JP2006036925A - Highly oriented film of poly(ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same - Google Patents

Highly oriented film of poly(ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same Download PDF

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JP2006036925A
JP2006036925A JP2004218886A JP2004218886A JP2006036925A JP 2006036925 A JP2006036925 A JP 2006036925A JP 2004218886 A JP2004218886 A JP 2004218886A JP 2004218886 A JP2004218886 A JP 2004218886A JP 2006036925 A JP2006036925 A JP 2006036925A
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block copolymer
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lamellar structure
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JP4389056B2 (en
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Akira Kaido
彰 海藤
Yongjin Li
ヨングジン リー
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National Institute of Advanced Industrial Science and Technology AIST
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a film having a new ordered structure, composed of a highly oriented film of a block copolymer having a lamellar structure and produced by controlling the arrangement of the block copolymer in high order and provide a method for producing the film. <P>SOLUTION: The highly oriented film is composed of a poly(ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure and satisfies the requirements that (1) the formed lamellar structure has an Mw/Mn ratio of ≤1.1 and a PEO/PS molar ratio of 65/35 to 35/65, (2) the lamella of the block copolymer is highly oriented on the film face and (3) the PEO crystal is highly oriented in the lamellar structure. The invention further provides a method for producing the film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、ブロック共重合体の配列制御により、新規な高次構造の形成と物性向上を図る。ラメラ構造を有するブロック共重合体の高配向膜およびその製造方法に関する。   The present invention aims to form a new higher order structure and improve physical properties by controlling the arrangement of the block copolymer. The present invention relates to a highly oriented film of a block copolymer having a lamella structure and a method for producing the same.

従来、せん断流動、電場、ゾーン熱処理などにより、高配向膜を作製することが知られている。また、低分子量のPEO-b-PS（PEOブロックおよびPSブロックのMn、それぞれ8,700および9,200）の結晶化による結晶配向に関する報告がある（非特許文献１）。   Conventionally, it is known to produce a highly oriented film by shear flow, electric field, zone heat treatment, and the like. There is also a report on crystal orientation by crystallization of low molecular weight PEO-b-PS (PEO block and PS block Mn, 8,700 and 9,200, respectively) (Non-patent Document 1).

Zhu etal., J. Am. Chem. Soc., 2000, 122, 5957.Zhu etal., J. Am. Chem. Soc., 2000, 122, 5957.

ブロック共重合体は、数十ナノメートルのナノ構造を形成するが、機能材料として利用する場合には、ナノ構造の配列制御が課題である。
本発明は、ブロック共重合体を高秩序に配列制御することにより、ラメラ構造を有するブロック共重合体の高配向膜である新規な秩序構造を有するフィルムおよびその製造方法を提供する。 The block copolymer forms a nanostructure of several tens of nanometers, but when used as a functional material, the control of the arrangement of the nanostructure is a problem.
The present invention provides a film having a novel ordered structure, which is a highly oriented film of a block copolymer having a lamellar structure, and a method for producing the same, by controlling the arrangement of the block copolymer in a highly ordered manner.

上記目的を達成するために本発明は、分子量数万以上のブロック共重合体を真空下、高温で長時間熱処理することによりブロック共重合体を配列制御する。
すなわち、本発明は、ラメラ構造を有するポリ（エチレンオキシド−スチレン）ブロック共重合体（PEO-b-PS）からなり、
１．Mw/Mn= 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を形成し、
２．ブロック共重合体のラメラがフィルム面に高度に配向し、かつ、
３．ラメラ構造の中でPEOの結晶が高度に配向したことを特徴とする高配向フィルムを提供する。
また、本発明は、Mw/Mn= 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を有する分子量（Mn）３０，０００以上のポリ（エチレンオキシド−スチレン）ブロック共重合体を真空下、１６０〜２００℃の温度で１０時間以上熱処理することを特徴とする高配向膜PEO-b-PSブロック共重合体の高配向フィルムの製造方法を提供する。 In order to achieve the above object, the present invention controls the arrangement of a block copolymer by subjecting a block copolymer having a molecular weight of tens of thousands or more to heat treatment under vacuum for a long time at a high temperature.
That is, the present invention comprises a poly (ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure,
1. Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio) to form a lamellar structure,
2. The block copolymer lamella is highly oriented on the film surface, and
3. Provided is a highly oriented film characterized by highly oriented PEO crystals in a lamellar structure.
Further, the present invention provides a poly (ethylene oxide-styrene) block copolymer having a molecular weight (Mn) of 30,000 or more having a lamellar structure with Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio). Provided is a method for producing a highly oriented film of a highly oriented film PEO-b-PS block copolymer, wherein the polymer is heat-treated at a temperature of 160 to 200 ° C. for 10 hours or more under vacuum.

