KR20200020255A - Compositon for neural layer - Google Patents

Abstract

The present invention relates to a neutral layer composition and, more specifically, to a neutral layer composition which can effectively control orientation, such as vertical orientation of a block copolymer, and is capable of forming a neutral layer showing excellent reaction selectivity and high cross-linking degree to a substrate within a short time even by a low temperature process.

Description

Neutral layer composition {COMPOSITON FOR NEURAL LAYER}

The present application relates to a neutral layer composition.

Block copolymers in which two or more chemically different polymer chains are covalently linked may be separated into regular microphases. The microphase separation phenomenon of such block copolymers is generally explained by the volume fraction, molecular weight, and floor-Huggins interaction parameter between 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 microphase. The orientation of the block copolymer may include a horizontal orientation in which the nanostructures are parallel to the substrate direction and a vertical orientation in which the nanostructures are perpendicular to the substrate direction, of which the vertical orientation is a horizontal orientation. It is often of greater importance than.

Selective wetting of the blocks of the block copolymer can determine the orientation of the nanostructures, which generally have the greater polarity among the blocks of the block copolymer because many substrates are polar and air is nonpolar. Wetting on the silver substrate, and blocks with smaller polarities are wetting at the interface with air, leading to horizontal orientation.

The present application provides a neutral layer composition. The present application is to provide a neutral layer composition that can effectively control the orientation, such as the vertical orientation of the block copolymer, and can form a neutral layer exhibiting excellent reaction selectivity and high crosslinking degree to the substrate within a short time even by a low temperature process For the purpose of.

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

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

As used herein, 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 linear, branched or cyclic, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, 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. The alkylene group may be a straight chain, branched or cyclic alkylene group, and may be optionally substituted with one or more substituents.

As used herein, the term alkenylene group or alkynylene group 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 unless otherwise specified. Can mean a group. The alkenylene group or alkynylene group may be linear, branched or cyclic, and may be optionally substituted with one or more substituents.

As used herein, unless otherwise specified, the term aryl group or arylene group is one benzene ring structure, at least two 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 containing 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 the present application, the term aromatic structure may mean the aryl group or the arylene group.

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

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

In the present application, as the substituent which 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 groupoxy, methacryloyl groupoxy 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.

The present application is directed to a neutral layer composition. The term neutral layer composition may mean a composition used to form a neutral layer. As used herein, the term neutral layer may refer to any kind of layer capable of inducing the vertical orientation of the block copolymer. The term vertical alignment of the block copolymer is well known in the art, and may mean, for example, when the block copolymer forms a phase separation structure, and the interface of the blocks constituting the phase separation structure is formed substantially perpendicular to the substrate. Can be.

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 including 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 (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , 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, in another example, an oxygen atom, a carbonyl group, -C (= 0) -O-, or -OC (= 0)-, or -C (= 0) -O-, 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 linked to a para position when P is a phenylene group.

Q in Formula 1 may be, in one example, 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, but is not limited to, a single bond, an oxygen atom, a carbonyl group, -C (= 0) -O-, or -OC (= 0)-.

Z in Formula 1 is a hydrocarbon chain having 8 to 20 carbon atoms. In other examples, the carbon number of 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, for example, may be a straight chain alkyl group, alkenyl group or alkynyl group. Carbon number of the said linear alkyl group, alkenyl group, or alkynyl group 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, the hydrocarbon chain is a chain including a straight chain structure, wherein the number of carbon atoms forming the straight chain structure may be in the range of 8 to 20. The chain may be linear or branched, but the number of carbon atoms calculated from only the number of carbon atoms forming the longest straight chain may be in the range of 8 to 20. In the case of branched chains, 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 a straight chain structure is five, and even when the chain is a 2-methylpentyl group, the number of carbon atoms forming a straight chain structure is five.

The hydrocarbon chain including the straight chain structure may be a linear or branched alkyl, alkenyl or alkynyl group, wherein the number of carbon atoms forming the straight chain is at least 8, at least 9, at least 10, at least 11 or 12 or less, 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 substituted 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 The hydrogen atom may be optionally substituted by another substituent.

The ratio of units of Formula 1 in the random copolymer may be included in an amount of 32 mol% or less based on the total copolymer. This ratio can be adjusted according to the kind of block copolymer to which the said neutral layer is applied, for example. In one example, the ratio of the units 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% or less Up to 15 mol%, up to 14 mol%, up to 13 mol%, up to 12 mol%, up to 11 mol% or up to 10 mol%, or at least 1 mol%, at least 2 mol%, at least 3 mol%, 4 It may be about mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more. The inventors confirmed that the ratio of units of the formula (1) included in the random copolymer may exhibit neutral properties in the above range. Since the random copolymer includes the units of the formula (1) in a range satisfying the above ratio, the neutral layer formed of the neutral layer composition of the present application further induces vertical alignment of the block copolymer, and further includes a functional monomer described below. The adhesion between the block copolymer and the neutral layer and the adhesion between the neutral layer and the substrate can be improved.

The unit having an aromatic structure including at least one halogen atom included in the random copolymer may be a unit represented by the following formula (4).

[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 including three or more halogen atoms.

