Copolymer, polymer for water repellent, composition for forming water-repellent film, resin film, and method for forming resist pattern

Abstract

Provided is a polymer which can form a resin film having a low retardation angle and a low slip angle with respect to a liquid for immersion during immersion exposure. This copolymer has a repeating unit represented by general formula (1) and a repeating unit derived from a compound having a polymerizable carbon-carbon double bond. (In general formula (1), R1 represents a hydrogen atom, a fluorine atom, a chlorine atom, or a C1-10 linear alkyl group or a C3-10 branched alkyl group. And some or all of hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. R2 represents a single bond, a linear chain, a branched chain, or an alkylene group optionally having a cyclic structure, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, and some of R2 may be fluorinated and / or chlorinated. And X represents a hydroxyl group, an alkoxy group, or a hydrogen atom).

Description

TECHNICAL FIELD

[0001] The present application relates to a copolymer, a water-repellent agent-use polymer, a water-repellent film-forming composition, a resin film, and a resist pattern forming method. BACKGROUND

[0002] In the field of microfabrication represented by the production of integrated circuit elements, in order to achieve higher integration, a photolithography technique capable of microfabrication is required.

[0003] As such a photolithography technique, immersion exposure (liquid immersion photolithography) is known.

[0004] The so-called immersion exposure is exposure processing in which an immersion liquid is filled between a lens of an exposure apparatus and a substrate such as a silicon wafer.

[0005] If the immersion liquid is filled between the lens of the exposure apparatus and the substrate, the incident angle of exposure light incident to the substrate through the lens can be reduced compared to the case where air is filled between the lens of the exposure apparatus and the substrate. Therefore, the numerical aperture of the lens can be increased, and the resolution can be improved (refer to Non-Patent Literature 1).

[0006] In pattern formation by immersion exposure, a resist film is formed on the surface of the substrate, and exposure processing is performed in which the resist film and the lens of the exposure apparatus are filled with the immersion liquid.

[0007] Note that, as the immersion liquid, water (pure water) is generally used.

[0008] If the resist film is in contact with the immersion liquid, there is a case where pattern formation failure occurs due to the penetration of the immersion liquid into the resist film. In addition, there is a case where pattern formation failure occurs due to the penetration of various components from the resist film into the immersion liquid. Furthermore, there is a case where a droplet remains on the substrate after immersion exposure, and thus there is a case where a pattern defect is formed.

[0009] In the case of performing immersion exposure, an upper layer film for preventing such pattern formation failure and the like is formed on the resist film.

[0010] In Patent Literatures 1 and 2, a method of forming such an upper layer film using a composition containing a fluorine-containing resin having a prescribed structure is described.

[0011] In addition, a method of adding the fluorine-containing resin described in Patent Literatures 1 and 2 to a resist film, forming a resist film without a surface coating layer without forming an upper layer film, and performing pattern formation by immersion exposure is also performed.

[0012] Prior Art Documents

[0013] Patent Literature

[0014] Patent Literature 1: Japanese Patent Application Laid-Open No. 2008-65098

[0015] Patent Literature 2: Japanese Patent Application Laid-Open No. 2022-92439

[0016] Non-Patent Literature

[0017] Non-Patent Literature 1: Advances in Patterning Materials for 193 nm Immersion Lithography, Chem. Rev. 2010, 110, 321-360 SUMMARY

[0018] PROBLEMS TO BE SOLVED BY THE INVENTION

[0019] In the case where the hysteresis angle (advancing contact angle - receding contact angle) of the resist film with respect to the immersion liquid is high, or the sliding-off angle is high, in the case of performing efficient exposure using an exposure apparatus, the liquid repellency of the immersion liquid at the time of exposure becomes poor, and pattern formation defects are easily generated.

[0020] The hysteresis angle or the sliding-off angle of the resist film with respect to the immersion liquid using the fluorine-containing resin described in Patent Literatures 1 and 2 has room for improvement.

[0021] TECHNICAL MEANS FOR SOLVING THE PROBLEMS

[0022] The present application has been made in order to solve the above problems, and an object of the present application is to provide a polymer which can form a resin film having a low hysteresis angle and a low sliding-off angle with respect to an immersion liquid at the time of immersion exposure.

[0023] The present application (1) is a copolymer having a repeating unit represented by the following general formula (1), and a repeating unit derived from a compound having a polymerizable carbon-carbon double bond.

[0024]

[0025] (In the general formula (1), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with fluorine atoms.

[0026] R 2 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, one part of which is optionally fluorinated and / or chlorinated.

[0027] X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0028] The present application (2) is the copolymer according to the present application (1), wherein the repeating unit represented by the general formula (1) contains a repeating unit represented by the following general formula (2).

[0029]

[0030] The present application (3) is the copolymer according to the present application (2), wherein the repeating unit represented by the general formula (2) contains a repeating unit represented by the following general formula (2-1).

[0031]

[0032] The present application (4) is the copolymer according to the present application (1), wherein the repeating unit represented by the general formula (1) contains a repeating unit represented by the following general formula (3).

[0033]

[0034] The present application (5) is the copolymer according to the present application (4), wherein the repeating unit represented by the general formula (3) contains a repeating unit represented by the following general formula (3-1).

[0035]

[0036] The present application (6) is the copolymer according to any one of the present application (1) to (5), wherein the repeating unit derived from the compound having a polymerizable carbon-carbon double bond contains a repeating unit represented by the following general formula (4).

[0037]

[0038] (In the general formula (4), R A is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One or more of the hydrogen atoms bonded to the carbon atom in the alkyl group are optionally substituted with a fluorine atom.

[0039] Y A is a monovalent organic group.

[0040] The present application (7) is the copolymer according to the present application (6), wherein the repeating unit represented by the general formula (4) contains a repeating unit having no fluorine atom.

[0041] The present application (8) is the copolymer according to the present application (6) or (7), wherein the repeating unit represented by the general formula (4) contains a repeating unit derived from at least one compound having a polymerizable carbon-carbon double bond selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, a compound represented by the following formula (4'-1), a compound represented by the following formula (4'-2), a compound represented by the following formula (4'-3), a compound represented by the following formula (4'-4), a compound represented by the following formula (4'-5), a compound represented by the following formula (4'-6), a compound represented by the following formula (4'-7), a compound represented by the following formula (4'-8), a compound represented by the following formula (4'-9), a compound represented by the following formula (4'-10), a compound represented by the following formula (4'-11), a compound represented by the following formula (4'-12), a compound represented by the following formula (4'-13), a compound represented by the following formula (4'-14), a compound represented by the following formula (4'-15), and a compound represented by the following formula (4'-16).

