Method for producing structural body including phase-separated structure, and composition

Abstract

To provide, e.g., a method for producing a structural body including a phase-separated structure, in which an undercoat agent layer and a self-organization layer are formed using the same composition containing a block copolymer.SOLUTION: A method for producing a structural body including a phase-separated structure includes (i) applying a composition containing a block copolymer represented by Formula (n1) onto a substrate so as to form an undercoat agent layer, (ii) applying the composition containing the block copolymer onto the undercoat agent layer so as to form a self-organization layer, and (iii) subjecting the self-organization layer to phase separation. In the formula: A represents a first polymer block; B represents a second polymer block; R1c and R1d each represent a substrate adsorptive group-containing group; R2c and R2d each represent a substituent other than the substrate adsorptive group-containing group; m1 and n1 each represent an integer from 0 to 5; m2 and n2 each represent an integer from 0 to 5; m1+n1≥1; m1+m2≤5; and n1+n2≤5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a structure containing a phase-separated structure, and a composition. [Background technology]

[0002] In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), there is a demand for technology to process even finer structures. In response to this demand, technology is being developed to form even finer structures by utilizing phase-separated structures formed by the self-organization of block copolymers, in which mutually incompatible blocks are bonded. In order to utilize the phase separation structure of a block copolymer, it is essential to form the self-organized nanostructure formed by microphase separation only in a specific region and to align it in a desired direction. To achieve this position control and orientation control, processes such as graphoepitaxy, which controls the phase separation pattern by a guide pattern, and chemical epitaxy, which controls the phase separation pattern by differences in the chemical state of the substrate, have been proposed (see, for example, Non-Patent Document 1).

[0003] As a method for forming a fine pattern by phase separation of a block copolymer, for example, a method of forming a base layer on a substrate is disclosed. For example, Patent Document 1 discloses a base containing a constitutional unit derived from styrene and a constitutional unit derived from hydroxyethyl acrylate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6475963 [Non-patent literature]

[0005] [Non-Patent Document 1] Proceedings of SPIE, Vol. 7637, No. 76370G-1 (2010). Summary of the Invention [Problem to be solved by the invention]

[0006] In the method described in Patent Document 1, compositions containing different block copolymers are used for the undercoat agent and the resin composition for forming a phase-separated structure. If the same composition can be used for the undercoat agent and the resin composition for forming a phase-separated structure, the effort of changing the composition can be eliminated. In addition, since the undercoat agent layer and the self-organized layer can be formed with a single composition, raw material management is also easy.

[0007] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a method for producing a structure including a phase-separated structure, in which a primer layer and a self-organized layer are formed using a composition containing the same block copolymer, and a composition containing a block copolymer for use in the method. [Means for solving the problem]

[0008] That is, a first aspect of the present invention is a method for producing a structure containing a phase-separated structure, comprising: a step (i) of applying a composition containing a block copolymer represented by the following general formula (n1) onto a substrate to form a primer layer; a step (ii) of applying a composition containing the block copolymer onto the primer layer to form a self-assembled layer; and a step (iii) of phase-separating the self-assembled layer.

[0009] [ka] wherein A represents a first polymer block; B represents a second polymer block; R 1c and R 1d each independently represents a substrate adsorptive group-containing group; R 2c and R 2deach independently represents a substituent other than the substrate adsorptive group-containing group; m1 and n1 each independently represent an integer of 0 to 5; m2 and n2 each independently represent an integer of 0 to 5; m1+n1≧1; m1+m2≦5; and n1+n2≦5. When m1 is an integer of 2 or more, a plurality of R 1c may be the same or different; when m2 is an integer of 2 or more, a plurality of R 2c may be the same or different; when n1 is an integer of 2 or more, multiple R 1d may be the same or different; when n2 is an integer of 2 or more, a plurality of R 2d may be the same as or different from each other.

[0010] A second aspect of the present invention is a composition containing the block copolymer represented by the general formula (n1), which is used in the method for producing a structure containing a phase-separated structure according to the first aspect. Effect of the Invention

[0011] According to the present invention, it is possible to provide a method for producing a structure including a phase-separated structure, in which a base agent layer and a self-assembled layer are formed using a composition containing the same block copolymer, and a composition containing a block copolymer for use in the method. [Brief description of the drawings]

[0012] [Figure 1] 1A to 1C are schematic process diagrams illustrating an embodiment of a method for producing a structure including a phase-separated structure. [Diagram 2] FIG. 13 is a diagram illustrating an embodiment of an optional step. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In this specification and claims, the term "aliphatic" is a relative concept to aromaticity and is defined as meaning a group, compound, etc. that does not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The term "halogenated alkyl group" refers to an alkyl group in which some or all of the hydrogen atoms have been substituted with halogen atoms, and examples of the halogen atoms include fluorine, chlorine, bromine and iodine atoms. The term "fluorinated alkyl group" or "fluorinated alkylene group" refers to an alkyl group or alkylene group in which some or all of the hydrogen atoms have been substituted with fluorine atoms. The term "structural unit" refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer). The phrase "optionally has a substituent" includes both the case where a hydrogen atom (-H) is replaced with a monovalent group and the case where a methylene group (-CH2-) is replaced with a divalent group. The term "exposure" is intended to include any concept including irradiation with radiation. Unless otherwise specified, the "α-position (carbon atom at the α-position)" refers to the carbon atom to which the side chain of the block copolymer is bonded. The "α-position carbon atom" of a methyl methacrylate unit refers to the carbon atom to which the carbonyl group of methacrylic acid is bonded. The "α-position carbon atom" of a styrene unit refers to the carbon atom to which a benzene ring is bonded. "Number average molecular weight" (Mn) is the number average molecular weight measured by size exclusion chromatography in terms of standard polystyrene unless otherwise specified. "Weight average molecular weight" (Mw) is the weight average molecular weight measured by size exclusion chromatography in terms of standard polystyrene unless otherwise specified. The value of Mn or Mw is expressed in units (gmol - ) indicates the molar mass. In the present specification and claims, some structures represented by chemical formulas may have asymmetric carbons and may have enantiomers or diastereomers, in which case a single formula represents all the isomers. These isomers may be used alone or as a mixture.

[0014] (Method of manufacturing a structure containing a phase-separated structure) A method for producing a structure including a phase-separated structure according to a first aspect of the present invention includes the steps of: applying a composition containing a block copolymer represented by the following general formula (n1) onto a substrate to form a primer layer; applying a composition containing the block copolymer onto the primer layer to form a self-assembled layer; and phase-separating the self-assembled layer.

[0015] <Composition containing block copolymer: BCP composition> In the production method of this embodiment, the same composition containing a block copolymer (hereinafter also referred to as "BCP composition") is used in step (i) and step (ii).

[0016] <Block copolymer (P1)> The composition containing a block copolymer contains a block copolymer represented by the following general formula (n1) (hereinafter also referred to as "block copolymer (P1)").

[0017] [ka] wherein A represents a first polymer block; B represents a second polymer block; R 1c and R 1d each independently represents a substrate adsorptive group-containing group; R 2c and R 2deach independently represents a substituent other than the substrate adsorptive group-containing group; m1 and n1 each independently represent an integer of 0 to 5; m2 and n2 each independently represent an integer of 0 to 5; m1+n1≧1; m1+m2≦5; and n1+n2≦5. When m1 is an integer of 2 or more, a plurality of R 1c may be the same or different; when m2 is an integer of 2 or more, a plurality of R 2c may be the same or different; when n1 is an integer of 2 or more, multiple R 1d may be the same or different; when n2 is an integer of 2 or more, a plurality of R 2d may be the same as or different from each other.

[0018] In the formula (n1), R 1c and R 1d The substrate adsorptive group-containing group in is a group containing a substrate adsorptive group. The substrate adsorptive group-containing group may be composed only of substrate adsorptive groups, or may contain groups other than the substrate adsorptive group. The substrate adsorptive group-containing group is preferably a substrate adsorptive group or an organic group containing a substrate adsorptive group. The substrate adsorbing group can be appropriately selected depending on the type of substrate.Specific examples of the substrate adsorbing group include, for example, a hydroxyl group, a carboxyl group, a thiol group, a vinyl group, a bromine atom, an iodine atom, an amino group, an azide group, a formyl group, an epoxy group, and a cyano group.The substrate adsorbing group is preferably a hydroxyl group, a carboxyl group, a thiol group, a vinyl group, a bromine atom, an iodine atom, or a cyano group, and more preferably a hydroxyl group. R 1c and R 1d The substrate adsorptive group-containing group in may contain only one substrate adsorptive group, or may contain two or more substrate adsorptive groups. When the substrate adsorptive group-containing group has two or more substrate adsorptive groups, the substrate adsorptive groups may be of one type, or of two or more types. 1c and R 1d The number of substrate adsorptive groups contained in the substrate adsorptive group-containing group in R is preferably 1 to 3, and more preferably 1 or 2. 1c and R 1dThe number of types of substrate adsorptive groups contained in the substrate adsorptive group-containing group in is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 type.

[0019] R in the above formula (n1) 1c and R 1d is preferably a group represented by the following general formula (r1).

[0020] [ka] [where, X 1 represents a single bond, a methylene group, -COO- or -O-; Y 1 represents a single bond or a divalent linking group; Z 1 represents a group containing a substrate adsorptive group; r1 represents an integer of 1 or more as far as the atomic valence allows. 1 When Y is -COO- or -O-, 1 cannot be a single bond. * represents a bond bonded to the benzene ring in general formula (n1).

[0021] In the formula (r1), Y 1 The divalent linking group in the above formula (I) includes a hydrocarbon group which may have a substituent, or a divalent linking group which contains a hetero atom.

[0022] Optionally substituted divalent hydrocarbon group: The divalent hydrocarbon group which may have a substituent may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0023] Aliphatic hydrocarbon groups The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.

[0024] Linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0025] The linear or branched aliphatic hydrocarbon group may or may not have a substituent. The substituent may be a monovalent substituent substituting a hydrogen atom in the aliphatic hydrocarbon chain, or a divalent substituent substituting a methylene group in the aliphatic hydrocarbon chain.

[0026] Aliphatic hydrocarbon groups containing rings in the structure Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclo[5.2.1.0] 2,6 ]decane, tetracyclododecane, and the like.

[0027] The cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a fluorine atom, a fluorinated alkyl group, a hydroxyl group, a carbonyl group, etc. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and further preferably a methoxy group or an ethoxy group. Examples of the fluorinated alkyl group as the substituent include the alkyl group in which some or all of the hydrogen atoms have been substituted with the fluorine atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0028] Aromatic hydrocarbon groups The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1 carbon atom.

[0029] The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a fluorine atom, a fluorinated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, fluorine atom and fluorinated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom in the cyclic aliphatic hydrocarbon group.

[0030] Divalent linking groups containing heteroatoms: Examples of the divalent linking group containing a hetero atom include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, an acyl group, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same as those described above. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. Y 22is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0031] Y 1 As the alkylene group, a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof is preferred, a single bond, a linear or branched alkylene group, or a combination of an ester bond [-C(=O)-O-, -OC(=O)-] or an ether bond (-O-) and a linear or branched alkylene group is more preferred, and a linear or branched alkylene group or a combination of an ether bond and an alkylene group is even more preferred. As a group which is a combination of an ether bond and an alkylene group, -[(CH2) k1 -O-] k2 -(k1 and k2 are integers of 1 to 6). The alkylene group may have 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The k1 is preferably 2 or 3, and more preferably 2. The k2 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0032] In the formula (r1), Z 1 Specific examples of the substrate adsorptive group contained in the substrate adsorptive group-containing group in Z include the same as those mentioned above. As the substrate adsorptive group, a hydroxy group, a carboxy group, a thiol group, a vinyl group, a bromine atom, an iodine atom, or a cyano group is preferable, and a hydroxy group is more preferable. 1 The substrate adsorptive group-containing group in is preferably a substrate adsorptive group or a linear or branched alkylene group in which one or more hydrogen atoms have been substituted with a substrate adsorptive group. The linear alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. The branched alkylene group preferably has 2 to 5 carbon atoms, more preferably 2 to 3 carbon atoms, and even more preferably 2 carbon atoms. Z 1 The substrate-adsorbing group-containing group preferably has 1 to 3 substrate-adsorbing groups, and more preferably 1 or 2 substrate-adsorbing groups.

[0033] In the formula (r1), r1 is preferably 1 to 3, more preferably 1 or 2, and further preferably 1.

[0034] R in the above formula (n1) 1c and R 1d is preferably a group represented by the following general formula (r1-1) or (r1-2).

[0035] [ka] [where, X 11 and X 12 each independently represents a single bond, a methylene group, -COO- or -O-; Y 11 and Y 12 each independently represents a single bond or a divalent linking group; Z11 ~Z 13 Each independently represents a substrate adsorptive group. 11 When Y is -COO- or -O-, 11 cannot be a single bond, X 12 When Y is -COO- or -O-, 12 does not become a single bond. * represents a bond bonded to the benzene ring in the general formula (n1).

[0036] In the formula (r1-1) or (r1-2), Y 11 and Y 12 As the divalent linking group, Y in the formula (r1) 1 The same can be mentioned. Y 11 and Y 12 The divalent linking group in is preferably a linear aliphatic hydrocarbon group which may have a substituent, and more preferably a linear alkylene group which may have a substituent. The substituent includes a divalent group substituting a methylene group, and the divalent group includes an ester bond or an ether bond, and an ether bond is preferred. Y 11 and Y 12 The divalent linking group in is a linear alkylene group having 1 to 10 carbon atoms, or -[(CH2) k1 -O-] k2 -(CH2) k3 A group represented by - (k1, k2, and k3 are integers of 1 to 6) is preferred. The alkylene group preferably has 1 to 8 carbon atoms, and more preferably has 1 to 6 carbon atoms. The k1 is preferably 2 or 3, and more preferably 2. The k2 is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3, and even more preferably 1 or 2. The k3 is preferably 2 or 3, and more preferably 2.

[0037] In the formula (r1-1) or (r1-2), Z 11 ~Z 13 In the above, examples of the substrate adsorptive group include the same as those mentioned above. As the substrate adsorptive group, a hydroxy group, a carboxy group, a thiol group, a vinyl group, a bromine atom, an iodine atom, or a cyano group is preferable, and a hydroxy group is more preferable.