X ₂ in the unit of Formula 4 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 the formula (4), a fluorine atom or a chlorine atom and the like 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 of formula 4 has 6 to 18 carbon atoms or 6 to 12 carbon atoms substituted with one or more, two or more, three or more, four or more or five halogen atoms (such as a fluorine atom or a chlorine atom) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms to be substituted 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 the following Formula 5 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 It may be three or more.

In Chemical 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, and R ₄ to R ₈ 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 or a chlorine atom. The halogen atoms contained 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 atom may be contained in a haloalkyl group, and at least one, at least two, at least three, at least four 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, 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more, but is not limited thereto. 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 having an aromatic structure including a unit represented by Formula 1 and at least one halogen atom may satisfy a ratio of the number of moles in the above range, so that an appropriate neutral surface may be formed.

The ratio of units having an aromatic group containing the halogen atom in the random copolymer may be 40 mol% or more based on the entire copolymer. The ratio may be adjusted according to the type of block copolymer to which the neutral layer is applied. In one example, the proportion of units having an aromatic group containing the halogen atom in the random copolymer is at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol% or 68 mol%. 90 mol% or less, 85 mol% or less, 80 mol% or less, or 75 mol% or less may be sufficient. The inventors confirmed that the ratio of the units included in the random copolymer may exhibit neutral properties in the above range. Through this, while the neutral layer formed of the neutral layer composition of the present application effectively induces the vertical orientation of the block copolymer, it may further include a functional monomer described later, and the binding force between the block copolymer and the neutral layer and the neutral layer and The adhesion between the substrates can be improved.

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

[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 (= 0) -L _1- , -C (= 0) -O-, -C (= 0) -OL _{Is a 1-} or alkylene group, R ₂ is a hydroxy group, hydroxyalkyl group, -SO ₃ H, -OSO ₃ H, -OPO ₃ H ₂ or -PO ₃ H, wherein L ₁ is alkylene having 1 to 4 carbon atoms It may be a flag.

In the above, the alkylene group of L may be, in one example, a straight, 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 the unit of Formula 2, L is a carbonyl group, -C (= 0) -L _1- , -C (= 0) -O-, -C (= 0) -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.

Since the unit of Formula 2 is present in the random copolymer together with the crosslinkable functional group-containing unit, it is possible to appropriately secure the desired degree of crosslinking even at low temperatures in the process of forming the neutral layer, and uniform coating of the composition is possible. The neutral layer which is excellent in adhesive force can be formed.

The said unit can be formed by polymerizing monomers, such as (meth) acrylic acid or phosphoethyl (meth) acrylate, in the manufacturing process of a random copolymer.

The random copolymer may include the unit of Formula 2 in a ratio of about 0.01 to 20 mole%. The ratio is, in another example, 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, 18 mol% or less, 16 mol% or less, 14 mol % 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 It may be% or less or 1 mol% or less.

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

The crosslinkable functional group-containing unit may be applied to implement the crosslinked structure in the process of forming the neutral layer. The said unit is a crosslinkable functional group, For example, a hydroxyl group, a glycidyl group, an epoxy group, an isocyanate group, a glycidyl group, the functional group of following formula A, a benzoyl phenoxy group, an alkenyloxy carbonyl group, a (meth) acryloyl group And / or a monomer having an alkenyloxyalkyl group or the like can be formed by copolymerizing a random copolymer.

[Formula A]

Y in formula (A) is a single bond, an alkylene group, an alkenylene group or an alkynylene group, L ₁ is a single bond, an oxygen atom, a sulfur atom, -S (= O) _2- , an alkylene group, an alkenylene group, alkynyl Or a -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 And an alkenylene group or an alkynylene group.

The functional group of formula (A) is a substituent in which a crosslinkable azide moiety is present at the terminal, and such functional group may be crosslinked.

In Formula A, Y may be, in another example, 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 Formula A, L ₁ may be a single bond, an oxygen atom, -C (= 0) -O-, or -OC (= 0)-in another example, but is not limited thereto.

As a monomer unit containing a crosslinkable functional group, the unit of following formula (3) can be illustrated.

[Formula 3]

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

In another embodiment, the alkyl group 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. Such alkyl groups may be linear, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents.

In Formula 3, T may be, in another example, an alkylene group, an alkenylene group, or an alkynylene group. 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. Such alkylene di groups may be straight, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents. 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. Such alkenylene di groups may be straight, branched or cyclic and may be optionally substituted by one or more of the aforementioned substituents. 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. Such alkynylene di groups may be linear, branched or cyclic and may be optionally substituted with one or more of the aforementioned substituents.

The divalent hydrocarbon group of T of formula (3) may further comprise a hetero atom, if necessary. In the above, the hetero atom is a hetero atom with respect to carbon, for example, oxygen, nitrogen or sulfur. Such hetero atoms may be included in one to four or less than T in the formula (3).

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

The ratio in the random copolymer of the said crosslinkable functional group containing unit is about 0.01-30 mol%. The ratio is at least about 0.1 mol%, at least 0.5 mol%, at least 1 mol%, at least 2 mol%, at least 3 mol%, at least 5 mol%, at least 7 mol% or at least 9 mol%, or in another example, 28 mol Up to 26 mol%, up to 24 mol%, up to 22 mol%, up to 20 mol%, up to 18 mol%, up to 16 mol%, up to 14 mol% or up to 12 mol%, but is not limited thereto. no.

