KR20180062161A - Block copolymer - Google Patents

Abstract

The present invention provides a block copolymer and uses thereof. The block copolymer of the present invention has excellent self-assembling properties or phase separation characteristics, is excellent in etching selectivity, and can be freely given various other required functions. The block copolymer comprises a polymer segment A represented by chemical formula 1 and a polymer segment B represented by chemical formula 2.

Description

BLOCK COPOLYMER < RTI ID = 0.0 >

The present application relates to block copolymers.

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

The present application provides block copolymers and uses thereof.

As used herein, the term alkyl group may mean an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be a straight chain, branched or cyclic alkyl group and may be optionally substituted by one or more substituents.

As used herein, unless otherwise specified, the term alkoxy group may mean an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkoxy groups may be straight, branched or cyclic alkoxy groups and may optionally be substituted by one or more substituents.

As used herein, the term alkenyl or alkynyl group means an alkenyl group or alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms unless otherwise specified can do. The alkenyl or alkynyl group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, unless otherwise specified, the alkylene group may mean an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be a straight, branched or cyclic alkylene group and may optionally be substituted by one or more substituents.

As used herein, the term alkenylene group or alkynylene group means an alkenylene group or an alkynylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, It can mean a group. The alkenylene or alkynylene group may be linear, branched or cyclic and may optionally be substituted by one or more substituents.

As used herein, the term "aryl" group or "arylene group" means, unless otherwise specified, one benzene ring structure, two or more benzene rings connected together sharing one or two carbon atoms, Or a monovalent or di-valent residue derived from a compound or a derivative thereof. The aryl group or the arylene group may be, for example, an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms unless otherwise specified.

The term aromatic structure in this application may mean the aryl group or the arylene group.

As used herein, the term alicyclic ring structure means a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. The alicyclic ring structure may be, for example, an alicyclic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms unless otherwise specified .

The term single bond in the present application may mean that no separate atom is present at the site. For example, in the structure represented by A-B-C, when B is a single bond, it may mean that no atom exists at a site represented by B and A and C are directly connected to form a structure represented by A-C.

Examples of the substituent which may optionally be substituted in the present application include an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, an alkynylene group, an alkoxy group, an aryl group, an arylene group, A carboxyl group, a glycidyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a thiol group, an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkenylene group, , An alkoxy group or an aryl group, but are not limited thereto.

In one aspect of the present application, the block copolymer includes a polymer segment (hereinafter referred to as polymer segment A) containing a unit represented by the following formula (1). The polymer segment A may include a unit represented by the following formula (1) as a main component. In the present specification, the polymer segment includes any unit as a main component, meaning that the polymer segment has a unit of 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% 90% or more, and 100% or less.

[Chemical Formula 1]

R 1 in the general formula (1) is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 2 may be a chain containing at least one halogen atom.

R1 in the formula (1) is hydrogen or an alkyl group having 1 to 4 carbon atoms in another example; Hydrogen or a methyl group; Or a methyl group.

In the formula (1), R2 is a chain containing at least one halogen atom, for example, a haloalkyl group, a haloalkenyl group or a haloalkynyl group.

The haloalkyl group is, for example, a haloalkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, and the haloalkenyl group or haloalkynyl group includes, A haloalkenyl group or a haloalkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms.

The haloalkyl group, haloalkenyl group or haloalkynyl group as described above may be in the form of a linear or branched chain.

The number of halogen atoms contained in the haloalkyl group and the like is not particularly limited, but may be, for example, from 1 to 10, from 1 to 9, from 1 to 8 1 to 6, 1 to 5, 1 to 4, 2 to 10, 2 to 9, 2 to 8, 2 to 6, 2 to 5, Two to four halogen atoms may be present.

Examples of such a halogen atom include, but are not limited to, a fluorine atom or a chlorine atom.

The block copolymer includes a polymer segment B different from the polymer segment A together with the polymer segment A.

