TW201630954A - Block copolymer - Google Patents

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

Block copolymer

This application relates to block copolymers and uses thereof.

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.

The present application provides block copolymers, polymeric films, methods of forming polymeric films, and methods of forming patterns.

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.

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.

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.

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.

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.

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.

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.

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) .

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.

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).

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).

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

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.

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).

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).

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.

[Math A] X=1+(D×M)/(K×L)

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.

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).

Hereinafter, the foregoing conditions will be described in more detail.

A. Condition 1

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.

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).

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.

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.

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. Condition 2

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.

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. Condition 3

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.

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.

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.

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.

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.

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.

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.

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.

A block copolymer satisfying the above mathematical formula can exhibit excellent phase separation or excellent self-organizing properties.

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. Condition 4

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.

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.

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).

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.

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 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. Condition 5

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.

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

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.

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.

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.

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. Condition 6

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.

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.

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. Condition 7

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.

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.

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. Condition 8

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.

[Math A] X=1+(D×M)/(K×L)

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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)-.

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.

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.

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.

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.

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.

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.

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).

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).

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.

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.

In another example, X in Structural Formula 1 also represents -C(=O)O- or -OC(=O)-.

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.

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.

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.

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.

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.

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.

In another example, X _{2 of} Structural Formula 3 can represent a single bond or an alkylene group.

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.

In another example, the structural unit shown in Structural Formula 3 can also be represented by the following Structural Formula 4.

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 .

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.

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.

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.

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).

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.

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.

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.

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)).

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.

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).

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

Further, the nanowires or nanopores in the above structure can be made to have a high aspect ratio.

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.

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.

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.

Each of Figures 1 and 2 presents a GISAXS diffraction pattern.

Each of Figures 3 to 11 shows an SEM image of the polymer film.

Each of Figures 12 through 17 presents the results of the GIGASS analysis.

FIG. 18 illustrates a method of calculating the K value in Math.

Each of Figures 19 through 21 shows a GISAXS diffraction pattern.

efficacy

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.

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 measurement

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.

<Abbreviation of application>

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. Gel Penetration Chromatography (GPC)

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 measurement conditions>

Device: 1200 Series from Agilent Technologies Inc.

Column: Two Polymer Laboratories' PLgel MIXED-B

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1mg/mL, injection 200L

Standard sample: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

3.GISAXS (low sweep angle small angle X-ray scattering)

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 analysis method

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. Surface energy measurement

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 (low sweep angle wide angle X-ray scattering)

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.

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 analysis

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. Determine the X by Mathematical Formula A

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.

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.

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.

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.

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.

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.

Preparation Example 1. Synthesis of Monomer A

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 analysis results>

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).

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 analysis results>

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).

In the structural formula A, R represents a linear alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Monomer G

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 analysis results>

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).

In the formula G, R represents a linear alkyl group having 4 carbon atoms.

Preparation 3. Synthesis of Monomer B

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 analysis results>

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).

In the formula B, R represents a linear alkyl group having 8 carbon atoms.

Preparation 4. Synthesis of Monomer C

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 analysis results>

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).

In the formula C, R represents a linear alkyl group having 10 carbon atoms.

Preparation Example 5. Synthesis of Monomer D

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 analysis results>

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).

In the formula D, R represents a linear alkyl group having 14 carbon atoms.

Preparation Example 6. Synthesis of Monomer E

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 analysis results>

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).

In the formula E, R represents a linear alkyl group having 16 carbon atoms.

Results of GIWAXS and DSC analysis

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.

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.

Example 1.

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.

Example 2.

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.

Example 3.

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.

Example 4.

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.

Example 5.

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.

Comparative Example 1.

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.

Comparative Example 2.

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.

Comparative Example 3.

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.

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.

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.

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 .

Test Example 1. Evaluation of self-organizing properties

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.

Test Example 2. Evaluation of self-organizing properties

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.

Test Example 3.

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.

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)

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. 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. 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. 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. 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. 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). The block copolymer of claim 1, wherein the first block or the second block comprises an aromatic structure. The block copolymer of claim 1, wherein the first block and the second block each comprise an aromatic structure. 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. 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. The block copolymer of claim 1, wherein the first block or the second block comprises one or more halogen atoms. 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. 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. The block copolymer of claim 13, wherein the side chain is bonded to the aromatic structure by an oxygen atom or a nitrogen atom. 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. 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. The block copolymer of claim 1, wherein the first block comprises a side chain comprising 8 or more chain-forming atoms. The block copolymer of claim 17, wherein the first block comprises a ring structure substituted with a side chain moiety. The block copolymer of claim 18, wherein the ring structure does not include a halogen atom. The block copolymer of claim 17, wherein the second block comprises 3 or more halogen atoms. The block copolymer of claim 20, wherein the second block comprises a ring structure partially substituted with a halogen atom. 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. 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. A polymer film comprising the block copolymer of claim 1 wherein the block copolymer is self-assembled. 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. 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.