[0038] R in the above formula (n1) 1c and R 1d Specific examples of are shown below, but are not limited to these: * represents a bond bonded to the benzene ring in the above formula (n1).

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] In the formula (n1), R 2c and R 2d The substituent other than the substrate adsorptive group-containing group in is not particularly limited. An example of the substituent other than the substrate adsorptive group-containing group is an alkyl group. The alkyl group may be linear or branched, but is preferably linear. The linear alkyl group may have 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. The branched alkyl group may have 3 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.

[0043] In the formula (n1), m1 and n1 are each independently preferably an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, and particularly preferably 0 or 1, provided that m1+n1≧1. Preferably, both m1 and n1 are 1, m1 is 1 and n1 is 0, or m1 is 0 and n1 is 1.

[0044] In the formula (n1), m2 and n2 each independently represent preferably an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, and particularly preferably 0 or 1.

[0045] The block copolymer (P1) is preferably a block copolymer represented by the following general formula (n1-1) or (n1-2).

[0046] [ka] [Wherein, A represents a first polymer block; B represents a second polymer block. R 11c and R 11d each independently represents a hydrogen atom or a group represented by the following general formula (r11), R 11c and R 11d Both R and R cannot be hydrogen atoms. 12c , R 13c , R 12d , and R 13d each independently represents a hydrogen atom or a group represented by the following general formula (r12), R 12c , R 13c , R 12d , and R 13d Not all of the atoms are hydrogen atoms. 21c , R 21d , R 22c , and R 22d each independently represents a substituent other than the substrate adsorptive group-containing group. m21 and n21 each independently represent an integer of 0 to 4. m22 and n22 each independently represent an integer of 0 to 3. When m21 is an integer of 2 or more, a plurality of R 21c may be the same or different. When n21 is an integer of 2 or more, 21d may be the same or different. When m22 is an integer of 2 or more, 22c may be the same or different. When n22 is an integer of 2 or more, 22d may be the same as or different from each other.

[0047] [ka] [In the formula, L 11 represents a single bond, -COO- or -O-; Rz 11 represents a group containing a substrate adsorptive group; Rz 12 represents a group containing a substrate adsorptive group or a hydrogen atom.

[0048] In the formula (n1-1), R 21c and R 21d In the formula (n1), the substituent other than the substrate adsorptive group-containing group is R 2c and R 2d Examples of the above-mentioned compounds include those described in the above. 21c and R 21d The substituent in may be a linear or branched alkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms, and even more preferably having 1 or 2 carbon atoms.

[0049] In the formula (n1-1), m21 and n21 are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0050] In the formula (n1-2), R 22c and R 22d In the formula (n1), the substituent other than the substrate adsorptive group-containing group is R 2c and R 2d Examples of the above-mentioned compounds include those described in the above. 22c and R 22d The substituent in may be a linear or branched alkyl group, preferably having 1 to 6 carbon atoms, more preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms, and even more preferably having 1 or 2 carbon atoms.

[0051] In the formula (n1-2), m22 and n22 are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 0.

[0052] In the formula (n1-1), R11c and R 11d each independently represents a hydrogen atom or a group represented by general formula (r11). In the formula (n1-2), R 12c , R 13c , R 12d , and R 13d each independently represents a hydrogen atom or a group represented by general formula (r12).

[0053] Rz in the formulas (r11) and (r12) 11 and Rz 12 As the substrate adsorptive group-containing group in the formula (n1), 1c and R 1d Examples of the above-mentioned compounds include those described in the above. Rz 11 and Rz 12 is preferably represented by the following general formula (r1-1-1) or (r1-2-1).

[0054] [ka] [In the formula, Y 111 and Y 112 each independently represents a single bond or a divalent linking group; Z 111 ~Z 113 each independently represents a substrate adsorptive group. 11 When Y is -COO- or -O-, 111 cannot be a single bond. * represents a bond.

[0055] In the above formula (r1-1-1) or (r1-2-1), Y 111 and Y 112 As the divalent linking group in the formula (r1-1) or (r1-2), Y 11 and Y 12 The divalent linking group in Y 111 and Y 112 The divalent linking group in is a linear alkylene group having 1 to 10 carbon atoms, or -[(CH2) k1 -O-] k2-(CH2) k3 A group represented by - (k1, k2, and k3 are integers of 1 to 6) is preferred. The alkylene group preferably has 1 to 8 carbon atoms, and more preferably has 1 to 6 carbon atoms. The k1 is preferably 2 or 3, and more preferably 2. The k2 is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3, and even more preferably 1 or 2. The k3 is preferably 2 or 3, and more preferably 2.

[0056] In the formula (r1-1-1) or (r1-2-1), Z 111 ~Z 113 In the above, examples of the substrate adsorptive group include the same as those mentioned above. As the substrate adsorptive group, a hydroxy group, a carboxy group, a thiol group, a vinyl group, a bromine atom, an iodine atom, or a cyano group is preferable, and a hydroxy group is more preferable.

[0057] R in the above formula (n1-1) 11c and R 11d Specific examples of the above include groups represented by any of the formulas (r11-1-1) to (r11-1-8) and (r11-2-1) to (r11-2-3). R in the above formula (n1-2) 21c , R 21d , R 22c , and R 22d Specific examples of the group include groups represented by any one of the above formulas (r12-1-1) to (r12-1-3) and (r12-2-1).

[0058] Specific examples of the block copolymer (P1) include, but are not limited to, the following: In the following formula, A and B are the same as those in the above formula (n1).

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] <First polymer block (A)> In the formula (n1), the first polymer block in A (hereinafter also referred to as "first polymer block (A)") is preferably a hydrophobic polymer block (hereinafter also referred to as "block (b12)").

[0066] The hydrophobic polymer block (b12) is a block composed of a polymer (hydrophobic polymer) formed by polymerization of a monomer that has a relatively low affinity for water compared to the monomers that provide the structural units of the other polymer blocks that make up the block copolymer.

[0067] The block (b12) preferably has a hydrophobic structural unit (Na). Examples of the structural unit (Na) include a block in which structural units derived from styrene or a styrene derivative are repeatedly bonded. Examples of the styrene derivative include those in which the hydrogen atom at the α-position of styrene is substituted with a substituent such as an alkyl group or a halogenated alkyl group, or derivatives thereof. Examples of these derivatives include those in which a substituent is bonded to the benzene ring of styrene in which the hydrogen atom at the α-position may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. Specific examples of styrene derivatives include α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, and 4-vinylbenzyl chloride.

[0068] As the structural unit (Na), a structural unit derived from styrene or a styrene derivative is preferred because it is easier to stabilize the surface of the primer layer, i.e., a structural unit (u1) containing a styrene skeleton which may have a substituent is more preferred.

[0069] About the constituent unit (u1) The structural unit (u1) is a structural unit that includes a styrene skeleton which may have a substituent. The styrene skeleton having a substituent refers to one in which some or all of the hydrogen atoms at the α-position of styrene or on the benzene ring are substituted with a substituent. Examples of the substituent in the structural unit (u1) include a halogen atom, or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms or a combination thereof which may contain an oxygen atom, a halogen atom or a silicon atom.

[0070] With regard to the substituent in the structural unit (u1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom, a chlorine atom and a bromine atom being preferred, and a fluorine atom being more preferred.

[0071] With regard to the substituent in the structural unit (u1), the hydrocarbon group has a carbon atom number of 1 to 20. In addition, such a hydrocarbon group is a linear, branched or cyclic hydrocarbon group or a combination thereof, and may contain an oxygen atom, a halogen atom or a silicon atom. Such hydrocarbon groups include, for example, linear, branched or cyclic alkyl groups, or aryl groups.

[0072] The alkyl group as such a hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms. The alkyl group here may be a partially or completely halogenated alkyl group (halogenated alkyl group), an alkylsilyl group in which a carbon atom constituting the alkyl group is substituted with a silicon atom or an oxygen atom, an alkylsilyloxy group, or an alkoxy group. The partially halogenated alkyl group means an alkyl group in which some of the hydrogen atoms bonded to the alkyl group are replaced with halogen atoms, and the completely halogenated alkyl group means an alkyl group in which all of the hydrogen atoms bonded to the alkyl group are replaced with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and the fluorine atom is more preferred (i.e., a fluorinated alkyl group is preferred). The alkylsilyl group is preferably a trialkylsilyl group or a trialkylsilylalkyl group, and suitable examples thereof include a trimethylsilyl group, a trimethylsilylmethyl group, a trimethylsilylethyl group, and a trimethylsilyl-n-propyl group. The alkylsilyloxy group is preferably a trialkylsilyloxy group or a trialkylsilyloxyalkyl group, and suitable examples thereof include a trimethylsilyloxy group, a trimethylsilyloxymethyl group, a trimethylsilyloxyethyl group, and a trimethylsilyloxy-n-propyl group. The alkoxy group preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and further preferably has 1 to 6 carbon atoms.

[0073] The aryl group as such a hydrocarbon group has 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

[0074] Preferred examples of the structural unit (u1) include structural units represented by the following general formula (u1-1) or (u1-2): In the present invention, the structural unit (u1) is preferably a structural unit represented by the following general formula (u1-1).

[0075] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 1 is a fluorine atom, or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms or a combination thereof which may contain an oxygen atom, a fluorine atom or a silicon atom. p is an integer of 0 to 5. n1 is 0 or 1. R 12 represents an aromatic hydrocarbon ring which may have a substituent, and p1 is an integer of 1 to 5.]

[0076] In the above formula (u1-1) or (u1-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The fluorinated alkyl group having 1 to 5 carbon atoms for R is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0077] In the formula (u1-1) or (u1-2), R 1 is a fluorine atom, or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms or a combination thereof which may contain an oxygen atom, a fluorine atom or a silicon atom. In the structural unit (u1), the benzene ring has the above-mentioned R 1 By bonding, the free energy of the surface of the undercoat layer is adjusted, and the layer containing the block copolymer formed on the undercoat layer can be well phase-separated into a vertical cylinder pattern or the like. R in the formula (u1-1) or (u1-2) 1 is the same as the explanation for the substituent in the structural unit (u1) described above (a fluorine atom, or a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms or a combination thereof which may contain an oxygen atom, a fluorine atom or a silicon atom). Among these, R 1 As the hydrocarbon group, a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms or a combination thereof which may contain an oxygen atom, a fluorine atom or a silicon atom is preferred, because the layer containing the block copolymer formed on the undercoat agent layer can be well phase-separated. Among these, an alkyl group having 1 to 20 carbon atoms which may contain an oxygen atom or a fluorine atom is more preferable. More preferably, the alkyl group has 1 to 6 carbon atoms, a fluorinated alkyl group has 1 to 6 carbon atoms, or an alkoxy group has 1 to 6 carbon atoms. An alkyl group having 1 to 6 carbon atoms is particularly preferred.

[0078] R 1 The number of carbon atoms in the alkyl group in R is preferably 1 to 6, more preferably 3 to 6, further preferably 3 or 4, and particularly preferably 4. 1 The alkyl group in is preferably a linear alkyl group or a branched alkyl group. Suitable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. An n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group are more preferred, an n-butyl group, an isobutyl group, and a tert-butyl group are even more preferred, and a tert-butyl group is particularly preferred. R 1 The fluorinated alkyl group in R 1 R 1 The fluorinated alkyl group in the formula (I) preferably has 1 to 6 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms. R 1 The number of carbon atoms in the alkoxy group in R is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 2. 1 The alkoxy group in is preferably a straight-chain alkoxy group or a branched-chain alkoxy group. Suitable examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a t-butoxy group, and an ethoxy group is particularly preferred.

[0079] In the formula (u1-1) or (u1-2), p is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, further preferably 0 or 1, and particularly preferably 1. In the above formula (u1-2), p1 is 0 or 1, and 0 is preferable.

[0080] In the above formula (u1-2), R 12 R is an aromatic hydrocarbon ring which may have a substituent. 12 Examples of the aromatic hydrocarbon ring of R include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene. 12 Examples of the substituent that may be contained in the alkyl group include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a trialkylsilyl group, and an alkoxysilyl group. In the above formula (u1-2), p1 is an integer of 1 to 5.

[0081] Specific examples of the structural unit of the block (b12) are given below. α is a hydrogen atom or a methyl group.

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] The structural unit of the block (b12) may be used alone or in combination of two or more types. The block (b12) preferably contains the structural unit (u1) as the structural unit (Na). The structural unit (u1) is preferably at least one selected from the group consisting of structural units represented by the chemical formulas (u1-1-1) to (u1-1-22), more preferably at least one selected from the group consisting of structural units represented by the chemical formulas (u1-1-1) to (u1-1-14), even more preferably at least one selected from the group consisting of structural units represented by the chemical formulas (u1-1-1) to (u1-1-11), particularly preferably at least one selected from the group consisting of structural units represented by the chemical formulas (u1-1-1) to (u1-1-6) and (u1-1-11), and most preferably at least one selected from the group consisting of structural units represented by the chemical formulas (u1-1-1) to (u1-1-3) and (u1-1-11).

[0091] The proportion of the structural unit (u1) in the block (b12) is preferably at least 25 mol %, more preferably at least 50 mol %, and even more preferably from 75 to 100 mol %, based on the total of all structural units constituting the block (b12). When the proportion of the structural unit (u1) in the block (b12) is at least the preferred lower limit, the surface of the primer layer becomes more stable, and the layer containing the block copolymer formed on the primer layer can be well phase-separated.

[0092] <Second Polymer Block (B)> In the formula (n1), the second polymer block in B (hereinafter also referred to as "second polymer block (B)") is preferably a hydrophilic polymer block (hereinafter also referred to as "block (b22)"). The hydrophilic polymer block (b22) is a block composed of a polymer (hydrophilic polymer) formed by polymerization of a monomer that has a relatively high affinity for water compared to the monomers that provide the structural units of the other polymer blocks that make up the block copolymer.

[0093] The block (b22) preferably has a hydrophilic structural unit (Nb). Examples of the structural unit (Nb) include a block in which structural units derived from an (α-substituted) acrylic acid ester are repeatedly bonded, and a block in which structural units derived from an (α-substituted) acrylic acid are repeatedly bonded.

[0094] Examples of the (α-substituted) acrylic ester include acrylic esters and acrylic esters in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. Specific examples of the (α-substituted) acrylic acid ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, octyl acrylate, nonyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, benzyl acrylate, anthracene acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethane acrylate, and propyltrimethoxysilane acrylate; and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, benzyl methacrylate, anthracene methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethane methacrylate, and propyltrimethoxysilane methacrylate.