The reason why the two kinds of polymer segments are the same in the present application is when the types of monomer units containing two kinds of polymer segments as main components are the same or when the kind of monomer units containing two kinds of polymer segments is 50% , More than 55%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85% or more than 90% of the total weight of the polymer segment Within 30%, within 25%, within 20%, within 20%, within 15%, within 10% or within 5%. If both polymer segments do not satisfy both of the above cases, they are polymer segments that are different from each other. The ratio of the monomer units common in the above may suitably be satisfied for the both polymer segment modes. For example, if one polymer segment 1 has monomer units of A, B, C, D and F and the other polymer segment 2 has monomer units of D, F, G and H, then polymer segments 1 and 2 The common proportions are 40% (= 100 x 2/5) because two common monomers are D and F in the case of polymer segment 1, and two of the five monomers are common in the case of polymer segment 1. In the case of polymer segment 2, Is 50% (= 100 x 2/5). Thus, in this case, both polymer segments may be regarded as not identical, since the common ratio is greater than 50% in polymer segment 2 alone. On the other hand, the deviation of the weight ratio of the common monomer in the above is a percentage of a numerical value obtained by dividing a value obtained by subtracting a small weight ratio from a large weight ratio by a small weight ratio. For example, in the above case, the weight ratio of the D monomer units of the segment 1 is about 40% based on the total weight percentage of the total monomer units of the segment 1, and the weight ratio of the D monomer units of the segment 2 is the whole of the segment 2 If the weight ratio of the monomer units is about 30% based on the total 100%, the weight ratio variation may be about 33% (= 100 x (40-30) / 30). When two or more monomer units common to two segments are used, in order to be the same segment, if the weight ratio deviation within 30% is satisfied with respect to all the common monomers, or if the monomer unit as the main component is satisfied, Can be considered. Each polymer segment recognized as being the same by the above criteria may be a polymer of a different type (for example, one segment is in the form of a block copolymer and the other segment is in the form of a random copolymer) Suitably it may be a polymer of the same type.

The block copolymer of the present application may be a diblock structure in which the polymer segment B is connected to the end of the polymer segment A as described above, or may be a multi-block copolymer.

In one example, the polymer segment B may be a polymer segment including a unit represented by the following formula (2). The polymer segment may include a unit of the formula (2) as a main component.

(2)

Wherein R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms and R 2 is a chain containing at least one halogen atom, R 2 is hydrogen or an alkyl group having 1 to 4 carbon atoms, X 2 is a single bond, (= O) -O- or -OC (= O) -, R 1 to R 5 are each independently and independently hydrogen, an alkyl group or a substituent of the following formula Lt; / RTI > is a substituent of the formula:

(3)

L is an oxygen atom, a sulfur atom, an alkylene group, an alkyleneoxy group, a carbonyl group, -C (= O) -O-, -OC (= O) -, -NR6-, -C (= O) -NR6- or -NR6-C (= O) -, Y is a chain having at least 8 chain-forming atoms, and R6 is hydrogen or an alkyl group.

X2 in Formula 3 may be a single bond, an oxygen atom, a carbonyl group, -C (= O) -O- or -OC (= O) - or -C (= O) -O- in another example, But is not limited to.

In the formula (3), each of R 1 to R 5 may independently be hydrogen, an alkyl group or a substituent of the following formula (3). In the above, R1 to R5 may not contain a halogen atom.

In Formula (3), Y includes a chain structure formed by at least eight chain-forming atoms.

The term chain forming atom in the present application means an atom forming a straight chain structure of a certain chain. The number of chain-forming atoms is calculated by the number of atoms forming the longest straight chain, and the number of the other atoms bonded to the chain-forming atoms (for example, the chain- A hydrogen atom bonded to the carbon atom in the case of a carbon atom, etc.) is not calculated. Also, in the case of a branched chain, the number of chain-forming atoms can be calculated as the number of chain-forming atoms forming the longest chain. For example, when the chain is an n-pentyl group, all of the chain-forming atoms are carbon, the number is 5, and even if the chain is a 2-methylpentyl group, all the chain-forming atoms are carbon, The chain-forming atom may be exemplified by carbon, oxygen, sulfur or nitrogen, and a suitable chain-forming atom may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of the chain-forming atoms may be 30 or less, 25 or less, 20 or less, or 16 or less.

The compound of the formula (1) can cause the block copolymer to exhibit excellent self-assembling properties when the block copolymer described later is formed due to the presence of the chain. Further, the functional group containing iron or silicon substituted in the chain can exhibit excellent etching selectivity after the formation of the self-assembled structure.

