TWI612066B - Block copolymer - Google Patents

Abstract

This application proposes block copolymers and their uses. The block copolymer of the present application exhibits excellent self-organizing properties or phase separation properties, and can be endowed with various required functions without limitation.

Description

Block copolymer

The present invention relates to block copolymers and uses thereof.

The block copolymer has a molecular structure in which polymer blocks each having a different chemical structure are connected to each other by a covalent bond. Block copolymers can be phase-separated to form regularly arranged structures such as spheres, cylinders, and layered structures. The size of the segment of the structure formed by the self-assembly phenomenon of the block copolymer can be adjusted within a wide range, and the segment can be made into various forms, which can be used in various next-generation nano devices, magnetic Storage media and patterns (by etching or the like): Specifically, high-density magnetic recording media, nanowires, quantum dots, metal dots, and the like are manufactured.

This application provides block copolymers and their uses.

Unless specifically stated, "alkyl" in this specification means 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 Alkyl. The above alkyl group may be linear, branched, or cyclic, and it may be optionally partially substituted with one or more substituents.

Unless specifically stated, "alkoxy" in this specification means 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. Atomic alkoxy. The above alkoxy group may be a linear type, a branched type, or a cyclic type, and it may be optionally partially substituted with one or more substituents.

Unless specified otherwise, "alkenyl" or "alkynyl" in this specification means having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 Alkenyl or alkynyl to 4 carbon atoms. The above alkenyl or alkynyl may be linear, branched or cyclic, and it may be optionally partially substituted with one or more substituents.

Unless specifically stated, "alkylene" in this specification means 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. Atomic alkylene. The above alkylene may be linear, branched, or cyclic, and it may be optionally partially substituted with one or more substituents.

Unless specified otherwise, "alkenyl" or "alkynyl" in this specification means having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, and 2 to 8 carbon atoms. Or an alkenyl or alkynyl group of 2 to 4 carbon atoms. The above alkenyl or alkynyl can be linear or branched Or cyclic, and it may be optionally partially substituted with one or more substituents.

Unless specified otherwise, "aryl" or "arylene" in this specification refers to a monohydroxy or dihydroxy moiety derived from a compound having a benzene ring structure or two or more benzene rings are connected to each other (by Compounds that share the structure of one or two carbon atoms or borrow any link) or derivatives derived from the above compounds. Unless specified otherwise, the above aryl or arylene refers to having, 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 Aryl or arylene of carbon atoms.

In the present application, "aromatic structure" refers to the above aryl or arylene.

In this specification, unless specified otherwise, "alicyclic structure" means a cyclic hydrocarbon atom structure other than an aromatic ring structure. Unless specified otherwise, the above alicyclic 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. Carbon atom alicyclic ring structure.

In the present application, "single bond" refers to a case where a particular atom does not exist in the corresponding region. For example, when B represents a single bond in the structure shown by A-B-C, it can be considered that no special atom exists in the region labeled B, resulting in a direct connection between A and C to form the structure shown in A-C.

In this application, alkyl, alkenyl, alkynyl, alkenyl, alkenyl, alkenyl, alkoxy, aryl, arylene, chain, aromatic structure or the like can be arbitrarily substituted Examples of the substituents of more parts may include, but are not limited to, a hydroxyl group, a halogen atom, a carboxyl group, an epoxy group, and acrylidine Methacryl, methacryl, methacryl, methacryl, thiol, alkyl, alkenyl, alkynyl, alkylene, alkenyl, alkenyl, alkoxy, and aryl Wait.

The block copolymer of the present application may contain a block containing a structural unit represented by the following structural formula 1 (hereinafter referred to as block 1). The block 1 may be composed of only the structural unit represented by the following structural formula 1 or may contain another structural unit in addition to the structural unit represented by the above structural formula 1.

In Structural Formula 1, R represents a hydrogen atom or an alkyl group; 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; Y represents a monohydroxy substituent, which includes a ring structure containing 8 or more chain-forming atoms connected directly to each other.

In another example, X of Structural Formula 1 represents a single bond, an oxygen atom, a carbonyl group, -C (= O) -O-, -OC (= O)-, or -C (= O) -O-, although Limited to this.

The monohydroxy substituent represented by Y in Structural Formula 1 includes a chain structure composed of at least 8 chain-forming atoms.

In this application, "chain-forming atoms" refer to those that form a predetermined chain Atoms in linear structure. This chain can be straight or branched, but the number of chained atoms is only based on the number of atoms forming the longest straight chain, and is bonded to other atoms of the above chained atoms (for example, when the chained atom is a carbon atom, (Such as hydrogen atoms bonded to carbon atoms) are not included in the calculation. In the case of a branched chain, the number of chain forming atoms is the number of chain forming atoms forming the longest chain. For example, when the chain is n-pentyl, all chain-forming atoms are carbon and the number of chain-forming atoms is 5, and when the chain is 2-methylpentyl, all chain-forming atoms are carbon and the number of chain-forming atoms is 5. Examples of chain-forming atoms may include carbon, oxygen, sulfur, and nitrogen; suitable chain-forming atoms may be any of carbon, oxygen, and nitrogen, or any of carbon and oxygen. The number of chain-forming atoms in the chain may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of chain-forming atoms in the chain may also be 30 or less, 25 or less, 20 or less, or 16 or less.

The structural unit shown in Structural Formula 1 can provide excellent self-assembly properties of the above block copolymers.

In one example, the above-mentioned chain may be a linear hydrocarbon chain, such as a linear alkyl group. Here, the alkyl group may be an alkyl group having 8 or more carbon atoms, 8 to 30 carbon atoms, 8 to 25 carbon atoms, 8 to 20 carbon atoms, or 8 to 16 carbon atoms. Each of the one or more carbon atoms in the above alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom in the alkyl group may be optionally substituted with another substituent.

