KR101821723B1 - Praparing method of block copolymer and preparing method of polymer film - Google Patents

Abstract

The present invention relates to a method for producing a block copolymer and a method for producing a polymer film. More particularly, the present invention relates to a method for producing a block copolymer which can form a plurality of blocks in a block copolymer, a plurality of blocks are individually vertically aligned, and an alignment is excellent, and a method for producing a block copolymer The present invention relates to a method for producing a polymer film.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a block copolymer and a method for producing a polymer film,

The present invention relates to a method for producing a block copolymer and a method for producing a polymer film. More particularly, the present invention relates to a method for producing a block copolymer which can form a plurality of blocks in a block copolymer, a plurality of blocks are individually vertically aligned, and an alignment is excellent, and a method for producing a block copolymer The present invention relates to a method for producing a polymer film.

Currently, photolithography used in information storage media or semiconductors has a limitation in patterning of 20 nm or less, so that a block copolymer capable of patterning very easily at a large area and at a low cost has attracted a great deal of attention. In order to actually apply the block copolymer thin film to the above fields, the nano structure of the lamella or the cylinder should be vertically aligned. In the case of the general block copolymer thin film, the horizontal orientation occurs due to the mutual attraction difference between each block and the substrate. Therefore, many methods have been developed to neutralize the reciprocal attraction difference between each block and substrate to induce vertical orientation.

Previously reported techniques for neutralization include brushing random copolymer on substrate surface, solvent annealing method, using electric field, forming rough surface on substrate, introducing graphene on substrate surface, A graphoepitaxy method, and a method of forming a single layer of nanoparticles on the substrate surface. However, additional pre- and post-processing methods, which are indispensably required for the above-mentioned vertical orientation, discourage the large-area and low-cost advantages of block copolymers, which are evaluated as competitiveness for practical applications, .

Accordingly, there is a demand for the development of block copolymers that can be vertically aligned during the thin film formation process without additional pre- and post-processing.

The present invention is to provide a method for producing a block copolymer capable of forming a large number of blocks in a block copolymer, a plurality of blocks are individually vertically aligned, and an alignment degree is excellent.

The present invention also provides a method for producing a polymer film using the block copolymer obtained by the method for producing a block copolymer.

In this specification, a method is provided for forming a first block through polymerization of a first monomer from a hydroxyl group end of a cyclic sugar compound containing from 15 to 30 hydroxyl groups; And forming a second block through polymerization of a second monomer from an end of the first block.

The present specification also provides a block copolymer obtained by the method for producing a block copolymer.

The present invention also provides a method for producing a polymer film, which comprises coating a mixture of the block copolymer and an organic solvent on a substrate.

The present invention also provides a polymer film obtained by the polymer film production method.

Hereinafter, a method for producing a block copolymer and a method for producing a polymer film according to a specific embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a method for preparing a polymer, comprising: forming a first block through polymerization of a first monomer from a hydroxyl group end of a cyclic sugar compound containing from 15 to 30 hydroxyl groups; And forming a second block from the end of the first block through polymerization of the second monomer.

The inventors of the present invention have found that by forming the first block and the second block sequentially from a plurality of hydroxyl groups contained in the cyclic sugar compound, the number of the hydroxyl groups contained in the cyclic sugar compound Not only the block can be formed but also the formed block is excellent in vertical orientation without pre- and post-treatment of the substrate due to the specific structure of the block copolymer extending from the center of the cyclic sugar compound like an arm , It has been confirmed through experiments that the hydroxy group is uniformly distributed evenly in the cyclic sugar compound and that the block grown therefrom also has an excellent degree of alignment, and completed the invention.

Particularly, since the cyclic sugar compound has a large number of reactive functional groups capable of inducing polymerization reaction in the molecular structure, it is easy for the block copolymerization reaction to proceed at the same time, and only by a simple operation of inputting different monomers in sequence Various blocks can be introduced and the efficiency of the block copolymer production process can be improved.