[0042]

[0043] The present application (9) is a polymer for water repellent agent, which contains a repeating unit represented by the following general formula (1).

[0044]

[0045] (In the general formula (1), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with a fluorine atom.

[0046] R 2 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, one part of which is optionally fluorinated and / or chlorinated.

[0047] X is a hydroxyl group, an alkoxy group, or a hydrogen atom).

[0048] The present application (10) is the polymer for water repellent agent according to the present application (9), wherein the repeating unit represented by the general formula (1) contains a repeating unit represented by the following general formula (2).

[0049]

[0050] The present application (11) is the water repellent agent use polymer according to the present application (10), wherein the repeat unit represented by general formula (2) contains the repeat unit represented by general formula (2-1) below.

[0051]

[0052] The present application (12) is the water repellent agent use polymer according to the present application (9), wherein the repeat unit represented by general formula (1) contains the repeat unit represented by general formula (3) below.

[0053]

[0054] The present application (13) is the water repellent agent use polymer according to the present application (12), wherein the repeat unit represented by general formula (3) contains the repeat unit represented by general formula (3-1) below.

[0055]

[0056] The water repellent film forming composition of the present application (14) contains the copolymer described in any one of the present application (1) to (8) or the water repellent agent use polymer described in any one of the present application (9) to (13).

[0057] The water repellent film forming composition of the present application (15) is the water repellent film forming composition according to the present application (14) containing 2 or more kinds of the copolymer described in any one of the present application (1) to (8) or the water repellent agent use polymer described in any one of the present application (9) to (13).

[0058] The water repellent film forming composition of the present application (16) is the water repellent film forming composition described in the present application (14) further containing an acid generator.

[0059] The resin film of the present application (17) contains the coating film of the water repellent film forming composition described in the present application (14).

[0060] The resin film of the present application (18) is the resin film described in the present application (17) used for immersion liquid exposure.

[0061] The resist pattern forming method of the present application (19) contains: a film forming step of forming a resin film by applying the water repellent film forming composition described in the present application (14) to the surface of a substrate or a primer film; and an immersion liquid exposure step of exposing the resin film by irradiating electromagnetic waves having a wavelength of 300 nm or less or high energy rays to the resin film in a state where water directly contacts the surface of the resin film.

[0062] Effects of the Invention

[0063] If the polymer of the present application is used, a resin film having a low hysteresis angle and a low sliding angle with respect to a liquid for immersion in immersion exposure can be formed. DETAILED DESCRIPTION

[0064] Hereinafter, the present application will be described in detail, but the description of the constituent elements described below is an example of the mode for carrying out the present application, and is not limited to the specific content. Various changes can be made within the scope of the gist thereof and implemented.

[0065] In the column of "mode for carrying out the invention" of the present specification, matters indicated by "[ ]" and "]", "<" and ">" are symbols and have no meaning by themselves.

[0066] (First Embodiment)

[0067] The copolymer of the first embodiment of the present application will be described.

[0068] The copolymer of the first embodiment of the present application is a copolymer having a repeating unit represented by the following general formula (1), and a repeating unit derived from a compound having a polymerizable carbon-carbon double bond.

[0069]

[0070] (In general formula (1), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having a carbon number of 1 to 10 or a branched alkyl group having a carbon number of 3 to 10. One part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with fluorine atoms.

[0071] R 2 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, one part of which is optionally fluorinated and / or chlorinated.

[0072] X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0073] The copolymer of the first embodiment of the present application is used to form an upper layer film or a resist film without a surface coating layer when immersion exposure is performed.

[0074] The upper layer film or the resist film without a surface coating layer formed using the copolymer of the first embodiment of the present application has a low hysteresis angle and a low sliding angle with respect to a liquid for immersion.

[0075] Therefore, the liquid-removing property of the liquid for immersion at the time of exposure becomes good, and the pattern formation becomes good.

[0076] Note that the repeating unit represented by the general formula (1) has a monochlorodifluoromethyl group (-CF2Cl).

[0077] The repeating unit contained in the existing polymer used to form the resist film of the upper layer film or the faceless coating has a trifluoromethyl group (-CF3).

[0078] The monochlorodifluoromethyl group (-CF2Cl) is more easily decomposed than the trifluoromethyl group (-CF3).

[0079] The waste liquid generated when the resist film of the upper layer film or the faceless coating is formed using the copolymer of the first embodiment of the present application contains a resin containing a monochlorodifluoromethyl group (-CF2Cl).

[0080] The resin contained in such a waste liquid is easily decomposed, and thus the waste liquid treatment becomes easy.

[0081] As the R 1 Examples of the alkyl group exemplified include a methyl group, an ethyl group, a propyl group, and the like.

[0082] As the R 2 Examples of the alkylene group exemplified include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a saturated chain hydrocarbon group such as a propylene group or a 2-propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, a heptadecamethylene group, an octadecamethylene group, a nonadecamethylene group, a eicosylene group, a 1-methyl-1,3-propylene group, a 2-methyl-1,3-propylene group, a 2-methyl-1,2-propylene group, a 1-methyl-1,4-butylene group, a 2-methyl-1,4-butylene group, a methylidene group, an ethylidene group, a propylidene group, or a 2-propylidene group, a monocyclic hydrocarbon ring group such as a 1,3-cyclobutylene group, a 1,3-cyclopentylene group, a 1,4-cyclohexylene group, or a 1,5-cyclooctylene group, a 2- to 4-ringed hydrocarbon ring group such as a norbornylene group, an adamantylene group, or a 2,6-adamantylene group, or the like.

[0083] R 2 The amide exemplified is a structure represented by (-C(=O)NA-) (A represents a hydrogen atom or a monovalent organic group).

[0084] R 2 The ether exemplified is a structure represented by (-O-).

[0085] R 2The exemplified amine is a structure represented by (-NB-) (B represents a hydrogen atom or a monovalent organic group).

[0086] The repeating unit represented by the general formula (1) can include a repeating unit represented by the following general formula (2).

[0087]

[0088] In the case where the repeating unit represented by the general formula (2) is included, since the terminal of the side chain is a hydroxyl group, a copolymer having properties such as water repellency, adhesion, alkali solubility, and the like can be obtained.

[0089] As the repeating unit represented by the general formula (2), a repeating unit represented by the following general formula (2-1) can be exemplified.

[0090]

[0091] In addition, the repeating unit represented by the general formula (1) can include a repeating unit represented by the following general formula (3).