In one example, the chain may be a straight chain hydrocarbon chain such as a straight chain alkyl group. In this case, the alkyl group may be an alkyl group having 8 or more carbon atoms, 8 to 30 carbon atoms, 8 to 25 carbon atoms, 8 to 20 carbon atoms, or 8 to 16 carbon atoms. At least one of the carbon atoms of the alkyl group may optionally be substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted by another substituent. The straight chain hydrocarbon chain may not contain a halogen atom.

The above-mentioned block copolymer of the present application can basically exhibit excellent phase separation or self-assembly characteristics, and is excellent in etching selectivity.

In the above-mentioned block copolymer, the volume fraction of the polymer segment A is in the range of 0.1 to 0.9, and the sum of the volume fractions of the polymer segment A and B may be 1. The block copolymer containing each polymer segment in the above volume fraction can exhibit excellent self-assembling properties. The volume fraction of each polymer segment of the block copolymer can be determined based on the density of each polymer segment and the molecular weight measured by GPC (Gel Permeation Chromatography).

The number average molecular weight (Mn) of the block copolymer may be in the range of, for example, 3,000 to 300,000. In the present specification, the term number average molecular weight refers to a value converted to standard polystyrene measured using GPC (Gel Permeation Chromatograph). In the present specification, the term molecular weight refers to a number average molecular weight unless otherwise specified. The molecular weight (Mn) may be, for example, 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000 or more, 13000 or more, or 15000 or more in other examples. In another example, the molecular weight (Mn) is not more than 250,000, less than 200,000, less than or equal to 180,000, less than or equal to 160,000, less than or equal to 140000, less than or equal to 120000, less than or equal to 100000, less than or equal to 90000, less than or equal to 80000, less than or equal to 70000, Or 25,000 or less. The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.60. In another example, the degree of dispersion may be at least about 1.1, at least about 1.2, at least about 1.3, or at least about 1.4.

In this range, the block copolymer can exhibit proper self-assembling properties. The number average molecular weight of the block copolymer and the like can be adjusted in consideration of the desired self-assembling structure and the like.

When the block copolymer contains at least the polymer segment A, B and C, the ratio of the polymer segment A, for example, the polymer segment including the chain described above, in the block copolymer is 10 mol% to 90 mol % ≪ / RTI >

Such block copolymers can be prepared in a known manner. For example, the block copolymer may be prepared by a living radical polymerization (LRP) method using a monomer forming a unit of each polymer segment. For example, anionic polymerization in which an organic rare earth metal complex is used as a polymerization initiator, or an organic alkali metal compound is used as a polymerization initiator in the presence of an inorganic acid salt such as a salt of an alkali metal or an alkaline earth metal, An atomic transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization initiator, and an atom transfer radical polymerization agent as a polymerization initiator, (ATRP), Initiators for Continuous Activator Regeneration (ATR), Atomic Transfer Radical Polymerization (ATRP), Inorganic Reducing Agent Reversible Additive - Reversible addition-cleavage chain transfer using cleavage chain transfer agent And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

For example, the block copolymer can be prepared in a manner that includes polymerizing the reactants, including monomers capable of forming the polymer segment, in the presence of a radical initiator and a living radical polymerization reagent by living radical polymerization have.

The method of forming the other polymer segment included in the copolymer together with the polymer segment formed by using the monomer in the production of the block copolymer is not particularly limited and a suitable monomer may be selected in consideration of the kind of the desired polymer segment Thereby forming the other polymer segment.

The production process of the polymer segment copolymer may further include, for example, a step of precipitating the polymerization product produced through the above process in the non-solvent.

The kind of the radical initiator is not particularly limited and may be appropriately selected in consideration of the polymerization efficiency. For example, AIBN (azobisisobutyronitrile) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2 ' -azobis- (2,4-dimethylvaleronitrile), and peroxides such as benzoyl peroxide (BPO) or di-t-butyl peroxide (DTBP).

The living radical polymerization process can be carried out in the presence of a base such as, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, Amide, dimethylsulfoxide or dimethylacetamide, and the like.

Examples of the non-solvent include ethers such as alcohols such as methanol, ethanol, n-propanol or isopropanol, glycols such as ethylene glycol, n-hexane, cyclohexane, n-heptane or petroleum ether, But is not limited thereto.

