KR101780100B1 - Block copolymer - Google Patents

Block copolymer Download PDF

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Publication number
KR101780100B1
KR101780100B1 KR1020140175414A KR20140175414A KR101780100B1 KR 101780100 B1 KR101780100 B1 KR 101780100B1 KR 1020140175414 A KR1020140175414 A KR 1020140175414A KR 20140175414 A KR20140175414 A KR 20140175414A KR 101780100 B1 KR101780100 B1 KR 101780100B1
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KR
South Korea
Prior art keywords
block
block copolymer
chain
example
nm
Prior art date
Application number
KR1020140175414A
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Korean (ko)
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KR20150067073A (en
Inventor
박노진
김정근
이제권
이미숙
구세진
최은영
윤성수
Original Assignee
주식회사 엘지화학
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Priority to KR1020130151867 priority Critical
Priority to KR20130151865 priority
Priority to KR1020130151865 priority
Priority to KR20130151867 priority
Priority to KR20130151866 priority
Priority to KR1020130151866 priority
Priority to KR1020130159994 priority
Priority to KR20130159994 priority
Priority to KR20140131964 priority
Priority to KR1020140131964 priority
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority claimed from EP14867808.9A external-priority patent/EP3078689A4/en
Publication of KR20150067073A publication Critical patent/KR20150067073A/en
Priority claimed from CN201580060099.7A external-priority patent/CN107075052B/en
Priority claimed from TW104132194A external-priority patent/TWI609029B/en
Priority claimed from US15/515,432 external-priority patent/US10287430B2/en
Priority claimed from PCT/KR2015/010327 external-priority patent/WO2016053005A1/en
Priority claimed from PCT/KR2015/010335 external-priority patent/WO2016053011A1/en
Priority claimed from JP2017517277A external-priority patent/JP6538158B2/en
Priority claimed from CN201580060150.4A external-priority patent/CN107075055B/en
Priority claimed from US15/514,929 external-priority patent/US10370529B2/en
Priority claimed from US15/515,821 external-priority patent/US10703897B2/en
Publication of KR101780100B1 publication Critical patent/KR101780100B1/en
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00Living radical polymerisation
    • C08F2438/03Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2353/00Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00

Abstract

The present application relates to block copolymers and uses thereof. The present application can provide a block copolymer and its use that can be effectively used in various applications because of its excellent self-assembling property.

Description

BLOCK COPOLYMER < RTI ID = 0.0 >

The present application relates to block copolymers and uses thereof.

The block copolymer has a molecular structure in which polymer blocks having different chemical structures are linked via covalent bonds. The block copolymer can form a periodically arranged structure such as a sphere, a cylinder or a lamella by phase separation. The size of the domain of the structure formed by the self-assembling phenomenon of the block copolymer can be widely controlled, and various types of structures can be manufactured. Thus, various next-generation nano-structures such as high density magnetic storage media, nanowire fabrication, And can be applied to pattern formation by devices, magnetic recording media, lithography, or the like.

The present application provides a block copolymer, a polymer membrane including the block copolymer, a method of forming the polymer membrane, a pattern forming method, and the like.

The block copolymer may include a first block and a second block different from the first block. The block copolymer may be a diblock copolymer containing only the first and second blocks, or may be a block copolymer further comprising other blocks besides the first and second blocks.

Since the block copolymer contains two or more chains of chains linked by covalent bonds, phase separation occurs. In the present application, the above-mentioned phase separation is very effectively performed by satisfying any one or two or more of the parameters described below, thereby forming a nanoscale structure by microphase seperation. In the present application, the shape and size of the nanostructure formed by the phase separation can be freely controlled by controlling the size of the block copolymer such as the molecular weight and the relative ratio of the blocks. Through the use of the block copolymer of the present application, phase separation structures such as spheres, cylinders, gyroids, lamellas, and inverted structures can be freely formed in various sizes. The inventors of the present invention have confirmed that the self-assembling property or phase separation property is greatly improved by satisfying at least one of the various parameters described below in the block copolymer. The block copolymer of the present application may satisfy either one of the following parameters or two or more parameters at the same time. It has been found that the block copolymer can be made to exhibit vertical orientation through the satisfaction of appropriate parameters. In the present application, the term " vertical orientation " refers to the orientation of the block copolymer, and the orientation of the nanostructure formed by the block copolymer may mean an orientation perpendicular to the substrate direction. The technique of adjusting the self-assembled structure of the block copolymer horizontally or vertically on various substrates occupies a very large proportion in the practical application of the block copolymer. Usually, the orientation of the nanostructure in the film of the block copolymer is determined by which of the blocks forming the block copolymer is exposed to the surface or air. In general, since a plurality of substrates are polar and air is non-polar, a block having a larger polarity among blocks of the block copolymer is wetted to the substrate, and a block having a smaller polarity is wetted at the interface with air ). Therefore, various techniques have been proposed to allow the blocks having different characteristics of the block copolymer to be wetted simultaneously on the substrate side, and the most representative technique is the adjustment of the orientation using neutral surface preparation. However, in one aspect of the present application, by properly adjusting the following parameters, it is possible to obtain a perpendicular orientation even for a substrate on which a known process is not performed, in which the block copolymer is known to achieve vertical alignment including neutral surface treatment and the like This is possible. For example, a block copolymer according to one aspect of the present application may exhibit vertical orientation both on a hydrophilic surface on which no particular pretreatment has been performed, or on a hydrophobic surface. Further, in a further aspect of the present application, such a vertical orientation may be induced in a short period of time by thermal annealing.

The block copolymer of one aspect of the present application may form a film exhibiting an in-plane diffraction pattern of Grazing Incidence Small Angle X-ray Scattering (GISAXS) on a hydrophobic surface. The block copolymer may form a film exhibiting an inflation impingement diffraction pattern on a hydrophilic surface by Grazing Incidence Small Angle X-ray Scattering (GISAXS).

Indicating the diffraction pattern of inflation in GISAXS in the present application may mean that it exhibits a peak perpendicular to the X coordinate in the GISAXS diffraction pattern in the GISAXS analysis. This peak is confirmed by the vertical orientation of the block copolymer. Therefore, the block copolymer exhibiting the inflation-induced diffraction pattern has vertical orientation. In a further example, the peak identified in the X coordinate of the GISAXS diffraction pattern may be at least two or more, and in the presence of a plurality of peaks, the scattering vectors (q values) of the peak may be identified with an integer ratio, In this case, the phase separation efficiency of the block copolymer can be further improved.

The term vertical in the present application is an expression in consideration of an error, and may mean an error including, for example, errors within ± 10 degrees, ± 8 degrees, ± 6 degrees, ± 4 degrees, or ± 2 degrees.

A block copolymer capable of forming a film exhibiting a diffraction pattern on inflation on both hydrophilic and hydrophobic surfaces can exhibit vertical orientation characteristics on various surfaces without performing any separate treatment to induce vertical orientation. The term hydrophobic surface in the present application means a surface having a wetting angle with respect to purified water in the range of 5 to 20 degrees. Examples of hydrophobic surfaces include, but are not limited to, surfaces of silicon treated with oxygen plasma, sulfuric acid or pyran solution. The term hydrophilic surface in the present application means a surface having a room temperature wetting angle with respect to purified water in the range of 50 to 70 degrees. Examples of the hydrophilic surface include a surface of PDMS (polydimethylsiloxane) treated with oxygen plasma, a surface of silicon treated with hexamethyldisilazane (HMDS), a surface of silicon treated with hydrofluoric acid (HF), and the like. no.

