BLOCK COPOLYMER

Abstract

The present application provides a block copolymer and uses thereof. The block copolymer of the present application exhibits an excellent self-assembling property or phase separation property, and can be provided with a variety of required functions without constraint.

Claims

1. A block copolymer comprising a first block that is a structural unit represented by Structural Formula 1 below and a second block that is a structural unit represented by Structural Formula 5 below: ##STR00010## where in the Structural Formula 1, R represents a hydrogen atom or an alkyl group; X represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.1— or —X.sub.1—C(═O)—, wherein the X.sub.1 represents an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; Y represents a monohydric substituent that includes a ring structure to which a linear chain including 8 or more chain-forming atoms is connected; and where in the Structural Formula 5, X.sub.2 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.2— or —X.sub.2—C(═O)—, wherein the X.sub.2 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; and each of R.sub.1 to R.sub.5 independently represents a hydrogen atom, an alkyl group, a haloalkyl group, a halogen atom or a substituent that is represented by Structural Formula 6 below, wherein one or more substituent (that is represented by the following Structural Formula 6) are included in positions marked as R.sub.1 to R.sub.5: ##STR00011## where in the Structural Formula 6, Y represents an alkyl group, and X.sub.3 represents an oxygen atom, a carbonyl group, —C(═O)—O—, or —O—C(═O)—.

2. The block copolymer of claim 1, wherein the X of the Structural Formula 1 represents a single bond, an oxygen atom, a carbonyl group, —C(═O)—O—, or —O—C(═O)—.

3. The block copolymer of claim 1, wherein the linear chain includes 8 to 20 chain-forming atoms.

4. The block copolymer of claim 1, wherein the chain-forming atom is carbon, oxygen, nitrogen, or sulfur.

5. The block copolymer of claim 1, wherein the chain-forming atom is carbon or oxygen.

6. The block copolymer of claim 1, wherein the ring structure of the Y is an aromatic ring structure or an alicyclic ring structure.

7. The block copolymer of claim 1, wherein the Y of the Structural Formula 1 is represented by Structural Formula 2 below:
-P-Q-Z  [Structural Formula 2] where in the Structural Formula 2, P represents an arylene group; Q represents a single bond, an oxygen atom or —NR.sub.3—, wherein the R.sub.3 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group; and Z represents a linear chain with 8 or more chain-forming atoms.

8. The block copolymer of claim 1, wherein one or more halogen atoms are included in the positions marked as R.sub.1 to R.sub.5 of the Structural Formula 5.

9. The block copolymer of claim 1, wherein the Y of the Structural Formula 6 represents a branched-type alkyl group with 1 to 20 carbons.

10. The block copolymer of claim 1 comprising: the second block that includes the structural unit of the Structural Formula 5 in a proportion ranging from 0.1 mol % to 5 mol %.

11. The block copolymer of claim 1, wherein the second block further includes a structural unit represented by Structural Formula 8 below: ##STR00012## where in the Structural Formula 8, X.sub.2 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.1— or —X.sub.1—C(═O)—, wherein the X.sub.1 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; and W represents an aryl group that includes at least one halogen atom.

12. The block copolymer of claim 1, wherein the second block further includes a structural unit represented by Structural Formula 9 below: ##STR00013## where in the Structural Formula 9, X.sub.2 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X.sub.1— or —X.sub.1—C(═O)—, wherein the X.sub.1 represents a single bond, an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group; and each of R.sub.1 to R.sub.5 independently represents a hydrogen atom, an alkyl group, a haloalkyl group or a halogen atom, wherein one or more halogen atoms are included in positions marked as R.sub.1 to R.sub.5.

13. The block copolymer of claim 12, wherein 3 or more halogen atoms are included in the positions marked as R.sub.1 to R.sub.5 of the Structural Formula 9.

14. The block copolymer of claim 12, wherein 5 or more halogen atoms are included in the positions marked as R.sub.1 to R.sub.5 of the Structural Formula 9.

15. The block copolymer of claim 12, wherein the halogen atom is a fluorine atom.

16. A polymer film comprising the block copolymer of claim 1, wherein the block copolymer is self-assembled.

17. A method of forming a polymer film, the method comprising: forming a polymer film that includes the block copolymer of claim 1 on a substrate, wherein the block copolymer is self-assembled.

18. A method of forming a pattern, the method comprising: selectively removing any one block of the block copolymer of claim 1 from a laminate that is made up of a substrate and a polymer film, which is formed on the substrate and includes the block copolymer, wherein the block copolymer is self-assembled.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0119] FIG. 1 illustrates the AFM results of the polymer film of Example 1.

