KR102096271B1 - Block copolymer - Google Patents

Abstract

In the present application, a block copolymer and its use can be provided. The block copolymer of the present application has excellent self-assembly characteristics or phase separation characteristics, excellent etching selectivity, and various other required functions can be freely provided.

Description

Block copolymer {BLOCK COPOLYMER}

This application relates to a block copolymer.

The block copolymer has a molecular structure in which polymer polymer segments having different chemical structures are connected through covalent bonds. The block copolymer may form a periodically arranged structure such as spheres, cylinders, or lamellas by phase separation. The size of the domain of the structure formed by the self-assembly phenomenon of the block copolymer can be widely controlled, and various types of structures can be manufactured, so that various next-generation nanos such as high-density magnetic storage media, nanowire fabrication, quantum dots, or metal dots can be produced. It can be applied to pattern formation by devices, magnetic recording media, lithography, or the like.

This application provides a block copolymer and its use.

The term alkyl group used herein 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.

The term alkoxy group used herein 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, unless otherwise specified. The alkoxy group may be a straight chain, branched or cyclic alkoxy group, and may be optionally substituted by one or more substituents.

The term alkenyl group or alkynyl group used herein refers to an alkenyl group or an 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 group or alkynyl group may be linear, branched or cyclic, and may be optionally substituted by one or more substituents.

In the present specification, the term 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, unless otherwise specified. The alkylene group may be a straight chain, branched or cyclic alkylene group, and may be optionally substituted by one or more substituents.

The term alkenylene group or alkynylene group in the present specification, unless otherwise specified, has 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or an alkenylene group with 2 to 4 carbon atoms or an alkynylene group Can mean The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted by one or more substituents.

In the present specification, the term aryl group or arylene group, unless specifically specified otherwise, one benzene ring structure, two or more benzene rings are linked while sharing one or two carbon atoms, or by any linker It may mean a monovalent or divalent residue derived from a compound containing a structure or derivatives thereof. The aryl group or 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.

In the present application, the term aromatic structure may mean the aryl group or arylene group.

In the present specification, the term alicyclic ring structure means a cyclic hydrocarbon structure that is not 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. .

In the present application, the term single bond may mean a case where a separate atom does not exist at a corresponding site. For example, in the structure represented by A-B-C, when B is a single bond, there are no separate atoms at the site represented by B, and it may mean that A and C are directly connected to form a structure represented by A-C.

In the present application, as a substituent that may be optionally substituted with 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 chain or an aromatic structure, a hydroxy group, a halogen atom , Carboxyl group, glycidyl group, acryloyl group, methacryloyl group, acryloyl group oxy, methacryloyl group oxy group, thiol group, alkyl group, alkenyl group, alkynyl group, alkylene group, alkenylene group, alkynylene group , An alkoxy group or an aryl group may be exemplified, but is not limited thereto.

In one aspect of the present application, the block copolymer includes a polymer segment (hereinafter, referred to as polymer segment A) comprising a unit represented by Formula 1 below. The polymer segment A may include a unit represented by the following Chemical Formula 1 as a main component. In the present specification, that a polymer segment includes a unit as a main component, the polymer segment includes 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more based on the weight of the unit. It means 90% or more and 100% or less.

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a carbonyl group, -C (= O) -X1- or -X1-C (= O)-, wherein X1 Is an oxygen atom, a sulfur atom, Y is a monovalent substituent including a ring structure in which chains having 8 or more chain-forming atoms are connected, and T is an alkylene group.

In Formula 1, X may be a single bond, an oxygen atom, a carbonyl group, -C (= O) -O- or -OC (= O)-, or -C (= O) -O- in another example. It is not limited.

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

The term chain forming atom in the present application means an atom forming a straight chain structure of a given chain. The chain may be straight-chain or branched, but the number of chain-forming atoms is calculated only by the number of atoms forming the longest straight chain, and other atoms (eg, chain-forming valences) attached to the chain-forming atom In the case of a carbon atom, the hydrogen atom or the like attached to the carbon atom) is not calculated. In addition, when the above-described hydrocarbon functional group is substituted in the chain, the carbon atom, hydrogen atom, silicon atom and / or iron atom contained in the hydrocarbon functional group is not calculated. Further, 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 carbons, and the number is 5, and even when the chain is a 2-methylpentyl group, all chain forming atoms are carbons and the number is 5. Carbon, oxygen, sulfur or nitrogen may be exemplified as the chain forming atom, and suitable chain forming atoms may be carbon, oxygen or nitrogen, or carbon or oxygen. The number of chain-forming atoms may be 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more. The number of chain-forming atoms may also be 30 or less, 25 or less, 20 or less, or 16 or less.