In Structural Formula 1, Y may include a ring structure, and the above chain may be connected to the ring structure. This ring structure can be used to further improve the self-organizing properties of the block copolymer to which the monomer belongs. The ring structure may be an aromatic structure or an alicyclic structure.

The upper chain can be connected to the upper ring structure directly or through a linker. Examples of the linker may include an oxygen atom, a sulfur atom, -NR _1- , -S (= O) _2- , a carbonyl group, an alkylene group, an alkenyl group, an alkenyl group, -C (= O) -X _1- And -X ₁ -C (= O)-, wherein R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and X ₁ represents a single bond, an oxygen atom, a sulfur atom, -NR _2- , -S (= O) _2- , alkylene, alkenyl or alkynyl, wherein R ₂ represents a hydrogen atom, alkyl, alkenyl, alkynyl, alkoxy, or aryl. Examples of suitable linkers include oxygen and nitrogen atoms. The above chain may be attached to an aromatic structure, for example, an oxygen atom or a nitrogen atom. Here, the above linker may be an oxygen atom or -NR _1- (where R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

In one example, Y in Structural Formula 1 may be one shown in Structural Formula 2 below.

[Structure formula 2] -P-Q-Z

In Structural Formula 2, P represents an arylene group; Q represents a single bond, an oxygen atom, or -NR _3- , wherein R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group; and Z represents The aforementioned chain having 8 or more chain-forming atoms. When Y of Structural Formula 1 is a substituent represented by Structural Formula 2, P of Structural Formula 2 may be directly connected to X of Structural Formula 1.

Suitable examples of P of Structural Formula 2 include, but are not limited to, arylene having 6 to 12 carbon atoms, for example, phenylene.

Suitable examples of Q of Structural Formula 2 include an oxygen atom and -NR _1- (wherein R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

Suitable examples of the structural unit of Structural Formula 1 may include the structural unit of Structural Formula 1, wherein R represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms), and X represents -C (= O)- O-, and Y is represented by Structural Formula 2, wherein P represents phenylene or aryl having 6 to 12 carbon atoms, Q represents an oxygen atom, and Z represents a group containing 8 or more chain-forming atoms The aforementioned chain.

Therefore, a suitable exemplary structural unit of Structural Formula 1 may include a structural unit shown in Structural Formula 3 below.

In Structural Formula 3, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents -C (= O) -O-, P represents an arylene group having 6 to 12 carbon atoms, and Q represents oxygen Atom, and Z represents the aforementioned chain containing 8 or more chain-forming atoms.

In another example, the structural unit (shown in Structural Formula 1) of block 1 may be shown in Structural Formula 4 below.

In Structural Formula 4, R ₁ and R ₂ each independently represent 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 , Alkylene, alkenyl, alkynyl, -C (= O) -X ₁ -or -X ₁ -C (= O)-, where X ₁ represents a single bond, oxygen atom, sulfur atom, -S (= O) _2- , alkylene, alkenyl or alkynyl; T represents a single bond or an arylene; Q represents a single bond or a carbonyl group; and Y represents a chain containing 8 or more chain-forming atoms.

In Structural Formula 4, X represents a single bond, an oxygen atom, a carbonyl group, -C (= O) -O-, or -O-C (= O)-.

A specific example of the chain of Y of Structural Formula 4 may be similar to that described with respect to Structural Formula 1.

In another example, the negative charge of at least one chain-forming atom of a chain (having 8 or more chain-forming atoms) contained in any structural unit of block 1 (shown by structural formulae 1, 3, and 4) Sex is 3 or higher. In another example, the anionic property of the above atom may be 3.7 or less. Examples of the atom having an anionic property of 3 or more may include, but are not limited to, a nitrogen atom and an oxygen atom.

The block 2 contained in the block copolymer together with the block 1 may contain the above-mentioned structural unit, and may contain at least the structural unit represented by the following structural formula 5.

In Structural Formula 5, 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)-, where X ₁ represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenyl group, or an alkynyl group; each of R ₁ to R ₅ Each independently represents a hydrogen atom, an alkyl group, a haloalkyl group, a halogen atom or a substituent represented by the following structural formula 6, wherein the number of the substituent represented by the structural formula 6 contained in the positions labeled R ₁ to R ₅ is 1 or more.

In Structural Formula 6, Y represents an alkyl group, and X ₃ represents an oxygen atom, a carbonyl group, -C (= O) -O-, or -OC (= O)-.

Block 2 may be composed of only the structural unit shown in Structural Formula 5 or contain one or more additional structural units to be described later in this specification. yuan. When Block 2 contains one or more additional structural units in addition to the structural unit shown in Formula 5, each structural unit may form an independent subblock in Block 2 or may be irregularly located in Block 2 .

As described above, the structural unit represented by Structural Formula 5 contains at least one of the aforementioned substituents represented by Structural Formula 6. By containing this substituent, the block copolymer can more effectively form a self-organizing structure and achieve a finer phase separation structure. Therefore, the efficiency of forming a micropattern is significantly improved during the pattern formation period.

There is no particular limitation on the type of the substituent (the one shown in Structural Formula 6) that can be contained in the structural unit shown in Structural Formula 5, as long as the above structural formula is satisfied. Examples of the above substituent may be a structural unit shown in Structural Formula 6, wherein X ₃ represents an oxygen atom, a carbonyl group, -C (= O) -O-, or -OC (= O)-.

In addition, Y of Structural Formula 6 representing the above substituents may be a branched alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, or 1 to 8 carbon atoms.

The structural unit represented by Structural Formula 5 may contain one or more substituents represented by Structural Formula 6; for example, at least R ₃ represents the above substituent represented by Structural Formula 6.