The random copolymer may, if necessary, additionally comprise lactone group containing units. Such a unit can help to form a neutral layer excellent in interfacial adhesion.

As such a unit, for example, a unit of 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 be.

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

In addition, the lactone group may be, for 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 and the like can be exemplified, but is not limited thereto.

When included, the ratio of the lactone group-containing unit in the random copolymer may be about 0.01 to 50 mol%. The ratio is, in another example, at least about 0.05 mol%, at least 0.1 mol%, at least 0.5 mol%, at least 1 mol%, at least 2 mol%, at least 3 mol%, at least 4 mol%, at least 5 mol%, 6 mol%. 7 mol% or more, 8 mol% or more, or 9 mol% or more, 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 more Or less, up to 34 mol%, up to 32 mol%, up to 30 mol%, up to 28 mol%, up to 26 mol%, up to 24 mol%, up to 22 mol%, up to 20 mol%, up to 18 mol%, up to 16 mol It may be about% or less, 14 mol% or less, 12 mol% or less, 10 mol% or less, 8 mol% or less, 6 mol% or less, or about 4 mol% or less, but is not limited thereto.

The random copolymer may further include other units as long as the desired effect is further secured to the units. The additional unit included in the random copolymer may include a functional monomer having various functional functional groups, and the functional monomer may be appropriately selected according to the 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 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, 2,000 to 500,000. The number average molecular weight may be, in another example, at least 3,000, at least 4,000, at least 5,000, at least 6,000, at least 7,000, at least 8,000, at least 9,000, at least 10,000, at least 20,000, at least 30,000, or at least about 35,000. In another example, the number average molecular weight may be about 400,000 or less, 300,000 or less, 200,000 or less, 100,000 or less, 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, or about 40,000 or less. As used herein, the term number average molecular weight is a conversion value with respect to standard polystyrene measured using a gel permeation chromatograph (GPC), and the term molecular weight means a number average molecular weight unless otherwise specified. In addition, unless otherwise stated, the unit of number average molecular weight is g / mol. The molecular weight of the random copolymer can be adjusted in consideration of the physical properties of the desired neutral layer.

The manner of producing 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 LRP (Living Radical Polymerization) method. Examples of the LRP method include an anionic polymerization and a polymerization agent which proceeds polymerization in the presence of an inorganic acid salt or an organoaluminum compound, such as a salt of an alkali metal or an alkaline earth metal, using an organic rare earth metal complex or an organic alkali metal compound as an initiator. An atomic transfer radical polymerization method (ATRP) using an atomic transfer radical polymerizer as a yesterday, ARGET (Activators Regenerated by Electron) using an atomic transfer radical polymerizer as a polymerization control agent, but proceeds polymerization under an organic or inorganic reducing agent that generates electrons Transfer (ATRP), Initiators for continuous activator regeneration (ICAR) Atomic radical polymerization, Inorganic reducing agent Reversible addition-breaking chain transfer using reversible addition-breaking chain transfer (RAFT) or organic The method using a tellurium compound as an initiator, etc. can be illustrated. , A suitable method may be employed in the method.

The kind of radical initiator that can be used in the polymerization process is not particularly limited. For example, aobisisobutyronitrile (AIBN), 1,1'-cyclohexanecarbonitrile (ABC) or 2,2'-azobis-2,4-dimethylvaleronitrile (2,2'-azobis- (2,4) Azo initiators such as -dimethylvaleronitrile)) or peroxide initiators such as benzoyl peroxide (BPO) or di-tert-butyl peroxide (DTBP) may be used. For example, thermal self-initiation of styrene monomers may be applied. Like the method using initiation), depending on the type of monomer, a polymerization method using no initiator may be applied.

The polymerization process can be carried out, for example, in a suitable solvent, in which case applicable solvents include methylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, benzene, toluene, anisole, 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, a random copolymer can be obtained by precipitation using a non-solvent, and non-solvents that can be used at this time include alcohols such as methanol, ethanol, n-propanol or isopropanol, ethylene glycol and the like. Ether-based solvents such as glycol, n-hexane, cyclohexane, n-heptane or petroleum ether may be exemplified, but is not limited thereto.

In the field of synthesis of polymers, a method of preparing a polymer by carrying out polymerization according to monomers forming the polymer is known, and any of the above methods may be applied when preparing a 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, may include other components in addition to the random copolymer. The neutral layer composition may include the random copolymer at least as a main component. Including the main ingredient herein, the composition comprises only the random copolymer, or based on solids, about 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, It may mean a case containing 75 wt% or more, 80 wt% or more, 85 wt% or more, or 90 wt% or more. The ratio may, in another example, be about 100 wt% or less or about 99 wt% or less. The ratio may be based on weight excluding the solvent when the neutral layer composition includes a solvent. As other components that may be included with the random copolymer, for example, an initiator or a crosslinking agent such as a thermal initiator or a photoinitiator required when the random copolymer includes the aforementioned crosslinkable functional groups may be exemplified.

The present application also relates to a neutral layer comprising the random copolymer. As used herein, the term neutral layer refers to a layer capable of inducing vertical alignment of the block copolymer as described above.

