KR101780098B1 - Boack copolymer - Google Patents

Abstract

The present application may provide block copolymers and uses thereof. The present application can provide a block copolymer having excellent self-assembling properties or phase separation characteristics and being freely given various functions as required.

Description

Block Copolymer {BOACK COPOLYMER}

The present application relates to block copolymers.

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

The present application provides block copolymers and uses thereof.

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]

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 a certain chain-forming atom bonded thereto.

Y is at least a substituent containing a cyclic structure. For example, when the cyclic structure is an aromatic ring, the number of the chain-forming atoms may be 3 or more, and when the cyclic structure is an alicyclic ring structure, The number of atoms can be eight or more. Even when the ring structure is an aromatic ring structure, the chain forming atoms may be 5 or more, 7 or 8 or more.

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 three or 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 the chain forming atoms may be 3 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 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 appropriate lower limit of the chain-forming atoms may be determined according to the type of ring structure as described above.

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 3 or more carbon atoms, 5 or more carbon atoms, 7 or more carbon atoms, 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)

In Formula (2), P is an arylene group or a cycloalkylene group, Q is a single bond, an oxygen atom or -NR ₃ -, and R ₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, Z is the above chain having 3 or more chain-forming atoms when P is an arylene group, and the chain having 8 or more chain-forming atoms when P is a cycloalkylene group. 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)

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]

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 includes the alicyclic ring structure in which the monovalent substituent group including an aromatic ring structure having a straight chain having three or more chain-forming atoms connected thereto or a straight chain having at least 8 chain- , And the specific examples of the respective substituents may be the same as those 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]

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]

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)

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]

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]

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]

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)

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]

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]

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]

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]

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]

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 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]

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]

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]

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-based 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 hexamethyldisilazane (HMDS), a surface of silicon treated with hydrofluoric acid (HF), and the like. no.

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

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

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

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

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

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

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

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

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

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

As will be described later, when at least one block of the block copolymer contains 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 effective microphase seperation by phase separation due to proper non-availability.

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

When the block copolymer includes the above-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, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation. The type of the substrate to be applied to this method is not particularly limited and may be selected as required. For example, silicon oxide or the like may be applied.

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

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

For example, according to the above method, a pattern in which nanostructures having a width of about 3 nm to 40 nm, for example, nanowires are arranged at intervals of about 6 nm to 80 nm, can be formed. In another example, it is possible to implement a structure in which the width is about 3 nm to 40 nm, for example, nanoholes having a diameter of about 6 nm to 80 nm are formed.

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

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

In addition, the ultraviolet irradiation may be followed by a step of treating the polymer membrane with an acid or the like to further remove the segment decomposed by ultraviolet rays.

The step of selectively etching the substrate using the polymer film having the removed block as a mask is not particularly limited. For example, the step of etching the substrate may be performed by a reactive ion etching step using CF 4 / Ar ions or the like. A step of removing the polymer membrane from the substrate by an oxygen plasma treatment or the like can also be performed.

The present application may provide block copolymers and uses thereof. The present application can provide a block copolymer having excellent self-assembling properties or phase separation characteristics and being freely given various functions as required.

1 to 15 are SEM or AFM photographs of a polymer membrane.
16 to 20 are views showing GISAXS results of the polymer membrane.

The present application will be described in more detail with reference to the following examples and comparative examples, but the scope of the present application is not limited by the following examples.

One. NMR  Measure

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The analytes were diluted to a concentration of about 10 mg / ml in a solvent for NMR measurement (CDCl ₃ ), and chemical shifts were expressed in ppm.

<Application Abbreviation>

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

2. GPC ( Come Permeation Chromatograph )

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

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

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

Manufacturing example  One.

The compound (DPM-C12) shown below was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were placed in a 250 mL flask and dissolved in 100 mL of acetonitrile. An excess of potassium Potassium carbonate was added, and the mixture was reacted at 75 DEG C for about 48 hours under a nitrogen atmosphere. After the reaction, the remaining potassium carbonate and acetonitrile used for the reaction were also removed. The mixture was worked up by adding a mixed solvent of DCM (dichloromethane) and water, and the separated organic layer was dehydrated with MgSO ₄ . Subsequently, the product was purified by DC (dichloromethane) in CC (Column Chromatography) to obtain a white solid intermediate with a yield of about 37%.