[0092]

[0093] In the case where the repeating unit represented by the general formula (3) is included, since the terminal of the side chain is a hydrogen group, a copolymer having properties such as water repellency, water resistance, and the like can be obtained.

[0094] As the repeating unit represented by the general formula (3), a repeating unit represented by the following general formula (3-1) can be exemplified.

[0095]

[0096] In the copolymer of the first embodiment of the present application, the repeating unit derived from a compound having a polymerizable carbon-carbon double bond refers to a repeating unit derived from a compound having a polymerizable carbon-carbon double bond which does not include the repeating unit represented by the general formula (1).

[0097] The repeating unit derived from a compound having a polymerizable carbon-carbon double bond can include, for example, a repeating unit represented by the following general formula (4).

[0098]

[0099] (In formula (4), R A is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One or more of the hydrogen atoms bonded to the carbon atom in the alkyl group are optionally substituted with a fluorine atom.

[0100] Y A is a monovalent organic group.)

[0101] as the R A Examples of the exemplified alkyl group include methyl, ethyl, 1-propyl, 2-propyl, and the like.

[0102] as the Y A Examples of the exemplified monovalent organic group include a linear, branched, or optionally cyclic alkyl group having 1 to 30 carbons, an alkenyl group having 2 to 30 carbons, an alkynyl group having 2 to 30 carbons, a phenyl group having 6 to 30 carbons, a naphthyl group, and a group in which a hydrogen atom of the group is substituted with a fluorine atom, an oxygen atom, or a nitrogen atom, and can include a hydroxyl group, an ester, a lactone, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof.

[0103] Note that the repeating unit represented by the general formula (4) is preferably a repeating unit having no fluorine atom.

[0104] In addition, the repeating unit represented by the general formula (4) can be a repeating unit represented by the following general formula (4a).

[0105] In the case where the copolymer of the first embodiment of the present application contains a repeating unit represented by the following general formula (4a), water repellency, water resistance, detachment of an acid dissociation group based on an acid generated by exposure, and alkali solubility accompanying the same, and the like can be exhibited.

[0106]

[0107] (In the general formula (4a), R 3 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated. L is an acid dissociation group.

[0108] As examples of the alkylene group, there can be mentioned methylene, ethylene, 1,3-propylene, 1,2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, methylidene, ethylidene, propylidene, or 2-propylidene, and the like saturated chain hydrocarbon group; 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and the like cycloalkylene group having 3 to 10 carbon atoms; 1,4-norbornylene, 2,5-norbornylene, and the like norbornylene group, 1,5-adamantylene, 2,6-adamantylene, and the like adamantylene group, and the like cross-linked cyclic hydrocarbon ring group.

[0109] As examples of the aromatic ring, there can be mentioned o-phenylene, m-phenylene, p-phenylene, and the like.

[0110] As examples of the acid dissociable group, there can be mentioned: t-butyl, t-amyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl, 1,1-dimethylbutyl, allyl, 1-pyrenylmethyl, 5-dibenzosuberenyl, triphenylmethyl, 1-ethyl-1-methylbutyl, 1,1-diethylpropyl, 1,1-dimethyl-1-phenylmethyl, 1-methyl-1-ethyl-1-phenylmethyl, 1,1-diethyl-1-phenylmethyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-isobornyl, 1-methyladamantyl, 1-ethyladamantyl, 1-isopropyladamantyl, 1-isopropylnorbornyl, 1-isopropyl-(4-methylcyclohexyl), t-butyloxycarbonyl, t-amyl-oxycarbonyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, methoxymethyl, ethoxyethyl, butoxyethyl, cyclohexyloxyethyl, benzyloxyethyl, phenethyl- oxyethyl, ethoxypropyl, benzyloxypropyl, phenethyloxypropyl, ethoxybutyl, ethoxyisobutyl, trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, t-butyldimethylsilyl, methyldi-t-butyisilyl, tri-t-butyisilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipoyl, pimeloyl, suberoyl, azelayl, sebacoyl, (meth)acryloyl, propynoyl, crotonoyl, oleyl, maleoyl, fumaryoyl, mesaconoyl, camphoroyl, benzoyl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, 2-phenylpropionoyl, 2-phenylpropenoyl, cinnamoyl, furanoyl, thienoyl, nicotinoyl, isonicotinoyl, and the like.

[0111] Specifically, the repeating unit represented by the general formula (4) can be a repeating unit derived from at least one compound having a polymerizable carbon-carbon double bond selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, a compound represented by the following formula (4'-1), a compound represented by the following formula (4'-2), a compound represented by the following formula (4'-3), a compound represented by the following formula (4'-4), a compound represented by the following formula (4'-5), a compound represented by the following formula (4'-6), a compound represented by the following formula (4'-7), a compound represented by the following formula (4'-8), a compound represented by the following formula (4'-9), a compound represented by the following formula (4'-10), a compound represented by the following formula (4'-11), a compound represented by the following formula (4'-12), a compound represented by the following formula (4'-13), a compound represented by the following formula (4'-14), a compound represented by the following formula (4'-15), and a compound represented by the following formula (4'-16).

[0112]

[0113] As a specific example of the repeating unit represented by the general formula (4), for example, a repeating unit represented by the following chemical formula is preferable.

[0114]

[0115] Further, the repeating unit derived from a compound having a polymerizable carbon-carbon double bond can include, for example, a repeating unit represented by the following general formula (5).

[0116] In the case where the copolymer of the first embodiment of the present application contains a repeating unit represented by the following general formula (5), it can have properties such as alkali solubility, and is thus suitable for the upper layer film application of a resist used in a liquid immersion exposure process.

[0117]

[0118] (In the general formula (5), R 4 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated.)

[0119] As the R 4Examples of the exemplified alkylene group include methylene, ethylene, 1,3- propylene, 1,2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, methylidene, ethylidene, propylidene, or 2-propylidene, and the like saturated chain hydrocarbon group; 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and the like cycloalkylene group having 3 to 10 carbons; 1,4-norbornylene, 2,5-norbornylene, and the like norbornylene group; 1,5-adamantylene, 2,6-adamantylene, and the like adamantylene group; and the like cross-linked cyclic hydrocarbon ring group.

[0120] As the R 4 Examples of the exemplified aromatic ring include o-phenylene, m-phenylene, p-phenylene, and the like.

[0121] In addition, the repeating unit derived from a compound having a polymerizable carbon-carbon double bond can include an acid-decomposable group.

[0122] If such a copolymer is used to form a resin film on a substrate and the resin film is exposed to electromagnetic waves having a wavelength of 300 nm or less or high-energy rays such as electron beams, the acid-decomposable group is decomposed to generate an acid in the resin film. By means of this acid, the solubility of the exposed portion of the resin film in an alkaline developing solution can be improved during development.