In addition to the above substituents represented by Structural Formula 6, the structural unit represented by Structural Formula 5 may contain 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. (E.g., fluorine atom). The number of halogen atoms (such as fluorine atoms) contained in the structural unit may also be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

In the structural unit represented by Structural Formula ₅ , at least one of R ₁ to R ₅ , and 1 to 3 or 1 to 2 may represent the above substituents represented by Structural Formula 6.

In the structural unit shown in Structural Formula 5, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms are contained at positions labeled R ₁ to R ₅ . The number of halogen atoms contained at the positions labeled R ₁ to R ₅ may also be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

When the block 2 contains an additional structural unit in addition to the structural unit shown in Structural Formula 5, the proportion of the structural unit shown in Structural Formula 5 can be adjusted within a range that can maintain or improve the self-organizing properties of the block copolymer. For example, the proportion of the above structural unit (shown in Structural Formula 5) in the block 2 may be about 0.1 mol% to 5 mol%, 0.5 mol% to 5 mol%, 1 mol% to 5 mol%, 1.5 mol% to 5 mol%, 1.5 mol% to 4 mol%, or 1.5 mol% to 3 mol%, which is based on the total moles of the structural units in block 2. This ratio can be adjusted depending on the type of structural unit or block contained in the block copolymer.

The block 2 of the block copolymer may contain another structural unit in addition to the structural unit represented by Structural Formula 5. Here, the type of the structural unit additionally contained is not particularly limited.

For example, block 2 may additionally contain a polyvinylpyrrolidone structural unit, a polylactic acid structural unit, a poly (vinylpyridine) structural unit, a polystyrene structural unit (such as polystyrene and poly (trimethylsilylbenzene) Ethylene)), polyalkylene oxide structural units (e.g. poly (ethylene oxide)), polybutylene Diene structural unit, polyisoprene structural unit, or polyolefin structural unit (such as polyethylene).

In one example, the block 2 may include a structural unit having an aromatic structure having one or more halogen atoms in addition to the structural unit shown in Structural Formula 5.

This second structural unit of the block 2 may be, for example, a structural unit represented by the following structural formula 7.

In Structural Formula 7, B represents a monohydroxy substituent having an aromatic structure having one or more halogen atoms.

By having excellent interaction with other blocks (such as block 1), the blocks containing the above structural units can impart excellent self-organizing properties to the block copolymers to which they belong.

In Structural Formula 7, the aromatic structure may be, for example, an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms.

Examples of the halogen atom of Structural Formula 7 may be a fluorine atom or a chlorine atom, and a fluorine atom is preferably selected, although not limited thereto.

In one example, B of Structural Formula 7 may have a moiety containing 6 to 12 carbon atoms and having 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. A monohydroxy substituent of a substituted aromatic structure. In the above description, there is no particular limitation on the number of halogen atoms, and There may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms present.

Here, the above structural unit (the one shown in Structural Formula 7) may be the one shown in the following Structural Formula 8.

In Structural Formula 8, 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 alkenyl group, or an alkynyl group; and W stands for including at least one An aryl group of a halogen atom. W may be an aryl group partially substituted with at least one halogen atom; for example, it may be 6 to 12 carbon atoms and be substituted with 2 or more, 3 or more, 4 or more, or 5 or more halogens Atom partially substituted aryl.

In another example, the above structural unit (the one shown in Structural Formula 7) may be the one shown in the following Structural Formula 9.

In Structural Formula 9, 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 alkenyl group, or an alkynyl group; and R ₁ to R ₅ Each independently represents a hydrogen atom, an alkyl group, a haloalkyl group, or a halogen atom, and the number of halogen atoms contained in the positions designated as R ₁ to R ₅ is 1 or more.

In another example, X _{2 of} Structural Formula 9 may represent a single bond, an oxygen atom, an alkylene group, -C (= O) -O-, or -OC (= O)-.

In Structural Formula 9, each of R ₁ to R ₅ independently represents a hydrogen atom, an alkyl group, a haloalkyl group, or a halogen atom, and has 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms (e.g., fluorine atom) contained in the marker for the location of the R ₁ to R _5. The number of halogen atoms (eg, fluorine atoms) contained in the positions labeled R ₁ to R ₂ may also be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

In addition to the structural unit shown in Structural Formula 5, the block 2 contains a structural unit having an aromatic structure having one or more halogen atoms as described above. (E.g., the structural unit shown in any one of structural formulae 7 to 9), the Mohr number (DH) of the structural unit of the above aromatic structure having one or more halogen atoms to the structural unit shown in structural formula 5 The molar number (D5) ratio (DH / D5) may be about 35 to 65, about 40 to 60, or about 40 to 50.

The block copolymer of the present application is a block copolymer composed of one or more of each of the aforementioned block 1 and block 2. It may be a diblock copolymer composed of only two types of blocks, or it may be a triblock or multiblock (with more than three types of blocks) copolymer, which contains blocks 1 and One or two or more of block 2 or other types of blocks in addition to block 1 and block 2.

The above block copolymers can inherently exhibit excellent phase separation or excellent self-organizing properties. This phase separation or self-organizing property can be further improved by appropriately selecting and merging the blocks and satisfying one or more parameters to be described later in the present specification.

