KR102484628B1 - Compositon for neural layer - Google Patents

Abstract

This application is for a neutral layer composition. The present application can provide a neutral layer composition capable of effectively controlling orientation such as vertical orientation of a block copolymer and forming a neutral layer showing excellent reaction selectivity to a substrate and high degree of crosslinking in a short time even by a low-temperature process. .

Description

Neutral layer composition {COMPOSITON FOR NEURAL LAYER}

This application relates to a neutral layer composition.

Block copolymers in which two or more chemically different polymer chains are covalently linked can be separated into regular microphases. The microphase separation phenomenon of these block copolymers is generally explained by the volume fraction, molecular weight, and mutual attraction coefficient (Flory-Huggins interaction parameter) between constituent components. In the microphase formed by the block copolymer, various structures such as nanoscale spheres, cylinders, gyroids, or lamellas exist.

An important issue in the practical application of block copolymers is to control the orientation of the microphases. The orientation of the block copolymer includes a horizontal orientation in which the orientation of the nanostructure is parallel to the substrate direction and a vertical orientation in which the orientation of the nanostructure is perpendicular to the substrate direction. are often of greater importance than

The orientation of the nanostructure can be determined by selective wetting of blocks of the block copolymer. In general, since many substrates are polar and air is non-polar, a block having greater polarity among the blocks of the block copolymer The silver substrate is wetting, and the block having a smaller polarity is wetting at the interface with air, and horizontal alignment is induced.

This application provides a neutral layer composition. The present application is one of providing a neutral layer composition capable of effectively controlling orientation such as vertical orientation of a block copolymer and forming a neutral layer showing excellent reaction selectivity to a substrate and high degree of crosslinking in a short time even by a low-temperature process. for the purpose of

In this specification, the term alkyl group may refer to 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 with one or more substituents.

In this specification, the term alkoxy group may refer to 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 with one or more substituents.

In this specification, the term alkenyl group 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 group or alkynyl group may be straight-chain, branched or cyclic, and may be optionally substituted with one or more substituents.

In this 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 with one or more substituents.

In this specification, the term alkenylene group or alkynylene group, unless otherwise specified, is an alkenylene group or alkynylene 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. can mean ki. The alkenylene group or alkynylene group may be straight-chain, branched or cyclic, and may be optionally substituted with one or more substituents.

In this specification, the term aryl group or arylene group, unless otherwise specified, has a benzene ring structure, two or more benzene rings are connected while sharing one or two carbon atoms, or connected by any linker It may mean a monovalent or divalent residue derived from a compound having a structure or a derivative thereof. Unless otherwise specified, 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.

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

In this specification, the term alicyclic ring structure refers to a cyclic hydrocarbon structure other than an aromatic ring structure unless otherwise specified. 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. .

In this application, the term single bond may mean a case in which no separate atom exists at the corresponding site. For example, in the structure represented by A-B-C, when B is a single bond, no separate atom exists at the site represented by B, and A and C are directly connected to form a structure represented by A-C.

In the present application, substituents that may be optionally substituted on 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, etc. include a hydroxyl 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.

This application is for a neutral layer composition. The term neutral layer composition may refer to a composition used to form a neutral layer. In this application, the term neutral layer may refer to any kind of layer capable of inducing vertical alignment of the block copolymer. The meaning of the vertical orientation of the term block copolymer is well known in the art, and for example, it means that the block copolymer forms a phase-separated structure and the interface of the blocks constituting the phase-separated structure is formed substantially perpendicular to the substrate. can

The neutral layer composition of the present application may include a predetermined random copolymer. The random copolymer is a unit represented by the following formula (1); and a unit having an aromatic structure containing one or more halogen atoms.

[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z may be a hydrocarbon chain having 8 to 20 carbon atoms.

In Formula 1, X may be an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, or -C(=O)-O- in another example, but is not limited thereto no.

In Formula 1, P may be an arylene group having 6 to 18 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a phenylene group.

In Formula 1, Q may be connected to the para position when P is a phenylene group.

Q in Formula 1, in one example, may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O)- , For example, it may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, but is not limited thereto.

Z in Formula 1 is a hydrocarbon chain having 8 to 20 carbon atoms. In another example, the number of carbon atoms in the hydrocarbon chain may be 9 or more, 10 or more, 11 or more, or 12 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less. The hydrocarbon chain may be a straight chain hydrocarbon chain, and may be, for example, a straight chain alkyl group, an alkenyl group or an alkynyl group. The number of carbon atoms in the straight-chain alkyl group, alkenyl group or alkynyl group is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, or 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, It may be 13 or less or 12 or less.

In one example, the hydrocarbon chain is a chain including a straight chain structure, and at this time, the number of carbon atoms forming the straight chain structure may be within the range of 8 to 20. The chain may be straight or branched, but the number of carbon atoms calculated only by the number of carbon atoms forming the longest straight chain may be within the range of 8 to 20. In the case of a branched chain, the number of carbon atoms forming the straight chain structure can be calculated as the number of carbon atoms forming the longest chain. For example, when the chain is an n-pentyl group, the number of carbon atoms forming the linear structure is 5, and when the chain is a 2-methylpentyl group, the number of carbon atoms forming the linear structure is 5.

The hydrocarbon chain including the straight-chain structure may be a straight-chain or branched-chain alkyl, alkenyl, or alkynyl group, wherein the number of carbon atoms forming the straight-chain structure is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less.

In one example, one or more of the carbon atoms of the alkyl group, alkenyl group, or alkynyl group, which is the hydrocarbon chain, may be optionally replaced with a hetero atom for a carbon atom such as an oxygen atom, and at least one of the alkyl group, alkenyl group, or alkynyl group A hydrogen atom may be optionally substituted by another substituent.

