TW201630954A - Block copolymer - Google Patents

Block copolymer Download PDF

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Publication number
TW201630954A
TW201630954A TW104132166A TW104132166A TW201630954A TW 201630954 A TW201630954 A TW 201630954A TW 104132166 A TW104132166 A TW 104132166A TW 104132166 A TW104132166 A TW 104132166A TW 201630954 A TW201630954 A TW 201630954A
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TW
Taiwan
Prior art keywords
block
block copolymer
chain
peak
atoms
Prior art date
Application number
TW104132166A
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Chinese (zh)
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TWI583710B (en
Inventor
金廷根
李濟權
李政圭
具世真
朴魯振
李美宿
崔銀英
尹聖琇
柳亨周
Original Assignee
Ｌｇ化學股份有限公司
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Priority claimed from KR1020140175414A external-priority patent/KR101780100B1/en
Application filed by Ｌｇ化學股份有限公司 filed Critical Ｌｇ化學股份有限公司
Publication of TW201630954A publication Critical patent/TW201630954A/en
Application granted granted Critical
Publication of TWI583710B publication Critical patent/TWI583710B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00388—Etch mask forming
    • B81C1/00428—Etch mask forming processes not provided for in groups B81C1/00396 - B81C1/0042
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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    • C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
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    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/18—Manufacture of films or sheets
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract

The present application relates to a block copolymer and uses thereof. The present application can provide a block copolymer - which exhibits an excellent self-assembling property and thus can be used effectively in a variety of applications - and uses thereof.

Description

嵌段共聚物 Block copolymer

本申請案係關於嵌段共聚物和其用途。 This application relates to block copolymers and uses thereof.

嵌段共聚物所具有的分子結構中，具有不同化學結構的聚合物嵌段各者藉共價鍵彼此連接。嵌段共聚物可經由相分離建構如球、圓柱和層狀結構。因為嵌段共聚物的自組現象的結果而形成的結構具有可在寬範圍內調整尺寸的區段，且其可構成各種形式，這些形式可用於製造各種下一代的奈米裝置、磁性儲存介質、和圖案(藉蝕刻之類)：特定言之，製造高密度磁性記錄介質、奈米線、量子點、金屬點之類。 In the molecular structure of the block copolymer, polymer blocks having different chemical structures are each linked by a covalent bond. The block copolymer can be constructed via phase separation such as spheres, cylinders, and layered structures. The structure formed as a result of the self-assembly phenomenon of the block copolymer has sections that can be sized in a wide range, and can be formed into various forms, which can be used to manufacture various next-generation nanodevices, magnetic storage media. And patterns (by etching): in particular, the manufacture of high-density magnetic recording media, nanowires, quantum dots, metal dots and the like.

本申請案提供嵌段共聚物、聚合物膜、形成聚合物膜之方法，及形成圖案之方法。 The present application provides block copolymers, polymeric films, methods of forming polymeric films, and methods of forming patterns.

說明性嵌段共聚物可含有嵌段1和不同於嵌段1的嵌段2。嵌段共聚物中的各嵌段可由僅一種類型的單體所構成，或者其可由二或更多種類型的單體所構成。嵌段共聚物可為僅含各一種嵌段1和嵌段2的二嵌段共聚物。嵌段聚合物亦可為除了嵌段1和嵌段2中之各一以外，含有嵌段1和嵌段2之一或二者，或僅為或與其他類型的嵌段一起之三嵌段或多嵌段(具有超過三種類型的嵌段)共聚物。 The illustrative block copolymer may contain block 1 and block 2 different from block 1. Each block in the block copolymer may be composed of only one type of monomer, or it may be composed of two or more types of monomers. The block copolymer may be a diblock copolymer containing only one of each of block 1 and block 2. The block polymer may also be a triblock containing one or both of block 1 and block 2, or only or together with other types of blocks, in addition to each of block 1 and block 2. Or a multi-block (with more than three types of blocks) copolymer.

嵌段共聚物含有2或更多個藉共價鍵彼此連接的聚合物鏈，因此發生相分離而形成所謂的自組結構。本發明者已確認，當嵌段共聚物滿足本說明書中以下提出之條件中之一、二或更多者時，更有效地發生前述相分離且，據此，因為微相分離而可形成奈米級結構。因此，本申請案係關於滿足本說明書中以下提出之條件中之至少一者之嵌段共聚物。可控制奈米級結構的形式或尺寸，例如，藉嵌段共聚物的尺寸(即，分子量之類)或嵌段之間的相對比。以此方式，本申請案之嵌段共聚物能夠無限制地形成相分離的結構，如各種尺寸的球、圓柱、螺旋二十四面體(gyroid)、層狀物和反轉結構。將簡單地依序描述該條件，且任何條件未凌駕於其他者之上。該嵌段共聚物滿足選自本說明書中以下描述條件中之任一、二或更多個條件。已確認藉由滿足任一條件，該嵌段共聚物可具有自組性質。本申請案中，術語“垂直定向(vertical orientation)” 是指嵌段共聚物定向的方向且可以指為嵌段共聚物所形成的奈米結構垂直定向於基板的方向；例如，介於嵌段共聚物的嵌段1所形成的區域和相同嵌段共聚物的嵌段2所形成的區域之間的介面可垂直於基板表面。本申請案中，術語“垂直”有誤差；例如，此術語的定義可包括在±10度，±8度，±6度，±4度，或±2度範圍內的誤差。 The block copolymer contains 2 or more polymer chains joined to each other by covalent bonds, and thus phase separation occurs to form a so-called self-assembled structure. The present inventors have confirmed that the above phase separation occurs more effectively when the block copolymer satisfies one, two or more of the conditions set forth in the specification below, and accordingly, since the microphase is separated, the naphthalene can be formed. Rice structure. Accordingly, the present application is directed to a block copolymer that satisfies at least one of the conditions set forth below in this specification. The form or size of the nanoscale structure can be controlled, for example, by the size of the block copolymer (i.e., molecular weight, etc.) or the relative ratio between the blocks. In this manner, the block copolymers of the present application are capable of forming, without limitation, phase-separated structures, such as spheres, cylinders, helical gyroids, layers, and inverted structures of various sizes. This condition will be described in a simple order, and any condition is not above the others. The block copolymer satisfies any one, two or more conditions selected from the conditions described below in the specification. It has been confirmed that the block copolymer can have self-organizing properties by satisfying any of the conditions. In the present application, the term "vertical orientation" Refers to the direction in which the block copolymer is oriented and may refer to the direction in which the nanostructure formed by the block copolymer is oriented perpendicular to the substrate; for example, the region formed by block 1 of the block copolymer and the same block The interface between the regions formed by the blocks 2 of the copolymer may be perpendicular to the surface of the substrate. In the present application, the term "vertical" has an error; for example, the definition of the term may include errors in the range of ±10 degrees, ±8 degrees, ±6 degrees, ±4 degrees, or ±2 degrees.

用於將各種基板上之嵌段共聚物的自組結構控制為水平或垂直的技術主要取決於嵌段共聚物的實際施用。嵌段共聚物膜中之奈米結構的定向通常由構成嵌段共聚物之嵌段間暴於表面或在空氣中的嵌段決定。通常，大部分基板係極性而空氣係非極性；因此，發現構成嵌段共聚物之嵌段中之具有較高極性的嵌段與基板接觸，且發現具有極性較低的嵌段與空氣的介面接觸。因此，提出各種技術以製造嵌段共聚物之有助於同時潤濕基板側之各具有不同性質的嵌段，此之中最常用的代表係製備中性表面以控制定向。 The technique used to control the self-assembled structure of the block copolymers on various substrates to be horizontal or vertical depends primarily on the actual application of the block copolymer. The orientation of the nanostructures in the block copolymer film is generally determined by the block that occupies the surface of the block copolymer or is in the air. In general, most of the substrates are polar and the air is non-polar; therefore, it is found that the blocks having higher polarity among the blocks constituting the block copolymer are in contact with the substrate, and the interface of the block having a lower polarity with air is found. contact. Accordingly, various techniques have been proposed to fabricate block copolymers that help to simultaneously wet blocks of different properties on the substrate side, the most common of which is to prepare a neutral surface to control orientation.

本發明者已證實，當所製備的嵌段共聚物滿足本說明書以下描述之條件中之任一、二或更多者、或全數時，該嵌段共聚物亦可垂直定向於尚未以任何方法(如表面中性化，其為此領域習知之用以達到垂直定向的方法)事先處理過的基板上。 The inventors have demonstrated that when the prepared block copolymer satisfies any, two or more, or all of the conditions described below in the specification, the block copolymer can also be oriented vertically without any means. (such as surface neutralization, which is known in the art to achieve vertical orientation) on previously processed substrates.

例如，本申請案的一個態樣之嵌段共聚物可以在親水表面和疏水表面二者(此二者皆未經過任何特別的前處理)上展現垂直定向。 For example, an aspect of the block copolymer of the present application can exhibit a vertical orientation on both a hydrophilic surface and a hydrophobic surface, both without any particular pretreatment.

本申請案的另一態樣中，藉熱退火，亦可以在短時間內大面積地誘發上述垂直定向。 In another aspect of the present application, the above-described vertical orientation can also be induced over a large area in a short time by thermal annealing.

據此，本申請案之說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，其可形成膜，該膜在具有對於純水的室溫潤濕角度為50度至70度的表面上製造低掠角小角度X射線散射(grazing-incidence small-angle X-ray scattering,GISAXS)的平面內(in-plane)繞射圖，並可形成膜，該膜亦在具有對於純水的室溫潤濕角度為5度至20度的表面上製造GISAXS平面內(in-plane)繞射圖(條件1)。 Accordingly, the illustrative block copolymers of the present application contain block 1 and block 2, each having a different chemical structure, which can form a film having a room temperature wetting angle of 50 degrees for pure water. An in-plane diffraction pattern of a grazing-incidence small-angle X-ray scattering (GISAXS) is fabricated on a surface of 70 degrees, and a film is formed, and the film is also formed A GISAXS in-plane diffraction pattern (condition 1) was fabricated on a surface having a room temperature wetting angle of 5 to 20 degrees for pure water.

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，其中嵌段1或嵌段共聚物整體能夠在低掠角廣角度X射線散射(GIWAXS)光譜的繞射圖中，在-90度至-70度及亦在70度至90度的方位角範圍中製造峰，其中散射向量q範圍由12nm-1至16nm-1(條件2)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, wherein the block 1 or block copolymer as a whole is capable of wide-angle X-ray scattering at low sweep angles ( In the diffraction pattern of the GIWAXS) spectrum, a peak is produced in an azimuthal range of -90 degrees to -70 degrees and also in the range of 70 degrees to 90 degrees, wherein the scattering vector q ranges from 12 nm -1 to 16 nm -1 (condition 2) .

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，其中嵌段1或嵌段共聚物整體能夠在差示掃描量熱法(DSC)分析期間內，在-80℃至200℃的範圍內製得熔化轉變峰或等向轉變峰(條件3)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, wherein the block 1 or block copolymer as a whole is capable of differential scanning calorimetry (DSC) During the analysis period, a melting transition peak or an isotropic transition peak (condition 3) was produced in the range of -80 ° C to 200 ° C.

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，其中嵌段1或嵌段共聚物整體能夠在XRD分析期間內的散射向量q範圍由 0.5nm-1至10nm-1時，製造具半高寬(FWHM)由0.2至0.9nm-1範圍的峰(條件4)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, wherein the block 1 or block copolymer as a whole is capable of scattering vector q range during XRD analysis From 0.5 nm -1 to 10 nm -1 , a peak having a full width at half maximum (FWHM) ranging from 0.2 to 0.9 nm -1 was produced (Condition 4).

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，其中嵌段1含有側鏈，側鏈中的成鏈原子數n和為嵌段1的XRD分析結果所得的散射向量q滿足以下的數學式2(條件5)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, wherein block 1 contains a side chain, and the number of chain atoms in the side chain is n and is a block. The scattering vector q obtained by the XRD analysis result of 1 satisfies the following Mathematical Formula 2 (Condition 5).

[數學式2]3nm-1至5nm-1=nq/(2×π) [Math 2] 3 nm -1 to 5 nm -1 = nq / (2 × π)

在該數學式2中，n代表前述側鏈中的該成鏈原子數，而q代表在含側鏈的嵌段上進行XRD分析的期間內，可偵測到的峰的最小散射向量q或觀察到具有最大峰面積之峰的散射向量q。 In the formula 2, n represents the number of the chain atoms in the aforementioned side chain, and q represents the minimum scattering vector q of the detectable peak during the XRD analysis on the side chain-containing block or The scattering vector q of the peak having the largest peak area was observed.

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，且介於嵌段1和嵌段2之間的表面能量差的絕對值可為10mN/m或更低(條件6)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, and the absolute value of the surface energy difference between block 1 and block 2 can be 10 mN/m or lower (condition 6).

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，且介於嵌段1和嵌段2之間的密度差的絕對值可為0.25g/cm3或更高(條件7)。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, and the absolute difference in density between block 1 and block 2 can be 0.25. g/cm 3 or higher (Condition 7).

本申請案的另一說明性嵌段共聚物含有嵌段1和嵌段2，各者具有不同的化學結構，且根據以下數學式A計算的X可具有1.25或更高的範圍(條件8)。此情況中，該嵌段共聚物可形成所謂的層狀結構。 Another illustrative block copolymer of the present application contains block 1 and block 2, each having a different chemical structure, and X calculated according to the following formula A may have a range of 1.25 or higher (condition 8) . In this case, the block copolymer can form a so-called layered structure.

[數學式A]X=1+(D×M)/(K×L) [Math A] X=1+(D×M)/(K×L)

數學式A中，D代表該第二嵌段的密度D2對該第一嵌段的密度D1之比D2/D1；M代表該第一嵌段的莫耳質量M1對該第二嵌段的莫耳質量M2之比M1/M2；K代表在1H-NMR光譜中，根據該第二嵌段製造的峰面積A2對根據該第一嵌段製造的峰面積A1之比A2/A1；而L代表該第一嵌段的1莫耳重複單元中的氫原子數H1對該第二嵌段的1莫耳重複單元中的氫原子數H2之比H1/H2。 In Mathematical Formula A, D represents the ratio D2/D1 of the density D2 of the second block to the density D1 of the first block; M represents the molar mass M1 of the first block to the second block. The ratio of the ear mass M2 is M1/M2; K represents the ratio A2/A1 of the peak area A2 produced according to the second block to the peak area A1 produced according to the first block in the 1 H-NMR spectrum; The ratio H1 to H2 of the number of hydrogen atoms H1 in the 1 molar repeating unit of the second block representing the number of hydrogen atoms in the 1 molar repeating unit of the first block.

以上嵌段共聚物各者中，嵌段1可為含有側鏈(本說明書中將於以下詳細描述)的嵌段。 In each of the above block copolymers, block 1 may be a block containing a side chain (which will be described in detail later in the specification).

下文中，將更詳細地描述前述條件。 Hereinafter, the foregoing conditions will be described in more detail.

A.條件1 A. Condition 1

本申請案之嵌段共聚物可在疏水表面和在親水表面上形成製造GISAXS平面內(in-plane)繞射圖的膜。本申請案中，在GISAXS期間內製造平面內(in-plane)繞射圖可指在GISAXS分析期間內，於GISAXS繞射圖中具有垂直的x-分量(x-component)的峰。因為嵌段共聚物的垂直定向，所以觀察到此峰。因此，製造平面內(in-plane)繞射圖的嵌段共聚物是指垂直定向。另一例子中，在GISAXS繞射圖的x-分量上觀察到的前述峰的數目可為至少2，但當多重峰存在時，可鑑定峰的散射向量q為具有整數比，此情況中，可進一步改良嵌段共聚物的相分離效率。 The block copolymer of the present application can form a film for making a GISAXS in-plane diffraction pattern on a hydrophobic surface and on a hydrophilic surface. In the present application, the in-plane diffraction pattern during the GISAXS period may refer to a peak having a vertical x-component (x-component) in the GISAXS diffraction pattern during the GISAXS analysis period. This peak was observed because of the vertical orientation of the block copolymer. Thus, a block copolymer that produces an in-plane diffraction pattern refers to a vertical orientation. In another example, the number of the aforementioned peaks observed on the x-component of the GISAXS diffraction pattern may be at least 2, but when multiple peaks are present, the scattering vector q of the identifiable peak may have an integer ratio, in which case The phase separation efficiency of the block copolymer can be further improved.

能夠在親水表面和在疏水表面二者上製造平面內(in-plane)繞射圖的膜之嵌段共聚物可在未事先以任何特別的方法處理以誘發垂直定向之各種表面上展現垂直定向。本申請案中，術語“親水表面”是指對於純水的潤濕角度在5度至20度範圍內的表面。親水表面的例子包括，但不限於，以氧電漿、硫酸或食人魚溶液(piranha solution)進行過表面處理的矽表面。本申請案中，術語“疏水表面”是指對於純水的室溫潤濕角度在50至70度範圍內的表面。疏水表面的例子可包括，但不限於，以氧電漿進行過表面處理的聚二甲基矽氧烷(PDMS)表面、以六甲基二矽氮烷(HMDS)進行過表面處理的矽表面，及以氟化氫(HF)進行過表面處理的矽表面。 A block copolymer capable of fabricating an in-plane diffraction pattern on both a hydrophilic surface and a hydrophobic surface can exhibit vertical orientation on various surfaces that have not been previously treated in any particular way to induce vertical orientation. . In the present application, the term "hydrophilic surface" means a surface having a wetting angle of from 5 to 20 degrees with respect to pure water. Examples of hydrophilic surfaces include, but are not limited to, tantalum surfaces that have been surface treated with oxygen plasma, sulfuric acid, or piranha solution. In the present application, the term "hydrophobic surface" means a surface having a room temperature wetting angle of from 50 to 70 degrees for pure water. Examples of hydrophobic surfaces may include, but are not limited to, polydimethyl siloxane (PDMS) surface surface treated with oxygen plasma, ruthenium surface surface treated with hexamethyldioxane (HMDS) And the surface of the crucible surface treated with hydrogen fluoride (HF).

除非特定指明，否則本申請案中視溫度而可改變的性質(如潤濕角度或密度)係於室溫測得的數值。術語“室溫”是指於其未經加熱或冷卻的常態溫度，且可以是指約10℃至30℃，約25℃，或約23℃的溫度。 Temperature-changeable properties (such as wetting angle or density) in this application are based on values measured at room temperature, unless otherwise specified. The term "room temperature" refers to a normal temperature at which it is not heated or cooled, and may refer to a temperature of about 10 ° C to 30 ° C, about 25 ° C, or about 23 ° C.

形成於親水或疏水表面上且在GISAXS期間內製造平面內(in-plane)繞射圖的膜可為已進行過熱退火處理的膜。用於GISAXS測定的膜可藉由，例如，將上述嵌段共聚物以約0.7重量%的濃度溶於溶劑(如，氟苯)中而製得的溶液以約25nm厚度和塗覆面積為2.25cm2(寬：1.5cm，長：1.5cm)施於對應親水或疏水表面上及熱退火經塗覆層而形成。此熱退火可藉例如使得以上的膜維持於約160℃溫度約1小時的方式進行。GISAXS可藉以前述 方式製得的膜上具有X-射線入射測定，其入射角度在約0.12至0.23度範圍內。膜散射的繞射圖可藉本領域習知的測定裝置(如2D marCCD)得到。使用繞射圖證實平面內(in-plane)繞射圖之存在與否之方法為本領域習知。 The film formed on the hydrophilic or hydrophobic surface and which produces an in-plane diffraction pattern during the GISAXS may be a film that has been subjected to a superheat annealing treatment. The film for the GISAXS measurement can be prepared, for example, by dissolving the above block copolymer in a solvent (e.g., fluorobenzene) at a concentration of about 0.7% by weight with a thickness of about 25 nm and a coated area of 2.25. Cm 2 (width: 1.5 cm, length: 1.5 cm) was applied to the corresponding hydrophilic or hydrophobic surface and thermally annealed to the coated layer. This thermal annealing can be carried out, for example, by maintaining the above film at a temperature of about 160 ° C for about 1 hour. The GISAXS can have an X-ray incident measurement on a film prepared in the manner described above with an incident angle in the range of about 0.12 to 0.23 degrees. The diffraction pattern of the film scattering can be obtained by an assay device (e.g., 2D marCCD) as is known in the art. Methods for verifying the presence or absence of an in-plane diffraction pattern using a diffraction pattern are known in the art.