When the block copolymer to be described later is formed due to the presence of the chain, the compound of Formula 1 may exhibit excellent self-assembly properties. In addition, due to the functional group containing iron or silicon substituted in the chain, it can exhibit excellent etching selectivity after 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 be optionally substituted with an oxygen atom, and at least one hydrogen atom of the alkyl group may be optionally substituted with another substituent.

In Formula 1, Y includes a ring structure, and the chain may be connected to the ring structure. The self-assembly characteristics of the block copolymer formed by the monomer may be further improved by such a ring structure. The ring structure may be an aromatic structure or an alicyclic structure. In one example, the ring structure may be a cyclohexenylene group, a phenylene group, a naphthalenylene group, or a biphenylene group.

The chain may be directly linked to the ring structure, or may be linked via a linker. Examples of the linker include oxygen atom, sulfur atom, -NR1-, -S (= O) 2-, carbonyl group, alkylene group, alkenylene group, alkynylene group, -C (= O) -X1- or -X1 -C (= O)-may be exemplified, wherein R1 may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, X1 is a single bond, an oxygen atom, a sulfur atom, -NR2-, -S (= O) 2-, an alkylene group, an alkenylene group, or an alkynylene group, wherein R2 may be hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group. As an appropriate linker, an oxygen atom or a nitrogen atom can be exemplified. The chain may be connected to an aromatic structure via, for example, an oxygen atom or a nitrogen atom. In this case, the linker may be an oxygen atom, or -NR1- (where R1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group).

Y in Formula 1 may be represented by Formula 2 in one example.

[Formula 2]

In Formula 2, P is an arylene group, for example, cyclohexylene group, phenylene group, naphthalenylene group or biphenylene group, Q is a single bond, an oxygen atom or -NR3-, wherein R3 is hydrogen, It is an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is the chain having 8 or more chain forming atoms. When Y in Formula 1 is a substituent of Formula 2, P in Formula 2 may be directly connected to X in Formula 1.

As an appropriate example of P in the formula (2), an arylene group having 6 to 12 carbon atoms, such as a phenylene group, may be exemplified, but is not limited thereto.

In the general formula (2), Q is a suitable example, an oxygen atom or -NR1- (where R1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group).

In Formula 1, T is an alkylene group, and in one example, it may be an alkylene group having 1 to 20 carbon atoms, 4 to 20 carbon atoms, 6 to 20 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 8 carbon atoms. These alkylene groups may be straight-chain.

The block copolymer includes the polymer segment A and the polymer segment B different from the polymer segment A.

In the present application, when two types of polymer segments are the same, when two types of polymer units have the same type of monomer units as the main component, or 50% of types of monomer units included in any two polymer segments are used. Or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, or 90% or more are common, and the variation in the weight ratio of the common monomer unit of each polymer segment is It is one of the cases within 30%, within 25%, within 20%, within 20%, within 15%, within 10% or within 5%. If both polymer segments do not satisfy both cases, they are different polymer segments. It may be appropriate that the ratio of the monomer units common to the above is satisfied for both polymer segment modes. For example, if one polymer segment 1 has monomer units of A, B, C, D and F, and another polymer segment 2 has monomer units of D, F, G and H, in polymer segments 1 and 2 The common monomer units are D and F. In the polymer segment 1 position, since 2 out of 5 monomers are common, the common ratio is 40% (= 100 × 2/5), but in the polymer segment 2 position, the ratio is the same. Is 50% (= 100 × 2/5). Therefore, in this case, since the common ratio is 50% or more only in the polymer segment 2, it can be recognized that both polymer segments are not the same. On the other hand, the deviation of the weight ratio of the common monomer in the above is a percentage of a value obtained by subtracting a small weight ratio from a large weight ratio divided by a small weight ratio. For example, in this case, the weight ratio of the D monomer units of segment 1 is about 40% based on 100% of the total weight ratio of the total monomer units of segment 1, and the weight ratio of the D monomer units of segment 2 is the total of segment 2 If the weight ratio of the monomer units is about 30% based on 100%, the weight ratio deviation may be about 33% (= 100 × (40-30) / 30). If there are two or more types of monomer units common to two segments, in order to be referred to as the same segment, if the weight ratio deviation within 30% is satisfied for all common monomers, or if it is satisfied for the main component monomer units, the common monomers are used. Can be considered. Each of the polymer segments recognized as the same by the above criteria may be different types of polymers (for example, one segment is in the form of a block copolymer, and the other segment is in the form of a random copolymer), It may suitably be a polymer of the same type.

The block copolymer of the present application may be in the form of a diblock 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 or more.

In one example, the polymer segment B may be a polymer segment having an aromatic structure including one or more halogen atoms.

