BLOCK COPOLYMER

Abstract

The present application relates to a monomer, a method for preparing a block copolymer, a block copolymer, and uses thereof. Each monomer of the present application exhibits an excellent self-assembling property and is capable of forming a block copolymer to which a variety of required functions are granted as necessary without constraint.

Claims

1. A block copolymer comprising a first block that is a structural unit represented by Structural Formula 1 below: ##STR00016## 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, —NR.sub.1—, —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 a single bond, an oxygen atom, a sulfur atom, —NR.sub.1—, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group, wherein the R.sub.1 represents a hydrogen atom or an alkyl group; and Y represents an aryl group substituted in at least one part by a substituent -Q-P, wherein the Q represents —K—C(═O)—X.sub.2—, —X.sub.2—C(═O)—K— or a cycloalkylene group, and the P represents a chain that contains 3 or more chain-forming atoms, wherein the X.sub.2 represents an oxygen atom, a sulfur atom, —S(═O).sub.2—, an alkylene group, an alkenylene group or an alkynylene group, the K represents an alkenylene group.

2. The block copolymer of claim 1, wherein the X of the Structural Formula 1 is —C(═O)—O— or —O—C(═O)—.

3. The block copolymer of claim 1, wherein the Y of the Structural Formula 1 is an aryl group with 6 to 12 carbons and is substituted in at least one part by the substituent -Q-P.

4. The block copolymer of claim 1, wherein the Y of the Structural Formula 1 is a phenyl group substituted in at least one part by the substituent -Q-P, wherein the substituent -Q-P is substituted in a para position (with respect to the X in the Structural Formula 1) of the phenyl group.

5. The block copolymer of claim 1, wherein the Q of the substituent -Q-P is —K—C(═O)—O— or —O—C(═O)—K—, wherein the K is an alkylene group with 2 to 20 carbons.

6. The block copolymer of claim 1, wherein the Q of the substituent -Q-P is a cycloalkylene group with 3 to 12 carbons.

7. The block copolymer of claim 1, wherein the P of the substituent -Q-P is an alkyl group with 3 to 30 carbons.

8. The block copolymer of claim 1 further comprising a second block which has an aromatic structure that includes one or more halogen atoms.

9. The block copolymer of claim 8, wherein the second block is represented by Structural Formula 2 below: ##STR00017## where in the Structural Formula 2, 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.

10. The block copolymer of claim 8, wherein the second block is represented by Structural Formula 3 below: ##STR00018## where in the Structural Formula 3, 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.

11. The block copolymer of claim 10, wherein three or more halogen atoms are included in the positions marked as R.sub.1 to R.sub.5.

12. The block copolymer of claim 10, wherein five or more halogen atoms are included in the positions marked as R.sub.1 to R.sub.5.

13. The block copolymer of claim 8, wherein the halogen atom is a fluorine atom.

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

15. A method of forming a polymer film that contains the block copolymer of claim 1 on a substrate, wherein the block copolymer is self-assembled.

16. A method of forming a pattern, the method comprising: selectively removing the first block or another 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

[0138] Each of FIGS. 1 and 2 is respectively an AFM image and SEM image of a film that is formed by using the block copolymer of Example 2.

EFFECT

[0139] 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

[0140] 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.

[0141] 1. NMR Measurement

[0142] NMR analysis was carried out at room temperature by using a NMR spectrometer that includes a Varian Unity Inova (500 MHz) spectrometer with a 5-mm triple resonance probe. The analysis subject material was diluted with a solvent (CDCl.sub.3) for an NMR measurement to a concentration of about 10 mg/ml for use, and the chemical shift was expressed in ppm.

Applied Abbreviations

[0143] br=broad signal, s=singlet, d=doublet, dd=doublet of doublets, t=triplet, dt=doublet of triplets, q=quartet, p=quintet, m=multiplet.

[0144] 2. Gel Permeation Chromatography (GPC)

[0145] The number average molecular weight (Mn) and molecular weight distribution were measured by GPC. The analysis subject material such as a macroinitiator or the block copolymer of the examples was put in a 5-mL vial and diluted with tetrahydrofuran (THF) to a concentration of about 1 mg/mL. Then, a standard specimen for calibration and the specimen to be analyzed were filtered with a syringe filter (pore size: 0.45 μm) and subsequently analyzed. ChemStation (Agilent Technologies Inc.) was used as the analytical program, each of the weight average molecular weight (Mw) and Mn was obtained by comparing the elution time of the specimen with the calibration curve, and then a molecular weight distribution (polydispersity index, PDI) was calculated as a ratio (Mw/Mn). The measuring condition of GPC is as follows:

[0146] <GPC Measuring Condition>

[0147] Device: 1200 Series of Agilent Technologies Inc.

[0148] Column: Two PLgel MIXED-B of Polymer Laboratories

[0149] Solvent: THF

[0150] Column temperature: 35° C.

[0151] Sample concentration: 1 mg/mL, 200 L is injected

[0152] Standard specimen: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

Example 1

[0153] Synthesis of Monomer A

[0154] Monomer A that is represented by the following Structural Formula A—where R represents a methyl group, X represents —C(═O)—X.sub.1—, X.sub.1 represents an oxygen atom, Y represents a phenylene group that is substituted in the para position by a substituent (that is represented by -Q-P), Q represents —K—C(═O)—X.sub.2—, K represents an ethylene group, X.sub.2 represents an oxygen atom, and P represents a linear-chain hexyl group—was synthesized by the following method: p-coumaric acid (10 g), 1-hexanol (6.2 g) and p-toluenesulfonic acid (10.5 g) were put in a 100-mL flask containing 1,4-dioxane and allowed to react while refluxing at 105° C.; upon completion of the reaction, the reaction products were mixed with dichloromethane and removed of p-toluenesulfonic acid by a silica column; subsequently, the substances were purified in a silica column by using ethyl acetate with hexane and removed of the remaining 1-hexanol by distillation under reduced pressure to obtain a liquid p-coumaric acid hexyl (8.3 g, 55% yield).

