TWI597300B - Block copolymer - Google Patents

Description

Block copolymer

This application is directed to a block copolymer.

The block copolymer has a molecular structure in which polymer subunits having different chemical structures are bonded to each other by covalent bonds. The block copolymer can form a periodic alignment structure, such as a sphere, cylinder or sheet, via phase separation. The size of the domains formed by the self-combination of the block copolymers can be adjusted over a wide range, and the shapes of various structures can be prepared. Thus, they can be used in patterning methods by lithography, various magnetic recording media or next generation nanodevices such as metal dots, quantum dots or nanowires, high density magnetic storage media, and the like.

The application provides a block copolymer and its use.

The term "alkyl" as used herein, unless otherwise defined, may refer to an alkyl group having from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 8, or from 1 to 4 carbon atoms. The alkyl group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term "alkoxy" as used herein, unless otherwise defined, may refer to an alkoxy group having from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 8, or from 1 to 4 carbon atoms. The alkoxy group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term "alkenyl or alkynyl" as used herein, unless otherwise defined, may mean an alkenyl or alkynyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. The alkenyl or alkynyl group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term "alkylene" as used herein, unless otherwise defined, may mean an alkylene group having from 1 to 20, from 1 to 16, from 1 to 12, from 1 to 8, or from 1 to 4 carbon atoms. The alkylene group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term "alkenyl or alkynyl" as used herein, unless otherwise defined, may mean an alkenyl group or a stretch having 2 to 20, 2 to 16, 2 to 12, 2 to 8 or 2 to 4 carbon atoms. Alkynyl. The alkenyl or alkynyl group may have a linear, branched or cyclic structure and may be optionally substituted with at least one substituent.

The term "aryl or aryl" as used herein, unless otherwise defined, may include a benzene ring structure or at least two benzenes thereof. A ring system shares one or two carbon atoms or a monovalent or divalent substituent derived from a compound of a structure linked by a random linker or a derivative of the compound. Unless otherwise defined, the aryl or extended aryl group can be an aryl group having 6 to 30, 6 to 25, 6 to 21, 6 to 18, or 6 to 13 carbon atoms.

The term "aromatic structure" as used herein may mean aryl or aryl.

The term "alicyclic structure" as used herein, unless otherwise defined, may refer to a cyclic hydrocarbon structure that is not the aromatic ring structure. Unless otherwise defined, the alicyclic structure can be a structure having 3 to 30, 3 to 25, 3 to 21, 3 to 18 or 3 to 13 carbon atoms.

The term "single bond" as used herein may refer to the case where the corresponding site is atom-free. For example, the case where "B" is a single bond in the structure indicated by "ABC" means that there is no atom in the "B" position, and therefore the structure represented by "AC" is directly connected to "C" by "A". form.

The substituent which may optionally be substituted for an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, an aryl group, a chain, an aromatic structure or the like may be a hydroxyl group or a halogen. Atom, carboxyl group, epoxypropyl group, propylene fluorenyl group, methacryl fluorenyl group, acryloxy group, methacryloxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkylene group A group, an alkynyl group, an alkoxy group or an aryl group, but is not limited thereto.

In one embodiment, a monomer having a novel structure represented by the following formula 1 and capable of forming a block copolymer can be provided.

In Formula 1, R is hydrogen or an alkyl group and X is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenyl group, an alkynyl group, -C(=O). ) -X ₁ - or -X ₁ -C(=O)-. In the above, X ₁ may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an extended alkenyl group or an alkynylene group, and Y may be a chain including an atom having 8 or more chain formation atoms. A monovalent substituent of the bonded cyclic structure.

In other embodiments, in Formula 1, X may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-; or X may be -C(=O). ) -O-, but not limited to this.

In Formula 1, the monovalent substituent Y includes a chain structure formed by forming atoms of at least 8 chains.

As used herein, the term "chain-forming atom" refers to an atom that forms a linear structure of a particular chain. The chain may have a linear or branched structure; however, the number of chain forming atoms is calculated only by the number of atoms forming the longest straight chain. Therefore, other atoms (such as a hydrogen atom bonded to the carbon atom or the like in the case where the chain forming atom is a carbon atom) are not counted in the number of chain forming atoms. Further, in the case of branching, the number of atoms forming the chain is the number of atoms forming the longest chain. For example, if the chain is n-pentyl, then all of the chain forming atoms are carbon atoms and the number is 5. If the chain is a 2-methylpentyl group, then all of the chain forming atoms are also carbon atoms and the number is 5. The chain forming atom may be carbon, oxygen, sulfur or nitrogen, and the appropriate chain forming atom may be carbon, Oxygen or nitrogen; or carbon or oxygen. The number of chain forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more; or 12 or more. The number of chain forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

When the compound of Formula 1 forms a block copolymer, the block copolymer exhibits excellent self-combining properties due to the presence of the chain.

In one embodiment, the chain can be a linear hydrocarbon chain, such as a linear alkyl group. In this case, the alkyl group may be an alkyl group having 8 or more, 8 to 30, 8 to 25, 8 to 20 or 8 to 16 carbon atoms. At least one carbon atom of the alkyl group may be optionally substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted with other substituents.

In Formula 1, Y may include a ring structure. The chain can be bonded to the ring structure. The self-combining properties of the block copolymer formed from the compound can be further improved by the cyclic structure. The cyclic structure may be an aromatic structure or an alicyclic structure.

The chain can be directly bonded to the ring structure or can be bonded to the ring structure via a bond. As the bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, a carbonyl group, an alkylene group, an alkenyl group, an alkynylene group, and -C(=O)-X _{1 may be} mentioned. -or-X ₁ -C(=O)- is an example. In the above, R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl and X1 may be a single bond, an oxygen atom, a sulfur atom, -NR ₂ -, -S(=O) ₂ - An alkyl group, an alkenyl group or an alkynyl group, and in the above, R ₂ may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group. Suitable linkages can be oxygen or nitrogen atoms. For example, the chain can be bonded to the aromatic structure via an oxygen atom or a nitrogen atom. In this case, the bond may be an oxygen atom or -NR ₁ -, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl.

In an embodiment, Y of Formula 1 can be represented by Formula 2 below.

[Formula 2]-P-Q-Z

In Formula 2, P may be an extended aryl group, and Q may be a single bond, an oxygen atom or -NR ₃ -, wherein R ₃ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and Z It may be a chain having eight chains forming atoms. In the case where Y of Formula 1 is a substituent of Formula 2, P of Formula 2 can be directly bonded to X of Formula 1.

In the formula 2, a suitable P may be an extended aryl group having 6 to 12 carbon atoms, such as a phenyl group, but is not limited thereto.