In the random copolymer, the proportion of units represented by Chemical Formula 1 may be included in 32 mol% or less based on the total copolymer. This ratio may be adjusted according to the type of block copolymer to which the neutral layer is applied, for example. In one example, the ratio of the unit of Formula 1 in the random copolymer is 32 mol% or less, 31 mol% or less, 30 mol% or less, 29 mol% or less, 28 mol% or less, 27 mol% or less, 26 mol% 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, 21 mol% or less, 20 mol% or less, 19 mol% or less, 18 mol% or less, 17 mol% or less, 16 mol% 15 mol% or less, 14 mol% or less, 13 mol% or less, 12 mol% or less, 11 mol% or less, or 10 mol% or less, or 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, or 9 mol% or more. The present inventors confirmed that the ratio of units represented by Chemical Formula 1 included in the random copolymer may exhibit neutral characteristics within the above range. By including the unit of Formula 1 in the random copolymer in a range satisfying the above ratio, the neutral layer formed of the neutral layer composition of the present application effectively induces vertical alignment of the block copolymer, and further includes a functional monomer described later. Thus, the bonding strength between the block copolymer and the neutral layer and the bonding strength between the neutral layer and the substrate can be improved.

The unit having an aromatic structure including one or more halogen atoms included in the random copolymer may be a unit represented by Formula 4 below.

[Formula 4]

In Formula 4, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms.

In the unit represented by Formula 4, X ₂ may be a single bond in one example.

In Formula 4, the aryl group may be, for example, an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms, or a phenyl group.

As the halogen atom included in Formula 4, a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately exemplified, but is not limited thereto. The halogen atom may be substituted with the aryl group.

In one example, W in Formula 4 has 6 to 18 carbon atoms or 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 (fluorine atoms or chlorine atoms, etc.) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms substituted in the above 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.

The unit of Formula 4 may be represented by Formula 5 below in another example.

[Formula 5]

In Formula 5, X ₂ is a single bond, an oxygen atom or a sulfur atom, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms included in R ₄ to R ₈ is There may be three or more.

In Formula 5, X ₂ may be a single bond in another example.

In Formula 5, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, but R ₄ to R ₈ are 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. , for example, a fluorine atom or a chlorine atom. The number of halogen atoms included in R ₄ to R ₈ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The halogen atoms may be included in a haloalkyl group, and one or more, two or more, three or more, four or more, or five of R ₄ to R ₈ may be halogen atoms. In this case, the halogen atom may be a fluorine atom or a chlorine atom.

In one example, the ratio (A/D) of the number of moles (D) of the unit represented by Formula 1 and the number of moles (A) of the unit having an aromatic structure having one or more halogen atoms may be in the range of 2 to 10. . The ratio (A/D) is 2.00 or more, 2.04 or more, 2.08 or more, 2.12 or more, 2,16 or more, 2.20 or more, 2.24 or more, 2.28 or more, 2.32 or more, 2.36 or more, 2.4 or more, 2.44 or more, 2.48 or more, It may be 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more, but is not limited thereto. In addition, the ratio (A / D) is 10 or less, 9.8 or less, 9.6 or less, 9.4 or less, 9.2 or less, 9.0 or less, 8.8 or less, 8.6 or less, 8.4 or less, 8.2 or less, 8.0 or less, 7.8 or less, 7.6 or less, 7.4 or less , 7.2 or less, 7.0 or less, 6.8 or less, or 6.6 or less, but is not limited thereto. A unit represented by Chemical Formula 1 and a unit having an aromatic structure containing at least one halogen atom may satisfy a molar ratio within the above range, so that an appropriate neutral surface may be formed.

In the random copolymer, the proportion of units having an aromatic group containing a halogen atom may be 40 mol% or more based on the total copolymer. The ratio may be adjusted according to the type of block copolymer to which the neutral layer is applied. In one example, the ratio of the unit having an aromatic group containing the halogen atom in the random copolymer is 45 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, or 68 mol% It may be greater than or equal to 90 mol%, 85 mol% or less, 80 mol% or less, or 75 mol% or less. The present inventors have confirmed that the ratio of the unit included in the random copolymer can exhibit neutral characteristics within the above range. Through this, the neutral layer formed of the neutral layer composition of the present application may additionally include a functional monomer described below while effectively inducing vertical alignment of the block copolymer, thereby increasing the bonding strength between the block copolymer and the neutral layer and the neutral layer Adhesion between substrates can be improved.

The random copolymer, as an additional unit, a unit represented by the following formula (2); and a unit containing a crosslinkable functional group.

[Formula 2]

In Formula 2, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxy group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylene having 1 to 4 carbon atoms it can be

In the above, the alkylene group of L may be a linear, branched or cyclic 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 in one example.

In one example, in the unit of Formula 2, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ -, or an alkylene group. R ₂ may be a hydroxy group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, and L ₁ may be an alkylene group having 1 to 4 carbon atoms. ..

By presenting the unit of Formula 2 together with the crosslinkable functional group-containing unit in the random copolymer, the desired degree of crosslinking can be appropriately secured even at a low temperature in the process of forming the neutral layer, uniform coating of the composition is possible, and A neutral layer with excellent adhesion can be formed.

The unit may be formed by polymerizing monomers such as (meth)acrylic acid or phosphoethyl (meth)acrylate in the process of preparing the random copolymer.

The random copolymer may include the unit of Chemical Formula 2 in an amount of about 0.01 to 20 mol%. In other examples, the ratio is about 0.05 mol% or more, 0.1 mol% or more, 0.15 mol% or more, 0.2 mol% or more, 0.25 mol% or more, or 0.3 mol% or more, or 18 mol% or less, 16 mol% or less, 14 mol% or less. % or less, 12 mol% or less, 10 mol% or less, 9 mol% or less, 8 mol% or less, 7 mol% or less, 6 mol% or less, 5 mol% or less, 4 mol% or less, 3 mol% or less, 2 mol % or less or 1 mol% or less may be sufficient.

Under this ratio, the action of the desired unit of formula (2) can be properly secured.

The crosslinkable functional group-containing unit may be applied to realize a crosslinked structure in the process of forming the neutral layer. The unit is a crosslinkable functional group, for example, a hydroxy group, a glycidyl group, an epoxy group, an isocyanate group, a glycidyl group, a functional group of the following formula A, a benzoylphenoxy group, an alkenyloxycarbonyl group, a (meth)acryloyl group And/or it can be formed by copolymerizing a monomer having an alkenyloxyalkyl group with a random copolymer.