In addition, the cyclic sugar compound has a structure in which a specific structure is regularly and repeatedly repeated, and a block formed while growing from the hydroxyl group of the cyclic sugar compound may have a columnar or plate-like characteristic nano structure, Functionalities due to the structural characteristics peculiar to the block copolymer can be realized when a thin film or the like using a copolymer is produced.

The finally prepared block copolymer has a specific structure in which the block copolymer is bonded to the cyclic sugar compound located at the center, and neutralizes the selective force with the substrate to form a vertically oriented structure without pre / post treatment of the substrate .

Specifically, the method for preparing a block copolymer of one embodiment includes forming a first block through polymerization of a first monomer from a hydroxyl group end of a cyclic sugar compound containing 15 to 30 hydroxyl groups; And forming a second block from the end of the first block through polymerization of the second monomer.

First, the method for preparing a block copolymer in one embodiment may include forming a first block through polymerization of a first monomer from a hydroxyl group end of a cyclic sugar compound containing 15 to 30 hydroxyl groups.

The cyclic sugar compound means a compound in which monomers forming the sugar compound are bonded to each other to form a cyclic structure. The ring structure may be formed in the molecular structure of the unit forming the sugar compound, but the cyclic sugar compound as referred to in the present specification does not simply include the ring structure in the sugar compound, Means that the monomers constituting the sugar bond form a ring structure.

The cyclic sugar compound may contain from 15 to 30 hydroxyl groups. The hydroxy group contained in the cyclic sugar compound is a highly reactive functional group, and the reaction for forming a block copolymer can proceed from the end of the hydroxyl group. Therefore, when the number of hydroxy groups contained in the cyclic sugar compound is reduced to less than 15, the number of the block copolymers formed per one cyclic saccharide compound decreases, Formation of the structure is difficult, and it may be difficult to induce vertical alignment without pre / post treatment.

Also, when the number of hydroxy groups contained in the cyclic sugar compound is excessively increased to more than 30, as the number of the block copolymers formed per one cyclic saccharide compound is excessively increased, the cyclic sugar compound Can be reduced. The cyclic sugar compound has a very small volume of about 1 nm ³ , and when 30 or more polymers are formed per one of the cyclic sugar compounds, polymerization may be difficult due to excessive density.

Specifically, the cyclic sugar compound containing 15 to 30 hydroxyl groups may include at least one member selected from the group consisting of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin. That is, the cyclic sugar compound containing 15 to 30 hydroxyl groups may use alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, or a mixture of two or more thereof.

The first block may be formed through polymerization of the first monomer from the hydroxyl group end of the cyclic sugar compound containing 15 to 30 hydroxyl groups. The step of forming the first block may be carried out in all of the hydroxyl groups contained in the cyclic sugar compound or a part of the hydroxyl groups and the polymerization is initiated from the end of the hydroxyl group, Can be formed.

The first monomer may be any of various compounds including a polymerizable reactive group in the molecular structure without limitation, and the homopolymer formed through the polymerization of the first monomer may form the first block.

More specifically, the first monomer may include at least one selected from the group consisting of styrene, (meth) acrylate, (meth) acrylamide and (meth) acrylonitrile.

The term "(meth) acrylic" as used herein means including both "acrylic" and "methacrylic". For example, the (meth) acrylate is meant to include both acrylate and methacrylate.

Particularly, in the method for producing a block copolymer of the embodiment, styrene or (meth) acrylate is used as the first monomer, the block can be easily formed through UV irradiation, and after the block formation, The block containing the polymer of the (meth) acrylate can be easily removed to prepare the nanoporous film.

Also, the polymerization of the first monomer may proceed under a transition metal complex catalyst. The transition metal complex catalyst means a catalyst containing a ligand compound together with a transition metal. Examples of the transition metal include, but are not limited to, copper (Cu), iron (Fe), ruthenium (Ru) Nickel (Ni), osmium (Os), or the like can be used, and the transition metal can be introduced into a halogenated transition metal state. Examples of the ligand compound included in the transition metal complex catalyst are also not limited in any way. For example, heteroaromatic compounds such as 2,2'-bipyridyl may be mentioned.