In Formula 2, a suitable Q may be an oxygen atom or -NR ₁ -, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl.

As a suitable embodiment of the monomer of Formula 1, a monomer of Formula 1 may be exemplified, wherein R is a hydrogen atom or an alkyl group; or a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X is -C. (=O)-O- and Y is a substituent of the formula 2, wherein P is an extended aryl group having 6 to 12 carbon atoms or a phenyl group, Q is an oxygen atom and Z is having 8 or more chains formed The chain of atoms.

Therefore, as a suitable embodiment, a monomer of the formula 3 can be exemplified.

In Formula 3, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is -C(=O)-O-, P is an extended aryl group having 6 to 12 carbon atoms, and Q is oxygen. An atom, and Z is a chain having 8 or more chain-forming atoms as described above.

Other embodiments of the present application are directed to a method of preparing a block copolymer comprising the steps of forming a block by polymerizing the monomer.

The specific method for producing the block copolymer is not particularly limited as long as it includes a step of forming at least one block of the block copolymer using the above monomers.

For example, the block copolymer can be prepared by using living radical polymerization (LRP) of a monomer. For example, there are many methods, such as in which a block copolymer is synthesized in the presence of a mineral acid salt such as a salt of an alkali metal or an alkaline earth metal by using an organic rare earth metal complex or an organic alkali metal compound as a polymerization initiator. Anionic polymerization; block copolymer is an anionic polymerization synthesized by using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound; an atom using a atom transfer radical polymerizer as a polymerization control agent Transfer radical polymerization (ATRP); ATRP of an electron transfer regeneration activator (ATGET) using an atom transfer radical polymerization agent as a polymerization control agent in the presence of electrons generated by an organic or inorganic reducing agent; for continuous activation Regeneration Initiator (ICAR) ATRP; reversible addition-open-loop chain transfer (RAFT) polymerization using an inorganic reducing agent reversible addition-ring-opening chain transfer agent; and a method using an organic cerium compound as an initiator, and Choose the appropriate method in the method.

In one embodiment, the block copolymer can be prepared by a method comprising polymerizing a material comprising a monomer capable of forming a block in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization.

In the preparation of the block copolymer, a method for forming other blocks included in the block copolymer together with a block formed of the above monomer is not particularly limited, and the other block may be borrowed It is formed by selecting an appropriate monomer in consideration of the kind of the block to be formed.

The method for preparing a block copolymer may further comprise precipitating a polymerization product produced by the above-described procedure in a non-solvent.

The kind of the radical initiator can be appropriately selected in consideration of the polymerization efficiency without particular limitation, and an azo compound such as azobisisobutyronitrile (AIBN) or 2,2'-azobis-(2,4) can be used. - dimethyl valeronitrile), or a peroxy compound such as benzammonium peroxide (BPO) or di(tert-butyl peroxide) (DTBP).

LRP can be carried out in a solvent such as methyl chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, Alkane, monoethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethylformamide, dimethyl hydrazine or dimethyl acetamide.

As a non-example, for example, an alcohol such as methanol, ethanol, n-propanol or isopropanol, a diol such as ethylene glycol, or an ether compound can be used. (such as n-hexane, cyclohexane, n-heptane or petroleum ether) without limitation.

Other embodiments of the present application are directed to block copolymers comprising blocks formed using the monomers (hereinafter referred to as first blocks).

This block can be represented, for example, by Formula 4.

In Formula 4, R, X and Y may be the same as those described in Formula 1 with respect to R, X and Y, respectively.

Therefore, in Formula 4, R may be hydrogen or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, an alkyl group, or a stretch. Alkenyl, alkynyl, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ may be an oxygen atom, a sulfur atom, -S(=O) ₂ -, An alkyl group, an alkenyl group or an alkynyl group, and Y may be a monovalent substituent comprising a cyclic structure to which a chain having 8 or more chain-forming atoms is bonded. As for the specific types of each of the above substituents, the above description can be applied in the same manner.

In one embodiment, the first block can be a block of formula 4 wherein R is hydrogen or an alkyl group; or hydrogen or an alkyl group having from 1 to 4 carbon atoms, and X is -C(=O) -O-, and Y is a substituent represented by Formula 2. Such a block may be referred to as a 1A block, but is not limited thereto. This block can be represented by the following formula 5.

In Formula 5, R may be a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, -C(=O)-O- or -OC(=O)-, P may be Is an aryl group, Q may be an oxygen atom or -NR ₃ -, wherein R ₃ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and Z is an atom having 8 or more chains Chain. In other embodiments, Q of Formula 5 can be an oxygen atom.

In other embodiments, the first block can be a block represented by Formula 6 below. Such a first block can be referred to herein as a 1B block.

In Formula 6, R ₁ and R ₂ may each independently be hydrogen or an alkyl group having 1 to 4 carbon atoms, and X may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, An alkyl group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ may be a single bond, an oxygen atom, a sulfur atom, or a -S (=O) ₂ -, alkyl, alkenyl or alkynyl, T may be a single bond or an aryl group, Q may be a single bond or a carbonyl group, and Y may be a chain having 8 chains forming atoms.

In the block of 1B of Formula 6, X may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -O-C(=O)-.

As a specific embodiment of the chain Y in the 1B block, the above invention relating to the formula 1 can be applied thereto in a similar manner.

In other embodiments, the first block may be a block represented by at least one of Formulas 4 to 6, wherein the at least one chain having 8 or more chain-forming atoms forms an electron-positive atom The degree is 3 or more. In other embodiments, the electron density of the chain forming atoms can be 3.7 or less. Here, such a block may be referred to as a 1C block. The atom having 3 or more electronegativity may be exemplified by a nitrogen atom or an oxygen atom, but is not limited thereto.

The kind of other blocks included in the block copolymer together with the first block (such as 1A, 1B or 1C) is not particularly limited.

For example, the second block can be a polyvinylpyrrolidone block, a polylactic acid block, a polyvinylpyridine block, a polystyrene block (such as a polystyrene block or polytrimethyldecyl styrene). a polyalkylene oxide block (such as a polyethylene oxide block), or a polyolefin (such as a polyethylene block or a polyisoprene block). The block used herein may be referred to as a 2A block.

In an embodiment, along with the first block (such as 1A, The second block included in the block copolymer of 1B or 1C) may be a block including an aromatic structure containing at least one halogen atom.

Such a second block can be represented, for example, by the following formula 7, and can be referred to as a 2B block.

In Formula 7, the B may be a monovalent substituent having an aromatic structure including at least one halogen atom.