[0123] If the copolymer of the first embodiment of the present application is composed of the repeating unit represented by the general formula (1) and the repeating unit derived from a compound having a polymerizable carbon-carbon double bond, the repeating unit represented by the general formula (1) can be one kind or a plurality of kinds, and the repeating unit derived from a compound having a polymerizable carbon-carbon double bond can be one kind or a plurality of kinds.

[0124] In the case where the copolymer of the first embodiment of the present application includes a plurality of the above-described repeating unit represented by the general formula (1), R 1 The R 2 and X are also the same.

[0125] In the case where the copolymer of the first embodiment of the present application includes a plurality of the above-described repeating unit represented by the general formula (4), R Amay be the same in each repeating unit, or may be different in each repeating unit. Y A Also the same.

[0126] In the case where the copolymer of the first embodiment of the present application contains a plurality of the above-described repeating units represented by the general formula (4a), R A may be the same in each repeating unit, or may be different in each repeating unit. R 3 Also the same.

[0127] In the case where the copolymer of the first embodiment of the present application contains a plurality of the above-described repeating units represented by the general formula (5), R 4 may be the same in each repeating unit, or may be different in each repeating unit.

[0128] In the case where the copolymer of the first embodiment of the present application contains two or more kinds of repeating units among the above-described repeating unit represented by the general formula (1) and the above-described repeating unit represented by the general formula (2), R 1 may be the same in each repeating unit, or may be different in each repeating unit.

[0129] In the copolymer of the first embodiment of the present application, as long as the above-described repeating unit represented by the general formula (1) and the repeating unit derived from the compound having a polymerizable carbon-carbon double bond are contained, a repeating unit other than the above-described repeating unit can be contained.

[0130] In the copolymer of the first embodiment of the present application, when the total repeating units are set to 100 mol%, the ratio of the repeating unit represented by the general formula (1) can be 22 mol% or more and 99 mol% or less, can be 30 mol% or more and 95 mol% or less, and further can be 40 mol% or more and 90 mol% or less.

[0131] The weight average molecular weight of the copolymer of the first embodiment of the present application can be 5000 to 20000, and further can be 7000 to 12000. In the present specification, the weight average molecular weight of a polymer means a value determined by a gel permeation chromatograph (GPC) under the following conditions.

[0132] [GPC conditions]

[0133] Apparatus: HLC-8320 GPC manufactured by Tosoh Corporation

[0134] Analytical column for polymerizable monomer: TSKgel series (G2500HXL, G2000HXL, G1000HXL, G1000HXL connected in series in this order) manufactured by Tosoh Corporation

[0135] Polymer analysis column: TSKgel series (G2500HXL, G2000HXL, G1000HXL, G1000HXL, manufactured by Tosoh Corporation, connected in series in this order)

[0136] Temperature program: 40°C (hold)

[0137] Flow rate: 1 mL / min

[0138] Detector: differential refractive detector (RI)

[0139] Eluent: tetrahydrofuran (THF)

[0140] Reference substance: polystyrene standard solution

[0141] Next, an example of the method for producing the copolymer of the first embodiment of the present application will be described.

[0142] The method for producing the copolymer of the first embodiment of the present application includes a fluorine-containing polymerizable monomer preparation step, a compound having a polymerizable carbon-carbon double bond preparation step, and a polymerization step.

[0143] <Fluorine-containing polymerizable monomer preparation step>

[0144] In the method for producing the copolymer of the first embodiment of the present application, first, a compound represented by the following general formula (6) is prepared.

[0145]

[0146] (In general formula (6), R 2 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, or a hydrogen atom.)

[0147] Next, the compound represented by general formula (6) is reacted with at least one selected from the group consisting of an acid halide, an anhydride, an ester, and a carboxylic acid.

[0148] As examples of the acid halide, there can be mentioned methacryloyl chloride, methacryloyl bromide, methacryloyl fluoride, acryloyl chloride, acryloyl bromide, acryloyl fluoride, and the like. As examples of the acid anhydride, there can be mentioned methacrylic anhydride, acrylic anhydride, and the like. As examples of the ester, there can be mentioned methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, and the like. As examples of the carboxylic acid, there can be mentioned methacrylic acid, acrylic acid, and the like.

[0149] The reaction of the compound represented by General Formula (6) with the compound can be performed with the addition of an acid or a base as necessary. As the reaction conditions, it is preferable to perform the reaction at 0 to 130°C for 0.5 to 10 hours.

[0150] The separation and purification of the product after the reaction can be performed by a conventional method, for example, concentration, distillation, extraction, recrystallization, filtration, column chromatography, or the like, and two or more of these methods can be combined and used.

[0151] The fluorine-containing polymerizable monomer represented by General Formula (7) can be produced by the above procedure. The fluorine-containing polymerizable monomer represented by General Formula (7) is a compound that becomes a repeating unit represented by General Formula (1) of the copolymer of the first embodiment of the present application.

[0152]

[0153] (In General Formula (7), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with a fluorine atom.

[0154] R 2 is a single bond, a linear, branched, or cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated, and X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0155] <Preparation procedure of compound having polymerizable carbon-carbon double bond>

[0156] Next, a compound having a polymerizable carbon-carbon double bond is prepared. Note that the compound having a polymerizable carbon-carbon double bond refers to a compound having a polymerizable carbon-carbon double bond other than the fluorine-containing polymerizable monomer represented by General Formula (7).

[0157] As the compound having a polymerizable carbon-carbon double bond, for example, a compound represented by the following general formula (8) can be exemplified.

[0158]

[0159] (In general formula (8), R A is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One or more of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with a fluorine atom.

[0160] Y A is a monovalent organic group.

[0161] The compound represented by the general formula (8) is preferably a compound having no fluorine atom, and specifically, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, a compound represented by the following formula (4'-1), a compound represented by the following formula (4'-2), a compound represented by the following formula (4'-3), a compound represented by the following formula (4'-4), a compound represented by the following formula (4'-5), a compound represented by the following formula (4'-6), a compound represented by the following formula (4'-7), a compound represented by the following formula (4'-8), a compound represented by the following formula (4'-9), a compound represented by the following formula (4'-10), a compound represented by the following formula (4'-11), a compound represented by the following formula (4'-12), a compound represented by the following formula (4'-13), a compound represented by the following formula (4'-14), a compound represented by the following formula (4'-15), a compound represented by the following formula (4'-16), and the like can be exemplified.