觀察到在GISAXS期間內具有前述峰之嵌段共聚物展現極佳的自組性質，其亦可取決於目的而經有效地控制。 It was observed that the block copolymer having the aforementioned peaks during the GISAXS exhibits excellent self-organizing properties, which can also be effectively controlled depending on the purpose.

B.條件2 B. Condition 2

本申請案之嵌段共聚物的任一嵌段能夠在GIWAXS光譜的繞射圖中，在-90度至-70度和70度至90度的二者方位角範圍中製造峰，其中散射向量q範圍由12nm-1至16nm-1(條件2)。以上峰可由含側鏈(本說明書中將於以下描述)的嵌段製造。本說明書中，嵌段1可為前述含有側鏈的嵌段。以上描述中，方位角是指藉由設定角度(將相對於繞射圖的向上方向(即，面外繞射方向)為0度而測量且以順時針方向測量)而決定的方位角。即，當在順時針方向測量時，角度具正值時，其於逆時針方向測量時，角度具負值。在前述方位角各者中觀察到的峰的FWHM範圍由5度至70度。另一例子中，FWHM可為7度或更高，9度或更高，11度或更高，13度或更高，15度或更高，17度或更高，19度或更高，21度或更高，25度或更高，30度或更高，35度或更高，40度或更高，或45度或更高。另一例子中，FWHM亦可為65度或更低，或60度或更低。未特別限制得到GIWAXS光譜之方法， 且可藉本說明書在以下的實例中所描述的方法得到。所得光譜之繞射圖的峰型可經Gaussian擬合，並自經擬合的結果得到FWHM。當僅觀察Gaussian擬合結果的一半時，FWHM可定義為自結果觀察到的一半得到的值的兩倍。Gaussian擬合的R-平方範圍由0.26至0.95。即，若觀察上述FWHM，當R-平方在以上範圍內時便已足夠。得到諸如以上資訊之方法為本領域習知者；例如，可以使用數值分析程式，如Origin。 Any of the blocks of the block copolymer of the present application is capable of producing a peak in a range of azimuth angles of -90 degrees to -70 degrees and 70 degrees to 90 degrees in a diffraction pattern of the GIWAXS spectrum, wherein the scattering vector The q range is from 12 nm -1 to 16 nm -1 (Condition 2). The above peaks can be made from blocks containing side chains (which will be described below in this specification). In the present specification, the block 1 may be the aforementioned block containing a side chain. In the above description, the azimuth angle refers to an azimuth angle determined by setting an angle (measured with respect to the upward direction of the diffraction pattern (ie, the out-of-plane diffraction direction) of 0 degrees and measured in the clockwise direction). That is, when measured in the clockwise direction, when the angle has a positive value, the angle has a negative value when measured in the counterclockwise direction. The FWHM of the peak observed in each of the aforementioned azimuth angles ranges from 5 degrees to 70 degrees. In another example, the FWHM can be 7 degrees or higher, 9 degrees or higher, 11 degrees or higher, 13 degrees or higher, 15 degrees or higher, 17 degrees or higher, 19 degrees or higher, 21 degrees or higher, 25 degrees or higher, 30 degrees or higher, 35 degrees or higher, 40 degrees or higher, or 45 degrees or higher. In another example, the FWHM can also be 65 degrees or less, or 60 degrees or less. The method of obtaining the GIWAXS spectrum is not particularly limited, and can be obtained by the method described in the following examples. The peak shape of the diffraction pattern of the obtained spectrum can be fitted by Gaussian, and the FWHM is obtained from the fitted result. When only half of the Gaussian fitting results are observed, the FWHM can be defined as twice the value obtained from half of the observed results. The R-square of the Gaussian fit ranges from 0.26 to 0.95. That is, if the above FWHM is observed, it is sufficient when the R-square is in the above range. Methods for obtaining information such as the above are well known in the art; for example, a numerical analysis program such as Origin can be used.

可以在僅一種單體(構成待測嵌段)所構成的聚合物上進行GIWAXS。滿足條件2的該嵌段可含有無鹵原子的芳族結構(此將在本說明書中述於下文)，或其可含有側鏈。於GIWAXS的前述方位角處製造上述峰的嵌段可具有安排好的定向性質且，當與一或多種其他類型的嵌段併用時，可展現極佳的相分離、自組和垂直定向。 The GIGASS can be carried out on a polymer composed of only one monomer (constituting the block to be tested). The block satisfying Condition 2 may contain an aromatic structure having no halogen atom (which will be described later in the specification), or it may contain a side chain. The blocks that produce the above peaks at the aforementioned azimuthal angles of GIWAXS can have well-arranged orientation properties and, when used in combination with one or more other types of blocks, exhibit excellent phase separation, self-assembly, and vertical orientation.

C.條件3 C. Condition 3

本申請案之嵌段共聚物或該嵌段共聚物的任一嵌段能夠在DSC分析期間內，在-80℃至200℃的範圍內製得熔化轉變峰或等向轉變峰。當嵌段共聚物的任一嵌段在DSC分析期間內具有以上的行為且含有以上嵌段之嵌段共聚物滿足條件2和條件3二者時，嵌段(在DSC分析期間內具有以上的行為者)可為製造之前的條件2中所描述之GIWAXS峰(即，在GIWAXS光譜的繞射圖中，在-90度至-70度和70度至90度二者的方位角範圍中出現的峰，其中散射向量範圍由12nm-1至16nm-1)的嵌段且 可為、例如，嵌段1。嵌段共聚物或嵌段共聚物的任一嵌段可製造熔化轉變峰和等向轉變峰之一或二者。此情況中，該嵌段共聚物可為含有具有晶體相和/或液晶相(此二者適用於自組)的嵌段之共聚物，或者該嵌段共聚物本身可具有晶體相和/或液晶相遍佈於分子結構。 The block copolymer of the present application or any block of the block copolymer is capable of producing a melting transition peak or an isotropic transition peak in the range of -80 ° C to 200 ° C during the DSC analysis. When any block of the block copolymer has the above behavior during the DSC analysis and the block copolymer containing the above block satisfies both conditions 2 and 3, the block (with the above during the DSC analysis) The actor can be the GWAXS peak described in Condition 2 before manufacture (ie, in the diffraction pattern of the GIWAXS spectrum, in the azimuthal range of -90 degrees to -70 degrees and 70 degrees to 90 degrees) The peak, wherein the scattering vector ranges from 12 nm -1 to 16 nm -1 ) and can be, for example, block 1. Either block or block copolymer can produce either or both of a melting transition peak and an isotropic transition peak. In this case, the block copolymer may be a copolymer containing a block having a crystal phase and/or a liquid crystal phase (both of which are suitable for self-assembly), or the block copolymer itself may have a crystal phase and/or The liquid crystal phase is distributed throughout the molecular structure.

在DSC期間內具有以上行為的該嵌段共聚物或嵌段共聚物的任一嵌段可進一步滿足下述條件3。 Any of the blocks of the block copolymer or the block copolymer having the above behavior during the DSC may further satisfy the following condition 3.

例如，出現等向轉變峰和熔化轉變峰二者時，出現等向轉變峰的溫度Ti與出現熔化轉變峰的溫度Tm差異可為5℃至70℃。另一例子中，Ti-Tm的溫度差可為10℃或更高，15℃或更高，20℃或更高，25℃或更高，30℃或更高，35℃或更高，40℃或更高，45℃或更高，50℃或更高，55℃或更高，或60℃或更高。當等向轉變峰溫度Ti和熔化轉變峰溫度Tm之間的差Ti-Tm落在以上範圍內時，嵌段共聚物或(在描述對應於特定嵌段且非對應於嵌段共聚物整體的情況中)含有此嵌段之嵌段共聚物的相分離或自組可維持於極佳程度。 For example, when both the isotropic transition peak and the melting transition peak occur, the difference between the temperature Ti at which the isotropic transition peak appears and the temperature Tm at which the melting transition peak appears may be 5 ° C to 70 ° C. In another example, the temperature difference of Ti-Tm may be 10 ° C or higher, 15 ° C or higher, 20 ° C or higher, 25 ° C or higher, 30 ° C or higher, 35 ° C or higher, 40 °C or higher, 45 ° C or higher, 50 ° C or higher, 55 ° C or higher, or 60 ° C or higher. When the difference Ti-Tm between the isotropic transition peak temperature Ti and the melting transition peak temperature Tm falls within the above range, the block copolymer or (in the description corresponding to the specific block and not corresponding to the block copolymer as a whole) In the case where the phase separation or self-assembly of the block copolymer containing this block can be maintained to an excellent degree.

另一例子中，當製造等向轉變峰和熔化轉變峰二者時，等向轉變峰的面積I對熔化轉變峰的面積M之比M/I可在0.1至500範圍內。當等向轉變峰的面積I對熔化轉變峰的面積M之比M/I落在以上範圍中時，嵌段共聚物或(在描述對應於特定嵌段且非對應於嵌段共聚物整體的情況中)含有此嵌段之嵌段共聚物的相分離或自組可維持於極佳程度。另一例子中，M/I比可為0.5或更 高，1或更高，1.5或更高，2或更高，2.5或更高，或3或更高。又，另一例子中，M/I比亦可為450或更低，400或更低，350或更低，300或更低，250或更低，200或更低，150或更低，100或更低，90或更低，或85或更低。 In another example, when both the isotropic transition peak and the melting transition peak are produced, the ratio M/I of the area I of the isotropic transition peak to the area M of the melting transition peak may be in the range of 0.1 to 500. When the ratio M/I of the area I of the isotropic transition peak to the area M of the melting transition peak falls within the above range, the block copolymer or (in the description corresponding to the specific block and not corresponding to the block copolymer as a whole) In the case where the phase separation or self-assembly of the block copolymer containing this block can be maintained to an excellent degree. In another example, the M/I ratio can be 0.5 or more. High, 1 or higher, 1.5 or higher, 2 or higher, 2.5 or higher, or 3 or higher. Also, in another example, the M/I ratio may also be 450 or lower, 400 or lower, 350 or lower, 300 or lower, 250 or lower, 200 or lower, 150 or lower, 100. Or lower, 90 or lower, or 85 or lower.

進行DSC分析之方法為本領域習知者，且本領域習知的任一方法可用以實施本申請案中之分析。 Methods of performing DSC analysis are well known in the art, and any method known in the art can be used to carry out the analysis in this application.

熔化轉變峰可出現在溫度Tm在-10℃至55℃範圍內。另一例子中，Tm可為50℃或更低，45℃或更低，40℃或更低，35℃或更低，30℃或更低，25℃或更低，20℃或更低，15℃或更低，10℃或更低，5℃或更低，或0℃或更低。 The melting transition peak may occur at a temperature Tm in the range of -10 ° C to 55 ° C. In another example, the Tm may be 50 ° C or lower, 45 ° C or lower, 40 ° C or lower, 35 ° C or lower, 30 ° C or lower, 25 ° C or lower, 20 ° C or lower, 15 ° C or lower, 10 ° C or lower, 5 ° C or lower, or 0 ° C or lower.

如將於本說明書中進一步描述者，嵌段共聚物可含有含側鏈的嵌段。此情況中，嵌段共聚物可滿足以下數學式1。 As will be further described in this specification, block copolymers may contain blocks containing side chains. In this case, the block copolymer can satisfy the following Mathematical Formula 1.

數學式1中，Tm代表以上嵌段共聚物或具有以上側鏈的嵌段之熔化轉變峰出現的溫度，而n代表以上側鏈中的成鏈原子數。 In Mathematical Formula 1, Tm represents the temperature at which the melting transition peak of the above block copolymer or the block having the above side chain appears, and n represents the number of chain-forming atoms in the above side chain.

滿足以上數學式之嵌段共聚物能夠展現極佳的相分離或極佳的自組性質。 A block copolymer satisfying the above mathematical formula can exhibit excellent phase separation or excellent self-organizing properties.

另一例子中，數學式1中的Tm-12.25℃×n+149.5℃可計算為約-8℃至8℃，約-6℃至6℃，或約-5℃至 5℃。 In another example, Tm-12.25 ° C × n + 149.5 ° C in Mathematical Formula 1 can be calculated to be about -8 ° C to 8 ° C, about -6 ° C to 6 ° C, or about -5 ° C to 5 ° C.

D.條件4 D. Condition 4

本申請案之嵌段共聚物可含有嵌段，該嵌段在X-射線繞射(XRD)分析期間內在預定的散射向量q範圍內製造至少一個峰。當嵌段共聚物除了前述條件2和/或條件3以外，亦滿足條件4時，滿足條件2和/或條件3之(嵌段共聚物的)嵌段亦滿足條件4。該滿足條件4的嵌段可為前述嵌段1。 The block copolymer of the present application may contain a block that produces at least one peak within a predetermined scattering vector q during X-ray diffraction (XRD) analysis. When the block copolymer satisfies Condition 4 in addition to Condition 2 and/or Condition 3 described above, the block (block copolymer) which satisfies Condition 2 and/or Condition 3 also satisfies Condition 4. The block satisfying the condition 4 may be the aforementioned block 1.

例如，以上嵌段共聚物中的任一嵌段可在XRD分析期間內，在0.5nm-1至10nm-1的散射向量q範圍內具有至少一個峰。另一例子中，以上峰出現處的散射向量q可為0.7nm-1或更高，0.9nm-1或更高，1.1nm-1或更高，1.3nm-1或更高，或1.5nm-1或更高。又，另一例子中，以上峰出現處的散射向量q亦可為9nm-1或更低，8nm-1或更低，7nm-1或更低，6nm-1或更低，5nm-1或更低，4nm-1或更低，3.5nm-1或更低，或3nm-1或更低。在以上散射向量q內觀察到的峰的半高寬(FWHM)可在0.2至0.9nm-1範圍內。另一例子中，以上FWHM可為0.25nm-1或更高，0.3nm-1或更高，或0.4nm-1或更高。又，另一例子中，以上FWHM亦可為0.85nm-1或更低，0.8nm-1或更低，或0.75nm-1或更低。 For example, any of the above block copolymers may have at least one peak in the range of scattering vectors q of 0.5 nm -1 to 10 nm -1 during XRD analysis. In another example, the scattering vector q at which the above peak appears may be 0.7 nm -1 or higher, 0.9 nm -1 or higher, 1.1 nm -1 or higher, 1.3 nm -1 or higher, or 1.5 nm. -1 or higher. Further, in another example, the scattering vector q at which the above peak appears may also be 9 nm -1 or lower, 8 nm -1 or lower, 7 nm -1 or lower, 6 nm -1 or lower, 5 nm -1 or Lower, 4 nm -1 or lower, 3.5 nm -1 or lower, or 3 nm -1 or lower. The full width at half maximum (FWHM) of the peak observed in the above scattering vector q may be in the range of 0.2 to 0.9 nm -1 . In another example, the above FWHM may be 0.25 nm -1 or higher, 0.3 nm -1 or higher, or 0.4 nm -1 or higher. Yet another example, the above may also be 0.85nm -1 FWHM or less, 0.8nm -1 or less, or 0.75 nm -1 or less.

條件4中，術語“半高寬”是指最大峰於一半最大振幅時的寬度(即，兩個極端散射向量q值之間的差)。 In Condition 4, the term "full width at half maximum" means the width at which the maximum peak is at half the maximum amplitude (i.e., the difference between the values of the two extreme scattering vectors q).

XRD分析中的以上散射向量q和FWHM係藉數值分析法(對XRD分析結果施以最小平方回歸)得到的數值。以上方法中，將對應於XRD繞射圖之最低強度的部分設定為基線且最低強度設定為零，之後以上XRD圖的峰型進行Gaussian擬合，且自擬合結果得到上述散射向量q和FWHM。當進行以上的Gaussian擬合時，R-平方值是至少0.9或更高，0.92或更高，0.94或更高，或0.96或更高。自XRD分析得到資訊之方法，如前述者，為本領域習知者；例如，可使用數值分析程式，如Origin。 The above scattering vectors q and FWHM in the XRD analysis are numerical values obtained by numerical analysis (least squares regression is performed on the XRD analysis results). In the above method, the portion corresponding to the lowest intensity of the XRD diffraction pattern is set as the baseline and the lowest intensity is set to zero, after which the peak shape of the above XRD pattern is Gaussian fitted, and the above scattering vector q and FWHM are obtained from the self-fitting result. . When the above Gaussian fit is performed, the R-square value is at least 0.9 or higher, 0.92 or higher, 0.94 or higher, or 0.96 or higher. Methods for obtaining information from XRD analysis, such as those described above, are well known in the art; for example, numerical analysis programs such as Origin can be used.

在前述散射向量q範圍中製造具有前述FWHM值的峰之嵌段共聚物可具有適用於自組的晶狀區域。已證實在前述散射向量q範圍中之嵌段共聚物能夠展現極佳的自組性質。 A block copolymer which produces a peak having the aforementioned FWHM value in the range of the aforementioned scattering vector q may have a crystalline region suitable for self-assembly. It has been confirmed that the block copolymer in the range of the aforementioned scattering vector q can exhibit excellent self-organizing properties.

XRD分析可藉由使得X-射線穿透嵌段共聚物試樣及之後測定關於散射向量之散射強度進行。可藉由使用藉由僅聚合構成嵌段共聚物之任一嵌段(如嵌段1)的單體而製得的聚合物進行XRD分析。XRD分析可以在此嵌段共聚物上進行，無須任何特別的前處理；例如，可藉由在適當條件下乾燥該嵌段共聚物及之後以X-射線穿透進行。可使用垂直尺寸為0.023mm且水平尺寸為0.3mm的X-射線。經由擷取得自試樣散射的2D繞射圖(其係藉由使用測量裝置(如2D marCCD)及以前述方法所得的繞射圖擬合之影像形式)，可得到散射向量和FWHM。 XRD analysis can be performed by passing X-rays through the block copolymer sample and then measuring the scattering intensity with respect to the scattering vector. XRD analysis can be carried out by using a polymer prepared by polymerizing only monomers constituting any block of the block copolymer (e.g., block 1). XRD analysis can be carried out on the block copolymer without any special pretreatment; for example, by drying the block copolymer under suitable conditions and then by X-ray penetration. X-rays having a vertical dimension of 0.023 mm and a horizontal dimension of 0.3 mm can be used. The scattering vector and FWHM are obtained by obtaining a 2D diffraction pattern from the sample scattering via enthalpy (which is obtained by using a measuring device (such as 2D marCCD) and a diffraction pattern obtained by the above method).

E.條件5 E. Condition 5

本申請案之嵌段共聚物可含有本說明書中以下描述之含側鏈的嵌段作為嵌段1，且側鏈中的成鏈原子數n和藉由前述條件4中描述之方法執行XRD分析得到的散射向量q可滿足以下數學式2。 The block copolymer of the present application may contain the side chain-containing block described below in the specification as block 1, and the number of chain-forming atoms n in the side chain and XRD analysis performed by the method described in Condition 4 above. The obtained scattering vector q can satisfy the following Math.

[數學式2]3nm-1至5nm-1=nq/(2×π) [Math 2] 3 nm -1 to 5 nm -1 = nq / (2 × π)

在該數學式2中，在含有側鏈的前述嵌段上進行XRD分析的期間n代表上述成鏈原子數，而q代表可偵測到的峰的最小散射向量q或觀察到具有最大峰面積之峰的散射向量q。此外，π代表數學式1中圓之圓周與其直徑的比。 In the mathematical formula 2, n during the XRD analysis on the aforementioned block containing the side chain represents the number of the above-mentioned chain-forming atoms, and q represents the minimum scattering vector q of the detectable peak or the largest peak area is observed. The scattering vector q of the peak. Further, π represents the ratio of the circumference of the circle in the mathematical formula 1 to its diameter.

數學式2的q等係以與前述XRD分析方法的描述中相同的方式得到的數值。 The q of the mathematical formula 2 is a numerical value obtained in the same manner as in the description of the aforementioned XRD analysis method.

數學式2的q可為，例如，在0.5nm-1至10nm-1範圍的散射向量。另一例子中，數學式2的散射向量q可為0.7nm-1或更高，0.9nm-1或更高，1.1nm-1或更高，1.3nm-1或更高，或1.5nm-1或更高。又，另一例子中，數學式2的散射向量q亦可為9nm-1或更低，8nm-1或更低，7nm-1或更低，6nm-1或更低，5nm-1或更低，4nm-1或更低，3.5nm-1或更低，或3nm-1或更低。 q of Math Figure 2 may be, for example, a scattering vector in the range of 0.5 nm -1 to 10 nm -1 . In another example, the scattering vector q of Math Figure 2 may be 0.7 nm -1 or higher, 0.9 nm -1 or higher, 1.1 nm -1 or higher, 1.3 nm -1 or higher, or 1.5 nm - 1 or higher. Further, in another example, the scattering vector q of Math Figure 2 may also be 9 nm -1 or lower, 8 nm -1 or lower, 7 nm -1 or lower, 6 nm -1 or lower, 5 nm -1 or more. Low, 4 nm -1 or lower, 3.5 nm -1 or lower, or 3 nm -1 or lower.