Such a second block can effectively interact with the first block described above such that the block copolymer can have excellent self-combining characteristics.

The aromatic structure of Formula 7 may be, for example, an aromatic structure having 6 to 18 or 6 to 12 carbon atoms.

Further, the halogen atom included in Formula 7 may be, but not limited to, a fluorine atom or a chlorine atom, and is suitably a fluorine atom.

In one embodiment, B of Formula 7 can be a monovalent substituent having an aromatic structure of 6 to 12 carbon atoms, which is 1 or more, 2 or more, 3 or more, 4 or more. Multiple, or substituted by 5 or more halogen atoms. The upper limit of the halogen atom is not particularly limited, but may have 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

For example, the block represented by Formula 7 (which is a 2B block) can be represented by the following Formula 8.

In Formula 8, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or - X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and W may be at least An aryl group substituted by a halogen atom. In the foregoing, W may be an aryl group substituted with at least one halogen atom, for example, having 6 to 12 carbon atoms and substituted by 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. The aryl group.

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

In Formula 9, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)-X ₁ - or - X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and R ₁ to R ₅ Each may independently be a hydrogen, an alkyl group, a halogenated alkyl group or a halogen atom. The number of halogen atoms included in R ₁ to R ₅ is 1 or more.

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

In Formula 9, R ₁ to R ₅ may each independently be hydrogen, an alkyl group, a halogenated alkyl group or a halogen atom, and R ₁ to R ₅ may include 1 or more, 2 or more, 3 or more, 4 or more. Many, or 5 or more halogen atoms, such as fluorine atoms. The number of halogen atoms (such as fluorine atoms) included in R ₁ to R ₅ may be, for example, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less.

In one embodiment, the second block can be a block represented by Formula 10 below. The block used herein may be referred to as a 2C block.

In Formula 10, T and K may each independently be an oxygen atom or a single bond, and U may be an alkylene group.

In one embodiment, in the 2C block, U of Formula 10 can be an alkylene group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms.

In other embodiments, the 2C block can be a block of formula 10, wherein T and K of formula 10 are single bonds, and T and K of formula 10 are oxygen atoms. In the above block, U may be 1 to 20, 1 to 16, 1 to 12, An alkyl group of 1 to 8 or 1 to 4 carbon atoms.

In still other embodiments, the 2C block can be a block of formula 10 wherein T and K of formula 10 are oxygen atoms. In the above block, U may be an alkylene group of 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms.

In still other embodiments, the second block can be a block comprising at least one metal atom or metalloid. Such a block can be referred to as a 2D block. The block can improve etch sensitivity when subjected to an etching process for, for example, a film comprising a self-assembling block copolymer.

The metal atom or metalloid atom in the 2D block may be a halogen atom, an iron atom or a boron atom, but is not particularly limited as long as it exhibits appropriate etching sensitivity due to a difference from other atoms in the block copolymer. Degree can be.

The 2D block may comprise 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms, such as a fluorine atom, together with the metal or metalloid atom. The 2D block may comprise 10 or less, 9 or less, 8 or less, 7 or less, or 6 or fewer halogen atoms, such as a fluorine atom.

The 2D block can be represented by Formula 11.

In Formula 11, B may have a halogen atom and have the same A monovalent substituent of an aromatic structure of a substituent of a metal atom or a metalloid atom.

The aromatic structure of Formula 11 may be an aromatic structure having 6 to 12 carbon atoms, such as an aryl group or an aryl group.

The 2D block of Formula 11 can be represented by Formula 12 below.

In Formula 12, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)- X ₁ - or -X ₁ -C(=0)-, wherein R ₁ is hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ is a single bond, an oxygen atom, a sulfur atom, —NR ₂ —, —S(=O) ₂ —, an alkylene group, an alkenyl group or an alkynyl group, and W may be an aryl group including at least one halogen atom and a substituent including the metal atom or a metalloid atom. .

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

The aryl group may include at least one or 1 to 3 substituents including the metal atom or metalloid, and 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more A halogen atom.

Which may include 10 or less, 9 or less, 8 or more Less, 7 or less, or 6 or fewer halogen atoms.

The 2D block of Formula 12 can be represented by Formula 13 below.

In Formula 13, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)- X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, sulfur Atom, -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, and R ₁ to R ₅ may each independently be hydrogen, alkyl, haloalkyl, halo or include The substituent of the metal or metalloid atom, the condition that at least one of R ₁ to R ₅ includes a halogen atom, and at least one of R ₁ to R ₅ is a substituent including the metal or metalloid atom.

In Formula 13, one or more of R ₁ to R ₅ , 1 to 3 or 1 to 2 may be a substituent including the metal or metalloid atom.

In Formula 13, in R ₁ to R ₅ , 1 or more, 2 or more, 3 or more, 4 or more or 5 or more halogen atoms may be included. The number of halogen atoms included in R ₁ to R ₅ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The above substituent including the metal or metalloid atom may be a carboranyl or a silsesquioxanyl such as a polyhedral oligomeric sesquioctyloxy group, a ferrocenyl group or a trialkyl group. Alkoxyalkyl group. However, they are not particularly limited as long as they are selected to obtain etching selectivity by including at least one metal or metalloid atom.

In still other embodiments, the second block may be a block comprising atoms that are having an electronegativity of 3 or greater or atoms that are not atoms of a halogen atom (hereinafter referred to as non-halogen atoms). Such a block can be referred to as a 2E block. In other embodiments, the non-halogen atoms in the 2E block may have an electronegativity of 3.7 or less.

The non-halogen atom in the 2E block may be, but not limited to, a nitrogen atom or an oxygen atom.

Along with the non-halogen atom having an electronegativity of 3 or more, the 2E block may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms ( For example, a fluorine atom). The number of halogen atoms (such as fluorine atoms) in the 2E block may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The 2E block can be represented by Formula 14.

In Formula 14, B may have a power density of 3 or greater. a substituent of a non-halogen atom and a monovalent substituent including an aromatic structure of a halogen atom.

The aromatic structure of Formula 14 may be an aromatic structure having 6 to 12 carbon atoms, such as an aryl group or an aryl group.

In other embodiments, the block of Formula 14 can be represented by Formula 15.

In Formula 15, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)- X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, sulfur An atom, -NR ₂ -, -S(=O) ₂ -, an alkylene group, an alkenyl group or an alkynyl group, and W may be a substituent including a non-halogen atom having an electronegativity of 3 or more and at least An aryl group of a halogen atom.

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

Such an aryl group may include at least one or 1 to 3 substituents including a non-halogen atom having an electronegativity of 3 or more. Further, the aryl group may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more Multiple halogen atoms. In the foregoing, the aryl group may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

In other embodiments, the block of Formula 15 can be represented by Formula 16.