The polymer segment B may be, for example, a polymer segment including a unit represented by Formula 5 below. The polymer segment may include the unit of Formula 7 as a main component.

[Formula 5]

In Formula 5, B is a monovalent substituent having an aromatic structure containing one or more halogen atoms.

When the polymer segment B is present on at least one side of the polymer segment A described above, the block copolymer may exhibit excellent self-assembly characteristics and the like.

The aromatic structure in Formula 5 may be, for example, an aromatic structure having 6 to 18 carbon atoms or 6 to 12 carbon atoms.

Further, as the halogen atom included in the formula (5), a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately used, but is not limited thereto.

In one example, B of Formula 5 may be a monovalent substituent having an aromatic structure having 6 to 12 carbon atoms substituted with 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. The upper limit of the number of halogen atoms is not particularly limited, and for example, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less halogen atoms may be present.

For example, Formula 5, which is the unit included in the polymer segment 2B, may be represented by Formula 6 below.

[Formula 6]

In Formula 6, X2 represents a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group, an alkynylene group, -C (= O) -X1- or -X1-C ( = O)-, wherein X1 is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group, or an alkynylene group, and W contains at least one halogen atom It is an aryl group. In the above, W may be an aryl group substituted with at least one halogen atom, for example, an aryl group having 6 to 12 carbon atoms substituted with 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms.

The unit included in the polymer segment 2B may be represented by, for example, Formula 7 below.

[Formula 7]

In the formula (7), X2 represents a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group, an alkynylene group, -C (= O) -X1- or -X1-C ( = O)-, wherein X1 is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group or an alkynylene group, and R1 to R5 are each independently hydrogen or an alkyl group. , A haloalkyl group or a halogen atom, and the number of halogen atoms included in R1 to R5 is 1 or more.

In Formula 7, X2 may be, in another example, a single bond, an oxygen atom, an alkylene group, -C (= O) -O- or -O-C (= O)-.

In formula (7), R1 to R5 are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and R1 to R5 are one or more, two or more, three or more, four or more or five or more halogen atoms, for example , It may contain a fluorine atom. The halogen atoms included in R1 to R5, for example, fluorine atoms, may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The block copolymer as described above of the present application may basically exhibit excellent phase separation or self-assembly characteristics.

In the 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 segments A and B may be 1. The block copolymer including each polymer segment in the above volume fraction may exhibit excellent self-assembly characteristics. 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 Chromatogrph).

The number average molecular weight (Mn (Number Average Molecular Weight) of the block copolymer, for example, may be in the range of 3,000 to 300,000. The term number average molecular weight in the present specification is a conversion value for standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight in this specification means a number average molecular weight unless otherwise specified. In another example, the molecular weight (Mn) may be 3000 or more, 5000 or more, 7000 or more, 9000 or more, 11000 or more, 13000 or more, or 15000 or more. In another example, the molecular weight (Mn) is 250000 or less, 200000 or less, 180000 or less, 160000 or less, 140000 or less, 120000 or less, 100000 or less, 90000 or less, 80000 or less, 70000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less Or 25000 or less. The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.01 to 1.60. The dispersion degree may be about 1.1 or more, about 1.2 or more, about 1.3 or more, or about 1.4 or more in other examples.

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

When the block copolymer contains at least the polymer segments A, B and C, the proportion of the polymer segment A in the block copolymer, for example, the polymer segment comprising the chain described above is 10 mol% to 90 mol %.

Such block copolymers can be prepared in a known manner. For example, the block copolymer may be prepared by LRP (Living Radical Polymerization) using monomers forming units of each polymer segment. For example, using an organic rare earth metal complex as a polymerization initiator, or using an organic alkali metal compound as a polymerization initiator, anionic polymerization synthesized in the presence of an inorganic acid salt such as an alkali metal or a salt of an alkaline earth metal or an organic alkali metal compound is polymerized. An anionic polymerization method synthesized in the presence of an organoaluminum compound using as an initiator, an atomic transfer radical polymerization method (ATRP) using an atomic transfer radical polymerization agent as a polymerization control agent, and an atomic transfer radical polymerization agent as a polymerization control agent. Activators Regenerated by Electron Transfer (ARGET) Atomic Radical Radiation Polymerization (ATRP), Initiators for continuous activator regeneration (ICAR) Atomic Radical Radical Polymerization (ATRP), reversible addition of inorganic reducing agents Reversible addition-polymerization by cleavage chain transfer using a cleavage chain transfer agent (RAFT) or a method using an organic tellurium compound as an initiator, and the like, and an appropriate method can be selected and applied.

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

The method of forming another polymer segment included in the copolymer together with the polymer segment formed using the monomer in the manufacture of the block copolymer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired polymer segment By doing so, other polymer segments can be formed.

