Polymer material, method for manufacturing polymer material, self-assembled film, method for manufacturing self-assembled film, pattern, and method for forming pattern

Abstract

To provide a polymeric material capable of forming a self-assembled film with a small half-pitch (hp) of the formed pattern, uniformity, film strength and excellent etching resistance.SOLUTION: A polymeric material contains a multi-block copolymer comprising first and second polymeric blocks connected together. The first polymeric block comprises a constitutional unit represented by the general formula (1) in the figure. The second polymeric block comprises a constitutional unit derived from (α-alkyl)styrene and / or a constitutional unit derived from (meth)acrylic acid alkyl ester. [In the general formula (1), R1 represents a hydrogen atom and a C1-3 alkyl group; a is from 1 to 1000 inclusive; and X is a trimethylsiloxy-oligo(dimethylsiloxy) group.]SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer material, a method for producing a polymer material, a self-assembled film, a method for producing a self-assembled film, a pattern, and a method for forming a pattern. [Background technology]

[0002] As electronic components, including semiconductors, become smaller, there is an increasing demand for lithography technology that can form fine patterns.

[0003] In particular, technology using directed self-assembly (DSA), which utilizes microphase separation of block copolymers, is attracting attention as a next-generation lithography technology because it is capable of forming fine patterns at low cost.

[0004] As an example of such a technique, Patent Document 1 discloses a polymer film in which a block copolymer resin, which is formed by bonding at least two or more types of mutually incompatible polymers at their terminals, is placed on a substrate having a surface roughness of at least 1 nm or more, and the block copolymer film has a microdomain structure oriented perpendicular to the substrate surface, and the block copolymer resin is a mixture of at least two or more types of block copolymer resins having different molecular weights. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-8701 Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors have examined conventional directed self-assembly materials and found that when the half pitch (hp) of the pattern to be formed is small and uniform, and a composition (polymer block configuration or weight average molecular weight) that allows the formation of a directed self-assembly film (also simply referred to as a self-assembly film) that has film strength is used, there is a problem in that the etching resistance during dry etching decreases. In other words, conventional guided self-assembly materials have not been able to form patterns with small and uniform half pitches (hp), have film strength, and exhibit excellent etching resistance during dry etching, and there is still room for further improvement.

[0007] The present invention has been made in view of the above problems, and aims to provide a polymeric material capable of forming a self-assembled film that has a small and uniform half pitch (hp) of the formed pattern, has film strength, and exhibits excellent etching resistance during dry etching. [Means for solving the problem]

[0008] The present inventors have conducted extensive research into the above-mentioned problems and have found that a multiblock copolymer formed by linking a first polymer block containing a structural unit represented by the general formula (1) described below with a second polymer block containing a structural unit represented by the general formula (3) described below and / or a structural unit derived from a (meth)acrylic acid alkyl ester can form a pattern with a small and uniform half pitch (hp) and can also impart film strength. Furthermore, they have found that the etching resistance can be improved, leading to the present invention.

[0009] Specifically, the present invention provides a polymeric material containing a multiblock copolymer formed by linking a first polymer block comprising a structural unit represented by the following general formula (1) with a second polymer block comprising a structural unit represented by the following general formula (3) and / or a structural unit derived from a (meth)acrylic acid alkyl ester; a method for producing a polymeric material, the method comprising the step of producing a multiblock copolymer formed by linking a first polymer block comprising a structural unit represented by the following general formula (1) with a second polymer block comprising a structural unit represented by the following general formula (3) and / or a structural unit derived from a (meth)acrylic acid alkyl ester; a self-assembled film obtained using the polymeric material; a method for producing a self-assembled film that forms a self-assembled film using the polymeric material; a pattern formed by etching the self-assembled film; and a method for forming a pattern, the method comprising the step of etching the self-assembled film to form a pattern.

[0010] [ka] [In general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 or more and 1000 or less, and X is a substituent represented by general formula (2). [ka] [In general formula (2), b is an integer of 1 or more and 5 or less.] [ka] [In general formula (3), R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and c is an integer of 1 or more and 1000 or less. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a polymeric material capable of forming a self-assembled film that has a small and uniform half pitch (hp) of the formed pattern, has film strength, and has excellent etching resistance during dry etching. DETAILED DESCRIPTION OF THE INVENTION

[0012] <Polymer materials> The polymer material of the present invention contains a multiblock copolymer formed by linking a first polymer block containing a structural unit represented by the following general formula (1) with a second polymer block containing a structural unit represented by the following general formula (3) and / or a structural unit derived from a (meth)acrylic acid alkyl ester:

[0013] [ka] [In general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 or more and 1000 or less, and X is a substituent represented by general formula (2). [ka] [In general formula (2), b is an integer of 1 or more and 5 or less.] [ka] [In general formula (3), R 2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and c is an integer of 1 or more and 1000 or less.

[0014] Directed self-assembly (DSA) technology utilizes the ability to form microphase separation, which occurs when two incompatible polymer chains are linked at a single point through copolymerization. In multiblock copolymers linked by covalent bonds, when identical polymer components aggregate intermolecularly and undergo microphase separation, the interfacial curvature during molecular aggregation changes depending on the volume fraction ratio (f) between the two polymer components, resulting in a change in the microdomain structure.

[0015] Known microdomain structures formed by two polymer components (e.g., a first polymer block and a second polymer block) include a spherical structure in which the first polymer block is finely dispersed in the second polymer block, a cylindrical structure in which the first polymer block is linearly dispersed in the second polymer block, a gyroid structure in which multiple first polymer blocks dispersed in the second polymer block are bonded to each other, and a lamellar structure in which the second polymer block and the first polymer block are laminated in layers. The polymer material of the present invention may exhibit any of the above microdomain structures, but from the viewpoint of semiconductor pattern formation, it is preferable that the polymer material exhibit a lamellar structure or a cylindrical structure. First, the first polymer block will be described.

[0016] (First polymer block) The first polymer block contains a constitutional unit represented by the above general formula (1).

[0017] R in the above general formula (1) 1 There are no particular restrictions on the alkyl group, as long as it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, R 1 As the group, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred, from the viewpoint of being able to reduce defects due to poor microphase separation sites and to form fine and minute repeated patterns.

[0018] In the above general formula (2), b is an integer of 1 or more and 5 or less. From the viewpoint of reducing the half pitch (hp), b is preferably 1 or 2, and more preferably 1.

[0019] The first polymer block may contain a structural unit other than the structural unit represented by the above general formula (1). Examples of constitutional units other than the constitutional unit represented by the above general formula (1) include constitutional units represented by the following general formula (4).

[0020] [ka] [In general formula (4), R 3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and d is an integer of 1 or more and 1000 or less.