In Formula 16, X ₂ may be a single bond, an oxygen atom, a sulfur atom, -NR ₁ -, -S(=O) ₂ -, an alkylene group, an alkenyl group, an alkynyl group, -C(=O)- X ₁ - or -X ₁ -C(=O)-, wherein R ₁ may be hydrogen, alkyl, alkenyl, alkynyl, alkoxy or aryl, and X ₁ may be a single bond, an oxygen atom, sulfur An atom, -NR ₂ -, -S(=O) ₂ -, alkylene, alkenyl or alkynyl, and R ₁ to R ₅ may each independently be hydrogen, alkyl, haloalkyl, halogen atom and include A substituent having a non-halogen atom having an electronegativity of 3 or more. In the foregoing, the R ₁ to R ₅ is at least one halogen atom, and R ₁ to R ₅ comprises at least one of which is a substituent electronegativity 3 or more of the non-halogen atoms.

In Formula 16, R ₁ to R ₅ may be at least one, 1 to 3, or 1 to 2, and may be the above-mentioned substituent including a non-halogen atom having an electronegativity of 3 or more.

In Formula 16, R ₁ to R ₅ may include 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. R ₁ to R ₅ may include 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms.

The above substituent including a non-halogen atom having an electronegativity of 3 or more may be, but not limited to, a hydroxyl group, an alkoxy group, a carboxyl group, a decylamino group, an oxiranyl group, a nitrile group, a pyridyl group or an amine group.

In other embodiments, the second block can include an aromatic structure having a heterocyclic substituent. Such a second block can be referred to herein as a 2F block.

The 2F block can be represented by Formula 17.

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

The aromatic structure of Formula 17 may include at least one halogen atom as necessary.

The block of Formula 17 can be represented by Formula 18.

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

The block of Formula 18 can be represented by Formula 19.

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

In Formula 19, at least one of R ₁ to R ₅ , for example, 1 to 3 or 1 to 2 may be a heterocyclic substituent, and the others may be a hydrogen atom, an alkyl group or a halogen atom; or a hydrogen atom or a halogen atom; ; or a hydrogen atom.

The above heterocyclic substituent may be, but not limited to, a substituent derived from a quinone imine, a substituent derived from thiophene, a substituent derived from thiazole, a substituent derived from carbazole, or a substituent derived from imidazole.

The block copolymer of the present application may include at least one of the above first blocks and at least one of the above second blocks. Such block copolymers may include 2 or 3 blocks, or 3 or more blocks. In one embodiment, the block copolymer can be a diblock copolymer comprising any of the first block and the second block.

The block copolymer may have a number average molecular weight (Mn) in the range of from about 3,000 to 300,000. The term "number average molecular weight" as used herein may refer to a conversion value for standard polystyrene measured by GPC (gel permeation chromatography). The term "molecular weight" as used herein, unless otherwise defined, may refer to a number average molecular weight. In other embodiments, the molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7,000 or more, 9000 or more, 11,000 or more, 13,000 or more, or 15,000 or more. In other embodiments, the molecular weight (Mn) may be, for example, 250,000 or less, 200,000 or less, 180,000 or less, 160,000 or less, 140,000 or less, 120,000 or less, 100,000 or less, 90,000. Or smaller, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, or 25,000 or less. The block copolymer may have a polydispersity (Mw/Mn) in the range of 1.01 to 1.60. In other embodiments, the polydispersity can be about 1.1 or greater, about 1.2 or greater, about 1.3 or greater, Or about 1.4 or more.

Within the above range, the block copolymer can exhibit suitable self-combining properties. The target self-assembling structure can be considered to control the number average molecular weight and the like of the block copolymer.

If the block copolymer comprises at least the first and second blocks, the ratio of the first block (eg, the block comprising the chain) in the block copolymer may range from 10 mol% to 90 mol% .

This application is directed to a polymer layer comprising the block copolymer. The polymer layer can be used in a variety of applications. For example, it can be used for a biosensor, a recording medium such as a flash memory, a magnetic storage medium or a pattern forming method, or an electric device or an electronic device.

In one embodiment, the block copolymers in the polymer layer can form a periodic structure by self-assembly, including spheres, cylinders, spiral tetrahedrons or sheets.

For example, in the block copolymer, a segment of the first block or the second block or other block of the above block may be bonded via a covalent bond, and the other segment may form a regular structure such as a sheet layer. Form, cylinder form, etc.

This application also relates to a method of forming a polymer layer using the block copolymer. The method can include forming a polymer layer comprising a block copolymer in a self-assembled state on a substrate. For example, the method may include forming a layer of the block copolymer on a substrate by coating or the like or a layer of a coating solution of a block copolymer diluted in a suitable solvent, and aging the layer if necessary Or heat treatment.

The aging or heat treatment can be carried out, for example, according to the phase transition temperature or the glass transition temperature of the block copolymer, and can be carried out, for example, at a temperature higher than the glass transition temperature or the phase transition temperature. The heat treatment time is not particularly limited, and the heat treatment can be carried out for about 1 minute to 72 hours, but the time can be changed if necessary. Further, the temperature of the heat treatment of the polymer layer may be, for example, 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer used herein.

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

This application also relates to a pattern forming method. The method can include selectively removing a first block or a second block of the block copolymer from a laminate comprising a substrate and a polymer layer formed on the surface of the substrate and comprising a self-assembling block copolymer. The method can be a method for forming a pattern on the above substrate. For example, the method can include forming the polymer layer on a substrate, selectively removing one block or two or more blocks of the block copolymer in the polymer layer; and then etching the substrate. By the above method, a nano-scale micropattern can be formed. Further, depending on the shape of the block copolymer in the polymer layer, various pattern shapes such as a nanorod or a nanopore can be formed by the above method. If necessary, the block copolymer may be mixed with other copolymers or homopolymers in order to form a pattern. The kind of the substrate to be applied to the method can be selected without particular limitation, and for example, ruthenium oxide or the like can be applied.

For example, according to this method, a nano-scale pattern of cerium oxide having a high aspect ratio can be formed. For example, various pattern types (such as nanorods or nanopore patterns) can be formed by forming the polymer layer on the yttrium oxide. The block copolymer in the polymer layer selectively removes any block of the block copolymer in a state of forming a predetermined structure, and etches the cerium oxide by various methods (for example, reactive ion etching). form. Further, according to the above method, a nano pattern having a high aspect ratio can be formed.