本発明は、ブロック共重合体のナノドメインの利用に向けた基盤技術でもあり、ナノリソグラフィー、ナノ多孔の配列制御にも応用することが出来る。   The present invention is also a basic technology for use of nano domains of block copolymers, and can also be applied to nanolithography and nanoporous array control.

本発明の高配向フィルムは、ラメラ構造を有するポリ（エチレンオキシド−スチレン）ブロック共重合体（PEO-b-PS）は、少なくとも数平均分子量（Mn）が約３０，０００以上のもの、好ましくは５０，０００以上であり、かつ、ラメラ構造を有するポリ（エチレンオキシド−スチレン）ブロック共重合体（PEO-b-PS）であって、
１．Mw/Mn= 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を形成し、
２．ブロック共重合体のラメラがフィルム面に高度に配向し、かつ、
３．ラメラ構造の中でPEOの結晶が高度に配向したことを特徴とする。 In the highly oriented film of the present invention, the poly (ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure has a number average molecular weight (Mn) of about 30,000 or more, preferably 50 A poly (ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure of not less than 1,000,
1. Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio) to form a lamellar structure,
2. The block copolymer lamella is highly oriented on the film surface, and
3. PEO crystals are highly oriented in the lamellar structure.

本発明の高配向フィルムは、Mw/Mn = 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を有する数平均分子量（Mn）が少なくとも３０，０００以上、好ましくは５０，０００以上のポリ（エチレンオキシド−スチレン）ブロック共重合体を真空下、１６０〜２００℃の温度で１０時間以上熱処理することにより得られる。   The highly oriented film of the present invention has a Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio) and a lamellar structure and a number average molecular weight (Mn) of at least 30,000, preferably It can be obtained by heat-treating 50,000 or more poly (ethylene oxide-styrene) block copolymer at a temperature of 160 to 200 ° C. for 10 hours or more under vacuum.

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。
（実施例１）
比較的高分子量のポリエチレンオキシド−ポリスチレンブロック共重合体（PEO-b-PS）の粉末を真空下、高温で長時間熱処理することによりブロック共重合体を配列制御し、さらにナノ空間（ミクロ相分離構造内）における結晶化を利用して、PEOの結晶配向を制御することを試みた。
比較的高分子量のポリエチレンオキシド−ポリスチレンブロック共重合体（PEO-b-PS）（分子量Mn（PEO）＝ 71,000、Mn(PS)＝ 58,600 Mw/Mn=1.04）の粉末を真空中、180℃で18時間、荷重を付加しながら粉末試料をプレスすることにより、フィルム（厚さ100〜500μm）を作成した。Edge入射（X軸）の小角X線散乱像（SAXS）には、ラメラ構造に由来するスポット状の散乱が４次まで観測され、ラメラがフィルム面に平行に配向していることが示された（図１、図２参照）。
SAXS像は、試料中の測定場所に依らず再現性があり、広い領域で配列構造が形成されている。さらに、PEOブロックを融解・再結晶化すると、広い結晶化温度域（-60℃〜40℃）でPEOの結晶ｃ軸がラメラ面に垂直に配向して結晶化することが明らかになった（図１参照）。 The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1
The block copolymer is aligned and controlled by heat-treating a relatively high molecular weight polyethylene oxide-polystyrene block copolymer (PEO-b-PS) powder under vacuum at high temperature for a long time. We tried to control the crystal orientation of PEO using crystallization in the structure.
Relatively high molecular weight polyethylene oxide-polystyrene block copolymer (PEO-b-PS) (molecular weight Mn (PEO) = 71,000, Mn (PS) = 58,600 Mw / Mn = 1.04) powder at 180 ° C in vacuum A film (thickness: 100 to 500 μm) was prepared by pressing the powder sample while applying a load for 18 hours. In the small angle X-ray scattering image (SAXS) of Edge incidence (X axis), spot-like scattering derived from the lamella structure was observed up to the 4th order, indicating that the lamella was oriented parallel to the film surface. (See FIGS. 1 and 2).
SAXS images are reproducible regardless of the measurement location in the sample, and an array structure is formed in a wide area. Furthermore, when the PEO block was melted and recrystallized, it became clear that the crystal c-axis of PEO was oriented perpendicular to the lamellar surface and crystallized in a wide crystallization temperature range (-60 ° C to 40 ° C) ( (See FIG. 1).

（比較例１）
上記ブロック共重合体を180℃で６時間熱処理を行ったが、熱処理時間が短いと十分な配向がえられない。 (Comparative Example 1)
The block copolymer was heat treated at 180 ° C. for 6 hours. However, if the heat treatment time is short, sufficient orientation cannot be obtained.