[0162]

[0163] <Polymerization Step>

[0164] Subsequently, the fluorine-containing polymerizable monomer represented by the general formula (7) is polymerized with the compound having a polymerizable carbon-carbon double bond.

[0165] The polymerization reaction in this polymerization is not particularly limited, and can be a radical polymerization reaction, an ionic polymerization reaction, a coordination anionic polymerization reaction, an active anionic polymerization reaction, or a cationic polymerization reaction. Among these, a radical polymerization reaction is preferred.

[0166] In the case where the polymerization reaction is a radical polymerization reaction, as the polymerization initiator, any compound can be used as long as it can generate a polymerization reaction, and there is no particular limitation. Examples of the azo compound include azobisisobutyronitrile. Examples of the peroxide compound include t-butyl peroxypivalate, di-t-butyl peroxide, peroxyl isobutyric acid, peroxyl lauryl acid, peroxyl succinic acid, di-cinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, and ammonium persulfate. Examples of the redox compound include combinations of an oxidizing agent and a reducing agent. Examples of the oxidizing agent include hydrogen peroxide, persulfate, cumene hydroperoxide, and the like. Examples of the reducing agent include iron (II) ion salts, copper (I) ion salts, ammonia, triethylamine, and the like.

[0167] Examples of the azo compound include azobisisobutyronitrile. Examples of the peroxide compound include t-butyl peroxypivalate, di-t-butyl peroxide, peroxyl isobutyric acid, peroxyl lauryl acid, peroxyl succinic acid, di-cinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, and ammonium persulfate.

[0168] Examples of the redox compound include combinations of an oxidizing agent and a reducing agent. Examples of the oxidizing agent include hydrogen peroxide, persulfate, cumene hydroperoxide, and the like. Examples of the reducing agent include iron (II) ion salts, copper (I) ion salts, ammonia, triethylamine, and the like.

[0169] In addition, a polymerization solvent can be used in the radical polymerization reaction.

[0170] As the polymerization solvent, any solvent can be used as long as it does not inhibit the radical polymerization reaction, and there is no particular limitation. The polymerization solvent can be an organic solvent or water. Examples of the organic solvent include hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, alcohol-based solvents, ether-based solvents, cyclic ether-based solvents, freon-based solvents, aromatic-based solvents, and the like. The solvent can be used alone or in combination with two or more kinds.

[0171] Examples of the ester-based solvent include acetic acid, n-butyl acetate, and the like.

[0172] Examples of the ketone-based solvent include acetone, methyl isobutyl ketone, and the like.

[0173] Examples of the hydrocarbon-based solvent include toluene, cyclohexane, and the like.

[0174] Examples of the alcohol-based solvent include methanol, isopropyl alcohol, ethylene glycol monomethyl ether, and the like.

[0175] In addition, a molecular weight adjusting agent such as a mercaptan can be used in the radical polymerization reaction.

[0176] The reaction temperature in the radical polymerization reaction is appropriately changed depending on the radical polymerization initiator or the kind of the radical polymerization initiator, and is preferably 20°C or higher and 200°C or lower, and further preferably 30°C or higher and 140°C or lower.

[0177] As a method for removing the organic solvent or water as the medium from the solution or dispersion liquid containing the synthesized copolymer after the polymerization step, a publicly known method can be used. Specifically, examples of the method include reprecipitation, filtration, heating distillation under reduced pressure, and the like.

[0178] The copolymer of the first embodiment of the present application can be produced by the above process.

[0179] (Second Embodiment)

[0180] The water repellent agent-use polymer of the second embodiment of the present application will be described.

[0181] The water repellent agent-use polymer of the second embodiment of the present application is a water repellent agent-use polymer containing a repeating unit represented by the following general formula (1).

[0182]

[0183] (In the general formula (1), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally substituted with fluorine atoms.

[0184] R 2 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, one part of which is optionally fluorinated and / or chlorinated.

[0185] X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0186] The resin film formed using the water repellent agent-use polymer of the second embodiment of the present application has high water repellency. That is, the water repellent agent-use polymer of the second embodiment of the present application is suitable for water repellent agent use.

[0187] Note that the repeating unit represented by the general formula (1) has a chlorodifluoromethyl group (-CF2Cl).

[0188] The repeating unit contained in the existing polymer used to form a resist film of an upper layer film or a faceless coating layer has a trifluoromethyl group (-CF3).

[0189] The chlorodifluoromethyl group (-CF2Cl) is more easily decomposed than the trifluoromethyl group (-CF3).

[0190] Therefore, the resin film formed using the water repellent agent-use polymer of the second embodiment of the present application is more easily decomposed than the resin film formed using the existing polymer. Thus, the energy necessary for decomposing the resin film can be reduced.

[0191] As the R 1 Examples of the alkyl group exemplified include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and the like.

[0192] As the R2 Examples of the exemplified alkylene group include methylene, ethylene, 1,3- propylene, 1,2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, methylidene, ethylidene, propylidene, or 2-propylidene, and the like saturated chain hydrocarbon group; 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and the like cycloalkylene group having 3 to 10 carbon atoms, and the like monocyclic hydrocarbon ring group; norbornylene group such as 1,4-norbornylene or 2,5-norbornylene; 1,5-adamantylene; 2,6-adamantylene; and the like cross-linked cyclic hydrocarbon ring group having 2 to 4 rings.

[0193] R 2 The exemplified amide is a structure represented by (-C(=O)NA-) (A represents a hydrogen atom or a monovalent organic group).

[0194] R 2 The exemplified ether is a structure represented by (-O-).

[0195] R 2 The exemplified amine is a structure represented by (-NB-) (B represents a hydrogen atom or a monovalent organic group).

[0196] The repeating unit represented by the general formula (1) can include a repeating unit represented by the following general formula (2).

[0197]

[0198] In the case of including the repeating unit represented by the general formula (2), since the terminal of the side chain is a hydroxyl group, it can become a water repellent polymer having water repellency, adhesion, alkali solubility, and the like.

[0199] As the repeating unit represented by the general formula (2), a repeating unit represented by the following general formula (2-1) can be exemplified.

[0200]

[0201] In addition, the repeating unit represented by the general formula (1) can include a repeating unit represented by the following general formula (3).

[0202]

[0203] In the case where the repeating unit represented by the general formula (3) is contained, since the terminal of the side chain is a hydrogen group, a water repellent polymer having water repellency, water resistance, and the like can be obtained.

[0204] As the repeating unit represented by the general formula (3), a repeating unit represented by the following general formula (3-1) can be exemplified.