Unless otherwise specified, physical properties that may vary with temperature, such as wetting angle in the present application, are values measured at room temperature. The term ambient temperature is a natural, non-warming or non-warming temperature and may refer to a temperature of about 10 ° C to 30 ° C, about 25 ° C, or about 23 ° C.

The film exhibiting the inflation impression diffraction pattern on the hydrophilic or hydrophobic surface and on the sagittal incident incidence scattering (GISAXS) may be a thermal annealed film. The film for measuring the fine angle incident incidence scattering (GISAXS) can be obtained, for example, by coating a coating solution prepared by diluting the above block copolymer with a solvent (for example, flourobenzene) at a concentration of about 0.7 wt% (thickness: 1.5 cm, length: 1.5 cm) and a thickness of 2.25 cm < 2 >. The thermal aging can be performed by, for example, The film may be maintained at a temperature of about 160 DEG C for about 1 hour. The grinding angle incident incidence angle scattering (GISAXS) is measured by incidence of X-rays at an incident angle within the range of about 0.12 to 0.23 degrees A diffraction pattern emerging from the film can be obtained with a known measuring device (for example, 2D marCCD). A method of confirming the presence of a diffraction pattern of inflation impression through the diffraction pattern is as follows: Jiyida.

The block copolymer exhibiting the aforementioned peaks in the fine angle incident incidence scattering (GISAXS) can exhibit excellent self-assembling properties, and such properties can be effectively controlled according to the purpose.

The block copolymer of the present application can exhibit at least one peak within a predetermined range of the scattering vector (q) in XRD analysis (X-ray diffraction analysis, X-ray diffraction analysis).

For example, the block copolymer may exhibit at least one peak within the range of the scattering vector (q) of 0.5 nm -1 to 10 nm -1 in the X-ray diffraction analysis. The scattering vector q at which the peak appears may be 0.7 nm -1 or more, 0.9 nm -1 or more, 1.1 nm -1 or more, 1.3 nm -1 or 1.5 nm -1 or more in another example. In another example, the scattering vector q at which the peak appears may be 9 nm -1 or less, 8 nm -1 or less, 7 nm -1 or less, 6 nm -1 or less, 5 nm -1 or less, 4 nm -1 or less, 3.5 nm -1 or 3 nm -1 or less.

The full width at half maximum (FWHM) of the peak identified within the range of the scattering vector (q) may be in the range of 0.2 to 0.9 nm -1 . The half-height width may be at least 0.25 nm -1, at least 0.3 nm -1, or at least 0.4 nm -1 in other examples. The half-height width may be 0.85 nm -1 or less, 0.8 nm -1 or 0.75 nm -1 or less in other examples.

The term half-height width in the present application may mean the width of the peak (the difference in the scattering vector q) at a position showing the intensity of 1/2 of the intensity of the maximum peak.

The scattering vector (q) and the half-height width in the XRD analysis are numerical values obtained by a numerical analytical method using a minimum left-hand method, as a result of XRD analysis described later. In this method, a portion showing the smallest intensity in the XRD diffraction pattern is taken as a baseline, and the intensity of the XRD pattern peak is set to a Gaussian and the scattering vector and the half height width can be obtained from the fitted results. The R square at the time of Gaussian fitting is at least 0.9, at least 0.92, at least 0.94, or at least 0.96. The manner of obtaining the above information from the XRD analysis is known, and for example, a numerical analysis program such as an origin can be applied.

The block copolymer exhibiting the half height width peak within the range of the scattering vector (q) may include a crystalline portion suitable for self-assembly. The block copolymer identified within the scope of the above-described scattering vector (q) can exhibit excellent self-assembling properties.

XRD analysis can be performed by passing X-rays through a block copolymer sample and measuring the scattering intensity according to the scattering vector. XRD analysis can be performed on the block copolymer without any special pretreatment, for example, after the block copolymer is dried under suitable conditions and then transmitted through X-rays. An X-ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm can be applied. A 2D diffraction pattern that is scattered in the sample is obtained as an image by using a measuring device (for example, 2D marCCD), and the obtained diffraction pattern is fitted in the above-described manner to obtain a scattering vector, a half-height width, .

As will be described later, when at least one block of the block copolymer contains a side chain, the number (n) of chain-forming atoms of the side chain is determined by the scattering vector (q) obtained by the X- The following equation (1) can be satisfied.

[Equation 1]

3 nm -1 to 5 nm -1 = nq / (2 x π)

In the formula 1, n is the number of the chain-forming atoms and q is the smallest scattering vector (q) in which the peak is observed in the X-ray diffraction analysis of the block copolymer, or a peak of the largest peak area is observed Is a scattering vector (q). In Equation (1),? Represents the circularity.

The scattering vector and the like introduced into the formula (1) are values obtained by the method mentioned in the above-mentioned X-ray diffraction analysis method.

The scattering vector q introduced in Equation 1 may be, for example, a scattering vector q within a range of 0.5 nm -1 to 10 nm -1 . In another example, the scattering vector q introduced into Equation 1 may be 0.7 nm -1 or more, 0.9 nm -1 or more, 1.1 nm -1 or more, 1.3 nm -1 or 1.5 nm -1 or more. In another example, the scattering vector q introduced into the above formula 1 is 9 nm -1 or less, 8 nm -1 or less, 7 nm -1 or less, 6 nm -1 or less, 5 nm -1 or less, 4 nm -1 or less , 3.5 nm -1 or less, or 3 nm -1 or less.

Formula (1) represents the relationship between the distance (D) between the blocks containing the side chain chain and the number of chain forming atoms of the side chain chain when the block copolymer is self-assembled to form a phase separation structure, When the number of chain-forming atoms of the side chain in the block copolymer satisfies the above-mentioned formula 1, the crystallinity represented by the side chain is increased and consequently the phase-separating property or the vertical orientation of the block copolymer can be greatly improved. The nq / (2 x pi) according to the above formula 1 may be 4.5 nm -1 or less in another example. The interval (D, unit: nm) between the blocks including the side chain in the above can be calculated by the following equation: D = 2 x? / Q where D is the interval , < / RTI > and < RTI ID = 0.0 > q < / RTI >

In the present application, the term chain-forming atom means an atom which forms the side-chain chain bonded to the block copolymer, and which forms a straight-chain structure of the chain. The side chain may be linear or branched, but the number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and other atoms bonded to the chain-forming atoms (for example, A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not calculated. For example, in the case of a branched chain, the number of chain forming atoms may be calculated as the number of chain forming atoms forming the longest chain region. For example, when the side chain is an n-pentyl group, all of the chain-forming atoms are carbon atoms, and the number of the chain-forming atoms is 5 even when the side chain is a 2-methylpentyl group. The chain-forming atom may be exemplified by carbon, oxygen, sulfur or nitrogen, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of the chain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

In one aspect of the present application, the absolute value of the difference between the surface energy of the first block of the block copolymer and the surface energy of the second block is 10 mN / m or less, 9 mN / m or less, 8 mN / m or less, 7.5 mN / m or less or 7 mN / m or less. The absolute value of the difference in surface energy may be 1.5 mN / m, 2 mN / m or 2.5 mN / m or more. The structure in which the first block and the second block having the absolute value of the difference in surface energy in this range are connected by covalent bonding can induce effective microphase seperation by phase separation due to proper non-availability. The first block may be, for example, a block having the above-described side chain.