The polymerization of the first monomer may be carried out at a temperature of 50 ° C to 150 ° C.

More specifically, the step of forming the first block through the polymerization of the first monomer from the hydroxyl group end of the cyclic sugar compound containing 15 to 30 hydroxyl groups may be carried out by reacting a cyclic sugar compound containing 15 to 30 hydroxyl groups Esterifying an acyl halide containing at least two halogens; And a step of subjecting the resultant product of the esterification step to a first polymerization reaction by charging the first monomer.

In the step of esterifying the cyclic sugar compound containing 15 to 30 hydroxyl groups and the acyl halide containing at least 2 halogens, the description of the cyclic sugar compound containing 15 to 30 hydroxyl groups is described in detail The acyl halide containing at least two halogens may specifically include a carbonyl group, a functional group containing an alkylene group having 1 to 20 carbon atoms, and at least two halogen atoms. The alkylene group is a polyfunctional group derived from an alkane, for example, a straight chain, branched or cyclic group such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec- a tert-butylene group, a pentylene group, a hexylene group, and the like. The at least one hydrogen atom contained in the alkylene group may be substituted with a substituent.

Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, A halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amido group, a carbonyl group, a hydroxyl group, a sulfonyl group, a carbamate group and an alkoxy group having 1 to 10 carbon atoms.

The substitution means that the alkyl group having 1 to 10 carbon atoms or the aryl group having 6 to 20 carbon atoms is bonded in place of the hydrogen atom contained in the straight chain or branched alkylene group having 1 to 20 carbon atoms, Although the number is not limited, at least one or more of them may be substituted.

The alkylene group having 1 to 20 carbon atoms may specifically include a linear alkylene group having 1 to 20 carbon atoms or an alkylene group having 3 to 20 carbon atoms.

On the other hand, a carbonyl group and an alkylene group having 1 to 20 carbon atoms may be directly bonded to the functional group. That is, one terminal of one terminal of the terminal of the carbonyl group and one terminal of the terminal of the alkylene group of the carbonaceous of 1 to 20 carbon atoms may form a bond with each other. And the other terminal of the carbonyl group is bonded to a halogen element, and the alkylene group having 1 to 20 carbon atoms may be substituted with at least one halogen element.

The halogen element is an element belonging to Group 17 of the periodic table, for example, chlorine (Cl), bromine (Br), iodine (I) or a mixture of two or more thereof. That is, at least two or more halogen elements contained in the halogenated compound may be the same or different.

Particularly, in the method for producing a block copolymer, in the step of esterifying the cyclic sugar compound containing 15 to 30 hydroxyl groups and the acyl halide containing at least 2 halogens, one halogen element contained in the acyl halide is removed And one further halogen element contained in the acyl halide is further removed in the subsequent first polymerization reaction step. Therefore, the acyl halide must contain at least two halogen elements, and the acyl halide is included in the acyl halide When the amount of the halogen element is less than 2, the block copolymer can not be produced.

Specific examples of the acyl halide are not limited, but include compounds represented by the following formula (1).

[Chemical Formula 1]

In the above formula (1), A is an alkylene group having 1 to 20 carbon atoms, and Z ₁ and Z ₂ are the same as or different from each other, and each independently represents a halogen atom. The description of the alkylene group includes the above description in one embodiment.

More specific examples of the halogenated compound include alpha -Bromoisobutyryl bromide (BIBB).

In the step of esterifying the cyclic sugar compound containing 15 to 30 hydroxyl groups and the acyl halide containing at least 2 halogens, it is preferable that the step of esterifying the cyclic saccharide compound containing 15 to 30 hydroxyl groups The content of the acyl halide including two or more halogens may be 10 to 100 mols, and the esterification reaction may proceed at room temperature and atmospheric pressure.

In the step of esterifying the cyclic sugar compound containing 15 to 30 hydroxyl groups and the acyl halide containing at least 2 halogens, a solvent may be used if necessary. Examples of the solvent include, but are not limited to, organic Various solvents used in the reaction can be used without limitation.