[0205]

[0206] The water repellent polymer of the second embodiment of the present application can be composed of only one kind of the repeating unit represented by the general formula (1), or can be composed of a plurality of kinds of the repeating unit represented by the general formula (1).

[0207] In addition, the water repellent polymer of the second embodiment of the present application can contain a repeating unit other than the repeating unit represented by the general formula (1).

[0208] In this case, when the total of the repeating units is assumed to be 100 mol%, the ratio of the repeating unit represented by the general formula (1) can be 22 mol% or more and 99 mol% or less, can be 30 mol% or more and 95 mol% or less, and further can be 40 mol% or more and 90 mol% or less.

[0209] As the repeating unit other than the repeating unit represented by the general formula (1), a repeating unit derived from a compound having a polymerizable carbon-carbon double bond other than the repeating unit represented by the general formula (1) can be exemplified.

[0210] As such a repeating unit derived from a compound having a polymerizable carbon-carbon double bond, for example, a repeating unit represented by the following general formula (4) can be exemplified.

[0211]

[0212] (In formula (4), R A is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. One or more of the hydrogen atoms bonded to the carbon atom in the alkyl group are optionally substituted with a fluorine atom.

[0213] Y A is a monovalent organic group.

[0214] As the R A Examples of the alkyl group exemplified include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and the like.

[0215] As the Y AExamples of the monovalent organic group include linear, branched, or optionally cyclic alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, phenyl groups having 6 to 30 carbon atoms, naphthyl groups, and groups in which a hydrogen atom of the group is substituted with a fluorine atom, an oxygen atom, or a nitrogen atom, and can include a hydroxyl group, an ester, a lactone, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof.

[0216] Note that the repeating unit represented by the general formula (4) is preferably a repeating unit not having a fluorine atom.

[0217] In addition, the repeating unit represented by the general formula (4) can be a repeating unit represented by the following general formula (4a).

[0218] In the case where the water repellent agent-use polymer of the second embodiment of the present application contains a repeating unit represented by the following general formula (4a), water repellency, water resistance, dissociation of an acid-dissociable group based on an acid generated by exposure, and alkali solubility accompanying the same, and the like can be exhibited.

[0219]

[0220] (In the general formula (4a), R 3 is a single bond, linear, branched, or optionally cyclic alkylene, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated. L is an acid-dissociable group.

[0221] Examples of the alkylene include methylene, ethylene, 1,3-propylene, 1,2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, methylidene, ethylidene, propylidene, or 2-propylidene, and the like saturated chain hydrocarbon groups; 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and the like cycloalkylene groups having 3 to 10 carbon atoms; norbornylene, 1,5-adamantylene, 2,6-adamantylene, and the like 2- to 4-ring hydrocarbon ring groups.

[0222] As examples of the aromatic ring, there can be mentioned: o-phenylene, m-phenylene, p-phenylene, and the like.

[0223] As examples of the acid dissociable group, there can be mentioned: t-butyl, t-amyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl, 1,1-dimethylbutyl, allyl, 1-pyrenylmethyl, 5-dibenzosuberenyl, triphenylmethyl, 1-ethyl-1-methylbutyl, 1,1-diethylpropyl, 1,1-dimethyl-1-phenylmethyl, 1-methyl-1-ethyl-1-phenylmethyl, 1,1-diethyl-1-phenylmethyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-isobornyl, 1-methyladamantyl, 1-ethyladamantyl, 1-isopropyladamantyl, 1-isopropylnorbornyl, 1-isopropyl-(4-methylcyclohexyl), t-butyloxycarbonyl, t-amyl-oxycarbonyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, methoxymethyl, ethoxyethyl, butoxyethyl, cyclohexyloxyethyl, benzyloxyethyl, phenethyl- oxyethyl, ethoxypropyl, benzyloxypropyl, phenethyl-oxypropyl, ethoxybutyl, ethoxyisobutyl, trimethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triethylsilyl, isopropyldimethylsilyl, methyldiisopropylsilyl, triisopropylsilyl, t-butyldimethylsilyl, methyldi-t-butyIsilyl, tri-t-butyIsilyl, phenyldimethylsilyl, methyldiphenylsilyl, triphenylsilyl, acetyl, propionyl, butyryl, heptanoyl, hexanoyl, pentanoyl, tert-butanoyl, isopentanoyl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, succinyl, glutaryl, adipoyl, pimeloyl, suberoyl, azelayl, sebacoyl, (meth)acryloyl, propynoyl, crotonoyl, oleoyl, maleoyl, fumaryl, phthaloyl, isophthaloyl, terephthaloyl, naphthoyl, toluoyl, 2-phenylpropionyl, 2-phenylpropenoyl, cinnamoyl, furanoyl, thienoyl, nicotinoyl, isonicotinoyl, and the like.

[0224] Specifically, the repeating unit represented by the general formula (4) can be a repeating unit derived from at least one compound having a polymerizable carbon-carbon double bond selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, amyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, amyl acrylate, a compound represented by the following formula (4'-1), a compound represented by the following formula (4'-2), a compound represented by the following formula (4'-3), a compound represented by the following formula (4'-4), a compound represented by the following formula (4'-5), a compound represented by the following formula (4'-6), a compound represented by the following formula (4'-7), a compound represented by the following formula (4'-8), a compound represented by the following formula (4'-9), a compound represented by the following formula (4'-10), a compound represented by the following formula (4'-11), a compound represented by the following formula (4'-12), a compound represented by the following formula (4'-13), a compound represented by the following formula (4'-14), a compound represented by the following formula (4'-15), and a compound represented by the following formula (4'-16).

[0225]

[0226] As a specific example of the repeating unit represented by the general formula (4), for example, a repeating unit represented by the following chemical formula is preferable.

[0227]

[0228] Further, the repeating unit derived from a compound having a polymerizable carbon-carbon double bond can include, for example, a repeating unit represented by the following general formula (5).

[0229] In the case where the water repellent agent-use polymer of the second embodiment of the present application contains a repeating unit represented by the following general formula (5), properties such as alkali solubility can be imparted.

[0230]

[0231] (In the general formula (5), R 4 is a single bond, a linear, branched, or optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated.)

[0232] As the R 4Examples of the exemplified alkylene group include methylene, ethylene, 1,3- propylene, 1,2-propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosylene, 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,2-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, methylidene, ethylidene, propylidene, or 2-propylidene, and the like saturated chain hydrocarbon group; 1,3-cyclobutylene, 1,3-cyclopentylene, 1,4-cyclohexylene, 1,5-cyclooctylene, and the like cycloalkylene group having 3 to 10 carbon atoms; 1,4-norbornylene, 2,5-norbornylene, and the like norbornylene group; 1,5-adamantylene, 2,6-adamantylene, and the like adamantylene group; and the like cross-linked cyclic hydrocarbon ring group.