[0021] R in the above general formula (4) 3 is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 1 The substituents exemplified in can be applied. Among these, R 3 As the group, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred, from the viewpoint of being able to reduce defects due to poor microphase separation sites and to form fine and minute repeated patterns.

[0022] The first polymer block may be, for example, a first polymer block A consisting of a structural unit represented by the general formula (1) above, or a first polymer block B formed by repeated random polymerization of a structural unit represented by the general formula (1) above and a structural unit different from the general formula (1) above (for example, a structural unit represented by the general formula (4) above).

[0023] The first polymer block preferably contains 90 mol % or more of the constitutional unit represented by the general formula (1) above, and more preferably 100 mol % of the constitutional unit represented by the general formula (1) above, based on the entire first polymer block. By including the constitutional unit represented by the general formula (1) in the above proportion relative to the entire first polymer block, it is possible to impart favorable film strength and etching resistance.

[0024] (Second polymer block) The second polymer block contains a structural unit represented by the above general formula (3) and / or a structural unit derived from an alkyl (meth)acrylate ester.

[0025] R in the above general formula (3) 2 is not particularly limited as long as it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 1 The substituents exemplified in can be applied. Among these, R 2 As the group, a hydrogen atom or a methyl group is preferred, and a hydrogen atom is more preferred, from the viewpoint of being able to reduce defects due to poor microphase separation sites and to form fine and minute repeated patterns.

[0026] Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate. Among these, methyl methacrylate is preferred from the viewpoint of providing suitable etching resistance. In this specification, (meth)acrylic acid means acrylic acid and methacrylic acid.

[0027] The second polymer block may be, for example, a second polymer block C formed by repeatedly polymerizing the same structural unit represented by the general formula (3) above, a second polymer block D formed by repeatedly polymerizing a structural unit derived from the alkyl (meth)acrylate ester, or a second polymer block E formed by randomly polymerizing a structural unit represented by the general formula (3) above and a structural unit derived from the alkyl (meth)acrylate ester.

[0028] In the second polymer block E, the molar ratio of the structural unit represented by the above general formula (3) to the structural unit derived from a (meth)acrylic acid alkyl ester is preferably within the range of 9:1 to 1:9.

[0029] (multiblock copolymer) The multiblock copolymer is formed by linking the above-mentioned first polymer block and second polymer block.

[0030] The multi-block copolymer is preferably a di-block or higher block copolymer.

[0031] As the diblock copolymer, a copolymer in which the above-mentioned first polymer blocks A and B and second polymer blocks C, D and E are arranged in any order such as AC, AD, AE, BC, BD, or BE can be used. From the viewpoint of being able to reduce defects due to poor microphase separation sites and being able to form fine and minute repeating patterns, a polymer (AC) in which a first polymer block A formed by repeatedly polymerizing the same structural unit represented by the general formula (1) above and a second polymer block C formed by repeatedly polymerizing the same structural unit represented by the general formula (3) above are arranged is preferred.

[0032] Even when the multiblock copolymer is a triblock copolymer or greater, from the viewpoint of reducing defects due to poor microphase separation sites and enabling the formation of fine and minute repeating patterns, it is preferable that the first polymer blocks A and the second polymer blocks C are arranged alternately, for example, in the form of (ACA), (CAC), (ACACAC), or (CACACA).

[0033] Preferably, the multi-block copolymer is a hexa-block copolymer or smaller. This is because it is difficult to synthesize a heptablock copolymer or a multiblock copolymer.

[0034] Regarding the ratio of the constituent units of the multiblock copolymer, from the viewpoint of improving the uniformity and regularity of the pattern of the microdomain structure formed by self-assembly, the molar ratio of the first polymer block to the second polymer block (moles of the first polymer block:moles of the second polymer block) is preferably within the range of 8:2 to 2:8.

[0035] When the above-mentioned lamellar structure or cylindrical structure is preferably formed, the molar ratio of the first polymer block to the second polymer block (moles of the first polymer block:moles of the second polymer block) is more preferably within the range of 4:6 to 6:4, and even more preferably 5:5, from the viewpoint of improving the uniformity and regularity of the pattern of the microdomain structure formed by self-assembly.

[0036] The multiblock copolymer preferably has a number average molecular weight (Mn) of 3,000 or more and 50,000 or less, from the viewpoint of improving the uniformity and regularity of the pattern of the microdomain structure formed by self-assembly. If the number-average molecular weight (Mn) is 3,000 or more, self-assembly proceeds to form a self-assembled film with a microdomain structure. If the number-average molecular weight (Mn) is 50,000 or less, the hydrogen bonds of the hydrophilic groups of the polymer compound function appropriately, making it easy to achieve a pattern size of 10.0 nm or less. The number average molecular weight (Mn) is more preferably at least 5,000, and even more preferably at least 6,000. The number average molecular weight (Mn) is more preferably at most 20,000.

[0037] The molecular weight distribution (PDI: Mw / Mn=PDI) of the multiblock copolymer is preferably 1.0 or more, more preferably 1.02 or more, and is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of being able to reduce defects due to poor microphase separation sites and to form fine and minute repeating patterns. If the PDI is 1.0 or more and 1.1 or less, there is almost no inclusion of low-molecular-weight polymers and high-molecular-weight polymers, and therefore the uniformity and regularity of the pattern of the microdomain structure formed by self-organization are improved.

[0038] The number average molecular weight (Mn) and PDI (and weight average molecular weight Mw) are measured by gel permeation chromatography (GPC) using polystyrene as the standard. The number average molecular weight measured by GPC is measured at a column temperature of 40°C using, for example, a GPC measuring device (trade name: HLC-8120, manufactured by Tosoh Corporation), a column (trade name: TSK GELGMH6, manufactured by Tosoh Corporation), and a mobile phase (THF), and calculated using a calibration curve of standard polystyrene.

[0039] The composition ratio of the multiblock copolymer can be determined by nuclear magnetic resonance (NMR) spectroscopy. The composition ratio by NMR can be measured, for example, using an NMR measurement device (trade name "JNM-ECZ400R", manufactured by JEOL, analysis software: Delta5.3.1, frequency: 400 MHz), at a temperature of 25°C, solvent (CDCl3), internal standard: tetramethylsilane (TMS), and with 16 accumulations. The composition of the multiblock copolymer means the constituent units that make up the multiblock copolymer, and the composition ratio means the molar ratio of the constituent units that make up the multiblock copolymer.