<For intermediate NMR  Analysis results>

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

(9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), DCC (dicyclohexylcarbodiimide) (10.8 g, 52.3 mmol) and p-dimethylaminopyridine (1.7 g, 13.9 mmol) 120 mL of methylene chloride was added, and the mixture was allowed to react for 24 hours in a nitrogen atmosphere at room temperature. After the reaction, the urea salt formed during the reaction was filtered off and the remaining methylene chloride was removed. The resulting product was recrystallized in a mixed solvent of methanol and water (mixed at a weight ratio of 1: 1) to obtain the title compound (DPM-C12) as a white solid, which was purified by CC (Column Chromatography) using hexane and dichloromethane as mobile phases, (7.7 g, 22.2 mmol) in 63% yield.

< DPM - C12 NMR  Analysis results>

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

(A)

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

Manufacturing example  2.

(DPM-C8) was synthesized by proceeding the reaction in the same manner as in Preparation Example 1, except that 1-bromooctane was used instead of 1-bromododecane. NMR analysis results for the above compound are as follows. < DPM - C8 NMR analysis results>

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

[Chemical Formula B]

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

Manufacturing example  3.

(DPM-C10) was synthesized by proceeding the reaction in the same manner as in Preparation Example 1, except that 1-bromododecane was used instead of 1-bromododecane. NMR analysis results for the above compound are as follows.

< DPM - C10 NMR  Analysis results>

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

&Lt; RTI ID = 0.0 &

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

Manufacturing example  4.

(DPM-C14) was synthesized by proceeding the reaction in the same manner as in Production Example 1, except that 1-bromotetradecane was used instead of 1-bromododecane. NMR analysis results for the above compound are as follows.

< DPM - C14 NMR  Analysis results>

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

[Chemical Formula D]

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

Manufacturing example  5.

(DPM-C16) was synthesized by proceeding the reaction in the same manner as in Preparation Example 1 except that 1-bromohexadecane was used instead of 1-bromododecane. NMR analysis results for the above compound are as follows.

< DPM C16 NMR  Analysis results>

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

(E)

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

Production Example 6

The compound of formula (F) (DPM-N2) was synthesized in the following manner. To a 500 mL flask was added Pd / C (palladium on carbon) (1.13 g, 1.06 mmol) and 200 mL of 2-propanol, and ammonium formate (6.68 g, 106.0 mmol) dissolved in 20 mL of water , And reacted at room temperature for 1 minute to activate Pd / C. Then, 4-aminophenol (1.15 g, 10.6 mmol) and lauric aldehyde (1.95 g, 10.6 mmol) were added, and the mixture was stirred at room temperature for about 1 hour under nitrogen, . After the reaction, Pd / C was removed, 2-propanol used in the reaction was removed, and the reaction mixture was extracted with water and methylene chloride to remove unreacted materials. The organic layer is collected, dehydrated with MgSO ₄ and the solvent is removed. The crude product was purified by column chromatography (mobile phase: hexane / ethyl acetate) to give a colorless solid (1.98, 7.1 mmol) as a solid (yield: 67% by weight).

<Intermediate NMR  Analysis results>

¹ H-NMR (DMSO-d):? 6.69 (dd, 2H); d 6.53 (dd, 2 H); d 3.05 (t, 2 H); d 1.59 (p, 2H); d 1.40-1.26 (m, 16H); d 0.88 (t, 3 H).

(1.98 g, 7.1 mmol), methacrylic acid (0.92 g, 10.7 mmol), dicyclohexylcarbodiimide (2.21 g, 10.7 mmol) and DMAP (p-dimethylaminopyridine) (0.35 g, 2.8 mmol) 100 mL of methylene chloride was added, and the reaction was allowed to proceed at room temperature under nitrogen for 24 hours. The salt (urea salt) formed during the reaction and the remaining methylene chloride were also removed after the reaction was completed. The obtained product was recrystallized from a mixed solvent of methanol and water (methanol: water = 3: 1 (weight ratio)) to obtain the title compound as a white solid ( DPM-N2) (1.94 g, 5.6 mmol) was obtained in a yield of 79% by weight.

< DPM - N2 NMR  Analysis results>

_{^{1 H-NMR (CDCl 3)}} : d6.92 (dd, 2H); d 6.58 (dd, 2 H); d6.31 (dt, 1 H); d 5.70 (dt, 1 H); d 3.60 (s, 1 H); d3.08 (t, 2H); d 2.05 (dd, 3H); d 1.61 (p, 2H); d 1.30-1.27 (m, 16H); d 0.88 (t, 3 H).