The neutral layer may be formed on a suitable 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 PET (poly (ethylene terephthalate)) film may be exemplified, but is not limited thereto.

The said neutral layer can be formed using the above-mentioned 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 layer of the coated neutral layer composition. The method of coating the neutral layer composition on the substrate in the above is not particularly limited, for example, bar coating, spin coating or comma coating may be applied, and a roll-to-roll coating may also be applied. have.

In addition, the method of fixing the layer of the neutral layer composition is not particularly limited, 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 in the layer. Etc. may be applied. For example, when the above process is performed by heat treatment, the heat treatment may be controlled 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 necessary, for example, it may be adjusted within the range of about 1 minute to 72 hours or about 1 minute to 24 hours. The temperature and time of the heat treatment may be adjusted to an appropriate level in consideration of the kind of the 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 100 nm, and in other examples, may have a thickness of about 2 nm to 50 nm. The uniformity of the surface of the neutral layer may be maintained within the thickness range, may induce a vertical orientation of the block copolymer, there may be an advantage that may not damage the etch selectivity in the subsequent etching process.

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

In the laminate as described above, the polymer film may be used in various applications. For example, various electronic or electronic devices, a process of forming the pattern or a recording medium such as a magnetic storage recording medium, a flash memory, or a biosensor or the like may be used. 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. . In the case of spheres or lamellaes of the structures, the block copolymer may be present in a vertically oriented state.

The block copolymer that can be included in the polymer film in the laminate as described above is not particularly limited, but the block copolymer showing more appropriate orientation and positioning on the above-mentioned neutral layer is a block copolymer 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 different from the first block may be applied. Each block of the block copolymer may be formed by only one kind of monomer, or may be formed by two or more kinds of monomers. The block copolymer may be a diblock copolymer comprising only one first block and one second block. The block copolymer also includes one each of the first and second blocks, and further includes one or both of the first and second blocks, or blocks other than the first and second blocks. It may further comprise a block copolymer of triblock or more.

Since the block copolymer includes two or more polymer chains connected by covalent bonds, phase separation occurs, thereby forming a so-called self-assembly structure. The inventors of the present invention confirmed that the block copolymer having the structure described below causes proper phase separation on the above-mentioned neutral layer, and also excellent in directionality and positioning.

The block copolymer of the present application may include a first block including a repeating unit that is a unit of Formula 7 and a second block including a repeating unit that is a unit of 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 (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, 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 including three or more halogen atoms.

X in Formula 7 may be, in another example, an oxygen atom, a carbonyl group, -C (= 0) -O-, or -OC (= 0)-, or -C (= 0) -O-, 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.

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

Q in Formula 7 may be, in one example, 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, but is not limited to, a single bond, an oxygen atom, a carbonyl group, -C (= 0) -O-, or -OC (= 0)-.

Z in Formula 7 is a hydrocarbon chain having 8 to 20 carbon atoms. In other examples, the carbon number of 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, for example, may be a straight chain alkyl group, alkenyl group or alkynyl group. Carbon number of the said linear alkyl group, alkenyl group, or alkynyl group 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, the hydrocarbon chain is a chain including a straight chain structure, wherein the number of carbon atoms forming the straight chain structure may be in the range of 8 to 20. The chain may be linear or branched, but the number of carbon atoms calculated from only the number of carbon atoms forming the longest straight chain may be in the range of 8 to 20. In the case of branched chains, 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 a straight chain structure is five, and even when the chain is a 2-methylpentyl group, the number of carbon atoms forming a straight chain structure is five.

The hydrocarbon chain including the straight chain structure may be a linear or branched alkyl, alkenyl or alkynyl group, wherein the number of carbon atoms forming the straight chain is at least 8, at least 9, at least 10, at least 11 or 12 or less, 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 substituted 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 The hydrogen atom may be optionally substituted by another substituent.

In the block copolymer of the present application, the first block may be made of only a repeating unit that is a unit of Formula 7, or may include another repeating unit in addition to the repeating unit. In one example, the first block includes at least about 80 mol%, at least 82 mol%, at least 84 mol%, at least 86 mol%, at least 88 mol%, or at least 90 mol% of the repeating unit that is a 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 about 90 mol% or less.

The kind of other units that can be additionally included in the first block is not particularly limited as long as it does not adversely affect the 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. The repeating unit which is an alkylene oxide unit, butadiene unit, isoprene unit, olefin unit, such as ethylene, etc. can be illustrated.

The second block having a repeating unit which is a unit of Formula 8 may exhibit excellent interaction with the first block and thus exhibit excellent vertical alignment on the neutral layer.

X ₂ in Formula 8 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 the formula (8), a fluorine atom or a chlorine atom may be exemplified, and a fluorine atom may be exemplified as appropriate, but is not limited thereto. The halogen atom may be substituted with the aryl group.

In one example, W of formula 2 has 6 to 18 carbon atoms or 6 to 12 carbon atoms substituted with one or more, two or more, three or more, four or more or five halogen atoms (such as a fluorine atom or a chlorine atom) It may be an aryl group or a phenyl group. The upper limit of the number of halogen atoms to be substituted 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 the following Formula 9 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 It may be three or more.