Block copolymers contain 2 or more polymer chains connected to each other by covalent bonds, and thus phase separation occurs. The block copolymers of the present application exhibit phase separation properties and, if necessary, can form nano-sized structures via microphase separation. The form and size of this nanostructure can be controlled by the size (such as molecular weight) of the block copolymer or the relative ratio between the blocks. Examples of structures that can be formed by phase separation may include spheres, cylinders, gyroids, layers, and inverted structures, and the ability of the block copolymer to form this structure is called " Self-assembling ". The inventors have identified that among the aforementioned various block copolymers in the present specification, the block copolymer satisfies at least one of various parameters described below in the present specification. This block copolymer inherently exhibits significantly improved self-organizing properties. The block copolymer of the present application satisfies any one parameter, or at the same time satisfies two or more parameters. In particular, it is recognized that by satisfying one or more appropriate parameters, the block copolymer can exhibit vertical orientation. In this application, “vertical orientation” refers to the direction in which the block copolymer is oriented and refers to the orientation of the nanostructure formed by the block copolymer perpendicular to the substrate direction. The techniques used to control the self-organizing structure of block copolymers either horizontally or vertically on various substrates rely mostly on the actual application of the block copolymers. The orientation of the nanostructure in the block copolymer film is usually determined by the blocks in the blocks constituting the block copolymer being exposed to the surface or in the air. Generally, the substrate is mostly polar and the air is non-polar; therefore, the block copolymer with a higher polarity in the block copolymer constitutes a wetting substrate, and the block with a lower polarity wets the interface with air. Therefore, several techniques are proposed to help different types of blocks of block copolymers with different properties simultaneously wet the substrate surface. The most representative is to make a neutral surface to control the orientation. However, in one aspect of the present application, when the following parameters are appropriately controlled, the block polymer is also vertically oriented without being processed in advance by any method (such as surface neutralization treatment, which is known in the art). On the substrate. In another aspect of the present application, the above-mentioned vertical orientation can be induced in a large area in a short time by thermal annealing.

The block copolymer of one aspect of the present invention is capable of forming a film that produces an in-plane winding on a hydrophobic surface during a grazing-incidence small-angle X-ray scattering (GISAXS) period Shooting map. The above block copolymers are capable of forming a film, which produces an in-plane diffraction pattern (in- p1ane diffraction pattern).

In the present application, during the GISAXS period, manufacturing an in-plane diffraction pattern means that during the GISAXS analysis period, a peak perpendicular to the x-component appears in the GISAXS diffraction pattern. This peak was noticed due to the vertical orientation of the block copolymer. Therefore, in-plane diffraction patterns for block copolymer fabrication represent 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 two, and when there are several peaks, the observed scattering vector (q value) of the peaks has an integer ratio In each case, the phase separation efficiency of the block copolymer can be further improved.

In this application, "vertical" may have errors; for example, the definition of this term may include errors in the range of ± 10 degrees, ± 8 degrees, ± 6 degrees, ± 4 degrees, or ± 2 degrees.

Block copolymers capable of forming a film that produces an in-plane diffraction pattern on both hydrophilic and hydrophobic surfaces can exhibit vertical orientation on a variety of surfaces that have not been previously processed to induce vertical orientation by any particular method. In the present application, the "hydrophilic surface" refers to a surface having a wetting angle to purified water in a range of 5 to 20 degrees. Examples of hydrophilic surfaces include, but are not limited to, silicon surfaces surface-treated with an oxygen plasma, sulfuric acid, or a piranha solution. In the present application, a "hydrophobic surface" refers to a surface having a wetting angle to purified water in a range of 50 degrees to 70 degrees. Examples of the hydrophobic surface may include, but are not limited to, a polydimethylsilazane (PDMS) surface surface treated with an oxygen plasma, and a silicon surface surface treated with hexamethyldisilazane (HMDS). , And silicon surfaces that have been surface treated with hydrogen fluoride (HF).

Unless otherwise specified, values (such as wetting angles) that can be changed depending on the temperature in this application are measured at room temperature. "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 producing the in-plane diffraction pattern during the GISAXS period may be a film that has been subjected to an overheat annealing treatment. The film used for the GISAXS measurement can be, for example, a solution prepared by dissolving the above block copolymer in a solvent (eg, fluorobenzene) at a concentration of about 0.7% by weight at a thickness of about 25 nm and a thickness of 2.25 cm ² (width: 1.5 cm, length: 1.5 cm) The coating area is formed on a hydrophilic or hydrophobic surface and the coating is thermally annealed. This thermal annealing can be performed, for example, by maintaining the above film at a temperature of about 160 ° C. for about 1 hour. GISAXS can be measured by X-ray incidence on a film made in the aforementioned manner, and its angle of incidence is in the range of about 0.12 to 0.23 degrees. The diffraction pattern of the film scattering is obtained by a measurement device known in the art (such as a 2D mar CCD). The method of using a diffraction pattern to verify the existence of an in-plane diffraction pattern is known to those skilled in the art.

It was observed that the block copolymer having the aforementioned peaks during the GISAXS period exhibits excellent self-organizing properties, which can also be effectively controlled depending on the purpose.

During the X-ray diffraction (XRD) analysis period, at least one peak of the block copolymer of the present application appears in a predetermined scattering vector q range.

For example, during the XRD analysis, the above block copolymer has at least one peak in a range of a scattering vector q ranging from 0.5 nm ^-1 to 10 nm ^-1 . In another example, a peak appears above the scattering vector q may 0.7nm ^-1 or greater, 0.9nm ^-1 or greater, 1.1nm ^-1 or greater, 1.5nm 1.3nm ^-1 or higher, or ^{- 1} or higher. In another example, the scattering vector q where 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, 4nm ^-1 or lower, 3.5nm ^-1 or lower, or 3nm ^-1 or lower.

The full width at half maximum (FWHM) of the peak observed in the above scattering vector q range is 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. In 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 this application, "FWHM" refers to the width of the maximum peak at half the maximum height (ie, the difference between the two extreme scattering vector q values).

The above scattering vectors q and FWHM in the XRD analysis are values obtained by applying a numerical analysis method of least squares regression to the results of the XRD analysis. In the above method, the part corresponding to the lowest intensity of the XRD diffraction pattern is set to the baseline and the lowest intensity is set to zero. Then, the peak shape of the above XRD pattern is subjected to Gaussian fitting, and the aforementioned scattering vectors q and FWHM are obtained from the fitting results . When the above Gaussian fitting is performed, the R-squared 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 mentioned above, are known in the art; for example, numerical analysis programs such as Origin can be used.

Fabricated with the aforementioned in the aforementioned range of scattering vectors q The block copolymer of the peak of the FWHM value has a crystalline region suitable for self-assembly. It has been confirmed that block copolymers in the aforementioned range of scattering vectors q can exhibit excellent self-organizing properties.

XRD analysis can be obtained by making X-rays penetrate the block copolymer sample and then measuring the relationship between the scattering intensity and the scattering vector. XRD analysis can be performed on this block copolymer without any special pretreatment; for example, it can be performed by drying the block copolymer under appropriate conditions and then X-ray penetrating. 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 can be obtained by capturing the 2D diffraction pattern scattered from the sample (by using a measuring device (such as a 2D mar CCD) and the image form of the diffraction pattern fitted by the aforementioned method).

When at least one of the blocks constituting the block copolymer contains the aforementioned chain to be described later in this specification, the number of chain-forming atoms n in the chain satisfies the scattering vector q (which is obtained from the aforementioned XRD analysis) and the following mathematical formula 1 both.

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

In Formula 1, n represents the aforementioned number of chain-forming atoms, and q represents the minimum scattering vector of a detectable peak or the peak with the largest peak area observed during the XRD analysis of the above block copolymer. Scattering vector. In addition, in Mathematical Formula 1, π represents the ratio of the circumference to its diameter.

The q and the like substituted into the above formula 1 are numerical values obtained in the same manner as described in the foregoing XRD analysis method.

Q and the like of Mathematical Formula 1 may be, for example, a scattering vector in a range of 0.5 nm ^-1 to 10 nm ^-1 . In another example, equation q 1 may be 0.7nm ^-1 or greater, 0.9nm ^-1 1.5nm ^-1 or higher, 1.1nm ^-1 or greater, 1.3nm ^-1 or higher, or, or higher. In another example, q in Mathematical Formula 1 may also be 9nm ^-1 or lower, 8nm ^-1 or lower, 7nm ^-1 or lower, 6nm ^-1 or lower, 5nm ^-1 or lower, 4nm ^-1 or lower, 3.5 nm ^-1 or lower, or 3 nm ^-1 or lower.

Mathematical Formula 1 describes the relationship between the distance D between the blocks containing the aforementioned chains and the number of chain-forming atoms when the block copolymer self-assembles to form a phase separation structure. When the number of chain-forming atoms in the block copolymer containing the aforementioned chain satisfies Mathematical Formula 1, the crystallinity of the chain is increased, and thereby phase separation or vertical alignment properties can be significantly improved. In another example, nq / (2 × π) in Formula 1 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 above-mentioned distance (D, Unit: nm), and π and q are as defined in Formula 1.

In one aspect of the present application, the absolute value of the difference between the surface energy of block 1 and the surface energy of block 2 in the block copolymer may be 10 mN / m or less, and 9 mN / m or less 8mN / m or less, 7.5mN / m or less, or 7mN / m or less. Also, 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 more. The structure in which the absolute value of the difference between the surface energies is within the above range, and the blocks 1 and 2 are connected to each other by a covalent bond can induce phase separation because the degree of immiscibility is sufficient. In the above description, the block 1 may be, for example, the aforementioned block containing the aforementioned chain.

The surface energy can be measured by using a Drop Shape Analyzer DSA100 (manufactured by KRUSS GmbH). In particular, it is prepared by dissolving a coating solution (a target sample to be measured (i.e., a block copolymer or a homopolymer) in fluorobenzene to a solid concentration of about 2% by weight) at a thickness of about 50 nm and The coating area is 4 cm ² (width: 2 cm, length: 2 cm), and the surface energy can be measured on the film prepared by applying the substrate on, drying at room temperature for about 1 hour, and thermal annealing at 160 ° C. for about 1 hour. The procedure of measuring the contact angle by repeating 5 times of deionized water droplets whose surface tension is known in the art on the above annealed film was repeated five times, and the five measured contact angle values were averaged. Similarly, the procedure of measuring the contact angle by dropping diiodomethane whose surface tension is known in the art on the above thermally annealed film was repeated 5 times, and the 5 measured contact angle values were averaged. Then, using the average value of the contact angles measured with deionized water and diiodomethane, respectively, and substituting the numerical value (Strom value) corresponding to the surface tension of the solvent into the mathematical formula according to the Owens-Wendt-Rabel-Kaelble method, Get the surface energy. By applying the above method to a homopolymer composed of only the monomers constituting the above blocks, a value corresponding to the surface energy of each block of the block copolymer can be obtained.

When the block copolymer contains the aforementioned chain, the surface energy of the block containing the chain is higher than that of other blocks. For example, when the above chain is contained in block 1 of the block copolymer, the surface energy of block 1 is higher than that of block 2. Here, the surface energy of the block 1 may be in a range of about 20 mN / m to 40 mN / m. The surface energy of the above block 1 can be 22mN / m or higher, 24mN / m or higher, 26mN / m or higher, or 28mN / m or higher. The surface energy of the above block 1 may also be 38 mN / m or lower, 36 mN / m or lower, 34 mN / m or lower, or 32 mN / m or lower. The aforementioned block copolymer containing block 1 and having a surface energy different from that of block 2 can exhibit excellent self-assembly properties.

In block copolymers, the absolute value of the density difference between block 1 and block 2 may be 0.25 g / cm ³ or higher, 0.3 g / cm ³ or higher, 0.35 g / cm ³ or higher High, 0.4 g / cm ³ or higher, or 0.45 g / cm ³ or higher. The absolute value of the foregoing 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. The absolute value of the density difference between the blocks 1 and 2 is within the above range and the structures connected to each other by covalent bonds can induce effective microphase separation due to phase separation caused by a sufficient degree of immiscibility.

The density of each block in the above block copolymers can be determined by using buoyancy methods known in the art; for example, by analyzing the block copolymer in a solvent such as ethanol, its mass in air and Density).

When a block copolymer contains the aforementioned chain, the density of the block containing the chain is lower than that of other blocks. For example, when the above-mentioned chain is contained in block 1 of the block copolymer, the density of block 1 is lower than that of block 2. Here, the density of the block 1 may be in a range of about 0.9 g / cm ³ to 1.5 g / cm ³ . The density of the above block 1 may be 0.95 g / cm ³ or higher. The density of the above block 1 may be 1.4 g / cm ³ or lower, 1.3 g / cm ³ or lower, 1.2 g / cm ³ or lower, 1.1 g / cm ³ or lower, or 1.05 g / cm ³ Or lower. The block copolymer containing the above block 1 (the density is different from the above block 2) can exhibit excellent self-assembly properties. The above surface energy and density may be values measured at room temperature.

The block copolymer may contain blocks having a volume fraction ranging from 0.4 to 0.8 and blocks having a volume fraction ranging from 0.2 to 0.6. When the block copolymer contains the above-mentioned chain, the volume fraction of the chain-containing block may be in the range of 0.4 to 0.8. For example, when this chain is contained in block 1, the volume fraction of block 1 can be in the range of 0.4 to 0.8, and the volume fraction of block 2 can be in the range of 0.2 to 0.6. The sum of the volume fractions of blocks 1 and 2 is equal to 1. The block copolymer containing each of the above-mentioned volume fractions exhibits excellent self-organizing properties. The volume fraction of each block in the block copolymer is obtained based on the density and molecular weight of the blocks, as measured by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the block copolymer may be, for example, in a range of 3,000 to 300,000. In the present specification, the "quantity average molecular weight" refers to a value measured by GPC and corrected based on a polystyrene standard, and in this specification, unless specified otherwise, "molecular weight" is an exponential average molecular weight. In another example, Mn may 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 yet 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, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, or 25,000 or less. The polydispersity (Mw / Mn) of the block copolymer may be in the range of 1.01 to 1.60. Another example In this case, Mw / Mn may 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 copolymer can exhibit sufficient self-assembly. The self-assembly structure and the like of interest can be considered, and the Mn and the like of the block copolymer can be adjusted.

When the block copolymer contains at least the aforementioned block 1 and block 2, the proportion of the block 1 (eg, the proportion of the block containing the aforementioned chain) in the above block copolymer may be in the range of 10 mol% to 90 mol%.

In this application, the detailed method for preparing the above block copolymer is not particularly limited as long as the method includes forming at least one block of the block copolymer by using a monomer that can form each of the aforementioned structural units .

For example, using the above monomers, a block copolymer is prepared in a living radical polymerization (LRP) method. Examples of this method include synthesis by anionic polymerization, in which an organic rare earth metal complex or an organic alkali metal compound is used as a polymerization initiator, which is performed in the presence of an alkali metal and an inorganic acid salt (such as an alkaline earth metal); by anionic polymerization Synthesis, in which an organic alkali metal compound is used as a polymerization initiator, which is performed in the presence of an organoaluminum compound; an atom transfer radical polymerization (ATRP) method, in which an ATRP agent is used as a polymerization control agent; ARGET) ATRP method, where the ATRP agent is used as a polymerization reaction control agent, but the polymerization reaction occurs in the presence of an organic or inorganic reducing agent (which generates electrons); an initiator (ICAR) ATRP method for continuous activator regeneration; Convergence of Addition-Split Chain Transfer (RAFT) Methods In the reaction, an inorganic reducing agent and a RAFT agent are used; and an organic tellurium compound is used as an initiator, and an appropriate method can be selected therefrom.

For example, the aforementioned block copolymer may be polymerized through a reactant (which includes a monomer capable of forming the aforementioned block) by a living radical polymerization method in the presence of a radical initiator and a living radical polymerization reaction agent. .

There is no particular limitation on the method of forming another block that is included in the block copolymer with the block formed by the aforementioned monomer during the preparation of the block copolymer; For the type of block of interest, the monomer is appropriately selected.

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 the polymerization efficiency may be considered in consideration of the polymerization efficiency; for example, an azo compound such as azobisisobutyronitrile (AIBN) and 2,2 'may be used. -Azobis- (2,4-dimethylvaleronitrile) or peroxide series (such as benzamidine peroxide (BPO) and di-tertiary butyl peroxide (DTBP)).

Living radical polymerization procedures can, for example, be performed in solvents such as dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglycan Monoglyme, diglyme, dimethylformamide, dimethylformamide, and dimethylacetamide).

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 related to polymer films containing the aforementioned block copolymers. The polymer film can be used in various applications (for example, various electronic or electric equipment), a procedure for forming the aforementioned pattern, a magnetic storage recording medium such as a flash memory, or a biosensor.

In one example, the aforementioned block copolymer may realize a regular structure, such as a sphere, a cylinder, a spiral icosahedron or a layer, through self-assembly in the aforementioned polymer film.

For example, block 1, block 2 or (in a segment covalently bonded to the other block of either block 1 or block 2) a segment forms a regular structure in a block copolymer, Such as layer form or cylindrical form.

The above polymer films in this application may have an in-plane diffraction pattern, which is a peak perpendicular to the x-component of the GISAXS diffraction pattern during the GISAXS analysis period. In another example, the number of peaks observed on the x-component of the above GISAXS diffraction pattern may be at least two, and when there are several peaks, the observed scattering vector q of the peaks is an integer ratio.