[Formula A]

In Formula A, Y is a single bond, an alkylene group, an alkenylene group, or an alkynylene group, and L ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group, an alkenylene group, or an alkynyl A rene group, -C(=O)-X ₁ - or -X ₁ -C(=O)-, wherein X ₁ is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, an alkylene group , an alkenylene group or an alkynylene group.

The functional group of Formula A is a substituent having a crosslinkable azide moiety at its terminal, and this functional group can be crosslinked.

In Formula A, Y may be 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 in another example.

In Formula A, L ₁ may be a single bond, an oxygen atom, -C(=O)-O- or -OC(=O)- in another example, but is not limited thereto.

As a monomeric unit containing a crosslinkable functional group, a unit represented by Formula 3 below may be exemplified.

[Formula 3]

In Formula 3, R ₃ is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom.

In another example, the alkyl group in Formula 3 may be 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. These alkyl groups may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents.

In Formula 3, T may be an alkylene group, an alkenylene group, or an alkynylene group in another example. In the above, the alkylene group may be 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. This alkylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents. In the above, the alkenylene group may be an alkenylene 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. This alkenylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents. In the above, the alkynylene group may be 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. This alkynylene group may be straight-chain, branched-chain or cyclic, and may be optionally substituted by one or more of the aforementioned substituents.

The divalent hydrocarbon group of T in Formula 3 may further contain a hetero atom, if necessary. In the above, the heteroatom is a heteroatom for carbon, and examples thereof include oxygen, nitrogen, or sulfur. 1 to 4 or less of these heteroatoms may be included in T of Formula 3.

Examples of monomers capable of forming the unit of Chemical Formula 3 are not particularly limited. For example, as a monomer capable of forming the unit of Chemical Formula 3, glycidyl (meth)acrylate and the like may be exemplified.

The ratio of the crosslinkable functional group-containing unit in the random copolymer is approximately 0.01 to 30 mol%. In other examples, the ratio is about 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, 5 mol% or more, 7 mol% or more, or 9 mol% or more, or 28 mol% or more. % or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, 20 mol% or less, 18 mol% or less, 16 mol% or less, 14 mol% or less, or 12 mol% or less, but is not limited thereto no.

The random copolymer may additionally contain a lactone group-containing unit, if necessary. Such a unit can help form a neutral layer with excellent interfacial adhesion.

As such a unit, for example, a unit represented by the following formula (6) may be exemplified.

[Formula 6]

In Formula 6, R ₉ is hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₁₀ is -L ₂ -U, wherein L ₂ is a single bond, an alkylene group having 1 to 4 carbon atoms or an oxygen atom, and U is a lactone group. can

Appropriately in the above formula, L ₂ may be an oxygen atom.

In addition, the lactone group may be, in one example, a lactone group having 2 to 12 carbon atoms or 2 to 6 carbon atoms, and examples thereof include an alpha-acetolactonyl group and a beta-propiolactonyl group. group) or gamma-butyrolactonyl, etc. may be exemplified, but are not limited thereto.

When included, the ratio of the lactone group-containing unit in the random copolymer may be approximately 0.01 to 50 mol%. In other examples, the ratio is about 0.05 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% 7 mol% or more, 8 mol% or more, or 9 mol% or more, or 48 mol% or less, 46 mol% or less, 44 mol% or less, 42 mol% or less, 40 mol% or less, 38 mol% or less, 36 mol% or less % or less, 34 mol% or less, 32 mol% or less, 30 mol% or less, 28 mol% or less, 26 mol% or less, 24 mol% or less, 22 mol% or less, 20 mol% or less, 18 mol% or less, 16 mol% or less % or less, 14 mol% or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, 6 mol% or less, or 4 mol% or less, but is not limited thereto.

The random copolymer may further include other units as long as the desired effect is secured in addition to the above units. Additional units included in the random copolymer may include functional monomers having various functional functional groups, and the functional monomers may be appropriately selected according to physical properties required for the neutral layer including the random copolymer. The functional monomer may be, for example, a unit of a monomer capable of improving adhesion in order to improve adhesion between substrates, but is not limited thereto.

The random copolymer may have a number average molecular weight (Mn) in the range of, for example, 2,200 to 50,000. In the present specification, the term number average molecular weight is a value in terms of standard polystyrene measured using GPC (Gel Permeation Chromatograph), and the term molecular weight refers to the number average molecular weight unless otherwise specified. In addition, unless otherwise specified, the unit of number average molecular weight is g/mol. The molecular weight of the random copolymer may be adjusted in consideration of desired physical properties of the neutral layer.

A method for preparing the random copolymer as described above is not particularly limited. For example, the random copolymer may be prepared by applying a free radical polymerization method or a living radical polymerization (LRP) method. Examples of the LRP method described above include anionic polymerization and polymerization in which an organic rare earth metal complex or an organic alkali metal compound is used as an initiator and polymerization is performed in the presence of an inorganic acid salt such as an alkali metal or alkaline earth metal salt or an organoaluminum compound. Atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerizer as yesterday, and ARGET (Activators Regenerated by Electron Regenerated by Electron), which uses an atom transfer radical polymerizer as a polymerization control agent and proceeds polymerization under an organic or inorganic reducing agent that generates electrons. Transfer) atom transfer radical polymerization (ATRP), Initiators for continuous activator regeneration (ICAR) atom transfer radical polymerization, reversible addition-cleavage chain transfer polymerization using inorganic reducing agent reversible addition-cleavage chain transfer (RAFT) or organic A method using a tellurium compound as an initiator and the like can be exemplified, and an appropriate method can be employed from among the above methods.