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

The type of the radical initiator is not particularly limited, and may be appropriately selected in consideration of polymerization efficiency, and for example, AIBN (azobisisobutyronitrile) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2 ') An azo compound such as -azobis- (2,4-dimethylvaleronitrile)) or a peroxide series such as BPO (benzoyl peroxide) or DTBP (di-t-butyl peroxide) may be used.

Living radical polymerization processes include, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, and dimethylform. It may be carried out in a solvent such as amide, dimethyl sulfoxide or dimethyl acetamide.

As a non-solvent, for example, alcohols such as methanol, ethanol, alcohols such as normal propanol or isopropanol, glycols such as ethylene glycol, ether ethers such as n-hexane, cyclohexane, n-heptane or petroleum ether, etc. can be used. It is not limited thereto.

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

In one example, the block copolymer in the polymer membrane may implement a periodic structure including a sphere, a cylinder, a gyroid, or a lamellar through self-assembly. .

For example, in the segment of the polymer segments A to C or other polymer segments covalently bonded to the block copolymer, other segments 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 film containing the block copolymer on a substrate in a self-assembled state. For example, the method may include a step of forming a layer of a coating solution obtained by diluting the block copolymer or an appropriate solvent on the substrate by application 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, for example, may be performed at a temperature above the glass transition temperature or the phase transition temperature. The time at which such heat treatment is performed is not particularly limited, and may be performed within a range of about 1 minute to 72 hours, for example, but may be changed as necessary. In addition, the heat treatment temperature of the polymer thin film may be, for example, about 100 ° C to 250 ° C, but this may be changed in consideration of the block copolymer 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.

This application also relates to a method of forming a pattern. The method may selectively select polymer segments A and / or B of the block copolymer in a laminate having a polymer film formed on a substrate and a surface of the substrate and including the self-assembled block copolymer. And removing. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film containing the block copolymer on a substrate and etching the substrate after selectively removing one or more polymer segments of the block copolymer present in the film. have. In this way, for example, it is possible to form nanoscale fine patterns. In addition, various types of patterns such as nanorods or nanoholes may be formed through the above method according to the type of block copolymer in the polymer film. If necessary, the block copolymer and other copolymers or homopolymers may be mixed for pattern formation. The type of the substrate applied to this method is not particularly limited, and may be selected as necessary, for example, silicon oxide or the like.

For example, the above method can form a nano-scale pattern of silicon oxide exhibiting a high aspect ratio. For example, after forming the polymer film on silicon oxide and selectively removing any polymer segment of the block copolymer in a state in which the block copolymer in the polymer film forms a predetermined structure, silicon oxide is removed in various ways, for example For example, it can be etched with reactive ion etching to implement various shapes including nanorods or nanohole patterns. In addition, through this method, it may be possible to implement a nano pattern having a large aspect ratio.

For example, the pattern may be implemented on a scale of several tens of nanometers, and such a pattern may be utilized for various uses including, for example, a magnetic recording medium for next-generation information electronics.

The method for selectively removing one polymer segment of the block copolymer in the above method is not particularly limited, and for example, by irradiating a suitable electromagnetic wave to the polymer film, for example, ultraviolet rays, etc., to remove the relatively soft polymer segment. Method can be used. In this case, the ultraviolet irradiation conditions are determined according to the type of the polymer segment of the block copolymer, for example, it may be performed by irradiating ultraviolet rays having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, it is also possible to perform a step of further removing the segment decomposed by ultraviolet rays by treating the polymer film with acid or the like after irradiation with ultraviolet rays.

In addition, the step of etching the substrate using the polymer film with the polymer segment selectively removed as a mask is not particularly limited. For example, it may be performed through a reactive ion etching step using CF4 / Ar ions, etc. Subsequently, a step of removing the polymer film from the substrate by oxygen plasma treatment or the like may also be performed.

In the present application, a block copolymer and its use can be provided. The block copolymer of the present application has excellent self-assembly characteristics or phase separation characteristics, excellent etching selectivity, and various other required functions can be freely provided.

1 to 3 are SEM pictures of the block copolymer self-assembled films of Examples 1 to 3, respectively.
4 is a view comparing the etching selectivity of the block copolymers of Examples 1 to 3.

Hereinafter, the present application will be described in more detail through examples and comparative examples according to the present application, but the scope of the present application is not limited by the examples presented below.

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 analyte was diluted with a concentration of about 10 mg / ml in a solvent for measuring NMR (CDCl3), and chemical shifts were expressed in ppm.

<Applied abbreviation>

br = wide signal, s = singlet, d = doublet, dd = doublet, t = triplet, dt = doublet, q = quartet, p = quintet, m = multiplet.