[Chemical Formula F]

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

Manufacturing example  7

(DPM-C4) was synthesized by proceeding the reaction in the same manner as in Preparation Example 1, except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results of the synthesized compound are as follows.

< DPM - C4 NMR  Analysis results>

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

[Formula G]

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

Example  One.

2.0 g of the compound (DPM-C12) of Preparation Example 1 and 64 mg of a reversible addition-fragmentation chain transfer (RAFT) reagent, 23 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of benzene were charged into a 10 mL plunger (Schlenk flask) The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, filtered under reduced pressure, and dried to obtain a pink macro initiator. The yield of the macro initiator was about 82.6%, and the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 9,000 and 1.16, respectively.

0.3 g of macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 mL of benzene were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Transfer polymerization reaction was carried out. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The yield of the block copolymer was about 18%, and the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the compound (DPM-C12) of Preparation Example 1 and a second block derived from the pentafluorostyrene.

Example  2.

A block copolymer was prepared by using a macromonomer and pentafluorostyrene in the same manner as in Example 1, except that the compound (DPM-C8) of Preparation Example 2 was used in place of the compound (DPM-C12) . The block copolymer comprises a first block derived from the compound (DPM-C8) of Preparation Example 2 and a second block derived from a pentafluorostyrene monomer.

Example  3.

A block copolymer was obtained by using a macromonomer and pentafluorostyrene in the same manner as in Example 1, except that the compound (DPM-C10) of Preparation Example 3 was used in place of the compound (DPM-C12) . The block copolymer comprises a first block derived from the compound (DPM-C10) of Preparation Example 3 and a second block derived from a pentafluorostyrene monomer.

Example  4.

A block copolymer was prepared by using a macromonomer and pentafluorostyrene in the same manner as in Example 1, except that the compound (DPM-C14) of Preparation Example 4 was used in place of the compound (DPM-C12) . The block copolymer comprises a first block derived from the compound (DPM-C14) of Production Example 4 and a second block derived from a pentafluorostyrene monomer.

Example  5.

A block copolymer was obtained by using a macromonomer and pentafluorostyrene in the same manner as in Example 1, except that the compound (DPM-C16) of Preparation Example 5 was used in place of the compound (DPM-C12) . The block copolymer comprises a first block derived from the compound (DPM-C16) of Production Example 5 and a second block derived from a pentafluorostyrene monomer.

Example  6.

Synthesis of monomers

3-hydroxy-1,2,4,5-tetrafluorostyrene was synthesized in the following manner. Pentafluorostyrene (25 g, 129 mmol) was added to a mixed solution of 400 mL of tert -butanol and potassium hydroxide (37.5 g, 161 mmol), and the reaction was refluxed for 2 hours reaction. The reaction mixture was cooled to room temperature, 1200 mL of water was added, and the remaining butanol used in the reaction was volatilized. The adducts were extracted three times with diethyl ether (300 mL), and the aqueous layer was acidified with 10% by weight hydrochloric acid solution to a pH of about 3 to precipitate the desired product. The product was precipitated three times with diethyl ether (300 mL) And the organic layer was collected. Dehydrating the organic layer with MgSO ₄ and the solvent was removed. The crude product was purified by column chromatography using hexane and DCM (dichloromethane) as mobile phases to obtain 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g) as a colorless liquid phase Respectively. NMR analysis results for the above are as follows.

< NMR  Analysis results>

^{1 H-NMR (DMSO-d} ): δ11.7 (s, 1H); [delta] 6.60 (dd, 1H); [delta] 5.89 (d, IH); [delta] 5.62 (d, IH)

Synthesis of block copolymer

2-cyano-2-propyl dodecyl trithiocarbonate (RAFT) and the compound of Preparation Example 1 (DPM-C12) were dissolved in benzene in a weight ratio of 50: 1: 0.2 (DPM (Number average molecular weight: 14,000, molecular weight distribution: 1.2) was synthesized by dissolving the compound in a solvent (C12: RAFT reagent: AIBN) (concentration: 70% by weight) and reacting in a nitrogen atmosphere at 70 DEG C for 4 hours. (TFS-OH: AIBN) at a weight ratio of 1: 200: 0.5 (giant initiator: TFS-OH: AIBN) to the synthesized macromonomer, 3-hydroxy-1,2,4,5-tetrafluorostyrene (Concentration: 30% by weight) and reacted at 70 DEG C under a nitrogen atmosphere for 6 hours to prepare a block copolymer (number average molecular weight: 35,000, molecular weight distribution: 1.2). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block derived from 3-hydroxy-1,2,4,5-tetrafluorostyrene.