The content of the first monomer includes the above-mentioned contents. Specifically, ATRP (Atom Transfer Radiation Polymerization) (ATRP) is used in the first polymerization reaction by introducing the first monomer into the product of the esterification reaction step. The reaction can proceed. The atom transfer radical polymerization may be carried out at a temperature ranging from 50 ° C to 150 ° C.

The first monomer may be added in an amount of 300 to 700 moles relative to 1 mole of the resultant product in the esterification step in the first polymerization reaction by introducing the first monomer into the product of the esterification reaction step.

In addition, the method for producing a block copolymer of one embodiment may include forming a second block through polymerization of a second monomer from an end of the first block. The step of forming the second block may proceed from the end of the first block at the end or all of the first block, and the polymerization may be started from the end of the first block, Two blocks may be formed.

The second monomer may be used without limitation in various compounds containing a polymerizable reactive functional group in the molecular structure, and the homopolymer formed through the polymerization of the second monomer may form the second block.

More specifically, the second monomer may include at least one selected from the group consisting of styrene, (meth) acrylate, (meth) acrylamide and (meth) acrylonitrile. However, the first monomer is different from the second monomer, so that a block copolymer containing the first and second blocks, which are different from each other, can be introduced. As described above, by introducing the block copolymer, it is possible to form a plate-like or cylindrical nanostructure by phase separation between different blocks. Thus, when a homopolymer using a single monomer is used, it is advantageous in that it is difficult to form a nanostructure.

Further, the polymerization of the second monomer may proceed in the presence of a transition metal complex catalyst. The transition metal complex catalyst means a catalyst containing a ligand compound together with a transition metal. Examples of the transition metal include, but are not limited to, copper (Cu), iron (Fe), ruthenium (Ru) Nickel (Ni), osmium (Os), or the like can be used, and the transition metal can be introduced into a halogenated transition metal state. Examples of the ligand compound included in the transition metal complex catalyst are also not limited in any way. For example, heteroaromatic compounds such as 2,2'-bipyridyl may be mentioned.

The polymerization of the second monomer may be carried out at a temperature of 50 ° C to 150 ° C.

For example, the step of forming the second block through the polymerization of the second monomer from the end of the first block may be carried out by adding the second monomer to the cyclic sugar compound in which the first block is formed.

In the step of adding the second monomer to the cyclic sugar compound in which the first block is formed, a solvent may be used if necessary. Examples of the solvent are not limited, and various solvents used in the organic reaction may be used without limitation have.

In the step of adding the second monomer to the cyclic sugar compound in which the first block is formed, the content of the second monomer includes the above-mentioned contents. Specifically, the ATRP reaction Can proceed.

In the step of adding the second monomer to the cyclic sugar compound in which the first block is formed, the content of the second monomer may be 300 to 700 moles per mole of the cyclic sugar compound in which the first block is formed.

Meanwhile, according to another embodiment of the present invention, a block copolymer obtained by the above-mentioned process for producing a block copolymer may be provided. That is, the block copolymer comprises a first block formed from a hydroxyl group end of a cyclic sugar compound containing from 15 to 30 hydroxyl groups; And a second block formed from the end of the first block, wherein the description of the cyclic sugar compound, the first block, and the second block containing the 15 to 30 hydroxyl groups is the same as that described in the above embodiment .

According to another embodiment of the present invention, there is provided a method for producing a polymer film, which comprises coating a mixture of a block copolymer and a solvent of the another embodiment on a substrate.

Examples of the specific types of solvents used in the polymer film production method are not limited, and various well-known organic solvents, inorganic solvents, and aqueous solvents may be used without limitation.

More specifically, examples of the solvent include water, NMP, acetone, N, N-dimethylformamide, DMSO, ethanol, toluene, isopropyl alcohol, methanol, butanol, 2-ethoxyethanol, 2 -Butoxyethanol, 2-methoxypropanol, tetrahydrofuran, ethylene glycol, pyridine, dimethylacetamide, N-vinylpyrrolidone, methyl ethyl ketone (butanone), alpha-terpineol, formic acid, ethyl acetate and Acrylonitrile, and acrylonitrile may be used.

The concentration of the block copolymer in the mixed solution may be 0.1 wt% to 10 wt%, or 1 wt% to 5 wt%. This makes it possible to easily produce a film having a uniform thickness without spattering by spin coating.

Examples of the substrate include, but are not limited to, various materials such as silicon wafers, paper, wood, metal, and polymers. The method of coating the block copolymer mixture on the substrate is also limited And various coating methods known in the art can be used without limitation.

In addition, the polymer film manufacturing method may further include a step of performing heat treatment at a temperature of 180 ° C to 200 ° C within 30 minutes. Through the heat treatment step, the degree of alignment of the block copolymer contained in the polymer film can be improved.

According to another embodiment of the present invention, a polymer film obtained by the polymer film production method of another embodiment may be provided. That is, the polymer film includes a polymer film in which the block copolymer of the other embodiment is dispersed, and the description of the block copolymer includes the above-mentioned contents in the other embodiments.

The present invention relates to a method for producing a block copolymer capable of forming a large number of blocks in a block copolymer, a plurality of blocks are individually vertically aligned and excellent in alignment, and a method for producing a block copolymer And a method for producing a film.

Fig. 1 schematically shows an example of a process for synthesizing a block copolymer of Example 1. Fig.
Fig. 2 schematically shows another example of the process for synthesizing a block copolymer of Example 3. Fig.
3 is an AFM image of the thin film of the block copolymer obtained in Examples 1 and 2 according to heat treatment time.
4 is an AFM image according to the thickness of the block copolymer thin film obtained in Examples 1 and 2. Fig.
5 is an AFM image of a substrate on which a block copolymer thin film obtained in Examples 1 and 2 is formed.
Fig. 6 shows GISAXS measurement results of the block copolymer thin films obtained in Examples 1 and 2. Fig.
7 is an SEM image of the block copolymer thin films obtained in Examples 1 and 2. Fig.
Fig. 8 shows TEM images of the block copolymer thin films obtained in Examples 3 and 4. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

≪ Examples 1 to 2: Preparation of block copolymer film >

Example 1: Block copolymer and film of lamellar structure (STAR-LAM)

1) Synthesis of Star Block Copolymer

1 mmol of? -Cyclodextrin (? -CD) was reacted with 50 mmol of alpha-bromo (? - cyclodextrin,? -CD) at room temperature and 4- (N, N-dimethylamino) pyridine Cyclodextrin (Br-CD) having 18 bromine groups (-Br) was synthesized by reacting with α-bromoisobutyryl bromide (BIBB) for 24 hours (FIG.

18 bromine groups present in 0.1 mmol of? -Cyclodextrin (Br-CD) having 18 bromine groups (-Br) were used as initiators for the Atom Transfer Radical Polymerization (ATRP) reaction to obtain 2,2'-bipyridyl / CuBr catalyst , 50 mmol of methyl methacrylate (MMA) monomer was added thereto, and the mixture was reacted in a vacuum environment at 90 ° C. for 12 hours to obtain 18 types of star polymers having a polymethyl methacrylate (PMMA) ₁₈ chain PMMA polymer was synthesized (Fig. 1B).

350 mmol of styrene monomer was added under a 2,2'-bipyridyl / CuBr catalyst using an initiator of Atom Transfer Radical Polymerization (ATRP) reaction at the end of 1 mmole of the star-shaped PMMA polymer. by reacting 18 polymethyl methacrylate-ethylamine - [block -polystyrene, (PMMA- b -PS) 18 poly (methyl methacrylate)] PS-PMMA star-shaped block copolymers having polystyrene chain. (Fig. 1C)

At this time, the volume ratio of polystyrene was made to be 0.60 as compared with the whole block copolymer.

2) Preparation of block copolymer film by spin coating

A toluene solvent was added so that the concentration of the star block copolymer was about 2.0 wt%, and a film was formed on a silicon wafer by spin coating.

