JP4389056B2 - 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 PDFInfo
- Publication number
- JP4389056B2 JP4389056B2 JP2004218886A JP2004218886A JP4389056B2 JP 4389056 B2 JP4389056 B2 JP 4389056B2 JP 2004218886 A JP2004218886 A JP 2004218886A JP 2004218886 A JP2004218886 A JP 2004218886A JP 4389056 B2 JP4389056 B2 JP 4389056B2
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- peo
- highly oriented
- lamellar structure
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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).
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.
The present invention also 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 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 by heat-treating a relatively high molecular weight polyethylene oxide-polystyrene block copolymer (PEO-b-PS) powder at high temperature for a long time under vacuum, and the nanospace (microphase separation) 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 perpendicularly 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. A highly oriented film characterized by highly oriented PEO crystals in a lamellar structure is easy to manufacture and can be used as a highly functional film, so it is industrially useful. is there.
Claims (2)
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 or less, PEO / PS = 65/35 to 35/65 (weight ratio), and a poly (ethylene oxide-styrene) block copolymer having a lamellar 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004218886A JP4389056B2 (en) | 2004-07-27 | 2004-07-27 | Highly oriented film of poly (ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004218886A JP4389056B2 (en) | 2004-07-27 | 2004-07-27 | Highly oriented film of poly (ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006036925A JP2006036925A (en) | 2006-02-09 |
| JP4389056B2 true JP4389056B2 (en) | 2009-12-24 |
Family
ID=35902270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004218886A Expired - Fee Related JP4389056B2 (en) | 2004-07-27 | 2004-07-27 | Highly oriented film of poly (ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4389056B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8563168B2 (en) | 2006-04-04 | 2013-10-22 | The Regents Of The University Of California | High elastic modulus polymer electrolytes |
| US8268197B2 (en) | 2006-04-04 | 2012-09-18 | Seeo, Inc. | Solid electrolyte material manufacturable by polymer processing methods |
| FR2930244B1 (en) * | 2008-04-18 | 2011-06-24 | Commissariat Energie Atomique | PROCESS FOR PREPARING A POLYMERIC FILM HAVING ON THE SURFACE NANOMETRIC PATTERNS AND MICROSTRUCTURE IN ITS THICKNESS ON ALL OR PART THEREOF ACCORDING TO A PARTICULAR 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 |
-
2004
- 2004-07-27 JP JP2004218886A patent/JP4389056B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006036925A (en) | 2006-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4389055B2 (en) | Highly oriented film of block copolymer-clay nanocomposite and method for producing the same | |
| An et al. | Preparation and electroactive properties of a PVDF/nano-TiO2 composite film | |
| Wang et al. | Impact of nanoscale confinement on crystal orientation of poly (ethylene oxide) | |
| Xiong et al. | Network chain density and relaxation of in situ synthesized polyacrylamide/hectorite clay nanocomposite hydrogels with ultrahigh tensibility | |
| Zhang et al. | Frequency dependence of orientation in dynamically sheared diblock copolymers | |
| KR101963924B1 (en) | Block copolymer materials for directed assembly of thin films | |
| Seguela | Dislocation approach to the plastic deformation of semicrystalline polymers: kinetic aspects for polyethylene and polypropylene | |
| Kofinas et al. | Morphology of highly textured poly (ethylene)/poly (ethylene-propylene)(E/EP) semicrystalline diblock copolymers | |
| Takagi et al. | Frank–Kasper σ phase in polybutadiene-poly (ε-caprolactone) diblock copolymer/polybutadiene blends | |
| Nojima et al. | Size dependence of crystallization within spherical microdomain structures | |
| Martín et al. | Directional crystallization of 20 nm width polymer nanorods by the inducement of heterogeneous nuclei at their tips | |
| KR20170143423A (en) | Laminated body | |
| Sun et al. | Effect of anodic alumina oxide pore diameter on the crystallization of poly (butylene adipate) | |
| Pinheiro et al. | Mixed Parallel− Perpendicular Morphologies in Diblock Copolymer Systems Correlated to the Linear Viscoelastic Properties of the Parallel and Perpendicular Morphologies | |
| Xu et al. | Sequential, orthogonal fields: A path to long-range, 3-D order in block copolymer thin films | |
| JP4389056B2 (en) | Highly oriented film of poly (ethylene oxide-styrene) block copolymer having lamellar structure and method for producing the same | |
| Liu et al. | Evolution of crystal orientation in one-dimensionally confined space templated by lamellae-forming block copolymers | |
| Polis et al. | Kink bands in a lamellar diblock copolymer induced by large amplitude oscillatory shear | |
| Liu et al. | Variable crystal orientation of poly (ethylene oxide) confined within the tubular space templated by anodic aluminum oxide nanochannels | |
| Djonlagic et al. | Hydrogels reinforced with nanoclays with improved response rate | |
| Mohammadi et al. | Nanoconfinement induced direct Formation of form I and III crystals inside in Situ formed poly (butene-1) nanofibrils | |
| Yavitt et al. | Power Law Relaxations in Lamellae Forming Brush Block Copolymers with Asymmetric Molecular Shape | |
| Agbolaghi et al. | Nascent lateral habits of solution crystallization of poly (ethylene glycol)-block-polystyrene diblock copolymers | |
| Laurer et al. | Persistence of surface-induced alignment in block copolymers upon large-amplitude oscillatory shear processing | |
| Shi et al. | Cooperative and Sequential Phase Transitions in it-Poly (propylene oxide)-b-poly (ethylene oxide)-b-it-poly (propylene oxide) Triblock Copolymers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Effective date: 20070129 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090909 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090915 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Effective date: 20090915 Free format text: JAPANESE INTERMEDIATE CODE: A61 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121016 Year of fee payment: 3 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |