KR101832025B1 - Monomer and block copolymer - Google Patents

Monomer and block copolymer Download PDF

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Publication number
KR101832025B1
KR101832025B1 KR1020140175402A KR20140175402A KR101832025B1 KR 101832025 B1 KR101832025 B1 KR 101832025B1 KR 1020140175402 A KR1020140175402 A KR 1020140175402A KR 20140175402 A KR20140175402 A KR 20140175402A KR 101832025 B1 KR101832025 B1 KR 101832025B1
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South Korea
Prior art keywords
block
block copolymer
example
group
formula
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KR1020140175402A
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Korean (ko)
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KR20150067066A (en
Inventor
김정근
이제권
박노진
윤성수
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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 JP2016536938A external-priority patent/JP6483694B2/en
Publication of KR20150067066A publication Critical patent/KR20150067066A/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 TW104132194A external-priority patent/TWI609029B/en
Priority claimed from US15/515,432 external-priority patent/US10287430B2/en
Priority claimed from US15/514,939 external-priority patent/US10310378B2/en
Priority claimed from CN201580060099.7A external-priority patent/CN107075052B/en
Priority claimed from PCT/KR2015/010334 external-priority patent/WO2016053010A1/en
Priority claimed from PCT/KR2015/010335 external-priority patent/WO2016053011A1/en
Priority claimed from US15/515,821 external-priority patent/US10703897B2/en
Publication of KR101832025B1 publication Critical patent/KR101832025B1/en
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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

This application relates to monomers, methods of making block copolymers, block copolymers and uses thereof. The monomers of the present application can form a block copolymer having excellent self-assembling properties or phase separation characteristics, and optionally imparting various functions as required.

Description

MONOMER AND BLOCK COPOLYMER < RTI ID = 0.0 >

The present application relates to a process for preparing block copolymers using monomers and monomers thereof.

The block copolymer has a molecular structure in which polymer blocks having different chemical structures are linked via covalent bonds. The block copolymer may 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 aims to provide a method for producing monomers and block copolymers thereof. The present application is directed to a novel monomer capable of forming a block copolymer having excellent self-assembling properties or phase separation characteristics and further improved various functions through further control, and a process for producing a block copolymer using the same. It can be done for the purpose.

As used herein, the term alkyl group may mean an alkyl 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, unless otherwise specified. The alkyl group may be a straight chain, branched or cyclic alkyl group and may be optionally substituted by one or more substituents.

As used herein, unless otherwise specified, the term alkoxy group may mean an alkoxy 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. The alkoxy groups may be straight, branched or cyclic alkoxy groups and may optionally be substituted by one or more substituents.

As used herein, the term alkenyl or alkynyl group means an alkenyl group or alkynyl 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 unless otherwise specified can do. The alkenyl or alkynyl group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, unless otherwise specified, the alkylene group may mean an 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. The alkylene group may be a straight, branched or cyclic alkylene group and may optionally be substituted by one or more substituents.

As used herein, the term alkenylene group or alkynylene group means an alkenylene group or an alkynylene 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, It can mean a group. The alkenylene or alkynylene group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, the term "aryl" group or "arylene group" means, unless otherwise specified, one benzene ring structure, two or more benzene rings connected together sharing one or two carbon atoms, Or a monovalent or di-valent residue derived from a compound or a derivative thereof. The aryl group or the 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 unless otherwise specified.

The term aromatic structure in this application may mean the aryl group or the arylene group.

As used herein, the term alicyclic ring structure means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic ring structure may be, for example, an alicyclic ring structure having 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 unless otherwise specified .

The term single bond in the present application may mean that no separate atom is present at the site. For example, in the structure represented by A-B-C, when B is a single bond, it may mean that no atom exists at a site represented by B and A and C are directly connected to form a structure represented by A-C.

Examples of the substituent which may optionally be substituted in the present application include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, A carboxyl group, a glycidyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a thiol group, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, , An alkoxy group or an aryl group, but are not limited thereto.

In one aspect of the present application, as a monomer having a novel structure capable of forming a block copolymer, a monomer represented by the following formula (1) may be provided.

A block copolymer-forming monomer represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

Figure 112014119423043-pat00001

X is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2- , a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) - is, in the X 1 is an oxygen atom, sulfur atom, -S (= O) 2 -, and the alkylene, alkenylene or alkynylene group, Y Is a monovalent substituent group including a ring structure having a chain having 8 or more chain forming atoms connected thereto.

X in the formula 1 may be a single bond, an oxygen atom, a carbonyl group, -C (= O) -O- or -OC (= O) - or -C (= O) -O- in another example, But is not limited to.

The monovalent substituent of Y in formula (1) includes a chain structure formed by at least eight chain-forming atoms.

The term chain forming atom in the present application means an atom forming a straight chain structure of a certain chain. The number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and the number of the other atoms bonded to the chain-forming atoms (for example, the chain- A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not calculated. Also, in the case of a branched chain, the number of chain-forming atoms can be calculated as the number of chain-forming atoms forming the longest chain. For example, when the chain is an n-pentyl group, all of the chain-forming atoms are carbon, the number is 5, and even if the chain is a 2-methylpentyl group, all the chain-forming atoms are carbon, 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.

The compound of the formula (1) can cause the block copolymer to exhibit excellent self-assembling properties when the block copolymer described later is formed due to the presence of the chain.

In one example, the chain may be a straight chain hydrocarbon chain such as a straight chain alkyl group. In this case, 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. At least one of the carbon atoms of the alkyl group may optionally be substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted by another substituent.

In Formula (1), Y may include a cyclic structure, and the chain may be connected to the cyclic structure. Such a ring structure can further improve the self-assembling property and the like of the block copolymer formed by the monomer. The ring structure may be an aromatic structure or an alicyclic structure.

The chain may be directly connected to the ring 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) - may be when there is, in the above R 1 may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl date, X 1 is a single bond, an oxygen atom, a sulfur atom , -NR 2 -, -S (═O) 2 -, an alkylene group, an alkenylene group or an alkynylene group, and R 2 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, have. An appropriate linker may be an oxygen atom or a nitrogen atom. The chain may be connected to the aromatic structure via, for example, an oxygen atom or a nitrogen atom. In this case, the linker may be an oxygen atom, or -NR 1 - (wherein R 1 may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group).

Y in the formula (1) may be represented by the following formula (2) in one example.

(2)

Figure 112014119423043-pat00002

In the formula 2 P is an arylene group, Q is a single bond, an oxygen atom or -NR 3 - and, at the R 3 is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, alkoxy group or aryl group, Z is 8 Or more of the chain forming atoms. When Y in the general formula (1) is a substituent of the general formula (2), P in the general formula (2) may be directly connected to X in the general formula (1).

Suitable examples of P in formula (2) include, but are not limited to, an arylene group having 6 to 12 carbon atoms, such as a phenylene group.

In formula (2), Q is an oxygen atom or -NR 1 - (where R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group) as a suitable example.

As a suitable example of the monomer represented by the formula (1), R is hydrogen or an alkyl group such as hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C (= O) -O-, In the formula (2), P is an arylene group having 6 to 12 carbon atoms or phenylene, Q is an oxygen atom, and Z is a group of the aforementioned chain having at least 8 chain-forming atoms.

Thus, suitable examples of monomers of formula (1) include the monomers of formula (3).

(3)

Figure 112014119423043-pat00003

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 >

Another aspect of the present application relates to a method for producing a block copolymer comprising polymerizing the monomer to form a block.

A specific method for producing the block copolymer in the present application is not particularly limited as long as it includes the step of forming at least one block of the block copolymer using the above-mentioned monomer.

For example, the block copolymer can be prepared by the LRP (Living Radical Polymerization) method using the above monomers. For example, anionic polymerization in which an organic rare earth metal complex is used as a polymerization initiator, or an organic alkali metal compound is used as a polymerization initiator in the presence of an inorganic acid salt such as a salt of an alkali metal or an alkaline earth metal, An atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization initiator, and an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Initiators for Continuous Activator Regeneration (ATR), Atomic Transfer Radical Polymerization (ATRP), Inorganic Reducing Agent Reversible Additive - Reversible addition-cleavage chain transfer using cleavage chain transfer agent And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

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 method of forming the other block included in the copolymer together with the block formed by using the monomer in the production of the block copolymer is not particularly limited and may be appropriately selected in consideration of the kind of the desired block, Block can be formed.

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.

In another aspect of the present application, a block copolymer comprising a block formed through the monomer (hereinafter, may be referred to as a first block) may be provided.

The block may be represented, for example, by the following formula (4).

[Chemical Formula 4]

Figure 112014119423043-pat00004

In the formula (4), R, X and Y may be the same with respect to R, X and Y in the formula (1).

Therefore, in the general formula (4), 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, Or an alkynylene group, and Y may be a monovalent substituent group including a ring structure having a chain having at least 8 chain-forming atoms linked thereto, and the specific examples of the respective substituents may be the same as described above.

In one embodiment, the first block is a compound wherein R is hydrogen or an alkyl group, for example, hydrogen or an alkyl group having 1 to 4 carbon atoms, X is -C (= O) -O-, May be a block which is a substituent of formula (2). Such a block may be referred to herein as the < RTI ID = 0.0 > 1A < / RTI > Such a block may be represented, for example, by the following formula (5).

[Chemical Formula 5]

Figure 112014119423043-pat00005

X is a single bond, an oxygen atom, -C (= O) -O- or -OC (= O) -, P is an arylene group, Q is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, An oxygen atom or -NR 3 -, wherein R 3 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is a straight chain having 8 or more chain forming atoms. In another example, Q in formula (5) may be an oxygen atom.

In another example, the first block may be represented by the following formula (6). This first block may be referred to herein as a first B block.

[Chemical Formula 6]

Figure 112014119423043-pat00006

In Formula (6), R 1 and R 2 are each independently 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, group, an alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) - is, in the X 1 is a single bond, oxygen atom, sulfur atom, -S (= O) 2 -, an alkylene group, an alkenylene group or an alkynylene group, T is a single bond or an arylene group, Q is a single bond or a carbonyl group, and Y is a chain having 8 or more chain forming atoms.

In the first block B, X may be a single bond, an oxygen atom, a carbonyl group, -C (= O) -O- or -O-C (= O) -.

As a specific example of the chain of Y included in the first B block, the contents described in the formula (1) may be similarly applied.

In another example, the first block may be a block in which at least one chain-forming atom of the chain having at least 8 chain-forming atoms in the formulas (4) to (6) has an electronegativity of 3 or more. The electronegativity of the atom may be 3.7 or less in another example. This block may be referred to herein as a first C block. In the above, the reactor having the electronegativity of 3 or more may be exemplified by nitrogen atom or oxygen atom, but is not limited thereto.

The type of another block (hereinafter referred to as a second block) that can be included in the block copolymer together with the first block such as the first 1A, 1B, or 1C block is not particularly limited.

For example, the second block may be a polystyrene block such as a polyvinyl pyrrolidone block, a polylactic acid block, a polyvinyl pyridine block, polystyrene or poly trimethylsilyl styrene, A polyalkylene oxide block such as polyethylene oxide, a polybutadiene block, a polyisoprene block, or a polyolefin block such as polyethylene may be exemplified. Such a block may be referred to herein as a 2A block.

In one example, the second block, which may be included with the first block such as the first 1A, 1B, or 1C block, may be a block having an aromatic structure comprising one or more halogen atoms.

Such a second block may be, for example, a block represented by the following general formula (7). Such a block may be referred to herein as a 2B block.

(7)

Figure 112014119423043-pat00007

In Formula (7), B is a monovalent substituent having an aromatic structure containing at least one halogen atom.

Such a second block exhibits excellent interaction with the above-mentioned first block, so that the block copolymer can exhibit excellent self-assembling properties and the like.

The aromatic structure in formula (7) may be, for example, an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms.

Examples of the halogen atom contained in the general formula (7) include a fluorine atom, a chlorine atom, and the like, and a fluorine atom may be used as appropriate, but the present invention is not limited thereto.

In one example, B in formula (7) may be a monovalent substituent having an aromatic structure of 6 to 12 carbon atoms substituted with at least 1, at least 2, at least 3, at least 4, or at least 5 halogen atoms. The upper limit of the number of halogen atoms is not particularly limited and may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

For example, the second B block, formula (7), may be represented by the following formula (8).

[Chemical Formula 8]

Figure 112014119423043-pat00008

In Formula 8 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. In the above, W may be an aryl group substituted with at least one halogen atom, for example, an aryl group having 6 to 12 carbon atoms substituted with at least 2, at least 3, at least 4, or at least 5 halolene atoms.

The 2B block can be represented, for example, by the following formula (9).

[Chemical Formula 9]

Figure 112014119423043-pat00009

In formula 9 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 -, and the alkylene, alkenylene or alkynylene group, R 1 to R 5 is Each independently represents a hydrogen atom, an alkyl group, a haloalkyl group or a halogen atom, and each of R 1 to R 5 contains one or more halogen atoms.

X 2 in Formula 9 may be a single bond, an oxygen atom, an alkylene group, -C (= O) -O- or -OC (= O) - in another example.

In formula 9 R 1 to R 5 each independently represent a hydrogen, an alkyl group, a haloalkyl group or a halogen are wonjayi, R 1 to R 5 are one or more, two or more, three or more, four or more or five or more halogen atoms , For example, a fluorine atom. The halogen atoms contained in R 1 to R 5 , for example, the fluorine atom, may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

In one example, the second block may be a block represented by Formula 10 below. Such a block may be referred to herein as a second C block.

[Chemical formula 10]

Figure 112014119423043-pat00010

In the formula (10), T and K are each independently an oxygen atom or a single bond, and U is an alkylene group.

In one example, the second C block may be a block of an 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 in the formula (10).

The second C block may be a block in which one of T and K in Formula 10 is a single bond and the other is an oxygen atom. In this block, U may be a block 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.

The second C block may be a block in which T and K in Formula 10 are all oxygen atoms. In this block, U may be a block 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.

The second block may be a block comprising at least one metal atom or a metalloid atom in another example. Such a block may be referred to herein as a second 2D block. Such a block can improve the etch selectivity, for example, when an etching process is performed on a self-assembled film formed using a block copolymer.

As the metal or metalloid atom contained in the second block, a silicon atom, an iron atom or a boron atom can be exemplified. However, if it is possible to show appropriate etching selectivity by a difference from other atoms contained in the block copolymer, It is not limited.

 The second block may contain at least one, more than two, at least three, at least four, or at least five halogen atoms, such as fluorine atoms, together with the metal or metalloid atoms. The halogen atoms such as fluorine atoms contained in the second D block may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The second block may be represented by the following formula (11).

(11)

Figure 112014119423043-pat00011

In formula (11), B may be a monovalent substituent having an aromatic structure including a substituent including a metal atom or a metalloid atom and a halogen atom.

The aromatic structure of formula (11) may be an aromatic structure having 6 to 12 carbon atoms, for example, an aryl group or an arylene group.

The second 2D block of formula (11) can be represented, for example, by the following formula (12).

[Chemical Formula 12]

Figure 112014119423043-pat00012

In the formula 12 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, -NR 2 -, -S (= O ) 2 -, an alkylene group, an alkenylene group, or alkynylene group, W is an aryl group containing a substituent, and at least one halogen atom, which comprises a metal atom or metalloid atom .

In the above, W may be a substituent group containing a metal atom or a metalloid atom, and an aryl group having 6 to 12 carbon atoms and containing at least one halogen atom.

In the aryl group, at least one or one to three substituents including the metal atom or the quasi metal atom are included, and the halogen atom may be substituted with one or more, two or more, three or more, four or five Or more.

In the above, the halogen atom may be contained in 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The second block of formula (12) can be represented, for example, by the following formula (13).

[Chemical Formula 13]

Figure 112014119423043-pat00013

In the formula 13 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, -NR 2 -, -S (= O ) 2 -, alkylene, alkenylene or alkynylene is a carbonyl group, R 1 to R 5 each independently represent a hydrogen, an alkyl group, a haloalkyl group, a halogen atom and a metal or metalloid atom , At least one of R 1 to R 5 is a halogen atom, and at least one of R 1 to R 5 is a substituent containing a metal or a metalloid atom.

In formula (13), at least one, one to three, or one to two of R 1 to R 5 may be a substituent including the above-described metal atom or metalloid atom.