數學式2描述當嵌段共聚物自組形成相分離結構時，含有前述鏈的嵌段中的距離D和成鏈原子數之間的關係。當含有前述鏈的嵌段共聚物中之成鏈原子數滿足 數學式2時，鏈的晶度提高，並藉此可明顯改良相分離或垂直定向性質。另一例子中，數學式2中的nq/(2×π)可為4.5nm-1或更低。以上描述中，藉由使用數學式D=2×π/q，可計算出含有以上鏈之嵌段中的距離D(單位：nm)，其中D代表上述嵌段中的距離D(單位：nm)，π和q如數學式2中之定義。 Mathematical Formula 2 describes the relationship between the distance D and the number of chain-forming atoms in the block containing the aforementioned chain when the block copolymer self-assembles to form a phase-separated structure. When the number of chain atoms in the block copolymer containing the aforementioned chain satisfies the formula 2, the crystallinity of the chain is increased, and thereby the phase separation or vertical alignment property can be remarkably improved. In another example, nq/(2×π) in Math. 2 may be 4.5 nm -1 or lower. In the above description, by using the mathematical formula D = 2 × π / q, the distance D (unit: nm) in the block containing the above chain can be calculated, where D represents the distance D in the above block (unit: nm ), π and q are as defined in Math.

F.條件6 F. Condition 6

本申請案之嵌段共聚物中，介於嵌段共聚物中之嵌段1的表面能量和嵌段2的表面能量之間的差的絕對值可為10mN/m或更低，9mN/m或更低，8或更低，7.5或更低，或7或更低。介於以上表面能量之間的差的絕對值亦可為1.5mN/m，2mN/m，或2.5mN/m或更高。具有表面能量之間的差的絕對值在以上範圍內之嵌段1和嵌段2彼此藉共價鍵連接的結構能夠誘發微相分離，此因不混溶程度足夠而相分離之故。以上描述中，嵌段1可為，例如，本說明書中以下描述之含有側鏈的嵌段，或者，其可為，例如，含有不鹵原子之芳族結構的嵌段。 In the block copolymer of the present application, the absolute value of the difference between the surface energy of the block 1 in the block copolymer and the surface energy of the block 2 may be 10 mN/m or less, 9 mN/m. Or lower, 8 or lower, 7.5 or lower, or 7 or lower. The absolute value of the difference between the above surface energies may also be 1.5 mN/m, 2 mN/m, or 2.5 mN/m or higher. The structure in which the absolute value of the difference between the surface energies is in the above range and the block 1 and the block 2 are linked by a covalent bond to each other can induce microphase separation, which is phase-separated because the degree of immiscibility is sufficient. In the above description, the block 1 may be, for example, a side chain-containing block described below in the present specification, or it may be, for example, a block containing an aromatic structure other than a halogen atom.

表面能量可藉由使用Drop Shape Analyzer DSA100(KRUSS GmbH生產)測定。特定言之，藉由將塗覆溶液(待測標的試樣(即，嵌段共聚物或均聚物)溶於氟苯中至固體濃度約2重量%而製得)施用在厚度約50nm且塗覆面積為4cm2(寬：2cm，長：2cm)的基板上，於室溫乾燥約1小時，及之後於160℃熱退火約1小時所製得的膜上可測得表面能量。重複5次測定接觸角度的程序(藉由將本領 域已知其表面張力的去離子水滴在以上經熱退火的膜上)，並將這5個測得的接觸角度值加以平均。同樣，重複5次測定接觸角度的程序(藉由將本領域已知其表面張力的二碘甲烷滴在以上經熱退火的膜上)，並將這5個測得的接觸角度值加以平均。然後，可以藉由使用分別以去離子水和二碘甲烷測得之接觸角度的平均值並將對應於溶劑之表面張力的數值(Strom值)代入根據Owens-Wendt-Rabel-Kaelble方法的數學式中得到表面能量。由將上述方法用於僅由構成以上嵌段之單體所構成的均聚物上，可得到對應於嵌段共聚物的各嵌段之表面能量的數值。 The surface energy can be measured by using a Drop Shape Analyzer DSA100 (manufactured by KRUSS GmbH). Specifically, by applying a coating solution (a sample to be tested (ie, a block copolymer or a homopolymer) in fluorobenzene to a solid concentration of about 2% by weight) is applied at a thickness of about 50 nm and The surface energy was measured on a film having a coating area of 4 cm 2 (width: 2 cm, length: 2 cm), dried at room temperature for about 1 hour, and then thermally annealed at 160 ° C for about 1 hour. The procedure for determining the contact angle was repeated 5 times (by using a deionized water droplet whose surface tension is known in the art on the above thermally annealed film), and the five measured contact angle values were averaged. Similarly, the procedure for determining the contact angle was repeated 5 times (by dropping the surface tension of diiodomethane on the above thermally annealed film), and the five measured contact angle values were averaged. Then, the value corresponding to the surface tension of the solvent (Strom value) can be substituted into the mathematical expression according to the Owens-Wendt-Rabel-Kaelble method by using the average value of the contact angles measured with deionized water and diiodomethane, respectively. Get surface energy. By applying the above method to a homopolymer composed only of the monomers constituting the above block, a value corresponding to the surface energy of each block of the block copolymer can be obtained.

當嵌段共聚物含有前述側鏈時，含有該側鏈的嵌段可具有高於其他嵌段的表面能量。例如，當嵌段共聚物在嵌段1中含有側鏈時，嵌段1的表面能量可高於嵌段2。此情況中，嵌段1的表面能量可在約20mN/m至40mN/m範圍內。嵌段1的表面能量可為22mN/m或更高，24mN/m或更高，26mN/m或更高，或28mN/m或更高。又，嵌段1的表面能量亦可為38mN/m或更低，36mN/m或更低，34mN/m或更低，或32mN/m或更低。前述之含有此嵌段1且嵌段1具有不同於嵌段2的表面能量之嵌段共聚物可展現極佳的自組性質。 When the block copolymer contains the aforementioned side chain, the block containing the side chain may have a higher surface energy than the other blocks. For example, when the block copolymer contains a side chain in block 1, the surface energy of block 1 can be higher than that of block 2. In this case, the surface energy of the block 1 may range from about 20 mN/m to 40 mN/m. The surface energy of the block 1 may be 22 mN/m or higher, 24 mN/m or higher, 26 mN/m or higher, or 28 mN/m or higher. Also, the surface energy of the block 1 may be 38 mN/m or less, 36 mN/m or less, 34 mN/m or less, or 32 mN/m or less. The aforementioned block copolymer containing this block 1 and having block 1 having a surface energy different from that of block 2 can exhibit excellent self-organizing properties.

G.條件7 G. Condition 7

嵌段共聚物中，介於嵌段1和嵌段2之間之密度差的絕對值可為0.25g/cm3或更高，0.3g/cm3或更高，0.35g/cm3或更高，0.4g/cm3或更高，或0.45g/cm3或 更高。前述密度差的絕對值可為0.9g/cm3或更高，0.8g/cm3或更低，0.7g/cm3或更低，0.65g/cm3或更低，或0.6g/cm3或更低。嵌段1和嵌段2具有之密度差的絕對值在以上範圍內且彼此藉共價鍵連接之結構因為足夠的不混溶程度造成的相分離而可誘發有效的微相分離。 In the block copolymer, the absolute value of the difference in density between the block 1 and the block 2 may be 0.25 g/cm 3 or higher, 0.3 g/cm 3 or higher, 0.35 g/cm 3 or more. High, 0.4 g/cm 3 or higher, or 0.45 g/cm 3 or higher. The absolute value of the aforementioned density difference may be 0.9 g/cm 3 or higher, 0.8 g/cm 3 or lower, 0.7 g/cm 3 or lower, 0.65 g/cm 3 or lower, or 0.6 g/cm 3 . Or lower. Block 1 and block 2 have an absolute value of the difference in density within the above range and the structure bonded to each other by covalent bonding can induce effective microphase separation due to phase separation due to a sufficient degree of immiscibility.

以上嵌段共聚物中之各嵌段的密度係藉使用本領域中習知的浮力法測定，可藉由分析嵌段共聚物在溶劑(如乙醇，已知其於空氣中之質量和密度)中的質量而測得密度。 The density of each block in the above block copolymers is determined by buoyancy methods well known in the art by analyzing the block copolymer in a solvent such as ethanol, known for its mass and density in air. The density is measured in the mass.

嵌段共聚物含有前述側鏈時，含有側鏈的嵌段可具有密度低於其他嵌段。例如，當嵌段共聚物在嵌段1中含有側鏈時，嵌段1可具有密度低於嵌段2。此情況中，嵌段1的密度可在約0.9g/cm3至1.5g/cm3範圍內。嵌段1的密度可為0.95g/cm3或更高。又，嵌段1的密度亦可為1.4g/cm3或更低，1.3g/cm3或更低，1.2g/cm3或更低，1.1g/cm3或更低，或1.05g/cm3或更低。含有以上嵌段1(具有密度不同於上述嵌段2)之嵌段共聚物可展現極佳的自組性質。 When the block copolymer contains the aforementioned side chain, the block containing the side chain may have a lower density than the other blocks. For example, when the block copolymer contains a side chain in block 1, block 1 may have a lower density than block 2. In this case, the density of the block 1 may range from about 0.9 g/cm 3 to 1.5 g/cm 3 . The density of the block 1 may be 0.95 g/cm 3 or higher. Further, the density of the block 1 may also be 1.4 g/cm 3 or less, 1.3 g/cm 3 or less, 1.2 g/cm 3 or less, 1.1 g/cm 3 or less, or 1.05 g/ Cm 3 or lower. A block copolymer containing the above block 1 (having a density different from the above block 2) can exhibit excellent self-organizing properties.

H.條件8 H. Condition 8

本申請案之嵌段共聚物中，藉以下數學式A計算的X值可為，例如，1.25或更高。其中的X值(藉數學式A計算)為1.25或更高之嵌段共聚物可為僅嵌段1和嵌段2構成的二嵌段共聚物。 In the block copolymer of the present application, the X value calculated by the following formula A may be, for example, 1.25 or more. The block copolymer in which the X value (calculated by Mathematical Formula A) is 1.25 or higher may be a diblock copolymer composed of only Block 1 and Block 2.

[數學式A]X=1+(D×M)/(K×L) [Math A] X=1+(D×M)/(K×L)

數學式A中，D代表該第二嵌段的密度D2對該第一嵌段的密度D1之比D2/D1；M代表該第一嵌段的莫耳質量M1對該第二嵌段的莫耳質量M2之比M1/M2；K代表在1H-NMR光譜中，根據該第二嵌段製造的峰面積A2對根據該第一嵌段製造的峰面積A1之比A2/A1；而L代表該第一嵌段的1莫耳重複單元中的氫原子數H1對該第二嵌段的1莫耳重複單元中的氫原子數H2之比H1/H2。 In Mathematical Formula A, D represents the ratio D2/D1 of the density D2 of the second block to the density D1 of the first block; M represents the molar mass M1 of the first block to the second block. The ratio of the ear mass M2 is M1/M2; K represents the ratio A2/A1 of the peak area A2 produced according to the second block to the peak area A1 produced according to the first block in the 1 H-NMR spectrum; The ratio H1 to H2 of the number of hydrogen atoms H1 in the 1 molar repeating unit of the second block representing the number of hydrogen atoms in the 1 molar repeating unit of the first block.

對於進行1H-NMR以得到代入數學式A中之K值的方法沒有特別的限制，且可使用本領域習知的任何方法。以上方法的一個例子述於本說明書的實例段落中。自NMR結果計算峰面積之方法為本領域習知者。例如，藉由檢視NMR結果，自嵌段1和嵌段2各者衍生的峰彼此未重疊時，可自各峰的面積簡單地計算峰面積的比；反之，當峰彼此重疊時，將重疊部分列入考慮，計算峰的比。有此領域知道各種解讀程式來經由解讀1H-NMR光譜以計算峰面積；例如，可以使用MestReC程式計算峰面積。 There is no particular limitation on the method of performing 1 H-NMR to obtain the K value substituted in Mathematical Formula A, and any method known in the art can be used. An example of the above method is described in the example paragraphs of this specification. Methods for calculating the peak area from NMR results are well known in the art. For example, by examining the NMR results, when the peaks derived from each of the block 1 and the block 2 do not overlap each other, the ratio of the peak areas can be simply calculated from the area of each peak; conversely, when the peaks overlap each other, the overlapping portions are overlapped. Consider the calculation and calculate the peak ratio. Various interpretation programs are known in the art to calculate the peak area by interpreting the 1 H-NMR spectrum; for example, the peak area can be calculated using the MestReC program.

嵌段共聚物之各嵌段的密度(其用以得到代入數學式A中的D值)可藉使用本領域習知的浮力法測定出。例如，可藉由分析沒入溶劑(如乙醇，已知其於空氣中之質量和密度)中之嵌段共聚物的質量而測得密度。例 如，使僅由構成以上嵌段之單體構成的均聚物進行浮力法，可測得嵌段的密度。 The density of each block of the block copolymer, which is used to obtain the value of D substituted in Mathematical Formula A, can be determined by buoyancy methods well known in the art. For example, the density can be measured by analyzing the mass of the block copolymer that is immersed in a solvent such as ethanol, which is known to be in mass and density in air. example For example, the density of the block can be measured by subjecting a homopolymer composed of only the monomers constituting the above block to a buoyancy method.

如前述者，代入數學式A中的M值對應於嵌段共聚物中之嵌段的重複單元的莫耳質量比。此莫耳質量可藉本領域習知的任何方法得到；例如，可得到M值為構成嵌段共聚物中之嵌段的單體的莫耳質量比。此情況中，嵌段共聚物的任一嵌段由二或更多種類型的單體所構成時，在以上嵌段中之以上二或更多類型的單體中，最大量(以莫耳數計)單體的莫耳質量可代入計算M值所須的莫耳質量值。 As described above, the M value substituted into Mathematical Formula A corresponds to the molar mass ratio of the repeating unit of the block in the block copolymer. This molar mass can be obtained by any method known in the art; for example, a molar mass ratio of the M value to the monomer constituting the block in the block copolymer can be obtained. In this case, when any block of the block copolymer is composed of two or more types of monomers, the maximum amount (in moles) of the above two or more types of monomers in the above block The molar mass of the monomer can be substituted into the molar mass value required to calculate the M value.

如前述者，代入數學式A中的L值對應於嵌段共聚物的1mole嵌段重複單元所含之氫原子數的比。以上比亦可基於各重複單元的化學結構而得到；例如，自構成嵌段共聚物之各嵌段的單體之化學結構中的氫原子數或藉1H-NMR得到。亦在此情況中，當嵌段共聚物中之任一嵌段係由二或更多種類型的單體所構成時，在以上嵌段中之以上二或更多類型的單體中之最大量的單體(以莫耳數計)之莫耳質量可代入計算L值所須之莫耳質量的值。 As described above, the L value substituted into Mathematical Formula A corresponds to the ratio of the number of hydrogen atoms contained in the 1mole block repeating unit of the block copolymer. The above ratio can also be obtained based on the chemical structure of each repeating unit; for example, the number of hydrogen atoms in the chemical structure of the monomer constituting each block of the block copolymer or by 1 H-NMR. Also in this case, when any of the block copolymers is composed of two or more types of monomers, the most of the above two or more types of monomers in the above block The mass of a large number of monomers (in moles) can be substituted into the value of the molar mass required to calculate the L value.

數學式A的X係嵌段共聚物中之嵌段1和嵌段2之間的量比的數值。嵌段共聚物中之各嵌段的比通常係基於分子量(由凝膠穿透層析法(GPC)之類得到)測定。但是，本發明者發現，使用以上的一般方法時，未正確地反映嵌段之間的比且，因此，該方法無法如原始設計地實現嵌段共聚物。例如，在試圖藉由使用嵌段共聚物的任一 嵌段作為巨引發劑地合成時(此將在本說明書中述於下文中)，GPC無法單獨驗證嵌段共聚物之合成(含有其各嵌段達到個別目標含量)中的偶發失誤，其發生取決於巨引發劑和單體的反應性。 The numerical value of the ratio between the block 1 and the block 2 in the X-based block copolymer of Math. The ratio of each block in the block copolymer is usually determined based on molecular weight (obtained by gel permeation chromatography (GPC) or the like). However, the inventors have found that when the above general method is used, the ratio between the blocks is not correctly reflected and, therefore, the method cannot realize the block copolymer as originally designed. For example, in an attempt to use any of the block copolymers When the block is synthesized as a macroinitiator (which will be described later in this specification), GPC cannot separately verify the occurrence of the block copolymer synthesis (including its individual blocks reaching individual target content), which occurs It depends on the reactivity of the macroinitiator and the monomer.

另一例子中，數學式A的X可為約1.3或更高，約1.35或更高，約1.4或更高，約1.45或更高，約1.5或更高，約1.6或更高，或約1.65或更高。另一例子中，數學式A的X亦可為10或更低，9.5或更低，9或更低，8.5或更低，8或更低，7.5或更低，或7或更低。 In another example, the X of Formula A can be about 1.3 or higher, about 1.35 or higher, about 1.4 or higher, about 1.45 or higher, about 1.5 or higher, about 1.6 or higher, or about 1.65 or higher. In another example, the X of Mathematical Formula A may also be 10 or lower, 9.5 or lower, 9 or lower, 8.5 or lower, 8 or lower, 7.5 or lower, or 7 or lower.

另一例子中，數學式A的X可在約2.5至6.7，約2.5至5，或約2.8至5範圍內。X值落在以上範圍內時，嵌段共聚物可形成所謂的圓柱形結構或主要為圓柱形的自組結構。另一例子中，數學式A的X亦可為約1.65至2.5，約1.8至2.5，或約1.8至2.3。當X值在以上範圍內時，嵌段共聚物可形成所謂的層狀結或主要為層狀結構的自組結構。 In another example, the X of Mathematical Formula A can range from about 2.5 to 6.7, from about 2.5 to 5, or from about 2.8 to 5. When the X value falls within the above range, the block copolymer may form a so-called cylindrical structure or a self-assembled structure which is mainly cylindrical. In another example, the X of Formula A can also be from about 1.65 to 2.5, from about 1.8 to 2.5, or from about 1.8 to 2.3. When the X value is in the above range, the block copolymer may form a so-called layered structure or a self-assembled structure mainly composed of a layered structure.

例如，當以上嵌段1係含有無鹵原子之芳族結構的嵌段且與被一或多個鹵原子部分取代的嵌段2一起含於嵌段共聚物中時，或者當嵌段1係含有側鏈的嵌段並與含有一或多個鹵原子的嵌段2一起含於嵌段共聚物中時，如本說明書以下描述者，X值落在前述範圍內的嵌段共聚物能夠有效地形成垂直定向結構。 For example, when the above block 1 contains a block of an aromatic structure having no halogen atom and is contained in the block copolymer together with the block 2 partially substituted by one or more halogen atoms, or when the block 1 is When a block containing a side chain is contained in a block copolymer together with a block 2 containing one or more halogen atoms, a block copolymer having an X value falling within the foregoing range can be effective as described later in the specification. The ground forms a vertical orientation structure.

如本說明書中前述者，該嵌段共聚物滿足選自前述條件1至8中之任一、二或更多個條件。 As described above in the present specification, the block copolymer satisfies a condition selected from any one of the foregoing conditions 1 to 8, two or more conditions.

例如，該嵌段共聚物可為滿足條件1、條件2、條件3、條件4、條件5、條件6、條件7、或條件8之嵌段共聚物。 For example, the block copolymer may be a block copolymer satisfying Condition 1, Condition 2, Condition 3, Condition 4, Condition 5, Condition 6, Condition 7, or Condition 8.

一個例子中，以上嵌段共聚物可含有嵌段1(其滿足前述條件中條件2至5中之任一、二或更多者)和嵌段2，其中嵌段的表面能量差述於條件6。 In one example, the above block copolymer may contain block 1 (which satisfies any one of the conditions 2 to 5, two or more of the foregoing conditions) and block 2, wherein the surface energy difference of the block is described in the condition 6.