[0040] The method for producing a polymer material of the present invention includes a step of producing a multiblock copolymer in which a first polymer block containing a structural unit represented by the above general formula (1) is linked to a second polymer block containing a structural unit represented by the above general formula (3) and / or a structural unit derived from a (meth)acrylic acid alkyl ester. As a method for producing a multiblock copolymer, for example, 4-(1-ethoxyethoxy)styrene protected with a protecting group is reacted with a monomer that forms the second polymer block by living anionic polymerization to synthesize the multiblock copolymer. The substituent is not particularly limited, and a t-butyl group, a trialkylsilyl group, or the like can be used. Next, after deprotection, the 4-(1-ethoxyethoxy)styrene moiety is converted to hydroxystyrene by acidolysis, which can be carried out using a known acid and solvent. Thereafter, the hydroxyl group of the hydroxystyrene is substituted with a sodium oxide group (or a potassium oxide group, etc.) to obtain a constitutional unit represented by the following general formula (5) (also referred to as the first-stage addition reaction). Finally, the sodium oxide group in the constitutional unit represented by the following general formula (5) is substituted with siloxane to produce the constitutional unit represented by the above general formula (1) (first polymer block) (this is also referred to as the second-stage addition reaction). The method for substituting the hydroxyl group in the first-stage addition reaction with a sodium oxide group or the like and the method for substituting the sodium oxide group in the second-stage addition reaction with a siloxane are not particularly limited, and known methods can be used.

[0041] [ka] [In general formula (5), R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a is an integer of 1 or more and 1000 or less.

[0042] The multi-block copolymer is preferably copolymerized by living anionic polymerization. A multiblock copolymer of a first polymer block mainly composed of structural units represented by the general formula (1) copolymerized by living anionic polymerization and a second polymer block mainly composed of structural units represented by the general formula (3) is preferred. By copolymerizing polymer materials using living anionic polymerization, it is possible to narrow the PDI and precisely obtain polymer compounds with the desired number-average molecular weight, which enables the uniformity and regularity of the microdomain structure patterns formed by self-organization to be improved.

[0043] There are no particular limitations on the method for producing a polymer compound that is a multiblock copolymer, as long as it can copolymerize the first polymer block and the second polymer block. Polymerization methods for obtaining polymeric materials include living anionic polymerization, living cationic polymerization, living radical polymerization, and coordination polymerization using an organometallic catalyst. Among these, living anionic polymerization is preferred because it causes less deactivation and side reactions during polymerization and allows living polymerization.

[0044] In living anionic polymerization, a polymerization monomer and an organic solvent that have been subjected to deoxidation and dehydration treatment are used. Examples of organic solvents include hexane, cyclohexane, toluene, benzene, diethyl ether, and tetrahydrofuran. In living anionic polymerization, a required amount of anionic species is added to these organic solvents, and then monomers are added as needed to carry out polymerization. Examples of anionic species include organic metals such as alkyllithium, alkylmagnesium halide, sodium naphthalene, and alkylated lanthanoid compounds. Since a substituted styrene is copolymerized as a monomer, among these, s-butyllithium and butylmagnesium chloride are preferred as the anion species. The polymerization temperature for living anionic polymerization is preferably within the range of -100°C or higher and 50°C or lower, and from the viewpoint of facilitating control of the polymerization, it is more preferably -70°C or higher and 40°C or lower.

[0045] <Self-assembled membrane> The self-assembled film of the present invention can be obtained using the above-described polymer material of the present invention. The polymer material of the present invention is preferably used for self-assembly (formation of a self-assembled film) because it can form a self-assembled film that has a small and uniform half pitch (hp) of the pattern to be formed, has film strength, and has excellent etching resistance during dry etching.

[0046] The self-assembled film of the present invention can be obtained by dissolving the polymer material of the present invention in an organic solvent and applying the solution.

[0047] The organic solvent is not particularly limited as long as it can form a self-assembled monolayer, and examples thereof include butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, 3-ethoxyethyl propionate, 3-ethoxymethyl propionate, 3-methoxymethyl propionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl pyruvate, ethyl pyruvate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether propionate. Examples of the solvent include propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, and tetramethylene sulfone. These solvents may be used alone or in combination of two or more.

[0048] The organic solvent is preferably propylene glycol alkyl ether acetate or alkyl lactate. Examples of the propylene glycol alkyl ether acetate include those having an alkyl group with 1 to 4 carbon atoms. Examples of such alkyl groups include methyl, ethyl, propyl, and butyl. Among these, methyl and ethyl are preferred. Furthermore, propylene glycol alkyl ether acetate has three isomers depending on the combination of substitution positions, including 1,2-substituted and 1,3-substituted isomers. These isomers may be used alone or two or more isomers may be used in combination.

[0049] Examples of alkyl lactate esters include those in which the number of carbon atoms in the alkyl group is 1 to 4. Examples of such alkyl groups include methyl, ethyl, propyl, and butyl groups. Among these, methyl and ethyl groups are preferred.

[0050] Regarding the concentration of the organic solvent, for example, when propylene glycol alkyl ether acetate is used, the propylene glycol alkyl ether acetate is preferably 50% by mass or more relative to the total mass of the organic solvent, and when alkyl lactate is used, the propylene glycol alkyl ether acetate is preferably 50% by mass or more relative to the total mass of the organic solvent. When a mixed solvent of propylene glycol alkyl ether acetate and alkyl lactate is used as the organic solvent, the total amount of the mixed solvent is preferably 50% by mass or more based on the total mass of the organic solvent. When using this mixed solvent, it is preferable to use propylene glycol alkyl ether acetate in a proportion of 60% by mass to 95% by mass and alkyl lactate in a proportion of 5% by mass to 40% by mass. By using propylene glycol alkyl ether acetate in a proportion of 60% by mass or more, the coatability of the polymer material is improved, and by using propylene glycol alkyl ether acetate in a proportion of 95% by mass or less, the solubility of the polymer material is improved.

[0051] The concentration of the solution in which the polymer material of the present invention is dissolved in an organic solvent is not particularly limited, as long as it allows a self-assembled film to be obtained by a conventionally known film-forming method. For example, the organic solvent is preferably 5,000 parts by mass or more and 50,000 parts by mass or less, and more preferably 7,000 parts by mass or more and 30,000 parts by mass or less, per 100 parts by mass of the solid content of the polymer material.

[0052] The self-assembled film of the present invention can be produced by applying a solution in which the polymer material of the present invention is dissolved in an organic solvent. The method for applying the solution in which a polymer material is dissolved in an organic solvent is not particularly limited as long as it can produce a self-assembled film, and examples thereof include spin coating, dipping, flexographic printing, inkjet printing, spraying, potting, and screen printing. The present invention also encompasses a method for producing a self-assembled film by forming a self-assembled film using the polymer material of the present invention.

[0053] The self-assembled film of the present invention is preferably coated on its surface with a top coating agent from the viewpoint of improving the handling properties and weather resistance of the self-assembled film, since the self-assembled film is sealed and protected.