Surface energy can be measured using a Drop Shape Analyzer (DSA100, KRUSS). Specifically, the surface energy of a sample solution (block copolymer or homopolymer) to be measured is diluted with fluorobenzene to a solid concentration of about 2% by weight, and the coating solution is applied to the substrate with a thickness of about 50 nm and a coating area of 4 cm 2 (2 cm in length, 2 cm in length) and dried at room temperature for about 1 hour and then thermally annealed at 160 ° C for about 1 hour. The process of dropping the deionized water whose surface tension is known in the film subjected to thermal aging and obtaining the contact angle is repeated 5 times to obtain an average value of the obtained five contact angle values and similarly, The process of dropping the known diiodomethane and determining the contact angle thereof is repeated five times, and an average value of the obtained five contact angle values is obtained. Thereafter, the surface energy can be obtained by substituting the value (Strom value) of the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angle with the deionized water and diiodo methane obtained. The numerical value of the surface energy for each block of the block copolymer can be obtained by the method described above for a homopolymer produced only of the monomers forming the block.

When the block copolymer includes the above-described side chain chain, the block including the side chain chain may have a higher surface energy than other blocks. For example, if the first block of the block copolymer comprises a side chain, the first block may have a higher surface energy than the second block. In this case, the surface energy of the first block may be in the range of about 20 mN / m to 40 mN / m. The surface energy of the first block may be greater than or equal to 22 mN / m, greater than or equal to 24 mN / m, greater than or equal to 26 mN / m, or greater than or equal to 28 mN / m. The surface energy of the first block may be 38 mN / m or less, 36 mN / m or less, 34 mN / m or less, or 32 mN / m or less. The first block is included, and the block copolymer showing the difference in surface energy as the second block and the like can exhibit excellent self-assembling properties.

The absolute value of the difference between the density of the first block and the second block in the block copolymer is 0.25 g / cm 3 or more, 0.3 g / cm 3 or more, 0.35 g / cm 3 or more, 0.4 g / cm 3 or more, or 0.45 g / cm < 3 >. The absolute value of the density difference may be 0.9 g / cm 3 or more, 0.8 g / cm 3 or less, 0.7 g / cm 3 or less, 0.65 g / cm 3 or less, or 0.6 g / cm 3 or less. The structure in which the first block having the absolute value of the density difference in this range and the second block are connected by the covalent bond can induce effective microphase seperation by phase separation due to proper non-availability.

The density of each block of the block copolymer can be measured by a known buoyancy method. For example, the mass of the block copolymer in a solvent such as ethanol, which is known in mass and density in air, is analyzed The density can be measured.

When the block copolymer includes the above-described side chain chain, the block including the side chain chain may have a lower density than other blocks. For example, if the first block of the block copolymer comprises a side chain, the first block may have a lower density than the second block. In this case, the density of the first block may be in the range of about 0.9 g / cm 3 to about 1.5 g / cm 3 . The density of the first block may be 0.95 g / cm < 3 > or more. The density of the first block is 1.4 g / cm < 3 > 1.3 g / cm < 3 > 1.2 g / cm < 3 > 1.1 g / cm < 3 > Or 1.05 g / cm < 3 > ≪ / RTI > Such a first block is included, and a block copolymer exhibiting such a density difference with the second block can exhibit excellent self-assembling properties. The above-mentioned surface energy and density may be values measured at room temperature.

The block copolymer may include a block having a volume fraction falling within a range of 0.4 to 0.8 and a block having a volume fraction falling within a range of 0.2 to 0.6. When the block copolymer comprises a side chain chain, the volume fraction of the block having the side chain chain may be in the range of 0.4 to 0.8. For example, when the side chain is included in the first block, the volume fraction of the first block may be in the range of 0.4 to 0.8, and the volume fraction of the second block may be in the range of 0.2 to 0.6. The sum of the volume fractions of the first block and the second block may be one. The block copolymer containing each block in the above volume fraction can exhibit excellent self-assembling properties. The volume fraction of each block of the block copolymer can be determined based on the density of each block and the molecular weight measured by GPC (Gel Permeation Chromatography).

The number average molecular weight (Mn) of the block copolymer may be in the range of, for example, 3,000 to 300,000. In the present specification, the term number average molecular weight refers to a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph). In the present specification, the term molecular weight refers to a number average molecular weight unless otherwise specified. The molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000 or more, 13000 or more, or 15000 or more in other examples. In another example, the molecular weight (Mn) is not more than 250,000, less than 200,000, less than or equal to 180,000, less than or equal to 160,000, less than or equal to 140000, less than or equal to 120000, less than or equal to 100000, less than or equal to 90000, less than or equal to 80000, less than or equal to 70000, Or 25,000 or less. The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.60. In another example, the degree of dispersion may be at least about 1.1, at least about 1.2, at least about 1.3, or at least about 1.4.

In this range, the block copolymer can exhibit proper self-assembling properties. The number average molecular weight of the block copolymer and the like can be adjusted in consideration of the desired self-assembling structure and the like.

When the block copolymer contains at least the first and second blocks, the ratio of the first block in the block copolymer, for example, the block including the above-described side chain chain is from 10 mol% to 90 mol% Lt; / RTI >

The block copolymer may be a diblock copolymer including the first and second blocks, or may be a block copolymer including another block covalently linked to the first or second block.

The above-mentioned parameters can be achieved, for example, through control of the structure of the block copolymer. For example, at least one or both of the first block and the second block of the block copolymer satisfying at least one of the above-mentioned parameters may comprise at least an aromatic structure. The first block and the second block may all include an aromatic structure, and in this case, the aromatic structures included in the first and second blocks may be the same or different. In addition, at least one of the first and second blocks of the block copolymer satisfying at least one of the above-mentioned parameters may contain the above-described side chain chain or may include at least one halogen atom described later, The halogen atom may be substituted in the aromatic structure. The block copolymer of the present application may comprise two blocks or may comprise more blocks.

As described above, the first block and / or the second block of the block copolymer may include an aromatic structure. The aromatic structure may be included in only one of the first and second blocks, or may be included in both blocks. When both blocks include an aromatic structure, the aromatic structures included in each block may be the same or different from each other.

As used herein, the term aromatic structure, aryl group or arylene group, unless otherwise specified, includes a benzene ring, or two or more benzene rings are linked together sharing one or two carbon atoms, A structure derived from a compound including a structure linked by a linker or a derivative thereof, a monovalent residue or a divalent residue. The aryl group or arylene group may be, for example, an aryl group having 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. Examples of the aryl group or the arylene group include benzene and the like, naphthalene, azobenzene, anthracene, phenanthrene, tetracene, pyrene, A monovalent or divalent residue derived from benzopyrene or the like may be exemplified.

The aromatic structure may be a structure contained in a block main chain or a structure in which a block main chain is connected in a side chain form. Adjustment of the above-described parameters may be possible through appropriate control of the aromatic structure that each block may contain.

For example, in order to control the above-mentioned parameters, the first block of the block copolymer may have chains with more than eight chain forming atoms connected to the side chains. In the present specification, the term chain and side chain chain may refer to the same object. When the first block comprises an aromatic structure, the chain may be connected to the aromatic structure.

The term branched chain may refer to a chain connected to the backbone of the polymer. The side chain chain may be a chain containing at least 8, at least 9, at least 10, at least 11 or at least 12 chain forming atoms as mentioned above. The number of chain-forming atoms may also be not more than 30, not more than 25, not more than 20, or not more than 16. The chain forming atom may be a carbon, oxygen, nitrogen or sulfur atom, and may suitably be carbon or oxygen.