EFFECT

[0120] The present application can provide a block copolymer and uses thereof. The block copolymer of the present application exhibits an excellent self-assembling property or phase separation property, and can be provided with a variety of required functions without constraint.

DETAILED DESCRIPTION OF EMBODIMENTS

[0121] The present application is described in more detail hereinafter through examples according to the present application, but the scope of the present application is not limited to the examples which are proposed hereinafter.

Example 1

[0122] Synthesis of Monomer

[0123] The compound represented by the following Structural Formula A (1,2,4,5-tetrafluorostyrene-3-pivalate) was synthesized by the following method: pentafluorostyrene (25 g, 129 mmol) was added to 400 mL of a mixed solution of tert-butanol and potassium hydroxide (37.5 g, 161 mmol), all of which were allowed to have a reflux reaction for 2 hours; the reactants were cooled to room temperature and then 1200 mL of water was added; the adducts were extracted with diethyl ether (300 mL) for 3 times through a process of volatilizing any remaining butanol that was used in the previous reaction; the aqueous solution layer was acidified with a 10-wt % hydrochloric acid solution to a pH of about 3 to precipitate the target materials; the organic layer was collected through extraction with diethyl ether (300 mL) again for 3 times, dehydrated with MgSO.sub.4, and removed of the solvent to obtain a crude product (3-hydroxy-1,2,4,5-tetrafluorostyrene); the crude product was purified by column chromatography by using hexane and dichloromethane (DCM) as the mobile phase to acquire colorless liquid 3-hydroxy-1,2,4,5-tetrafluorostyrene (11.4 g). The results of NMR analysis on the above substance are as follows.

[0124] <NMR Analysis Results>

[0125] .sup.1H-NMR (DMSO-d): M1.7 (s, 1H); δ6.60 (dd, 1H); δ5.89 (d, 1H); δ5.62 (d, 1H)

[0126] 3-hydroxy-1,2,4,5-tetrafluorostyrene (4.0 g, 21 mmol) was dissolved in DCM (200 mL) to which methacrylic acid (2.0 g, 23 mmol), N,N′-dicyclohexylcarbodiimide (DCC) (4.7 g, 23 mmol) and p-dimethylaminopyridine (DMAP) (1. g, 8.4 mmol) were added in written order; the substances were allowed to react for 24 hours, filtered to remove a urea side product, removed of the solvent, and then purified by column chromatography that uses a DCM/hexane solution to acquire a transparent liquid target compound of 1,2,4,5-tetrafluorostyrene-3-pivalate (5.1 g, 19 mmol, 88%) that is represented by the following Structural Formula A. The results of NMR analysis on the above compound are as follows.

[0127] <NMR Analysis Results>

[0128] .sup.1H-NMR (CDCl3): δ6.64 (dd, 1H); δ6.07 (d, 1H); δ5.68 (d, 1H); δ1.38 (s, 9H).

##STR00009##

[0129] Synthesis of Block Copolymer

[0130] In order to polymerize a block copolymer by using synthesized monomers, azobisisobutyronitrile (AIBN) was used as the polymerization initiator, which was dissolved with a reversible addition-fragmentation chain transfer (RAFT) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) and the above compound, which is represented by Structural Formula A, in anisole in a weight ratio of 30:2:0.2 (compound represented by Structural Formula A:RAFTreagent:AIBN) (solid concentration: 30 wt %). The above solution was allowed to react at 70° C. for 4 hours under a nitrogen atmosphere to synthesize a macroinitiator (number average molecular weight: 6800, molecular weight distribution: 1.16), which was dissolved with pentafluorostyrene and AIBN in anisole at a weight ratio of 1:490:10:0.5 (macroinitiator:pentafluorostyrene:compound represented by Structural Formula A:AIBN) (solid concentration: 70 wt %). The prepared solution was allowed to react at 70° C. for 5 hours under a nitrogen atmosphere to prepare a block copolymer. The number average molecular weight and molecular weight distribution of the prepared block copolymer were 13800 and 1.15, respectively.

Test Example 1

[0131] A self-assembled polymer film was formed by using the block copolymer that was synthesized in Example 1, and the results were observed. The block copolymer was dissolved in a solvent at a concentration of 0.7 wt % and then spin-coated on a silicon wafer for about 60 seconds at a speed of 3000 rpm to form a polymer thin film. The film was thermal-annealed at 160° C. for 1 hour to induce microphase separation, and the results are provided in the following FIG. 1.