[0095] Examples of the (α-substituted) acrylic acid include acrylic acid and acrylic acid in which the hydrogen atom bonded to the carbon atom at the α-position is substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. Specific examples of the (α-substituted) acrylic acid include acrylic acid and methacrylic acid.

[0096] As the structural unit (Nb), a structural unit derived from an (α-substituted) acrylic acid ester or a structural unit derived from (α-substituted) acrylic acid (i.e., a structural unit (u2) derived from acrylic acid or an ester thereof in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent) is preferred, since this makes it easier to stabilize the surface of the primer layer.

[0097] About the structural unit (u2) The structural unit (u2) is a structural unit derived from acrylic acid or an ester thereof in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. A preferred example of the structural unit (u2) is a structural unit represented by the following general formula (u2-1).

[0098] [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 2 is a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. 2 does not have a substrate-adsorptive group.

[0099] In the formula (u2-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. R in the formula (u2-1) is the same as R in the above formula (u1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0100] In the above formula (u2-1), R 2 is a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. 2 does not have a substrate adsorptive group as a substituent. R 2 The alkyl group in the formula (I) has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. R 2 The alkyl group in may be linear or branched. R 2 The alkyl group in is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0101] The structural unit (u2) may be a structural unit represented by the following general formula (u2-2). [ka] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. 4 is a hydrogen atom or a hydroxyl group. 1 and k 2 R is each independently an integer of 1 to 5. 2 is an alkyl group which may have a silicon atom or a fluorine atom.

[0102] In the formula (u2-2), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. R in the formula (u2-2) is the same as R in the above formula (u1-1). R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0103] In the above formula (u2-2), R 2is an alkyl group which may have a silicon atom or a fluorine atom. The alkyl group is preferably a linear or branched alkyl group, more preferably a linear alkyl group. When the alkyl group is linear, the number of carbon atoms may be 1 or more, but preferably 2 or more. The upper limit of the number of carbon atoms of the linear alkylene group is not particularly limited, but from the viewpoint of phase separation performance, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. When the alkyl group is branched, the number of carbon atoms may be 3 or more. The upper limit of the number of carbon atoms of the branched alkyl group is not particularly limited, but from the viewpoint of phase separation performance, the number of carbon atoms is preferably 15 or less, more preferably 10 or less, even more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. The alkyl group preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, even more preferably 2 to 8 carbon atoms, still more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 5 carbon atoms. R 2 The alkyl group is preferably a linear alkyl group having 2 to 5 carbon atoms.

[0104] R 2 The alkyl group of R may have a silicon atom or a fluorine atom. 2 When the alkyl group has a fluorine atom or a carboxy group, the fluorine atom or the carboxy group may be a substituent that replaces a hydrogen atom of the alkyl group. The number of hydrogen atoms replaced by the group is not particularly limited, but is preferably 1 to 3. R 2 When the alkyl group has a silicon atom, the silicon atom may be a substituent that replaces a methylene group (-CH2-) in the alkyl group. The number of methylene groups substituted with silicon atoms is not particularly limited, but is preferably 1. R 2is preferably an alkylsilyl group or an alkyl group which may be substituted with a fluoromethyl group. The alkyl group in the alkylsilyl group preferably has 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms. The alkylsilyl group is preferably a trialkylsilyl group, more preferably a triethylsilyl group or a trimethylsilyl group, and even more preferably a trimethylsilyl group. The fluoromethyl group is preferably a trifluoromethyl group.

[0105] In the formula (u2-2), k1 and k2 are preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

[0106] Specific examples of the structural unit of the block (b22) are given below. α is a hydrogen atom or a methyl group.

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] The structural unit of the block (b22) may be used alone or in combination of two or more types. The structural unit (Nb) preferably contains the structural unit (u2). The structural unit (u2) is preferably at least one type selected from the group consisting of structural units represented by chemical formulas (u2-1-1) to (u1-1-7).

[0111] The proportion of the structural unit (u2) in block (b22) is preferably at least 25 mol %, more preferably at least 50 mol %, and even more preferably from 75 to 100 mol %, based on the total of all structural units constituting block (b22). When the proportion of the structural unit (u2) in the block (b22) is at least the preferred lower limit, the surface of the primer layer becomes more stable, and the layer containing the block copolymer formed on the primer layer can be well phase-separated.

[0112] The first polymer block (A) and the second polymer block (B) preferably do not have a substrate adsorptive group bonded to a primary carbon atom. It is preferable that the first polymer block (A) and the second polymer block (B) do not have a structural unit (u0) represented by any of the following general formulas (u0-1) to (u0-4).

[0113] [ka] [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms; 1 , Yu 2 , Yu 3 and Yu 4 each independently represents a divalent linking group; 1 , Zu 21 , Zu 22 , Zu 31 , Zu 32 , Zu 33 and Zu 4 each independently represents a substrate adsorptive group; Wu 4 represents a cyclic group; and nu represents an integer equal to or greater than 1, as far as valence permits.

[0114] In the above formulas (u0-1) to (u0-4), Yu 1 , Yu 2 , Yu 3 and Yu 4 The divalent linking group in the formula (r1) is 1 The divalent linking group in the formula (I) is the same as that in the formula (I).1 , Yu 2 , Yu 3 and Yu 4 The divalent linking group in the formula (I) includes a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. In the formulae (u0-1) to (u0-4), Z 1 , Zu 21 , Zu 22 , Zu 31 , Zu 32 , Zu 33 and Zu 4 Examples of the substrate-adsorbing group in Zu include a hydroxy group, a carboxy group, a thiol group, a vinyl group, a bromine atom, an iodine atom, an amino group, an azide group, a formyl group, an epoxy group, and a cyano group. 1 The substrate-adsorbing group in is preferably a hydroxy group, a carboxy group, a thiol group, a vinyl group, a bromine atom, an iodine atom, or a cyano group, and more preferably a hydroxy group. In the formula (u0-4), Wu 4 The cyclic group in may be an aromatic hydrocarbon cyclic group, an aromatic heterocyclic group, or an alicyclic group. Examples of the cyclic group include a group in which two hydrogen atoms have been removed from a monocycloalkane, a group in which two hydrogen atoms have been removed from a polycycloalkane, and a group in which two hydrocarbon groups have been removed from an aromatic ring. These groups may have a substituent that replaces a hydrogen atom of the cyclic group, or a substituent that replaces a carbon atom that constitutes the ring skeleton.

[0115] Since the first polymer block (A) and the second polymer block (B) do not have the structural unit (u0), when the block copolymer (P1) is used as an undercoat, the number of substrate-adsorbing groups that are not involved in substrate adsorption is reduced, and the uniformity of the undercoat film surface is maintained.

[0116] When the first polymer block (A) has a structural unit (u0), the proportion (mol %) of the structural unit (u0) is preferably 40 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, and particularly preferably 10 mol % or less, relative to all structural units (100 mol %) contained in the first polymer block (A). When the second polymer block (B) has a structural unit (u0), the proportion (mol %) of the structural unit (u0) is preferably 40 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, and particularly preferably 10 mol % or less, relative to all structural units (100 mol %) contained in the second polymer block (B).

[0117] The number average molecular weight (Mn) of the block copolymer (P1) (based on polystyrene conversion by size exclusion chromatography) is not particularly limited, but is preferably 5,000 to 200,000, more preferably 6,000 to 100,000, further preferably 8,000 to 80,000, and particularly preferably 10,000 to 60,000. When the content is equal to or less than the upper limit of this preferred range, the composition is sufficiently soluble in an organic solvent and has excellent coatability onto a substrate, whereas when the content is equal to or more than the lower limit of this preferred range, the composition has excellent production stability of the polymer compound and excellent coatability onto a substrate. The molecular weight dispersity (Mw / Mn) of the block copolymer (P1) is not particularly limited, and is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0, and even more preferably from 1.0 to 2.5, where Mw represents the mass average molecular weight.

[0118] Specific examples of the block copolymer (P1) are shown below, but are not limited thereto. In the following formula, a, b, x, and y represent the molar ratio of the constituent units. a and b represent integers of 1 or more. a:b may be 10:90 to 90:10, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40. x and y are greater than 0 and less than 1. x and y can be appropriately determined depending on the type of the desired phase separation structure. x and y may be, for example, 0.01 to 0.3.

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] <Production method of block copolymer (P1)> The block copolymer (P1) can be produced by combining known methods as shown in the examples below, for example, by a production method having the steps shown below.

[0125] Step (p1): synthesizing a first polymer block (A) by living anionic polymerization; Step (p2): reacting the first polymer block (A) with a diphenylethylene derivative (hereinafter referred to as "DPE") having a substrate-adsorbing group-containing group; and Step (p3): A step of synthesizing a second polymer block (B) by living anionic polymerization.

[0126] [ka] [In the formula, A, B, R 1c , R 1d , R 2c 、 R 2d , m1, n1, m2 and n2 are the same as those in the formula (n1). M(Na) and M(Nb) represent monomer (Na) and monomer (Nb), respectively.

[0127] Process (p1): The first polymer block (A) can be synthesized, for example, by a living anionic polymerization reaction of a monomer (hereinafter referred to as "monomer (Na)" that derives the structural unit (Na), for example, styrene or a derivative thereof). The living anionic polymerization can be carried out by a known method. As the polymerization initiator, for example, organic alkali metals such as n-butyl lithium, sec-butyl lithium, tert-butyl lithium, ethyl lithium, ethyl sodium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, etc. can be used. In the above formula, an example in which sec-butyl lithium is used as the initiator is shown.

[0128] Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, octane, etc.; ethers such as diethyl ether, tetrahydrofuran, etc.; ketones such as acetone, methyl ethyl ketone, methyl amyl ketone, etc.; alcohols such as methanol, ethanol, propanol, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; alkyl halides such as chloroform, bromoform, methylene chloride, methylene bromide, carbon tetrachloride, etc.; esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves, etc.; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, etc.; water, etc.

[0129] Process (p2): DPE is added to the reaction solution after step (p1) and reacted. Examples of the solvent for DPE include tetrahydrofuran. The substrate adsorptive group of DPE may be protected with a protecting group such as tert-butyldimethylsilyl group.

[0130] Process (p3): To the reaction solution after step (p2), for example, a monomer that derives the structural unit (Nb) (hereinafter referred to as "monomer (Nb)"; for example, an (α-substituted) acrylic acid ester or a derivative thereof) is added, and a polymerization reaction is carried out.

[0131] The reaction temperature, reaction time, etc. in each step are not particularly limited and may be appropriately determined depending on, for example, the type of polymerization initiator, etc.

[0132] In step (p2), when the substrate-adsorbing group of the DPE is protected with a protecting group, a deprotection step may be carried out after step (p3). The deprotection conditions may be appropriately determined depending on the type of the protecting group.

[0133] ≪Optional ingredients≫ The BCP composition may further contain, as desired, compatible additives, such as additional resins for improving the performance of the undercoat layer, surfactants for improving coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, sensitizers, base multipliers, basic compounds (nitrogen-containing compounds such as imidazole), and the like, provided the effects of the present invention are not impaired.

[0134] Organic solvents (component (S)) The BCP composition can be produced by dissolving each component, such as the block copolymer (P1), in an organic solvent (hereinafter also referred to as "component (S)"). The (S) component may be any solvent capable of dissolving each of the components used to form a homogeneous solution, and one or more solvents may be appropriately selected from those conventionally known as solvents for film compositions mainly composed of resins.

[0135] Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the above polyhydric alcohols or the above compounds having an ester bond, or monophenyl ethers having an ether bond. Examples of suitable organic solvents include derivatives of polyhydric alcohols such as compounds having the formula (among which, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred)]; cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, and mesitylene.

[0136] The component (S) may be used alone, or as a mixed solvent of two or more kinds. Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and EL are preferred as the (S) component. A mixed solvent obtained by mixing PGMEA and a polar solvent is also preferred. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, and is preferably within the range of 1:9 to 9:1, more preferably 2:8 to 8:2. For example, when EL is mixed as the polar solvent, the mass ratio of PGMEA:EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. When PGME is mixed as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. When PGME and cyclohexanone are mixed as the polar solvent, the mass ratio of PGMEA:(PGME+cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. The component (S) is preferably a mixed solvent of PGMEA, EL, or a mixed solvent of the PGMEA and a polar solvent, and γ-butyrolactone, in which the mass ratio of the former to the latter is preferably 70:30 to 95:5.

[0137] The amount of component (S) used is not particularly limited and is set appropriately according to the coating film thickness at a concentration that allows application to a substrate, etc.; however, it is generally used so that the solids concentration of the primer falls within the range of 0.1 to 20 mass %, preferably 0.2 to 15 mass %.

[0138] <Method of manufacturing the structure> Hereinafter, a method for producing a structure containing a phase-separated structure will be specifically described with reference to Fig. 1. However, the present invention is not limited thereto.

[0139] FIG. 1 shows an embodiment of a method for producing a structure containing a phase-separated structure. First, the BCP composition is applied onto a substrate 1 to form a base layer 2 (FIG. 1(I); step (i)). Next, the BCP composition is applied onto the undercoat layer 2 to form a self-assembled layer 3 (FIG. 1(II); step (ii)). Next, an annealing treatment is performed by heating, and the self-assembled layer 3 is separated into a phase 3a and a phase 3b (FIG. 1(III); step (iii)). According to the manufacturing method of this embodiment described above, that is, the manufacturing method including steps (i) to (iii), a structure 3' including a phase-separated structure is produced on the substrate 1 on which the undercoat agent layer 2 is formed.

[0140] [Step (i)] In step (i), the BCP composition is applied onto a substrate 1 to form a base layer 2 . In step (i), the BCP composition is used as a primer for forming the primer layer 2. By providing the primer layer 2 on the support 1, the adhesion between the surface of the support 1 and the self-assembled layer is improved.