In Chemical 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, and R ₄ to R ₈ 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 or a chlorine atom. The halogen atoms contained 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 atom may be contained in a haloalkyl group, and at least one, at least two, at least three, at least four 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 of only repeating units of units of Formula 8 or 9, or may include other repeating units in addition to the repeating units. In one example, the second block is 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 the repeating unit that is the unit of Formula 8 or 9 About 100 mol% or less, 98 mol% or less, 96 mol% or less, 94 mol% or less, 92 mol% or less, or about 90 mol% or less.

The kind of other units that can be additionally included in the second block is not particularly limited as long as it does not adversely affect the 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. The repeating unit which is an alkylene oxide unit, butadiene unit, isoprene unit, olefin unit, such as ethylene, etc. can be illustrated.

The second block, in one example, may further include an alkyl styrene unit or a styrene unit with the repeating unit of the formula (8) or (9). Through such additional units, it is possible to implement a better phase separation pattern on the neutral layer.

The alkyl group in the alkyl styrene unit may be included in the 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 is hydrogen or an alkyl group in Formula 10, wherein any one of R ₁₁ to R ₁₅ is at least an alkyl group, and in one example, the para-alkyl styrene unit may be 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 straight or branched chain 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 .

On the other hand, the styrene unit is a unit in which R ₁₁ to R ₁₅ are all hydrogen in the following Formula 10.

[Formula 10]

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

If the second block further includes a unit of Formula 10, the second block may include a repeating unit which is a unit of Formula 8 or 9 within a range of 60 mol% to 97 mol%. The ratio may in another example be at least about 65 mole percent or at least 70 mole percent, or may be at most 95 mole percent, at most 93 mole percent, at most 91 mole percent or at most 90 mole percent.

Meanwhile, when the second block includes the alkyl styrene unit or the styrene unit, the second block may be included in the range of 3 mol% to 40 mol%. The ratio is, in another example, at least about 5 mole%, at least about 7 mole%, at least about 9 mole% or at least about 10 mole%, about 38 mole% or less, about 36 mole% or less, about 34 mole% or less, about 32 mol% or less, or about 30 mol% or less may be sufficient.

When the volume of the first block and the second block in the block copolymer is 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 be.

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. . Also, in another example, 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. The block copolymer including the first and second blocks in the ratio may exhibit excellent self-assembly characteristics. The sum of the volume fractions of the first block and the second block may be one. The volume fraction of each block of the block copolymer can be determined based on the density of each block and the molecular weight measured by Gel Permeation Chromatogrph (GPC).

The number average molecular weight (Mn) of the block copolymer may be, for example, in the range of 10,000 to 100,000. The molecular weight (Mn) may be, for example, at least about 12,000, at least 14,000, at least 16,000, at least 18,000, at least about 19,000, at least 20,000, at least 22,000, at least 24,000, at least 26,000, at least 28,000, or at least 30,000. The molecular weight (Mn) may be up to 95,000, up to 90,000, up to 85,000, up to 80,000, up to 75,000, up to 70,000, up to 65,000, up to 60,000, up to 55,000, up to 50,000, up to 45,000, up to 40,000 or up to 35,000. . The block copolymer may have a polydispersity (Mw / Mn) in the range of 1.05 to 1.45. In another example, 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 this range, the block copolymer may exhibit suitable self-assembly characteristics. The number average molecular weight of the block copolymer can be adjusted in view of the desired self-assembly structure (ex. Pitch of lamellar pattern, etc.).

The specific method for producing such a block copolymer is not particularly limited, and for example, the block copolymer may be manufactured by applying a known method for producing a block copolymer using a monomer capable of forming each block. can do.

For example, the block copolymer may be manufactured by LRP (Living Radical Polymerization). For example, an anionic polymerization or an organic alkali metal compound synthesized in the presence of an inorganic acid such as an alkali metal or a salt of an alkaline earth metal is polymerized using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator. Anion polymerization method synthesized in the presence of an organoaluminum compound using as an initiator, atom transfer radical polymerization method (ATRP) using an atom transfer radical polymerization agent as a polymerization control agent, an atom transfer radical polymerization agent as a polymerization control agent is used. Activators Regenerated by Electron Transfer (ARRP) Atomic Radical Polymerization (ATRP), Initiators for continuous activator regeneration (ICAR), and Reversible Addition of Inorganic Reductants Reversible addition-cleavage chain transfer using cleavage chain transfer agents And a method using the polymerization method of (RAFT) or an organic tellurium compound, etc. as an initiator, may be subject to a suitable method among these methods is selected.

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

The method of forming the other block included in the copolymer together with the block formed using the monomer in the production of the block copolymer is not particularly limited, and the appropriate monomer is selected in consideration of the type of the desired block. Blocks can be formed.

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

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

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

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

The present application also provides a method of manufacturing a laminate as described above, comprising a first block and a second block chemically distinguished from the first block on the neutral layer formed on a substrate, It relates to a method for producing a laminate comprising the step of forming a polymer film comprising a coalescence. As the block copolymer in the above, the above-described block copolymer may be used.

The method for forming such a polymer film using a 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 liquid diluted in a suitable solvent on the neutral layer by applying, and if necessary, aging or heat-treating the layer.