The kind of radical initiator that can be used in the polymerization process is not particularly limited. For example, AIBN (azobisisobutyronitrile), ABCN (1,1'-Azobis (cyclohexanecarbonitrile)) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis-(2,4 Azo-based initiators such as -dimethylvaleronitrile) or peroxide-based initiators such as BPO (benzoyl peroxide) or DTBP (di-tert-butyl peroxide) may be applied. For example, thermal self-initiation of styrene-based monomers Like the method using initiation), a polymerization method without using an initiator may also be applied depending on the type of monomer.

The polymerization process may be carried out, for example, in an appropriate solvent. In this case, applicable solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, anisole, and acetone. , Solvents such as chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylformamide, dimethylsulfoxide or dimethylacetamide may be exemplified, but are not limited thereto. After formation of the random copolymer, the random copolymer can be obtained by precipitation using a non-solvent. Non-solvents that can be used at this time include alcohols such as methanol, ethanol, n-propanol or isopropanol, ethylene glycol, etc. Ether solvents such as glycol, n-hexane, cyclohexane, n-heptane, or petroleum ether may be exemplified, but are not limited thereto.

In the field of polymer synthesis, a method of preparing a polymer by performing polymerization according to a monomer forming the polymer is known, and any of the above methods may be applied to the preparation of the random copolymer of the present application.

The neutral layer composition including the random copolymer as described above may include only the random copolymer or, if necessary, other components other than the random copolymer may be appropriately included. The neutral layer composition may include the random copolymer as at least a main component. In the present specification, included as a main component means that the composition includes only the random copolymer, or about 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, based on solid content. 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more. The ratio may be about 100% by weight or less or about 99% by weight or less in another example. When the neutral layer composition includes a solvent, the ratio may be based on weight excluding the solvent. Other components that may be included with the random copolymer include, for example, an initiator such as a thermal initiator or a photoinitiator or a crosslinking agent required when the random copolymer includes the aforementioned crosslinkable functional group.

This application also relates to a neutral layer comprising the random copolymer. In this application, the term neutral layer, as described above, means a layer capable of inducing vertical alignment of the block copolymer.

The neutral layer may be formed on an appropriate substrate. As the substrate on which the neutral layer is formed, a silicon wafer, a silicon oxide substrate, a silicon nitride substrate, or a crosslinked poly(ethylene terephthalate) (PET) film may be exemplified, but is not limited thereto.

The neutral layer may be formed using the aforementioned neutral layer composition. For example, the process of forming the neutral layer may include coating the neutral layer composition on a substrate and fixing the coated layer of the neutral layer composition. The method of coating the neutral layer composition on the substrate is not particularly limited, and for example, a method such as bar coating, spin coating, or comma coating may be applied, and coating by a roll-to-roll method may also be applied. there is.

In addition, the method of fixing the layer of the neutral layer composition is not particularly limited, and for example, a method of inducing a covalent bond between the layer and the substrate by an appropriate method or inducing a chemical crosslinking reaction within the layer etc. may be applied. For example, when the above process is performed by heat treatment, the heat treatment may be adjusted within a range of about 100 °C to 250 °C or about 100 °C to 200 °C. In addition, the time required for the heat treatment may be changed as needed, and may be adjusted within a range of about 1 minute to 72 hours or about 1 minute to 24 hours, for example. The temperature and time of the heat treatment may be adjusted to an appropriate level in consideration of the type of functional group of the random copolymer of the neutral layer composition.

The neutral layer may have a thickness of, for example, about 2 nm to about 100 nm, and in another example, about 2 nm to about 50 nm. Surface uniformity of the neutral layer may be maintained within the thickness range, vertical alignment of the block copolymer may be induced, and etching selectivity may not be impaired in a subsequent etching process.

The present application also relates to a substrate, a neutral layer comprising the random copolymer formed on the substrate, and a block air formed on the neutral layer and having a first block and a second block chemically distinct from the first block. It relates to a laminate comprising a polymer film including a composite.

In the above-described laminate, the polymer membrane can be used for various purposes, for example, various electronic or electronic devices, the process of forming the pattern, or a magnetic storage recording medium, a recording medium such as a flash memory, or a biosensor or a separator. It can be used in manufacturing processes and the like.

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. . Among the structures, in the case of spheres or lamellas, the block copolymer may exist in a vertically aligned state.

The block copolymer that can be included in the polymer film in the above laminate is not particularly limited, but block copolymers showing more appropriate orientation and positioning on the above-mentioned neutral layer are the block copolymers exemplified below.

In the present application, a block copolymer including a first block to be described later and a second block to be described later that is different from the first block may be applied. Each block of the block copolymer may be formed of only one type of monomer or two or more types of monomers. The block copolymer may be a diblock copolymer including only one first block and one second block. The block copolymer further includes one of each of the first and second blocks, further includes any one or both of the first and second blocks, or blocks other than the first and second blocks. It may be a block copolymer of more than triblock including additionally.

Since the block copolymer includes two or more polymer chains linked by covalent bonds, phase separation occurs and a so-called self-assembling structure is formed. The present inventors have confirmed that the block copolymer having the structure described below causes appropriate phase separation in the above-mentioned neutral layer, and excellent directionality and positioning properties are also ensured.

The block copolymer of the present application may include a first block including repeating units represented by Formula 7 below and a second block including repeating units represented by Formula 8 below.

[Formula 7]

In Formula 7, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:

[Formula 8]

In Formula 8, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms.

In Formula 7, X may be an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, or -C(=O)-O- in another example, but is not limited thereto. no.

In Formula 7, P may be an arylene group having 6 to 18 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a phenylene group.

In Formula 7, Q may be connected to the para position when P is a phenylene group.

Q in Formula 7, in one example, may be a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O)- , For example, it may be a single bond, an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-, but is not limited thereto.

Z in Formula 7 is a hydrocarbon chain having 8 to 20 carbon atoms. In another example, the number of carbon atoms in the hydrocarbon chain may be 9 or more, 10 or more, 11 or more, or 12 or more, or 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less. The hydrocarbon chain may be a straight chain hydrocarbon chain, and may be, for example, a straight chain alkyl group, an alkenyl group or an alkynyl group. The number of carbon atoms in the straight-chain alkyl group, alkenyl group or alkynyl group is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, or 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, It may be 13 or less or 12 or less.