[0141] The type of the substrate 1 is not particularly limited as long as the phase-separated structure forming resin composition can be applied onto the surface of the substrate. For example, substrates made of inorganic substances such as metals (silicon, copper, chromium, iron, aluminum, etc.), glass, titanium oxide, silicon dioxide (SiO2), silica, and mica; substrates made of nitrides such as SiN; substrates made of oxynitrides such as SiON; and substrates made of organic substances such as acrylic, polystyrene, cellulose, cellulose acetate, and phenol resin. Among these, metal substrates 1 are suitable, and a cylindrical structure is formed on, for example, a silicon substrate (Si substrate), a silicon dioxide substrate (SiO2 substrate), or a copper substrate (Cu substrate). Among these, Si substrates and SiO2 substrates are particularly suitable. The size and shape of the substrate 1 are not particularly limited. The substrate 1 does not necessarily have to have a smooth surface, and substrates of various shapes can be appropriately selected. For example, substrates having a curved surface, flat plates with an uneven surface, and substrates having a flaky shape can be mentioned.

[0142] The surface of the substrate 1 may be provided with an inorganic and / or organic film. Examples of inorganic films include inorganic anti-reflective coatings (inorganic BARCs). Examples of organic films include organic anti-reflective coatings (organic BARCs). The inorganic film can be formed, for example, by applying an inorganic anti-reflective coating composition, such as a silicon-based material, onto a substrate and baking it. The organic film can be formed, for example, by applying an organic film-forming material, which is a resin component that constitutes the film, dissolved in an organic solvent, onto a substrate using a spinner or the like, and baking the material at a temperature of preferably 200 to 300° C., preferably for 30 to 300 seconds, more preferably for 60 to 180 seconds. This organic film-forming material does not necessarily need to be sensitive to light or electron beams, as in the case of a resist film, and may or may not be sensitive. Specifically, resists and resins that are commonly used in the manufacture of semiconductor elements and liquid crystal display elements can be used. In addition, the organic film forming material is preferably a material capable of forming an organic film that can be etched, particularly dry etched, so that the organic film pattern can be formed by etching the organic film using a pattern made of a block copolymer formed by processing the layer 3. Among them, it is preferable that the material is a material capable of forming an organic film that can be etched by oxygen plasma etching or the like. Such an organic film forming material may be a material that has been used to form an organic film such as an organic BARC. For example, the ARC series manufactured by Nissan Chemical Industries, Ltd., the AR series manufactured by Rohm and Haas, and the SWK series manufactured by Tokyo Ohka Kogyo Co., Ltd. can be mentioned.

[0143] The method for forming the undercoat layer 2 by applying the BCP composition onto the substrate 1 is not particularly limited, and the undercoat layer 2 can be formed by a conventionally known method. For example, the BCP composition is applied onto the substrate 1 by a conventionally known method such as spin coating or using a spinner to form a coating film, which is then dried to form the undercoat layer 2. The method for drying the coating film may be any method capable of volatilizing the solvent contained in the BCP composition, such as a baking method. In this case, the baking temperature is preferably 80 to 300° C., more preferably 180 to 270° C., and further preferably 220 to 250° C. The baking time is preferably 30 to 500 seconds, and more preferably 60 to 400 seconds. The thickness of the undercoat agent layer 2 after the coating film has dried is preferably about 10 to 100 nm, and more preferably about 30 to 90 nm.

[0144] The surface of the substrate 1 may be washed in advance before forming the primer layer 2 on the substrate 1. Washing the surface of the substrate 1 improves the applicability of the primer. The cleaning treatment may be carried out by any of the conventional methods known in the art, including, for example, oxygen plasma treatment, ozone oxidation treatment, acid-alkali treatment, and chemical modification treatment.

[0145] After forming the undercoat agent layer 2, the undercoat agent layer 2 may be rinsed with a rinsing liquid such as a solvent, if necessary. The rinsing removes uncrosslinked parts and the like in the undercoat agent layer 2, improving the affinity with the self-assembled layer 3 and facilitating the formation of a phase-separated structure oriented in a direction perpendicular to the surface of the substrate 1. The rinse liquid may be any liquid capable of dissolving the uncrosslinked portions, and solvents such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate (EL), or commercially available thinners can be used. After the cleaning, post-baking may be performed to volatilize the rinsing liquid. The temperature condition for this post-baking is preferably 80 to 300°C, more preferably 100 to 270°C, and further preferably 120 to 250°C. The baking time is preferably 30 to 500 seconds, and more preferably 60 to 240 seconds. The thickness of the undercoat agent layer 2 after such post-baking is preferably about 1 to 20 nm, and more preferably about 2 to 10 nm.

[0146] [Step (ii)] In step (ii), the BCP composition is applied onto the undercoat agent layer 2 to form a self-assembled layer 3. The BCP composition used is the same as that used in step (i).

[0147] The method for forming the self-assembled layer 3 on the undercoat layer 2 is not particularly limited, and examples of the method include a method in which a BCP composition is applied onto the undercoat layer 2 by a conventionally known method such as using spin coating or a spinner to form a coating film, and then drying.

[0148] The thickness of the self-assembled layer 3 need only be sufficient for phase separation to occur, and taking into consideration the type of substrate 1, the structural period size of the phase-separated structure formed, the uniformity of the nanostructure, etc., the thickness is preferably 10 to 100 nm, and more preferably 20 to 80 nm. For example, when the substrate 1 is a Si substrate or a SiO2 substrate, the thickness of the layer 3 is preferably 10 to 100 nm, more preferably 20 to 80 nm. When the substrate 1 is a Cu substrate, the thickness of the layer 3 is preferably from 10 to 100 nm, more preferably from 20 to 80 nm.

[0149] [Step (iii)] In the step (iii), the self-assembled layer 3 is subjected to phase separation. By heating the substrate 1 after step (ii) for annealing, the block copolymer is selectively removed to form a phase-separated structure exposing at least a part of the surface of the substrate 1. That is, a structure 3' including a phase-separated structure separated into a phase 3a and a phase 3b is produced on the substrate 1. The annealing temperature is preferably equal to or higher than the glass transition temperature of the block copolymer (P1) and lower than the thermal decomposition temperature. The annealing temperature is preferably, for example, 180 to 270° C. The heating time is preferably 30 to 3600 seconds. The annealing process is preferably carried out in a low-reactivity gas such as nitrogen.

[0150] [Optional process] The method for producing a structure containing a phase-separated structure is not limited to the above-mentioned embodiment, and may include steps (optional steps) other than steps (i) to (iii). Optional steps include a step of selectively removing, from a layer containing a block copolymer, a phase consisting of at least one type of block among the multiple types of blocks constituting the block copolymer (hereinafter referred to as “step (iv)”), a guide pattern formation step, and the like.

[0151] Regarding step (iv) In step (iv), a phase consisting of at least one type of block among the multiple types of blocks constituting the block copolymer in the layer containing the block copolymer formed on the undercoat layer is selectively removed, thereby forming a fine pattern (polymer nanostructure).

[0152] As a method for selectively removing the phase consisting of blocks, there are a method of subjecting a layer containing a block copolymer to an oxygen plasma treatment, a method of subjecting a layer containing a block copolymer to a hydrogen plasma treatment, and the like. In the following, among the blocks constituting the block copolymer, the block that is not selectively removed is referred to as P A Blocks,P,blocks to be selectively removed B For example, after phase separation of a layer containing a PS-PMMA block copolymer, the layer is subjected to oxygen plasma treatment or hydrogen plasma treatment, etc., to selectively remove the PMMA phase. In this case, the PS portion is P A The PMMA part is P B It is a block.

[0153] FIG. 2 shows an example embodiment of step (iv). In the embodiment shown in FIG. 2, the structure 3′ produced on the substrate 1 in step (iii) is subjected to an oxygen plasma treatment, whereby the phase 3a is selectively removed to form a pattern (polymer nanostructure) consisting of spaced phases 3b. In this case, the phase 3b is P A Phase 3a is a phase consisting of P BIt is a phase made up of blocks.

[0154] The substrate 1 on which a pattern has been formed by phase separation of the self-assembled layer 3 as described above can be used as is, but the shape of the pattern (polymer nanostructure) on the substrate 1 can also be changed by further heating. The heating temperature is preferably equal to or higher than the glass transition temperature of the block copolymer used and lower than its thermal decomposition temperature, and is preferably carried out in a gas with low reactivity such as nitrogen.

[0155] Guide pattern formation process In the method for producing a structure containing a phase-separated structure, a step of providing a guide pattern on the undercoat agent layer (guide pattern forming step) may be included between steps (i) and (ii), which allows control of the arrangement of the phase-separated structure. For example, even if a block copolymer forms a random fingerprint-like phase separation structure when no guide pattern is provided, a phase separation structure oriented along the grooves can be obtained by providing a groove structure of the resist film on the surface of the undercoat layer. Based on this principle, a guide pattern may be provided on the undercoat layer 2. In addition, if the surface of the guide pattern has affinity with any of the polymers constituting the block copolymer, a phase separation structure consisting of a cylindrical structure oriented perpendicular to the substrate surface is easily formed.

[0156] The guide pattern can be formed using, for example, a resist composition. The resist composition for forming the guide pattern can be appropriately selected from among resist compositions generally used for forming resist patterns and their modifications, and can be used by selecting one that has affinity with any of the polymers constituting the block copolymer. The resist composition can be either a positive resist composition for forming a positive pattern in which the exposed portion of the resist film is dissolved and removed, or a negative resist composition for forming a negative pattern in which the unexposed portion of the resist film is dissolved and removed, but is preferably a negative resist composition. For example, the negative resist composition is preferably a resist composition that contains an acid generator and a base material component whose solubility in a developer containing an organic solvent is reduced by the action of an acid, and the base material component contains a resin component having a structural unit that is decomposed by the action of an acid to increase polarity. After the BCP composition is poured onto the undercoat layer on which the guide pattern is formed, an annealing treatment is performed to cause phase separation. Therefore, it is preferable that the resist composition for forming the guide pattern is one capable of forming a resist film having excellent solvent resistance and heat resistance.

[0157] According to the method for producing a structure including a phase-separated structure of the present embodiment described above, the undercoat layer and the self-assembled layer are formed using the same BCP composition. Since there is no need to use different materials for the undercoat layer and the composition for forming the self-assembled layer, the time and effort required for production is simplified. In addition, the raw materials used in the production of the structure including a phase-separated structure are easily managed.

[0158] (Composition containing block copolymer) A composition according to a second aspect of the present invention is a composition used in a method for producing a structure containing a phase-separated structure according to the first aspect. The composition of the present embodiment is a composition containing the block copolymer (P1), and is the same as the above-mentioned BCP composition. EXAMPLES

[0159] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0160] (Synthesis of block copolymer: P1-1) <Synthesis of diphenylethylene derivatives: DPE1> Imidazole (7.05 g, 103 mmol) and 6-chloro-1-hexanol (7.10 g, 52.0 mmol) were added to a two-neck flask, and nitrogen substitution was performed. Under a nitrogen atmosphere, ultra-dehydrated N,N-dimethylformamide (DMF) (160 mL) was added, cooled in an ice bath, and tert-butyldimethylsilyl chloride (30.7 g, 203 mmol) was added. Ultra-dehydrated DMF (160 mL) was further added, and the mixture was stirred in an ice bath for 1 hour and at room temperature for 2 hours. Then, water was added to quench the reaction, and extraction with hexane and washing with water were repeated three times each. The organic layer was dried over magnesium sulfate. The solvent was then distilled off under reduced pressure, and purification was performed by column chromatography using hexane. The intermediate Int (1-1) was obtained by distilling off the solvent under reduced pressure (12.4 g, 95% yield). 1H NMR (CDCl3, 400MHz): δ(ppm)=0.02(s,6H,-Si(CH3)2),0.89(s,9H,-SiC(CH3)3),1.30-1.60(m,6H,-CH2C H2CH2-),1.75-1.82(m,2H,ClCH2CH2-),3.54(t,2H,ClCH2-),3.61(t,2H,-CH2O-).

[0161] [ka]

[0162] Int(1-1) (11.7 g, 46.5 mmol) was added to a two-neck flask, followed by 4,4'-dihydroxybenzophenone (1.69 g, 7.85 mmol), potassium carbonate (6.50 g, 47.1 mmol), potassium iodide (0.405 g, 2.45 mmol), and DMF (125 mL). After stirring at 60°C for 48 hours, water was added to quench the reaction, and extraction with hexane and washing with water were repeated three times each. The organic layer was dried over magnesium sulfate. The solvent was then removed under reduced pressure, and purification was performed by column chromatography using a mixed solvent of hexane:ethyl acetate = 10:1. The solvent was removed under reduced pressure to obtain intermediate Int(2-1) (3.75 g, 75% yield). 1H NMR (CDCl3, 400MHz): δ(ppm)=0.05(s,12H,-Si(CH3)2),0.90(s,18H,-SiC(CH3)3),1.38-1.61(m,12H,-CH2CH2CH2-),1.79-1. 86(m,4H,-CH2CH2OSi-),3.62(t,4H,-CH2OSi-),4.03(t,4H,-ArOCH2-),6.94(d,4H,Ar),7.77(d,4H,Ar).

[0163] [ka]

[0164] Int(2-1) (3.02 g, 4.70 mmol) was added to a two-necked flask, and the inside of the two-necked flask was heated with a dryer while reducing the pressure. While cooling in an ice bath, potassium tert-butoxide (1.07 g, 9.54 mmol) and methyltriphenylphosphonium bromide (5.04 g, 14.1 mmol) were added, and nitrogen substitution was carried out. Tetrahydrofuran (THF) (120 mL) was added under a nitrogen atmosphere, and the mixture was stirred in an ice bath for 1 hour and at room temperature for 16 hours. Then, water was added to quench the reaction, and extraction with diethyl ether and washing with water were repeated three times each. The organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and the resulting white precipitate was removed by filtration while washing with hexane. The solvent was distilled off again under reduced pressure, and purification was carried out by column chromatography using a mixed solvent of hexane:ethyl acetate = 20:1. DPE1 was obtained by distilling off the solvent under reduced pressure (2.98 g, yield 99%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 12H, -Si(CH3)2), 0.90 (s, 18H, -SiC(CH3)3), 1.36 - 1.61 (m, 12H, -CH2CH2CH2-), 1.76 - 1.83 (m, 4H, -CH2CH2OSi-), 3.62 (t, 4H, -CH2OSi-), 3.97 (t, 4H, -ArOCH2-), 5.28 (s, 2H, C=CH2), 6.84 (d, 4H, Ar), 7.26 (d, 4H, Ar).