[0054] Examples of the top coating agent include polyester-based top coating agents, polyamide-based top coating agents, polyurethane-based top coating agents, epoxy-based top coating agents, phenol-based top coating agents, (meth)acrylic-based top coating agents, polyvinyl acetate-based top coating agents, polyolefin-based top coating agents such as polyethylene aluminum and polypropylene, and cellulose-based top coating agents. The coating amount of the above top coating agent (solid content equivalent) is 3 g / m 2 More than 7g / m 2 The following is preferred: The above-mentioned top coating agent can be applied onto the self-assembled monolayer by a conventionally known application method. The present invention also encompasses a method for producing a self-assembled film, which includes a step of applying a top coating agent onto the self-assembled film.

[0055] The self-assembled film of the present invention may be coated with an undercoating agent. As the undercoating agent, various conventionally known undercoating agents can be used.

[0056] The self-assembled film of the present invention preferably forms a self-assembled film within a guide pattern. In this case, for example, a solution of a polymer material can be applied to a silicon substrate with a guide pattern to form a self-assembled film. Then, a pattern of the self-organized microdomain structure is obtained on the silicon substrate by annealing at 200° C. to 300° C. for 5 minutes to 1 hour. By etching the resulting microdomain structure pattern with oxygen plasma gas, an L / S (line / space) pattern and a CH (fine hole) pattern with a half pitch (hp) of 10.0 nm or less can be obtained. The present invention also encompasses a pattern formed by etching the self-assembled film, and a method for forming a pattern including the step of etching the self-assembled film to form a pattern.

[0057] The cohesive strength of the multiblock copolymer can be evaluated by transmission electron microscope (TEM) observation and small-angle X-ray scattering (SAXS) measurement. A sample for evaluating cohesive strength can be prepared, for example, by preparing a 50 mg sample film of the multiblock copolymer, dissolving the prepared sample in 1 g of additive-free THF, transferring the sample to a Teflon petri dish, casting it in the Teflon petri dish for 10 days, and vacuum drying it.

[0058] For TEM observation, first, the sample film is cut to an appropriate size and placed in an embedding mold, then epoxy resin is poured into it and left to stand at 60°C for 12 hours to harden the epoxy resin and perform the embedding process. The embedded sample film is then cut into sections approximately 50 nm thick using a microtome, and the sections are then collected on Cu grids and stained with Cs2CO3 before being observed with a transmission electron microscope to measure hp.

[0059] In the SAXS measurement, for example, a block copolymer powder is heat-treated on a heat-resistant film, and microphase separation in the bulk state can be measured using a small-angle X-ray scattering (SAXS) analyzer (ultrafine periodic structure analysis system Nano-Viewer AXIS IV, manufactured by Rigaku).

[0060] In this microphase separation measurement, for example, X-rays are incident on a sample film of a block copolymer, and the angular dependence of scattering that appears on the small angle side is measured for 60 minutes using an imaging plate. Regarding measurement data processing, background correction such as air scattering is performed to obtain q / nm -1 After calculating and performing Fourier transform analysis, the half pitch (hp) of the self-assembled monolayer, which is half the identity period (d) of the average repeating pattern size width of the microdomain structure formed by self-assembly of the block copolymer, can be measured.

[0061] The present specification discloses the following:

[0062] The present disclosure (1) is a polymer material containing a multiblock copolymer formed by linking a first polymer block containing a structural unit represented by the above general formula (1) and a second polymer block containing a structural unit represented by the above general formula (3) and / or a structural unit derived from a (meth)acrylic acid alkyl ester.

[0063] The present disclosure (2) is the polymer material according to the present disclosure (1), wherein the multiblock copolymer is a diblock copolymer or more and a hexablock copolymer or less.

[0064] The present disclosure (3) is the polymer material according to the present disclosure (1) or (2), in which the multiblock copolymer is copolymerized by living anionic polymerization.

[0065] The present disclosure (4) is the polymer material according to any one of the present disclosures (1) to (3), wherein the multiblock copolymer has a number average molecular weight of 3,000 or more and 50,000 or less.

[0066] The present disclosure (5) is a method for producing a polymer material, comprising a step of producing a multiblock copolymer in which a first polymer block containing a constitutional unit represented by the above general formula (1) and a second polymer block containing a constitutional unit represented by the above general formula (3) and / or a constitutional unit derived from a (meth)acrylic acid alkyl ester are linked together.

[0067] The present disclosure (6) is a self-assembled film obtained by using the polymer material according to any one of the present disclosures (1) to (4).

[0068] The present disclosure (7) is the self-assembled film according to the present disclosure (6), the surface of which is coated with a top coating agent.

[0069] The present disclosure (8) is a method for producing a self-assembled film, which uses the polymer material according to any one of the present disclosures (1) to (4).

[0070] The present disclosure (9) is a method for producing a self-assembled film according to the present disclosure (8), which forms a self-assembled film within a guide pattern.

[0071] The present disclosure (10) is a method for producing a self-assembled film according to the present disclosure (8) or (9), which includes a step of applying a top coating agent onto the self-assembled film.

[0072] The present disclosure (11) is a pattern obtained by etching the self-assembled film according to the present disclosure (6) or (7).

[0073] The present disclosure (12) is a method for forming a pattern, including a step of etching the self-assembled film according to the present disclosure (6) or (7) to form a pattern. [Example]

[0074] Examples and comparative examples conducted to clarify the effects of the present invention will be described below, but the present invention is not limited to the following examples and comparative examples.

[0075] Example 1: Synthesis of diblock copolymer (BP-3) After drying a 5 L anionic polymerization reactor under reduced pressure, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been distilled and purified was added dropwise, adjusting the dropping rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymer block precursor). Next, 48.0 g of styrene that had been subjected to a distillation dehydration treatment was added dropwise and reacted for 30 minutes (formation of a second polymer block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 130 g of a diblock copolymer (BP-1).

[0076] Next, 50 g of the obtained diblock copolymer (BP-1) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-2). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of diblock copolymer (BP-2).

[0077] Next, 38 g of the obtained diblock copolymer (BP-2) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was then added, and the atmosphere was replaced with nitrogen. After that, stirring was started and the temperature was raised to 130°C, followed by stirring at the same temperature for 8 hours (first-stage addition reaction). Next, 29.6 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction).The polymerization reaction was then stopped, and the reaction solution was concentrated to obtain 62 g of the target diblock copolymer (BP-3).