In Formula 13, R 1 to R 5 may contain one or more halogen atoms, two or more, three or more, four or more, or five or more halogen atoms. The halogen atoms contained in R 1 to R 5 may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

In the above description, examples of the substituent containing a metal or a metalloid atom include silsesquioxane such as a trialkylsiloxy group, a ferrocenyl group, a polyhedral oligomeric silsesquioxane group, Or a carboranyl group can be exemplified. However, these substituents are not particularly limited as long as they include at least one metal or a metalloid atom and are selected so that etching selectivity can be ensured.

The second block may be a block including an atom other than a halogen atom (hereinafter, may be referred to as a non-halogen atom) as an atom having an electronegativity of 3 or more in another example. Such a block may be referred to herein as a second E block. The electronegativity of the non-halogen atom included in the second E block may be 3.7 or less in another example.

Examples of the non-halogen atom contained in the second E block include, but are not limited to, a nitrogen atom or an oxygen atom.

The second E block may contain one or more, two or more, three or more, four or more, or five or more halogen atoms, for example, a fluorine atom, together with a non-halogen atom having an electronegativity of 3 or more . Halogen atoms such as fluorine atoms included in the second E block may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The second E block may be represented by the following formula (14).

[Chemical Formula 14]

Figure 112014119423043-pat00014

In formula (14), B may be a substituent containing a non-halogen atom having an electronegativity of 3 or more and a monovalent substituent having an aromatic structure containing a halogen atom.

The aromatic structure of formula (14) may be an aromatic structure having 6 to 12 carbon atoms, for example, an aryl group or an arylene group.

The block of formula (14) may be represented by the following formula (15) in another example.

[Chemical Formula 15]

Figure 112014119423043-pat00015

In the formula 15 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, -NR 2 -, -S (= O ) 2 -, an alkylene group, an alkenylene group, or alkynylene group, W is a substituent containing at least one halogen atom and containing a non-halogen atoms is 3 or greater electronegativity Lt; / RTI >

In the above, W may be a substituent group containing a non-halogen atom having an electronegativity of 3 or more and an aryl group having 6 to 12 carbon atoms and containing at least one halogen atom.

In the aryl group, at least one or one to three substituents including a non-halogen atom having an electronegativity of 3 or more may be included. Also, the halogen atom may be contained in one or more, two or more, three or more, four or more, or five or more. In the above, the halogen atom may be contained in 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The block of formula (15) may be represented by the following formula (16) in another example.

[Chemical Formula 16]

Figure 112014119423043-pat00016

In the formula 16 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, -NR 2 -, -S (= O ) 2 -, an alkylene group, an alkenylene group, or alkynylene group, R 1 to R 5 are independently hydrogen, an alkyl group, a haloalkyl group, a halogen atom and an electronegativity of each of three At least one of R 1 to R 5 is a halogen atom, and at least one of R 1 to R 5 is a substituent containing a non-halogen atom having an electronegativity of 3 or more.

In formula (16), at least one, one to three, or one to two of R 1 to R 5 may be a substituent containing a non-halogen atom having three or more electronegativity as described above.

In Formula 16, R 1 to R 5 may contain one or more halogen atoms, two or more, three or more, four or more, or five or more halogen atoms. The halogen atoms contained in R 1 to R 5 may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

In the above description, examples of the substituent containing a non-halogen atom having an electronegativity of 3 or more include a hydroxyl group, an alkoxy group, a carboxyl group, an amido group, an ethylene oxide group, a nitrile group, a pyridine group or an amino group , But is not limited thereto.

In another example, the second block may comprise an aromatic structure having a heterocyclic substituent. This second block may be referred to herein as a second F block.

The second F block may be represented by the following formula (17).

[Chemical Formula 17]

Figure 112014119423043-pat00017

In Formula 17, B is a monovalent substituent having an aromatic structure having 6 to 12 carbon atoms substituted with a heterocyclic substituent.

The aromatic structure of formula (17) may, if necessary, contain one or more halogen atoms.

The unit of the formula (17) can be represented by the following formula (18).

[Chemical Formula 18]

Figure 112014119423043-pat00018

In the formula 18 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, -NR 2 -, -S (= O ) 2 -, an alkylene group, an alkenylene group or an alkynylene group, W is an aryl group having 6 to 12 carbon atoms having a heterocyclic substituent.

The unit of the formula (18) may be represented by the following formula (19).