[0165]

Chemical Structure

[0166] <Synthesis of BCP Precursor: Pre(1)> DPE1 (0.134 g, 0.209 mmol) was weighed into a Schlenk tube and heated with a heat gun while reducing the pressure inside the Schlenk tube. THF was added to another Schlenk tube under an argon (Ar) atmosphere, cooled to -78°C, and sec-butyllithium was added until the solution turned yellow. THF was frozen and degassed, and then transferred to the Schlenk tube containing DPE1 by trap-to-trap distillation to prepare a THF solution of DPE1. Lithium chloride (10.3 mg, 0.243 mmol) was weighed into the Schlenk tube, and heated with a heat gun while reducing the pressure inside the Schlenk tube. After returning the Schlenk tube to room temperature, THF (20 mL) was added and cooled to -78 ° C. sec-butyl lithium (0.3 mL) was added, and it was confirmed that the color of the solution changed from transparent to yellow. Then, it was stirred at room temperature until the yellow color disappeared. It was cooled again to -78 ° C, and an initiator amount of sec-butyl lithium (32.5 μL, 0.0400 mmol) was added, and styrene (1.03 mL, 8.99 mmol) was added and stirred for 30 minutes. Next, the entire amount of the prepared THF solution of DPE1 was dropped and stirred for 30 minutes. Next, methyl methacrylate (0.790 mL, 7.43 mmol) was added and stirred for 30 minutes. Finally, an excess amount of methanol (3 mL) with Ar bubbling was added to quench the reaction. The THF solution in the Schlenk flask was added to methanol (400 mL) for precipitation purification. The solid collected by filtration was dried under reduced pressure at 40°C, and then oligomer components generated during polymerization were removed by Soxhlet extraction using cyclohexane. The solid in the cylindrical filter paper was dissolved in THF (20 mL) and added to methanol (400 mL) for precipitation purification. The solid collected by filtration was dried under reduced pressure at 40°C to obtain precursor Pre (1) (1.18 g, yield 70%). The Mn and polydispersity (PDI = Mw / Mn) of Pre (1) measured by size exclusion chromatography (SEC) were 40.9 kg mol -1 and 1.03. 1H NMR (CDCl3, 400MHz): δ(ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0167]

Chem.

[0168] <Synthesis of BCP: P1-1> Pre(1) (202 mg, 5.05 μmol) was weighed into a two-necked flask and purged with Ar. After adding THF (1.25 mL), tetra-n-butylammonium fluoride (0.75 mL, 150 μmol) was added under an Ar atmosphere, and the mixture was stirred at room temperature for 24 h. The THF solution in the two-necked flask was added to methanol (40 mL) for precipitation purification. The solid recovered by filtration was dried under reduced pressure at 40 °C to obtain P1-1 (197 mg, yield 98%). The Mn and dispersity (PDI = Mw / Mn) of P1-1 measured by size exclusion chromatography (SEC) were 41.4 kg mol -1 and 1.03, respectively. The synthesis of P1-1 was confirmed by the disappearance of the 1H-NMR peak derived from the tert-butyldimethylsilyl group (TBDMS).

[0169]

Chem.

[0170] (Synthesis of block copolymer: P1-2) <Synthesis of BCP precursor: Pre(2)> The precursor Pre(2) was obtained (0.69 g, yield 60%) in the same manner as Pre(1), except that the amount of styrene used was changed to (0.65 mL, 5.7 mmol) and the amount of methyl methacrylate used was changed to (0.59 mL, 5.5 mmol). The Mn and dispersity (PDI = Mw / Mn) of precursor 2 measured by size exclusion chromatography (SEC) were 28.2 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0171] [Chemical formula]

[0172] [Synthesis of BCP: P1-2] P1-2 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(2). The Mn and dispersity (PDI = Mw / Mn) of P1-2 measured by size exclusion chromatography (SEC) were 28.5 kg mol -1 and 1.03, respectively. The synthesis of P1-2 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0173] [Chemical formula]

[0174] (Synthesis of block copolymer: P1-3) [Synthesis of BCP precursor: Pre(3-1)] Styrene was changed to a mixed monomer of styrene (0.83 mL, 7.2 mmol) and 4-trimethylsilylstyrene (0.19 mL, 0.94 mmol), and methyl methacrylate was changed to a mixed monomer of methyl methacrylate (0.67 mL, 6.2 mmol) and glycidyl methacrylate (0.15 mL, 1.2 mmol). Otherwise, the precursor Pre(3-1) was obtained in the same manner as Pre1 (1.13 g, yield 66%). The Mn and dispersity (PDI = Mw / Mn) of Pre(3-1) measured by size exclusion chromatography (SEC) were 42.5 kg mol -1 and 1.05, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.20 - 0.30 (-PhSi(CH3)3, PTMSS), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA and PGMA), 1.23 - 1.69 (-CH2CH-, PS and PTMSS), 1.74 - 2.02 (-CH2CH-, PS and PTMSS, -CH2C(CH3)-, PMMA and PGMA), 2.63 (-CH2-CH(CH2)-O-, PGMA), 2.84 (-CH2CH(CH2)-O-, PGMA), 3.60 (-COOCH3, PMMA), 3.79 (-(C=O)O-CH2-, PGMA), 4.28 (-(C=O)O-CH2-, PGMA), 6.20 - 7.50 (Ar, PS and PTMSS).

[0175]

Chemical Structure

[0176] <Synthesis of BCP Precursor: Pre(3-2)> Pre(3-1) (1.00 g, 23.5 μmol) and THF (5 mL) were added to a two-necked flask, and after cooling in an ice bath, a 1 wt% aqueous lithium hydroxide solution (LiOH 0.05 molar equivalent / GMA unit) and 2,2,2-trifluoroethanethiol (2 molar equivalents / GMA unit) were added. After stirring at room temperature for 20 minutes, the mixture was stirred at 40 °C for 3 hours. The THF solution in the two-necked flask was added to methanol (50 mL) for precipitation purification. The solid recovered by filtration was dried under reduced pressure at 40 °C to obtain the precursor Pre(3-2) (0.95 g, yield 95%). The Mn and dispersity (PDI = Mw / Mn) of Pre(3-2) measured by size exclusion chromatography (SEC) were 45.0 kg mol -1 and 1.05, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.20 - 0.30 (-PhSi(CH3)3, PTMSS), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA and PHFMA), 1.23 - 1.69 (-CH2CH-, PS and PTMSS), 1.74 - 2.02 (-CH2CH-, PS and PTMSS, -CH2C(CH3)-, PMMA and PHFMA), 2.85 (-CH(OH)-CH2-S-, PHFMA), 3.20 - 3.45 (-S-CH2-CF3, PHFMA), 3.60 (-COOCH3, PMMA), 3.79 (-(C=O)O-CH2-, PHFMA), 3.95 - 4.20 (-CH(OH)-, PHFMA), 4.45 - 4.57 (-CH(OH)-, PHFMA), 6.20 - 7.50 (Ar, PS and PTMSS).

[0177]

Chemical formula

[0178] <Synthesis of BCP: P1-3> P1-3 was obtained in the same manner as P1-1, except that Pre(1) was replaced with Pre(3-2). The Mn and polydispersity (PDI=Mw / Mn) of P1-3 measured by size exclusion chromatography (SEC) were 45.6 kg mol -1 and 1.05. The synthesis of P1-3 was confirmed by the disappearance of the 1H-NMR peak due to TBDMS.

[0179] [ka]

[0180] (Synthesis of block copolymer: P1-4) <Synthesis of diphenylethylene derivatives: DPE2> Intermediate Int (2-2) was obtained (2.43 g, 75% yield) in the same manner as for Int (2-1), except that 4,4'-dihydroxybenzophenone (1.69 g, 7.85 mmol) was replaced with 4-hydroxybenzophenone (1.56 g, 7.87 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=0.05(s,6H,-Si(CH3)2),0.90(s,9H,-SiC(CH3)3),1.38-1.61(m,6H,-CH2CH2CH2CH2-),1.79-1.86(m,2H,-CH2CH2OSi-),3. 62(t,2H,-CH2OSi-),4.03(t,2H,-ArOCH2-),6.94(d,2H,Ar),7.48(t,2H,Ar),7.53(m,1H,Ar),7.72(d,2H,Ar),7.77(d,2H,Ar).

[0181] [ka]

[0182] DPE2 (1.83 g, 95% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-2) (1.94 g, 4.70 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.36 - 1.61 (m, 6H, -CH2CH2CH2-), 1.76 - 1.83 (m, 2H, -CH2CH2OSi-), 3.62 (t, 2H, -CH2OSi-), 3.97 (t, 2H, -ArOCH2-), 5.32 (s, 2H, C=CH2), 6.83 (d, 2H, Ar), 7.26 (d, 4H, Ar), 7.30 - 7.34 (m, 3H, Ar).

[0183]

Chem.

[0184] <Synthesis of BCP Precursor: Pre(4)> A THF solution of DPE2 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE2 (0.086 g, 0.21 mmol).

[0185] The precursor Pre(4) (1.20 g, yield 66%) was obtained in the same manner as Pre(1), except that the amount of styrene used was changed to (1.05 mL, 9.21 mmol), the THF solution of DPE1 was changed to the THF solution of DPE2, and the amount of methyl methacrylate used was changed to (0.91 mL, 8.6 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(4) measured by size exclusion chromatography (SEC) were 44.0 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0186] [Chemistry]

[0187] <Synthesis of BCP: P1-4> P1-4 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(4). The Mn and dispersity (PDI = Mw / Mn) of P1-4 measured by size exclusion chromatography (SEC) were 44.6 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.85, 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0188] [Chemistry]

[0189] (Synthesis of block copolymer: P1-5) (Synthesis of diphenylethylene derivative: DPE3) Intermediate Int(1-2) was obtained (15.0 g, 94% yield) in the same manner as Int(1-1), except that 6-chloro-1-hexanol (7.10 g, 52.0 mmol) was changed to 10-chloro-1-decanol (10.0 g, 51.9 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.02 (s, 6H, -Si(CH3)2), 0.89 (s, 9H, -SiC(CH3)3), 1.30 - 1.60 (m, 14H, -(CH2)7-), 1.75 - 1.82 (m, 2H, ClCH2CH2-), 3.54 (t, 2H, ClCH2-), 3.61 (t, 2H, -CH2O-).

[0190] [ka]

[0191] Intermediate Int(2-3) was obtained in the same manner as Int(2-1), except that 4,4'-dihydroxybenzophenone (1.69 g, 7.85 mmol) was replaced with 4-fluoro-4'-hydroxybenzophenone (1.70 g, 7.86 mmol) and Int(1-1) (11.7 g, 46.5 mmol) was replaced with Int(1-2) (14.3 g, 46.5 mmol). (3.06 g, 80% yield) 1H NMR (CDCl3, 400MHz): δ(ppm)=0.05(s,6H,-Si(CH3)2),0.90(s,9H,-SiC(CH3)3),1.38-1.61(m,14H,-(CH2)7-),1.79-1.86(m,2H,-CH2 CH2OSi-),3.62(t,2H,-CH2OSi-),4.03(t,2H,-ArOCH2-),7.03(d,2H,Ar),7.39(d,2H,Ar),7.72-7.74(m,4H,Ar).

[0192] [ka]

[0193] DPE3 (2.19 g, 96% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-3) (2.28 g, 4.70 mmol). 1H NMR (CDCl3, 400MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.38 - 1.61 (m, 14H, -(CH2)7-), 1.79 - 1.86 (m, 2H, -CH2CH2OSi-), 3.62 (t, 2H, -CH2OSi-), 3.97 (t, 2H, -ArOCH2-), 5.34 (s, 2H, C=CH2), 6.88 (d, 2H, Ar), 7.24 (d, 2H, Ar), 7.32 - 7.34 (m, 4H, Ar).

[0194]

Chem.

[0195] <Synthesis of BCP Precursor: Pre(5)> A THF solution of DPE3 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE3 (0.101 g, 0.209 mmol).

[0196] Precursor Pre5 (1.47 g, yield 73%) was obtained in the same manner as Pre(1), except that the amount of styrene used was changed to (1.11 mL, 9.69 mmol), the THF solution of DPE1 was changed to the THF solution of DPE3, and the amount of methyl methacrylate used was changed to (1.13 mL, 10.6 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(5) measured by size exclusion chromatography (SEC) were 50.4 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0197] [Chemical formula]

[0198] <Synthesis of BCP: P1-5> P1-5 was obtained in the same manner as Pre(1), except that Pre(1) was changed to Pre(5). The Mn and dispersity (PDI = Mw / Mn) of P1-5 measured by size exclusion chromatography (SEC) were 51.0 kg mol -1 and 1.03, respectively. The synthesis of P1-5 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0199] [Chemical formula]

[0200] (Synthesis of block copolymer: P1-6) (Synthesis of diphenylethylene derivative: DPE4) Intermediate Int(1-3) was obtained (13.5 g, yield 92%) in the same manner as Int(1-1), except that 6-chloro-1-hexanol (7.10 g, 52.0 mmol) was changed to 2-[2-(2-chloroethoxy)ethoxy]ethanol (8.77 g, 52.0 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.02 (s, 6H, -Si(CH3)2), 0.89 (s, 9H, -SiC(CH3)3), 3.52 - 3.65 (m, 8H, -CH2OCH2CH2OCH2-), 3.83 (t, 2H, ClCH2-), 3.96 (t, 2H, -CH2OSi-).

[0201] [Chemical formula]

[0202] Intermediate Int(2-4) (2.69 g, 6.06 mmol) was obtained in the same manner as Int(2-2), except that Int(1-1) (11.7 g, 46.5 mmol) was changed to Int(1-3) (13.2 g, 46.5 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 3.52 - 3.59 (m, 6H, -CH2OCH2CH2OCH2-), 3.77 (t, 2H, -ArOCH2CH2-), 3.96 (t, 2H, -CH2OSi-), 4.31 (t, 2H, -ArOCH2-), 6.95 (d, 2H, Ar), 7.50 - 7.53 (m, 3H, Ar), 7.73 (d, 2H, Ar), 7.81 (d, 2H, Ar).

[0203]

Chem.

[0204] DPE4 (1.96 g, 4.42 mmol) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-4) (2.09 g, 4.70 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 3.52 - 3.59 (m, 6H, -CH2OCH2CH2OCH2-), 3.77 (t, 2H, -ArOCH2CH2-), 3.96 (t, 2H, -CH2OSi-), 4.31 (t, 2H, -ArOCH2-), 5.32 (s, 2H, C=CH2), 6.88 (d, 2H, Ar), 7.33 - 7.38 (m, 7H, Ar).