For example, the pattern can be formed on the order of tens of nanometers, and such a pattern can be applied to various purposes, including next generation information electronic magnetic recording media.

For example, a nanostructure (e.g., a nanowire) having a width of about 3 to 40 nm can be formed by a pattern of about 6 to 80 nm at intervals. In other embodiments, a nanopore having a width of, for example, a diameter of about 3 to 40 nm may be disposed at intervals of about 6 to 80 nm.

Further, in this structure, a nanowire or a nanopore having a high aspect ratio can be formed.

In the method, the method of selectively removing any one of the block copolymers is not particularly limited, and, for example, a method of removing a relatively soft block by irradiating a polymer layer with an appropriate electromagnetic wave (for example, ultraviolet rays) may be used. . In this case, the conditions of the ultraviolet radiation may be determined depending on the type of the block of the block copolymer, and the ultraviolet rays having a wavelength of about 254 nm may be irradiated for 1 to 60 minutes.

Further, after ultraviolet irradiation, the polymer layer may be acid treated to further remove the ultraviolet-degraded fragment.

In addition, etching of the substrate using the polymer layer from which the block has been selectively removed may be performed by reactive ion etching using CF ₄ /Ar ions, followed by the above procedure, and further processing by oxygen plasma treatment may be performed. The substrate removes the polymer layer.

Figures 1 through 15 are SEM or AFM images of the polymer layer and show the results of the GISAXS analysis on the polymer layer.

effect

The present application can provide block copolymers and applications thereof. The block copolymer has excellent self-combination properties and phase separation, and can be freely imparted with various desired functions as necessary.

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

NMR analysis

NMR analysis was performed at room temperature using a Varian Unity Inova (500 MHz) spectrometer including a triple resonance 5 mim probe. The sample to be analyzed was used after diluting it in a solvent for NMR analysis (CDCl ₃ ) to a concentration of about 10 mg/ml, and the chemical shift (δ) was expressed in ppm.

<abbreviation>

Br=wide signal, s=single state, d=doublet, dd=double double State, t = triplet state, dt = double triplet state, q = quadruple state, p = quintuple state, m = multiple state

2. GPC (gel permeation chromatography)

The number average molecular weight and polydispersity are measured by GPC (gel permeation chromatography). The block copolymer or microinitiator to be measured of the examples and the comparative examples was placed in a 5 mL vial and then diluted to a concentration of about 1 mg/mL. Then, the standard sample for calibration and the sample to be analyzed were filtered by a syringe filter (pore size: 0.45 μm), and then analyzed. ChemStation from Agilent Technologies, Co. was used as an analytical program. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained by comparing the elution time of the sample with the calibration curve, and then the polydispersity (PDI) was obtained from the ratio (Mw/Mn). The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Device: 1200 Series from Agilent technologies, Co.

String: Use two PLgel mixed B from Polymer laboratories, Co.

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1mg/mL, 200L injection

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

Preparation Example 1.

The compound of the formula A (DPM-C12) was synthesized by the following method. In a 250 mL flask, hydroquinone (10.0 g, 94.2 mmole) and 1-bromododecane (23.5 g, 94.2 mmole) were added and dissolved in 100 mL of acetonitrile, and excess potassium carbonate was added thereto, followed by nitrogen at 75 ° C. The mixture was reacted for 48 hours. After the reaction, the residual potassium carbonate and acetonitrile used in the reaction were removed. Treatment was carried out by adding a mixed solvent of dichloromethane (DCM) and water, and the separated organic layer was collected and dried over MgSO ₄ . Subsequently, a white solid intermediate was obtained via column chromatography using DCM with a yield of approximately 37%.

<Results of NMR analysis of intermediates>

¹ H-NMR (CDCl ₃ ): δ 6.77 (dd, 4H); δ 4.45 (s, 1H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p , 2H); δ1.33-1.26(m, 16H); δ0.88(t, 3H)

The synthesized intermediate (9.8 g, 35.2 mmole), methacrylic acid (6.0 g, 69.7 mmole), dicyclohexylcarbodiimide, (DCC; 10.8 g, 52.3 mmole) and p-dimethylaminopyridine (DMPA; 1.7 g, 13.9 mmol) was placed in a flask, 120 ml of dichloromethane was added, and the reaction was carried out under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt produced in the reaction was removed via a filter, and residual dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as a mobile phase, and the product obtained by recrystallization in a mixed solvent of methanol and water (mixed in a 1:1 weight ratio), Thus, a white solid product (DPM-C12) (7.7 g, 22.2 mmol) was obtained with a yield of 63%.

<NMR analysis results for DPM-C12>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.43 (p, 2H); 1.34-1.27 (m, 16H); δ 0.88 (t, 3H)

In the above, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 2.

The compound of the following formula B (DPM-C8) was synthesized according to the method of Preparation Example 1, except that 1-bromooctane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR analysis results for DPM-C8>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.76 (p, 2H); δ 1.45 (p, 2H); 1.33-1.29 (m, 8H); δ 0.89 (t, 3H)

In the above, R is a linear alkyl group having 8 carbon atoms.

Preparation Example 3.

The compound of the following formula C (DPM-C10) is based on Preparation Example 1 The method was synthesized by using 1-bromodecane instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR analysis results for DPM-C10>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.72 (dt, 1H); δ 3.94 (t) , 2H); δ2.06 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.34-1.28 (m, 12H); δ 0.89 (t, 3H)

In the above, R is a linear alkyl group having 10 carbon atoms.

Preparation Example 4.

The compound of the following formula D (DPM-C14) was synthesized according to the method of Preparation Example 1, except that 1-bromotetradecane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR analysis results for DPM-C14>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); δ 6.89 (dd, 2H); δ 6.33 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t) , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.27 (m, 20H); δ 0.88 (t, 3H.)

[Formula D]

In the above, R is a linear alkyl group having 14 carbon atoms.

Preparation Example 5.

The compound of the following formula E (DPM-C16) was synthesized according to the method of Preparation Example 1, except that 1-bromohexadecane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR analysis results for DPM-C16>

¹ H-NMR (CDCl ₃ ): δ 7.01 (dd, 2H); δ 6.88 (dd, 2H); δ 6.32 (dt, 1H); δ 5.73 (dt, 1H); δ 3.94 (t , 2H); δ2.05 (dd, 3H); δ 1.77 (p, 2H); δ 1.45 (p, 2H); 1.36-1.26 (m, 24H); δ 0.89 (t, 3H)

In the above, R is a linear alkyl group having 16 carbon atoms.

Preparation Example 6.