As the branched chain, a hydrocarbon chain such as an alkyl group, an alkenyl group or an alkynyl group can be exemplified. At least one of the carbon atoms of the hydrocarbon chain may be replaced by a sulfur atom, an oxygen atom or a nitrogen atom.

When the side chain is connected to an aromatic structure, the chain may be directly connected to the aromatic structure or may be connected via a linker. The linker is an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, a carbonyl group, an alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, and the like can be exemplified, in the above R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl can be date, X 1 is a single bond, an oxygen atom, a sulfur atoms, -NR 2 -, -S (= O) 2 -, alkylene, alkenylene, or alkynylene may be an, at the R 2 is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group or aryl date . Suitable linkers may be exemplified by oxygen atoms. The side chain may be connected to the aromatic structure via, for example, an oxygen atom or a nitrogen atom.

When the aromatic structure is connected to the main chain of the block in the form of a side chain, the aromatic structure may be directly connected to the main chain or may be connected via a linker. In this case, linker, oxygen atom, sulfur atom, -S (= O) 2 - , a carbonyl group, an alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 - C (= O) - and the like can be exemplified, wherein X 1 may be a single bond, an oxygen atom, a sulfur atom, -S (= O) 2 -, an alkylene group, an alkenylene group or an alkynylene group. Suitable linkers connecting the aromatic structure to the backbone include, but are not limited to, -C (= O) -O- or -OC (= O) -.

In another example, the aromatic structure included in the first and / or second block of the block copolymer may comprise one or more, two or more, three or more, four or more, or five or more halogen atoms. The number of halogen atoms may be, for example, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. Examples of the halogen atom include fluorine or chlorine, and the use of a fluorine atom may be advantageous. As described above, a block having an aromatic structure containing a halogen atom can efficiently realize a phase separation structure through proper interaction with other blocks.

Examples of the aromatic structure containing a halogen atom include, but are not limited to, aromatic structures having 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.

In the case where both the first and second blocks in the block copolymer include an aromatic structure, the first block includes an aromatic structure not containing a halogen atom and the second block contains a halogen atom Containing aromatic structure. The aromatic structure of the first block may be linked to the above-mentioned side chain chain directly or via a linker including oxygen or nitrogen.

When the block copolymer comprises a block having a side chain chain, this block may be, for example, a block represented by the following general formula (1).

[Chemical Formula 1]

Figure 112014119427250-pat00001

Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2 -, a carbonyl group, an alkylene group, an alkenylene 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, And Y is a monovalent substituent group comprising a ring structure having a chain having 8 or more chain forming atoms linked thereto.

The term single bond in the present application means that no separate atom is present at that site. For example, when X in the general formula (1) is a single bond, a structure in which Y is directly connected to a polymer chain can be realized.

As used herein, unless otherwise specified, the alkyl group may be a straight, branched or cyclic alkyl group of 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 optionally be substituted by one or more substituents, provided that when the side chain is an alkyl group, the alkyl group may have 8 or more, 9 or more, 10 or more, 11 or 12 or more carbons Atoms, and the number of carbon atoms of the alkyl group may be 30 or less, 25 or less, 20 or less, or 16 or less).

As used herein, the term alkenyl or alkynyl group means a straight, branched or cyclic alkyl group 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, Alkenyl group or alkynyl group which may optionally be substituted by one or more substituents, provided that the above-mentioned alkenyl or alkynyl group as the side chain is at least 8, at least 9, at least 10, at least 11, Or more than 12 carbon atoms, and the number of carbon atoms of the alkenyl group or alkynyl group may be 30 or less, 25 or less, 20 or less, or 16 or less).

The term alkylene group as used herein includes, unless otherwise specified, a linear, branched or cyclic alkylene group having 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 optionally be substituted by one or more substituents.

The term alkenylene group or alkynylene group as used herein means a straight chain, branched chain or ring having 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, Lt; / RTI > alkylene group, which may optionally be substituted by one or more substituents.

Further, X in the general formula (1) may be -C (= O) O- or -OC (= O) - in another example.

In the general formula (1), Y is a substituent containing the above-mentioned chain, and may be, for example, a substituent containing an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms. The chain may be, for example, a straight chain alkyl group containing at least 8, at least 9, at least 10, at least 11, or at least 12 carbon atoms. The alkyl group may contain up to 30, up to 25, up to 20 or up to 16 carbon atoms. Such a chain may be directly connected to the aromatic structure or via the above-mentioned linker.

The first block may be represented by the following formula (2) in another example.

(2)

Figure 112014119427250-pat00002

R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C (= O) -O-, P is an arylene group having 6 to 12 carbon atoms, Q is an oxygen atom, Z is a chain- Lt; RTI ID = 0.0 > 8 < / RTI >

In Formula (3), P may be phenylene in another example, and Z may be a straight chain alkyl group having 9 to 20 carbon atoms, 9 to 18 carbon atoms, or 9 to 16 carbon atoms in another example. In the above, when P is phenylene, Q may be connected to the para position of the phenylene. In the above, the alkyl group, arylene group, phenylene group and chain may be optionally substituted with one or more substituents.

When the block copolymer includes a block having an aromatic structure containing a halogen atom, the block may be, for example, a block represented by the following formula (3).

(3)

Figure 112014119427250-pat00003

In formula 3 X 2 is a single bond, an oxygen atom, sulfur atom, -S (= O) 2 - , alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) - and, in the X 1 is a single bond, oxygen atom, sulfur atom, -S (= O) 2 - , alkylene group, alkenyl group or alkynyl group, and W is at least one halogen Is an aryl group containing an atom.

X 2 in Formula (3) may be a single bond or an alkylene group in another example.

In formula (3), the aryl group of W may be an aryl group having 6 to 12 carbon atoms or may be a phenyl group, and the aryl group or phenyl group may have one or more, two or more, three or more, four or five or more halogen atoms . The number of halogen atoms in the above may 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 may be exemplified.

The block of formula (3) may be represented by the following formula (4) in another example.

[Chemical Formula 4]

Figure 112014119427250-pat00004

In formula (4), X 2 is as defined in formula (2), R 1 to R 5 are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms contained in R 1 to R 5 is 1 or more to be.

In formula (4), R 1 to R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or halogen, wherein the halogen may be chlorine or fluorine.

In Formula 4, at least 2, at least 3, at least 4, at least 5 or at least 6 of R 1 to R 5 may contain a halogen. The upper limit of the number of halogen atoms is not particularly limited and may be, for example, 12 or less, 8 or less, or 7 or less.

The block copolymer may be a block copolymer containing either one or both of the above two types of blocks together with another block or containing only the two types of blocks.

The manner of producing the block copolymer is not particularly limited. The block copolymer is polymerized by, for example, an LRP (Living Radical Polymerization) method. Examples thereof include an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator to form an alkali metal or alkaline earth metal , An anion polymerization method in which an organic alkali metal compound is used as a polymerization initiator and synthesized in the presence of an organoaluminum compound, an anion polymerization method using an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Atomic Transfer Radical Polymerization (ATRP), and ICAR (Atomization Transfer), which perform polymerization under an organic or inorganic reducing agent that generates electrons using an atom transfer radical polymerization agent as a polymerization initiator. Initiators for continuous activator regeneration) Atom Transfer Radical Polymerization (ATRP) (RAFT) using a reversible addition-cleavage chain transfer agent using a reducing agent addition-cleavage chain transfer agent, or a method using an organic tellurium compound as an initiator. Among these methods, an appropriate method can be selected and applied.