2.GPC (Gel Permeation Chromatograph)

The number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). Into a 5 mL vial, water samples to be analyzed such as block copolymers or macroinitiators of Examples or Comparative Examples are added, and diluted in tetrahydro furan (THF) to a concentration of about 1 mg / mL. Then, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. As the analysis program, ChemStation of Agilent technologies was used, and the elution time of the sample was compared with the calibration curve to obtain the weight average molecular weight (Mw) and number average molecular weight (Mn), respectively, and the molecular weight distribution (PDI) at the ratio (Mw / Mn). ) Was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Instrument: 1200 series from Agilent technologies

Column: 2 PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1mg / mL, 200L injection

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

Preparation Example 1.

The compound of Formula A (DCHM) was synthesized in the following manner. To the flask, 1,4-cyclohexanediol (1,4-cyclohexanediol) (54.7 g, 471 mmol) was added and dissolved in DMF (dimethylformamide) (400 mL). A mixed dispersion of sodium hydride (22.6 g, 518 mmol) and 70 mL of DMF was slowly added to the solution with vigorous stirring. After stirring for 10 minutes, the temperature was raised to 50 ° C, and after reacting for about 2 hours, 1-bromododecane (88.0 g, 353 mmol) was slowly added. The reaction solution was stirred at 65 ° C. and reacted for 16 hours. After the reaction, unreacted sodium hydride was removed while hydrochloric acid was slowly added. After adding excess water and extracting with diethyl ether, diethyl ether and DMF were removed using a rotary evaporator. The remaining liquid was column-purified with a mixed solution of EA (ethyl acetate) / hexane to obtain a colorless liquid 4- (dodecyloxy) cyclohexanol (25.0 g, 87.9 mmol).

<NMR analysis results for intermediates>

1H-NMR (CDCl3): δ3.73-3.66 (m, 1H), δ 3.42-3.37 (m, 2H), δ 3.35-3.21 (m, 1H), δ 2.00-1.95 (m, 2H), δ 1.80 (m, 1H), δ 1.70-1.62 (m, 2H) δ 1.57-1.52 (m, 4H), δ 1.34-1.25 (m, 20H), δ 0.87 (t, 3H)

After adding the synthesized intermediate (25.0 g, 87.9 mmol), methacrylic acid (8.3 g, 96.7 mmol) to the flask, and dissolving in methylene chloride, dicyclohexylcarbodiimide (DCC) (20.0 g, 96.7 mmol) and DMAP (p-dimethylaminopyridine) ( 4.3 g, 35.2 mmol) was added and reacted overnight in a nitrogen atmosphere at room temperature. After the reaction, the solids were removed by filtering, and the remaining solution was collected and columned with a mixed solution of EA (ethyl acetate) / hexane to obtain a colorless liquid target (DCHM, Formula A) (20.5 g, 58.1 mmol).

<NMR analysis results>

1H-NMR (CDCl3): δ 6.10-6.07 (s, 1H), δ 5.52 (s, 1H), δ 4.92-4.83 (m, 1H), δ 3.41 (m, 2H), δ 3.32 (m, 1H) , δ 1.99 (m, 2H), δ 1.94-1.93 (s, 3H), δ 1.88 (m, 1H), δ 1.70 (m, 2H), δ 1.61 (m, 1H), δ 1.54 (m, 2H) , δ 1.47 (m, 2H), δ 1.30-1.25 (m, 18H), δ 0.87 (t, 3H)

[Formula A]

In Formula A, R is a straight-chain alkyl group having 12 carbon atoms.

Preparation Example 2.

The compound of Formula B (DPHM) was synthesized in the following manner. Hydroquinone (88.4 g, 802 mmol), 1-bromododecane (100 g, 401 mmol) and potassium carbonate (110.8 g, 802 mmol) were placed in a flask and dissolved in DMSO (dimethyl sulfoxide). The reaction was carried out at 70 ° C overnight, acidified with acetic acid after precipitation in excess water. The precipitated solution was filtered to remove moisture as much as possible, 1500 mL of ethanol was added to the remaining solid phase, and the mixture was stirred for 2 hours. The undissolved precipitate was removed by filtering, and the remaining ethanol solution was recrystallized in a freezer to filter to obtain 4-dodecyloxyphenol (55.5 g, 199.3 mmol) as a white solid intermediate.