[0205]

Chem.

[0206] <Synthesis of BCP Precursor: Pre(6)> A THF solution of DPE4 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE4 (0.925 g, 0.209 mmol).

[0207] The precursor Pre(6) was obtained in the same manner as Pre(1) (1.10 g, yield 68%), except that the amount of styrene used was changed to (0.83 mL, 7.3 mmol), the THF solution of DPE1 was changed to the THF solution of DPE4, and the amount of methyl methacrylate used was changed to (0.92 mL, 8.6 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(6) measured by size exclusion chromatography (SEC) were 39.5 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0208]

Chemical formula

[0209] <Synthesis of BCP: P1-6> P1-6 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(6). The Mn and dispersity (PDI = Mw / Mn) of P1-6 measured by size exclusion chromatography (SEC) were 40.0 kg mol -1 and 1.03, respectively. The synthesis of P1-6 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0210]

Chemical formula

[0211] (Synthesis of block copolymer: P1-7) <Synthesis of diphenylethylene derivatives: DPE5> Int (2-5) was obtained (3.1 g, 75% yield) in the same manner as Int (2-1), except that Int (1-1) (11.7 g, 46.5 mmol) was replaced with 4-(4-chlorobutyl)-2,2-dimethyl-1,3-dioxolane (8.96 g, 46.5 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,12H,>C(CH3)2),1.25-1.38(m,8H,-CH2CH3CH<),1.69(q,4H,-OCH2CH2CH2-),3.62(d ,2H,>CHCH2O-),3.82-3.87(m,4H,>CHCH2-),4.06(t,4H,-ArOCH2-),7.03(d,4H,Ar),7.73(d,4H,Ar)

[0212] [ka]

[0213] DPE5 (2.24 g, 91% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-5) (2.48 g, 4.70 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,12H,>C(CH3)2),1.25-1.38(m,8H,-CH2CH3CH<),1.69(q,4H,-OCH2CH2CH2-),3.62(d,2H,>CHC H2O-),3.82-3.87(m,4H,>CHCH2-),4.06(t,4H,-ArOCH2-),5.32(s,2H,C=CH2),6.88(d,4H,Ar),7.34(d,4H,Ar) 13CNMR(CDCl3,100MHz): δ(ppm) = 22.61, 26.20, 29.97, 31.99, 68.70, 69.20, 77.82, 114.20 - 114.31, 119.25, 129.00, 133.24, 150.20, 158.68.

[0214] [Chemical formula]

[0215] <Synthesis of BCP Precursor: Pre(7)> A THF solution of DPE5 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE5 (0.110 g, 0.210 mmol).

[0216] Precursor Pre(7) (1.17 g, yield 66%) was obtained in the same manner as Pre(1), except that the amount of styrene used was changed to (1.09 mL, 9.49 mmol), the THF solution of DPE1 was changed to the THF solution of DPE5, and the amount of methyl methacrylate used was changed to (0.84 mL, 7.8 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(7) measured by size exclusion chromatography (SEC) were 43.0 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ(ppm) = 0.85 (α-CH3, PMMA), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS). 13C NMR (CDCl3, 100 MHz): δ(ppm) = 16.37 - 16.47, 18.56, 22.60, 25.90, 26.20, 29.90, 40.20 - 40.42, 44.43, 44.75, 51.73, 52.36, 54.04 - 54.31, 69.20, 77.80, 119.20, 125.37 - 125.52, 127.18 - 128.14, 145.15 - 145.54, 176.88, 177.70, 178.00.

[0217]

Chem.

[0218] <Synthesis of BCP: P1 - 7> Precursor 7 (1.00 g, 24.4 μmol) was weighed into a two - necked flask, and after adding THF (5.0 mL), 1N hydrochloric acid (0.10 mL) was added, and the mixture was stirred at 50 °C for 2 hours. After returning the reaction solution to room temperature, sodium hydrogen carbonate (0.09 g) was added and stirred for 10 minutes, and the solid content was removed by filtration. The filtrate was added to methanol (150 mL) for precipitation purification. The solid recovered by filtration was dried under reduced pressure at 40 °C to obtain P1 - 7 (0.90 g, yield 90%). The Mn and dispersity (PDI = Mw / Mn) of P1 - 7 measured by size - exclusion chromatography (SEC) were 43.5 kg mol -1 and 1.03, respectively. The synthesis of P1 - 7 was confirmed by the disappearance of the 13C - NMR peak derived from 2,2 - dimethyl - 1,3 - dioxolane.

[0219]

Chem.

[0220] (Synthesis of Block Copolymer: P1 - 8) <Synthesis of BCP Precursor: Pre(8)> A THF solution of 1,1-bis[4-[(tert-butyl)dimethylsilyloxy]phenyl]ethylene was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to 1,1-bis[4-[(tert-butyl)dimethylsilyloxy]phenyl]ethylene (0.092 g, 0.21 mmol) (R. P. Quirk, Y. Wang, Polym. Int. 1993, 31, 51).

[0221] The amount of styrene used was changed to (1.10 mL, 9.61 mmol), the THF solution of DPE1 was changed to the THF solution of 1,1-bis[4-[(tert-butyl)dimethylsilyloxy]phenyl]ethylene, and the amount of methyl methacrylate used was changed to (0.99 mL, 9.3 mmol). Otherwise, the precursor Pre(8) was obtained in the same manner as Pre(1) (1.32 g, yield 68%). The Mn and dispersity (PDI = Mw / Mn) of Pre(8) measured by size exclusion chromatography (SEC) were 46.9 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0222] [Chemical formula]

[0223] <Synthesis of BCP: P1-8> P1-8 was obtained in the same manner as P1-1, except that Pre(1) was replaced with Pre(8). The Mn and polydispersity (PDI=Mw / Mn) of P1-8 measured by size exclusion chromatography (SEC) were 47.5 kg mol -1 and 1.03. The synthesis of P1-8 was confirmed by the disappearance of the 1H-NMR peak due to TBDMS.

[0224] [ka]

[0225] (Synthesis of block copolymer: P1-9) <Synthesis of diphenylethylene derivatives: DPE6> Intermediate Int(2-6) was obtained in the same manner as Int(2-1), except that 4,4'-dihydroxybenzophenone (1.69 g, 7.85 mmol) was replaced with bis[3-(bromomethyl)phenyl]methanone (2.89 g, 7.85 mmol) and Int(1-1) (11.7 g, 46.5 mmol) was replaced with 3-[[tert-butyl(dimethyl)silyl]oxy]-1-propanol (8.85 g, 46.5 mmol). (3.41 g, 74% yield) 1H NMR (CDCl3, 400MHz): δ(ppm)=0.05(s,12H,-Si(CH3)2),0.90(s,18H,-SiC(CH3)3),1.82(q,4H,-OCH2CH2CH2O-),3.35(t,4H ,-ArCH2OCH2-),3.77(t,4H,-CH2OSi-),4.80(m,4H,-ArCH2-),7.37(m,2H,Ar),7.66-7.71(m,6H,Ar).

[0226] [ka]

[0227] DPE6 was obtained (2.42 g, yield 88%) in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-6) (2.76 g, 4.70 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 12H, -Si(CH3)2), 0.90 (s, 18H, -SiC(CH3)3), 1.82 (q, 4H, -OCH2CH2CH2O-), 3.35 (t, 4H, -ArCH2OCH2-), 3.77 (t, 4H, -CH2OSi-), 4.80 (m, 4H, -ArCH2-), 5.32 (s, 2H, C=CH2), 7.22 (m, 2H, Ar), 7.28 - 7.35 (m, 6H, Ar).

[0228]

Chemical Structure

[0229] <Synthesis of BCP Precursor: Pre(9)> A THF solution of DPE6 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE6 (0.122 g, 0).

[0230] Precursor Pre(9) was obtained (1.06 g, yield 62%) in the same manner as Pre(1), except that the amount of styrene used was changed to (1.03 mL, 8.98 mmol), the THF solution of DPE1 was changed to the THF solution of DPE6, and the amount of methyl methacrylate used was changed to (0.82 mL, 7.7 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(9) measured by size exclusion chromatography (SEC) were 41.5 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ(ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0231]

Chem.

[0232] <Synthesis of BCP: P1-9> P1-9 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(9). The Mn and dispersity (PDI = Mw / Mn) of P1-9 measured by size exclusion chromatography (SEC) were 42.0 kg mol -1 and 1.03, respectively. The synthesis of P1-9 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0233]

Chem.

[0234] (Synthesis of Block Copolymer: P1-10) <Synthesis of Diphenylethylene Derivative: DPE7> 4,4'-Dihydroxybenzophenone (1.69 g, 7.85 mmol) was changed to 3-benzoylbenzyl bromide (2.16 g, 7.85 mmol), and Int(1-1) (11.7 g, 46.5 mmol) was changed to 6-[[tert-butyl(dimethyl)silyl]oxy]-1-hexanol (10.8 g, 46.5 mmol). Intermediate Int(2-7) was obtained in the same manner as Int(2-1) (2.48 g, yield 74%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.38 - 1.61 (m, 6H, -CH2CH2CH2-), 1.79 - 1.86 (m, 2H, -CH2CH2OSi-), 3.35 (t, 2H, ArCH2OCH2-), 3.62 (t, 2H, -CH2OSi-), 4.80 (m, 2H, -ArCH2-), 7.37 (m, 1H, Ar), 7.51 (m, 2H, Ar), 7.61 - 7.68 (m, 4H, Ar), 7.81 (d, 2H, Ar).

[0235]

Chem.

[0236] Except for changing Int(2-1) (3.02 g, 4.70 mmol) to Int(2-7) (2.01 g, 4.70 mmol), DPE7 was obtained in the same manner as DPE1 (1.74 g, yield 87%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.38 - 1.61 (m, 6H, -CH2CH2CH2-), 1.79 - 1.86 (m, 2H, -CH2CH2OSi-), 3.35 (t, 2H, ArCH2OCH2-), 3.62 (t, 2H, -CH2OSi-), 4.80 (m, 2H, -ArCH2-), 5.32 (s, 2H, C=CH2), 7.22 (m, 1H, Ar), 7.28 - 7.37 (m, 8H, Ar).

[0237]

Chem.

[0238] <Synthesis of BCP Precursor: Pre(10)> Except for changing DPE1 (0.134 g, 0.209 mmol) to DPE7 (0.089 g, 0.21 mmol), a THF solution of DPE7 was prepared in the same manner as the THF solution of DPE1.

[0239] The amount of styrene used was changed to (1.04 mL, 9.12 mmol), the THF solution of DPE1 was changed to the THF solution of DPE7, and the amount of methyl methacrylate used was changed to (0.80 mL, 7.5 mmol). Otherwise, the precursor Pre(10) was obtained in the same manner as Pre(1) (1.02 g, yield 60%). The Mn and dispersity (PDI = Mw / Mn) of Pre(10) measured by size exclusion chromatography (SEC) were 41.2 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0240]

Chemical formula

[0241] <Synthesis of BCP: P1-10> P1-10 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(10). The Mn and dispersity (PDI = Mw / Mn) of P1-10 measured by size exclusion chromatography (SEC) were 41.7 kg mol -1 and 1.03, respectively. The synthesis of P1-10 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0242]

Chemical formula

[0243] (Synthesis of block copolymer: P1-11) <Synthesis of diphenylethylene derivative: DPE8> Except that 6-[[tert-butyl(dimethyl)silyl]oxy]-1-hexanol (10.8 g, 46.5 mmol) was changed to Int(1-3) (13.2 g, 46.5 mmol), Intermediate Int(2-8) was obtained in the same manner as Int(2-7) (2.70 g, yield 75%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 3.52 - 3.59 (m, 10H, -OCH2CH2OCH2CH2OCH2-), 3.96 (t, 2H, -CH2OSi-), 4.80 (t, 2H, ArCH2-), 7.37 (m, 1H, Ar), 7.51 - 7.81 (m, 8H, Ar).

[0244]

Chemical formula

[0245] Except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-8) (2.16 g, 4.70 mmol), DPE8 was obtained in the same manner as DPE1 (1.87 g, yield 87%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 3.52 - 3.59 (m, 10H, -OCH2CH2OCH2CH2OCH2-), 3.96 (t, 2H, -CH2OSi-), 4.80 (t, 2H, ArCH2-), 5.32 (s, 2H, C=CH2), 7.22 - 7.37 (m, 9H, Ar).

[0246]

Chemical formula

[0247] <Synthesis of BCP Precursor: Pre(11)> A THF solution of DPE8 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE8 (0.096 g, 0.21 mmol).

[0248] The precursor Pre(11) was obtained in the same manner as Pre(1), except that the amount of styrene used was changed to (1.01 mL, 8.87 mmol), the THF solution of DPE1 was changed to the THF solution of DPE8, and the amount of methyl methacrylate used was changed to (0.88 mL, 8.3 mmol) (1.19 g, yield 68%). The Mn and dispersity (PDI = Mw / Mn) of Pre(11) measured by size exclusion chromatography (SEC) were 42.5 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0249]

Chemical formula

[0250] <Synthesis of BCP: P1-11> P1-11 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(11). The Mn and dispersity (PDI = Mw / Mn) of P1-111 measured by size exclusion chromatography (SEC) were 43.0 kg mol -1 and 1.03, respectively. The synthesis of P1-11 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0251]

Chemical formula

[0252] (Synthesis of Block Copolymer: P1-12) (Synthesis of BCP Precursor: Pre(12)) A THF solution of 1,1-bis[3-(tert-butyldimethylsilyloxymethyl)phenyl]ethene was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to 1,1-bis[3-(tert-butyldimethylsilyloxymethyl)phenyl]ethene (0.098 g, 0.21 mmol) (Synthesis of Chain-End-Functionalized Poly(methyl methacrylate)s with a Definite Number of Benzyl Bromide Moieties and Their Application to Star-Branched Polymers | Macromolecules (acs.org)).

[0253] The precursor Pre(12) was obtained in the same manner as Pre1, except that the amount of styrene used was changed to (1.05 mL, 9.17 mmol), the THF solution of DPE1 was changed to the THF solution of 1,1-bis[3-(tert-butyldimethylsilyloxymethyl)phenyl]ethene, and the amount of methyl methacrylate used was changed to (0.81 mL, 7.6 mmol) (1.10 g, yield 64%). The Mn and dispersity (PDI = Mw / Mn) of Pre(12) measured by size exclusion chromatography (SEC) were 41.5 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0254]

Chem.