另一例子中，以上嵌段共聚物可含有嵌段1(其滿足條件2至5中之任一、二或更多者)和嵌段2，其滿足條件8中所述之嵌段1對嵌段2的比，其中嵌段的表面能量差如條件6中所述者。 In another example, the above block copolymer may contain block 1 (which satisfies any, two or more of conditions 2 to 5) and block 2, which satisfy the block 1 pair described in Condition 8. The ratio of block 2, wherein the surface energy difference of the block is as described in Condition 6.

不欲限於理論，滿足條件2至5中之任一者的嵌段1可具有晶體或液晶的性質，並，因此，可在形成自組結構的期間內被規則地包裝。此情況中，當嵌段1和嵌段2滿足與表面能量差相關的條件6時，嵌段1和嵌段2各者形成的區域實質上經中和並，因此，自組膜可垂直定向，無論膜形成於其上的表面之性質如何。當前述嵌段比滿足條件8中的X值時，以上中和作用的效果被最大化，並因此，垂直定向的效果亦被最大化。 Without wishing to be bound by theory, the block 1 satisfying any of the conditions 2 to 5 may have a property of crystal or liquid crystal, and, therefore, may be regularly packaged during the formation of the self-assembled structure. In this case, when the block 1 and the block 2 satisfy the condition 6 related to the surface energy difference, the regions formed by each of the block 1 and the block 2 are substantially neutralized and, therefore, the self-assembled film can be vertically oriented. Regardless of the nature of the surface on which the film is formed. When the aforementioned block ratio satisfies the X value in Condition 8, the effect of the above neutralization is maximized, and therefore, the effect of the vertical orientation is also maximized.

作為額外條件，嵌段共聚物的數量平均分子量(Mn)可為，例如，在3,000至300,000範圍內。本說明書中，術語“數量平均分子量”是指以GPC測定並基於聚苯乙烯標準品校正的數值，且，除非特定指明，否則本說明書中之術語“分子量”是指數量平均分子量。另一例子中，Mn可為，例如，3000或更高，5000或更高，7000 或更高，9000或更高，11000或更高，13000或更高，或15000或更高。又另一例子中，Mn可為約250000或更低，200000或更低，180000或更低，160000或更低，140000或更低，120000或更低，100000或更低，90000或更低，80000或更低，70000或更低，60000或更低，50000或更低，40000或更低，30000或更低，或25000或更低。嵌段共聚物可具有多分散性(Mw/Mn)在1.01至1.60範圍內。另一例子中，Mw/Mn可為約1.1或更高，約1.2或更高，約1.3或更高，或約1.4或更高。 As an additional condition, the number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 3,000 to 300,000. In the present specification, the term "number average molecular weight" means a value measured by GPC and corrected based on a polystyrene standard, and the term "molecular weight" in the present specification means a number average molecular weight unless specifically specified. In another example, Mn can be, for example, 3000 or higher, 5000 or higher, 7000 Or higher, 9000 or higher, 11000 or higher, 13000 or higher, or 15000 or higher. In still another example, Mn may be about 250,000 or less, 200,000 or less, 180,000 or less, 160,000 or less, 140,000 or less, 120,000 or less, 100,000 or less, 90,000 or less, 80000 or lower, 70,000 or lower, 60,000 or lower, 50,000 or lower, 40,000 or lower, 30,000 or lower, or 25,000 or lower. The block copolymer may have a polydispersity (Mw/Mn) in the range of 1.01 to 1.60. In another example, Mw/Mn can be about 1.1 or higher, about 1.2 or higher, about 1.3 or higher, or about 1.4 or higher.

在此範圍內，嵌段共聚物能展現足夠的自組性質。可以考慮感興趣的自組結構等，調整嵌段共聚物的Mn等。 Within this range, the block copolymers exhibit sufficient self-organizing properties. The Mn or the like of the block copolymer can be adjusted in consideration of the self-assembled structure or the like of interest.

可藉，例如，控制嵌段共聚物的結構，達到前述條件。例如，滿足以上條件之一或多者的嵌段共聚物的嵌段1和嵌段2之一或二者可包括至少一個芳族結構。嵌段1和嵌段2二者可各自包括芳族結構；此情況中，嵌段1或嵌段2之任一者含括的芳族結構可以與其他嵌段的芳族結構相同或不同。此外，滿足以上條件之一或多者的嵌段共聚物中之嵌段1和嵌段2中之至少一者可含有前述側鏈或一或多個本說明書中下文將描述的鹵原子，且該側鏈和鹵原子可取代以上芳族結構的一或多個部分。本申請案之嵌段共聚物可含有二或更多個嵌段。 The foregoing conditions can be achieved, for example, by controlling the structure of the block copolymer. For example, one or both of block 1 and block 2 of the block copolymer satisfying one or more of the above conditions may include at least one aromatic structure. Both block 1 and block 2 may each comprise an aromatic structure; in this case, the aromatic structure encompassed by either of block 1 or block 2 may be the same or different from the aromatic structure of the other blocks. Further, at least one of the block 1 and the block 2 in the block copolymer satisfying one or more of the above conditions may contain the aforementioned side chain or one or more halogen atoms which will be described later in the specification, and The side chain and halogen atom can replace one or more moieties of the above aromatic structure. The block copolymer of the present application may contain two or more blocks.

如前述者，以上嵌段共聚物的嵌段1和/或嵌段2可各自包括芳族結構。芳族結構含括於嵌段1和嵌段 2中的一或二者。兩種類型的嵌段各自包括芳族結構時，一種類型的嵌段含括的芳族結構可以與其他類型的嵌段中含括者相同或不同。 As mentioned above, block 1 and/or block 2 of the above block copolymer may each comprise an aromatic structure. Aromatic structure is included in block 1 and block One or both of 2. Where the two types of blocks each comprise an aromatic structure, one type of block may comprise the same aromatic structure as the other types of blocks.

本說明書中，術語“芳族結構”可指芳族化合物的結構，“芳基”可指自芳族化合物衍生的單價基團，而“伸芳基”可指自芳族化合物衍生的二價基團。除非特定指明，否則以上描述中的“芳族化合物”是指含有苯環或二或更多個苯環之化合物(其藉共享一或兩個碳原子或藉任何鏈接劑彼此連接)，或是指該化合物的衍生物。因此，以上芳基，其為自芳族化合物衍生的單價基團，可指氫原子自芳族化合物斷裂所形成的基團共價鍵結的取代基，而以上伸芳基，其係自芳族化合物衍生的二價基團，可指兩個氫原子自芳族化合物斷裂所形成的基團共價鍵結之取代基。以上芳基或伸芳基可為具有，例如，6至30個碳原子，6至25個碳原子，6至21個碳原子，6至18個碳原子，或6至13個碳原子，的芳基或伸芳基。例示芳基或伸芳基亦可為單價或二價基團，其衍生自苯、萘、偶氮苯、蒽、菲、稠四苯(tetracene)、芘(pyrene)、苯并芘之類。 In the present specification, the term "aromatic structure" may refer to the structure of an aromatic compound, "aryl" may refer to a monovalent group derived from an aromatic compound, and "extended aryl" may refer to a divalent derived from an aromatic compound. Group. Unless otherwise specified, "aromatic compound" in the above description means a compound containing a benzene ring or two or more benzene rings (which are linked to each other by sharing one or two carbon atoms or by any linking agent), or Refers to a derivative of this compound. Therefore, the above aryl group, which is a monovalent group derived from an aromatic compound, may refer to a substituent in which a hydrogen atom is covalently bonded to a group formed by cleavage of an aromatic compound, and the above aryl group is derived from an aromatic group. A divalent group derived from a group compound may refer to a substituent in which two hydrogen atoms are covalently bonded to a group formed by cleavage of an aromatic compound. The above aryl or extended aryl group may have, for example, 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. Aryl or aryl. Exemplary aryl or extended aryl groups can also be monovalent or divalent groups derived from benzene, naphthalene, azobenzene, anthracene, phenanthrene, tetracene, pyrene, benzindene, and the like.

以上芳族結構可為含括於嵌段的主鏈中之結構，或其可為連接至嵌段的主鏈之呈側鏈形式之結構。藉由適當地控制各嵌段中可含有的芳族結構，可控制前述條件。 The above aromatic structure may be a structure included in the main chain of the block, or it may be a structure in the form of a side chain attached to the main chain of the block. The aforementioned conditions can be controlled by appropriately controlling the aromatic structure which can be contained in each block.

一個例子中，滿足前述條件之一或多者的嵌 段共聚物可含有嵌段1(其含有側鏈)和不同於嵌段1的嵌段2。以上描述中，側鏈可為含有8或更多個成鏈原子的側鏈，此將於以下述於本說明書中。此情況中，嵌段1可為滿足前述條件2、3、4和5中之任一、二或更多者或全數的嵌段。 In one example, an inlay that satisfies one or more of the foregoing conditions The segment copolymer may contain block 1 (which contains a side chain) and block 2 different from block 1. In the above description, the side chain may be a side chain containing 8 or more chain-forming atoms, which will be described below in the present specification. In this case, block 1 may be a block that satisfies any, two or more, or all of the foregoing conditions 2, 3, 4, and 5.

以上嵌段1可包括環結構，且以上側鏈可取代環結構的一或多個部分。此環結構可為前述芳族結構(即，芳基或伸芳基)或脂環狀環結構。此情況中，環結構可為不含有鹵原子的環結構。 The above block 1 may include a ring structure, and the above side chain may replace one or more portions of the ring structure. This ring structure may be the aforementioned aromatic structure (i.e., aryl or aryl group) or a alicyclic ring structure. In this case, the ring structure may be a ring structure containing no halogen atom.

本說明書中，除非特定指明，否則“脂環狀環結構”是指芳族環結構以外的環型烴原子結構。脂環狀環結構可以單價基團或二價基團形式含於嵌段共聚物中。除非特定指明，否則以上脂環狀環結構是指具有，例如，例如，3至30個碳原子，3至25個碳原子，3至21個碳原子，3至18個碳原子，或3至13個碳原子，的脂環狀環結構。 In the present specification, unless otherwise specified, the "alicyclic ring structure" means a cyclic hydrocarbon atom structure other than the aromatic ring structure. The alicyclic ring structure may be contained in the block copolymer in the form of a monovalent group or a divalent group. Unless otherwise specified, the above aliphatic cyclic ring structure means having, for example, 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms, a lipid ring structure.

與以上嵌段1一起含於嵌段共聚物中之嵌段2係化學上與嵌段1不同的嵌段。以上嵌段2可為含鹵原子(例如，氯原子或氟原子)的嵌段。以上嵌段2可含有1或更多，2或更多，3或更多，4或更多或5或更多個鹵原子。鹵原子數亦可為，例如，30或更少，25或更少，20或更少，15或更少，10或更少，9或更少，8或更少，7或更少，6或更少，或5或更少。以上嵌段2可包括環結構，且該環結構可經以上鹵原子部分取代。以上環結構可 為前述芳族結構，其為芳基或伸芳基。 The block 2 contained in the block copolymer together with the above block 1 is a block which is chemically different from the block 1. The above block 2 may be a block containing a halogen atom (for example, a chlorine atom or a fluorine atom). The above block 2 may contain 1 or more, 2 or more, 3 or more, 4 or more or 5 or more halogen atoms. The number of halogen atoms may also be, for example, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 Or less, or 5 or less. The above block 2 may include a ring structure, and the ring structure may be partially substituted with the above halogen atom. The above ring structure can In the foregoing aromatic structure, it is an aryl group or an aryl group.

本申請案中，術語“側鏈”是指連接至聚合物主鏈的鏈，且術語“成鏈原子”是指形成嵌段共聚物的以上側鏈之原子，即，形成側鏈的直鏈結構之原子。此側鏈可為直鏈型或支鏈型，但成鏈原子數僅以形成最長直鏈的原子數計，而鍵結至以上成鏈原子的其他原子(如，當成鏈原子係碳原子、氫原子之類，其鍵結至碳原子)不列入計算。例如，在支鏈型鏈的情況中，成鏈原子數可計為形成最長鏈之成鏈原子數。例如，側鏈是正戊基時，所有的成鏈原子是碳且成鏈原子數是5，同樣地，當側鏈是2-甲基戊基時，所有的成鏈原子是碳且成鏈原子數是5。成鏈原子的例子可包括碳、氧、硫、和氮；適當的成鏈原子可為碳、氧和氮中之任一者，或碳和氧中之任一者。在鏈中的成鏈原子數可為8或更多，9或更多，10或更多，11或更多，或12或更多。鏈中的成鏈原子數亦可為30或更少，25或更少，20或更少，或16或更少。 In the present application, the term "side chain" refers to a chain attached to a polymer backbone, and the term "chained atom" refers to an atom forming the above side chain of a block copolymer, ie, a linear chain forming a side chain. The atom of the structure. The side chain may be linear or branched, but the number of chain atoms is only the number of atoms forming the longest straight chain, and the other atoms bonded to the above chain atoms (for example, when forming a chain atomic carbon atom, Hydrogen atoms and the like, which are bonded to carbon atoms are not included in the calculation. For example, in the case of a branched chain, the number of chain atoms can be counted as the number of chain atoms forming the longest chain. For example, when the side chain is n-pentyl, all of the chain-forming atoms are carbon and the number of chain atoms is 5. Similarly, when the side chain is 2-methylpentyl, all of the chain-forming atoms are carbon and form a chain atom. The number is 5. Examples of the chain-forming atom may include carbon, oxygen, sulfur, and nitrogen; a suitable chain-forming atom may be any of carbon, oxygen, and nitrogen, or any of carbon and oxygen. The number of chained atoms in the chain can be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of chain atoms in the chain may also be 30 or less, 25 or less, 20 or less, or 16 or less.

可藉由使得嵌段共聚物中的嵌段1包括具8個更多個成鏈原子的鏈作為連接至嵌段的側鏈而控制前述條件。本說明書中，術語“鏈”和“側鏈”可指共通標的。 The foregoing conditions can be controlled by making the block 1 in the block copolymer include a chain having 8 more chain-forming atoms as a side chain attached to the block. In the present specification, the terms "chain" and "side chain" may refer to a common standard.

如前述者，側鏈可為含有8或更多，9或更多，10或更多，11或更多或12或更多個成鏈原子的鏈。側鏈中的成鏈原子數亦可為30或更少，25或更少，20或更少，或16或更少。成鏈原子各者可為碳、氧、氮和硫中之任一者，或其可適當地為碳和氧中之任一者。 As the foregoing, the side chain may be a chain containing 8 or more, 9 or more, 10 or more, 11 or more or 12 or more chain-forming atoms. The number of chain atoms in the side chain may also be 30 or less, 25 or less, 20 or less, or 16 or less. Each of the chain-forming atoms may be any of carbon, oxygen, nitrogen, and sulfur, or it may suitably be any of carbon and oxygen.

烴鏈(如烷基、烯基和炔基)可為側鏈的例子。以上烴鏈中的至少一個碳原子可經硫原子、氧原子、或氮原子取代。 Hydrocarbon chains such as alkyl, alkenyl and alkynyl groups can be examples of side chains. At least one carbon atom in the above hydrocarbon chain may be substituted with a sulfur atom, an oxygen atom, or a nitrogen atom.

側鏈連接至環結構(如芳族結構)時，該鏈可直接或藉鏈接劑連接至環結構。鏈接劑的例子包括氧原子、硫原子、-NR1-、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-和-X1-C(=O)-，其中R1可代表氫原子、烷基、烯基、炔基、烷氧基或芳基，且X1可代表單鍵、氧原子、硫原子、-NR2-、-S(=O)2-、伸烷基、伸烯基或伸炔基，其中R2可代表氫原子、烷基、烯基、炔基、烷氧基、或芳基。氧原子可例示為適當鏈接劑。側鏈可連接至芳族結構，例如，藉氧原子或氮原子。 When the side chain is attached to a ring structure (such as an aromatic structure), the chain can be attached to the ring structure either directly or by a linker. Examples of the linking agent include an oxygen atom, a sulfur atom, -NR 1 -, -S(=O) 2 -, a carbonyl group, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X 1 - and -X 1 -C(=O)-, wherein R 1 may represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and X 1 may represent a single bond, an oxygen atom, a sulfur atom, NR 2 -, -S(=O) 2 -, alkylene, alkenyl or alkynyl, wherein R 2 may represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group. The oxygen atom can be exemplified as a suitable linker. The side chain can be attached to an aromatic structure, for example, by an oxygen atom or a nitrogen atom.

前述環結構(如芳族結構)連接(以側鏈形式)至嵌段的主鏈時，以上芳族結構亦可直接或藉鏈接劑連接至主鏈。此情況中，鏈接劑的例子可包括氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1可代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基。芳族結構連接至主鏈之適當鏈接劑的例子可包括，但不限於，-C(=O)-O-和-O-C(=O)-。 When the aforementioned ring structure (e.g., an aromatic structure) is attached (in the form of a side chain) to the main chain of the block, the above aromatic structure may be attached to the main chain directly or by a linking agent. In this case, examples of the linking agent may include an oxygen atom, a sulfur atom, -S(=O) 2 -, a carbonyl group, an alkylene group, an alkenyl group, an alkynylene group, -C(=O)-X 1 - or -X 1 -C(=O)-, wherein X 1 may represent a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an alkenyl group or an alkynyl group. Examples of suitable linking agents for attachment of the aromatic structure to the backbone can include, but are not limited to, -C(=O)-O- and -OC(=O)-.

另一實例中，含括於嵌段共聚物的嵌段1和/或嵌段2中之芳族結構可含有1或更多，2或更多，3或更多，4或更多或5或更多個鹵原子。鹵原子數亦可為，例如，30或更少，25或更少，20或更少，15或更少，或 10或更少。鹵原子的例子可包括氟和氯，且其可有利地使用氟。包括具一或多個鹵原子的芳族結構的此嵌段可以藉由與其他嵌段具有足夠的作用而有效率地實現相分離結構。 In another example, the aromatic structure included in block 1 and/or block 2 of the block copolymer may contain 1 or more, 2 or more, 3 or more, 4 or more or 5 Or more halogen atoms. The number of halogen atoms may also be, for example, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. Examples of the halogen atom may include fluorine and chlorine, and it may be advantageous to use fluorine. This block including an aromatic structure having one or more halogen atoms can efficiently realize a phase separation structure by having a sufficient effect with other blocks.

含有一或多個鹵原子的說明性芳族結構可為具6至30個碳原子，6至25個碳原子，6至21個碳原子，6至18個碳原子或6至13個碳原子的芳族結構，但不限於此。 An illustrative aromatic structure containing one or more halogen atoms may have from 6 to 30 carbon atoms, from 6 to 25 carbon atoms, from 6 to 21 carbon atoms, from 6 to 18 carbon atoms or from 6 to 13 carbon atoms. The aromatic structure, but is not limited to this.

嵌段共聚物的嵌段1和嵌段2二者包括芳族結構，以在結構中實現足夠程度的相分離時，嵌段1可設定為不含括鹵原子的芳族結構，而嵌段2設定為含括具一或多個鹵原子的芳族結構。此外，前述側鏈可直接或藉含氧或氮的鏈接劑連接至以上嵌段1的芳族結構。 Both block 1 and block 2 of the block copolymer comprise an aromatic structure, in order to achieve a sufficient degree of phase separation in the structure, block 1 can be set to contain no aromatic structures including halogen atoms, and blocks 2 is set to include an aromatic structure having one or more halogen atoms. Further, the aforementioned side chain may be attached to the aromatic structure of the above block 1 directly or by a linking agent containing oxygen or nitrogen.

嵌段共聚物含有具側鏈的嵌段時，該嵌段可為，例如，以下結構式1所示嵌段。以上嵌段可為含有以下結構式1所示結構單元作為主要組份之嵌段。本說明書中，含有特別的結構單元作為主要組份之嵌段可指嵌段含有結構單元為(以重量計)60%或更多，70%或更多，80%或更多，90%或更多，或95%或更多之情況，或者該結構單元在該嵌段中的所含比例為60mol%或更高，70mol%或更高，80mol%或更高，90mol%或更高，或95mol%或更高之情況。 When the block copolymer contains a block having a side chain, the block may be, for example, a block represented by the following structural formula 1. The above block may be a block containing a structural unit represented by the following structural formula 1 as a main component. In the present specification, a block containing a specific structural unit as a main component may mean that the block contains structural units of (by weight) 60% or more, 70% or more, 80% or more, 90% or More, or 95% or more, or the proportion of the structural unit in the block is 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, Or 95 mol% or higher.