The present application is also directed to a polymer membrane comprising said block copolymer. The polymer membrane can be used for various purposes, for example, various electronic or electronic devices, a process of forming the pattern, a recording medium such as a magnetic storage medium, a flash memory, or a biosensor.

In one example, the block copolymer in the polymer membrane may be self-assembled to implement a cyclic structure including a sphere, a cylinder, a gyroid or a lamellar, .

For example, in the block copolymer, other segments within the segments of polymer segments A through C or other polymer segments covalently bonded thereto may form a regular structure such as a lamellar shape or a cylinder shape.

The present application also relates to a method for forming a polymer film using the block copolymer. The method may include forming a polymer membrane including the block copolymer on a substrate in a self-assembled state. For example, the method may include forming a layer of the block copolymer or a coating liquid in which the block copolymer is diluted with a suitable solvent on the substrate by applying or the like, and if necessary, aging or heat-treating the layer.

The aging or heat treatment may be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and may be performed at, for example, the glass transition temperature or a temperature higher than the phase transition temperature. The time at which this heat treatment is performed is not particularly limited, and can be performed within a range of, for example, about 1 minute to 72 hours, but this can be changed if necessary. The heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but may be changed in consideration of the block copolymer to be used.

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

The present application also relates to a method of pattern formation. The method comprises, for example, selectively polymerizing the polymer segment A and / or B of the block copolymer in a laminate having a substrate and a polymer membrane formed on the surface of the substrate and self-assembled with the polymer block And removing it. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymeric film comprising the block copolymer on a substrate, selectively removing one or more polymer segments of the block copolymer present in the film, and then etching the substrate have. In this way, it is possible to form, for example, a nanoscale fine pattern. In addition, various patterns such as nano-rods, nano-holes, and the like can be formed through the above-described method depending on the type of the block copolymer in the polymer film. If necessary, the block copolymer may be mixed with another copolymer or homopolymer for pattern formation. The type of the substrate to be applied to this method is not particularly limited and may be selected as required. For example, silicon oxide or the like may be applied.

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

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

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

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

In addition, the step of selectively etching the substrate using the polymer film having the polymer segment removed as a mask is not particularly limited, and the step may be performed through a reactive ion etching step using, for example, CF 4 / Ar ions or the like. And then removing the polymer membrane from the substrate by an oxygen plasma treatment or the like.

The present application may provide block copolymers and uses thereof. The block copolymer of the present application has excellent self-assembling properties or phase separation characteristics, is excellent in etching selectivity, and can be freely given various other required functions.

1 to 3 are SEM photographs of polymer membranes formed by the block copolymers of Examples 1 to 3, respectively.
FIG. 4 is a graph comparing etch selectivities of the respective blocks applied in Examples 1 and 3 and Comparative Example 1. FIG.

Hereinafter, the present application will be described in detail by way of examples and comparative examples according to the present application, but the scope of the present application is not limited by the following examples.

1. NMR measurement

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with a triple resonance 5 mm probe. The analytes were diluted to a concentration of about 10 mg / ml in a solvent for NMR measurement (CDCl3), and chemical shifts were expressed in ppm.

<Application Abbreviation>

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

2. Gel Permeation Chromatograph (GPC)

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

&Lt; GPC measurement condition >

Devices: 1200 series from Agilent Technologies

Column: Using PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ° C

Sample concentration: 1 mg / mL, 200 L injection

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

Production Example 1

The compound (DPM-C12) shown below was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were placed in a 250 mL flask and dissolved in 100 mL of acetonitrile. An excess of potassium Potassium carbonate was added thereto and reacted at 75 ° C for about 48 hours under a nitrogen atmosphere. After the reaction, the remaining potassium carbonate and acetonitrile used for the reaction were also removed. The mixture was worked up by adding a mixed solvent of DCM (dichloromethane) and water, and the separated organic layer was dehydrated with MgSO4. Subsequently, the product was purified by DC (dichloromethane) in CC (Column Chromatography) to obtain a white solid intermediate with a yield of about 37%.

&Lt; NMR analysis results on intermediates >

1 H-NMR (CDCl 3):? 6.77 (dd, 4H); [delta] 4.45 (s, 1H); [delta] 3.89 (t, 2H); [delta] 1.75 (p, 2H); [delta] 1.43 (p, 2H); [delta] 1.33-1.26 (m, 16H); [delta] 0.88 (t, 3H).