The compound of the formula F (DPM-N2) was synthesized by the following method. In a 500 mL flask, Pd/C (palladium on carbon) (1.13 g, 1.06 mmole) and 200 mL of 2-propanol were added, then ammonium formate dissolved in 20 mL of water was added, and then the reaction was carried out at room temperature. The Pd/C was activated in 1 minute. Then, 4-aminophenol (1.15 g, 10.6 mmole) and lauric acid aldehyde (1.95 g, 10.6 mmole) were added thereto, and the mixture was allowed to react at room temperature for 1 minute by stirring under nitrogen. After the reaction, Pd/C was removed and 2-propanol for the reaction was removed, and then the mixture was extracted with water and dichloromethane to remove unreacted product. The organic layer was collected and dehydrated by MgSO _4. The crude product was purified by column chromatography (mobile phase: hexane/ethyl acetate) to afford colourless solid intermediate (1.98 g, 7.1 mmole) (yield: 67%).

<Results of NMR analysis of intermediates>

¹ H-NMR (DMSO-d): δ 6.69 (dd, 2H); δ 6.53 (dd, 2H); δ 3.05 (t, 2H); δ 1.59 (p, 2H); δ 1.40- 1.26(m,16H);δ0.88(t,3H)

The synthesized intermediate (1.98 g, 7.1 mmole), methacrylic acid (0.92 g, 10.7 mmole), dicyclohexylcarbodiimide, (DCC; 2.21 g, 10.7 mmole) and p-dimethylaminopyridine (DMPA; 0.35 g, 2.8 mmol) was placed in a flask, 100 ml of dichloromethane was added, and the reaction was carried out under nitrogen at room temperature for 24 hours. After the reaction was completed, the urea salt produced during the reaction was removed via a filter, and residual dichloromethane was also removed. The impurities were removed by column chromatography using hexane and DCM (dichloromethane) as the mobile phase, and recrystallized in a mixed solvent of methanol and water (methanol: water = 3:1 (weight ratio)). The product was obtained to give a white solid product (DPM-N2) (1.94 g, 5.6 mmole).

<NMR analysis results for DPM-N2>

¹ H-NMR (CDCl ₃ ): δ 6.92 (dd, 2H); δ 6.58 (dd, 2H); δ 6.31 (dt, 1H); δ 5.70 (dt, 1H); δ 3.60 (s) ,1H);δ3.08 (t,2H);δ2.05(dd,3H);δ1.61(p,2H);δ1.30-1.27(m,16H);δ0.88(t,3H)

In the above, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 7.

The compound of the following formula G (DPM-C4) was synthesized according to the method of Preparation Example 1, except that 1-bromobutane was used instead of 1-bromododecane. The NMR analysis results for the above compounds are as follows.

<NMR analysis results for DPM-C4>

_{^{1 H-NMR (CDCl 3)}} : δ7.02 (dd, 2H); δ6.89 (dd, 2H); δ6.33 (dt, 1H); δ5.73 (dt, 1H); δ3.95 (t , 2H); δ2.06 (dd, 3H); δ 1.76 (p, 2H); δ 1.49 (p, 2H); δ 0.98 (t, 3H)

In the above, R is a linear alkyl group having 4 carbon atoms.

Example 1

2.0 g of the compound of Preparation Example 1 (DPM-C12), 64 mg of RAFT (reversible addition fragmentation chain transfer) agent (cyanoisopropyl dithiobenzoate), 23 mg of AIBN (azobisisobutyronitrile) And 5.34ml of benzene It was added to a 10 mL flask, and then stirred at room temperature for 30 minutes, and then subjected to RAFT (reversible addition fragmentation chain transfer) polymerization at 70 ° C for 4 hours. After the polymerization, the reacted solution was precipitated in 250 ml of methanol as an extraction solvent, vacuum filtered and dried to obtain a pink macroinitiator. The macroinitiator yield was about 86%, and its number average molecular weight (Mn) and polydispersity (Mw/Mn) were 9,000 and 1.16, respectively.

0.3 g of the macroinitiator, 2.7174 g of pentafluorostyrene and 1.306 ml of benzene were added to a 10 mL Schlenk flask, followed by stirring at room temperature for 30 minutes, followed by RAFT at 115 ° C (reversible addition fragmentation chain transfer) ) Polymerization for 4 hours. After the polymerization, the reacted solution was precipitated in 250 ml of methanol as an extraction solvent, vacuum filtered and dried to obtain a light pink block copolymer. The yield of the block copolymer was about 18%, and the number average molecular weight (Mn) and polydispersity (Mw/Mn) thereof were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 (DPM-C12) and a second block derived from the pentafluorostyrene.

Example 2

A block copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 2 (DPM-C8) was used instead of the compound of Preparation Example 1 (DPM-C12) and the pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from the compound of Preparation Example 2 (DPM-C8) and a second block derived from the pentafluorostyrene.

Example 3

A block copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 3 (DPM-C10) was used instead of the compound of Preparation Example 1 (DPM-C12) and the pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from the compound of Preparation Example 3 (DPM-C10) and a second block derived from the pentafluorostyrene.

Example 4

A block copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 4 (DPM-C14) was used instead of the compound of Preparation Example 1 (DPM-C12) and the pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from the compound of Preparation Example 4 (DPM-C14) and a second block derived from the pentafluorostyrene.

Example 5

A block copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 5 (DPM-C16) was used instead of the compound of Preparation Example 1 (DPM-C12), and the pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from the compound of Preparation Example 5 (DPM-C16) and a second block derived from the pentafluorostyrene.

Example 6

Synthetic monomer

3-Hydroxy-1,2,4,5-tetrafluorostyrene was synthesized according to the method described below. Pentafluorostyrene (25 g, 129 mmole) was added to a mixed solution of 400 mL of a third butanol and potassium hydroxide (37.5 g, 161 mmole); and then a reflux reaction was carried out for 2 hours. The product after the reaction was cooled to room temperature, 1200 mL of water was added, and the remaining butanol for the reaction was volatilized. The adduct was extracted three times with diethyl ether (300 mL), and the aqueous layer was acidified with a 10% by weight hydrochloric acid solution until the pH became 3 to precipitate the target product. The precipitated product was extracted three times with diethyl ether (300 mL) and organic layer was collected. The organic layer was dehydrated by MgSO ₄ and the solvent was removed. The crude product was purified by column chromatography using hexane and DCM (dichloromethane) as mobile phase to afford colorless liquid 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g) . The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (DMSO-d): δ 11.7 (s, 1H); δ 6.60 (dd, 1H); δ 5.89 (d, 1H); δ 5.62 (d, 1H)