Example 2: Block copolymer and film of cylinder structure (STAR-CYL)

50 mmol of methyl methacrylate (MMA) monomer was added and reacted in a vacuum environment for 12 hours. 350 mmol of styrene monomer was added and reacted in a vacuum environment for 24 hours. The volume ratio of polystyrene to total block copolymer Star-shaped block copolymer and film were prepared in the same manner as in Example 1, except that the ratio was 0.75.

Example 3: Block copolymer and film of lamellar structure (STAR-LAM)

1) Synthesis of Star Block Copolymer

1 mmol of? -Cyclodextrin (? -CD) was reacted with 50 mmol of alpha-bromo (? - cyclodextrin,? -CD) at room temperature and 4- (N, N-dimethylamino) pyridine Cyclodextrin (Br-CD) having 18 bromine groups (-Br) was synthesized by reacting with α-bromoisobutyryl bromide (BIBB) for 24 hours (FIG.

18 bromine groups present in 0.1 mmol of? -Cyclodextrin (Br-CD) having 18 bromine groups (-Br) were used as initiators for the Atom Transfer Radical Polymerization (ATRP) reaction to obtain 2,2'-bipyridyl / CuBr catalyst 50 mmol of styrene monomer was added thereto and reacted in a vacuum environment at 90 캜 for 24 hours to synthesize a star PS polymer having ₁₈ polystyrenes (PS) ₁₈ chains (FIG. 2B).

350 mmol of methyl methacrylate (MMA) monomer was added under a 2,2'-bipyridyl / CuBr catalyst using an initiator of Atom Transfer Radical Polymerization (ATRP) Polystyrene- block -poly (methyl methacrylate) (PS- b- PMMA) ₁₈ with 18 polystyrene-polymethylmethacrylate chains was reacted in a vacuum environment for 12 hours. Were synthesized. (Fig. 2C)

At this time, the volume ratio of polymethyl methacrylate was adjusted to be 0.48 as compared with the entire block copolymer.

2) Preparation of block copolymer film by spin coating

A toluene solvent was added so that the concentration of the star block copolymer was about 2.0 wt%, and a film was formed on a silicon wafer by spin coating.

Example 4: Block copolymer and film of cylinder structure (STAR-CYL)

50 mmol of styrene monomer was added and reacted for 24 hours in a vacuum environment. Then, 350 mmol of methyl methacrylate (MMA) monomer was added and reacted in a vacuum environment for 6 hours to obtain a poly (methyl methacrylate) A star block copolymer and a film were prepared in the same manner as in Example 3 except that the total block copolymer was 0.38.

<Experimental Example: Measurement of Physical Properties of the Block Copolymer Film Obtained in the Examples>

The physical properties of the block copolymer film obtained in the above Examples were measured by the following methods.

Experimental Example 1: Atomic Force Microscopy (AFM)

The surface of the star block copolymer film obtained in Examples 1 and 2 was confirmed by atomic force microscopy (AFM), and the results are shown in Figs. 2 to 4.

As shown in Fig. 3 (a), it was confirmed that the star-shaped block copolymer film obtained in Example 1 had well-vertical orientation of the lamellar structure. As shown in Fig. 3 (d) It was confirmed that the obtained star-shaped block copolymer film had a well-vertical orientation of the cylinder structure.

When the star-shaped block copolymer film obtained in Example 1 was heat-treated for 10 minutes or 30 minutes, as shown in Figs. 3 (b) and 3 (c) Respectively. When the star-shaped block copolymer film obtained in Example 2 was also subjected to a heat treatment for 10 minutes or 30 minutes, excellent alignment was exhibited only by a short heat treatment within 30 minutes as shown in (e) and (f) .

In addition, for the nanostructure equilibrium state of the block copolymer film, heat treatment was sufficiently performed at a temperature of 180 ° C for 24 hours, and films having various thicknesses were formed. 4 (a) to 4 (d), the nanostructure was vertically oriented to a thickness of 51 nm to 100 nm, and in Example 2, h), the nanostructures were vertically oriented to a thickness of 53 nm to 160 nm.