In one example, the hydrocarbon chain is a chain including a straight chain structure, and at this time, the number of carbon atoms forming the straight chain structure may be within the range of 8 to 20. The chain may be straight or branched, but the number of carbon atoms calculated only by the number of carbon atoms forming the longest straight chain may be within the range of 8 to 20. In the case of a branched chain, the number of carbon atoms forming the straight chain structure can be calculated as the number of carbon atoms forming the longest chain. For example, when the chain is an n-pentyl group, the number of carbon atoms forming the linear structure is 5, and when the chain is a 2-methylpentyl group, the number of carbon atoms forming the linear structure is 5.

The hydrocarbon chain including the straight-chain structure may be a straight-chain or branched-chain alkyl, alkenyl, or alkynyl group, wherein the number of carbon atoms forming the straight-chain structure is 8 or more, 9 or more, 10 or more, 11 or more, or 12 or more, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less.

In one example, one or more of the carbon atoms of the alkyl group, alkenyl group, or alkynyl group, which is the hydrocarbon chain, may be optionally replaced with a hetero atom for a carbon atom such as an oxygen atom, and at least one of the alkyl group, alkenyl group, or alkynyl group A hydrogen atom may be optionally substituted by another substituent.

In the block copolymer of the present application, the first block may consist only of repeating units comprising the units of Chemical Formula 7, or may include other repeating units in addition to the repeating units. In one example, the first block contains about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, or 90 mol% or more of repeating units of the unit of Formula 7, or , About 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or 90 mol% or less.

Types of other units that may be additionally included in the first block are not particularly limited as long as they do not adversely affect desired directionality and positioning. The unit may be, for example, a vinylpyrrolidone unit, a lactic acid unit, a vinylpyridine unit, a styrene unit such as styrene or trimethylsilylstyrene, or an ethylene oxide unit. An alkylene oxide unit, a butadiene unit, an isoprene unit, or an olefin unit such as ethylene, or a repeating unit composed of such a unit may be exemplified.

The second block having a repeating unit represented by Chemical Formula 8 exhibits excellent interaction with the first block and thus exhibits excellent homeotropic alignment on the neutral layer.

In Formula 8, X ₂ may be a single bond in one example.

In Formula 8, the aryl group may be, for example, an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms, or a phenyl group.

As the halogen atom included in Chemical Formula 8, a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be appropriately exemplified, but is not limited thereto. The halogen atom may be substituted with the aryl group.

In one example, W in Formula 2 has 6 to 18 carbon atoms or 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 (fluorine atoms or chlorine atoms, etc.) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms substituted in the above 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.

The unit of Formula 8 may be represented by Formula 9 below in another example.

[Formula 9]

In Formula 9, X ₂ is a single bond, an oxygen atom or a sulfur atom, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and the number of halogen atoms included in R ₄ to R ₈ is There may be three or more.

In Formula 9, X ₂ may be a single bond in another example.

In Formula 9, R ₄ to R ₈ are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, but R ₄ to R ₈ are 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more halogen atoms. , for example, a fluorine atom or a chlorine atom. The number of halogen atoms included in R ₄ to R ₈ may be 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The halogen atoms may be included in a haloalkyl group, and one or more, two or more, three or more, four or more, or five of R ₄ to R ₈ may be halogen atoms. In this case, the halogen atom may be a fluorine atom or a chlorine atom.

In the block copolymer, the second block may consist only of repeating units comprising the units of Chemical Formula 8 or 9, or may include other repeating units in addition to the repeating units. In one example, the second block contains about 80 mol% or more, 82 mol% or more, 84 mol% or more, 86 mol% or more, 88 mol% or more, or 90 mol% or more of repeating units of Formula 8 or 9. or about 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or 90 mol% or less.

Types of other units that may be additionally included in the second block are not particularly limited as long as they do not adversely affect desired directionality and positioning. The unit may be, for example, a vinylpyrrolidone unit, a lactic acid unit, a vinylpyridine unit, a styrene unit such as styrene or trimethylsilylstyrene, or an ethylene oxide unit. An alkylene oxide unit, a butadiene unit, an isoprene unit, or an olefin unit such as ethylene, or a repeating unit composed of such a unit may be exemplified.

In one example, the second block may further include an alkyl styrene unit or a styrene unit together with a repeating unit represented by Formula 8 or 9. Through these additional units, a more excellent phase separation pattern can be implemented on the neutral layer.

In the alkyl styrene unit, an alkyl group may be included in a para position, and thus the alkyl styrene unit may be a para-alkyl styrene unit.

The alkyl group included in the alkyl styrene unit may be a linear or branched 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.

The alkyl styrene unit may be a unit in which R ₁₁ to R ₁₅ are hydrogen or an alkyl group and at least one of R ₁₁ to R ₁₅ is an alkyl group in Formula 10 below. In one example, the para-alkyl styrene unit is represented by the following formula 10 may be a unit in which R ₁₃ is an alkyl group and R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ are hydrogen atoms.

The alkyl group of the alkyl styrene unit may be a linear or branched 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. Such an alkyl group may be an alkyl group of any one of R ₁₁ to R ₁₅ or an alkyl group of R ₁₃ .

Meanwhile, the styrene unit is a unit in which R ₁₁ to R ₁₅ in Formula 10 are all hydrogen.

[Formula 10]

The present inventors have confirmed that the alkyl styrene unit or the styrene unit, together with the repeating unit comprising the unit of Chemical Formula 8 or 9 in the second block, allows the second block to properly interact with the first block.

If the second block further includes a unit of Formula 10, it may include a repeating unit of Formula 8 or 9 within the range of 60 mol% to 97 mol%. In another example, the ratio may be about 65 mol% or more or 70 mol% or more, or may be 95 mol% or less, 93 mol% or less, 91 mol% or less, or 90 mol% or less.