結構式1中，R代表氫原子或具1至4個碳原子的烷基；X代表單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1代表氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基；和Y代表單價取代基，其包括含括8或更多個成鏈原子之上述側鏈所連接的環結構。 In the formula 1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, a carbonyl group, an alkylene group, an alkenyl group , an alkynyl group, -C(=O)-X 1 - or -X 1 -C(=O)-, wherein X 1 represents an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, An alkenyl group or an alkynyl group; and Y represents a monovalent substituent comprising a ring structure to which the above-mentioned side chain comprising 8 or more chain-forming atoms is attached.

本申請案中，術語“單鍵”是指任何特別的原子不存在於對應區域中。例如，在結構式1中的X代表單鍵的情況中，可實現具有Y直接連接至聚合物鏈的結構。 In the present application, the term "single bond" means that any particular atom is not present in the corresponding region. For example, in the case where X in Structural Formula 1 represents a single bond, a structure having Y directly bonded to a polymer chain can be realized.

除非特定指明，否則本說明書中的術語“烷基”是指直鏈型、支鏈型或環型的烷基，其具1至20個碳原子，1至16個碳原子，1至12個碳原子，1至8個碳原子或1至4個碳原子，其可經一或多個取代基任意地部分取代(但是，當前述側鏈是指烷基時，該烷基可含8或更多，9或更多，10或更多，11或更多或12或更多個碳原子，此處烷基的碳原子數亦可為30或更少，25或更少，20或更少，或16或更少)。 Unless specifically indicated otherwise, the term "alkyl" as used in this specification refers to a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms, from 1 to 16 carbon atoms, from 1 to 12 a carbon atom, 1 to 8 carbon atoms or 1 to 4 carbon atoms, which may be optionally partially substituted by one or more substituents (however, when the aforementioned side chain means an alkyl group, the alkyl group may contain 8 or More, 9 or more, 10 or more, 11 or more or 12 or more carbon atoms, wherein the alkyl group may have a carbon number of 30 or less, 25 or less, 20 or more. Less, or 16 or less).

除非特定指明，否則本說明書中的術語“烯基”或“炔基”是指直鏈型、支鏈型或環型烯基或炔基，其 具2至20個碳原子，2至16個碳原子，2至12個碳原子，2至8個碳原子或2至4個碳原子，其可經一或多個取代基任意地部分取代(但是，作為前述側鏈的烯基或炔基可含有8或更多，9或更多，10或更多，11或更多或12或更多個碳原子，烯基或炔基的碳原子數亦可為30或更低，25或更低，20或更低，或16或更低)。 The term "alkenyl" or "alkynyl" as used herein, unless otherwise specified, refers to a straight-chain, branched or cyclic alkenyl or alkynyl group, which Having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms or 2 to 4 carbon atoms, which may be optionally partially substituted by one or more substituents ( However, the alkenyl or alkynyl group as the aforementioned side chain may contain 8 or more, 9 or more, 10 or more, 11 or more or 12 or more carbon atoms, a carbon atom of an alkenyl group or an alkynyl group. The number can also be 30 or lower, 25 or lower, 20 or lower, or 16 or lower).

除非特定指明，否則本說明書中的術語“伸烷基”是指直鏈型、支鏈型或環型伸烷基，其具1至20個碳原子，1至16個碳原子，1至12個碳原子，1至8個碳原子或1至4個碳原子，其可經一或多個取代基任意地部分取代。 Unless otherwise specified, the term "alkylene" as used in this specification refers to a linear, branched or cyclic alkylene group having from 1 to 20 carbon atoms, from 1 to 16 carbon atoms, from 1 to 12 One carbon atom, 1 to 8 carbon atoms or 1 to 4 carbon atoms, which may be optionally partially substituted with one or more substituents.

除非特定指明，否則本說明書中的術語“伸烯基”或“伸炔基”是指直鏈型、支鏈型或環型伸烯基或伸炔基，其具1至20個碳原子，1至16個碳原子，1至12個碳原子，1至8個碳原子或1至4個碳原子，其可經一或多個取代基任意地部分取代。 The term "alkenyl" or "alkenyl" as used in this specification, unless otherwise specified, means a straight-chain, branched or cyclic alkenyl or alkynyl group having from 1 to 20 carbon atoms. 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, which may be optionally partially substituted by one or more substituents.

另一例子中，結構式1中的X亦代表-C(=O)O-或-OC(=O)-。 In another example, X in Structural Formula 1 also represents -C(=O)O- or -OC(=O)-.

結構式1中的Y代表含有前述鏈的取代基，其可為，例如，包括具6至18個碳原子或6至12個碳原子之芳族結構的取代基。上述鏈可為，例如，具8或更多，9或更多，10或更多，11或更多或12或更多個碳原子的直鏈烷基。此烷基亦含有30或更少，25或更少，20或更少或16或更少個碳原子。上述鏈可直接或藉前述鏈 接劑連接至芳族結構。 Y in the structural formula 1 represents a substituent containing the aforementioned chain, and may be, for example, a substituent including an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms. The above chain may be, for example, a linear alkyl group having 8 or more, 9 or more, 10 or more, 11 or more or 12 or more carbon atoms. The alkyl group also contains 30 or less, 25 or less, 20 or less or 16 or fewer carbon atoms. The above chain can be directly or by the aforementioned chain The binder is attached to the aromatic structure.

另一例子中，由以上結構式1表示之嵌段1結構單元亦可藉以下結構式2表示。 In another example, the block 1 structural unit represented by the above structural formula 1 may also be represented by the following structural formula 2.

結構式2中，R代表氫原子或具1至4個碳的烷基；X代表-C(=O)-O-，P代表具6至12個碳原子的伸芳基，Q代表氧原子，Z代表具8或更多個成鏈原子的前述側鏈。 In Structural Formula 2, R represents a hydrogen atom or an alkyl group having 1 to 4 carbons; X represents -C(=O)-O-, P represents an extended aryl group having 6 to 12 carbon atoms, and Q represents an oxygen atom. Z represents the aforementioned side chain having 8 or more chain-forming atoms.

另一例子中，結構式2的P可代表伸苯基，且，在另一例子中，Z可代表具9至20個碳原子，9至18個碳原子，9至16個碳原子，10至16個碳原子，11至16個碳原子，或12至16個碳原子的直鏈烷基。P代表伸苯基時，Q可連接至以上伸苯基的對位。一或多個取代基可任意地部分取代以上烷基、伸芳基、伸苯基和側鏈。 In another example, P of Structural Formula 2 can represent a phenylene group, and, in another example, Z can represent 9 to 20 carbon atoms, 9 to 18 carbon atoms, 9 to 16 carbon atoms, 10 A linear alkyl group of 16 carbon atoms, 11 to 16 carbon atoms, or 12 to 16 carbon atoms. When P represents a phenyl group, Q can be attached to the para position of the above phenyl group. One or more substituents may optionally partially replace the above alkyl group, aryl group, phenyl group and side chain.

當嵌段共聚物含有包括具一或多個鹵原子的芳族結構之嵌段(例如，嵌段2)時，該嵌段可由包含藉以下結構式3表示的結構單元之嵌段例示。此情況中，以下 結構式3所示結構單元可含於嵌段中作為主要組份。 When the block copolymer contains a block including an aromatic structure having one or more halogen atoms (for example, block 2), the block may be exemplified by a block containing a structural unit represented by the following structural formula 3. In this case, the following The structural unit represented by Structural Formula 3 may be contained in the block as a main component.

在結構式3中，X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基；和W代表具有至少一個鹵原子的芳基。 In Structural Formula 3, X 2 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X 1 - or -X 1 -C(=O)-, wherein X 1 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an extended alkenyl group or an alkynylene group; and W represents at least An aryl group of a halogen atom.

另一例子中，結構式3的X2可代表單鍵或伸烷基。 In another example, X 2 of Structural Formula 3 can represent a single bond or an alkylene group.

結構式3中，W所代表的芳基可為具6至12個碳原子的芳基或苯基，其中芳基或苯基可含1或更多，2或更多，3或更多，4或更多或5或更多個鹵原子。鹵原子數亦可為，例如，30或更少，25或更少，20或更少，15或更少，或10或更少。對於鹵原子，可例示為氟原子。 In the structural formula 3, the aryl group represented by W may be an aryl group or a phenyl group having 6 to 12 carbon atoms, wherein the aryl group or the phenyl group may have 1 or more, 2 or more, 3 or more, 4 or more or 5 or more halogen atoms. The number of halogen atoms may also be, for example, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. As the halogen atom, a fluorine atom can be exemplified.

另一例子中，結構式3所示結構單元亦可藉以下結構式4表示。 In another example, the structural unit shown in Structural Formula 3 can also be represented by the following Structural Formula 4.

結構式4中，X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基；且R1至R5各者獨立地代表氫、烷基、鹵烷基或鹵原子，其中一或多個鹵原子含於標記為R1至R5的位置。 In the formula 4, X 2 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X 1 - or - X 1 -C(=O)-, wherein X 1 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an extended alkenyl group or an alkynylene group; and R 1 to R 5 Each independently represents a hydrogen, an alkyl group, a haloalkyl group or a halogen atom, wherein one or more halogen atoms are contained at positions labeled R 1 to R 5 .

結構式4中，R1至R5各者獨立地代表氫原子、具1至4個碳原子的烷基、具1至4個碳原子的鹵烷基、或鹵素，其中鹵素可為氯或氟。 In the formula 4, each of R 1 to R 5 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or a halogen, wherein the halogen may be chlorine or fluorine.

結構式4中，R1至R5中之2或更多，3或更多，4或更多，5或更多者或6或更多者可各自代表鹵素。對於以上鹵素的最大數目沒有特別的限制；其可為，例如，12或更少，8或更少，或7或更少。 In Structural Formula 4, 2 or more of R 1 to R 5 , 3 or more, 4 or more, 5 or more or 6 or more may each represent a halogen. There is no particular limitation on the maximum number of halogens above; it may be, for example, 12 or less, 8 or less, or 7 or less.

如說明書中早先所述者，嵌段共聚物可為含有任何兩個前述結構單元的二嵌段共聚物，或者其可為除了前兩種類型的嵌段的一或二者以外，另含有其他類型的 嵌段之嵌段共聚物。 As described earlier in the specification, the block copolymer may be a diblock copolymer containing any two of the foregoing structural units, or it may be in addition to one or both of the first two types of blocks, and other Type of Block copolymers of blocks.

一個例子中，嵌段共聚物中之兩種類型的嵌段之任一者(例如，嵌段1和嵌段2)可為可交聯的嵌段。施用可交聯的嵌段作為嵌段之任一者，可改良嵌段共聚物的蝕刻選擇性之類。藉由將交聯取代基引至嵌段中，嵌段可轉變成可交聯的嵌段。交聯官能基的例子可包括，但不限於官能基，如苄醯基-苯氧基、烯氧羰基、(甲基)丙烯醯基、烯氧烷基、含疊氮化物的官能基(如疊氮化烷基羰氧基、環氧丙基疊氮化物、和羥基苯基疊氮化物)、含硫官能基和含有不飽和雙鍵(其可因暴於紫外射線或熱而形成交聯結構)的官能基。 In one example, any of the two types of blocks in the block copolymer (eg, block 1 and block 2) can be crosslinkable blocks. The application of the crosslinkable block as a block can improve the etching selectivity of the block copolymer and the like. By introducing a cross-linking substituent into the block, the block can be converted into a crosslinkable block. Examples of cross-linking functional groups may include, but are not limited to, functional groups such as benzhydryl-phenoxy, olefinoxycarbonyl, (meth)acrylinyl, oxyalkylene, azide-containing functional groups (eg, Alkyl carbonyloxy alkoxylate, epoxypropyl azide, and hydroxyphenyl azide), sulfur-containing functional groups and containing unsaturated double bonds (which can form crosslinks due to exposure to ultraviolet radiation or heat) Functional group).

以上交聯官能基可含於前述嵌段各者中或引至各嵌段中作為獨立的結構單元。 The above cross-linking functional groups may be contained in each of the aforementioned blocks or introduced into each block as a separate structural unit.

對於製備嵌段共聚物之方法沒有特別的限制。嵌段共聚物可經聚合，例如，藉活性基團聚合反應(LRP)方法，其例子包括藉陰離子聚合反應合成，其中有機稀土金屬錯合物或有機鹼金屬化合物作為聚合反應引發劑，此在鹼金屬和無機酸鹽(如鹼土金屬)存在下進行；藉陰離子聚合法合成，其中有機鹼金屬化合物作為聚合反應引發劑，此在有機鋁化合物存在下進行；原子轉移自由基聚合反應(ATRP)方法，其中ATPR劑作為聚合反應控制劑；藉電子轉移(ARGET)ATRP方法再生的活化劑，其中ATRP劑用作為聚合反應控制劑，但聚合反應發生於有機或無機還原劑(其產生電子)存在時；用於連續活化劑再生 (ICAR)ATRP方法之引發劑；藉可逆性加成-裂鏈轉移(RAFT)之聚合反應，其中，使用無機還原劑和RAFT劑；及使用有機碲化合物作為引發劑之方法，可於其中選用適當的方法。 There is no particular limitation on the method of preparing the block copolymer. The block copolymer may be polymerized, for example, by a reactive group polymerization (LRP) method, and examples thereof include synthesis by an anionic polymerization in which an organic rare earth metal complex or an organic alkali metal compound is used as a polymerization initiator. In the presence of an alkali metal and a mineral acid salt (such as an alkaline earth metal); synthesized by an anionic polymerization method in which an organic alkali metal compound is used as a polymerization initiator, which is carried out in the presence of an organoaluminum compound; atom transfer radical polymerization (ATRP) a method in which an ATPR agent is used as a polymerization control agent; an activator regenerated by an electron transfer (ARGET) ATRP method, wherein an ATRP agent is used as a polymerization control agent, but a polymerization reaction occurs in an organic or inorganic reducing agent (which generates electrons). Time; for continuous activator regeneration (ICAR) initiator of the ATRP method; polymerization by reversible addition-fragmentation chain transfer (RAFT), wherein an inorganic reducing agent and a RAFT agent are used; and an organic cerium compound is used as an initiator, and a method can be selected therein The appropriate method.

例如，前述嵌段共聚物可經由反應物(其包括能夠形成前述嵌段的單體)之聚合反應，藉由活性自由基聚合法，在自由基引發劑和活性自由基聚合反應劑存在下進行。此製備嵌段共聚物之程序可進一步包括，例如，將經由以上程序製得的聚合反應產物沉澱於非溶劑中。 For example, the aforementioned block copolymer may be subjected to a polymerization reaction of a reactant (which includes a monomer capable of forming the aforementioned block) by living radical polymerization in the presence of a radical initiator and a living radical polymerization agent. . The procedure for preparing the block copolymer may further include, for example, precipitating the polymerization reaction product obtained through the above procedure in a non-solvent.

對於自由基引發劑的類型沒有特別的限制，且可以考慮聚合效能，適當地選擇自由基引發劑；例如，可以使用偶氮化合物(如偶氮雙異丁腈(AIBN)和2,2’-偶氮雙-(2,4-二甲基戊腈))或過氧化物系列(如苄醯過氧化物(BPO)和二-三級丁基過氧化物(DTBP))。 There is no particular limitation on the type of the radical initiator, and a polymerization initiator can be considered, and a radical initiator is appropriately selected; for example, an azo compound such as azobisisobutyronitrile (AIBN) and 2,2'- can be used. Azobis-(2,4-dimethylvaleronitrile) or a series of peroxides (such as benzamidine peroxide (BPO) and di-tertiary butyl peroxide (DTBP)).

活性自由基聚合程序可以，例如，在溶劑(如二氯甲烷、1,2-二氯乙烷、氯苯、二氯苯、苯、甲苯、丙酮、氯仿、四氫呋喃、二噁烷、單甘二甲醚(monoglyme)、二甘二甲醚(diglyme)、二甲基甲醯胺、二甲亞碸、和二甲基乙醯胺)中進行。 The living radical polymerization procedure can be, for example, in a solvent such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, mono-ganyl It is carried out in monoglyme, diglyme, dimethylformamide, dimethyl hydrazine, and dimethyl acetamide.

非溶劑的例子包括，但不限於，醇(如甲醇、乙醇、正丙醇、和異丙醇)、二醇(如乙二醇)、正己烷、環己烷、正庚烷、和醚(如石油醚)。 Examples of non-solvents include, but are not limited to, alcohols (such as methanol, ethanol, n-propanol, and isopropanol), glycols (such as ethylene glycol), n-hexane, cyclohexane, n-heptane, and ether ( Such as petroleum ether).

本申請案亦係關於含有前述嵌段共聚物之聚合物膜。該聚合物膜可用於各種應用(例如，各種電子或 電力設備)、用於形成前述圖案之程序、用於磁性儲存記錄介質(如快閃記憶體)或用於生物感知器。 This application is also directed to a polymer film containing the aforementioned block copolymer. The polymer film can be used in a variety of applications (eg, various electronic or Power equipment), a program for forming the aforementioned pattern, for magnetic storage of a recording medium such as a flash memory, or for a bio-perceptor.

一個例子中，前述嵌段共聚物可實現規則結構，如球、圓柱、螺旋二十四面體或層狀，此經由前述聚合物膜中之自組達成。此結構可為垂直定向。例如，嵌段1、嵌段2或(在共價鍵結至嵌段1和嵌段2中之任何者之其他嵌段的鏈段中)鏈段可在嵌段共聚物中形成規則結構，如層狀形式或圓柱形式，且此結構可為垂直定向。 In one example, the aforementioned block copolymer can achieve a regular structure, such as a sphere, a cylinder, a helix, a tetrahedron or a layer, which is achieved by self-assembly in the aforementioned polymer film. This structure can be oriented vertically. For example, block 1, block 2 or (in a segment covalently bonded to other blocks of any of block 1 and block 2) segments can form a regular structure in the block copolymer, Such as a layered form or a cylindrical form, and this structure can be vertically oriented.

本申請案中之以上聚合物膜可具有平面內(in-plane)繞射圖，其係在GISAXS分析期間內垂直於GISAXS繞射圖的x-分量的峰。另一例子中，延著以上GISAXS繞射圖的x-分量觀察到的峰數可為至少2且，當有數個峰存在時，可觀察到的峰之散射向量q值為整數比。 The above polymer film in the present application may have an in-plane diffraction pattern that is perpendicular to the x-component peak of the GISAXS diffraction pattern during the GISAXS analysis. In another example, the number of peaks observed over the x-component of the above GISAXS diffraction pattern may be at least 2 and, when a plurality of peaks are present, the observed scattering vector q value is an integer ratio.

本申請案亦係關於使用前述嵌段共聚物形成聚合物膜之方法。該方法可包括將含有以上嵌段共聚物之聚合物膜以自組狀態形成於基板上。例如，以上方法包括沈積以上嵌段共聚物，或塗覆含有該嵌段共聚物之溶液，以形成層及之後使此層退火。以上退火程序可指熱退火程序或溶劑退火程序。 The present application is also directed to a method of forming a polymer film using the aforementioned block copolymer. The method may include forming a polymer film containing the above block copolymer on a substrate in an unconstituted state. For example, the above method includes depositing the above block copolymer, or coating a solution containing the block copolymer to form a layer and then annealing the layer. The above annealing procedure may refer to a thermal annealing procedure or a solvent annealing procedure.

以上熱退火可以，例如，基於嵌段共聚物的相轉變溫度或玻璃轉變溫度而進行；例如，可以在等於或大於以上玻璃轉變溫度或相轉變溫度的溫度進行。未特別限制此熱退火的期間且可為，例如，在約1分鐘至72小 時的範圍內，但可視須要地加以改變。此外，熱退火程序期間內的熱處理溫度可為，例如，約100℃至250℃，其可取決於所用嵌段共聚物而改變。 The above thermal annealing may be performed, for example, based on the phase transition temperature or the glass transition temperature of the block copolymer; for example, it may be performed at a temperature equal to or greater than the above glass transition temperature or phase transition temperature. The period of this thermal annealing is not particularly limited and may be, for example, about 1 minute to 72 hours. Within the scope of the time, but can be changed as needed. Further, the heat treatment temperature during the thermal annealing process may be, for example, about 100 ° C to 250 ° C, which may vary depending on the block copolymer used.

此外，以上溶劑退火程序可以在適當室溫非極性溶劑和/或極性溶劑中進行約1分鐘至72小時。 Further, the above solvent annealing procedure can be carried out in a suitable room temperature non-polar solvent and/or polar solvent for about 1 minute to 72 hours.