Example  7.

Synthesis of monomers

The following compound of formula (H) was synthesized in the following manner. Phthalimide (10.0 g, 54 mmol) and chloromethyl styrene (8.2 g, 54 mmol) were placed in 50 mL of DMF and heated at 55 ° C for 18 h Lt; / RTI &gt; After the reaction, 100 mL of ethyl acetate and 100 mL of distilled water were added to the reaction product, and then the organic layer was extracted and the organic layer was washed again with a brine solution. The collected organic layer was treated with MgSO ₄ to remove water, and after the solvent was finally removed, the residue was recrystallized in pentane to obtain 11.1 g of the objective white solid compound. NMR analysis results for the above compound are as follows.

&Lt; NMR analysis result >

_{^{1 H-NMR (CDCl 3)}} : δ7.84 (dd, 2H); [delta] 7.70 (dd, 2H); [delta] 7.40-7.34 (m, 4H); [delta] 6.67 (dd, 1H); [delta] 5.71 (d, IH); [delta] 5.22 (d, IH); [delta] 4.83 (s, 2H)

[Formula H] &lt;

Synthesis of block copolymer

2-cyano-2-propyl dodecyl trithiocarbonate (RAFT) and the compound of Preparation Example 1 (DPM-C12) were dissolved in benzene in a weight ratio of 50: 1: 0.2 (DPM (Number average molecular weight: 14,000, molecular weight distribution: 1.2) was synthesized by dissolving the compound in a solvent (C12: RAFT reagent: AIBN) (concentration: 70% by weight) and reacting in a nitrogen atmosphere at 70 DEG C for 4 hours. The synthesized macromonomer, the compound of Formula H (TFS-PhIM) and AIBN were dissolved in benzene in a weight ratio of 1: 200: 0.5 (macro initiator: TFS-PhIM: AIBN) Under the atmosphere at 70 캜 for 6 hours to prepare a block copolymer (number average molecular weight: 35000, molecular weight distribution: 1.2). The block copolymer comprises a first block derived from the compound of Preparation Example 1 and a second block derived from the compound of Formula H.

Example  8.

0.8662 g of the compound of Preparation Example 1 (DPM-C12), and a macro-PEO (poly (ethylene glycol) -4-cyano-4- ( phenylcarbonothioylthio) pentanoate, 0.5 g of a weight average molecular weight (MW) 10,000, manufactured by Sigma Aldrich), 4.1 mg of AIBN (azobisisobutyronitrile) and 3.9 mL of anisole were placed in a 10 mL flask (Schlenk flask) And then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in a silicone oil vessel at 70 ° C for 12 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent and then dried by filtration under reduced pressure to obtain a pale pink new block copolymer (yield: 30.5%, number average molecular weight (Mn): 34300, molecular weight distribution Mw / Mn): 1.60). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a polyethylene oxide block (second block).

Example  9.

2.0 g of the compound of Preparation Example 1 (DPM-C12), 25.5 mg of a reversible addition-fragmentation chain transfer (RAFT) reagent, 9.4 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of benzene were placed in a 10 mL flask (Schlenk flask) The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to a reversible addition-fragmentation chain transfer (RAFT) polymerization in a silicone oil container at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to prepare a pink macro initiator having a reversible addition-Fragmentation chain transfer (RAFT) reagent bound to both ends of the polymer. The yield, number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the macro initiator were 81.6 wt%, 15400 and 1.16, respectively. 1.177 g of styrene, 0.3 g of the macroinitiator and 0.449 mL of benzene were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation (RAFT) chain transfer polymerization reaction. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink new block copolymer. The yield, number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 39.3 wt%, 31800 and 1.25, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a polystyrene block (second block).

Example  10

0.33 g of the macro initiator synthesized in Example 9, 1.889 g of 4-trimethylsilylstyrene, 2.3 mg of AIBN (azobisisobutyronitrile) and 6.484 mL of benzene were placed in a 10 mL flask (Schlenk flask) Min, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in a silicone oil vessel at 70 ° C. for 24 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a light pink new block copolymer. The yield of the block copolymer, the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 44.2 wt%, 29600 and 1.35, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a poly (4-trimethylsilylstyrene) block (second block).