The aging or heat treatment may be performed based on, for example, the phase transition temperature or the glass transition temperature of the block copolymer, and may be performed, for example, at a temperature above the glass transition temperature or the phase transition temperature. The time for which such heat treatment is performed is not particularly limited, and for example, it may be performed in the range of about 1 minute to 72 hours, but this 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, in another example, be solvent aged for about 1 minute to 72 hours in a nonpolar solvent and / or a polar solvent at room temperature.

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

For example, this approach can form nanoscale patterns of silicon oxide that exhibit high aspect ratios. For example, after forming the polymer film on silicon oxide, and selectively removing any block of the block copolymer in a state in which the block copolymer in the polymer film forms a predetermined structure, the silicon oxide is removed in various ways, for example, By etching with reactive ion etching, various forms including nanorods or nanohole patterns may be realized. In addition, it may be possible to implement a nanopattern with a high aspect ratio through this method.

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

The method of selectively removing any block of the block copolymer in the above method is not particularly limited. For example, a method of removing a relatively soft block by irradiating an appropriate electromagnetic wave, for example, ultraviolet rays, to the polymer membrane may be employed. Can be used In this case, UV irradiation conditions are determined according to the type of the block of the block copolymer, for example, it can be carried out by irradiating ultraviolet rays of about 254 nm wavelength for 1 minute to 60 minutes.

In addition, after the ultraviolet irradiation, the polymer film may be treated with an acid or the like to further remove the segment decomposed by the ultraviolet ray.

In addition, the step of etching the substrate using the polymer film with the selectively removed block as a mask is not particularly limited, and may be performed by, for example, a reactive ion etching step using CF ₄ / Ar ions or the like. Subsequently, the step of removing the polymer film from the substrate by oxygen plasma treatment or the like may also be performed.

The present application can effectively control the orientation of the block copolymer, such as the vertical alignment, and can provide a neutral layer composition capable of forming a neutral layer exhibiting excellent reaction selectivity and high crosslinking degree to the substrate within a short time even by a low temperature process. .

1 to 7 are SEM images of block copolymer films in Examples or Comparative Examples.

Hereinafter, the present application will be described in more detail with reference to Examples and Comparative Examples according to the present application, but the scope of the present application is not limited to the examples given below.

1. NMR measurement

NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer with 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 chemical shifts were expressed in ppm.

<Applicable abbreviation>

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

2.Gel Permeation Chromatograph

The number average molecular weight (Mn) and molecular weight distribution were measured using gel permeation chromatography (GPC). The polymer material to be measured was placed in a 5 mL vial, and diluted with tetrahydrofuran (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 measured. The analysis program used ChemStation of Agilent Technologies, and compared the sample's elution time with the calibration curve to obtain the weight average molecular weight (Mw) and the number average molecular weight (Mn), respectively, and the molecular weight distribution (PDI) as the ratio (Mw / Mn). ) Was calculated. The measurement conditions of GPC are as follows.

<GPC measurement condition>

Instrument: 1200 series by Agilent technologies

Column: Uses 2 PLgel mixed Bs from Polymer laboratories

Solvent: THF

Column temperature: 35 ℃

Sample concentration: 1 mg / mL, 200 L infusion

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

Preparation Example 1 Synthesis of Monomer (A)

The compound of formula A (DPM-C12) was synthesized in the following manner. Into a 250 mL flask, add hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol), dissolve in 100 mL acetonitrile, and remove excess Potassium carbonate was added and reacted at 75 ° C. for about 48 hours under nitrogen conditions. Remaining potassium carbonate after the reaction was filtered off and the acetonitrile used in the reaction was also removed. A mixed solvent of dichloromethane (DCM) and water was added thereto to work up, and the separated organic layers were collected and passed through MgSO ₄ to be dehydrated. Dichloromethane (DCM) was then used in column chromatography to give the title compound (4-dodecyloxyphenol) (9.8 g, 35.2 mmol) as a white solid in a yield of about 37%.

<NMR analysis result>

¹ H-NMR (CDCl ₃ ): δ 6.77 (dd, 4H); δ 4.45 (s, 1 H); δ 3.89 (t, 2H); δ 1.75 (p, 2H); δ 1.43 (p, 2H); δ 1.33-1.26 (m, 16H); δ 0.88 (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) synthesized in the flask (1.7 g) , 13.9 mmol) were 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 produced during the reaction was removed with a filter, and the remaining methylene chloride was also removed. In the column chromatography, hexane and DCM (dichloromethane) were used as a mobile phase to remove impurities, and the obtained product was recrystallized in a mixed solvent of methanol and water (1: 1 mixture) to obtain a target compound (7.7 g, 22.2 mmol) as a white solid. Obtained at a yield of 63%.

<NMR analysis result>

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

[Formula A]

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

Preparation Example 2 Synthesis of Block Copolymer

30 g of Monomer (A) of Preparation Example 1 and 356 mg of cyanoisoprotyldithiobenzoate as a Reversible Addition-Fragmentation Chain Transfer (RAFT) reagent, 24 mg of Azobisisobutyronitrile (AIBN) as a radical initiator and anisole 71 Into a 250 mL round flask (Round flask) was stirred for 1 hour at room temperature under a nitrogen atmosphere and then subjected to RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization reaction at 95 ℃ for 1 hour. After polymerization, the reaction solution was precipitated in methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a pink macroinitiator. The yield of the macroinitiator was about 60% by weight, and the number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were 12,800 and 1.17, respectively.