For example, the block copolymer can be prepared in a manner that includes polymerizing a reactant containing monomers capable of forming the block in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization . The preparation of the block copolymer may further include, for example, a step of precipitating the polymerization product produced through the above process in the non-solvent.

The kind of the radical initiator is not particularly limited and may be appropriately selected in consideration of the polymerization efficiency. For example, AIBN (azobisisobutyronitrile) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2 ' -azobis- (2,4-dimethylvaleronitrile), and peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP).

The living radical polymerization process can be carried out in the presence of a base such as, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, Amide, dimethylsulfoxide or dimethylacetamide, and the like.

Examples of the non-solvent include ethers such as alcohols such as methanol, ethanol, n-propanol or isopropanol, glycols such as ethylene glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, But is not limited thereto.

The present application is also directed to a polymer membrane comprising said block copolymer. The polymer membrane can be used for various purposes, for example, various electronic or electronic devices, a process of forming the pattern, a recording medium such as a magnetic storage medium, a flash memory, or a biosensor.

In one example, the block copolymer in the polymer membrane may be self-assembled to implement a cyclic structure including a sphere, a cylinder, a gyroid or a lamellar, . Such a structure may be vertically oriented. For example, in a block copolymer, other segments within the segments of the first or second block or other covalently bonded blocks may form a regular structure such as a lamellar or cylinder shape, And may be vertically oriented.

The polymer membrane of the present application can exhibit a peak perpendicular to the X coordinate in the above-described inflation impression diffraction pattern, that is, the GISAXS diffraction pattern in the GISAXS analysis. In a further example, the peak identified in the X coordinate of the GISAXS diffraction pattern may be at least two or more, and when there are a plurality of peaks, the scattering vector (q values) of the peak may be identified with an integer ratio.

The present application also relates to a method for forming a polymer film using the block copolymer. The method may include forming a polymer membrane including the block copolymer on a substrate in a self-assembled state. For example, the method may include coating the block copolymer or a coating solution containing the block copolymer to form a layer, and then aging the layer. The aging process may be a thermal annealing process or a solvent annealing process.

Thermal aging can be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and can be performed at, for example, a temperature above the glass transition temperature or the phase transition temperature. The time at which such thermal aging is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed as required. The heat treatment temperature in the thermal aging process may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used.

Further, the solvent aging step may be performed in a non-polar solvent and / or a polar solvent at a suitable room temperature for about 1 minute to 72 hours.

The present application also relates to a method of pattern formation. The above method is a method for selectively removing the first or second block of the block copolymer in a laminate having a substrate and a polymer film formed on the surface of the substrate and self-assembled with the block copolymer . ≪ / RTI > The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymeric film comprising the block copolymer on a substrate, selectively removing one or more blocks of the block copolymer present in the film, and then etching the substrate . In this way, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation. The type of the substrate to be applied to this method is not particularly limited and may be selected as required. For example, silicon oxide or the like may be applied.

For example, the method can form a nanoscale pattern of silicon oxide that exhibits a high aspect ratio. For example, the polymer film is formed on silicon oxide, and one block of the block copolymer is selectively removed while the block copolymer in the polymer film forms a predetermined structure. Thereafter, the silicon oxide is removed in various ways, for example, , Reactive ion etching, or the like to form various patterns including patterns of nano-rods or nano holes. In addition, it is possible to realize a nano pattern having a large aspect ratio through such a method.

For example, the pattern can be implemented in a scale of several tens of nanometers, and such a pattern can be utilized for various purposes including, for example, a next-generation information electronic magnetic recording medium and the like.

For example, the method can form a pattern in which nanostructures having a width of about 10 nm to 40 nm, for example, nanowires are disposed at intervals of about 20 nm to 80 nm. In another example, it is possible to implement a structure in which a width of about 10 nm to 40 nm, for example, nano holes having a diameter of about 20 nm to 80 nm is formed.

Also, in the above structure, the nanowires and nano holes can have a large aspect ratio.

The method of selectively removing one block of the block copolymer in the above method is not particularly limited. For example, a method of removing a relatively soft block by irradiating an appropriate electromagnetic wave, for example, ultraviolet light, Can be used. In this case, the ultraviolet ray irradiation conditions are determined depending on the type of the block of the block copolymer, and can be performed, for example, by irradiating ultraviolet light having a wavelength of about 254 nm for 1 minute to 60 minutes.

Following the ultraviolet irradiation, the polymer membrane may be treated with an acid or the like to further remove the segment decomposed by ultraviolet rays.

The step of selectively etching the substrate using the polymer film from which the block is removed is not particularly limited and may be performed by, for example, a reactive ion etching step using CF 4 / Ar ions, etc., followed by an oxygen plasma Removing the polymer membrane from the substrate by treatment or the like.

The present application can provide a block copolymer and its use that can be used effectively in various applications because of its excellent self-assembly property or phase separation property.

1 and 2 are diagrams showing a GISAXS diffraction pattern.
3 to 11 are SEM photographs of the polymer membrane.
12 to 14 are diagrams showing a GISAXS diffraction pattern.

Hereinafter, the present application will be described in detail by way of examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

One. NMR  Measure

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. NMR measurement solvent (CDCl3) Was diluted to a concentration of about 10 mg / ml, and the chemical shift was expressed in ppm.

<Application Abbreviation>

br = broad signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = double triplet, q = quartet, p = octet, m = polyline.

2. GPC ( Come Permeation Chromatograph )

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel Permeation Chromatography). Add a sample to be analyzed such as a block copolymer or a macroinitiator of the example or comparative example into a 5 mL vial and dilute with tetrahydrofuran (THF) to a concentration of about 1 mg / mL. After that, the calibration standard sample and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. The analytical program used was a ChemStation from Agilent Technologies. The elution time of the sample was compared with a calibration curve to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the molecular weight distribution (PDI ) Were calculated. The measurement conditions of GPC are as follows.

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

Standard samples: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

3. GISAXS ( Grazing Incidence Small Angle  X ray Scattering )

The GISAXS analysis was performed using a Pohang accelerator 3C beamline. The block copolymer to be analyzed was diluted with fluorobenzene to a solid concentration of about 0.7 wt% to prepare a coating solution, and the coating solution was spin-coated on the substrate to a thickness of about 5 nm. The coating area is 2.25 cm2 (Width: 1.5 cm, length: 1.5 cm). The coated polymer membrane was dried at room temperature for about 1 hour and then thermally annealed at about 160 ° C for about 1 hour to induce a phase separation structure. Then, a film having a phase separation structure was formed. An X-ray diffraction pattern was obtained by scattering in a film with a detector (2D marCCD) after the X-ray was incident on the film at an incident angle within the range of about 0.12 to 0.23 degrees corresponding to the angle between the critical angle of the film and the critical angle of the substrate. At this time, the distance from the film to the detector was selected within a range of about 2 m to 3 m so that the self-assembly pattern formed on the film was well observed. The substrate may be a substrate having a hydrophilic surface (a silicon substrate treated with a piranha solution and having a room temperature wetting angle of about 5 degrees relative to pure water) or a substrate having a hydrophobic surface (HMDS (hexamethyldisilazane) A silicon substrate having a recessed angle of about 60 degrees) was used.