[0078] <Measurement of number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (PDI) of diblock copolymer (BP-3)> The number average molecular weight and molecular weight distribution of the obtained diblock copolymer (BP-3) were measured by gel permeation chromatography (GPC). The measurement conditions are shown below. The measurement results are shown below and in Table 2 below. GPC measuring device: Product name: "HLC-8120", manufactured by Tosoh Corporation Column: Product name "TSK GEL GMH6", manufactured by Tosoh Corporation Mobile phase: THF Column temperature: 40℃ Standard material: polystyrene

[0079] As a result of GPC measurement using standard polystyrene as a standard, the obtained diblock copolymer (BP-3) had an Mn of 10032, an Mw of 10835, and a PDI of 1.08.

[0080] <Measurement of composition ratio of diblock copolymer (BP-3)> Nuclear Magnetic Resonance (NMR) spectroscopy ( 1 The composition ratio of the obtained diblock copolymer (BP-3) was measured by H-NMR under the following measurement conditions. NMR measurement equipment: Product name "JNM-ECZ400R, manufactured by JEOL Corporation, Analysis software: Delta5.3.1" Frequency: 400MHz Temperature: 25℃ Solvent: CDCl3 Internal standard: tetramethylsilane (TMS) Accumulation count: 16 times

[0081] From the area ratio of each signal, it was found that the composition ratio (molar ratio) of the diblock copolymer (BP-3) was first polymer block:second polymer block=48:52.

[0082] In the SAXS measurement, the block copolymer powder was heat-treated on a heat-resistant film, and microphase separation in the bulk state was measured using small-angle X-ray scattering (SAXS) and an analytical device (ultrafine periodic structure analysis system: product name "Nano-Viewer AXIS IV", manufactured by Rigaku). X-rays were incident on a sample film of diblock copolymer (BP-3), and the angular dependence of scattering that appears on the small angle side was measured for 60 minutes using an imaging plate. Regarding measurement data processing, background correction such as air scattering was performed and the q / nm -1 was calculated, and after performing Fourier transform analysis, the half pitch (hp) of the self-assembled film, which is half the identity period (d) of the average repeat pattern size width of the microdomain structure formed by self-assembly of the block copolymer, was measured. As a result, the identity period (d) was 18.0 nm and the half pitch (hp) was 9.0 nm. The measurement results are shown in Table 2 below.

[0083] Example 2: Synthesis of tetrablock copolymer (BP-6) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 40.5 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymer block A precursor). Next, 24.0 g of styrene that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymer block A precursor). Next, 40.5 g of 4-(1-ethoxyethoxy)styrene, which had been further dehydrated by distillation, was added dropwise, and the mixture was allowed to react for another 30 minutes (formation of a first polymer block B precursor). Next, 24.0 g of styrene, which had been further dehydrated by distillation, was added dropwise, and the mixture was allowed to react for another 30 minutes (formation of a second polymer block B precursor). The polymerization reaction was then terminated by adding 30 g of methanol, and the reaction solution was concentrated to obtain 130 g of tetrablock copolymer (BP-4).

[0084] Next, 50 g of the resulting tetrablock copolymer (BP-4) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected tetrablock copolymer. The deprotected tetrablock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the tetrablock copolymer (BP-5). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of the tetrablock copolymer (BP-5).

[0085] Next, 38 g of the obtained tetrablock copolymer (BP-5) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was then added, and the atmosphere was replaced with nitrogen. After that, stirring was started and the temperature was raised to 130°C, followed by stirring at the same temperature for 8 hours (first-stage addition reaction). Next, 29.6 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction).The polymerization reaction was then stopped, and the reaction solution was concentrated to yield 62 g of the target tetrablock copolymer (BP-6).

[0086] The resulting tetrablock copolymer (BP-6) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the tetrablock copolymer (BP-6) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block (A+B): Second polymer block (A+B)=48:52 Mn=9983 Mw=10681 PDI=1.07

[0087] Next, the uniform period (d) and hp of the pattern fabricated by the above-mentioned method were measured. As a result, the uniform period (d) was 9.0 nm and hp was 4.5 nm. The measurement results are shown in Table 2 below.

[0088] Example 3: Synthesis of hexablock copolymer (BP-9) After drying a 5 L anionic polymerization reactor under reduced pressure, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 27.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymer block A precursor). Next, 16.0 g of styrene that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymer block A precursor). Next, 27.0 g of 4-(1-ethoxyethoxy)styrene that had been further dehydrated by distillation was added dropwise, and after completion of the dropwise addition, the mixture was allowed to react for an additional 30 minutes (formation of a precursor of the first polymer block B). Next, 16.0 g of styrene that had been further dehydrated by distillation was added dropwise, and the mixture was allowed to react for an additional 30 minutes (formation of a precursor of the second polymer block B). Next, 27.0 g of 4-(1-ethoxyethoxy)styrene, which had been further dehydrated by distillation, was added dropwise, and the mixture was allowed to react for another 30 minutes after the addition (formation of a precursor for the first polymer block C). Next, 16.0 g of styrene, which had been further dehydrated by distillation, was added dropwise, and the mixture was allowed to react for another 30 minutes (formation of a precursor for the second polymer block C). The polymerization reaction was then terminated by adding 30 g of methanol, and the reaction solution was concentrated to obtain 130 g of a hexablock copolymer (BP-7).

[0089] Next, 50 g of the resulting hexablock copolymer (BP-7) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected hexablock copolymer. The deprotected hexablock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the hexablock copolymer (BP-8). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a hexablock copolymer (BP-8).

[0090] Next, 38 g of the obtained hexablock copolymer (BP-8) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was then added, and the atmosphere was replaced with nitrogen. After stirring, the temperature was raised to 130°C and the mixture was stirred at the same temperature for 8 hours (first-stage addition reaction). Next, 29.6 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction).The polymerization reaction was then stopped, and the reaction solution was concentrated to yield 62 g of the target hexablock copolymer (BP-9).

[0091] The resulting hexablock copolymer (BP-9) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the hexablock copolymer (BP-9) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block (A+B+C): Second polymer block (A+B+C) = 48:52 Mn=10082 Mw=10989 PDI=1.09

[0092] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 8.4 nm and hp was 4.2 nm. The measurement results are shown in Table 2 below.

[0093] Example 4: Synthesis of diblock copolymer (BP-12) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 24.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymerization block precursor). Next, 48.0 g of styrene that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymerization block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 132 g of a diblock copolymer (BP-10).

[0094] Next, 50 g of the obtained diblock copolymer (BP-10) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-11). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 39 g of a white powder solid of a diblock copolymer (BP-11).

[0095] Next, 39 g of the resulting diblock copolymer (BP-11) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was added, and after nitrogen substitution, stirring was started. The temperature was raised to 130 °C and the mixture was stirred at the same temperature for 8 hours (first-stage addition reaction). Next, 29.1 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to obtain 62 g of the desired diblock copolymer (BP-12).