Example  11.

Synthesis of monomers

The following compounds of formula (I) were synthesized in the following manner. Pentafluorostyrene (25 g, 129 mmol) was added to a mixed solution of 400 mL of tert -butanol and potassium hydroxide (37.5 g, 161 mmol), and the reaction was refluxed for 2 hours reaction. The reaction mixture was cooled to room temperature, 1200 mL of water was added, and the remaining butanol used in the reaction was volatilized. The adducts were extracted three times with diethyl ether (300 mL), and the aqueous layer was acidified with 10% by weight hydrochloric acid solution to a pH of about 3 to precipitate the desired product. The product was precipitated three times with diethyl ether (300 mL) And the organic layer containing the target substance was collected. Dehydrating the organic layer with MgSO ₄ and the solvent was removed. Crude product was purified by column chromatography using hexane and dichloromethane as mobile phases to obtain a colorless liquid phase intermediate (3-hydroxy-1,2,4,5-tetrafluorostyrene) (11.4 g ). NMR analysis results for the above are as follows.

< NMR  Analysis results>

^{1 H-NMR (DMSO-d} ): δ11.7 (s, 1H); [delta] 6.60 (dd, 1H); [delta] 5.89 (d, IH); [delta] 5.62 (d, IH)

Imidazole (8.0 g, 118 mmol), DMAP (p-dimethylaminopyridine) (0.29 g, 2.4 mmol) and tert ( tert -butoxycarbonylamino) pyridine were added to a solution of the above intermediate (11.4 g, 59 mmol) in dichloromethane -Butylchlorodimethylsilane (17.8 g, 118 mmol). After stirring for 24 hours at room temperature, 100 mL of brine was added to terminate the reaction, followed by further extraction with DCM. The collected organic layer of DCM was dehydrated with MgSO ₄ and the solvent was removed to give a crude product. Purification by column chromatography using hexane and DCM as mobile phases gave a colorless target (10.5 g) as a liquid phase. The NMR results of the obtained object are as follows.

< NMR  Analysis results>

_{^{1 H-NMR (CDCl 3)}} : d6.62 (dd, 1H); d 6.01 (d, 1 H); d5.59 (d, 1 H); d 1.02 (t, 9H), d 0.23 (t, 6H)

(I)

Synthesis of block copolymer

2-cyano-2-propyl dodecyl trithiocarbonate (RAFT) and the compound of Preparation Example 1 (DPM-C12) were dissolved in benzene in a weight ratio of 50: 1: 0.2 (DPM (Number average molecular weight: 14,000, molecular weight distribution: 1.2) was synthesized by dissolving the compound in a solvent (C12: RAFT reagent: AIBN) (concentration: 70% by weight) and reacting in a nitrogen atmosphere at 70 DEG C for 4 hours. The synthesized macromonomer, the compound of Formula I (TFS-S) and AIBN (Azobisisobutyronitrile) were dissolved in benzene in a weight ratio of 1: 200: 0.5 (macro initiator: TFS-S: AIBN) ) And reacted at 70 캜 for 6 hours under a nitrogen atmosphere to prepare a block copolymer (number average molecular weight: 35,000, molecular weight distribution: 1.2). The block copolymer comprises a first block derived from the compound of Preparation Example 1 and a second block derived from the above-mentioned Formula I.

Example  12.

AIBN (Azobisisobutyronitrile), RAFT reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the compound (DPM-N1) prepared in Preparation Example 6 were mixed in a weight ratio (DPM-N1: RAFT reagent: AIBN) of 26: (Concentration: 70% by weight) and reacted at 70 캜 for 4 hours under a nitrogen atmosphere to synthesize a macro initiator (number average molecular weight: 9700, molecular weight distribution: 1.2). (Concentration: 30% by weight) with a large initiator, pentafluorostyrene (PFS) and AIBN in a weight ratio of 1: 600: 0.5 (macro initiator: PFS: AIBN) To obtain a block copolymer (number average molecular weight: 17,300, molecular weight distribution: 1.2).

The block copolymer includes a first block derived from the compound of Preparation Example 6 and a second block derived from pentafluorostyrene.

Comparative Example  One.