4. XRD  Analysis method

The XRD analysis was performed by measuring the scattering intensity according to the scattering vector (q) by passing X-rays through the sample at the Pohang accelerator 4C beamline. As a sample, a block copolymer synthesized in the absence of a specific pretreatment was purified and then dried in a vacuum oven for one day to obtain a powdery block copolymer, which was used in an XRD measurement cell. For XRD pattern analysis, an X-ray with a vertical size of 0.023 mm and a horizontal size of 0.3 mm was used and a 2D marCCD was used as a detector. A scattered 2D diffraction pattern was obtained as an image. The obtained diffraction patterns were analyzed by numerical analytical method using the minimum left - hand method to obtain information such as the scattering vector and the half - height width. In the analysis, an origin program was applied. A portion having the smallest intensity in the XRD diffraction pattern was taken as a baseline, and the intensity was set to be 0, The profile of the XRD pattern peak was subjected to Gaussian fitting, and the above scattering vector and half height width were obtained from the fitted results. The R square was at least 0.96 at the time of Gaussian fitting.

5. Measurement of surface energy

Surface energy was measured using a Drop Shape Analyzer (product of DSU100, KRUSS). The material to be measured (polymer) was diluted with flourobenzene to a solid concentration of about 2% by weight to prepare a coating solution. The coating solution was applied to a silicon wafer at a thickness of about 50 nm and a coating area of 4 cm 2 : 2 cm, length: 2 cm). The coating layer was dried at room temperature for about 1 hour and then subjected to thermal annealing at about 160 ° C for about 1 hour. The process of dropping the deionized water whose surface tension is known in the film subjected to thermal aging and obtaining the contact angle thereof was repeated 5 times to obtain an average value of the obtained five contact angle values. In the same manner, the process of dropping the diiodomethane having known surface tension and determining the contact angle thereof was repeated five times, and an average value of the obtained five contact angle values was obtained. The surface energy was determined by substituting the value (Strom value) of the surface tension of the solvent by the Owens-Wendt-Rabel-Kaelble method using the average value of the contact angle with the deionized water and diiodo methane obtained. The numerical values of surface energy for each block of the block copolymer were obtained by the method described above with respect to a homopolymer made only of the monomer forming the block.

6. Volume Fractional  Measure

The volume fraction of each block of the block copolymer was calculated based on the density at room temperature of each block and the molecular weight measured by GPC. The density was measured using a buoyancy method. Specifically, a sample to be analyzed was put into a solvent (ethanol) having a known mass and density in the air, and the mass was calculated.

Manufacturing example  One. Of the monomer (A)  synthesis

The compound (DPM-C12) shown below was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were placed in a 250-mL flask and dissolved in 100 mL of acetonitrile. Potassium carbonate was added and reacted at 75 ° C for about 48 hours under nitrogen. After the reaction, the remaining potassium carbonate was filtered off and acetonitrile used in the reaction was removed. A mixed solvent of DCM (dichloromethane) and water was added thereto to work up, and the separated organic layers were collected and dehydrated by passing through MgSO 4 . Subsequently, the title compound (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as white solid was obtained in a yield of about 37% using dichloromethane in column chromatography.

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d6.77 (dd, 4H); d4.45 (s, 1 H); d3.89 (t, 2H); d 1.75 (p, 2H); d1.43 (p, 2H); d 1.33-1.26 (m, 16H); d 0.88 (t, 3 H).

(9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol) and DMAP (p-dimethylaminopyridine) , 13.9 mmol), 120 mL of methylene chloride was added, and the reaction was allowed to proceed at room temperature under nitrogen for 24 hours. After completion of the reaction, the salt (urea salt) produced during the reaction was filtered off and the remaining methylene chloride was removed. The resulting product was recrystallized in a mixed solvent of methanol and water (1: 1 mixture) to obtain the title compound (7.7 g, 22.2 mmol) as a white solid. 1H-NMR (DMSO-d6) 63%. &Lt; / RTI &gt;

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d7.02 (dd, 2H); d 6.89 (dd, 2 H); d6.32 (dt, 1 H); d5.73 (dt, 1 H); d 3.94 (t, 2 H); d 2.05 (dd, 3H); d, 1.76 (p, 2H); d1.43 (p, 2H); 1.34-1.27 (m, 16H); d 0.88 (t, 3 H).

(A)

Figure 112017041858705-pat00027

In formula (A), R is a straight chain alkyl group having 12 carbon atoms.

Manufacturing example  2. Of the monomer (G)  synthesis

A compound of the following formula G was synthesized in the same manner as in Preparation Example 1 except that 1-bromobutane was used instead of 1-bromododecane. NMR analysis results of the above compound are as follows.

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d7.02 (dd, 2H); d 6.89 (dd, 2 H); d6.33 (dt, 1 H); d5.73 (dt, 1 H); d 3.95 (t, 2 H); d 2.06 (dd, 3 H); d, 1.76 (p, 2H); d1.49 (p, 2H); d0.98 (t, 3H).

[Formula G]

Figure 112017041858705-pat00028

In formula (G), R is a straight-chain alkyl group having 4 carbon atoms.

Manufacturing example  3. Of the monomer (B)  synthesis

A compound of the following formula (B) was synthesized in the same manner as in Preparation Example 1 except that 1-bromo octane was used instead of 1-bromododecane. NMR analysis results for the above compounds are shown below. & Lt; NMR analysis result & gt ;

1 H-NMR (CDCl 3) : d7.02 (dd, 2H); d 6.89 (dd, 2 H); d6.32 (dt, 1 H); d5.73 (dt, 1 H); d 3.94 (t, 2 H); d 2.05 (dd, 3H); d, 1.76 (p, 2H); d1.45 (p, 2H); 1.33-1.29 (m, 8H); d0.89 (t, 3H).

[Chemical Formula B]

Figure 112017041858705-pat00029

In formula (B), R is a straight chain alkyl group having 8 carbon atoms.

Manufacturing example  4. Of the monomer (C)  synthesis

A compound of the following formula (C) was synthesized in the same manner as in Preparation Example 1 except that 1-bromododecane was used instead of 1-bromododecane. NMR analysis results for the above compounds are shown below.

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d7.02 (dd, 2H); d 6.89 (dd, 2 H); d6.33 (dt, 1 H); d5.72 (dt, 1 H); d 3.94 (t, 2 H); d 2.06 (dd, 3 H); d 1.77 (p, 2H); d1.45 (p, 2H); 1.34-1.28 (m, 12H); d0.89 (t, 3H).

&Lt; RTI ID = 0.0 &

Figure 112017041858705-pat00030

In formula (C), R is a straight chain alkyl group having 10 carbon atoms.

Manufacturing example  5. Of the monomer (D)  synthesis

A compound of the following formula (D) was synthesized in the same manner as in Preparation Example 1 except that 1-bromotetradecane was used instead of 1-bromododecane. NMR analysis results for the above compounds are shown below.

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d7.02 (dd, 2H); d 6.89 (dd, 2 H); d6.33 (dt, 1 H); d5.73 (dt, 1 H); d 3.94 (t, 2 H); d 2.05 (dd, 3H); d 1.77 (p, 2H); d1.45 (p, 2H); 1.36-1.27 (m, 20H); d 0.88 (t, 3H.)

[Chemical Formula D]

Figure 112017041858705-pat00031

In formula (D), R is a straight chain alkyl group having 14 carbon atoms.

Manufacturing example  6. Of the monomer (E)  synthesis

A compound of the following formula (E) was synthesized in the same manner as in Preparation Example 1 except that 1-bromohexadecane was used instead of 1-bromododecane. NMR analysis results for the above compounds are shown below.