<NMR analysis results for intermediates>

1H-NMR (CDCl3): δ6.76 (q, 4H), δ 4.37 (s, 1H), δ 3.89 (t, 2H), δ 1.75 (tt, 2H), δ 1.43 (tt, 2H), δ 1.26 (m, 16H), δ 0.88 (t, 3H)

The synthesized intermediate (10.0 g, 35.9 mmol), 6-bromo-1-hexanol (9.7 g, 53.9 mmol), potassium carbonate (7.4 g, 53.9 mmol) was added to the flask, and DMF (dimethylformamide) (120 mL) ). The reaction was carried out at 70 ° C overnight and precipitated in excess water. After filtering and dissolving the impurities by adding an excessive amount of ethanol, the undissolved solids were filtered to give an intermediate (6- (4- (dodecyloxy) phenoxy) hexane-1-ol) (6.2 g, 16.4 mmol) as a white solid. Got

<NMR analysis results for intermediates>

1H-NMR (CDCl3): δ6.82 (s, 4H), δ3.90 (q, 4H), δ 3.66 (t, 2H), δ 1.76 (m, 4H), δ 1.61 (tt, 2H), δ 1.49 (tt, 2H), δ 1.43 (m, 4H), δ 1.26 (m, 16H), δ 1.21 (s, 1H), δ 0.88 (t, 3H)

The intermediate (6- (4- (dodecyloxy) phenoxy) hexane-1-ol) (6.2 g, 16.4 mmol) and methacrylic acid (1.6 g, 18 mmol) were added, dissolved in methylene chloride, and then DCC ( Dicyclohexylcarbodiimide (3.7 g, 18 mmol) and DMAP (p-dimethylaminopyridine) (0.8 g, 6.6 mmol) were added and reacted overnight in a nitrogen atmosphere at room temperature. After the reaction, the solids were removed by filtering, and the remaining solution was collected and columned with a mixed EA (ethyl acetate) / hexane solution to obtain a colorless liquid target (DPHM, Formula B) (5.7 g, 12.8 mmol).

<NMR analysis results>

1H-NMR (CDCl3): δ 6.81 (s, 4H), δ6.09 (tt, 1H), δ5.55 (tt, 1H), δ4.15 (t, 2H), δ 3.90 (m, 4H), δ 1.94 (s, 3H), δ 1.76 (m, 4H), δ 1.71 (m, 2H), δ 1.51 (m, 2H), δ 1.45 (m, 4H), δ 1.26 (m, 16H), δ 0.88 (t, 3H)

[Formula B]

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

Preparation Example 3.

The compound of Formula C (DBPHM) was synthesized in the following manner. 4,4'-biphenol (22.4 g, 120.4 mmol), 1-bromododecane (15 g, 60.2 mmol), potassium carbonate (16.6 g, 120.4 mmol) was placed in a flask and dissolved in DMSO (dimethyl sulfoxide). . The reaction was carried out at 70 ° C overnight, acidified with acetic acid after precipitation in excess water. The precipitate solution was filtered to remove moisture as much as possible, acetone was added to the remaining solid phase, and the mixture was sufficiently stirred. Filtration gave an undissolved solid. The solid was dissolved in tetrahydrofuran (THF) and filtered to remove undissolved solid. The solvent was removed from the obtained THF solution to obtain 4 '-(dodecyloxy)-[1,1'-biphenyl] -4-ol (13.6 g, 38.4 mmol) as a white solid.

<NMR analysis results for intermediates>

1H-NMR (CDCl3): δ7.44 (t, 4H), δ6.94 (d, 2H), δ6.88 (d, 2H), δ4.66 (s, 1H), δ3.98 (t, 2H ), δ1.80 (tt, 2H), δ1.47 (tt, 2H), δ 1.27 (m, 16H), δ 0.88 (t, 3H)

4 '-(dodecyloxy)-[1,1'-biphenyl] -4-ol (8 g, 22.6 mmol), 6-bromo-1-hexanol (8.1 g, 45.1 mmol), potassium carbonate (6.2 g, 45.1 mmol) was added and dissolved in DMF (dimethylformamide) (120 mL). The reaction was carried out at 80 ° C overnight, and precipitated in excess water. Filtered to obtain a precipitate, and THF was added in excess to dissolve impurities, and the undissolved solid was filtered to give a white solid intermediate (6-((4 '-(dodecyloxy)-[1,1'-biphenyl] -4- yl) hexan-1-ol) (7.5 g, 16.5 mmol).

<NMR analysis results for intermediates>

1H-NMR (CDCl3): δ7.45 (d, 4H), δ6.94 (d, 4H), δ 3.99 (q, 4H), δ3.67 (t, 2H), δ1.80 (m, 4H) , δ1.61 (tt, 2H), δ1.52 (tt, 2H), δ1.47 (m, 4H), δ1.26 (m, 17H), δ 0.88 (t, 3H)

The intermediate (6-((4 '-(dodecyloxy)-[1,1'-biphenyl] -4-yl) hexan-1-ol) (7.5 g, 16.5 mmol) and methacrylic acid (1.6 g, 18 mmol) ), Dissolved in methylene chloride, added DCC (dicyclohexylcarbodiimide) (3.7 g, 18 mmol) and DMAP (p-dimethylaminopyridine) (0.8 g, 6.6 mmol), and reacted overnight in a nitrogen atmosphere at room temperature. The solids were removed, dissolved in THF, and precipitated in methanol to obtain an undissolved solid.The obtained solid was dissolved in acetone to remove the undissolved precipitate, and the obtained solid was dissolved in EA (ethyl acetate) to remove the undissolved solid. The solvent was removed from the white solid to obtain the target product (DBPHM, Formula C) (4.3 g, 8.2 mmol).