Except that the compound (DPM-C4) of Preparation Example 7 was used in place of the compound (DPM-C12) of Production Example 1, a block copolymer was prepared by using a macro initiator and pentafluorostyrene in the manner similar to Example 1 . The block copolymer comprises a first block derived from the compound (DPM-C4) of Preparation Example 7 and a second block derived from pentafluorostyrene.

Comparative Example  2.

Except that 4-methoxyphenyl methacrylate was used in place of the compound (DPM-C12) of Preparation Example 1, a block copolymer was prepared using a macromonomer and pentafluorostyrene as monomers in the manner similar to Example 1 Respectively. The block copolymer comprises a first block derived from the 4-methoxyphenyl methacrylate and a second block derived from the pentafluorostyrene.

Comparative Example  3.

A block copolymer was prepared in the same manner as in Example 1 except that dodecyl methacrylate was used in place of the compound (DPM-C12) in Production Example 1, using a macro initiator and pentafluorostyrene as monomers. The block copolymer includes a first block derived from the dodecyl methacrylate and a second block derived from the pentafluorostyrene.

Test Example  One.

Self-assembled polymer membranes were formed using the block copolymers synthesized in Examples 1 to 12 and Comparative Examples 1 to 3, and the results were confirmed. Specifically, each copolymer was dissolved in a solvent at a concentration of about 1.0% by weight, and spin-coated on a silicon wafer at a speed of 3000 rpm for 60 seconds. Then, solvent self-assembly was performed by solvent annealing or thermal annealing. The solvent applied to each block copolymer, the aging method, etc. are summarized in Table 1 below. Then, each polymer membrane was photographed by scanning electron microscope (SEM) or atomic force microscopy (AFM) to evaluate self-assembly efficiency. 1 to 12 are the results for Examples 1 to 12, respectively, and Figs. 13 to 15 are the results for Comparative Examples 1 to 3, respectively.

Coating liquid Annealing Solvent used Block copolymer concentration Aging method Aging condition Example 1 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 2 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 3 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 4 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 5 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 6 toluene 1.0 wt% Solvent aging 2 hours Example 7 Dioxin 1.0 wt% Solvent aging 1 hours Example 8 toluene 1.0 wt% Solvent aging 2 hours Example 9 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 10 toluene 1.0 wt% Solvent aging 2 hours Example 11 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 12 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Comparative Example 1 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Comparative Example 2 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Comparative Example 3 toluene 1.0 wt% Heat ripening 160 ° C, 1 hour Example 12 Applied solvent for aging solvent: THF (tetrahydrofuran) and water (THF: water = 4: 6 weight ratio)
Example 13 Applied when the solvent was aged Solvent: chloroform
Example 14 Applied when the solvent was aged Solvent: a mixed solvent of THF (tetrahydrofuran) and water (weight ratio of THF: water = 4: 6)
Example 16 Applied when the solvent was aged Solvent: Cyclohexane

Test Example  2.

From the Test Example 1, it can be confirmed that the block copolymer produced in the Examples basically exhibits excellent self-assembly properties. Among the examples, the GISAXS (Grazing Incidence Small Angle X-ray Scattering) property was further evaluated for the block copolymer prepared in Example 1. [ The above characteristics were measured using a Pohang accelerator 3C beam line. The coating solution prepared by diluting the block copolymer of Example 1 with 0.7% by weight of solid content in fluorobezene was spin-coated on a hydrophilic surface or a substrate having a hydrophobic surface to a thickness of about 5 nm Length = 1.5 cm, vertical length = 1.5 cm), dried at room temperature for about 1 hour, and then subjected to thermal annealing at a temperature of about 160 캜 for about 1 hour to form a film. An X-ray was incident on the formed film at an incident angle within a range of about 0.12 to 0.23 degrees corresponding to the angle between the critical angle of the film and the critical angle of the substrate, and then an X-ray diffraction pattern was obtained which was scattered in the film with 2D marCCD. At this time, the distance from the film to the detector was selected within a range of about 2 m to 3 m so that the self-assembly pattern formed on the film was well observed. As the substrate having a hydrophilic surface, a substrate having a room temperature wetting angle of about 5 degrees with respect to pure water was used. As the substrate having a hydrophobic surface, a substrate having a room temperature wetting angle of about 60 degrees relative to pure water was used. The results of measurement of GISAXS (Grazing Incidence Small Angle X-ray Scattering) on a surface having a room temperature wetting angle of 5 degrees with respect to pure water are shown in FIG. 16. The results are shown in FIG. 16. As a hydrophobic surface, The results of the GISAXS (Grazing Incidence Small Angle X-ray Scattering) measured on the surface of the sample are shown in FIG. From any of the figures, the diffraction pattern above infinity was confirmed in any case, and it can be confirmed from this that the block copolymer of Example 1 exhibits vertical orientation.