Meanwhile, when the second block includes the alkyl styrene unit or the styrene unit, it may be included within a range of 3 mol% to 40 mol%. In other examples, the ratio is about 5 mol% or more, about 7 mol% or more, about 9 mol% or more, or about 10 mol% or more, or about 38 mol% or less, about 36 mol% or less, about 34 mol% or less, about It may be 32 mol% or less or about 30 mol% or less.

In the block copolymer, when the volume of the first block and the second block is set to 1, the volume fraction of the first block is in the range of 0.3 to 0.8, and the volume fraction of the second block is in the range of 0.2 to 0.7 can

In another example, the volume fraction of the first block may be about 0.35 or more, about 0.4 or more, or about 0.45 or more, or about 0.75 or less, about 0.7 or less, about 0.65 or less, about 0.6 or less, about 0.55 or less, or about 0.5 or less. . In addition, the volume fraction of the second block may be about 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, or about 0.5 or more, or about 0.65 or less, about 0.6 or less, or about 0.55 or less in another example. A block copolymer including the first and second blocks in the above ratio may exhibit excellent self-assembly characteristics. The sum of the volume fractions of the first block and the second block may be 1. The volume fraction of each block of the block copolymer can be obtained based on the density of each block and the molecular weight measured by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 10,000 to 100,000. In other examples, the molecular weight (Mn) may be, for example, about 12,000 or more, 14,000 or more, 16,000 or more, 18,000 or more, about 19,000 or more, 20,000 or more, 22,000 or more, 24,000 or more, 26,000 or more, 28,000 or more, or 30,000 or more. In another example, the molecular weight (Mn) may be 95,000 or less, 90,000 or less, 85,000 or less, 80,000 or less, 75,000 or less, 70,000 or less, 65,000 or less, 60,000 or less, 55,000 or less, 50,000 or less, 45,000 or less, 40,000 or less, or 35,000 or less. . The block copolymer may have a polydispersity (Mw/Mn) within a range of 1.05 to 1.45. The degree of dispersion may be about 1.1 or more, 1.15 or more, or about 1.2 or more, or about 1.40 or less or about 1.35 or less in another example.

Within this range, the block copolymer may exhibit appropriate self-assembly characteristics. The number average molecular weight of the block copolymer may be adjusted in consideration of the desired self-assembly structure (ex. pitch of lamellar pattern, etc.).

A specific method for preparing the block copolymer as described above is not particularly limited, and, for example, the block copolymer is prepared by applying a known method for producing block copolymers using monomers capable of forming each block. can do.

For example, the block copolymer may be prepared by a Living Radical Polymerization (LRP) method. 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 an alkali metal or alkaline earth metal salt, or an organic alkali metal compound is polymerized. Anionic polymerization method synthesized in the presence of an organoaluminum compound using an initiator, an atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerizer as a polymerization control agent, and an atom transfer radical polymerization method using an atom transfer radical polymerizer as a polymerization control agent but electrons ARGET (Activators Regenerated by Electron Transfer) atom transfer radical polymerization (ATRP), ICAR (Initiators for continuous activator regeneration) atom transfer radical polymerization (ATRP), inorganic reducing agent reversible addition- A polymerization method by reversible addition-cleavage chain transfer (RAFT) using a cleavage chain transfer agent or a method using an organic tellurium compound as an initiator may be used, and an appropriate method may be selected and applied from among these methods.

For example, the block copolymer may be prepared by a method comprising polymerizing a reactant including monomers capable of forming the block by a living radical polymerization method in the presence of a radical initiator and a living radical polymerization reagent. .

In the preparation of the block copolymer, the method of forming other blocks included in the copolymer together with the block formed using the monomer is not particularly limited, and an appropriate monomer is selected in consideration of the type of the desired block, and the other blocks are formed. blocks can be formed.

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

The living radical polymerization process is, for example, methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, acetone, chloroform, tetrahydrofuran, dioxane, monoglyme, diglyme, dimethylform amide, dimethylsulfoxide or dimethylacetamide and the like.

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

The present application is also a method for manufacturing a laminate as described above, wherein the neutral layer formed on the substrate has a first block and a second block chemically distinct from the first block, and the self-assembled block air It relates to a method for manufacturing a laminate comprising forming a polymer film including a composite. As the block copolymer in the above, the above-described block copolymer may be used.

A method of forming such a polymer film using the block copolymer is not particularly limited. For example, the method may include forming a polymer film including the block copolymer on the neutral layer in a self-assembled state. For example, the method may include forming a layer of the block copolymer or a coating solution diluted in an appropriate solvent on the neutral layer by application or the like, and aging or heat-treating the layer, if necessary.

The aging or heat treatment may be performed, for example, based on the phase transition temperature or glass transition temperature of the block copolymer, and may be performed, for example, at a temperature equal to or higher than the glass transition temperature or phase transition temperature. The time for performing this heat treatment 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, 100° C. to 250° C., but may be changed in consideration of the block copolymer used.

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

This application also relates to a pattern forming method. The method may include, for example, a process of selectively removing the first or second block of the block copolymer from the polymer film of the laminate. The method may be a method of forming a pattern on the substrate. For example, the method may include forming a polymer film including the block copolymer on a substrate, selectively removing any one or more blocks of the block copolymer present in the film, and then etching the substrate. . In this way, it is possible to form fine patterns on the nanoscale, for example. In addition, various types of patterns such as nanorods or nanoholes may be formed through the method according to the shape of the block copolymer in the polymer film. If necessary, the block copolymer and other copolymers or homopolymers may be mixed to form patterns. The type of substrate applied in this manner is not particularly limited and may be selected as necessary, and for example, silicon oxide or the like may be applied.

For example, the method can form a nanoscale pattern of silicon oxide exhibiting a high aspect ratio. For example, after forming the polymer film on silicon oxide and selectively removing any one block of the block copolymer in a state where the block copolymer in the polymer film forms a predetermined structure, silicon oxide is formed in various ways, for example, , reactive ion etching, etc., to implement various shapes including patterns of nanorods or nanoholes. In addition, through this method, it is possible to implement a nanopattern with 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 purposes including, for example, a magnetic recording medium for next-generation information and electronics.