[0155] <NMR Analysis Results>

[0156] .sup.1H-NMR (CDCl.sub.3): δ7.61 (d, 1H); δ7.41 (d, 2H); δ6.83 (d, 2H); δ6.28 (d, 1H); 5.47 (s, 1H); δ4.17 (t, 2H); δ1.68 (tt, 2H); δ1.38 (tt, 2H); δ1.31 (m, 4H); δ0.88 (t, 3H).

[0157] The above p-coumaric acid hexyl (8.3 g), methacrylic acid (3.2 g) and dichloromethane (300 mL) were introduced into a flask to which N,N′-dicyclohexylcarbodiimide (DCC, 7.6 g) and N,N-dimethylaminopyridine (DMAP, 1.6 g) were added and allowed to react. Upon completion of the reaction, the substances were removed of dichloromethane and then purified in a silica column by using ethyl acetate and hexane to obtain the liquid monomer A (9.6 g, 91% yield) that is represented by the following Structural Formula A.

[0158] <NMR Analysis Results>

[0159] .sup.1H-NMR (CDCl.sub.3): δ7.67 (d, 1H); δ7.55 (d, 2H); δ7.16 (d, 2H); δ6.41 (d, 1H); δ6.36 (s, 1H); δ5.78 (s, 1H); δ4.20 (t, 2H); δ2.06 (s, 3H); δ1.70 (tt, 2H); δ1.40 (tt, 2H); δ1.33 (m, 4H); δ0.91 (t, 3H).

##STR00015##

[0160] Synthesis of Polymer A

[0161] The above monomer A, a RAFT reagent (CPDB, 2-cyanoprop-2-yl-benzodithioate) and a thermal initiator (AIBN, azobisisobutyronitrile) were introduced into a flask in an equivalent ratio of 20:1:0.5 (monomer A:RAFT reagent:thermal initiator) and diluted with anisole to prepare a solution with a solid concentration of about 30 wt %. Subsequently, the prepared solution was allowed to react at about 70° C. for about 2 hours under a nitrogen atmosphere and, upon completion of the reaction, precipitated in methanol to obtain the polymer A. The M.sub.n and M.sub.w/M.sub.n of the above polymer A were 8,100 and 1.35, respectively.

Example 2

[0162] Synthesis of Monomer B

[0163] Monomer B that is represented by Structural Formula A of Example 1—where R represents a methyl group, X represents —C(═O)—X.sub.1—, X.sub.1 represents an oxygen atom, Y represents phenylene that is substituted in the para position by a substituent (that is represented by -Q-P), Q represents a cyclohexylene group, P is a linear-chain pentyl group that is substituted for part of the above cyclohexylene group in the para position—was synthesized by the following method: 4-(trans-4-pentylcyclohexyl)phenol (15.0 g) and methacrylic acid (5.8 g) were introduced into a flask and dissolved in 400 mL of dichloromethane; dicyclohexylcarbodiimide (DCC) (13.8 g) and N,N-dimethylaminopyridine (DMAP) (3.0 g) were added to the prepared solution and allowed to react. Upon completion of the reaction, the reaction products were removed of dichloromethane, purified in a silica column by using ethyl acetate with hexane, and removed of the solvent to obtain the white solid monomer B (16.7 g, 87% yield).

[0164] <NMR Analysis Results>

[0165] .sup.1H-NMR (CDCl.sub.3): δ7.21 (d, 2H); δ7.02 (d, 2H); δ6.33 (s, 1H); δ5.73 (s, 1H); δ2.47 (t, 1H); δ2.06 (s, 3H); δ1.88 (t, 4H); 1.43 (q, 2H); δ1.33-1.21 (m, 8H); δ1.04 (q, 2H); δ0.90 (t, 3H)

[0166] Synthesis of Polymer B

[0167] The above monomer B, a RAFT reagent (CPDB) and a thermal initiator (AIBN) were introduced into a flask in an equivalent ratio of 15:1:0.1 (monomer B:RAFT reagent:thermal initiator) and diluted with anisole to prepare a solution with a solid concentration of about 22 wt %. Subsequently, the liquid mixture was allowed to react at about 70° C. for about 3 hours under a nitrogen atmosphere to obtain a macroinitiator. The above macroinitiator had M.sub.n and M.sub.w/M.sub.n of 7,400 and 1.35, respectively, and showed a melting point of about 50° C. during DSC analysis.

[0168] The above macroinitiator, PFS (pentafluorostyrene) and a thermal initiator (AIBN) were mixed in a weight ratio of 1:500:0.5 (macroinitiator:PFS:AIBN) and diluted with anisole to prepare a solution with a solid concentration of about 70 wt %. Subsequently, the liquid mixture was allowed to react at about 70° C. for about 1 hour and 50 minutes under a nitrogen atmosphere to obtain the block copolymer B. The M.sub.n and M.sub.w/M.sub.n of the above block copolymer B were 13,400 and 1.27, respectively.

Test Example 1

[0169] A self-assembled polymer film was formed by using the block copolymer B synthesized in Example 2 and the results were observed. Specifically, a coating solution that was prepared by dissolving a copolymer in a solvent to a concentration of about 1.0 wt % was spin-coated on a silicon wafer for about 60 seconds at a speed of about 3000 rpm, and the coated layer was thermal-annealed at about 220° C. to form a film that contains a self-assembled block copolymer. FIG. 1 is an AFM image of a polymer film that was formed in the above method, and FIG. 2 is an SEM image of the same film.