（比較例２）
ポリ（エチレンオキシド−スチレン）ブロック共重合体のPEO-b-PS（PEOブロックおよびPSブロックのMn、それぞれ8,700および9,200）について同様の実験を行ったが、分子量が低いと十分な配向が得られない。 (Comparative Example 2)
A similar experiment was conducted with PEO-b-PS (PEO block and PS block Mn, 8,700 and 9,200, respectively), a poly (ethylene oxide-styrene) block copolymer, but sufficient orientation could not be obtained at low molecular weights. .

本発明のラメラ構造を有するポリ（エチレンオキシド−スチレン）ブロック共重合体（PEO-b-PS）からなり、
１．Mw/Mn= 1.1以下、 PEO/PS = 65/35〜35/65（モル比）でラメラ構造を形成し、
２．ブロック共重合体のラメラがフィルム面に高度に配向し、かつ、
３．ラメラ構造の中でPEOの結晶が高度に配向したことを特徴とする高配向フィルム、は、製造が簡単であり、機能性が高いフィルムとして、利用することができるので、産業上有用なものである。 The poly (ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure of the present invention,
1. Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (molar ratio) to form a lamellar structure,
2. The block copolymer lamella is highly oriented on the film surface, and
3. Highly oriented films characterized by highly oriented PEO crystals in a lamellar structure are industrially useful because they are easy to manufacture and can be used as highly functional films. is there.

ポリエチレンオキシド−ポリスチレンブロック共重合体（PEO-b-PS）（分子量Mn（PEO）＝ 71,000、Mn(PS)＝ 58,600 Mw/Mn=1.04）の粉末を真空中、180℃で18時間、荷重を付加しながらプレスすることにより作成したフィルム（厚さ100〜500μm）の小角X線散乱像（左）と広角X線回折像（右）Polyethylene oxide-polystyrene block copolymer (PEO-b-PS) (molecular weight Mn (PEO) = 71,000, Mn (PS) = 58,600 Mw / Mn = 1.04) powder in vacuum at 180 ° C for 18 hours Small-angle X-ray scattering image (left) and wide-angle X-ray diffraction image (right) of a film (thickness 100 to 500 μm) created by pressing while adding 配列制御したブロック共重合体の模式図Schematic diagram of sequence controlled block copolymer

Claims (2)

ラメラ構造を有するポリ（エチレンオキシド−スチレン）ブロック共重合体（PEO-b-PS）からなり、
１．Mw/Mn= 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を形成し、
２．ブロック共重合体のラメラがフィルム面に高度に配向し、かつ、
３．ラメラ構造の中でPEOの結晶が高度に配向したことを特徴とする高配向フィルム。 It consists of a poly (ethylene oxide-styrene) block copolymer (PEO-b-PS) having a lamellar structure,
1. Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio) to form a lamellar structure,
2. The block copolymer lamella is highly oriented on the film surface, and
3. A highly oriented film characterized by highly oriented PEO crystals in a lamellar structure. Mw/Mn = 1.1以下、 PEO/PS = 65/35〜35/65（重量比）でラメラ構造を有する分子量（Mn）３０，０００以上のポリ（エチレンオキシド−スチレン）ブロック共重合体を真空下、１６０〜２００℃の温度で１０時間以上熱処理することを特徴とする高配向膜PEO-b-PSブロック共重合体の高配向フィルムの製造方法。
















Mw / Mn = 1.1 or less, PEO / PS = 65/35 to 35/65 (weight ratio), and a poly (ethylene oxide-styrene) block copolymer having a lamella structure and a molecular weight (Mn) of 30,000 or more under vacuum. A method for producing a highly oriented film of a highly oriented film PEO-b-PS block copolymer, characterized by heat-treating at a temperature of 160 to 200 ° C. for 10 hours or more.
















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WO2010039606A2 (en) * 2008-10-01 2010-04-08 The Regents Of The University Of California High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries
US8268197B2 (en) 2006-04-04 2012-09-18 Seeo, Inc. Solid electrolyte material manufacturable by polymer processing methods
US8563168B2 (en) 2006-04-04 2013-10-22 The Regents Of The University Of California High elastic modulus polymer electrolytes

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8268197B2 (en) 2006-04-04 2012-09-18 Seeo, Inc. Solid electrolyte material manufacturable by polymer processing methods
US8563168B2 (en) 2006-04-04 2013-10-22 The Regents Of The University Of California High elastic modulus polymer electrolytes
US8703310B2 (en) 2006-04-04 2014-04-22 The Regents Of The University Of California High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries
JP2009263668A (en) * 2008-04-18 2009-11-12 Commissariat A L'energie Atomique Method for preparing polymer film having feature of nanoscale on its surface and microstructured in all or part of its thickness according to specific system
WO2010039606A2 (en) * 2008-10-01 2010-04-08 The Regents Of The University Of California High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries
WO2010039606A3 (en) * 2008-10-01 2010-07-29 The Regents Of The University Of California High elastic modulus polymer electrolytes suitable for preventing thermal runaway in lithium batteries

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