[0096] The resulting diblock copolymer (BP-12) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (BP-12) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block:second polymer block=48:52 Mn=3387 Mw=3590 PDI=1.06

[0097] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 10.0 nm and hp was 5.0 nm. The measurement results are shown in Table 2 below.

[0098] Example 5: Synthesis of diblock copolymer (BP-15) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 1.60 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymerization block precursor). Next, 48.0 g of styrene that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymerization block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 129 g of a diblock copolymer (BP-13).

[0099] Next, 50 g of the obtained diblock copolymer (BP-13) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected block copolymer. The deprotected block copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-14). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a diblock copolymer (BP-14).

[0100] Next, 38 g of the resulting diblock copolymer (BP-14) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was added, and after nitrogen substitution, stirring was started. The temperature was raised to 130 °C and the mixture was stirred at the same temperature for 8 hours (first-stage addition reaction). Next, 29.8 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to obtain 62 g of the desired diblock copolymer (BP-15).

[0101] The composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (BP-15) obtained were measured by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block:second polymer block=48:52 Mn=49408 Mw=53361 PDI=1.08

[0102] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 20.0 nm and hp was 10.0 nm. The measurement results are shown in Table 2 below.

[0103] Example 6: Synthesis of diblock copolymer (BP-18) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymerization block precursor). Next, 48.0 g of styrene that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymerization block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 130 g of a diblock copolymer (BP-16).

[0104] Next, 50 g of the obtained diblock copolymer (BP-16) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-17). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a diblock copolymer (BP-17).

[0105] Next, 38 g of the resulting diblock copolymer (BP-17) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was added, and after nitrogen substitution, stirring was started. The temperature was raised to 130 °C and the mixture was stirred at that temperature for 8 hours (first-stage addition reaction). Next, 48.2 g of 1-chloro-1,1,3,3,5,5,5-heptamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to yield 81 g of the desired diblock copolymer (BP-18).

[0106] The resulting diblock copolymer (BP-18) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (BP-18) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block:second polymer block=48:52 Mn=12981 Mw=14019 PDI=1.08

[0107] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 20.0 nm and hp was 10.0 nm. The measurement results are shown in Table 2 below.

[0108] Example 7: Synthesis of diblock copolymer (BP-21) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the addition rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the addition was completed, the reaction was continued for an additional 30 minutes (formation of the first polymer block precursor). Next, 46.0 g of methyl methacrylate that had been distilled and dehydrated was added dropwise and allowed to react for an additional 30 minutes (formation of the second polymer block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 128 g of a diblock copolymer (BP-19).

[0109] Next, 50 g of the obtained diblock copolymer (BP-19) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-20). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a diblock copolymer (BP-20).

[0110] Next, 38 g of the resulting diblock copolymer (BP-20) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.4 g of potassium t-butoxide was added, and after nitrogen substitution, stirring was started. The temperature was raised to 130 °C and the mixture was stirred at the same temperature for 8 hours (first-stage addition reaction). Next, 30.1 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to obtain 62 g of the desired diblock copolymer (BP-21).

[0111] The resulting diblock copolymer (BP-21) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (BP-21) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block:second polymer block=48:52 Mn=9908 Mw=10701 PDI=1.08

[0112] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 20.0 nm and hp was 10.0 nm. The measurement results are shown in Table 2 below.

[0113] Example 8: Synthesis of diblock copolymer (BP-24) After vacuum drying a 5 L anionic polymerization reactor, 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70 °C. Next, 8.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 81.0 g of 4-(1-ethoxyethoxy)styrene that had been purified by distillation was added dropwise, adjusting the dropping rate so that the internal temperature of the reaction solution did not exceed -60 °C. After the dropwise addition, the reaction was continued for an additional 30 minutes (formation of the first polymer block precursor). Next, a mixed solution of 24.0 g of styrene and 23.0 g of methyl methacrylate that had been further distilled and dehydrated was added dropwise and allowed to react for 30 minutes (formation of the second polymer block precursor). Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 129 g of a diblock copolymer (BP-22).

[0114] Next, 50 g of the obtained diblock copolymer (BP-22) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (BP-23). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a diblock copolymer (BP-23).

[0115] Next, 38 g of the resulting diblock copolymer (BP-23) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating and stirring device and a cooling device. 0.3 g of potassium t-butoxide was added, and after nitrogen substitution, stirring was started. The temperature was raised to 130 °C and the mixture was stirred at the same temperature for 8 hours (first-stage addition reaction). Next, 29.8 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to obtain 62 g of the desired diblock copolymer (BP-24).

[0116] The resulting diblock copolymer (BP-24) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (BP-24) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. First polymer block:second polymer block=48:52 Mn=9970 Mw=10768 PDI=1.08

[0117] Next, the uniform period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the uniform period (d) was 19.0 nm and hp was 9.5 nm. The measurement results are shown in Table 2 below.

[0118] (Comparative Example 1: Synthesis of diblock copolymer (RBP-2)) A 5 L anionic polymerization reactor was dried under reduced pressure, and then 4500 g of a tetrahydrofuran (THF) solution that had been distilled and dehydrated using metallic sodium and anthracene was poured into the reactor and cooled to -70°C. Next, 5.00 ml of s-butyllithium (cyclohexane solution: 2.03 mol / L) was poured into the cooled THF solution. Next, 48.9 g of styrene that had been purified by distillation was added dropwise, adjusting the dropping rate so that the internal temperature of the reaction solution did not exceed -60°C. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes. Next, 90.0 g of 4-(1-ethoxyethoxy)styrene that had been further subjected to a distillation dehydration treatment was added dropwise and reacted for 30 minutes. Thereafter, 30 g of methanol was added to terminate the polymerization reaction, and the reaction solution was concentrated to obtain 100 g of a diblock copolymer (RBP-1).

[0119] Next, 50 g of the obtained diblock copolymer (RBP-1) was dissolved in 300 g of THF and poured into a 1 L reaction vessel, after which 175 g of methanol and 1 g of oxalic acid were added and a deprotection reaction was carried out for 20 hours at 40°C under a nitrogen atmosphere. Next, the reaction solution was cooled to around room temperature, and then 2 g of pyridine was added to carry out a neutralization reaction. The resulting reaction solution was concentrated under reduced pressure, and then 100 g of THF and 100 g of acetone were added to redissolve the deprotected diblock copolymer. The deprotected diblock copolymer solution was then added to 4.5 L of ultrapure water to precipitate the diblock copolymer (RBP-2). Thereafter, the solid component was filtered and then dried under reduced pressure at 50° C. for 20 hours to obtain 38 g of a white powder solid of a diblock copolymer (RBP-2).