本申請案亦係關於形成圖案之方法。以上方法可包括，例如，自基板和形成於基板上並含有以上自組的嵌段共聚物之聚合物膜所構成的積層物選擇性地移除嵌段共聚物的嵌段1或嵌段2之方法。以上方法可為在以上基板上形成圖案之方法。例如，以上方法可包括在基板上形成含有以上嵌段共聚物的聚合物膜，選擇性地移除存在於以上膜中之嵌段共聚物的任一或多個嵌段，及之後蝕刻此基板。以上方法有助於形成微細圖案，例如，奈米尺寸。此外，藉以上方法可形成多種圖案(如奈米條和奈米孔)，此取決於聚合物膜中的嵌段共聚物結構。必要時，以上嵌段共聚物可以與另一共聚物、均聚物之類混合以形成圖案。未特別限制施用於以上方法之基板的類型且可經選擇以適合此應用；例如，可使用氧化矽。 This application is also directed to a method of forming a pattern. The above method may include, for example, selectively removing the block 1 or block 2 of the block copolymer from a substrate and a laminate formed of a polymer film formed on the substrate and containing the above-described self-assembled block copolymer. The method. The above method may be a method of forming a pattern on the above substrate. For example, the above method may include forming a polymer film containing the above block copolymer on a substrate, selectively removing any one or more blocks of the block copolymer present in the above film, and then etching the substrate . The above method helps to form a fine pattern, for example, a nanometer size. In addition, a variety of patterns (such as nano-bars and nanopores) can be formed by the above method depending on the structure of the block copolymer in the polymer film. If necessary, the above block copolymer may be mixed with another copolymer, a homopolymer or the like to form a pattern. The type of substrate applied to the above method is not particularly limited and may be selected to suit the application; for example, cerium oxide may be used.

例如，以上方法可形成展現高深寬比的氧化矽奈米級圖案。可實現各種形式(如奈米條和奈米孔)，例如，藉由在氧化矽上形成以上的聚合物膜，選擇性地移除以上聚合物膜(其中，嵌段共聚物構成預定結構)中之嵌段共聚物的任一嵌段，及之後藉各種技巧(例如，藉反應性離子蝕刻)中之任一者蝕刻氧化矽。此外，以上方法可有 助於實現具有高深寬比的奈米圖案。 For example, the above method can form a yttrium oxide nanoscale pattern exhibiting a high aspect ratio. Various forms (such as nanorods and nanopores) can be realized, for example, by forming the above polymer film on cerium oxide, the above polymer film is selectively removed (wherein the block copolymer constitutes a predetermined structure) Any block of the block copolymer, and thereafter etched yttrium oxide by any of a variety of techniques (eg, by reactive ion etching). In addition, the above methods may have Helps achieve nanopatterns with high aspect ratios.

例如，可以數十奈米尺寸實現以上圖案，且此圖案可用於各種應用包括，例如，用於下一代資訊和電子產品的磁性記錄介質。 For example, the above pattern can be implemented in tens of nanometer sizes, and this pattern can be used in various applications including, for example, magnetic recording media for next generation information and electronic products.

例如，可藉以上方法形成其寬度約10nm至40nm的奈米結構(如奈米線)間隔(如，間隔20nm至80nm)放置的圖案。另一例子中，亦可實現以約20nm至80nm間隔放置的奈米孔(其寬度(如直徑)約10nm至40nm)的結構。 For example, a pattern in which nanostructures (e.g., nanowires) having a width of about 10 nm to 40 nm are interposed (e.g., spaced by 20 nm to 80 nm) can be formed by the above method. In another example, a structure in which nanopores (having a width (e.g., diameter) of about 10 nm to 40 nm) placed at intervals of about 20 nm to 80 nm can also be realized.

此外，以上結構中的奈米線或奈米孔可製成具有高深寬比。 Further, the nanowires or nanopores in the above structure can be made to have a high aspect ratio.

以上方法中，對於選擇性地移除嵌段共聚物之任一嵌段的方法沒有特別的限制；例如，可以使用藉由使得聚合膜以適當電磁波(如紫外射線)照射以移除相對軟嵌段之方法。此情況中，紫外射線照射條件由嵌段共聚物中的嵌段類型決定；例如，其可包括照射波長約254nm的紫外射線1分鐘至60分鐘。 In the above method, there is no particular limitation on the method of selectively removing any block of the block copolymer; for example, it is possible to remove the relatively soft inlay by irradiating the polymer film with an appropriate electromagnetic wave such as ultraviolet rays. The method of paragraph. In this case, the ultraviolet ray irradiation conditions are determined by the type of the block in the block copolymer; for example, it may include irradiating ultraviolet rays having a wavelength of about 254 nm for 1 minute to 60 minutes.

紫外射線照射之後，可藉由以酸之類處理聚合物膜的方式，進行進一步移除已事先藉紫外射線瓦解之鏈段的程序。 After the ultraviolet ray irradiation, the procedure of further removing the segment which has been disintegrated by the ultraviolet ray can be carried out by treating the polymer film with an acid or the like.

對於使用經選擇性地移除某些嵌段的聚合物膜作為遮罩來蝕刻基板之程序沒有特別的限制；例如，以上蝕刻可以經由以CF4/Ar離子之類進行反應性離子蝕刻的方式進行。以上蝕刻之後可為經由氧電漿處理之類進行 自基板移除聚合物膜的程序。 There is no particular limitation on the procedure for etching a substrate using a polymer film that selectively removes certain blocks as a mask; for example, the above etching may be performed by reactive ion etching using CF 4 /Ar ions or the like. get on. The above etching may be followed by a procedure of removing the polymer film from the substrate via an oxygen plasma treatment or the like.

圖1和2各者出示GISAXS繞射圖。 Each of Figures 1 and 2 presents a GISAXS diffraction pattern.

圖3至11各者出示聚合物膜的SEM影像。 Each of Figures 3 to 11 shows an SEM image of the polymer film.

圖12至17各者出示GIWAXS分析結果。 Each of Figures 12 through 17 presents the results of the GIGASS analysis.

圖18例示計算數學式A中的K值之方法。 FIG. 18 illustrates a method of calculating the K value in Math.

圖19至21各者出示GISAXS繞射圖。 Each of Figures 19 through 21 shows a GISAXS diffraction pattern.

功效 efficacy

本申請案提出嵌段共聚物-其展現極佳的自組性質或相分離性質並因此而可有效地用於多種應用-及其用途。 The present application proposes block copolymers which exhibit excellent self-organizing properties or phase separation properties and are therefore effective for a variety of applications - and their uses.

下文經藉由根據本申請案之實例與比較例更詳細地描述本申請案，但本申請案之範圍不限於下文提出的實例。 The present application is described in more detail below by way of examples and comparative examples in accordance with the present application, but the scope of the present application is not limited to the examples set forth below.

1.NMR測定 1. NMR measurement

使用NMR光譜儀(其包括Varian Unity Inova(500MHz)光譜儀和5-mm三重共振探頭)於室溫進行NMR分析。分析標的材料以用於NMR測定的溶劑(CDCl3)稀釋至濃度約10mg/ml，且化學位移以ppm表示。 NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz spectrometer and a 5-mm triple resonance probe). The analytical target material was diluted with a solvent (CDCl 3 ) for NMR determination to a concentration of about 10 mg/ml, and the chemical shift was expressed in ppm.

<施用的縮寫> <Abbreviation of application>

br=寬訊號，s=單峰，d=雙峰，dd=雙雙峰，t=三峰，dt=雙三峰，q=四峰，p=五峰，m=多峰。 Br = wide signal, s = single peak, d = doublet, dd = doublet, t = triplet, dt = double triplet, q = four peaks, p = five peaks, m = multiple peaks.

2.凝膠穿透層析術(GPC) 2. Gel Penetration Chromatography (GPC)

數量平均分子量(Mn)和分子量分佈係藉GPC測定。分析標的材料(如實例或比較例的巨引發劑或嵌段共聚物)置於5-mL瓶中並以四氫呋喃(THF)稀釋至約1mg/mL濃度。之後，用於校正的標準試樣和待分析的試樣以針筒濾器(孔尺寸：0.45μm)過濾，之後分析。使用ChemStation(Agilent Technologies Inc.)作為分析程式，藉由比較試樣的沖提時間和校正曲線，得到Mw和Mn各者，之後計算分子量分佈(多分散性指數，PDI)為比(Mw/Mn)。GPC的測定條件如下： The number average molecular weight (Mn) and molecular weight distribution were determined by GPC. The assay target material (such as the macroinitiator or block copolymer of the examples or comparative examples) was placed in a 5-mL vial and diluted with tetrahydrofuran (THF) to a concentration of about 1 mg/mL. Thereafter, the standard sample for calibration and the sample to be analyzed were filtered with a syringe filter (pore size: 0.45 μm), and then analyzed. Using ChemStation (Agilent Technologies Inc.) as an analytical program, by comparing the elution time and calibration curve of the sample, Mw and Mn were obtained, and then the molecular weight distribution (polydispersity index, PDI) was calculated as the ratio (Mw/Mn). ). The measurement conditions of GPC are as follows:

<GPC測定條件> <GPC measurement conditions>

裝置：Agilent Technologies Inc.的1200 Series。 Device: 1200 Series from Agilent Technologies Inc.

管柱：兩個Polymer Laboratories的PLgel MIXED-B Column: Two Polymer Laboratories' PLgel MIXED-B

溶劑：THF Solvent: THF

管柱溫度：35℃ Column temperature: 35 ° C

樣品濃度：1mg/mL，注射200L Sample concentration: 1mg/mL, injection 200L

標準試樣：聚苯乙烯(Mp：3900000，723000，316500，52200，31400，7200，3940，485) Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

3.GISAXS(低掠角小角度X射線散射) 3.GISAXS (low sweep angle small angle X-ray scattering)

GISAXS分析係藉由使用Pohang加速器的3C離子束進行。藉由將待分析的嵌段共聚物溶於氟苯至固體 濃度約0.7重量%而製得塗覆溶液，將其旋轉塗覆於約5nm厚的基材上。塗覆面積經調整為約2.25cm2(寬：1.5cm，長：1.5cm)。經塗覆的聚合物膜於室溫乾燥約1小時，之後於約160℃的溫度再度熱退火約1小時，以誘發相分離結構之形成。之後，形成具有相分離結構的膜。X-射線以約0.12度至0.23度(其為大於膜之臨界角和基材之臨界角之一並小於另一者的角度)的入射角度入射於膜上後，藉偵測器(2D marCCD)得到自膜散射的X-射線繞射圖。此情況中，膜與偵測器之間的距離設定在約2m和3m之間的範圍內，於此範圍內可良好地觀察到膜之自組圖案。使用具有親水表面的基材(經食人魚溶液處理以具有對於純水之約5度的室溫潤濕角度的矽基材)或具有疏水表面的基材(藉六甲基二矽氮烷(HMDS)處理以具有對於純水之約60度的室溫潤濕角度的矽基材)作為基材。 GISAXS analysis was performed by using a 3C ion beam of the Pohang accelerator. A coating solution was prepared by dissolving the block copolymer to be analyzed in fluorobenzene to a solid concentration of about 0.7% by weight, which was spin coated onto a substrate having a thickness of about 5 nm. The coated area was adjusted to be about 2.25 cm 2 (width: 1.5 cm, length: 1.5 cm). The coated polymer film was dried at room temperature for about 1 hour and then re-thermally annealed at a temperature of about 160 ° C for about 1 hour to induce formation of a phase separation structure. Thereafter, a film having a phase separation structure is formed. X-rays are incident on the film at an incident angle of about 0.12 degrees to 0.23 degrees, which is greater than the critical angle of the film and one of the critical angles of the substrate and less than the angle of the other, by means of a detector (2D marCCD). An X-ray diffraction pattern obtained from film scattering is obtained. In this case, the distance between the film and the detector is set in a range between about 2 m and 3 m, and the self-assembled pattern of the film is well observed in this range. Using a substrate having a hydrophilic surface (a ruthenium substrate treated with a piranha solution to have a room temperature wetting angle of about 5 degrees for pure water) or a substrate having a hydrophobic surface (by hexamethyldioxane (HMDS) A ruthenium substrate having a room temperature wetting angle of about 60 degrees for pure water was treated as a substrate.

4.XRD分析方法 4.XRD analysis method

XRD分析係藉由以Pohang加速器的4C離子束發射X-射線穿透試樣並測定反應於散射向量q之散射強度變化的方式進行。純化已合成且未以特別方式進行前處理的聚合物，之後在真空烤箱中乾燥約一天以形成粉末，並置於用於XRD測定的樣品管(cell)中作為試樣。用於XRD圖分析，使用垂直尺寸為0.023mm且水平尺寸為0.3mm的X-射線，並使用2D marCCD偵測器。得到自試樣散射的2D繞射圖為影像形式。藉施用最小平方回歸的數值分析法，分析所得的繞射圖，以得到資訊，如散射向 量和FWHM。Origin程式用於以上分析，且將對應於XRD繞射圖的最小強度部份設定為基線並將最小強度設定為0，之後將以上XRD圖的峰型進行Gaussian擬合，並自擬合結果得到前述散射向量和FWHM。進行以上Gaussian擬合時，R-平方值設定為至少0.96。 The XRD analysis was carried out by emitting X-rays through a 4C ion beam of a Pohang accelerator and measuring the change in the scattering intensity of the reaction vector q. The polymer which had been synthesized and not pretreated in a special manner was purified, and then dried in a vacuum oven for about one day to form a powder, and placed in a sample cell for XRD measurement as a sample. For XRD pattern analysis, X-rays with a vertical dimension of 0.023 mm and a horizontal dimension of 0.3 mm were used and a 2D marCCD detector was used. The 2D diffraction pattern obtained from the sample scattering is in the form of an image. By using the numerical analysis method of least squares regression, the obtained diffraction pattern is analyzed to obtain information such as scattering direction. Volume and FWHM. The Origin program is used for the above analysis, and the minimum intensity portion corresponding to the XRD diffraction pattern is set as the baseline and the minimum intensity is set to 0. Then, the peak shape of the above XRD pattern is Gaussian fitted, and the self-fit result is obtained. The aforementioned scattering vector and FWHM. When the above Gaussian fitting is performed, the R-square value is set to at least 0.96.

5.表面能量測定 5. Surface energy measurement

可藉由使用Drop Shape Analyzer DSA100(KRUSS GmbH生產)測定表面能量。待測定的材料(即，聚合物)溶於氟苯中至固體濃度約2重量%以製得塗覆溶液，將其旋轉塗覆於約50nm厚的基材上且塗覆面積為4cm2(寬：2cm，長：2cm)。經塗覆的層於室溫乾燥約1小時，之後於約160℃熱退火約1小時。重複5次測定接觸角度的程序(藉由將本領域已知其表面張力的去離子水滴在以上經熱退火的膜上)，並將這5個測得的接觸角度值加以平均。同樣，重複5次測定接觸角度的程序(藉由將本領域已知其表面張力的二碘甲烷滴在以上經熱退火的膜上)，並將這5個測得的接觸角度值加以平均。然後，藉由使用分別以去離子水和二碘甲烷測得之接觸角度的平均值及將對應於溶劑之表面張力的數值(Strom值)代入根據Owens-Wendt-Rabel-Kaelble方法的數學式中得到表面能量。使用上述方法用於僅由構成以上嵌段之單體所構成的均聚物上，得到對應於嵌段共聚物的各嵌段之表面能量的數值。 The surface energy can be measured by using a Drop Shape Analyzer DSA100 (manufactured by KRUSS GmbH). The material to be determined (i.e., the polymer) was dissolved in fluorobenzene to a solid concentration of about 2% by weight to prepare a coating solution, which was spin-coated on a substrate having a thickness of about 50 nm and a coating area of 4 cm 2 ( Width: 2cm, length: 2cm). The coated layer was dried at room temperature for about 1 hour and then thermally annealed at about 160 ° C for about 1 hour. The procedure for determining the contact angle was repeated 5 times (by using a deionized water droplet whose surface tension is known in the art on the above thermally annealed film), and the five measured contact angle values were averaged. Similarly, the procedure for determining the contact angle was repeated 5 times (by dropping the surface tension of diiodomethane on the above thermally annealed film), and the five measured contact angle values were averaged. Then, by using the average value of the contact angles measured with deionized water and diiodomethane, respectively, and the value corresponding to the surface tension of the solvent (Strom value), the equation according to the Owens-Wendt-Rabel-Kaelble method is substituted. Get surface energy. Using the above method for the homopolymer composed of only the monomers constituting the above block, the value corresponding to the surface energy of each block of the block copolymer was obtained.

6.GIWAXS(低掠角廣角度X射線散射) 6.GIWAXS (low sweep angle wide angle X-ray scattering)

GIWAXS分析係藉由使用Pohang加速器的3C離子束進行。藉由將待分析的嵌段共聚物溶於甲苯至固體濃度約1重量%而製得塗覆溶液，且將其旋轉塗覆於約30nm厚的基材上。塗覆面積經調整為約2.25cm2(寬：1.5cm，長：1.5cm)。經塗覆的聚合物膜於室溫乾燥約1小時，之後於約160℃的溫度再度熱退火約1小時，以形成膜。之後，形成具有相分離結構的膜。X-射線以約0.12度至0.23度(其為大於膜之臨界角和基材之臨界角之一並小於另一者的角度)的入射角度入射於膜上後，藉偵測器(2D marCCD)得到自膜散射的X-射線繞射圖。此情況中，膜與偵測器之間的距離設定在約0.1m和0.5m之間的範圍內，於此範圍內良好地觀察到膜的晶狀或液晶結構。使用經食人魚溶液處理以具有對於純水之約5度的室溫潤濕角度的矽基材作為基材。 GIWAXS analysis was performed by using a 3C ion beam of the Pohang accelerator. A coating solution was prepared by dissolving the block copolymer to be analyzed in toluene to a solid concentration of about 1% by weight, and spin coating it onto a substrate of about 30 nm thickness. The coated area was adjusted to be about 2.25 cm 2 (width: 1.5 cm, length: 1.5 cm). The coated polymer film was dried at room temperature for about 1 hour and then thermally annealed at a temperature of about 160 ° C for about 1 hour to form a film. Thereafter, a film having a phase separation structure is formed. X-rays are incident on the film at an incident angle of about 0.12 degrees to 0.23 degrees, which is greater than the critical angle of the film and one of the critical angles of the substrate and less than the angle of the other, by means of a detector (2D marCCD). An X-ray diffraction pattern obtained from film scattering is obtained. In this case, the distance between the film and the detector is set in a range between about 0.1 m and 0.5 m, and the crystal or liquid crystal structure of the film is well observed in this range. A ruthenium substrate having a room temperature wetting angle of about 5 degrees with respect to pure water was treated as a substrate using a piranha solution.

GIWAXS光譜的繞射圖中之範圍為-90度至90度的方位角(即，將繞射圖的向上方向中測得角度的方位角(即，面外繞射圖的角度)設定為0度時之散射強度)-此處的散射向量範圍由12nm-1至16nm-1-繪成圖，且經由圖的Gaussian擬合測得FWHM。在Gaussian擬合僅觀察到峰的一半時，將所得(所觀察)峰的FWHM值的兩倍定義為峰的FWHM。 The range of the diffraction pattern of the GIWAXS spectrum is an azimuth angle of -90 degrees to 90 degrees (ie, the azimuth angle of the angle measured in the upward direction of the diffraction pattern (ie, the angle of the out-of-plane diffraction pattern) is set to 0. Scattering intensity at time) - The scattering vector range here is plotted from 12 nm -1 to 16 nm -1 - and the FWHM is measured via the Gaussian fit of the graph. When only half of the peak was observed in the Gaussian fitting, twice the FWHM value of the obtained (observed) peak was defined as the FWHM of the peak.

7.DSC分析 7.DSC analysis

藉由使用DSC800(PerkinElmer Inc)進行DSC分析。藉施用以上設備之方法(其中，待分析的標的試樣 在氮氣氛下以10℃/分鐘的速率自25℃加熱至200℃，以-10℃/分鐘的速率自200℃冷卻至-80℃，及再度以10℃/分鐘的速率自-80℃加熱至200℃)得到吸熱曲線。分析所得吸熱曲線以估計出現熔化轉變峰的溫度(即，熔化轉變溫度，Tm)、出現等向轉變峰的溫度(即，等向轉變溫度，Ti)、及各峰的面積。此處，藉由對應於各峰頂的溫度測定以上溫度各者。藉由以峰面積除以試樣的質量測定各個峰之每單位質量的面積，且藉DSC設備提供的程式可完成此計算。 DSC analysis was performed by using DSC800 (PerkinElmer Inc). By the method of applying the above equipment (wherein the target sample to be analyzed) Heating from 25 ° C to 200 ° C at a rate of 10 ° C / minute under nitrogen atmosphere, cooling from 200 ° C to -80 ° C at a rate of -10 ° C / minute, and again heating from -80 ° C at a rate of 10 ° C / minute An endothermic curve was obtained up to 200 ° C. The resulting endothermic curve is analyzed to estimate the temperature at which the melting transition peak appears (i.e., the melting transition temperature, Tm), the temperature at which the isotropic transition peak occurs (i.e., the isotropic transition temperature, Ti), and the area of each peak. Here, each of the above temperatures is measured by the temperature corresponding to each peak. The area per unit mass of each peak is determined by dividing the peak area by the mass of the sample, and this calculation can be done by a program provided by the DSC device.