[0233] As the R 4 Examples of the exemplified aromatic ring include o-phenylene, m-phenylene, p-phenylene, and the like.

[0234] Further, the repeating unit derived from a compound having a polymerizable carbon-carbon double bond can include an acid-decomposable group.

[0235] If such a water repellent agent polymer is used to form a resin film on a substrate and the resin film is exposed to high-energy rays such as electromagnetic waves having a wavelength of 300 nm or less or electron beams, the acid-decomposable group is decomposed and an acid is generated in the resin film. By this acid, the solubility of the exposed portion of the resin film in the alkaline developer in the development can be improved.

[0236] In the case where the water repellent agent polymer of the second embodiment of the present application includes a plurality of the above-described repeating units represented by General Formula (1), R 1 The R 2 The R and X are also the same.

[0237] In the case where the water repellent agent polymer of the second embodiment of the present application includes a plurality of the above-described repeating units represented by General Formula (4), R A The R A The R is also the same.

[0238] In the case where the water repellent agent polymer of the second embodiment of the present application includes a plurality of the above-described repeating units represented by General Formula (4a), R Amay be the same in each repeating unit or may be different in each repeating unit. R 3 and L are also the same.

[0239] In the case where the water repellent agent-use polymer of the second embodiment of the present application contains a plurality of the above-described repeating units represented by General Formula (5), R 4 may be the same in each repeating unit or may be different in each repeating unit.

[0240] In the case where the water repellent agent-use polymer of the second embodiment of the present application contains two or more kinds of repeating units among the above-described repeating unit represented by General Formula (1) and the above-described repeating unit represented by General Formula (2), R 1 may be the same in each repeating unit or may be different in each repeating unit.

[0241] The weight average molecular weight of the water repellent agent-use polymer of the second embodiment of the present application can be 5000 to 20000, and further can be 7000 to 12000. In the present specification, the weight average molecular weight of the polymer refers to a value determined by a gel permeation chromatograph (GPC) under the following conditions.

[0242] [GPC conditions]

[0243] Apparatus: HLC-8320 GPC manufactured by Tosoh Corporation

[0244] Column for analysis of polymerizable monomer: TSKgel series (G2500HXL, G2000HXL, G1000HXL, G1000HXL connected in series in this order) manufactured by Tosoh Corporation

[0245] Column for analysis of polymer: TSKgel series (G2500HXL, G2000HXL, G1000HXL, G1000HXL connected in series in this order) manufactured by Tosoh Corporation

[0246] Temperature program: 40°C (hold)

[0247] Flow rate: 1 mL / minute

[0248] Detector: differential refractive detector (RI)

[0249] Eluent: tetrahydrofuran (THF)

[0250] Reference substance: polystyrene standard solution

[0251] Next, an example of the method for producing the water repellent agent-use polymer of the second embodiment of the present application will be described.

[0252] The manufacturing method of the water repellent agent polymer of the second embodiment of the present application includes a fluorine-containing polymerizable monomer preparation step and a polymerization step.

[0253] <Fluorine-containing polymerizable monomer preparation step>

[0254] In the manufacturing method of the water repellent agent polymer of the second embodiment of the present application, first, a compound represented by the following general formula (6) is prepared.

[0255]

[0256] (In general formula (6), R 2 is a single bond, a linear chain, a branched chain, or an optionally cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated.

[0257] X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0258] Subsequently, the compound represented by general formula (6) is reacted with at least one selected from the group consisting of an acid halide, an anhydride, an ester, and a carboxylic acid.

[0259] As examples of the acid halide, methacryloyl chloride, methacryloyl bromide, methacryloyl fluoride, acryloyl chloride, acryloyl bromide, acryloyl fluoride, and the like can be given. As examples of the anhydride, methacrylic anhydride, acrylic anhydride, and the like can be given. As examples of the ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, and the like can be given. As examples of the carboxylic acid, methacrylic acid, acrylic acid, and the like can be given.

[0260] The reaction of the compound represented by general formula (6) and the compound can be performed with the addition of an acid or a base as necessary. As the reaction conditions, it is preferable to perform the reaction at 0 to 130°C for 0.5 to 10 hours.

[0261] The separation and purification of the product after the reaction can be performed by a conventional method, and, for example, concentration, distillation, extraction, recrystallization, filtration, column chromatography, and the like can be used, and two or more of these methods can be combined and used.

[0262] The fluorine-containing polymerizable monomer represented by the following general formula (7) can be produced by the above steps. The fluorine-containing polymerizable monomer represented by general formula (7) is a compound that becomes the repeating unit represented by general formula (1) of the water repellent agent polymer of the second embodiment of the present application.

[0263]

[0264] (in General Formula (7), R 1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, and a part or all of hydrogen atoms bonded to carbon atoms in the alkyl group are optionally substituted with fluorine atoms.

[0265] R 2 is a single bond, a linear, branched, or cyclic alkylene group, an aromatic ring, an ester, a carbonyl group, an ether, an amide, an amine, or a complex substituent thereof, a part of which is optionally fluorinated and / or chlorinated, and X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

[0266] <Polymerization Step>

[0267] Subsequently, the fluorine-containing polymerizable monomer represented by General Formula (7) is polymerized.

[0268] Note that the polymerization can be performed together with a monomer other than the fluorine-containing polymerizable monomer represented by General Formula (7).

[0269] The polymerization reaction in the polymerization is not particularly limited, and can be a radical polymerization reaction, an ionic polymerization reaction, a coordination anionic polymerization reaction, an active anionic polymerization reaction, or a cationic polymerization reaction. Among them, the radical polymerization reaction is preferable.

[0270] In the case where the polymerization reaction is a radical polymerization reaction, as a polymerization initiator, any compound can be used as long as it generates a polymerization reaction, and there is no particular limitation, and an azo compound, a peroxide compound, or a redox compound can be used.

[0271] As an example of the azo compound, azobisisobutyronitrile can be given. As an example of the peroxide compound, t-butyl peroxypivalate, di-t-butyl peroxide, peroxyl isobutyric acid, peroxyl lauryl acid, peroxyl succinic acid, di-cinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monooxide, benzoyl peroxide, hydrogen peroxide, or ammonium persulfate, etc. can be given.