[0255] <Synthesis of BCP: P1-12> P1-12 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(12). The Mn and dispersity (PDI = Mw / Mn) of P1-12 measured by size exclusion chromatography (SEC) were 42.0 kg mol -1 and 1.03, respectively. The synthesis of P1-12 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0256]

Chem.

[0257] (Synthesis of block copolymer: P1-13) <Synthesis of diphenylethylene derivative: DPE9> Intermediate Int(2-9) was obtained (2.14 g, yield 74%) in the same manner as Int(2-7), except that 6-[[tert-butyl(dimethyl)silyl]oxy]-1-hexanol (10.8 g, 46.5 mmol) was changed to 4-(4-hydroxybutyl)-2,2-dimethyl-1,3-dioxolane (8.10 g, 46.5 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 1.21 (s, 6H, >C(CH3)2), 1.25 - 1.44 (m, 6H, -CH2CH2CH2CH<), 3.35 (t, 2H, -OCH2CH2CH2-), 3.62 (d, 1H, >CHCH2O-), 3.82 - 3.87 (m, 2H, >CHCH2-), 4.80 (m, 2H, ArCH2-), 7.37 (m, 1H, Ar), 7.51 - 7.81 (m, 8H, Ar).

[0258]

Chem.

[0259] Except that Int(2 - 1) (3.02 g, 4.70 mmol) was changed to Int(2 - 9) (1.73 g, 4.70 mmol), DPE9 was obtained in the same manner as DPE1 (1.48 g, yield 86%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 1.21 (s, 6H, >C(CH3)2), 1.25 - 1.44 (m, 6H, -CH2CH2CH2CH<), 3.35 (t, 2H, -OCH2CH2CH2-), 3.62 (d, 1H, >CHCH2O-), 3.82 - 3.87 (m, 2H, >CHCH2-), 4.80 (m, 2H, ArCH2-), 5.32 (s, 2H, C=CH2), 7.22 - 7.37 (m, 9H, Ar). 13C NMR (CDCl3, 100 MHz): δ (ppm) = 22.61, 26.20, 30.33, 31.99, 69.20, 70.04, 73.41, 77.82, 114.20, 119.25, 125.00, 127.46 - 128.60, 137.44, 139.97, 141.66, 150.20.

[0260]

Chem.

[0261] <Synthesis of BCP Precursor: Pre(13)> A THF solution of DPE9 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE9 (0.077 g, 0.21 mmol).

[0262] The precursor Pre(13) was obtained in the same manner as Pre(1) (1.15 g, yield 69%), except that the amount of styrene used was changed to (1.06 mL, 9.25 mmol), the THF solution of DPE1 was changed to the THF solution of DPE9, and the amount of methyl methacrylate used was changed to (0.75 mL, 7.0 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(13) measured by size exclusion chromatography (SEC) were 40.2 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.85 (α-CH3, PMMA), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS). 13C NMR (CDCl3, 100 MHz): δ (ppm) = 16.37 - 16.47, 18.56, 22.61, 25.90, 26.20, 29.90, 30.35, 40.20 - 40.42, 44.43, 44.75, 51.73, 52.36, 54,04 - 54.31, 69.20, 70.04, 77.80, 119.25, 125.37 - 125.52, 127.18 - 128.14, 145.15 - 145.54, 176.88, 177.70, 178.00.

[0263]

Chemical Structure

[0264] <Synthesis of BCP: P1-13> P1-13 was obtained in the same manner as P1-7, except that Pre(7) was replaced with Pre(13). The Mn and polydispersity (PDI=Mw / Mn) of P1-13 measured by size exclusion chromatography (SEC) were 40.7 kg mol -1 and 1.03. The synthesis of P1-13 was confirmed by the disappearance of the 13C-NMR peak derived from 2,2-dimethyl-1,3-dioxolane.

[0265] [ka]

[0266] (Synthesis of block copolymer: P1-14) <Synthesis of diphenylethylene derivatives: DPE10> Intermediate Int (2-10) was obtained (12.9 g, 70% yield) in the same manner as for Int (1-1), except that 6-chloro-1-hexanol (7.10 g, 52.0 mmol) was replaced with [4-(3-hydroxypropyl)phenyl]phenylmethanone (12.5 g, 52.0 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=0.05(s,6H,-Si(CH3)2),0.90(s,9H,-SiC(CH3)3),1.87(q,2H,ArCH2CH2CH2-),2.77(m,2H,A rCH2-),3.77(t,2H,-CH2O-),6.92(d,2H,Ar),7.51(m,2H,Ar),7.61-7.72(m,3H,Ar),7.81(d,2H,Ar).

[0267] [ka]

[0268] DPE10 (1.38 g, 83% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-10) (1.67 g, 4.70 mmol). 1H NMR (CDCl3, 400MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.87 (q, 2H, ArCH2CH2CH2-), 2.77 (m, 2H, ArCH2-), 3.77 (t, 2H, -CH2O-), 5.32 (s, 2H, C=CH2), 6.77 (d, 2H, Ar), 7.34 - 7.37 (m, 7H, Ar).

[0269]

Chem.

[0270] <Synthesis of BCP Precursor: Pre(14)> A THF solution of DPE10 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE10 (0.074 g, 0.21 mmol).

[0271] The precursor Pre(14) (1.02 g, yield 61%) was obtained in the same manner as Pre(1), except that the amount of styrene used was changed to (0.91 mL, 8.0 mmol), the THF solution of DPE1 was changed to the THF solution of DPE10, and the amount of methyl methacrylate used was changed to (0.89 mL, 8.4 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(14) measured by size exclusion chromatography (SEC) were 40.6 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0272]

Chem.

[0273] <Synthesis of BCP: P1-14> P1-14 was obtained in the same manner as P1-1, except that Pre(1) was changed to Pre(14). The Mn and dispersity (PDI = Mw / Mn) of P1-14 measured by size exclusion chromatography (SEC) were 41.1 kg mol -1 and 1.03, respectively. The synthesis of P1-14 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0274]

Chemical Structure

[0275] (Synthesis of Block Copolymer: P1-15) <Synthesis of Diphenylethylene Derivative: DPE11> 4,4'-Dihydroxybenzophenone (1.69 g, 7.85 mmol) was changed to [4-(3-bromopropyl)phenyl]phenylmethane (1.38 g, 7.85 mmol) (Journal of Physical Chemistry A (2008), 112(7), 1403-1407.), and Int(1-1) (11.7 g, 46.5 mmol) was changed to 2-[[tert-butyl(dimethyl)silyl]oxy]ethanol (8.20 g, 46.5 mmol). Intermediate Int(2-11) was obtained in the same manner as Int(2-1) (2.32 g, yield 74%). 1HNMR(CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.80 (q, 2H, ArCH2CH2CH2-), 2.77 (m, 2H, ArCH2-), 3.35 (t, 2H, ArCH2CH2CH2O-), 3.59 (t, 2H, -OCH2CH2O-), 3.96 (t, 2H, -OCH2CH2O-), 6.92 (d, 2H, Ar), 7.51 (m, 2H, Ar), 7.61 - 7.72 (m, 3H, Ar), 7.81 (d, 2H, Ar).

[0276]

Chem.

[0277] Except for changing Int(2 - 1) (3.02 g, 4.70 mmol) to Int(2 - 11) (1.87 g, 4.70 mmol), DPE11 was obtained in the same manner as DPE1 (1.60 g, yield 86%). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 1.80 (q, 2H, ArCH2CH2CH2-), 2.77 (m, 2H, ArCH2-), 3.35 (t, 2H, ArCH2CH2CH2O-), 3.59, 3.96 (t, 2H, -OCH2CH2O-), 5.32 (s, 2H, C=CH2), 6.77 (d, 2H, Ar), 7.34 - 7.37 (m, 7H, Ar).

[0278]

Chem.

[0279] <Synthesis of BCP Precursor: Pre(15)> Except for changing DPE1 (0.134 g, 0.209 mmol) to DPE11 (0.083 g, 0.21 mmol), a THF solution of DPE11 was prepared in the same manner as the THF solution of DPE1.

[0280] The amount of styrene used was changed to (1.08 mL, 9.44 mmol), the THF solution of DPE1 was changed to the THF solution of DPE11, and the amount of methyl methacrylate used was changed to (1.02 mL, 9.53 mmol). Except for these changes, the precursor Pre(15) was obtained in the same manner as Pre(1) (1.26 g, yield 65%). The Mn and dispersity (PDI = Mw / Mn) of Pre(15) measured by size exclusion chromatography (SEC) were 47.0 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0281]

Chemical formula

[0282] <Synthesis of block copolymer: P1-15> Except for changing Pre(1) to Pre(15), P1-15 was obtained in the same manner as P1-1. The Mn and dispersity (PDI = Mw / Mn) of P1-15 measured by size exclusion chromatography (SEC) were 47.6 kg mol -1 and 1.03, respectively. The synthesis of P1-15 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0283]

Chemical formula

[0284] (Synthesis of block copolymer: P1-16) <Synthesis of diphenylethylene derivative: DPE12> Intermediate Int (2-12) was obtained in the same manner as Int (2-11), except that 2-[[tert-butyl(dimethyl)silyl]oxy]ethanol (8.20 g, 46.5 mmol) was replaced with 4-(2-hydroxyethyl)-2,2-dimethyl-1,3-dioxolane (6.80 g, 46.5 mmol) (2.11 g, 73% yield). 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,6H,>C(CH3)2),1.64(m,2H,-CH2CH<),1.80(q,2H,ArCH2CH2CH2-),2.77(m,2H,ArCH2-),3.35(t,4H,-CH2OCH2- ),3.62(d,1H,>CHCH2O-),3.82-3.87(m,2H,>CHCH2-),6.92(d,2H,Ar),7.51(m,2H,Ar),7.61-7.72(m,3H,Ar),7.81(d,2H,Ar).

[0285] [ka]

[0286] DPE12 (1.43 g, 83% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-12) (1.73 g, 4.70 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,6H,>C(CH3)2),1.64(m,2H,-CH2CH<),1.80(q,2H,ArCH2CH2CH2-),2.77(m,2H,ArCH2-),3.35(t,4H,-CH 2OCH2-),3.62(d,1H,>CHCH2O-),3.82-3.87(m,2H,>CHCH2-),5.32(s,2H,C=CH2),6.77(d,2H,Ar),7.34-7.37(m,7H,Ar). 13CNMR(CDCl3,100MHz): δ(ppm) = 22.61, 26.20, 31.30, 32.00, 32.99, 69.20 - 69.30, 72.00, 75.41, 114.20, 119.25, 125.00, 127.46 - 128.60, 134.74, 138.95, 141.66, 150.20.

[0287]

Chem.

[0288] <Synthesis of BCP Precursor: Pre(16)> A THF solution of DPE12 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE12 (0.077 g, 0.21 mmol).

[0289] The precursor Pre(16) was obtained in the same manner as Pre(1) (1.35 g, yield 68%), except that the amount of styrene used was changed to (1.17 mL, 10.3 mmol), the THF solution of DPE1 was changed to the THF solution of DPE12, and the amount of methyl methacrylate used was changed to (0.98 mL, 9.2 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(16) measured by size exclusion chromatography (SEC) were 48.0 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ(ppm) = 0.85 (α-CH3, PMMA), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.42 (Ar, PS). 13C NMR (CDCl3, 100 MHz): δ(ppm) = 16.37 - 16.47, 18.56, 22.61, 25.90, 26.20, 31.30, 32.00, 32.99, 40.20 - 40.42, 44.43, 44.75, 51.73, 52.36, 54.04 - 54.31, 69.20, 72.00, 75.80, 119.25, 125.37 - 125.52, 127.18 - 128.60, 134.74, 138.95, 141.66, 145.15 - 145.54, 176.88, 177.70, 178.00.

[0290]

Chem.

[0291] <Synthesis of BCP: P1 - 16> P1 - 16 was obtained in the same manner as P1 - 7, except that Pre(7) was changed to Pre(16). The Mn and dispersity (PDI = Mw / Mn) of P1 - 16 measured by size exclusion chromatography (SEC) were 48.6 kg mol -1 and 1.03, respectively. The synthesis of P1 - 16 was confirmed by the disappearance of the 13C - NMR peak derived from 2,2 - dimethyl - 1,3 - dioxolane.

[0292]

Chem.

[0293] (Synthesis of Block Copolymer: P1 - 17) <Synthesis of BCP Precursor: Pre(17)> A THF solution of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]-oxazole was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]-oxazole (0.058 g, 0.21 mmol) (Gabriel J. Summers & Roderic P. Quirk Polymer International 1996, 40, 79.).

[0294] The amount of styrene used was changed to (0.99 mL, 8.7 mmol), the THF solution of DPE1 was changed to the THF solution of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]-oxazole, and the amount of methyl methacrylate used was changed to (0.86 mL, 8.1 mmol). Otherwise, the precursor Pre(17) was obtained in the same manner as Pre(1) (1.20 g, yield 70%). The Mn and dispersity (PDI = Mw / Mn) of Pre(17) measured by size exclusion chromatography (SEC) were 41.4 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.85 (α-CH3, PMMA), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 4.08 (-OCH2C(CH3)2-, oxazoline) 6.39 - 6.85, 6.91 - 7.42 (Ar, PS).

[0295]

Chemical Structure

[0296] <Synthesis of BCP: P1-17> Pre(17) (1.00 g, 24.2 μmol) was weighed into a two-neck flask, THF (10.0 mL) was added, and then 6N hydrochloric acid (1.0 mL) was added and stirred at 50° C. for 5 hours. The reaction solution was returned to room temperature, and the solids were removed by filtration. The filtrate was added to methanol (300 mL) for precipitation purification. The solid collected by filtration was dried under reduced pressure at 40° C. to obtain P1-17 (0.70 g, 70% yield). The Mn and polydispersity (PDI=Mw / Mn) of P1-17 measured by size exclusion chromatography (SEC) were 41.9 kg mol -1 and 1.03. The synthesis of P1-17 was confirmed by the disappearance of the 1H-NMR peak derived from the oxazoline ring.