8.藉數學式A測定出X 8. Determine the X by Mathematical Formula A

可藉以下方式得到數學式A中的各個變數-D、M、K和L：首先，將待分析的試樣(即，僅以構成嵌段1的單體製得的均聚物或僅以構成嵌段2的單體製得的均聚物)置於溶劑(即，乙醇，已知其於空氣中的質量和密度)，由試樣的質量得到各嵌段的密度，且計算不同類型的試樣之質量比而可得到D。 The respective variables -D, M, K and L in Mathematical Formula A can be obtained in the following manner: First, the sample to be analyzed (i.e., the homopolymer obtained only from the monomers constituting Block 1 or only The homopolymer obtained by constituting the monomer of block 2 is placed in a solvent (i.e., ethanol, known in mass and density in air), the density of each block is obtained from the mass of the sample, and different types are calculated. The mass ratio of the sample can be obtained as D.

亦可得到M為構成嵌段共聚物之嵌段的單體之莫耳質量的比。例如，在實例之各嵌段共聚物的情況中，製備例1之單體(其為構成嵌段1的單體，將於之後述於本說明中)的莫耳質量是346.5g/mol，構成嵌段2的五氟苯乙烯的莫耳質量是194.1g/mol，且由此比，可計算得知M值為約1.79。 It is also possible to obtain a molar mass ratio of M which is a monomer constituting a block of the block copolymer. For example, in the case of each block copolymer of the example, the molar mass of the monomer of Preparation Example 1, which is a monomer constituting the block 1, which will be described later in the description, is 346.5 g/mol, The molar mass of the pentafluorostyrene constituting the block 2 was 194.1 g/mol, and from this ratio, the M value was calculated to be about 1.79.

此外，可得到L為構成嵌段共聚物之嵌段的 單體中之氫原子數的比。例如，在實例之各嵌段共聚物的情況中，製備例1之單體(其為構成嵌段1的單體)的氫原子數是34，構成嵌段2的五氟苯乙烯的氫原子數是3，且由此比，可計算得知L值為約11.3。 In addition, it can be obtained that L is a block constituting the block copolymer. The ratio of the number of hydrogen atoms in the monomer. For example, in the case of each block copolymer of the example, the number of hydrogen atoms of the monomer of Preparation Example 1 which is a monomer constituting the block 1 is 34, and the hydrogen atom of the pentafluorostyrene constituting the block 2 The number is 3, and as a result, it can be calculated that the L value is about 11.3.

最後，由藉前述NMR分析法得到的光譜面積可計算K。此情況中，當峰(其中的各者得自嵌段共聚物中的各嵌段)未彼此重疊時，簡單地分析自各嵌段衍生的峰面積，而以峰面積的比得到K。 Finally, K can be calculated from the spectral area obtained by the aforementioned NMR analysis. In this case, when the peaks (each of which is obtained from each block in the block copolymer) do not overlap each other, the peak areas derived from the respective blocks are simply analyzed, and K is obtained in the ratio of the peak areas.

反之，當衍生自嵌段共聚物之不同嵌段的峰彼此至少部分重疊時，在得到K值時，應將重疊的部分列入考慮。例如，隨附之圖18係嵌段共聚物的說明性NMR光譜，該嵌段共聚物含有根據製備例1製備並施用於以下實例和比較例之自結構式A所示化合物衍生的結構單元，及自五氟苯乙烯衍生的結構單元。圖18中，標記為e的部分和標記為d的部分是指來自嵌段2(即，衍生自五氟苯乙烯的前述結構單元)的峰，而餘者(a，b，c，f，g，h，i和j)係來自製備例1之化合物(結構式A所示者)衍生的結構單元的峰。由圖可看出，標記為e和g的峰和標記為d和f的峰彼此重疊；此情況中，得到K值時，應將峰之重疊列入考慮。 Conversely, when the peaks derived from the different blocks of the block copolymer at least partially overlap each other, the overlapped portion should be taken into consideration when the K value is obtained. For example, the accompanying FIG. 18 is an illustrative NMR spectrum of a block copolymer containing the structural unit derived from the compound of Structural Formula A prepared according to Preparation Example 1 and applied to the following Examples and Comparative Examples, And structural units derived from pentafluorostyrene. In Fig. 18, the portion labeled with e and the portion labeled with d refer to the peak derived from block 2 (i.e., the aforementioned structural unit derived from pentafluorostyrene), and the remainder (a, b, c, f, g, h, i and j) are the peaks derived from the structural unit derived from the compound of Preparation Example 1 (expressed by Structural Formula A). As can be seen from the figure, the peaks labeled e and g and the peaks labeled d and f overlap each other; in this case, when the K value is obtained, the overlap of the peaks should be taken into consideration.

此情況中，藉由將峰之重疊列入考慮而得到K值的方法為本領域習知者；例如，藉由使用NMR解讀程式(如MestReC程式)，可得到此值。 In this case, the method of obtaining the K value by taking the overlap of the peaks into consideration is known in the art; for example, this value can be obtained by using an NMR interpretation program such as the MestReC program.

製備例1.單體A之合成 Preparation Example 1. Synthesis of Monomer A

藉以下方法合成以下結構式A所示化合物(DPM-C12)：氫醌(10.0g，94.2mmol)和1-溴十二烷(23.5g，94.2mmol)引至250mL瓶中，溶於100mL乙腈中；之後，過量碳酸鉀加至以上溶液中並使其在氮氣下於約75℃反應約48小時；反應完全之後，反應產物經過濾以移除用於反應之殘留的碳酸鉀和乙腈；之後，添加二氯甲烷(DCM)和水的混合溶劑以處理此物質，且收集分離的有機層並以MgSO4脫水；然後，此物質藉管柱層析術(CC)以DCM純化，以得到白色固態標的材料(即4-(十二烷氧基)酚)，產率約37%。 The following compound of formula A (DPM-C12) was synthesized by the following method: hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were introduced into a 250 mL bottle, dissolved in 100 mL of acetonitrile. After that, excess potassium carbonate is added to the above solution and allowed to react at about 75 ° C for about 48 hours under nitrogen; after the reaction is completed, the reaction product is filtered to remove residual potassium carbonate and acetonitrile for the reaction; , a mixed solvent of dichloromethane (DCM) and water was added to treat the material, and the separated organic layer was collected and dehydrated with MgSO 4 ; then, this material was purified by DC column chromatography (CC) to afford white The solid state material (i.e., 4-(dodecyloxy)phenol) has a yield of about 37%.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ6.77(dd,4H)；δ4.45(s,1H)；δ3.89(t,2H)；δ1.75(p,2H)；δ1.43(p,2H)；δ1.33-1.26(m,16H)；δ0.88(t,3H)。 1 H-NMR (CDCl 3 ): δ 6.77 (dd, 4H); δ 4.45 (s, 1H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p , 2H); δ 1.33-1.26 (m, 16H); δ 0.88 (t, 3H).

合成的4-(十二烷氧基)酚(9.8g，35.2mmol)、甲基丙烯酸(6.0g，69.7mmol)、二環己基碳化二醯亞胺(DCC)(10.8g，52.3mmol)和對-二甲基胺基吡啶(DMAP)(1.7g，13.9mmol)引至瓶中，添加120mL二氯甲烷，之後使其在氮氣氛下於室溫反應24小時；反應完全之後，反應產物經過濾以移除在反應期間內製造的脲鹽及剩餘的二氯甲烷；之後，藉管柱層析術(CC)(其使用己烷和二氯甲烷(DCM)作為移動相)移除物質中的雜質，所得產物在甲醇和水的混合溶劑(以1：1的重量比混合)中 再結晶，以得到白色固態標的材料(7.7g，22.2mmol)，產率是63%。 Synthesis of 4-(dodecyloxy)phenol (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC) (10.8 g, 52.3 mmol) and p-Dimethylaminopyridine (DMAP) (1.7 g, 13.9 mmol) was introduced into a bottle, 120 mL of dichloromethane was added, and then allowed to react at room temperature for 24 hours under a nitrogen atmosphere; after the reaction was completed, the reaction product was subjected to a reaction. Filtration to remove the urea salt and the remaining methylene chloride produced during the reaction; afterwards, the column chromatography (CC) (which uses hexane and dichloromethane (DCM) as the mobile phase) removes the material. Impurity, the product obtained in a mixed solvent of methanol and water (mixed in a weight ratio of 1:1) Recrystallization gave a white solid material (7.7 g, 22.2 mmol), yield 63%.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.02(dd,2H)；δ6.89(dd,2H)；δ6.32(dt,1H)；δ5.73(dt,1H)；δ3.94(t,2H)；δ2.05(dd,3H)；δ1.76(p,2H)；δ1.43(p,2H)；1.34-1.27(m,16H)；δ0.88(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 0.88 (t, 3H).

結構式A中，R代表具12個碳原子的直鏈烷基。 In the structural formula A, R represents a linear alkyl group having 12 carbon atoms.

製備例2.單體G之合成 Preparation Example 2. Synthesis of Monomer G

藉製備例1之方法合成以下結構式G所示化合物，但使用1-溴丁烷代替1-溴十二烷。以上化合物的NMR分析結果如下。 The compound of the following formula G was synthesized by the method of Preparation Example 1, except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results of the above compounds are as follows.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.02(dd,2H)；δ6.89(dd,2H)；δ6.33(dt,1H)；δ5.73(dt,1H)；δ3.95(t,2H)；δ2.06(dd,3H)；δ1.76(p,2H)；δ1.49(p,2H)；δ0.98(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.95 (t) , 2H); δ2.06 (dd, 3H); δ 1.76 (p, 2H); δ 1.49 (p, 2H); δ 0.98 (t, 3H).

結構式G中，R代表具4個碳原子的直鏈烷基。 In the formula G, R represents a linear alkyl group having 4 carbon atoms.

製備例3.單體B之合成 Preparation 3. Synthesis of Monomer B

藉製備例1之方法合成以下結構式B所示化合物，但使用1-溴辛烷代替1-溴十二烷。以上化合物的NMR分析結果如下。 The compound of the following structural formula B was synthesized by the method of Preparation Example 1, except that 1-bromooctane was used instead of 1-bromododecane. The NMR analysis results of the above compounds are as follows.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.02(dd,2H)；δ6.89(dd,2H)；δ6.32(dt,1H)；δ5.73(dt,1H)；δ3.94(t,2H)；δ2.05(dd,3H)；δ1.76(p,2H)；δ1.45(p,2H)；1.33-1.29(m,8H)；δ0.89(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.45 (p, 2H); 1.33-1.29 (m, 8H); δ 0.89 (t, 3H).

結構式B中，R代表具8個碳原子的直鏈烷基。 In the formula B, R represents a linear alkyl group having 8 carbon atoms.

製備例4.單體C之合成 Preparation 4. Synthesis of Monomer C

藉製備例1之方法合成以下結構式C所示化 合物，但使用1-溴癸烷代替1-溴十二烷。以上化合物的NMR分析結果如下。 The following structural formula C was synthesized by the method of Preparation Example 1. Compound, but using 1-bromodecane instead of 1-bromododecane. The NMR analysis results of the above compounds are as follows.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.02(dd,2H)；δ6.89(dd,2H)；δ6.33(dt,1H)；δ5.72(dt,1H)；δ3.94(t,2H)；δ2.06(dd,3H)；δ1.77(p,2H)；δ1.45(p,2H)；1.34-1.28(m,12H)；δ0.89(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.72 (dt, 1H); δ 3.94 (t) , 2H); δ2.06 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.34-1.28 (m, 12H); δ 0.89 (t, 3H).

結構式C中，R代表具10個碳原子的直鏈烷基。 In the formula C, R represents a linear alkyl group having 10 carbon atoms.

製備例5.單體D之合成 Preparation Example 5. Synthesis of Monomer D

藉製備例1之方法合成以下結構式D所示化合物，但使用1-溴十四烷代替1-溴十二烷。以上化合物的NMR分析結果如下。 The compound of the following structural formula D was synthesized by the method of Preparation Example 1, except that 1-bromotetradecane was used instead of 1-bromododecane. The NMR analysis results of the above compounds are as follows.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.02(dd,2H)；δ6.89(dd,2H)；δ6.33(dt,1H)；δ5.73(dt,1H)；δ3.94(t,2H)；δ2.05(dd,3H)；δ1.77(p,2H)；δ1.45(p,2H)；1.36-1.27(m,20H)；δ0.88(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.27 (m, 20H); δ 0.88 (t, 3H).

結構式D中，R代表具14個碳原子的直鏈烷基。 In the formula D, R represents a linear alkyl group having 14 carbon atoms.

製備例6.單體E之合成 Preparation Example 6. Synthesis of Monomer E

藉製備例1之方法合成以下結構式E所示化合物，但使用1-溴十六烷代替1-溴十二烷。以上化合物的NMR分析結果如下。 The compound of the following structural formula E was synthesized by the method of Preparation Example 1, except that 1-bromohexadecane was used instead of 1-bromododecane. The NMR analysis results of the above compounds are as follows.

<NMR分析結果> <NMR analysis results>

1H-NMR(CDCl3)：δ7.01(dd,2H)；δ6.88(dd,2H)；δ6.32(dt,1H)；δ5.73(dt,1H)；δ3.94(t,2H)；δ2.05(dd,3H)；δ1.77(p,2H)；δ1.45(p,2H)；1.36-1.26(m,24H)；δ0.89(t,3H)。 1 H-NMR (CDCl 3 ): δ 7.01 (dd, 2H); δ 6.88 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.26 (m, 24H); δ 0.89 (t, 3H).

結構式E中，R代表具16個碳原子的直鏈烷基。 In the formula E, R represents a linear alkyl group having 16 carbon atoms.

GIWAXS和DSC分析之結果 Results of GIWAXS and DSC analysis

使用根據製備例1至6之一製得的單體各者 製備6種類型的均聚物，且彙整各均聚物的GIWAXS和DSC分析結果並示於下表1。此處，均聚物係根據以下實例或比較例，藉由使用各種類型的單體合成巨引發劑之方法而製得。製備例的GIWAXS分析示於圖12至17。圖12至17各者分別對應於出示製備例1至6各者的GIWAXS分析結果之影像。 Using the monomers prepared according to one of Preparation Examples 1 to 6 Six types of homopolymers were prepared, and the GIGASS and DSC analysis results of each homopolymer were combined and shown in Table 1 below. Here, the homopolymer is obtained by a method of synthesizing a macroinitiator using various types of monomers according to the following examples or comparative examples. The GIGASS analysis of the preparation examples is shown in Figures 12 to 17. Each of FIGS. 12 to 17 corresponds to an image showing the results of the GIWAXS analysis of each of Preparation Examples 1 to 6.

圖12中，Gaussian擬合的R-平方是約0.264，在圖16中，R-平方是約0.676，而在圖17中，R-平方是約0.932。 In Figure 12, the R-square of the Gaussian fit is about 0.264, in Figure 16, the R-square is about 0.676, and in Figure 17, the R-square is about 0.932.

實例1. Example 1.

1.785g製備例1的單體A、38mg可逆性加成 裂鏈轉移(RAFT)劑(氰基異丙基二硫代苯甲酸酯)、14mg自由基引發劑(偶氮雙異丁腈，AIBN)、和4.765mL之苯引至10-mL Schlenk瓶中，在氮氣氛下於室溫攪拌30分鐘，之後於70℃進行為時4小時的RAFT聚合反應。完成聚合反應之後，反應溶液沉澱於250mL萃取溶劑(甲醇)中及之後在減壓下藉過濾而乾燥，製得粉紅色的巨引發劑。此巨引發劑的產率約83.1重量%，而數量平均分子量(Mn)和分子量分佈(Mw/Mn)分別是11,400和1.15。0.3086g巨引發劑、1.839g五氟苯乙烯單體和0.701mL之苯引至10-mL Schlenk瓶中，在氮氣氛下於室溫攪拌30分鐘，之後於115℃進行為時4小時的RAFT聚合反應。完成聚合反應之後，反應溶液沉澱於250mL萃取溶劑(甲醇)中及之後在減壓下藉過濾而乾燥，製得淡粉紅色的嵌段共聚物。此嵌段共聚物的產率約27.1重量%，而Mn和Mw/Mn分別是18,900和1.19。以上的嵌段共聚物含有嵌段1(其衍生自根據製備例1製得的單體A)和嵌段2(其衍生自前述五氟苯乙烯單體)。以前述方式，在嵌段共聚物的親水表面(對於純水的室溫潤濕角度為5度的表面)上進行GISAXS測定之結果示於圖1，而在疏水表面(對於純水的室溫潤濕角度為60度的表面)上進行GISAXS測定之結果示於圖2。圖1和2指出在任何情況中，自GISAXS製造平面內(in-plane)繞射圖。 1.785g of monomer A, 38mg reversible addition of preparation example 1. Split chain transfer (RAFT) agent (cyanoisopropyl dithiobenzoate), 14 mg free radical initiator (azobisisobutyronitrile, AIBN), and 4.765 mL of benzene are introduced to a 10-mL Schlenk bottle The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to RAFT polymerization at 70 ° C for 4 hours. After completion of the polymerization reaction, the reaction solution was precipitated in 250 mL of an extraction solvent (methanol) and then dried under reduced pressure by filtration to obtain a pink macroinitiator. The yield of this macroinitiator was about 83.1% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 11,400 and 1.15, respectively. 0.3086 g of macroinitiator, 1.839 g of pentafluorostyrene monomer, and 0.701 mL. The benzene was introduced into a 10-mL Schlenk bottle, and stirred at room temperature for 30 minutes under a nitrogen atmosphere, followed by a RAFT polymerization reaction at 115 ° C for 4 hours. After completion of the polymerization reaction, the reaction solution was precipitated in 250 mL of an extraction solvent (methanol) and then dried under reduced pressure by filtration to give a pale pink block copolymer. The yield of this block copolymer was about 27.1% by weight, while Mn and Mw/Mn were 18,900 and 1.19, respectively. The above block copolymer contains Block 1 (derived from Monomer A prepared according to Preparation Example 1) and Block 2 (derived from the aforementioned pentafluorostyrene monomer). In the foregoing manner, the results of the GISAXS measurement on the hydrophilic surface of the block copolymer (the surface having a room temperature wetting angle of 5 degrees for pure water) are shown in Fig. 1, while on the hydrophobic surface (wetting at room temperature for pure water) The results of the GISAXS measurement on the surface having an angle of 60 degrees are shown in Fig. 2. Figures 1 and 2 indicate that in any case, an in-plane diffraction pattern is fabricated from GISAXS.

實例2. Example 2.

根據實例1之方法，藉由使用巨引發劑及五 氟苯乙烯作為單體，除了使用得自製備例3的單體B代替得自製備例1的單體A，製備嵌段共聚物。該嵌段共聚物含有嵌段1(其衍生自製備例3的單體B)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，而在親水表面和疏水表面二者上觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, by using a giant initiator and five A fluorostyrene was used as a monomer, and a block copolymer was prepared except that the monomer B obtained in Preparation Example 3 was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from monomer B of Preparation Example 3) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). The GISAXS was carried out on the block copolymer by the method described in Example 1, while an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

實例3. Example 3.

根據實例1之方法，藉由使用巨引發劑及五氟苯乙烯作為單體，除了使用得自製備例4的單體C代替得自製備例1的單體A，製備嵌段共聚物。該嵌段共聚物含有嵌段1(其衍生自製備例4的單體C)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，在親水表面和疏水表面二者上觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, a block copolymer was prepared by using a macroinitiator and pentafluorostyrene as a monomer, except that the monomer C obtained in Preparation Example 4 was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from monomer C of Preparation 4) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). The GISAXS was carried out on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

實例4. Example 4.

根據實例1之方法，藉由使用巨引發劑及五氟苯乙烯作為單體，除了使用得自製備例5的單體D代替得自製備例1的單體A，製備嵌段共聚物。該嵌段共聚物含有嵌段1(其衍生自製備例5的單體D)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，在親水表面和疏水表面二者上觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, a block copolymer was prepared by using a macroinitiator and pentafluorostyrene as a monomer, except that the monomer D obtained in Preparation Example 5 was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from monomer D of Preparation 5) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). The GISAXS was carried out on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

實例5. Example 5.