This application also relates to a method for forming a polymer film by using the aforementioned block copolymer. The method may include forming a polymer film containing the above block copolymer on a substrate in a self-assembled state. For example, the above method includes forming a layer of the above block copolymer or a coating solution (where the block copolymer is dissolved in a suitable solvent) on the substrate by deposition or the like, and, if necessary, it may also include The procedure of annealing or heat treating the above layers.

The above annealing or heat treatment may be performed, for example, based on the phase transition temperature or 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 heat treatment is not particularly limited and may be, for example, in a range of about 1 minute to 72 hours, although it may be changed as necessary. The heat treatment temperature of the polymer film may also be, for example, about 100 ° C to 250 ° C, which may vary depending on the block copolymer used.

In another example, the layer formed in the above manner may be subjected to a solvent annealing in a non-polar solvent and / or a polar solvent at room temperature for about 1 minute to 72 hours.

This application also relates to a method for forming a pattern. The above method may include, for example, selectively removing blocks 1 of the block copolymer from a laminate made of a substrate and a polymer film formed on the substrate and containing the above self-assembled block copolymer. Or block 2 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 this Substrate. The above method helps to form fine patterns, for example, nanometer size. In addition, various patterns (such as nano-stripes and nano-pores) can be formed by the above method, which depends on the block copolymer structure 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 by the above method is not particularly limited and may be selected to suit the application; for example, silicon oxide may be used.

For example, the above methods can form oxides that exhibit high aspect ratios Silicon nano size pattern. Various forms (such as nano strips and nanopores) can be realized, for example, by forming the above polymer film on silicon oxide, the above polymer film can be selectively removed (where the block copolymer constitutes a predetermined structure) Either any block of the block copolymer, and later by any of a variety of techniques (e.g., by reactive ion etching) to etch the silicon oxide. The above method also helps to achieve a nano pattern with a high aspect ratio.

For example, the above pattern can be implemented in a size of tens of nanometers, and this pattern can be used in various applications including, for example, magnetic recording media for next-generation information and electronic products.

For example, the above method can be used to form a pattern of nanostructures (such as nanowires) with a width of about 3nm to 40nm, such as 6nm to 80nm. In another example, a structure in which nanopores having a width (such as a diameter) of about 3 nm to 40 nm are arranged at intervals of about 6 nm to 80 nm can be realized.

In addition, 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 a method for selectively removing any block of the block copolymer; for example, a polymer film can be irradiated with an appropriate electromagnetic wave (such as ultraviolet rays) to remove relatively soft blocks method. Here, the ultraviolet 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.

In addition, after UV radiation, the polymer film can be further removed by treating the polymer film with an acid or the like. Procedures for disintegrating links.

In addition, 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 can be performed by reactive ion etching such as CF ₄ / Ar ions get on. After the above etching, the process of removing the polymer film from the substrate may be performed by an oxygen plasma treatment or the like.

This application proposes block copolymers and uses thereof. The block copolymer of the present application exhibits excellent self-organizing properties or phase separation properties, and thus can be endowed with various required functions without limitation.

FIG. 1 shows the AFM results of the polymer film of Example 1.

Hereinafter, the present application will be described in more detail by examples based on the present application, but the scope of the application is not limited to the examples set forth below.

Example 1. Synthesis of monomers

The following formula (1,2,4,5-tetrafluorostyrene-3-tertiary valerate) was synthesized by the following method: Pentafluorostyrene (25 g, 129 mmol) was added to tertiary butanol and In a 400 mL mixed solution of potassium hydroxide (37.5 g, 161 mmol), the resulting mixture was refluxed for 2 hours; the reaction was cooled to room temperature and then 1200 mL of water was added; the adduct was extracted 3 times with diethyl ether (300 mL) The residual butanol used in the previous reaction was volatilized; the aqueous solution layer was acidified to a pH of about 3 with a 10% by weight hydrochloric acid solution to precipitate the target substance; extracted again with diethyl ether (300 mL) 3 times, and the organic layer was collected, Dehydrate with MgSO ₄ and remove the solvent to give the crude product (3-hydroxy-1,2,4,5-tetrafluorostyrene); this crude product was subjected to column chromatography using hexane and dichloromethane ( DCM) was purified as a mobile phase to give 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g) as a colorless liquid. The NMR analysis results of the above substances are as follows.

<NMR analysis result>

¹ H-NMR (DMSO-d): δ11.7 (s, 1H); δ6.60 (dd, 1H); δ5.89 (d, 1H); δ5.62 (d, 1H)

3-Hydroxy-1,2,4,5-tetrafluorostyrene (4.0 g, 21 mmol) was dissolved in DCM (200 mL), and methacrylic acid (2.0 g, 23 mmol), N, N 'were sequentially added thereto. -Dicyclohexylcarbodiimide (DCC) (4.7 g, 23 mmol) and p-dimethylaminopyridine (DMAP) (1.g, 8.4 mmol); react this material for 24 hours, remove urea by filtration By-product, the solvent was removed, and then purified by column chromatography using DCM / hexane solution to obtain the transparent liquid target compound 1,2,4,5-tetrafluorostyrene-3-terevalerate (5.1 g, 19 mmol, 88%), which is represented by the following structural formula A. NMR of the above compounds The analysis results are as follows.

<NMR analysis result>

¹ H-NMR (CDCl3): δ6.64 (dd, 1H); δ6.07 (d, 1H); δ5.68 (d, 1H); δ1.38 (s, 9H).