[Chemical Formula 19]

Figure 112014119423043-pat00019

In the formula 19 X 2 is a single bond, an oxygen atom, a sulfur atom, -NR 1 -, -S (= O) 2 -, alkylene group, alkenylene group, alkynylene group, -C (= O) -X 1 - or -X 1 -C (= O) -, wherein R 1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, wherein X 1 is a single bond, an oxygen atom, and, an alkylene group, an alkenylene group, or alkynylene group, R 1 to R 5 each independently represent a hydrogen, an alkyl group, a haloalkyl group, a halogen atom, and the heterocyclic substituent, - -NR 2 -, -S ( = O) 2 At least one of R 1 to R 5 is a heterocyclic substituent.

At least one, for example, 1 to 3 or 1 to 2 of R 1 to R 5 in the formula (19) is the above-mentioned heterocyclic substituent and the others are a hydrogen atom, an alkyl group or a halogen atom, Atom or a hydrogen atom.

Examples of the above-mentioned heterocyclic substituent include phthalimide -derived substituents, thiophene-derived substituents, thiazole-derived substituents, carbazole-derived substituents, and imidazole-derived substituents.

The block copolymer of the present application includes at least one of the above-described first blocks, and may also include at least one of the above-mentioned second blocks. Such a block copolymer may include two blocks or three blocks, or may include more blocks. For example, the block copolymer may be a diblock copolymer including any one of the first blocks and the second blocks.

The above-mentioned block copolymer can exhibit excellent phase separation or self-assembling properties basically. Further, by satisfying at least one of the selection and combination of each block and the parameters described below, it is possible to further improve the phase separation or self-assembly characteristics.

Since the block copolymer contains two or more chains of chains linked by covalent bonds, phase separation occurs. The block copolymer of the present application exhibits excellent phase separation characteristics and can form a nanoscale structure by microphase seperation if necessary. The shape and size of the nanostructure can be controlled by the size (molecular weight, etc.) of the block copolymer, the relative ratio of the blocks, and the like. Examples of the structure formed by phase separation include spheres, cylinders, gyroids, lamellas and inverted structures, and the ability of the block copolymer to form such a structure can be referred to as self-assembling property. The inventors of the present invention have found that a copolymer satisfying at least one of the various parameters described below among the above-described variously-structured block copolymers has a substantially improved self-assembly property possessed by each 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. In particular, it has been found that the block copolymer can be made to exhibit vertical orientation by satisfying 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. 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 HMDS (hexamethyldisilazane), a surface of silicon treated with hydrofluoric acid (HF), etc. However, 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 the chain, the number (n) of chain-forming atoms of the 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.

(1) represents the relationship between the distance (D) between the blocks in which the chain is included and the number of chain forming atoms of the chain when the block copolymer is self-assembled to form a phase separation structure, When the number of chain-forming atoms of the chain in the block copolymer satisfies the above-mentioned formula 1, the crystallinity exhibited by the chain is increased, and thus 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. (D, unit: nm) between the blocks including the chain can be calculated by the following equation: D = 2 x? / Q where D is the interval (D, unit: nm) between the blocks , < / RTI > and < RTI ID = 0.0 > q < / RTI >

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. In the above, the first block may be, for example, a block having the chain described above.

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-mentioned chain, the block including the chain may have a higher surface energy than other blocks. For example, if the first block of the block copolymer comprises the 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 an effective microphase seperation by phase separation due to suitable 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-mentioned chain, the block including the chain may have a lower density than other blocks. For example, if the first block of the block copolymer comprises the 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 the chain, the volume fraction of the block having the chain may be in the range of 0.4 to 0.8. For example, when the 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 chain described above, is from 10 mol% to 90 mol% Lt; / RTI >

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, .

For example, within the block of the first or second block or another block covalently bonded thereto, the other segment in the block copolymer may form a regular structure such as a lamellar shape or a cylinder shape.

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 forming a layer of the block copolymer or a coating liquid in which the block copolymer is diluted with a suitable solvent on the substrate by applying or the like, and if necessary, aging or heat-treating the layer.

The aging or heat treatment may be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and may be performed at, for example, the glass transition temperature or a temperature higher than the phase transition temperature. The time at which this heat treatment 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 if necessary. The heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used.

The formed layer may be solvent aged for about 1 minute to 72 hours in a non-polar solvent and / or a polar solvent at room temperature in another example.

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, i