< NMR  Analysis results>

1 H-NMR (CDCl 3) : d7.01 (dd, 2H); d 6.88 (dd, 2 H); d6.32 (dt, 1 H); d5.73 (dt, 1 H); d 3.94 (t, 2 H); d 2.05 (dd, 3H); d 1.77 (p, 2H); d1.45 (p, 2H); 1.36-1.26 (m, 24H); d0.89 (t, 3H)

(E)

Figure 112017041858705-pat00032

In formula (E), R is a straight chain alkyl group having 16 carbon atoms.

Example  One.

2.0 g of the monomer (A) of Preparation Example 1, 64 mg of cyanoisoproyldithiobenzoate as a reversible addition fragmentation chain transfer (RAFT) reagent, 23 mg of azobisisobutyronitrile (AIBN) as a radical initiator and 5.34 mL of benzene were dissolved in 10 mL of Schlenk flask and stirred at room temperature for 30 minutes under a nitrogen atmosphere. Reversible Addition-Fragmentation chain transfer (RAFT) polymerization was carried out at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to give a giant initiator of pink color. The yield of the macromonomer was about 82.6% by weight and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 9,000 and 1.16, respectively. 0.3 g of a macroinitiator, 2.7174 g of pentafluorostyrene monomer, and 1.306 mL of benzene were placed in a 10 mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) The reaction was carried out. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The yield of the block copolymer was about 18% by weight, and the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the monomer (A) of Production Example 1 and a second block derived from the pentafluorostyrene monomer. The results of measurement of GISAXS (Grazing Incidence Small Angle X-ray Scattering) in the manner described above with respect to a surface having a room temperature wetting angle of 5 degrees against pure water as a hydrophilic surface for a block copolymer are shown in FIG. 1, The results of GISAXS (Grazing Incidence Small Angle X-ray Scattering) measured on the surface at a room temperature wetting angle of 60 degrees are shown in FIG. It can be seen from Figs. 1 and 2 that the GISAXS shows a diffraction pattern of inflation in either case.

Example  2.

A block copolymer was prepared in the same manner as in Example 1, except that the monomer (B) of Production Example 3 was used instead of the monomer (A) of Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer includes a first block derived from the monomer (B) of Production Example 3 and a second block derived from the pentafluorostyrene monomer. The GISAXS was performed on the block copolymer in the same manner as in Example 1, and the diffraction pattern of inflation on both hydrophilic and hydrophobic surfaces was confirmed.

Example  3.

A block copolymer was prepared in the same manner as in Example 1, except that the monomer (C) of Production Example 4 was used instead of the monomer (A) of Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer includes a first block derived from the monomer (C) of Production Example 4 and a second block derived from the pentafluorostyrene monomer. The GISAXS was performed on the block copolymer in the same manner as in Example 1, and the diffraction pattern of inflation on both hydrophilic and hydrophobic surfaces was confirmed.

Example  4.

A block copolymer was prepared in the same manner as in Example 1, except that the monomer (D) of Production Example 5 was used in place of the monomer (A) of Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer includes a first block derived from the monomer (D) of Production Example 5 and a second block derived from the pentafluorostyrene monomer. The GISAXS was performed on the block copolymer in the same manner as in Example 1, and the diffraction pattern of inflation on both hydrophilic and hydrophobic surfaces was confirmed.

Example  5.

A block copolymer was prepared in the same manner as in Example 1 except that the monomer (E) of Production Example 6 was used in place of the monomer (A) of Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer comprises a first block derived from the monomer (E) of Production Example 6 and a second block derived from the pentafluorostyrene monomer. The GISAXS was performed on the block copolymer in the same manner as in Example 1, and the diffraction pattern of inflation on both hydrophilic and hydrophobic surfaces was confirmed.

Comparative Example  One.

A block copolymer was prepared in the same manner as in Example 1 except that the monomer (G) of Production Example 2 was used in place of the monomer (A) of Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer includes a first block derived from the monomer (G) of Production Example 2 and a second block derived from the pentafluorostyrene monomer. GISAXS was performed on the block copolymer in the same manner as in Example 1, but the diffraction pattern of the inflation impression was not confirmed on both hydrophilic and hydrophobic surfaces.

Comparative Example  2.

Except that 4-methoxyphenylmethacrylate was used in place of the monomer (A) in Production Example 1, a block copolymer was prepared using a macromonomer and pentafluorostyrene as monomers in the same manner as in Example 1 Respectively. The block copolymer comprises a first block derived from the 4-methoxyphenyl methacrylate and a second block derived from the pentafluorostyrene monomer. GISAXS was performed on the block copolymer in the same manner as in Example 1, but the diffraction pattern of the inflation impression was not confirmed on both hydrophilic and hydrophobic surfaces.

Comparative Example  3.

A block copolymer was prepared in the same manner as in Example 1, except that dodecyl methacrylate was used instead of the monomer (A) in Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer comprises a first block derived from the dodecyl methacrylate and a second block derived from the pentafluorostyrene monomer. GISAXS was performed on the block copolymer in the same manner as in Example 1, but the diffraction pattern of the inflation impression was not confirmed on both hydrophilic and hydrophobic surfaces.

The results of GPC measurement of each of the macro initiators and the prepared block copolymers in the Examples and Comparative Examples are summarized in Table 1 below.


Example Comparative Example
One 2 3 4 5 One 2 3 MI
Mn 9000 9300 8500 8700 9400 9000 7800 8000
PDI 1.16 1.15 1.17 1.16 1.13 1.16 1.17 1.19 BCP
Mn 16300 19900 17100 17400 18900 18800 18700 16700
PDI 1.13 1.20 1.19 1.17 1.17 1.22 1.25 1.18 MI:
BCP: block copolymer
Mn: number average molecular weight
PDI: molecular weight distribution

The results of evaluating the properties of each of the above-prepared block copolymers in the above-mentioned manner are summarized in Table 2 below.


Example Comparative Example Ref
One 2 3 4 5 One 2 3
The first block
SE 30.83 31.46 27.38 26.924 27.79 37.37 48.95 19.1 38.3
De One 1.04 1.02 0.99 1.00 1.11 1.19 0.93 1.05 VF 0.66 0.57 0.60 0.61 0.61 0.73 0.69 0.76 - The second block

SE 24.4 24.4 24.4 24.4 24.4 24.4 24.4 24.4 41.8
De 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.57 1.18 VF 0.34 0.43 0.40 0.39 0.39 0.27 0.31 0.24 - SE difference 6.43 7.06 2.98 3.39 3.39 12.98 24.55 5.3 3.5 De Difference 0.57 0.53 0.55 0.57 0.57 0.46 0.38 0.64 0.13 Chain forming atom 12 8 10 16 16 4 One 12 - n / D 3.75 3.08 3.45 4.24 4.44 2.82 1.98 - - SE: surface energy (unit: mN / m)
De: density (unit: g / cm 3 )
VF: volume fraction
SE difference: the absolute value of the difference between the surface energy of the first block and the surface energy of the second block
De difference: the absolute value of the difference between the density of the first block and the density of the second block
Chain forming atom: the number of chain forming atoms of the first block
(n: number of chain-forming atoms, q is the largest peak area in the range of 0.5 nm -1 to 10 nm -1 of the scattering vector), n / D is the numerical value calculated by the equation 1 (nq / Scattering vector value at which the branching peak is identified)
Ref: Polystyrene-polymethyl methacrylate block copolymer (first block: polystyrene block, second block: polymethyl methacrylate block)

The results of analyzing the XRD patterns for each of the above block copolymers are summarized in the following Table 3 (in the case of Comparative Example 3, no peak was observed within the range of 0.5 nm -1 to 10 nm -1 of the scattering vector) .