0.76 g of the macroinitiator, 3.46 g of pentafluorostyrene monomer, and 4.22 g of trifluorotoluene were added to a 10 mL Schlenk flask, stirred at room temperature for 1 hour under nitrogen atmosphere, and then RAFT (Reversible) at 95 ° C. for 20 hours. Addition-Fragmentation chain Transfer) polymerization was carried out. After polymerization, the reaction solution was precipitated in 250 mL of 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 50% by weight, and the number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were 30,500 and 1.20, respectively. The block copolymer comprises a first block (volume fraction of the first block: 0.41) derived from the monomer (A) of Preparation Example 1 and a agent derived from the pentafluorostyrene monomer (volume fraction of the second block: 0.59). Contains 2 blocks.

Preparation Example 3 Synthesis of Random Copolymer (A)

0.992 g of Compound (DPM) of Preparation Example 1, 4.074 g of pentafluorostyrene (PFS), 0.427 g of glycidyl methacrylate (GMA), 0.013 g of methacrylic acid (MAA), and 0.511 g of gamma-Butyrolactone-3-yl methacrylate (GBLMA) ) Was mixed to a molar ratio (DPM: PFS: GMA: MAA: GBLMA) of 9.5: 70: 10: 0.5: 10, and then placed in 6.114 g of THF (tetrahydrofuran) with 0.099 g of AIBN (Azobisisobutyronitrile) as an initiator. After stirring for about 30 minutes, free radical polymerization was performed at 60 ° C. for 12 hours. After polymerization, the reaction solution was precipitated in 250 mL of methanol as an extraction solvent, and then filtered under reduced pressure and dried to prepare a random copolymer. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the random copolymer were 33,700 g / mol and 2.27, respectively.

Preparation Examples 4 to 9. Synthesis of Random Copolymer

Six kinds of random copolymers were further prepared by controlling the reaction conditions such that the number and average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) of the random copolymer and the type and molar ratio of the monomers applied were as shown in Table 1 below. In Table 1 below, the unit of content of each monomer is mol%.

Random copolymer DPM PFS GMA MAA MAP GBLMA Mn PDI My
article
Yes 3 A 9.5 70 10 0.5 10 33.7 2.27 4 B 9.6 70.1 10 0.3 10 36.5 2.02 5 C 9.6 70.3 10 0.1 10 34.3 1.97 6 D 9.5 70 10 0.5 10 51.8 5.52 7 E 9.6 70.1 10 0.3 10 50.7 5.51 8 F 9.6 70.3 10 0.1 10 45.7 5.40 9 G 9.6 70.4 10 10 33.6 2.12 DPM: Compound of Formula A of Preparation Example 1
PFS: pentafluorostyrene
GMA: glycidyl methacrylate
MAA: methacrylic acid
MAP: (methacryloxy) methyl phosphonic acid
GBLMA: gammabutyrolactone-3-yl methacrylate
Mn: number average molecular weight of the random copolymer (unit: kg / mol)
PDI: Molecular Weight Distribution of Random Bodies

Example 1.

The block copolymer of Preparation Example 2 and the random copolymer (A) of Preparation Example 3 were used to form a crosslinked neutral layer and a self-assembled polymer film, respectively, and the results were confirmed. First, a coating solution was prepared by dissolving random copolymer (A) of Preparation Example 3 in a concentration of about 0.2% by weight in fluorobenzene, and coating the prepared coating solution on a silicon wafer with a thickness of about 10 nm by spin coating. After baking at a temperature of about 250 ℃ for about 5 minutes to form a neutral layer. Subsequently, the coating liquid prepared by dissolving the block copolymer of Preparation Example 2 in a concentration of about 1.0% by weight in fluorobenzene was spin-coated to a thickness of about 35 nm on the neutral layer, and thermally aged at about 230 ° C. for 1 hour. thermal annealing to form a film comprising the self-assembled block copolymer. 1 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Example 2.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (B) of Preparation Example 4, and the results were confirmed. 2 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Example 3.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (C) of Preparation Example 5, and the results were confirmed. 3 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Example 4.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (D) of Preparation Example 6, and the results were confirmed. 4 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Example 5.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (E) of Preparation Example 7, and the results were confirmed. 5 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Example 6.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (F) of Preparation Example 8, and the results were confirmed. 6 is a result of the self-assembled block copolymer film, it can be seen from the figure that the self-assembled lamellar structure is effectively formed.

Comparative Example 1.

A self-assembled polymer film was formed in the same manner as in Example 1 except that the crosslinked neutral layers were formed using the random copolymer (G) of Preparation Example 9, and the results were confirmed. 7 is a result of the self-assembled block copolymer film, and it can be seen from the figure that the self-assembled lamellar structure is not properly formed.

Test example.

In order to verify the result of an Example and a comparative example, the crosslinking efficiency of the random copolymer of manufacture examples 3-9 was evaluated as follows.