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

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

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

The volume fraction of each block of the block copolymer was calculated on the basis of the density at room temperature of each block and the molecular weight measured by GPC (Gel Permeation Chromatograph). The density was measured using the buoyancy method. Specifically, the density was calculated through mass in a solvent (ethanol) in which mass and density in air were known, and GPC was calculated according to the above-described method. The results of measurement of GISAXS in the above-mentioned manner for each sample are shown in Figs. 18 to 20. Fig. Figs. 18 to 20 are the results for Samples 1 to 3, respectively, from which it can be seen that the infra-red diffraction pattern is confirmed on the GISAXS, from which it can be predicted to have vertical orientation.

Test Example  3.

From the Test Example 1, it can be confirmed that the block copolymer produced in the Examples basically exhibits excellent self-assembly properties. Surface energy and density and the like were evaluated for the results of Examples 1 to 5 and Comparative Examples 1 and 3 in which particularly appropriate results were confirmed among the examples.

Surface energy was measured using a Drop Shape Analyzer (product of DSU100, KRUSS). The coating liquid prepared by diluting the substance to be measured with surface energy to flourobenzene to a solid concentration of about 2% by weight was spin-coated on a silicon wafer to a thickness of about 50 nm (coating area: width = 2 cm, length = ), Dried at room temperature for about 1 hour, and then subjected to thermal annealing at about 160 ° C for about 1 hour to form a film, and the surface energy was measured for the formed film. The surface energy was calculated by calculating the average value of the contact angle by dropping the deionized water (H ₂ O) and the diiodomethane, which are surface tension known liquids, 5 times each. 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 by applying the average contact angle. In the following table, the surface energy of each block is the surface energy measured in the above manner for the homopolymer obtained by polymerizing only the monomer forming the block.

The density measurement method is as described in the above test example.

The above measurement results are summarized in the following table.

Example Comparative Example One 2 3 4 5 One 2 My
One
block SE 30.83 31.46 27.38 26.924 27.79 37.37 48.95 DE One 1.04 1.02 0.99 1.00 1.11 1.19 VF 0.66 0.57 0.60 0.61 0.61 0.73 0.69 My
One
block SE 24.4 24.4 24.4 24.4 24.4 24.4 24.4 DE 1.57 1.57 1.57 1.57 1.57 1.57 1.57 VF 0.34 0.43 0.40 0.39 0.39 0.27 0.31 SE difference 6.43 7.06 2.98 2.524 3.39 12.98 24.55 DE difference 0.57 0.53 0.55 0.58 0.57 0.46 0.38 SE: surface energy (unit: mN / m)
De: density (unit: g / cm ³ )
SE difference: the absolute value of the difference between the surface energy of the first block and the surface energy of the second block
De difference: the absolute value of the difference between the density of the first block and the density of the second block

From the results of the above table, it can be seen that when the proper self-assembly characteristics are realized (Examples 1 to 5), the difference in surface energy shows a specific tendency. Specifically, in the case of the block copolymers of Examples 1 to 5, the absolute value of the difference in surface energy between the first block and the second block is in the range of 2.5 mN / m to 7 mN / m, The absolute value of the surface energy difference was shown. Also, the first block exhibited a higher surface energy than the second block, and the range was within the range of about 20 mN / m to 35 mN / m. In the block copolymers of Examples 1 to 5, the absolute value of the difference between the density of the first block and the density of the second block was 0.3 g / cm ³ or more.

Test Example  4.

The results of the XRD pattern analysis on the results of Examples 1 to 5 and Comparative Examples 1 and 2, which confirmed excellent results in the self-assembly characteristics test, are summarized in Table 4 below.