Synthetic block copolymer

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) agent (2-cyano-2-propyl triester dithiocarbonate) and the compound of Preparation Example 1 ( DPM-C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT agent: AIBN) (concentration: 70% by weight), and then the mixture was subjected to a reaction at 70 ° C for 4 hours under nitrogen to prepare a macromolecule. Initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Then, in benzene, the synthetic macroinitiator, 3-hydroxy-1,2,4,5-tetrafluorostyrene (TFS-OH) and AIBN (azobisisobutyronitrile) are 1:200 : 0.5 (macromolecule initiator: TFS-OH: AIBN) was dissolved in a weight ratio (concentration: 30% by weight), and then the mixture was subjected to a reaction at 70 ° C for 6 hours under nitrogen to prepare a block copolymer (quantitative average molecular weight: 35000, polydispersity: 1.2). The block copolymer included 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

Synthetic monomer

The compound of the following formula H was synthesized according to the method described below. Iridium imine (10.0 g, 54 mmole) and chloromethylstyrene (8.2 g, 54 mmole) were added to 50 mL of DMF (dimethylformamide), and then reacted under nitrogen at 55 ° C for 18 hours. 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 collected, and then washed with brine. The collected organic layer was treated with MgSO ₄ to remove water, and then solvent was finally removed, and then recrystallized from pentane to obtain a white solid target compound (11.1 g). The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 7.84 (dd, 2H); δ 7.70 (dd, 2H); δ 7.40-7.34 (m, 4H); δ 6.67 (dd, 1H); δ 5.71 (d, 1H); δ 5.22 (d, 1H); δ 4.83 (s, 2H)

Synthetic block copolymer

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) agent (2-cyano-2-propyl triester dithiocarbonate) and the compound of Preparation Example 1 ( DPM-C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT agent: AIBN) (concentration: 70% by weight), and then the mixture was subjected to a reaction at 70 ° C for 4 hours under nitrogen to prepare a macromolecule. Initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Then, in benzene, the synthetic macroinitiator, the compound of formula H (TFS-PhIM) and AIBN (azobisisobutyronitrile) are 1:200:0.5 (macroinitiator: TFS-OH: The weight ratio of AIBN) was dissolved (concentration: 30% by weight), and then the mixture was subjected to a reaction at 70 ° C for 6 hours under nitrogen to prepare a block copolymer (number average molecular weight: 35,000, polydispersity: 1.2). The block copolymer comprises a first block derived from the compound of Example 1 and a second block derived from a compound of formula H.

Example 8

In a 10 mL flask (Schlenk flask), 0.8662 g of the compound of Preparation Example 1 (DPM-C12), 0.5 g of a macroinitiator in which a RAFT (Reversible Addition Fragmentation Chain Transfer) agent was bonded to both ends thereof was added ( Macro-PEO) (poly(ethylene glycol)-4-cyano-4-(phenylcarbosulfonate) valerate, weight average molecular weight (Mw): 10,000, Sigma Aldrich), 4.1 mg of AIBN (even Nitrogen bisisobutyronitrile) and 3.9 mL of phenylmethyl ether, then stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT (reversible addition fragmentation chain transfer) polymerization in a 70 ° C polyoxo oil container 12 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol which is an extraction solvent, and then vacuum filtered and dried to obtain a light pink block. Polymer (yield: 30.5%, number average molecular weight (Mn): 34,300, polydispersity (Mw/Mn): 1.60). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of polyethylene oxide.

Example 9

In a 10 mL flask (Schlenk flask), 2.0 g of the compound of Preparation Example 1 (DPM-C12), 25.5 mg of RAFT (reversible addition fragmentation chain transfer) agent (cyanoisopropyl dithiobenzoate), 9.4 mg of AIBN (azobisisobutyronitrile) and 5.34 mL of benzene, then stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT (reversible addition fragmentation chain transfer) in a 70 ° C polyoxo oil container ) Polymerization for 4 hours. After the polymerization, the reaction solution is precipitated in 250 mL of methanol which is an extraction solvent, and then vacuum-filtered and dried to obtain a pink macroinitiator in which pink ends are linked with RAFT (reversible addition fragmentation chain transfer) agent. . The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the macroinitiator were 81.6 wt%, 15400 and 1.16, respectively. In a 10 mL flask (Schlenk flask), 1.177 g of styrene, 0.3 g of the macroinitiator and 0.449 mL of benzene were added, followed by stirring at room temperature for 30 minutes under nitrogen, and then at 115 ° C. RAFT (reversible addition fragmentation chain transfer) polymerization was carried out in an oil container for 4 hours. After the polymerization, the reaction solution was precipitated by dissolving 250 mL of methanol as an extraction solvent, followed by vacuum filtration and drying to prepare a pale pink novel block copolymer. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the block copolymer were 39.3% by weight, 31,800 and 1.25, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of polystyrene.

Example 10

In a 10 mL flask (Schlenk flask), 0.33 g of the macroinitiator prepared in Example 9, 1.889 g of 4-trimethyldecylstyrene, and 2.3 mg of AIBN (azobisisobutyronitrile) were added. And 6.484 mL of benzene, and then stirred at room temperature for 30 minutes under nitrogen, and then subjected to RAFT (reversible addition fragmentation chain transfer) polymerization in a polyoxygen acid vessel at 70 ° C for 24 hours. After the polymerization, the reaction solution was precipitated by dissolving 250 mL of methanol as an extraction solvent, followed by vacuum filtration and drying to prepare a pale pink novel block copolymer. The yield, number average molecular weight (Mn) and polydispersity (Mw/Mn) of the block copolymer were 44.2% by weight, 29600 and 1.35, respectively. The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block of poly(4-trimethyldecylstyrene).

Example 11

Synthetic monomer

The compound of the following formula I was synthesized according to the method described below. Pentafluorostyrene (25 g, 129 mmole) was added to a mixed solution of 400 mL of a third butanol and potassium hydroxide (37.5 g, 161 mmole); and then a reflux reaction was carried out for 2 hours. The product after the reaction was cooled to room temperature, 1200 mL of water was added, and the remaining butanol for the reaction was volatilized. The adduct was extracted three times with diethyl ether (300 mL), and the aqueous layer was acidified with a 10% by weight hydrochloric acid solution until the pH became 3 to precipitate the target product. The precipitated product was extracted three times with diethyl ether (300 mL) and organic layer was collected. The organic layer was dehydrated by MgSO ₄ and the solvent was removed. The crude product was purified by column chromatography using hexanes and DCM (dichloromethane) as a mobile phase to give a colorless liquid intermediate (3-hydroxy-1,2,4,5-tetrafluorostyrene) (11.4g). The NMR analysis results are as follows.