In the above method, the method of selectively removing any one block of the block copolymer is not particularly limited, and, for example, a method of removing a relatively soft block by irradiating a polymer film with appropriate electromagnetic waves, such as ultraviolet rays, etc. can be used In this case, the UV irradiation condition is determined according to the type of block of the block copolymer, and for example, it may be performed by irradiating UV light having a wavelength of about 254 nm for 1 minute to 60 minutes.

In addition, a step of further removing segments decomposed by ultraviolet rays by treating the polymer film with an acid or the like may be performed following irradiation with ultraviolet rays.

In addition, the step of etching the substrate using the selectively block-removed polymer film as a mask is not particularly limited, and may be performed, for example, through a reactive ion etching step using CF4 / Ar ions, etc., followed by A step of removing the polymer film from the substrate by oxygen plasma treatment or the like can also be performed.

The present application can provide a neutral layer composition capable of effectively controlling orientation such as vertical orientation of a block copolymer and forming a neutral layer showing excellent reaction selectivity to a substrate and high degree of crosslinking in a short time even by a low-temperature process. .

1 is a SEM image of a block copolymer film in Example.

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 to a concentration of about 10 mg/ml in a solvent for NMR measurement (CDCl ₃ ), and the chemical shift was expressed in ppm.

<Applicable Abbreviations>

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

2. Gel Permeation Chromatograph (GPC)

Number average molecular weight (Mn) and molecular weight distribution were measured using GPC (Gel permeation chromatography). A polymer to be measured was put in a 5 mL vial, and diluted in tetrahydro furan (THF) to a concentration of about 1 mg/mL. Subsequently, 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. The analysis program used ChemStation from Agilent technologies. 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) was calculated using the ratio (Mw/Mn). ) was calculated. The measurement conditions of GPC are as follows.

<GPC measurement conditions>

Device: 1200 series by Agilent technologies

Column: Use 2 PLgel mixed B from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1mg/mL, 200L injection

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

Preparation Example 1. Synthesis of monomer (A)

A compound of Formula A (DPM-C12) was synthesized in the following manner. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were put in a 250 mL flask, dissolved in 100 mL of acetonitrile, and the excess Potassium carbonate was added and reacted at 75° C. for about 48 hours under nitrogen conditions. After the reaction, the remaining potassium carbonate was removed by filtering, and acetonitrile used in the reaction was also removed. Here, a mixed solvent of DCM (dichloromethane) and water was added to work up, and the separated organic layer was collected and dehydrated by passing through MgSO ₄ . Subsequently, the target product (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) was obtained as a white solid in a yield of about 37% by column chromatography using dichloromethane (DCM).

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ6.77 (dd, 4H); δ4.45 (s, 1H); [delta] 3.89 (t, 2H); δ1.75 (p, 2H); δ1.43 (p, 2H); δ 1.33-1.26 (m, 16 H); δ0.88 (t, 3H).

4-Dodecyloxyphenol (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC) (10.8 g, 52.3 mmol) and p-dimethylaminopyridine (DMAP) (1.7 g) synthesized in a flask. , 13.9 mmol) was added, and 120 mL of methylene chloride was added, followed by reaction at room temperature under nitrogen for 24 hours. After completion of the reaction, the salt (urea salt) generated during the reaction was removed with a filter, and the remaining methylene chloride was also removed. In column chromatography, impurities were removed using hexane and dichloromethane (DCM) as mobile phases, and the obtained product was recrystallized from a mixed solvent of methanol and water (1:1 mixture) to obtain the target product (7.7 g, 22.2 mmol) as a white solid. It was obtained in a yield of 63%.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 7.02 (dd, 2H); [delta]6.89 (dd, 2H); δ6.32 (dt, 1H); [delta]5.73 (dt, 1H); δ3.94(t, 2H); [delta] 2.05 (dd, 3H); δ1.76 (p, 2H); δ1.43 (p, 2H); 1.34-1.27 (m, 16H); δ0.88 (t, 3H).

[Formula A]

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

Preparation Example 2. Synthesis of Block Copolymer

2 g of the monomer (A) of Preparation Example 1, 64 mg of RAFT (Reversible Addition-Fragmentation chain transfer) reagent cyanoisoprotyl dithiobenzoate, 23 mg of AIBN (Azobisisobutyronitrile) as a radical initiator, and 5.3 mL of benzene were added to 10 mL. After putting it in a Schlenk flask and stirring at room temperature for 30 minutes under a nitrogen atmosphere, RAFT (Reversible Addition-Fragmentation chain transfer) polymerization reaction was performed at 70 ° C. for 4 hours. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the macro initiator was about 80% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 13,000 and 1.15, respectively.

0.3 g of the macroinitiator, 2.7 g of pentafluorostyrene monomer, and 1.3 mL of benzene were put in a 10 mL Schlenk flask and stirred at room temperature for 30 minutes under a nitrogen atmosphere, followed by RAFT (Reversible Addition-Fragmentation chain transfer) at 115 ° C. for 4 hours A polymerization reaction was performed. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered and dried under reduced pressure to prepare a light pink block copolymer. The yield of the block copolymer was about 65% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were 38,000 and 1.15, respectively. The block copolymer is a first block (volume fraction of the first block: 0.5) derived from the monomer (A) of Preparation Example 1 and a second block derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.5). Contains 2 blocks.

Preparation Example 3. Synthesis of Random Copolymer (A)

Compound of Preparation Example 1 (DPM) 0.107 g, pentafluorostyrene (PFS) 1.434 g, GMA (glycidyl methacrylate) 0.142 g), methacrylic acid (MAA) 0.026 g) and GBLMA (gamma-Butyrolactone-3-yl methacrylate) 0.170 g) was mixed to a molar ratio of 3.1:73.9:10:3:10 (DPM:PFS:GMA:MAA:GBLMA), and then put into 2mL of THF (tetrahydrofuran) together with 0.033 g of AIBN (Azobisisobutyronitrile) as an initiator, and nitrogen A free radical polymerization reaction was performed at 60° C. for 12 hours in an atmosphere. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a random copolymer. The number average molecular weight (Mn) of the random copolymer was about 24,100 g/mol.