[0297] [ka]

[0298] (Synthesis of block copolymer: P1-18) <Synthesis of diphenylethylene derivatives: DPE13> 2-[[tert-Butyl(dimethyl)silyl]oxy]ethanol (1.76 g, 10.0 mmol), dichloromethane (50 mL), pyridine (8.0 mL), and 4-dimethylaminopyridine (3.05 g, 25.0 mmol) were added to a two-neck flask and stirred at room temperature to completely dissolve. The solution was cooled in an ice bath, and 4-benzoylbenzoyl chloride (12.2 g, 50.0 mmol) (Gabriel J. Summers & Roderic P. Quirk Polymer International 1996, 40, 79.) was gently added dropwise, and the mixture was then returned to room temperature and stirred for 2 hours. The reaction solution was washed four times with 1N hydrochloric acid (30 mL), and the combined aqueous layer was extracted with dichloromethane (50 mL). The organic layer was dried over magnesium sulfate, the solvent was removed under reduced pressure, and purification was performed by column chromatography using hexane. The solvent was removed under reduced pressure to give intermediate Int (2-13) (2.70 g, 70% yield). 1H NMR (CDCl3, 400MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 4.25, 4.44 (t, 2H, -COOCH2CH2O-), 7.51 (m, 2H, Ar), 7.61 (m, 1H, Ar), 7.80 - 7.82 (m, 6H, Ar).

[0299]

Chem.

[0300] DPE13 was obtained (1.49 g, yield 83%) in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-13) (1.81 g, 4.70 mmol). 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.05 (s, 6H, -Si(CH3)2), 0.90 (s, 9H, -SiC(CH3)3), 4.25, 4.44 (t, 2H, -COOCH2CH2O-), 5.32 (s, 2H, C=CH2), 7.33 - 7.37 (m, 5H, Ar), 7.45 (d, 2H, Ar), 7.67 (d, 2H, Ar).

[0301]

Chem.

[0302] <Synthesis of BCP Precursor: Pre(18)> A THF solution of DPE13 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE13 (0.080 g, 0.21 mmol).

[0303] The amount of styrene used was changed to (1.12 mL, 9.77 mmol), the THF solution of DPE1 was changed to the THF solution of DPE13, and the amount of methyl methacrylate used was changed to (0.73 mL, 6.9 mmol). Except for these changes, the precursor Pre(18) was obtained in the same manner as Pre(1) (1.16 g, yield 68%). The Mn and dispersity (PDI = Mw / Mn) of Pre(18) measured by size exclusion chromatography (SEC) were 41.0 kg mol -1 and 1.03, respectively. 1H NMR (CDCl3, 400 MHz): δ (ppm) = 0.06 - 0.07 (-Si(CH3)2), 0.85 (α-CH3, PMMA), 0.90 (-SiC(CH3)3), 1.02 (α-CH3, PMMA), 1.23 - 1.69 (-CH2CH-, PS), 1.74 - 2.02 (-CH2CH-, PS, -CH2C(CH3)-, PMMA), 3.60 (-COOCH3, PMMA), 6.39 - 6.85, 6.91 - 7.67 (Ar, PS).

[0304]

Chemical formula

[0305] <Synthesis of BCP: P1-18> Except for changing Pre(1) to Pre(18), P1-18 was obtained in the same manner as P1-1. The Mn and dispersity (PDI = Mw / Mn) of P1-18 measured by size exclusion chromatography (SEC) were 41.5 kg mol-1 and 1.03, respectively. The synthesis of P1-18 was confirmed by the disappearance of the 1H-NMR peak derived from TBDMS.

[0306]

Chemical formula

[0307] (Synthesis of block copolymer: P1-19) <Synthesis of diphenylethylene derivative: DPE14> Intermediate Int (2-14) was obtained in the same manner as Int (2-13), except that 2-[[tert-butyl(dimethyl)silyl]oxy]ethanol (1.76 g, 10.0 mmol) was replaced with 4-(2-hydroxyethyl)-2,2-dimethyl-1,3-dioxolane (1.46 g, 10.0 mmol). (2.34 g, 66% yield) 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,6H,>C(CH3)2),1.93(m,2H,-CH2CH<),3.62(d,1H,>CHCH2O-),3.82-3.87(m, 2H,>CHCH2-),4.23(t,2H,-COOCH2-),7.51(m,2H,Ar),7.61(m,1H,Ar),7.80-7.82(m,6H,Ar).

[0308] [ka]

[0309] DPE14 (1.42 g, 86% yield) was obtained in the same manner as DPE1, except that Int(2-1) (3.02 g, 4.70 mmol) was changed to Int(2-14) (1.67 g, 4.70 mmol). 1H NMR (CDCl3, 400MHz): δ(ppm)=1.21(s,6H,>C(CH3)2),1.93(m,2H,-CH2CH<),3.62(d,1H,>CHCH2O-),3.82-3.87(m,2H,>CHCH2 -),4.23(t,2H,-COOCH2-),5.32(s,2H,C=CH2),7.33-7.37(m,5H,Ar),7.45(d,2H,Ar),7.67(d,2H,Ar). 13CNMR(CDCl3,100MHz): δ(ppm)=26.20,30.70,58.93,68.90,75.31,114.20,119.25,125.00,127.46-128.60,141.66,145.93,150.20,165.98.

[0310] [Chemical]

[0311] <Synthesis of BCP Precursor: Pre(19)> A THF solution of DPE14 was prepared in the same manner as the THF solution of DPE1, except that DPE1 (0.134 g, 0.209 mmol) was changed to DPE14 (0.074 g, 0.21 mmol).

[0312] Precursor Pre(19) was obtained in the same manner as Pre(1) (1.19 g, yield 64%), except that the amount of styrene used was changed to (1.14 mL, 9.98 mmol), the THF solution of DPE1 was changed to the THF solution of DPE14, and the amount of methyl methacrylate used was changed to (0.88 mL, 8.2 mmol). The Mn and dispersity (PDI = Mw / Mn) of Pre(19) measured by size exclusion chromatography (SEC) were 45.0 kg mol -1 and 1.03, respectively. 13C NMR (CDCl3, 100 MHz): δ (ppm) = 16.37 - 16.47, 18.56, 25.90, 26.20, 30.70, 40.20 - 40.42, 44.43, 44.75, 51.73, 52.36, 54.04 - 54.31, 58.93, 68.90, 75.31, 114.20, 119.25, 125.00 - 125.52, 127.18 - 128.60, 141.66, 145.15 - 145.93, 150.20, 165.98, 176.88, 177.70, 178.00.

[0313] [Chemical]

[0314] <Synthesis of BCP: P1 - 19> P1-19 was obtained in the same manner as P1-7, except that Pre(7) was changed to Pre(19). The Mn and polydispersity (PDI = Mw / Mn) of P1-19 measured by size exclusion chromatography (SEC) were 45.5 kg mol -1 and 1.03, respectively. The synthesis of P1-19 was confirmed by the disappearance of the 13C-NMR peak derived from 2,2-dimethyl-1,3-dioxolane.

[0315]

Chemical formula

[0316] <Preparation of BCP Composition> Each component shown in Table 1 was mixed and dissolved to prepare the BCP composition (solid content concentration: 1% by mass) for each example.

[0317]

Table 1

[0318] In Table 1, each abbreviation has the following meaning. The numerical value in [ ] is the blending amount (parts by mass). The number average molecular weight (Mn) of each polymer was determined by size exclusion chromatography (SEC). The copolymer composition ratio of each polymer (the ratio of each structural unit in the structural formula (molar ratio)) was 3 determined by 13C-NMR.

[0319] P1-1: The BCP of the above P1-1. P2-1: The BCP represented by the following chemical formula (P2-1). Mn = 45.0 (kg mol -1 . P2-2: The BCP represented by the following chemical formula (P2-2). Mn = 42.1 (kg mol -1 ).

[0320]

Chemical formula

[0321] (S)-1: Propylene glycol monomethyl ether acetate (PGMEA).

[0322] <Production of Structure Including Phase Separation Structure> After forming a guide pattern with the resist composition, a structure including a phase-separated structure was obtained by the steps described below using the resin composition for forming a phase-separated structure of each of the above examples.

[0323] Process (i): An organic antireflective coating composition "ARC-29A" (product name, Brewer Science) was applied onto a 12-inch silicon wafer using a spinner, and baked on a hot plate at 205°C for 60 seconds to dry, forming an organic antireflective coating with a thickness of 89 nm. The BCP composition shown in Table 3 was spin-coated onto the organic antireflective coating, and then heated at 250°C for 30 minutes. As a result, a 10-nm-thick undercoat layer made of the crosslinked neutral coating composition was formed on the surface of the substrate.

[0324] Forming the guide pattern: A resist film for forming a guide pattern was applied on the undercoat layer, coated using a spinner, prebaked (PAB) on a hot plate, and dried to form a resist film for forming a guide pattern with a thickness of 90 nm. An ArF excimer laser (193 nm) was selectively irradiated through a mask pattern using an ArF exposure device XT-1900Gi (manufactured by ASML). Then, a post-exposure bake (PEB) process was performed, and the film was developed with butyl acetate and dried by shaking. Next, a post-baking process was performed at 100°C for 1 minute, and then at 230°C for 10 minutes to form a guide pattern that was matched to a space dimension four times the d value of the block copolymer used.

[0325] Step (ii): On the substrate on which the guide pattern was formed, the BCP composition shown in Table 3 was spin-coated to a film thickness of 24 nm to form a self-assembled layer.

[0326] Step (ii): The self-assembled layer formed on the substrate was pre-baked at 90° C. for 60 seconds in a nitrogen atmosphere, and then annealed at 200° C. for 30 minutes in a nitrogen atmosphere to form a phase-separated structure.

[0327] Step (iv): The substrate on which the phase-separated structure was formed was subjected to oxygen plasma treatment (200 mL / min, 40 Pa, 40°C, 200 W, 20 seconds) using TCA-3822 (Tokyo Ohka Kogyo Co., Ltd.) to selectively remove the PMMA phase.

[0328] [Measurement of periodicity of structures including phase-separated structures] Small angle X-ray scattering (SAXS) measurements were performed, and the period (nm) of the structure was determined from the first scattering peak of the SAXS pattern curve. The results are shown in Table 3 as "period."

[0329] [Morphology Observation] The surface (phase-separated state) of the obtained substrate was observed with a critical dimension SEM (scanning electron microscope, product name: CG6300, manufactured by Hitachi High-Technologies Corporation) to confirm the morphology of the phase-separated structure. It was evaluated based on the following evaluation criteria, and the results are shown in Table 3 as "morphology". Evaluation criteria ◯: Vertical alignment was observed. ×: Vertical alignment was not observed.

[0330] [Evaluation of pattern defects] The pattern after step (ii) in <Production of structure containing phase separation structure> was observed from above ten sheets at a magnification of 100,000 times using a length measuring SEM (scanning electron microscope, product name: CG6300, manufactured by Hitachi High-Technologies Corporation), and the number of defects was counted. As a result of the counting, the pattern defects were evaluated based on the following evaluation criteria. The results are shown in Table 3 as "Defects". Evaluation criteria Good: Total number of defects is less than 5. ×: The total number of defects is 5 or more.

[0331] [Table 2]

[0332] From the results shown in Table 3, in Example 1, a phase-separated structure with good morphology and reduced number of defects was formed. On the other hand, in Comparative Example 1, the morphology was good, but the reduction in the number of defects was not sufficient. In Comparative Example 2, a phase-separated structure could not be formed. From the above results, it was confirmed that by using the block copolymer (P1), a phase-separated structure with few defects and good phase separation performance can be formed even when the primer layer and the self-assembled layer are formed from the same BCP composition. [Explanation of symbols]

[0333] 1... Support, 2... Base layer, 3... Self-assembled layer, 3'... Structure, 3a... Phase, 3b... Phase.

Claims

1. A step (i) of applying a composition containing a block copolymer represented by the following general formula (n1) onto a substrate to form a base layer; (ii) applying a composition containing the block copolymer onto the undercoat layer to form a self-assembled layer; (iii) phase-separating the self-assembled layer; A method for producing a structure containing a phase-separated structure, comprising: 【Chemistry 1】 wherein A represents a first polymer block; B represents a second polymer block; R １ｃ and R １ｄ each independently represents a substrate adsorptive group-containing group; R ２ｃ and R ２ｄ each independently represents a substituent other than the substrate adsorbent group-containing group; m1 and n1 each independently represent an integer of 0 to 5; m2 and n2 each independently represent an integer of 0 to 5; m1+n1≧1; m1+m2≦5; and n1+n2≦5. When m1 is an integer of 2 or more, a plurality of R １ｃ may be the same or different from each other; when m2 is an integer of 2 or more, ２ｃ may be the same or different from each other; when n1 is an integer of 2 or more, １ｄ may be the same or different from each other; when n2 is an integer of 2 or more, ２ｄ may be the same or different from each other.

2. The method for producing a structure containing a phase-separated structure according to claim 1, wherein the first polymer block and the second polymer block do not have a structural unit (u0) represented by any of the following general formulas (u0-1) to (u0-4): 【Chemistry 2】 [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms; １ , Yu ２ , Yu ３ and Yu ４ each independently represents a divalent linking group; １ , Z ２１ , Z ２２ , Z ３１ , Z ３２ , Z ３３ and Z ４ each independently represents a substrate adsorptive group; ４ represents a cyclic group; and nu represents an integer of 1 or greater, as far as valence permits.

3. The R １ｃ and R １ｄ The method for producing a structure containing a phase-separated structure according to claim 1 or 2, wherein is a group represented by the following general formula (r1): 【Chemistry 3】 [In the formula, X １ represents a single bond, a methylene group, —COO— or —O—; Y １ represents a single bond or a divalent linking group; Z １ represents a group containing a substrate adsorptive group; r1 represents an integer of 1 or more as far as the atomic valence allows. １ When Y is —COO— or —O—, １ does not become a single bond. * represents a bond bonded to a benzene ring in general formula (n1).

4. 3. The method for producing a structure containing a phase-separated structure according to claim 1, wherein the substrate-adsorbing group is a hydroxy group, a carboxy group, a thiol group, a vinyl group, a halogen atom, an amino group, an azide group, a formyl group, an epoxy group, or a cyano group.

5. The first polymer block has a hydrophobic structural unit (Na), The second polymer block has a hydrophilic structural unit (Nb); A method for producing a structure comprising the phase-separated structure according to claim 1 or 2.

6. A composition containing a block copolymer represented by the general formula (n1), which is used in the method for producing a structure containing a phase-separated structure according to claim 1 or 2.

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