is melted at 215 ° C. with a hot press and formed into a sheet. Furthermore, it is uniaxially stretched 4 times at 145 ° C. Thereafter, the morphology was restrained, PVdF was melted at 170 ° C. for 5 minutes, and then PVdF was crystallized at 120 ° C.
When stained with fluorescein and observed with a confocal laser scanning microscope, it is observed that domains of PVdF having a diameter of 2 to 10 μm and a length of 10 to 50 μm are arranged in a nylon alignment matrix. According to wide-angle X-ray diffraction, for nylon, the crystal axis in the molecular chain direction (crystal c axis) is oriented in the stretching direction, whereas for PVdF, the crystal a axis that is the crystal axis perpendicular to the molecular chain It can be confirmed that is oriented in the stretching direction and a multiaxial crystal orientation structure is formed. (Fig. 2d)
According to the tensile test and dynamic viscoelasticity measurement, the breaking strength was 140 MPa, the breaking elongation was 32.5%, and the dynamic storage elastic modulus was 2.1 GPa. (Figure 3)
実施例1と同様にブレンドシートを作製し、145℃において、４倍に一軸延伸した。その後、形態を拘束して、170℃においてPVｄFを5分間融解した後、85℃においてPVｄFを結晶化した。広角X線回折によると、ナイロンについては分子鎖方向の結晶軸（結晶c軸）が延伸方向に配向しているのに対し、PVdFについては、分子鎖と垂直方向の結晶軸である結晶ａ軸が延伸方向に配向し、多軸結晶配向構造が形成されているのが確認できる。（図２c） A blend sheet was prepared in the same manner as in Example 1, and uniaxially stretched 4 times at 145 ° C. Thereafter, the morphology was constrained, PVdF was melted at 170 ° C. for 5 minutes, and then PVdF was crystallized at 85 ° C. According to wide-angle X-ray diffraction, for nylon, the crystal axis in the molecular chain direction (crystal c axis) is oriented in the stretching direction, whereas for PVdF, the crystal a axis that is the crystal axis perpendicular to the molecular chain It can be confirmed that is oriented in the stretching direction and a multiaxial crystal orientation structure is formed. (Figure 2c)
（比較例１）
実施例と同様にブレンドシートを作製し、145℃において、４倍に一軸延伸した。PVdFの融解・結晶化は行わなかった。
共焦点レーザスキャン顕微鏡観察を行うと、直径 2〜10μm、長さ 10〜50μmのPVdFのドメインがナイロンの配向マトリックス中に配列しているのが観測される。広角X線回折によると、ナイロンについてもPVdFについても分子鎖方向の結晶軸（ナイロンについてもPVｄFについても結晶c軸）が延伸方向に配向している。（図1a）
引っ張り試験、動的粘弾性測定によると、破断強度164MPa、破断伸度17％、動的貯蔵弾性率 2.1GPaであった。（図３）
(Comparative Example 1)
A blend sheet was prepared in the same manner as in the Examples, and uniaxially stretched four times at 145 ° C. PVdF was not melted or crystallized.
When confocal laser scanning microscope observation is performed, it is observed that PVdF domains having a diameter of 2 to 10 μm and a length of 10 to 50 μm are arranged in a nylon alignment matrix. According to wide-angle X-ray diffraction, the crystal axis in the molecular chain direction of both nylon and PVdF (the crystal c axis for both nylon and PVdF) is oriented in the stretching direction. (Figure 1a)
According to the tensile test and dynamic viscoelasticity measurement, the breaking strength was 164 MPa, the breaking elongation was 17%, and the dynamic storage elastic modulus was 2.1 GPa. (Figure 3)
（比較例２）
実施例と同様にブレンドシートを作製し、145℃において、４倍に一軸延伸した。170℃においてPVｄFを5分間融解した後、氷水中で0℃においてPVｄFを結晶化した。
共焦点レーザスキャン顕微鏡観察を行うと、直径 2〜10μm、長さ 10〜50μmのPVdFのドメインがナイロンの配向マトリックス中に配列しているのが観測される。広角X線回折によると、ナイロンについてもPVdFについても分子鎖方向の結晶軸（ナイロンについてもPVｄFについても結晶c軸）が延伸方向に配向している。（図2a）
引っ張り試験、動的粘弾性測定によると、破断強度138MPa、破断伸度23％、動的貯蔵弾性率 2.2GPaであった。
(Comparative Example 2)
A blend sheet was prepared in the same manner as in the Examples, and uniaxially stretched four times at 145 ° C. After melting PVdF at 170 ° C. for 5 minutes, PVdF was crystallized at 0 ° C. in ice water.
When confocal laser scanning microscope observation is performed, it is observed that PVdF domains having a diameter of 2 to 10 μm and a length of 10 to 50 μm are arranged in a nylon alignment matrix. According to wide-angle X-ray diffraction, the crystal axis in the molecular chain direction of both nylon and PVdF (the crystal c axis for both nylon and PVdF) is oriented in the stretching direction. (Figure 2a)
According to the tensile test and dynamic viscoelasticity measurement, the breaking strength was 138 MPa, the breaking elongation was 23%, and the dynamic storage elastic modulus was 2.2 GPa.
（比較例３）
ブレンドシート（ナイロン-11/PVdF＝5/5）の未延伸膜（無配向膜）の力学物性を評価した。破断強度24MPa、破断伸度4.2％、動的貯蔵弾性率 1.2GPaであった。
(Comparative Example 3)
The mechanical properties of the unstretched film (non-oriented film) of the blend sheet (nylon-11 / PVdF = 5/5) were evaluated. The breaking strength was 24 MPa, the breaking elongation was 4.2%, and the dynamic storage elastic modulus was 1.2 GPa.
（比較例４）
実施例と同様にブレンドシートを作製し、145℃において、４倍に一軸延伸した。170℃においてPVｄFを5分間融解した後、形態を拘束することなく氷水中で0℃においてPVｄFを結晶化した。PVdFの配向が乱れ、無配向の結晶組織が形成された。（図１ｂ）
(Comparative Example 4)
A blend sheet was prepared in the same manner as in the Examples, and uniaxially stretched four times at 145 ° C. After melting PVdF at 170 ° C for 5 minutes, PVdF was crystallized at 0 ° C in ice water without constraining the morphology. The orientation of PVdF was disturbed and a non-oriented crystal structure was formed. (Fig. 1b)
本発明の多軸結晶配向材料の製造方法は、ナイロン−１１の配向マトリックス中でPVｄFを結晶化することにより、PVｄFの配向を制御することにより、PVｄFの優れた物理的特性（耐薬品性、耐摩耗性、圧電性）などを維持したまま、機械的特性の向上を図ることができるため、高強度プラスチックフィルムなど各種構造材料として広範な用途に応用することが可能である。 The method for producing a multiaxial crystal alignment material of the present invention is characterized by controlling the orientation of PVdF by crystallizing PVdF in a nylon-11 alignment matrix, thereby improving the excellent physical properties (chemical resistance, The mechanical properties can be improved while maintaining the wear resistance, piezoelectricity, etc., and therefore, it can be applied to various uses as various structural materials such as high-strength plastic films.
Claims (2)
〜 ７ ０ ： ６ ０ 〜 ３ ０ （ 質量比） からなるブレンドフィルムである請求項１ に記載した多軸結晶配向材料の製造方法。 Nylon-11: Polyvinylidene fluoride (PV d F) = 40
The method for producing a multiaxial crystal alignment material according to claim 1, wherein the film is a blend film comprising: 70:60 to 30 (mass ratio).
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