<NMR analysis results>

¹ H-NMR (DMSO-d): δ 11.7 (s, 1H); δ 6.60 (dd, 1H); δ 5.89 (d, 1H); δ 5.62 (d, 1H)

This intermediate (11.4 g, 59 mmole) was dissolved in DCM (dichloromethane) (250 mL), and then, then, imidazole (8.0 g, 118 mmole), DMPA (p-dimethylaminopyridine (0.29 g, 2.4 mmole) and The third butyl chlorodimethyl decane (17.8 g, 118 mmole) was reacted for 24 hours by stirring at room temperature, and the reaction was terminated by the addition of 100 mL of brine, followed by additional extraction by DCM. The organic layer collected by DCM was dried over MgSO ₄ and solvent was evaporated to give the crude product. </ RTI></RTI></RTI><RTIgt; The NMR results of the product are as follows.

<NMR analysis results>

¹ H-NMR (CDCl ₃ ): δ 6.62 (dd, 1H); δ 6.01 (d, 1H); δ 5.59 (d, 1H); δ 1.02 (t, 9H), δ 0.23 (t , 6H)

[Formula I]

Synthetic block copolymer

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible addition fragmentation chain transfer) agent (2-cyano-2-propyl triester dithiocarbonate) and the compound of Preparation Example 1 ( DPM-C12) was dissolved in a weight ratio of 50:1:0.2 (DPM-C12:RAFT agent: AIBN) (concentration: 70% by weight), and then the mixture was subjected to a reaction at 70 ° C for 4 hours under nitrogen to prepare a macromolecule. Initiator (quantitative average molecular weight: 14,000, polydispersity: 1.2). Then, in benzene, the synthetic macroinitiator, the compound of formula I (TFS-S) and AIBN (azobisisobutyronitrile) are 1:200:0.5 (macroinitiator: TFS-S: The weight ratio of AIBN) was dissolved (concentration: 30% by weight), and then the mixture was subjected to a reaction at 70 ° C for 6 hours under nitrogen to prepare a block copolymer (number average molecular weight: 35,000, polydispersity: 1.2). The block copolymer includes a first block derived from the compound of Preparation Example 1 and a second block derived from the compound of Formula I.

Example 12

In benzene, AIBN (azobisisobutyronitrile), RAFT (reversible) The addition fragmentation chain transfer agent (2-cyano-2-propyl triester dithiocarbonate) and the compound of Preparation Example 6 (DPM-N1) are 26:1:0.5 (DPM-C12:RAFT) The weight ratio of the agent: AIBN) was dissolved (concentration: 70% by weight), and then the mixture was subjected to a reaction at 70 ° C for 4 hours under nitrogen to prepare a macroinitiator (quantitative average molecular weight: 9,700, polydispersity: 1.2). Then, in benzene, the synthetic macroinitiator, pentafluorostyrene (PFS) and AIBN (azobisisobutyronitrile) are weighted by 1:600:0.5 (macroinitiator: PFS: AIBN). The ratio was dissolved (concentration: 30% by weight), and then the mixture was subjected to a reaction at 115 ° C for 6 hours under nitrogen to prepare a block copolymer (number average molecular weight: 17300, polydispersity: 1.2). The block copolymer includes a first block derived from the compound of Preparation Example 6 and a second block derived from the pentafluorostyrene.

Comparative example 1

A block copolymer was prepared in the same manner as in Example 1, except that the compound of Preparation Example 7 (DPM-C4) was used instead of the compound of Preparation Example 1 (DPM-C12) and the pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from the compound of Preparation Example 7 (DPM-C4) and a second block derived from the pentafluorostyrene.

Comparative example 2

A block copolymer was prepared in the same manner as in Example 1, except that 4-methoxyphenyl methacrylate was used instead of the compound of Preparation Example 1 (DPM-C12) and pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from 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 the dodecyl methacrylate was used instead of the compound of Preparation Example 1 (DPM-C12) and pentafluorostyrene was used to prepare a macroinitiator. The block copolymer includes a first block derived from dodecyl methacrylate and a second block derived from the pentafluorostyrene.

Test case 1

Self-assembled polymer layers were prepared using the block copolymers of Examples 1 to 12 and Comparative Examples 1 to 3, and the results were observed. Specifically, each block copolymer was dissolved in a solvent to a concentration of 1.0% by weight, and then spin-coated on a polyfluorene oxide wafer at a speed of 3000 rpm for 60 seconds. Then, self-assembly is performed by solvent annealing or thermal annealing. The solvent and aging methods used are listed in Table 1 below. The self-combining properties were then evaluated by SEM (Scanning Electron Microscopy) or AFM (Atomic Fluorescence Microscopy) analysis of each polymer layer. 1 to 12 are the results of Examples 1 to 12, respectively, and Figs. 13 to 15 are the results of Comparative Examples 1 to 3, respectively.

Claims (10)

A block copolymer comprising a first block and a second block of the following formula 5, the second block being selected from the group consisting of a polyvinylpyrrolidone block, a polylactic acid block, Polyvinylpyridine block, polystyrene block, polyalkylene oxide block, polybutadiene block, polyisoprene block and polyolefin block: Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, -C(=O)-O- or -OC(=O)-, and P is a stretch having 6 to 30 carbon atoms. Aryl, Q is oxygen or -NR ₃ -, wherein R ₃ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms An alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and Z is a linear chain having a chain-forming atom, wherein the chain-forming atom is carbon, oxygen, nitrogen or sulfur and wherein The number of atoms forming the chain is 8 to 20. The block copolymer of claim 1, wherein the chain forming atom is carbon or oxygen. Such as the block copolymer of claim 1 of the patent range, wherein the straight The chain is a hydrocarbon chain. The block copolymer of claim 1, wherein the second block is represented by the following formula 10: Wherein T and K are each independently an oxygen or a single bond, and U is an alkylene group having 1 to 20 carbon atoms. The block copolymer of claim 4, wherein U of the formula 10 is an alkylene group having 1 to 8 carbon atoms. The block copolymer of claim 4, wherein one of T and K of Formula 10 is the single bond, and the other is oxygen. The block copolymer of claim 4, wherein X and K of the formula 10 are oxygen. A polymer layer comprising the self-assembled product of the block copolymer of claim 1 of the patent application. A method for forming a polymer layer comprising forming a polymer layer comprising a self-assembled product of the block copolymer of claim 1 of the patent application. A pattern forming method comprising selectively removing a block copolymer from a laminate comprising a substrate and a polymer layer formed on the substrate and comprising a self-assembled product of the block copolymer of claim 1 The first or second block of matter.