根據實例1之方法，藉由使用巨引發劑及五 氟苯乙烯作為單體，除了使用得自製備例6的單體E代替得自製備例1的單體A，製備嵌段共聚物。該嵌段共聚物含有嵌段1(其衍生自製備例6的單體E)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，在親水表面和疏水表面二者上觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, by using a giant initiator and five A fluorostyrene was used as a monomer, and a block copolymer was prepared except that the monomer E obtained in Preparation Example 6 was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from monomer E of Preparation Example 6) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). The GISAXS was carried out on the block copolymer by the method described in Example 1, and an in-plane diffraction pattern was observed on both the hydrophilic surface and the hydrophobic surface.

比較例1. Comparative Example 1.

根據實例1之方法，藉由使用巨引發劑及五氟苯乙烯作為單體，除了使用得自製備例2的單體G代替得自製備例1的單體A，製備嵌段共聚物。該嵌段共聚物含有嵌段1(其衍生自製備例2的單體G)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，但在親水表面和疏水表面任一者上未觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, a block copolymer was prepared by using a macroinitiator and pentafluorostyrene as a monomer, except that the monomer G obtained in Preparation Example 2 was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains Block 1 (which is derived from Monomer G of Preparation Example 2) and Block 2 (which is derived from the aforementioned pentafluorostyrene monomer). GISAXS was carried out on the block copolymer by the method described in Example 1, but no in-plane diffraction pattern was observed on either the hydrophilic surface or the hydrophobic surface.

比較例2. Comparative Example 2.

根據實例1之方法，藉由使用巨引發劑和五氟苯乙烯作為單體，製備嵌段共聚物，但使用甲基丙烯酸4-甲氧基苯酯代替得自製備例1的單體A。該嵌段共聚物含有嵌段1(其衍生自甲基丙烯酸4-甲氧基苯酯)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，但在親水表面和疏水表面任一者上未觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, a block copolymer was prepared by using a macroinitiator and pentafluorostyrene as a monomer, but 4-methoxyphenyl methacrylate was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from 4-methoxyphenyl methacrylate) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). GISAXS was carried out on the block copolymer by the method described in Example 1, but no in-plane diffraction pattern was observed on either the hydrophilic surface or the hydrophobic surface.

比較例3. Comparative Example 3.

根據實例1之方法，藉由使用巨引發劑和五 氟苯乙烯作為單體，製備嵌段共聚物，但使用甲基丙烯酸十二酯代替得自製備例1的單體A。該嵌段共聚物含有嵌段1(其衍生自甲基丙烯酸十二酯)和嵌段2(其衍生自前述五氟苯乙烯單體)。藉實例1描述之方法，在嵌段共聚物上進行GISAXS，但在親水表面和疏水表面任一者上未觀察到平面內(in-plane)繞射圖。 According to the method of Example 1, by using a giant initiator and five A fluorostyrene was used as a monomer to prepare a block copolymer, but dodecyl methacrylate was used instead of the monomer A obtained in Preparation Example 1. The block copolymer contains block 1 (which is derived from dodecyl methacrylate) and block 2 (which is derived from the aforementioned pentafluorostyrene monomer). GISAXS was carried out on the block copolymer by the method described in Example 1, but no in-plane diffraction pattern was observed on either the hydrophilic surface or the hydrophobic surface.

彙整以上實例和比較例的巨引發劑和製得的嵌段共聚物的GPC測定結果並示於以下的表2。 The GPC measurement results of the macroinitiator of the above examples and comparative examples and the obtained block copolymer are shown in Table 2 below.

藉前述方式評估上述製得之嵌段共聚物的性質，並彙整其結果且示於以下表3。 The properties of the above-obtained block copolymers were evaluated in the foregoing manner, and the results were summarized and shown in Table 3 below.

彙整製備以上嵌段共聚物各者中所用的巨引發劑(即，嵌段1)之XRD圖的分析結果並示於以下表4(比較例3的情況中，在0.5nm-1至10nm-1的散射向量範圍內未觀察到單一峰)。 The results of analysis of the XRD patterns of the macroinitiators (i.e., block 1) used in each of the above block copolymers were summarized and shown in Table 4 below (in the case of Comparative Example 3, at 0.5 nm -1 to 10 nm - A single peak was not observed in the scattering vector range of 1 .

試驗例1.自組性質之評估 Test Example 1. Evaluation of self-organizing properties

將實例或比較例的嵌段共聚物溶於氟苯中至固體濃度為0.7重量%所製得之塗覆溶液旋轉塗覆(塗覆面積：寬×長=1.5cm×1.5cm)在矽晶圓上至厚度約5nm，於室溫乾燥約1小時，之後於約160℃的溫度熱退火約1小時以形成自組膜。取得膜的掃描式電子顯微(SEM)影像。圖3至7各者分別對應於實例1至5的各個膜的SEM影像。如影像中所示者，實例的各嵌段共聚物具有自組膜，其有效地形成線圖案。反之，比較例的情況中，誘發的相分離程度不足。例如，圖8出示比較例3的SEM結果，其指出未有效地誘發相分離。 The coating solution prepared by dissolving the block copolymer of the example or the comparative example in fluorobenzene to a solid concentration of 0.7% by weight was spin-coated (coating area: width × length = 1.5 cm × 1.5 cm) in twin crystal The film was dried to a thickness of about 5 nm, dried at room temperature for about 1 hour, and then thermally annealed at a temperature of about 160 ° C for about 1 hour to form a self-assembled film. A scanning electron microscopy (SEM) image of the film was taken. 3 to 7 correspond to SEM images of the respective films of Examples 1 to 5, respectively. As shown in the image, each block copolymer of the example has a self-assembled film that effectively forms a line pattern. On the contrary, in the case of the comparative example, the degree of phase separation induced was insufficient. For example, FIG. 8 shows the SEM results of Comparative Example 3, which indicates that phase separation is not effectively induced.

試驗例2.自組性質之評估 Test Example 2. Evaluation of self-organizing properties

藉試驗例1中描述的方法，以實例1中製得的嵌段共聚物形成聚合物膜。各個聚合物膜形成於矽基板(其經食人魚溶液處理，對於純水的室溫潤濕角度是5度)、氧化矽基板(其中，以上潤濕角度是約45度)、和經HMDS處理的矽基板(其中，以上潤濕角度是約60度)各者上。圖9至11出示具有以上潤濕角度分別是5度、45度和60度的聚合物膜的SEM影像。影像指出，無論基板的表面性質如何，該嵌段共聚物能夠有效地實現相分離結 構。 A polymer film was formed from the block copolymer obtained in Example 1 by the method described in Test Example 1. Each polymer film is formed on a ruthenium substrate (which is treated with a piranha solution, the room temperature wetting angle for pure water is 5 degrees), a ruthenium oxide substrate (wherein the above wetting angle is about 45 degrees), and HMDS treated The crucible substrate (wherein the above wetting angle is about 60 degrees) is on each. Figures 9 through 11 show SEM images of polymer films having the above wetting angles of 5, 45 and 60 degrees, respectively. The image indicates that the block copolymer can effectively achieve phase separation regardless of the surface properties of the substrate. Structure.

試驗例3. Test Example 3.

藉實例1中描述的方法製備嵌段共聚物BCP1至BCP4，但藉由控制介於單體和巨引發劑之間的莫耳比之類，調整數學式A中的X值。 The block copolymers BCP1 to BCP4 were prepared by the method described in Example 1, but the X value in Mathematical Formula A was adjusted by controlling the molar ratio between the monomer and the macroinitiator.

將以上嵌段共聚物各者溶於氟苯中至固體濃度為0.7重量%而製得的塗覆溶液旋轉塗覆(塗覆面積：寬×長=1.5cm×1.5cm)在矽晶圓上至厚度約5nm，於室溫乾燥約1小時，之後於約160℃的溫度熱退火約1小時以形成膜。在以上膜上進行GISAXS，而測得的結果製成影像。圖19至21分別出示BCP1、BCP2和BCP3的結果。影像中指出，在以上嵌段共聚物中觀察到GISAXS平面內(in-plane)繞射圖。但在BCP4的情況中，無法辨視任何清楚的結果。 The coating solution prepared by dissolving each of the above block copolymers in fluorobenzene to a solid concentration of 0.7% by weight was spin-coated (coating area: width × length = 1.5 cm × 1.5 cm) on a silicon wafer. To a thickness of about 5 nm, it was dried at room temperature for about 1 hour, and then thermally annealed at a temperature of about 160 ° C for about 1 hour to form a film. GISAXS was performed on the above film, and the measured results were made into images. Figures 19 to 21 show the results of BCP1, BCP2 and BCP3, respectively. The image indicates that a GISAXS in-plane diffraction pattern was observed in the above block copolymer. However, in the case of BCP4, no clear results can be discerned.

Claims (26)

一種包含第一嵌段和第二嵌段之嵌段共聚物，其中該第一嵌段滿足以下的條件1至4中之一或多者，且該第一嵌段和該第二嵌段具有彼此不同的化學結構和10mN/m或更低之表面能量差的絕對值，其中，條件1：在低掠角廣角度X射線散射(grazing-incidence wide-angle X-ray scattering,GIWAXS)光譜的繞射圖中，在-90度至-70度和70度至90度的方位角範圍中觀察到5度至70度範圍的半高寬的峰(方位角係藉由GIWAXS光譜的面外繞射圖角度設定為0度而測得)，其中散射向量範圍由12nm-1至16nm-1：條件2：在DSC分析期間內，在-80℃至200℃的範圍內製得熔化轉變峰或等向轉變峰：條件3：當在X-射線繞射(XRD)分析期間內的散射向量(q)範圍由0.5nm-1至10nm-1時，觀察到其半高寬由0.2至0.9nm-1範圍的峰：條件4：該第一嵌段包括側鏈，其中在XRD分析期間內，側鏈中的成鏈原子數(n)和散射向量(q)滿足以下的數學式：[數學式1]3nm-1至5nm-1=nq/(2×π)其中，在該數學式1中，n代表該側鏈中包括的該成鏈原子數，而q代表在該嵌段共聚物上進行XRD分析的 期間內，其可偵測到的峰的最小散射向量(q)或觀察到具有最大峰面積之峰的散射向量(q)。 A block copolymer comprising a first block and a second block, wherein the first block satisfies one or more of the following conditions 1 to 4, and the first block and the second block have The chemical structure different from each other and the absolute value of the surface energy difference of 10 mN/m or lower, wherein condition 1: the grazing-incidence wide-angle X-ray scattering (GIWAXS) spectrum at low sweep angle In the diffraction pattern, a half-height width peak in the range of 5 degrees to 70 degrees is observed in the azimuth range of -90 degrees to -70 degrees and 70 degrees to 90 degrees (the azimuth angle is the out-of-plane winding by the GIWAXS spectrum) The angle of the image is set to 0 degrees, where the scattering vector ranges from 12 nm -1 to 16 nm -1 : Condition 2: During the DSC analysis, a melting transition peak is obtained in the range of -80 ° C to 200 ° C or Isotropic transition peak: Condition 3: When the scattering vector (q) during X-ray diffraction (XRD) analysis ranges from 0.5 nm -1 to 10 nm -1 , its full width at half maximum is observed from 0.2 to 0.9 nm. peak-1 range: condition 4: the first block includes a side chain wherein the XRD analysis period, the number of chain atoms to the side chain (n) and the scattering vector (q) satisfies the following Mathematical formula: [Mathematical Formula 1] 3nm -1 to 5nm -1 = nq / (2 × π) wherein, in the mathematical formula 1, n represents the number of atoms in the chain to the side chain included, and q represents The minimum scattering vector (q) of the detectable peak or the scattering vector (q) of the peak having the largest peak area was observed during the XRD analysis on the block copolymer. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段製造根據條件2的該熔化轉變峰和該等向轉變峰二者，其中介於製造該等向轉變峰的溫度(Ti)和製造該熔化轉變峰的溫度(Tm)之間的溫度差(Ti-Tm)是5℃至70℃。 The block copolymer of claim 1, wherein the first block produces both the melting transition peak and the isotropic transition peak according to Condition 2, wherein a temperature at which the isotropic transition peak is produced (Ti The temperature difference (Ti-Tm) between the temperature (Tm) at which the melting transition peak is produced is 5 ° C to 70 ° C. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段製造根據條件2的該熔化轉變峰和該等向轉變峰二者，其中該熔化轉變峰的面積(M)對該等向轉變峰的面積(I)之比(M/I)的範圍由0.1至500。 The block copolymer of claim 1, wherein the first block produces both the melting transition peak and the isotropic transition peak according to Condition 2, wherein the area (M) of the melting transition peak is such The ratio (M/I) of the area (I) to the transition peak ranges from 0.1 to 500. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段製造根據條件2之介於-10℃和55℃之間的該熔化轉變峰。 The block copolymer of claim 1, wherein the first block produces the melting transition peak between -10 ° C and 55 ° C according to Condition 2. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括側鏈並滿足以下的數學式1，此根據條件2： 其中在該數學式1中，Tm代表出現該熔化轉變峰的溫度，而n代表該側鏈中含括的成鏈原子數。 The block copolymer of claim 1, wherein the first block comprises a side chain and satisfies the following Mathematical Formula 1, according to Condition 2: In the mathematical formula 1, Tm represents the temperature at which the melting transition peak appears, and n represents the number of chain-forming atoms included in the side chain. 如申請專利範圍第1項之嵌段共聚物，其中以下的數學式2中的X是1.25或更高：[數學式2]X=1+(D×M)/(K×L)其中在該數學式A中，D代表該第二嵌段的密度(D2)對該第一嵌段的密度(D1)之比(D2/D1)； M代表該第一嵌段的莫耳質量(M1)對該第二嵌段的莫耳質量(M2)之比(M1/M2)；K代表在1H-NMR光譜中，根據該第二嵌段製造的峰面積(A2)對根據該第一嵌段製造的峰面積(A1)之比(A2/A1)；而L代表該第一嵌段的1莫耳重複單元中的氫原子數(H1)對該第二嵌段的1莫耳重複單元中的氫原子數(H2)之比(H1/H2)。 The block copolymer of claim 1, wherein X in the following Mathematical Formula 2 is 1.25 or higher: [Math 2] X = 1 + (D × M) / (K × L) In the formula A, D represents the ratio of the density (D2) of the second block to the density (D1) of the first block (D2/D1); M represents the molar mass of the first block (M1) a molar mass (M2) ratio (M1/M2) to the second block; K represents a peak area (A2) pair produced according to the second block in the 1 H-NMR spectrum according to the first The ratio of the peak area (A1) produced by the block (A2/A1); and L represents the number of hydrogen atoms (H1) in the 1 molar repeating unit of the first block, and 1 mole of the second block The ratio of the number of hydrogen atoms (H2) in the unit (H1/H2). 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段或該第二嵌段包括芳族結構。 The block copolymer of claim 1, wherein the first block or the second block comprises an aromatic structure. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段和該第二嵌段各者包括芳族結構。 The block copolymer of claim 1, wherein the first block and the second block each comprise an aromatic structure. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括無鹵原子的芳族結構，而該第二嵌段包括含括一或多個鹵原子的芳族結構。 The block copolymer of claim 1, wherein the first block comprises an aromatic structure free of halogen atoms, and the second block comprises an aromatic structure comprising one or more halogen atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段或該第二嵌段包括含括8或更多個成鏈原子的側鏈。 The block copolymer of claim 1, wherein the first block or the second block comprises a side chain comprising 8 or more chain-forming atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段或該第二嵌段包括一或多個鹵原子。 The block copolymer of claim 1, wherein the first block or the second block comprises one or more halogen atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括具8或更多個成鏈原子的側鏈，而該第二嵌段包括一或多個鹵原子。 The block copolymer of claim 1, wherein the first block comprises a side chain having 8 or more chain-forming atoms, and the second block comprises one or more halogen atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第 一嵌段或該第二嵌段包括具8或更多個成鏈原子的側鏈所連接的芳族結構。 Such as the block copolymer of claim 1, wherein the The one block or the second block includes an aromatic structure to which a side chain having 8 or more chain-forming atoms is attached. 如申請專利範圍第13項之嵌段共聚物，其中該側鏈藉氧原子或氮原子連接至芳族結構。 The block copolymer of claim 13, wherein the side chain is bonded to the aromatic structure by an oxygen atom or a nitrogen atom. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段1或該第二嵌段包括經一或多個鹵原子部分取代的芳族結構。 The block copolymer of claim 1, wherein the first block 1 or the second block comprises an aromatic structure partially substituted with one or more halogen atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括含括8或更多個成鏈原子的側鏈所連接的芳族結構，且該第二嵌段包括含括鹵原子的芳族結構。 The block copolymer of claim 1, wherein the first block comprises an aromatic structure comprising a side chain comprising 8 or more chain-forming atoms, and the second block comprises a halogen-containing The aromatic structure of an atom. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括含括8或更多個成鏈原子的側鏈。 The block copolymer of claim 1, wherein the first block comprises a side chain comprising 8 or more chain-forming atoms. 如申請專利範圍第17項之嵌段共聚物，其中該第一嵌段包括經側鏈部分取代的環結構。 The block copolymer of claim 17, wherein the first block comprises a ring structure substituted with a side chain moiety. 如申請專利範圍第18項之嵌段共聚物，其中該環結構不包括鹵原子。 The block copolymer of claim 18, wherein the ring structure does not include a halogen atom. 如申請專利範圍第17項之嵌段共聚物，其中該第二嵌段包括3或更多個鹵原子。 The block copolymer of claim 17, wherein the second block comprises 3 or more halogen atoms. 如申請專利範圍第20項之嵌段共聚物，其中該第二嵌段包括經鹵原子部分取代的環結構。 The block copolymer of claim 20, wherein the second block comprises a ring structure partially substituted with a halogen atom. 如申請專利範圍第1項之嵌段共聚物，其中該第一嵌段包括藉以下結構式1表示的結構單元： 其中在該結構式1中，R代表氫原子或具1至4個碳原子的烷基；X代表單鍵、氧原子、硫原子、-S(=O)2-、羰基、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1代表氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基；和Y代表單價取代基，其包括含括8或更多個成鏈原子之鏈所連接的環結構。 The block copolymer of claim 1, wherein the first block comprises a structural unit represented by the following structural formula 1: Wherein in the structural formula 1, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, a carbonyl group, an alkylene group, An alkenyl group, an alkynyl group, -C(=O)-X 1 - or -X 1 -C(=O)-, wherein X 1 represents an oxygen atom, a sulfur atom, -S(=O) 2 -, An alkyl group, an alkenyl group or an alkynylene group; and Y represents a monovalent substituent comprising a ring structure comprising a chain comprising 8 or more chain-forming atoms. 如申請專利範圍第1項之嵌段共聚物，其中該第二嵌段包括以下結構式3所示的結構單元： 其中在該結構式3中，X2代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基、伸炔基、-C(=O)-X1-或-X1-C(=O)-，其中X1代表單鍵、氧原子、硫原子、-S(=O)2-、伸烷基、伸烯基或伸炔基；和 W代表包括至少一個鹵原子的芳基。 The block copolymer of claim 1, wherein the second block comprises the structural unit represented by the following structural formula 3: Wherein in the structural formula 3, X 2 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X 1 - or -X 1 -C(=O)-, wherein X 1 represents a single bond, an oxygen atom, a sulfur atom, -S(=O) 2 -, an alkylene group, an extended alkenyl group or an alkynylene group; and W represents An aryl group including at least one halogen atom. 一種包括如申請專利範圍第1項之嵌段共聚物的聚合物膜，其中該嵌段共聚物經自組(self-assembled)。 A polymer film comprising the block copolymer of claim 1 wherein the block copolymer is self-assembled. 一種形成聚合物膜之方法，其包含：包括申請專利範圍第1項之嵌段共聚物之聚合物膜形成於基板上，其中該嵌段共聚物經自組。 A method of forming a polymer film comprising: forming a polymer film comprising the block copolymer of claim 1 of the invention on a substrate, wherein the block copolymer is self-assembled. 一種形成圖案之方法，該方法包含：自形成於基板上並包括嵌段共聚物的聚合物膜移除申請專利範圍第1項之嵌段共聚物的第一嵌段或第二嵌段，其中該嵌段共聚物經自組。 A method of forming a pattern, the method comprising: removing a first block or a second block of a block copolymer of claim 1 from a polymer film formed on a substrate and comprising a block copolymer, wherein The block copolymer is self-assembled.
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