As shown in FIG. 4, the block copolymer films of Examples 1 and 2 were respectively laminated on a polyethylene naphthalate (PEN) substrate (FIGS. 5B and 5C) and a gold substrate (FIG. 5 (f), (g)) on the surface of which the PS is brushed, and on the substrate (FIG. 5 , It was confirmed that the lamellar structure or the cylinder structure is vertically aligned with excellent alignment.

Experimental Example 2: Grazing-incidence small-angle X-ray scattering (GISAXS)

The degree of orientation of the star block copolymer films obtained in Examples 1 to 4 was confirmed by grazing-incidence small-angle X-ray scattering (GISAXS) and the results are shown in FIG.

Specifically, the grazing-incidence small-angle X-ray scattering (GISAXS) measurement was performed in the following manner. W / B4C double multi-layer X-ray scattering was measured using a two-dimensional CCD camera (Princeton Instrument, SCX-TE / CCD-1242) by supplying a monochromatic X-ray at a wavelength of 0.1608 nm and a distance of 3 m. The star block copolymer film was quenched with liquid nitrogen, annealed in a vacuum for 24 hours at 220 DEG C, and then taken at a thickness of 1.0 mm, and the exposure time was 10 seconds.

Referring to FIG. 6A of the star block copolymer film obtained in Example 1, peaks were formed at a ratio of 1: 2: 3, indicating that the lamellar structure was vertically oriented in the entire thickness.

6B of the star block copolymer film obtained in Example 2 shows that the peak is formed at a ratio of 1: 3, which indicates that the cylinder structure is vertically oriented in the entire thickness.

Similarly, in FIG. 6C relating to the star block copolymer film obtained in Example 3, peaks were formed at a ratio of 1: 3, indicating that the lamellar structure was vertically oriented in the entire thickness. 6d of the block copolymer film shows a peak at a ratio of 1: 4, indicating that the cylinder structure is vertically oriented in the entire thickness.

Experimental Example 3: Scanning electron microscopy (SEM)

The star block copolymer films obtained in Examples 1 and 2 were subjected to UV irradiation and acetic acid treatment to remove PMMA, followed by scanning electron microscopy (SEM) to confirm the surface structure, and the results are shown in FIG.

FIG. 7A is a SEM cross-sectional image after PMMA removal according to Example 1. It can be visually confirmed that the lamellar structure from which the PMMA portion is removed is well formed from the surface to the bottom. Also, FIG. 7B for Example 2 shows that the PMMA-removed cylinder pore structure is well formed from the surface to the bottom.

Experimental Example 4: Transmission electron microscopy (TEM)

The surface structure of the star block copolymer films obtained in Examples 3 and 4 was confirmed by transmission electron microscopy (TEM) and the results are shown in FIG.

Specifically, the TEM measurement was carried out in the following manner. The star block copolymer film was quenched with liquid nitrogen and then annealed at 220 캜 for 24 hours under vacuum. The sample was sampled at a thickness of about 40 nm, and the sample was sampled at S-7600 (Hitachi) at 80 kV at room temperature .

FIG. 8A is a TEM image for Example 3, and it was visually confirmed that the lamellar structure was well formed from the surface to the bottom. 8B of Example 4, it can be seen that the cylinder pore structure is well formed from the surface to the bottom.

Claims (15)

delete delete delete delete delete delete delete delete delete delete delete Forming a first block through polymerization of a first monomer from the hydroxyl group end of the alpha-cyclodextrin and forming a second block from the end of the first block through polymerization of the second monomer Coating a mixture of the block copolymer and the solvent obtained by the method on a substrate; And
Treating at a temperature of from 180 캜 to 200 캜 for 30 minutes or less,
Wherein the first monomer is styrene and the second monomer is (meth) acrylate,
Wherein the first monomer is (meth) acrylate and the second monomer is styrene.
13. The method of claim 12,
Wherein the concentration of the block copolymer contained in the mixed solution is 0.1 wt% to 10 wt%.
delete A polymer film obtained by the method for producing a polymer film according to claim 12.

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