Each of the random copolymers formed in Preparation Examples 3 to 9 was dissolved in fluorobenzene at a concentration of about 0.2% by weight to prepare a coating solution, and the thickness of the prepared coating solution before washing shown in Table 2 by spin coating on a silicon wafer. After coating to have (T1) it was baked for about 5 minutes at the temperature shown in Table 1 to form a neutral layer.

Thereafter, the formed neutral layer was cleaned by using a solvent (Fluorobenzene) in an ultrasonic washing method, and then summarized and described in Table 2 by comparing the thickness before and after the washing.

In Table 2, the thickness T1 is the thickness of the neutral layer before the solvent washing, the unit is nm, and the thickness T2 is the thickness of the neutral layer after the solvent washing, and the unit is nm.

Low temperature crosslinking (250 ℃ or less) High temperature crosslinking (above 250 ° C) Temperature Duplex (T1) Thickness (T2) Temperature Thickness (T1) Thickness (T2) Random Copolymer (A) 200 ℃ 7.5 nm 7.4 nm 320 ℃ 7.5 nm 7.4 nm Random Copolymer (B) 230 ℃ 8.8 nm 8.4 nm 320 ℃ 8.8 nm 8.5 nm Random Copolymer (C) 250 ℃ 9.2 nm 7.7 nm 320 ℃ 9.2 nm 8.8 nm Random Copolymer (D) 200 ℃ 9.2 nm 8.7 nm 320 ℃ 9.2 nm 9.0 nm Random Copolymer (E) 200 ℃ 7.9 nm 7.4 nm 320 ℃ 7.9 nm 7.7 nm Random Copolymer (F) 200 ℃ 8.6 nm 8.4 nm 320 ℃ 8.6 nm 8.4 nm Random Copolymer (G) 200 ℃ 9.3 nm 4.9 nm 320 ℃ 9.3 nm 5.5 nm

The random copolymers of Preparation Examples 3 to 8 from Table 2 can be confirmed that the thickness is almost constant before and after the solvent wash by implementing a sufficient degree of crosslinking even by a short baking at low temperature (250 ℃ or less). .

Therefore, it can be seen that the formation efficiency of the vertically oriented structure varies in Examples and Comparative Examples according to the degree of crosslinking of the neutral layer formed through the above contents.

Claims (14)

A unit represented by the following formula (1); A unit represented by the following formula (2); Crosslinkable functional group-containing unit; And a random copolymer having a unit including an aromatic group containing a halogen atom, wherein the neutral layer composition comprises:
[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 (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, Z is a hydrocarbon chain of 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 (= 0) -L _1- , -C (= 0) -O-, -C (= 0) -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 group having 1 to 4 carbon atoms to be. The neutral layer composition of claim 1, wherein X in Formula 1 is an oxygen atom, a carbonyl group, —C (═O) —O—, or —O—C (═O) —. The neutral layer composition of claim 1, wherein the random copolymer comprises a unit represented by the formula (1) in a proportion of 32 mol% or less. The neutral layer composition of claim 1, wherein the random copolymer comprises a unit represented by Formula 2 in a ratio of 0.01 to 20 mol%. The neutral layer composition of claim 1, wherein the crosslinkable functional group-containing unit is represented by the following Formula 3:
[Formula 3]

In formula (3), R ₃ is hydrogen or an alkyl group, T is a divalent hydrocarbon group with or without a single bond or hetero atom. The neutral layer composition of Claim 1 in which a random copolymer contains a crosslinkable functional group containing unit in the ratio of 0.01-30 mol%. The neutral layer composition of claim 1, wherein the unit including an aromatic group containing a halogen atom is represented by the following Chemical Formula 4:
[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 including three or more halogen atoms. The neutral layer composition of Claim 1 in which a random copolymer contains the unit containing the aromatic group containing a halogen atom in the ratio of 40 mol% or more. A unit represented by the following formula (1); A unit represented by the following formula (2); Crosslinkable functional group-containing unit; And a neutral copolymer comprising a random copolymer having a unit comprising an aromatic group containing a halogen atom:
[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 (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, Z is a hydrocarbon chain of 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 (= 0) -L _1- , -C (= 0) -O-, -C (= 0) -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 group having 1 to 4 carbon atoms to be. A method of forming a neutral layer, comprising coating the neutral layer composition of claim 1 onto a substrate and fixing the layer of the coated neutral layer composition. Board; A neutral layer of claim 9 formed on said 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 distinguished from the first block. The laminate according to claim 11, wherein the first block of the block copolymer comprises a repeating unit which is a unit of Formula 7, and the second block comprises a repeating unit which is a unit of 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 (= 0) _2- , a carbonyl group, -C (= 0) -O- or -OC (= 0 ), P is an arylene group having 6 to 18 carbon atoms, Q is a single bond, oxygen atom, sulfur atom, -S (= O) _2- , carbonyl group, -C (= O) -O- or -OC (= O)-, 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 including three or more halogen atoms. A laminate comprising: forming a polymer film on a neutral layer formed on a substrate, the polymer film comprising a block copolymer having a first block and a second block chemically distinct from the first block, in a self-assembled state. Method of preparation. 14. A method of forming a pattern comprising the step of selectively removing the first or second block of the block copolymer from the polymer film of the laminate of claim 13.

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