<NMR analysis results>

1H-NMR (CDCl3): δ7.46 (d, 4H), δ6.94 (m, 4H), δ6.10 (m, 1H), δ5.55 (m, 1H), δ4.17 (t, 2H ), δ3.99 (m, 4H), δ1.95 (s, 3H), δ1.81 (m, 4H), δ1.73 (tt, 2H), δ1.54 (tt, 2H), δ1.47 (m, 4H), δ1.27 (m, 16H), δ0.88 (t, 3H)

[Formula C]

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

Example 1.

3.0 g of the compound of Preparation Example 1 (DCHM) and RAFT (Reversible Addition-Fragmentation chain Transfer) reagent (2-cyano-2-propyl dodecyl trithiocarbonate) 58.8 mg, AIBN (Azobisisobutyronitrile) 14 mg and anisole 7.035 mL After putting in a 10 mL Schlenk flask and stirring for 60 minutes at room temperature under a nitrogen atmosphere, a RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed at 70 ° C for 6 hours. After polymerization, the reaction solution was precipitated in 300 mL of methanol as an extraction solvent, filtered and dried under reduced pressure to prepare a light yellow giant initiator. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the macroinitiator were 13,500 and 1.19, respectively. The macroinitiator 0.3 g, pentafluorostyrene 2.157 g, AIBN (Azobisisobutyronitrile) 1.8 mg and 0.823 mL of anisole were placed in a 10 mL Schlenk flask, stirred at room temperature for 60 minutes under a nitrogen atmosphere, and then stirred at 70 ° C for 7 hours. During the RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure to dry to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 35,400 and 1.22, respectively. The block copolymer includes polymer segment A derived from DCHM of Preparation Example 1 and polymer segment B derived from the pentafluorostyrene.

The block copolymer was diluted with fluorobenzene at a concentration of about 1.0% by weight, and spin coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. Subsequently, the membrane was thermally aged at about 160 ° C. for 1 hour to induce a self-assembled structure. 1 is a SEM photograph of the induced self-assembly structure.

Example 2.

10 g of 2.0 g of the compound of Preparation Example 2 (DPHM) and 39.6 mg of Reversible Addition-Fragmentation chain Transfer (RAFT) reagent (2-Cyano-2-propyl benzodithioate), 14.7 mg of AIBN (Azobisisobutyronitrile) and 8.040 mL of anisole After putting in a mL Schlenk flask and stirring for 60 minutes at room temperature under a nitrogen atmosphere, a RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed at 70 ° C for 4 hours. After polymerization, the reaction solution was precipitated in 300 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink giant initiator. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the macroinitiator were 8,400 and 1.11, respectively. 0.3 g of the macroinitiator, 2.773 g of pentafluorostyrene, 2.9 mg of AIBN (Azobisisobutyronitrile) and 3.088 mL of anisole were placed in a 10 mL Schlenk flask, stirred at room temperature for 60 minutes under a nitrogen atmosphere, and then stirred at 70 ° C for 5 hours. During the RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed. After polymerization, the reaction solution was precipitated twice in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure to dry to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 17,100 and 1.22, respectively. The block copolymer includes polymer segment A derived from DPHM of Preparation Example 2 and polymer segment B derived from the pentafluorostyrene.

The block copolymer was diluted with fluorobenzene at a concentration of about 1.0% by weight, and spin coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. Subsequently, the membrane was thermally aged at about 160 ° C. for 1 hour to induce a self-assembled structure. 2 is a SEM photograph of the induced self-assembly structure.

Example 3.