Synthesis of block copolymer

In order to use synthetic monomers to polymerize block copolymers, azobisisobutyronitrile (AIBN) is used as a polymerization initiator, which is combined with a reversible addition-chain-splitting transfer (RAFT) agent (2-cyano-2 -Propyl dodecyl trithiocarbonate) and the above compound (shown in Structural Formula A) are dissolved in benzyl in a weight ratio of 30: 2: 0.2 (Compound shown in Structural Formula A: RAFT agent: AIBN). In ether (solid concentration: 30% by weight). The above solution was reacted at 70 ° C. for 4 hours under a nitrogen atmosphere to synthesize a macroinitiator (number average molecular weight: 6800, molecular weight distribution: 1.16), which was 1: 490: 10: 0.5 (pentapriming) with pentafluorostyrene and AIBN. Agent: Pentafluorostyrene: Structure The weight ratio of the compound represented by Formula A: AIBN) was dissolved in anisole (solid concentration: 70% by weight). The prepared solution was reacted at 70 ° C. for 5 hours under a nitrogen atmosphere to prepare a block copolymer. The number average molecular weight and molecular weight distribution of the obtained block copolymer were 13,800 and 1.15, respectively.

Test example 1.

An ad hoc polymer film was formed using the block copolymer synthesized in Example 1, and the results were observed. This block copolymer was dissolved in a solvent at a concentration of 0.7% by weight, and then spin-coated on a silicon wafer at a rate of 3000 rpm for about 60 seconds to form a polymer film. This film was thermally annealed at 160 ° C for 1 hour to induce microphase separation. The results are shown in Figure 1 below.

Claims (17)

A block copolymer comprising a first block having a structural unit represented by the following structural formula 1 and a second block having a structural unit represented by the following structural formula 5, wherein the first block and the The second block is connected by a covalent bond:

Among them, in Structural Formula 1, R represents a hydrogen atom or an alkyl group; X represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , a carbonyl group, an alkylene group, an alkenyl group, an alkenyl group, -C (= O) -X ₁ -or -X ₁ -C (= O)-, where X ₁ represents an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkylene group, or an alkylene group Alkynyl; Y represents a monohydroxy substituent, which includes a ring structure containing 8 or more chain-forming atoms connected directly to one another, the ring structure being an aromatic ring structure; and wherein, in Structural Formula 5, X ₂ Represents a single bond, oxygen atom, sulfur atom, -S (= O) _2- , alkylene, alkenyl, alkynyl, -C (= O) -X ₃ -or -X ₃ -C (= O )-, Wherein X ₃ represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenyl group, or an alkynyl group; and each of R ₁ to R ₅ independently represents a hydrogen atom , Alkyl, haloalkyl, halogen atom or substituents represented by the following structural formula 6, in which one or more substituents (which are represented by the following structural formula 6) are included in the designation R ₁ to R ₅ position:

In Formula 6, Y represents an alkyl group, and X ₃ represents an oxygen atom, a carbonyl group, -C (= O) -O-, or -OC (= O)-; wherein the first block is copolymerized in the block The proportion is in the range of 10 mol% to 90 mol%. For example, the block copolymer of item 1 of the patent application range, wherein X of the structural formula 1 represents a single bond, an oxygen atom, a carbonyl group, -C (= O) -O-, or -O-C (= O)-. For example, the block copolymer of claim 1 in which the linear chain includes 8 to 20 chain-forming atoms. For example, the block copolymer of claim 1 in which the chain-forming atoms are carbon, oxygen, nitrogen, or sulfur. For example, the block copolymer of item 1 of the patent application, wherein The chain atom is carbon or oxygen. For example, the block copolymer of item 1 of the patent application scope, wherein Y of the structural formula 1 is shown by the following structural formula 2: [Structural formula 2] -PQZ wherein in the structural formula 2, P represents an aryl group; Q Represents a single bond, an oxygen atom, or -NR _3- , wherein R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group; and Z represents a straight chain having 8 or more chain-forming atoms . The patentable scope of application of the block copolymer of item 1, wherein one or more halogen atoms in the structural formula encompasses the designated 5 for the location of the R ₁ to R _5. For example, the block copolymer of item 1 of the patent application range, wherein Y of the structural formula 6 represents a branched alkyl group having 1 to 20 carbons. For example, the block copolymer of item 1 of the patent application range, wherein the proportion of the structural unit of structural formula 5 in the second block is from 0.1 mol% to 5 mol%. For example, the block copolymer of item 1 of the patent application scope, wherein the second block further includes a structural unit represented by the following structural formula 8:

In Structural Formula 8, X ₂ represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenyl group, an alkenyl group, -C (= O) -X _1- Or -X ₁ -C (= O)-, where X ₁ represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenyl group, or an alkynyl group; and W represents a group including An aryl group of at least one halogen atom. For example, the block copolymer of item 1 of the patent application scope, wherein the second block further includes a structural unit represented by the following structural formula 9:

In Structural Formula 9, X ₂ represents a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenyl group, an alkenyl 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 alkenyl group, or an alkynyl group; and R ₁ to Each of R ₅ independently represents a hydrogen atom, an alkyl group, a haloalkyl group, or a halogen atom, and one or more of the halogen atoms are included in positions designated as R ₁ to R ₅ . For example, the block copolymer of item 11 in the scope of patent application, in which 3 or more halogen atoms are included in the positions designated as R ₁ to R ₅ in Structural Formula 9. For example, the block copolymer of item 11 in the scope of patent application, wherein 5 or more halogen atoms are included in the positions designated as R ₁ to R ₅ in Structural Formula 9. For example, the block copolymer of claim 11 in which the halogen atom is a fluorine atom. A polymer film comprising a block copolymer according to item 1 of the application, wherein the block copolymer is self-assembled. A method for forming a polymer film, the method comprises: forming a polymer film including a block copolymer as described in item 1 of the patent application on a substrate, wherein the block copolymer is self-assembled. A method for forming a pattern, the method comprising: selectively removing a block copolymer such as the first item in the patent application scope from a laminate composed of a substrate and a polymer film (which is formed on the substrate and includes a block copolymer) Any of the blocks, wherein the block copolymer is self-assembled.