[0120] The resulting diblock copolymer (RBP-2) was used to measure the composition ratio (molar ratio), Mn, Mw, and PDI of the diblock copolymer (RBP-2) by the above-mentioned measurement methods. The measurement results are shown below and in Table 2 below. Styrene (St): 4-hydroxystyrene (HSt) = 50:50 Mn=10423 Mw=10840 PDI=1.04

[0121] Next, the identity period (d) and hp of the pattern produced by the above-mentioned method were measured. As a result, the identity period (d) was 20.0 nm and hp was 10.0 nm. The measurement results are shown in Table 2 below.

[0122] (Etching rate measurement) Polymers for evaluation were prepared from the structural units of the block copolymers prepared in the Examples and Comparative Examples, and the etching rates (nm / sec) of each were measured.

[0123] The polystyrene (PSt) described below is a polymer having styrene (St) as a constituent unit. Polymethyl methacrylate (PMMA) is a polymer whose structural unit is methyl methacrylate (MMA). The random copolymer of PSt and PMMA is a random copolymer of polystyrene (PSt) and polymethyl methacrylate (PMMA). Poly(4-(4,4,4-tri-PSt-PMMA random copolymer methylsiloxy-2,2-dimethylsiloxy)styrene (PTMSDMSSt, in general formula (1), R 1 represents a hydrogen atom, and X is a substituent represented by general formula (2) where b is 1) is a polymer having 4-(4,4,4-trimethylsiloxy-2,2-dimethylsiloxy)styrene (TMSDMSSt) as a constituent unit. Poly(4-(6,6,6-trimethylsiloxy-4,4-dimethylsiloxy-2,2-dimethylsiloxy)styrene (PTMSTMDSSt, in general formula (1), R 1 represents a hydrogen atom, and X is a substituent represented by general formula (2) where b is 2) is a polymer having 4-(6,6,6-trimethylsiloxy-4,4,2,2-tetramethyldisiloxy)styrene (TMSTMDSSt) as a constituent unit. Poly(4-hydroxystyrene) (PHSt) is a polymer whose building block is 4-hydroxystyrene (HSt).

[0124] <Polystyrene (PSt)> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Subsequently, 20.5 g of styrene (St) and 20.0 g of toluene were added, and the reaction solution in the flask was stirred with a magnetic stirrer while bubbling nitrogen at 0°C for 15-20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask. The precipitate was collected by vacuum filtration and dried under vacuum at 60°C to obtain 15 g of polystyrene (PSt).

[0125] The weight average molecular weight and molecular weight distribution of the obtained polystyrene (PSt) were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0126] <Polymethyl methacrylate (PMMA)> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Subsequently, 20.5 g of methyl methacrylate (MMA) and 20.0 g of toluene were added, and the reaction solution in the flask was stirred with a magnetic stirrer while bubbling nitrogen at 0°C for 15-20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask, and the resulting precipitate was collected by vacuum filtration. The collected precipitate was then dried in vacuo at 60°C to obtain 15 g of polymethyl methacrylate (PMMA).

[0127] The weight average molecular weight and molecular weight distribution of the obtained polymethyl methacrylate (PMMA) were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0128] <PSt-PMMAランダムコポリマー> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Subsequently, 10.3 g of styrene (St), 10.3 g of methyl methacrylate (MMA), and 20.0 g of toluene were added. The reaction solution in the flask was stirred with a magnetic stirrer while bubbling with nitrogen at 0°C for 15–20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask. The precipitate was collected by vacuum filtration and dried in vacuo at 60°C to yield 15 g of PSt-PMMA random copolymer.

[0129] The weight average molecular weight and molecular weight distribution of the obtained PSt-PMMA random copolymer were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0130] <Poly 4-(4,4,4-trimethylsiloxy-2,2-dimethylsiloxy)styrene (PTMSDMSSt)> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Next, 9.2 g of 4-hydroxystyrene (HSt) and 20.0 g of toluene were added, and the reaction solution in the flask was stirred with a magnetic stirrer while bubbling nitrogen at 0°C for 15-20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask. The precipitate was collected by vacuum filtration and dried under vacuum at 60°C to obtain 7 g of poly(4-hydroxystyrene) (PHSt).

[0131] Next, 7 g of the resulting poly(4-hydroxystyrene) (PHSt) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating / stirring device and a cooling device. 0.1 g of potassium t-butoxide was added, and the mixture was purged with nitrogen. The mixture was then heated to 130°C and stirred at that temperature for 8 hours (first-stage addition reaction). Next, 14.1 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to yield 20 g of the desired poly(4-(4,4,4-trimethylsiloxy-2,2-dimethylsiloxy)styrene (PTMSDMSSt).

[0132] The weight average molecular weight and molecular weight distribution of the resulting poly 4-(4,4,4-trimethylsiloxy-2,2-dimethylsiloxy)styrene (PTMSDMSSt) were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0133] <Poly 4-(6,6,6-trimethylsiloxy-4,4,2,2-tetramethyldisiloxy)styrene (PTMSTMDSSt)> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Subsequently, 6.5 g of 4-hydroxystyrene (HSt) and 20.0 g of toluene were added, and the reaction solution in the flask was stirred with a magnetic stirrer while bubbling nitrogen at 0°C for 15-20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask. The precipitate was collected by vacuum filtration and dried under vacuum at 60°C to obtain 5 g of poly(4-hydroxystyrene) (PHSt).

[0134] Next, 5 g of the resulting poly(4-hydroxystyrene) (PHSt) was dissolved in 100 g of THF and poured into a glass reactor equipped with a heating / stirring device and a cooling device. 0.1 g of potassium t-butoxide was added, and the mixture was purged with nitrogen. The mixture was then heated to 130°C and stirred at that temperature for 8 hours (first-stage addition reaction). Next, 37.2 g of 1-chloro-1,1,3,3,3-pentamethyldisiloxane was added dropwise at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 3 hours until the pressure reached equilibrium (second-stage addition reaction). The polymerization reaction was then terminated, and the reaction solution was concentrated to yield 20 g of the desired poly(4-(6,6,6-trimethylsiloxy-4,4,2,2-tetramethyldisiloxy)styrene (PTMSTMDSSt).