Example Comparative Example
One 2 3 4 5 One 2 3 q peak value (unit: nm -1 ) 1.96 2.41 2.15 1.83 1.72 4.42 3.18 - Half height width (unit: nm -1 ) 0.57 0.72 0.63 0.45 0.53 0.97 1.06 -

Test Example  1. Evaluation of Self-Assembly Characteristics

The coating solution prepared by diluting the block copolymer of Example or Comparative Example to a solid content concentration of 0.7% by weight in fluorobenzene was spin-coated (coating area: width × length = 1.5) on the silicon wafer to a thickness of about 5 nm cm x 1.5 cm), dried at room temperature for about 1 hour, and then thermally annealed at about 160 ° C for about 1 hour to form a self-assembled film. Scanning electron microscope (SEM) images were taken of the formed film. Figs. 3 to 7 are SEM images taken with respect to Examples 1 to 5. Fig. As can be seen from the figure, in the case of the block copolymer of the examples, the self-assembled polymer film in the line pattern was effectively formed. In contrast, in the case of the comparative example, proper phase separation was not induced. For example, FIG. 8 shows the SEM results for Comparative Example 3, confirming that effective phase separation was not induced.

Test Example  2. Evaluation of self-assembly characteristics

A polymer membrane was formed on the block copolymer prepared in Example 1 in the same manner as in Test Example 1 above. The polymer film was formed on a silicon substrate treated with a pyranase solution having a room temperature wetting angle of 5 degrees for pure water, a silicon oxide substrate having a wetting angle of about 45 degrees and a hexamethyldisilazane (HMDS) treated silicon substrate having the wetting angle of about 60 degrees. FIGS. 9 to 11 are SEM images of the polymer membrane formed with respect to the wiping angles of 5 degrees, 45 degrees, and 60 degrees, respectively. From the figure, it can be confirmed that the block copolymer realizes a phase separation structure effectively regardless of the surface characteristics of the substrate.

Test Example  3.

In the same manner as in Example 1 Block copolymers were prepared, and block copolymers having different volume fractions were prepared by controlling the molar ratio of monomers to macro initiators.

The volume fractions of the prepared block copolymers are as follows.

The volume fraction of the first block The volume fraction of the second block Sample 1 0.7 0.3 Sample 2 0.59 0.41 Sample 3 0.48 0.52

The volume fraction of each block of the block copolymer was calculated on the basis of the density at room temperature of each block and the molecular weight measured by GPC (Gel Permeation Chromatograph). The density was measured using the buoyancy method. Specifically, the density was calculated through mass in a solvent (ethanol) in which mass and density in air were known, and GPC was calculated according to the above-described method.

A coating solution prepared by diluting a block copolymer of each sample with 0.7% by weight of solid content in fluorobenzene was spin-coated on a silicon wafer to a thickness of about 5 nm (coating area: width = 1.5 cm, Vertical length = 1.5 cm), dried at room temperature for about 1 hour, and then subjected to thermal annealing at a temperature of about 160 DEG C for about 1 hour to form a film. GISAXS was measured for the formed film in the manner described above and the results are shown in the figure. Figs. 12 to 14 are the results for Samples 1 to 3, respectively, from which it can be seen that the infra-red diffraction pattern is confirmed on the GISAXS, from which it can be predicted to have a vertical orientation.

Claims (22)

  1. A first block and a second block different from the first block,
    Forming a film showing a peak perpendicular to the X coordinate in a fine-angle incident incidence angle scattering (GISAXS) diffraction pattern on a surface at a room temperature wetting angle of pure water within a range of 5 to 20 degrees,
    (GISAXS) diffraction pattern on the surface at a room temperature wetting angle of pure water in the range of 50 to 70 degrees,
    Wherein the first block comprises an aromatic structure to which chains having at least 8 chain-forming atoms are connected.
  2. The block copolymer exhibiting a peak in the method, X-ray range in the scattering vector (q) in the diffraction 0.5 nm -1 to 10 -1 nm full width at half maximum is 0.2 nm -1 to 1.5 nm -1 to 1 coalescence.
  3. 2. The block copolymer according to claim 1, wherein the number (n) of chain-forming atoms in the chain of the first block satisfies the following formula:
    [Equation 1]
    3 nm -1 to 5 nm -1 = nq / (2 x π)
    In the formula 1, n is the number of the chain-forming atoms and q is the smallest scattering vector (q) in which the peak is observed in the X-ray diffraction analysis of the block copolymer, or a peak of the largest peak area is observed Is a scattering vector (q), and? Is a circularity.
  4. The method of claim 1, wherein the volume fraction of the first block is in the range of 0.4 to 0.8, the volume fraction of the second block is in the range of 0.2 to 0.6, the sum of the volume fractions of the first block and the second block is 1 In block copolymer.
  5. The block copolymer according to claim 1, wherein the absolute value of the difference in surface energy between the first block and the second block is in the range of 2.5 mN / m to 7 mN / m.
  6. 6. The block copolymer according to claim 5, wherein the surface energy of the first block is higher than the surface energy of the second block.
  7. The block copolymer according to claim 1, wherein the surface energy of the first block is in the range of 20 mN / m to 35 mN / m.
  8. The block copolymer according to claim 1, wherein the absolute value of the difference between the density of the first block and the density of the second block is 0.3 g / cm 3 or more.
  9. delete
  10. delete
  11. The block copolymer according to claim 1, wherein the chain is connected to the aromatic structure through an oxygen atom or a nitrogen atom.
  12. 2. The block copolymer of claim 1, wherein the second block comprises an aromatic structure comprising at least one halogen atom.
  13. The block copolymer according to claim 12, wherein the halogen atom is a fluorine atom.
  14. The block copolymer according to claim 1, wherein the aromatic structure of the first block contains an aromatic structure containing no halogen atom and the second block comprises a halogen atom.
  15. delete
  16. delete
  17. 2. The block copolymer according to claim 1, wherein the first block is a block copolymer represented by the following formula (1)
    [Chemical Formula 1]
    Figure 112014119427250-pat00011

    Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms and X is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2 -, a carbonyl group, an alkylene group, an alkenylene 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, And Y is a monovalent substituent group comprising a ring structure having a chain having 8 or more chain forming atoms linked thereto.
  18. 2. The block copolymer according to claim 1, wherein the second block is a block copolymer represented by the following formula (3)
    (3)
    Figure 112014119427250-pat00012

    In formula 3 X 2 is a single bond, an oxygen atom, sulfur atom, -S (= O) 2 - , alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) - and, in the X 1 is a single bond, oxygen atom, sulfur atom, -S (= O) 2 - , alkylene group, alkenyl group or alkynyl group, and W is at least one halogen Is an aryl group containing an atom.
  19. A polymer membrane comprising the self-assembled block copolymer of claim 1.
  20. 20. The polymeric membrane according to claim 19, wherein the polymer film exhibits a peak perpendicular to the X coordinate in the grating angle incidence angle scattering (GISAXS) diffraction pattern.
  21. A method for forming a polymer membrane, which comprises forming on a substrate a self-assembled polymer membrane comprising the block copolymer of claim 1.
  22. And removing the first or second block of the block copolymer in a laminate having a substrate and a polymer membrane including self-assembled block copolymer of claim 1 formed on the surface of the substrate.
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US15/515,432 US10287430B2 (en) 2014-09-30 2015-09-30 Method of manufacturing patterned substrate
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US15/514,939 US10310378B2 (en) 2014-09-30 2015-09-30 Block copolymer
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US15/514,929 US10370529B2 (en) 2014-09-30 2015-09-30 Method of manufacturing patterned substrate
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