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

<DPM-C12 NMR analysis result>

1 H-NMR (CDCl 3):? 7.02 (dd, 2H); [delta] 6.89 (dd, 2H); [delta] 6.32 (dt, IH); [delta] 5.73 (dt, 1H); delta 3.94 (t, 2H); delta 2.05 (dd, 3H); delta 1.76 (p, 2H); [delta] 1.43 (p, 2H); 1.34-1.27 (m, 16H); [delta] 0.88 (t, 3H).

(A)

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

Production Example 2

The compound of formula (B) (DVPA-C12) was synthesized in the following manner. To the flask, 300 mL of water was added, and potassium hydroxide (21.6 g, 385 mmol) was added and dissolved with stirring. The flask was placed in an ice bath, cooled, and 4-vinylphenylacetate (25.0 g, 154 mmol) was added thereto. The flask was taken out at room temperature and reacted until the reaction solution became transparent. Acetic acid was added to the reaction solution to acidify it, and the resulting white precipitate was filtered off and washed with water. The water was removed in vacuo to give 4-hydroxystyrene (HOST, 15.3 g, 127 mmol) as a white solid.

&Lt; NMR analysis result >

1 H-NMR (CDCl 3):? 7.30 (d, 2H),? 6.79 (d, 2H),? 6.65 s, 1 H)

Dodecylamine (15.0 g, 80.9 mmol) was added to the flask, dissolved in MC (methylene chloride) (200 mL), and then immersed in an ice bath and cooled. Chloroacetyl chloride (13.7 g, 121.4 mmol) was slowly added to the reaction solution, TEA (thioethyl acetamide) (12.3 g, 121.4 mmol) was slowly added, and the flask was taken out at room temperature and reacted overnight. After completion of the reaction, EA (ethyl acetate) and hexane were added and the precipitated salts were removed by filtration. The organic layer was collected and the solvent was removed. The resulting crude product was dissolved in methanol and recrystallized to obtain 2-chloro-N-dodecylacetamide (14.9 g, 56.9 mmol) as a white solid.

&Lt; NMR analysis result >

2H, NMR (CDCl3):? 6.57 (s, 1H),? 4.05 (s, 2H),? 3.30 (dt, 2H),? 1.54 [delta] 0.88 (t, 3H)

To the flask was added the above 4-hydroxystyrene (8.8 g, 74.0 mmol) and 2-chloro-N-dodecylacetamide (14.9 g, 56.9 mmol) and dissolved in DMF (dimethylformamide) (200 mL) Potassium carbonate (15.7 g, 113.8 mmol) and potassium iodide (1.0 g, 5.69 mmol) were added and reacted at 80 ° C for 3 hours. The reaction solution was poured into an excess of ice water and the resulting white precipitate was obtained by filtration. The resulting solid was subjected to column chromatography using a 1: 3 mixed solution of EA (ethyl acetate) / hexane (EA: hexane) to obtain a crude product, which was recrystallized from methanol. DVPA (12.0 g, 34.7 mmol) as white solid (yield formula B) was obtained.

&Lt; NMR analysis result >

(D, 2H), 6 6.88 (d, 2H), 6 6.66 (dd, 1H),? 6.54 (br, 1H),? 5.64 (d, 1H),? 4.49 (s, 2H),? 3.34 (q, 2H),? 1.53 (tt, 2H)

[Chemical Formula B]

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

Production Example 3

The compound (AS-C16) shown below was synthesized in the following manner. 4-Chloromethylstyrene (22.1 g, 144.8 mmol) and 1-hexadecanol (30.0 g, 160.1 mmol) were placed in a 500 mL flask and dissolved in 200 mL of tetrahydrofuran and cooled to 0 占 폚. Sodium hydride (7.7 g, 320.8 mmol) was slowly added in small portions while maintaining the above temperature, stirred for 2 hours, and then the temperature was raised to 70 ° C and allowed to react for about 24 hours. After the completion of the reaction, the reaction mixture was placed in an ice bath, and a small amount of water was added thereto to react with remaining sodium hydride to terminate the reaction, and the salt in the reaction solution was removed through a filter. Tetrahydrofuran as a reaction solvent was removed, and dichloromethane and water were added thereto to work up. The organic layer was collected, and the obtained crude product was purified by column chromatography using hexane / dichloromethane mixed solution as an eluent to obtain a clear liquid (AS-C16) (23.9 g, 79.0 mmol).