10 g of 2.0 g of the compound of Preparation Example 3 (DBPHM) and 39.6 mg of Reversible Addition-Fragmentation chain Transfer (RAFT) reagent (2-Cyano-2-propyl benzodithioate), 14.7 mg of AIBN (Azobisisobutyronitrile) and 8.040 mL of anisole After putting in a mL Schlenk flask and stirring for 60 minutes at room temperature under a nitrogen atmosphere, a RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed at 70 ° C for 4 hours. After polymerization, the reaction solution was precipitated in 300 mL of methanol as an extraction solvent, filtered under reduced pressure, and dried to prepare a light pink giant initiator. The number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the macroinitiator were 13,100 and 1.11, respectively. 0.3 g of the macroinitiator, 2.773 g of pentafluorostyrene, 2.9 mg of AIBN (Azobisisobutyronitrile) and 3.088 mL of anisole were placed in a 10 mL Schlenk flask, stirred at room temperature for 60 minutes under a nitrogen atmosphere, and then stirred at 70 ° C for 5 hours. During the RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction was performed. After polymerization, the reaction solution was precipitated twice in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure to dry to prepare a light pink block copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the block copolymer were 27,500 and 1.19, respectively. The block copolymer includes polymer segment A derived from DBPHM of Preparation Example 3 and polymer segment B derived from the pentafluorostyrene.

The block copolymer was diluted with fluorobenzene at a concentration of about 1.0% by weight, and spin coated on a silicon wafer at a speed of 3000 rpm for about 60 seconds to form a polymer film. Subsequently, the membrane was thermally aged at about 160 ° C. for 1 hour to induce a self-assembled structure. 2 is a SEM photograph of the induced self-assembly structure.

Test Example 1.

The etching selectivity of the block copolymers of Examples 1 to 3 was evaluated. Specifically, etching was performed using the etching apparatus (Plasmalab system 100) under the same conditions (RF source 25 W, pressure 10 mTorr), and the etching selectivity of each block was compared. The results are shown in FIG. 4. In FIG. 4, the X-axis is the etching time, and the Y-axis is a percentage of the thickness of the film remaining in the etching process. The graphs labeled PDCHM, PDPHM, and PDBPHM in FIG. 4 are the results for the homopolymers prepared with the compounds of Preparation Examples 1 to 3, respectively.

Claims (16)

Block copolymer comprising a polymer segment A having a unit represented by the following formula (1) and a polymer segment B different from the polymer segment A:
[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a carbonyl group, -C (= O) -X1- or -X1-C (= O)-, wherein X1 Is an oxygen atom or a sulfur atom, Y is a monovalent substituent containing a ring structure in which chains having 8 or more chain forming atoms are connected, and T is an alkylene group. The block copolymer of claim 1, wherein X is a single bond, an oxygen atom, -C (= O) -O- or -O-C (= O)-. The block copolymer of claim 1, wherein X is -C (= O) -O-. The block copolymer of claim 1, wherein the chain comprises 8 to 20 chain forming atoms. The block copolymer of claim 1, wherein the chain forming atom is carbon, oxygen, nitrogen or sulfur. The block copolymer of claim 1, wherein the chain forming atom is carbon or oxygen. The block copolymer of claim 1, wherein the chain is a hydrocarbon chain. The block copolymer according to claim 1, wherein the ring structure is a cyclohexenylene group, a phenylene group, a naphthalenylene group or a biphenylene group. According to claim 1, Y is a block copolymer represented by the formula (2):
[Formula 2]

In Formula 2, U is a single bond or an oxygen atom, P is a cyclohexenylene group, a phenylene group, a naphthalenylene group or a biphenylene group, Q is a single bond, an oxygen atom or -NR3-, wherein R3 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, Z is a chain having up to eight or more chain-forming atoms. The block copolymer according to claim 1, wherein T in Formula 1 is a straight chain alkylene group having 6 to 20 carbon atoms. According to claim 1, Polymer segment B is a block copolymer comprising a unit of formula (5):
[Formula 5]

In Formula 5, B is a monovalent substituent having an aromatic structure containing one or more halogen atoms. The block copolymer according to claim 1, wherein the polymer segment B comprises a unit represented by the following formula (6):
[Formula 6]

In Formula 6, X ₂ is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group, an alkynylene group, -C (= O) -X1- or -X1-C (= O)-, wherein X1 is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group or an alkynylene group, and W contains at least one halogen atom It is an aryl group. According to claim 1, Polymer segment B is a block copolymer comprising a unit of formula (7):
[Formula 7]

In Formula 7, X ₂ is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group, an alkynylene group, -C (= O) -X1- or -X1-C (= O)-, wherein X1 is a single bond, an oxygen atom, a sulfur atom, -S (= O) 2-, an alkylene group, an alkenylene group or an alkynylene group, and R ₁ to R ₅ are each independently It is a hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms contained in R ₁ to R ₅ is one or more. A polymer membrane comprising the self-assembled block copolymer of claim 1. A method of forming a polymer film comprising forming a polymer film comprising the self-assembled block copolymer of claim 1 on a substrate. A pattern forming method comprising selectively removing any one of the polymer segments of the block copolymer from a laminate formed on the substrate and the polymer film comprising the self-assembled block copolymer of claim 1 .

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