[0135] The weight average molecular weight and molecular weight distribution of the resulting poly 4-(6,6,6-trimethylsiloxy-4,4,2,2-tetramethyldisiloxy)styrene (PTMSTMDSSt) were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0136] <Poly 4-hydroxystyrene (PHSt)> A 50 mL three-neck flask was charged with 0.063 g of 2,2'-azobis(2-isobutyronitrile) (AIBN) (manufactured by Nippon Finechem Co., Ltd.). The flask was equipped with a Dimroth condenser, a thermometer, and a vacuum line. The pressure was reduced and the contents were purged with nitrogen three times. Subsequently, 20.5 g of 4-hydroxystyrene (HSt) and 20.0 g of toluene were added, and the reaction solution in the flask was stirred with a magnetic stirrer while bubbling nitrogen at 0°C for 15-20 minutes. The reaction solution was then heated to 70°C in an oil bath and stirred for 5 hours. The three-neck flask was removed from the oil bath and cooled on ice. Next, 100 g of methanol was added to the three-neck flask. The resulting precipitate was collected by vacuum filtration and dried under vacuum at 60°C to obtain 15 g of poly(4-hydroxystyrene) (PHSt).

[0137] The weight average molecular weight and molecular weight distribution of the obtained poly(4-hydroxystyrene) (PHSt) were measured in the same manner as in Example 1. The measurement results are as follows. Mw:100000 ·Molecular weight distribution (Mw / Mn)=1.90

[0138] Each solution was prepared by dissolving 1 g of each polymer for evaluation in 99 g of propylene glycol monomethyl ether acetate. The resulting solution was applied to a silicon wafer using a spin coater (MIKASA, SPINCOATER 1H-360S). The coating was heated at 120°C for 60 seconds to form a polymer layer (approximately 600 nm thick) for use as a sample for etching rate measurement. The etching equipment used was a batch-type plasma cleaner PX-250 manufactured by March Plasma Systems, Inc. The thickness of the polymer layer before and after etching was measured using an Filmetrics F20 and compared to determine the etching rate (nm / sec). The ratio of the etching rate of each polymer layer to the etching rate of the polystyrene (PSt) film was calculated as the etching rate ratio. The smaller the etching rate ratio of the second polymer block to the first polymer block, the more difficult it is to remove by etching, and the larger the etching rate ratio of the second polymer block to the first polymer block, the more easily it is to remove by etching.

[0139] [Table 1]

[0140] As shown in Table 1, PTMSDMSSt and PTMSTMDST, which correspond to the first polymerized block, showed smaller etching rate ratios than PSt, PMMA, and the random copolymer of PSt and PMMA, which correspond to the second polymerized block. These results confirmed that domains mainly containing the second polymer block can be removed with high selectivity from the lamellar structures formed by phase separation of the block copolymers of Examples 1 to 8, which had first polymer blocks corresponding to PTMSDMSSt and PTMSTMDSt, and second polymer blocks corresponding to PSt, PMMA, and a random copolymer of PSt and PMMA. The first polymer block of the copolymers prepared in Examples 1 to 5 and 7 to 8 corresponds to PTMSDMSSt, and the first polymer block of the copolymer prepared in Example 6 corresponds to PTMSTMDSt. The second polymer block of the copolymers prepared in Examples 1 to 6 corresponds to PSt, the second polymer block of the copolymer prepared in Example 7 corresponds to PMMA, and the second polymer block of the copolymer prepared in Example 8 corresponds to a random copolymer of PSt and PMMA. The first polymer block of the copolymer prepared in Comparative Example 1 corresponds to PSt, and the second polymer block corresponds to PHSt.

[0141] <Etching resistance evaluation results> For the examples, the ratio of the etching rate of the evaluation polymer corresponding to the first polymer block to the etching rate of the PSt, PMMA, and random copolymer of PSt and PMMA corresponding to the second polymer block of each block copolymer was calculated as the rate ratio, and evaluated according to the following criteria. For example, in the case of Example 1, the ratio of the etching rate of PTMSDMSSt to the etching rate of PSt was calculated as the rate ratio, and the rate ratio was found to be 0.20. In the comparative example, the etching rate of PHSt is faster than that of PSt, and the first polymer block corresponds to PSt and the second polymer block corresponds to PHSt, so the ratio of the etching rate of PSt to the etching rate of PHSt was calculated as the rate ratio. The results are shown in Table 2. ◯: The etching rate ratio was 0.30 or less. ×: The etching rate ratio exceeded 0.30.

[0142] <Half pitch (hp) evaluation results> The half pitch (hp) of the self-assembled monolayer measured in the examples and comparative examples was evaluated according to the following criteria. The results are shown in Table 2. ◯: The half pitch (hp) of the self-assembled monolayer was 10.0 nm or less. ×: The half pitch (hp) of the self-assembled monolayer exceeded 10.0 nm.

[0143] [Table 2]

[0144] From Table 2, it was confirmed that in Examples 1 to 8, the half pitch (hp) was sufficiently small and the PDI was small, so that a uniform self-assembled film could be formed, and that the etching resistance was also excellent.

Claims

1. A first polymer block including a constitutional unit represented by the following general formula (1), a second polymer block including a structural unit represented by the following general formula (3) and / or a structural unit derived from an alkyl (meth)acrylate; A polymer material containing a multiblock copolymer in which the following are linked: 【Chemistry 1】 [In general formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 or more and 1000 or less, and X is a substituent represented by general formula (2). 【Chemistry 2】 [In general formula (2), b is an integer of 1 or more and 5 or less.] 【Transformation 3】 [In general formula (3), R ２ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and c is an integer of 1 to 1,000.

2. The polymer material according to claim 1 , wherein the multiblock copolymer is a diblock copolymer or more and a hexablock copolymer or less.

3. 3. The polymer material according to claim 1, wherein the multiblock copolymer is copolymerized by living anionic polymerization.

4. 3. The polymer material according to claim 1, wherein the multiblock copolymer has a number average molecular weight of 3,000 or more and 50,000 or less.

5. A first polymer block including a constitutional unit represented by the following general formula (1), and a second polymer block comprising a structural unit represented by the following general formula (3) and / or a structural unit derived from an alkyl (meth)acrylate ester. 【Chemistry 4】 [In general formula (1), R １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a is an integer of 1 or more and 1000 or less, and X is a substituent represented by general formula (2). 【Transformation 5】 [In general formula (2), b is an integer of 1 or more and 5 or less.] 【Transformation 6】 [In general formula (3), R ２ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and c is an integer of 1 to 1,000.

6. A self-assembled film obtained by using the polymer material according to claim 1 or 2.

7. The self-assembled film according to claim 6, wherein the surface is coated with a top coating agent.

8. A method for producing a self-assembled film, comprising forming a self-assembled film using the polymer material according to claim 1 or 2.

9. The method for producing a self-assembled film according to claim 8, wherein the self-assembled film is formed within the guide pattern.

10. The method for producing a self-assembled film according to claim 8 , further comprising the step of applying a top coating agent onto the self-assembled film.

11. A pattern obtained by etching the self-assembled film according to claim 6.

12. A method for forming a pattern, comprising the step of etching the self-assembled film according to claim 6 to form a pattern.

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