&Lt; NMR analysis result >

1H NMR (CDCl3):? 7.38 (dd, 2H),? 7.30 (dd, 2H),? 6.72 (s, 2H),? 3.45 (t, 23H),? 162-1.22 (m, 28H)

&Lt; RTI ID = 0.0 &

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

Example 1.

2.0 g of the compound (DPM) of Preparation Example 1 and 8.1 mg of 4-cyano-4- (phenylcarbonothioylthio) pentanoic acid (RAFT) reagent, 2.4 mg of AIBN (Azobisisobutyronitrile) and 4.69 mL of anisole The mixture was stirred in a Schlenk flask under nitrogen atmosphere at room temperature for 30 minutes, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) for 4 hours at 70 ° C. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to give a giant initiator of pink color. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the macromonomer were 35,300 and 1.20, respectively. 0.3 g of the giant initiator, 0.68 g of tetrafluoropropyl methacrylate, 0.7 mg of azobisisobutyronitrile (AIBN) and 0.98 mL of anisole were placed in a 10 mL Schlenk flask, stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then at 70 DEG C for 3 hours Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization reaction was carried out. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the block copolymer were 49,900 and 1.36, respectively. The block copolymer includes a polymer segment A derived from DPM of Production Example 1 and a polymer segment B derived from the tetrafluoropropyl methacrylate.

The block copolymer was diluted with fluorobenzene to a concentration of about 1.6% by weight, and spin-coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. The membrane was then thermally aged at about 160 ° C for 1 hour to induce a self-assembled structure. 1 is a SEM photograph of the self-assembling structure.

Example 2.

4 g of tetrafluoropropyl methacrylate, 44.2 mg of CPBD (2-cyano-2-propyl benzodithioate), 3.3 mg of azobisisobutyronitrile (RAFT) and 4.7 mL of anisole were added to a 10 mL Schlenk flask And the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization at 60 ° C for 15 hours. After the polymerization, the reaction solution was precipitated in 250 mL of hexane as an extraction solvent, and then dried under reduced pressure to give a giant initiator of pink color. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the macromonomer were 15,300 and 1.25, respectively. 2.0 g of the compound (DVPA-C12) of Preparation Example 2, 1.6 mg of AIBN (Azobisisobutyronitrile), and 7.026 mL of a mixed solution of anisole and fluorobenzene were placed in a 10 mL Schlenk flask, After stirring at room temperature for 30 minutes, Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was carried out at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the block copolymer were 42,500 and 1.26, respectively.

The block copolymer was diluted with fluorobenzene to a concentration of about 1.6 wt%, and spin-coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. The membrane was then thermally aged at about 160 ° C for 1 hour to induce a self-assembled structure. 2 is a SEM photograph of the self-assembling structure.

Example 3.

4 g of tetrafluoroethyl methacrylate, 42.1 mg of CPBD (2-cyano-2-propyl benzodithioate), 15.6 mg of azobisisobutyronitrile (RAFT) and 4.1 mL of anisole were added to a 10 mL Schlenk flask The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) at 60 ° C. for 3 hours. After the polymerization, the reaction solution was precipitated in 250 mL of hexane as an extraction solvent, and then dried under reduced pressure to give a giant initiator of pink color. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the macro initiator were 12,300 and 1.30, respectively. 0.3 g of the macromonomer, 0.87 g of the compound of Preparation Example 3 (AS-C16), 1.0 mg of azobisisobutyronitrile (AIBN) and 2.74 mL of anisole were placed in a 10 mL Schlenk flask and stirred at room temperature for 30 minutes under a nitrogen atmosphere Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was carried out at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and then dried under reduced pressure to obtain a pale pink block copolymer. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the block copolymer were 22,300 and 1.26, respectively.

The block copolymer was diluted with fluorobenzene to a concentration of about 1.6 wt%, and spin-coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. The membrane was then thermally aged at about 160 ° C for 1 hour to induce a self-assembled structure. 3 is a SEM image of the self-assembling structure.