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

The XRD pattern was obtained by measuring the scattering intensity according to the scattering vector (q) by passing X-rays through the sample at the Pohang accelerator 4C beamline. As a sample, a block copolymer in powder form obtained by purifying a block copolymer to be measured without any special pretreatment and removing impurities was applied to a cell for XRD measurement. For XRD pattern analysis, an X-ray with a vertical size of 0.023 mm and a horizontal size of 0.3 mm was used and a 2D marCCD was used as a detector. The diffraction pattern obtained after obtaining the scattered 2D diffraction pattern as an image is calibrated to a scattering vector q using silver behenate and circularly averaged to obtain the scattering intensity for the scattering vector q, respectively. The scattering intensity according to the scattering vector (q) was plotted and the position of the peak and the half-height width (FWHM) were obtained through peak fitting. From the above results, it can be seen that a block copolymer showing excellent self-assembly properties exhibits a unique XRD pattern as compared with the comparative example. Specifically, in the case of the block copolymer of the embodiment, a peak whose half-height width is within the range of 0.2 nm ^-1 to 1.5 nm ^-1 within the scattering vector (q) of 0.5 nm ^-1 to 10 nm ^{-1 in} the XRD pattern is confirmed However, these peaks were not confirmed in the comparative example.

Claims (21)

A half height width in a range of 0.2 to 1.5 nm ^-1 in X-ray diffraction analysis, and a block having a half height width in the range of 0.2 to 1.5 nm ^-1 Wherein the scattering vector value (q value) in the X-ray diffraction analysis is in the range of 0.5 to 10 nm &lt; ^{-1 &} gt ;.
[Chemical Formula 4]

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 an alicyclic ring structure having a straight chain having three or more chain forming atoms connected thereto, or a monovalent substituent group including an alicyclic ring structure having a straight chain having at least eight chain forming atoms connected to each other. The block copolymer according to claim 1, wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. The block copolymer according to claim 1, wherein X is a single bond, an oxygen atom, -C (= O) -O-, or -O-C (= O) -. The block copolymer according to claim 1, wherein X is -C (= O) -O-. The block copolymer according to claim 1, wherein the chain connected to the aromatic ring structure or the alicyclic ring structure comprises 8 to 20 chain-forming atoms. The block copolymer of claim 1, wherein the chain-forming atoms are carbon, oxygen, or nitrogen. The block copolymer according to claim 1, wherein the chain is a hydrocarbon chain. The block copolymer according to claim 1, wherein the chain is connected to the aromatic ring structure or the alicyclic ring structure directly or via a linker. The method of claim 8, wherein the linker is an oxygen atom, a sulfur _{atom, -NR 3 -, -S (=} O) 2 -, an alkylene group, an alkenylene group or an alkynylene group, in the R ₃ is hydrogen, an alkyl group , An alkenyl group, an alkynyl group, an alkoxy group or an aryl group. The block copolymer according to claim 1, wherein the aromatic ring structure has 6 to 12 carbon atoms, and the alicyclic ring structure has 3 to 12 carbon atoms. 2. The block copolymer according to claim 1, wherein Y is a block copolymer represented by the following formula (2): &lt; EMI ID =
(2)

In Formula (2), P is an arylene group or a cycloalkylene group, Q is a single bond, an oxygen atom or -NR ₃ -, and R ₃ is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, Z is the above chain having 3 or more chain-forming atoms when P is an arylene group, and the chain having 8 or more chain-forming atoms when P is a cycloalkylene group. delete The method of claim 1, wherein the distance between the first block of the number (n) of the chain-forming atoms of the chain and the self-assembled condition: The ratio of (D, units of nm) (n / D) is 2.5 nm to 5 nm ^{-1 -1} . &Lt; / RTI &gt; The block copolymer according to claim 1, wherein the volume fraction of the block represented by the general formula (4) is in the range of 0.4 to 0.8. The block copolymer according to claim 1, further comprising a second block having an absolute value of a surface energy difference with a block represented by the general formula (4) is in the range of 2.5 mN / m to 7 mN / m. 16. The block copolymer according to claim 15, wherein the surface energy of the block represented by the general formula (4) is higher than the surface energy of the second block. The block copolymer according to claim 1, wherein the surface energy of the block represented by the general formula (4) is in the range of 20 to 35 mN / m. The block copolymer according to claim 1, further comprising a second block having an absolute density difference of 0.3 g / cm ³ or more with respect to the block represented by the general formula (4). A polymer membrane comprising the self-assembled block copolymer of claim 1. A method for forming a polymer membrane, which comprises forming on a substrate a self-assembled polymer membrane comprising the block copolymer of claim 1. (4) of the block copolymer or a block different therefrom in a laminate having a substrate and a polymer film formed on the substrate and self-assembled with the polymer block comprising the block copolymer of claim 1 &Lt; / RTI &gt;

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