Preparation Example 4. Synthesis of Random Copolymer (B)

1.844 g of pentafluorostyrene (PFS) and 0.065 g of 2-hydroxyethyl methacrylate (HEMA)) were mixed to a molar ratio of 95:5 (PFS:HEMA), followed by 0.033 g of azobisisobutyronitrile (AIBN) as an initiator. It was put in 2 mL of THF (tetrahydrofuran), and free radical polymerization was performed at 60° C. for 12 hours under a nitrogen atmosphere. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, filtered under reduced pressure and dried to prepare a random copolymer. The number average molecular weight (Mn) of the random copolymer was about 15,000 g/mol.

Example 1.

After diluting the random copolymer (A) of Preparation Example 3 in fluorobenzene (FB) at a concentration of about 0.2% by weight, it is applied on a silicon wafer, maintained at 200 ° C. for about 5 minutes, and the excess polymer that does not react is A neutral layer substrate having a neutral layer having a thickness of about 9 nm was formed by washing with a FB (Fluoro benzene) solvent. On the neutral layer substrate, a coating solution obtained by diluting the random copolymer (F) of Preparation Example 4 in a FB (Fluoro benzene) solvent at a concentration of about 1.0% by weight was applied, and after heat treatment at 180 ° C. for 5 minutes, unreacted components were added to FB ( Fluoro benzene) was removed by ultrasonic washing with a solvent.

Subsequently, a coating solution diluted with the block copolymer of Preparation Example 2 in a solvent (Fluorobenzene) at a concentration of 1% by weight was applied and coated thereon, and thermal annealing was performed at 230 ° C. for 5 minutes to form a self-assembled lamellar pattern. 1 is a photograph showing the result. Whether the substrate on which the neutral layer is formed and the pinning brush (including the random copolymer (F)) are halves can be confirmed according to whether defects in the vertical lamella pattern occur due to changes in physical properties of the surface of the neutral layer. In the case of 1, it was confirmed that the surface properties of the neutral layer were maintained and the vertical lamellar pattern was effectively formed.

Claims (14)

A unit represented by Formula 1 below; a unit represented by Formula 2 below; cross-linkable functional group-containing units; And has a unit containing an aromatic group containing a halogen atom,
The unit containing an aromatic group containing a halogen atom is represented by the following formula (4),
A neutral layer composition comprising a random copolymer having a number average molecular weight in the range of 22,000 to 50,000 g/mol:
[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, Z is a hydrocarbon chain having 8 to 20 carbon atoms,
[Formula 2]

In Formula 2, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxyl group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylene group having 1 to 4 carbon atoms ego,
[Formula 4]

In Formula 4, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms. The neutral layer composition according to claim 1, wherein X in Formula 1 is an oxygen atom, a carbonyl group, -C(=O)-O- or -OC(=O)-. The neutral layer composition according to claim 1, wherein the random copolymer contains the unit represented by Formula 1 in an amount of 32 mol% or less. The neutral layer composition according to claim 1, wherein the random copolymer contains the unit represented by Formula 2 in an amount of 0.01 to 20 mol%. The neutral layer composition according to claim 1, wherein the crosslinkable functional group-containing unit is represented by Formula 3 below:
[Formula 3]

In Formula 3, R ₃ is hydrogen or an alkyl group, and T is a divalent hydrocarbon group with or without a single bond or hetero atom. The neutral layer composition according to claim 1, wherein the random copolymer contains a crosslinkable functional group-containing unit in an amount of 0.01 to 30 mol%. delete The neutral layer composition according to claim 1, wherein the random copolymer contains a unit containing an aromatic group containing a halogen atom in an amount of 40 mol% or more. A unit represented by Formula 1 below; a unit represented by Formula 2 below; cross-linkable functional group-containing units; And has a unit containing an aromatic group containing a halogen atom,
The unit containing an aromatic group containing a halogen atom is represented by the following formula (4),
A neutral layer comprising a random copolymer having a number average molecular weight in the range of 22,000 to 50,000:
[Formula 1]

In Formula 1, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, Z is a hydrocarbon chain having 8 to 20 carbon atoms,
[Formula 2]

In Formula 2, R ₁ is hydrogen or an alkyl group having 1 to 4 carbon atoms, L is a carbonyl group, -C(=O)-L ₁ -, -C(=O)-O-, -C(=O)-OL ₁ - or an alkylene group, R ₂ is a hydroxyl group, a hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is an alkylene group having 1 to 4 carbon atoms ego,
[Formula 4]

In Formula 4, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms. A method of forming a neutral layer comprising the steps of coating the neutral layer composition of claim 1 on a substrate and fixing the layer of the coated neutral layer composition. Board; The neutral layer of claim 9 formed on the substrate; and a polymer film formed on one surface of the neutral layer and including a block copolymer having a first block and a second block chemically distinct from the first block. The laminate according to claim 11, wherein the first block of the block copolymer includes repeating units represented by the following formula (7), and the second block includes repeating units represented by the following formula (8):
[Formula 7]

In Formula 7, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC(=O )-, P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, an oxygen atom, a sulfur atom, -S(=O) ₂ -, a carbonyl group, -C(=O)-O- or -OC (=O)-, and Z is a hydrocarbon chain of 8 to 20 carbon atoms:
[Formula 8]

In Formula 8, X ₂ is a single bond, an oxygen atom or a sulfur atom, and W is an aryl group having 6 to 18 carbon atoms and containing 3 or more halogen atoms. A laminate comprising the step of forming, in a self-assembled state, a polymer film comprising a block copolymer having a first block and a second block chemically distinct from the first block on the neutral layer of claim 9 formed on a substrate. manufacturing method. A pattern formation method comprising the step of selectively removing the first or second block of the block copolymer from the polymer film of the laminate of claim 11 or claim 12.

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