Comparative Example 1

2.0 g of the compound of Preparation Example 1 (DPM-C12), 66.4 mg of a reversible addition-fragmentation chain transfer (RAFT) reagent, 3.2 mg of azobisisobutyronitrile and 4.8 mL of anisole were dissolved in 25 mL of Schlenk flask, , And the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then subjected to Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization at 70 ° C for 4 hours. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, filtered under reduced pressure, and dried to obtain a pink macro initiator. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the macro initiator were 12,600 and 1.18, respectively.

0.3 g of the giant initiator, 4.8 g of pentafluorostyrene, 0.8 mg of azobisisobutyronitrile (AIBN) and 1.8 mL of anisole were placed in a 10 mL flask (Schlenk flask), stirred at room temperature for 30 minutes under a nitrogen atmosphere, Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization was carried out for a period of time. After the polymerization, the reaction solution was precipitated in 250 mL of methanol, which was an extraction solvent, and dried under reduced pressure to obtain a pale yellow block copolymer. The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the block copolymer were 45,300 and 1.24, respectively.

Test Example 1

The etching selectivity of the block copolymers of Examples 1 and 3 and Comparative Example 1 was evaluated. Specifically, the etching selectivity of each block was compared using the etching apparatus (Plasmalab system 100) under the same conditions (RF output 25 W, pressure 10 mTorr) while performing etching. The results are shown in FIG. 4, the X axis represents the etching time, and the Y axis represents the thickness of the remaining film in the etching process as a percentage. 4, hPDPM is a result of a homopolymer prepared from the compound of Preparation Example 1, hPPFS is a result of a homopolymer derived from pentafluorostyrene applied in Comparative Example, and hPHOS is a compound of Production Example 3 (AS-C16 ), And hPTFPMA is the result for a homopolymer derived from tetrafluoropropyl methacrylate of Example 1.

Claims (13)

A block copolymer comprising a polymer segment A having a unit represented by the following formula 1 and a B having a unit represented by the following formula 2:
[Chemical Formula 1]

(2)

Wherein R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₂ is a chain containing at least one halogen atom, R ₂ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X ₂ is a single bond (= O) -O- or -OC (= O) -, R ₁ to R ₅ are each independently and independently hydrogen, an alkyl group or a substituent of the following formula , At least one of R ₁ to R ₅ is a substituent of the following formula:
(3)

In the formula 3 L is an oxygen atom, a sulfur atom, an alkylene group, an alkyleneoxy group, a carbonyl group, -C (= O) -O-, -OC (= O) -, -NR 6 -, -C (= O ) -NR ₆ - or -NR ₆ -C (= O) -, Y is a chain having at least 8 chain-forming atoms, and R ₆ is hydrogen or an alkyl group. The block copolymer according to claim 1, wherein R ₂ in the formula (1) is a haloalkyl group, a haloalkenyl group or a haloalkynyl group. The block copolymer according to claim 2, wherein the haloalkyl group is a haloalkyl group having 1 to 20 carbon atoms, and the haloalkenyl group or haloalkynyl group is a haloalkenyl group or haloalkynyl group having 2 to 20 carbon atoms. The block copolymer according to claim 1, wherein R ₂ in the formula (1) contains 1 to 10 halogen atoms. The block copolymer according to claim 1, wherein the halogen atom is a fluorine atom. 2. The block copolymer according to claim 1, wherein X2 in the formula (2) is a single bond, an oxygen atom, -C (= O) -O- or -O-C (= O) -. The block copolymer of claim 1, wherein the chain of formula (2) comprises from 8 to 20 chain forming atoms. 2. The block copolymer according to claim 1, wherein the chain-forming atom of formula (2) is carbon, oxygen, nitrogen or sulfur. The block copolymer according to claim 1, wherein the chain-forming atom of the formula (2) is carbon or oxygen. The block copolymer according to claim 1, wherein the chain of formula (2) is a hydrocarbon chain having no halogen atom. A polymer membrane comprising the self-assembled block copolymer of claim 1. A method for forming a polymer membrane, which comprises forming on a substrate a self-assembled polymer membrane comprising the block copolymer of claim 1. A pattern forming method comprising the steps of: selectively removing one of polymer segments of a block copolymer in a laminate having a substrate and a polymer membrane including the block copolymer of claim 1 formed on the substrate and self-assembled .

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