[0272] As an example of the redox compound, a combination of an oxidizing agent and a reducing agent can be used, and as the oxidizing agent side, hydrogen peroxide, persulfate, cumene hydroperoxide, etc. can be given, and as the reducing agent side, iron (II) ion salt, copper (I) ion salt, ammonia, triethylamine, etc. can be given.

[0273] In addition, a polymerization solvent can be used in the radical polymerization reaction.

[0274] As the polymerization solvent, there is no particular limitation as long as it is one that does not inhibit the radical polymerization reaction, and it can be an organic solvent or water. As the organic solvent, there can be mentioned a hydrocarbon-based solvent, an ester-based solvent, a ketone-based solvent, an alcohol-based solvent, an ether-based solvent, a cyclic ether-based solvent, a fluorocarbon-based solvent, an aromatic-based solvent, and the like. The solvent can be used alone or in combination of two or more.

[0275] As the ester-based solvent, there can be mentioned acetic acid, n-butyl acetate, and the like.

[0276] As the ketone-based solvent, there can be mentioned acetone, methyl isobutyl ketone, and the like.

[0277] As the hydrocarbon-based solvent, there can be mentioned toluene, cyclohexane, and the like.

[0278] As the alcohol-based solvent, there can be mentioned methanol, isopropyl alcohol, ethylene glycol monomethyl ether.

[0279] In addition, a molecular weight modifier such as a mercaptan can be used in the radical polymerization reaction.

[0280] The reaction temperature in the radical polymerization reaction is appropriately changed depending on the radical polymerization initiator or the kind of the radical polymerization initiator, and is preferably 20°C or higher and 200°C or lower, and further preferably 30°C or higher and 140°C or lower.

[0281] As the method for removing the organic solvent or water as the medium from the solution or dispersion liquid containing the synthesized polymer after the polymerization step, a publicly known method can be used. Specifically, there can be mentioned a method such as reprecipitation, filtration, heating distillation under reduced pressure, and the like.

[0282] The water-repellent agent-use polymer of the second embodiment of the present application can be produced through the above procedure.

[0283] (Third Embodiment)

[0284] Next, the water-repellent film-forming composition of the third embodiment of the present application will be described.

[0285] The water-repellent film-forming composition of the third embodiment of the present application contains the copolymer of the first embodiment or the water-repellent agent-use polymer of the second embodiment.

[0286] The water-repellent film-forming composition of the third embodiment of the present application can contain two or more kinds of the copolymer of the first embodiment or the water-repellent agent-use polymer of the second embodiment.

[0287] The water-repellent film-forming composition of the third embodiment of the present application can be used for forming a resin film (water-repellent film) having water repellency.

[0288] For example, other components such as a solvent can be added to the water repellent film-forming composition of the third embodiment of the present application, and the water repellent film-forming composition is applied to a substrate and hardened or dried, thereby forming a coating film.

[0289] Note that a resin film including the coating film of the water repellent film-forming composition of the third embodiment of the present application is also a resin film of the present application.

[0290] The water repellent film-forming composition of the third embodiment of the present application can be used as a resist film without a surface coating layer, or a component of an upper layer film for protecting a resist film.

[0291] In addition, the water repellent film formed using the water repellent film-forming composition of the third embodiment of the present application can be used not only for the above-mentioned uses, but also for water repellent coating of plastics, waterproof materials for houses, electronic machines such as smart phones, partition walls of biosensors and the like, micro flow paths, and glass for automobiles.

[0292] Hereinafter, a case where the water repellent film-forming composition of the third embodiment of the present application is used as a resist film without a surface coating layer, or a component of an upper layer film for protecting a resist film will be described in detail.

[0293] In a case where the water repellent film-forming composition of the third embodiment of the present application is used to form a resist film without a surface coating layer, the water repellent film-forming composition of the third embodiment of the present application can include an acid generator and a solvent.

[0294] In a case where the water repellent film-forming composition of the third embodiment of the present application is used to form an upper layer film, the water repellent film-forming composition of the third embodiment of the present application can include a solvent.

[0295] The resist film without a surface coating layer formed using the water repellent film-forming composition of the third embodiment of the present application can be either of a negative type and a positive type.

[0296] There is no particular limitation on the substrate on which the resist film without a surface coating layer is formed, and examples thereof include a silicon substrate, a germanium substrate, a silicon carbide (SiC) substrate, a gallium nitride (GaN) substrate, a compound semiconductor substrate, an insulating substrate, and the like. The substrate can be one on which an antireflection film is formed.

[0297] In addition, in a case where an upper layer film is formed, the water repellent film-forming composition of the third embodiment of the present application can be applied to a resist film (a bottom layer film).

[0298] In a case where the water repellent film-forming composition of the third embodiment of the present application is used to form a resist film without a surface coating layer, the water repellent film-forming composition of the third embodiment of the present application is applied to a substrate to form a resist film without a surface coating layer. Thereafter, the resist film without a surface coating layer can be subjected to exposure or immersion exposure.

[0299] In addition, in the case where the water repellent film-forming composition of the third embodiment of the present application is used to form an upper layer film, the water repellent film-forming composition of the third embodiment of the present application can be applied to an etching resist film to form an upper layer film. Thereafter, the upper layer film can be subjected to exposure or immersion exposure.

[0300] Note that the resin film of the coated film containing the water repellent film-forming composition of the third embodiment of the present application is a resin film having a low hysteresis angle and a low sliding angle with respect to a liquid for immersion in immersion exposure, and is thus preferably used for immersion exposure.

[0301]

[0302] As described above, in the case where the water repellent film-forming composition of the third embodiment of the present application is used to form an etching resist film having a faceless coating, the water repellent film-forming composition of the third embodiment of the present application can contain an acid generator and a solvent in addition to the copolymer of the first embodiment or the water repellent agent-containing polymer of the second embodiment.

[0303] Examples of the acid generator include onium salt-based acid generators such as iodonium salts or sulfonium salts; oxime sulfonate-based acid generators; diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyl diazomethanes and poly(bis sulfonyl) diazomethanes; nitrobenzyl sulfonate-based acid generators; imino sulfonate-based acid generators; disulfone-based acid generators; and the like.

[0304] ​As the onium salt-based acid generator, specifically, mention can be made of: a trifluoromethanesulfonic acid salt or a nonafluorobutanesulfonic acid salt of diphenyliodonium; a trifluoromethanesulfonic acid salt or a nonafluorobutanesulfonic acid salt of bis(4-tert-butylphenyl)iodonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of triphenylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of tri(4-methylphenyl)sulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of dimethyl(4-hydroxynaphthyl)sulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of monophenyl dimethylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of diphenyl monomethylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of (4-methylphenyl)diphenylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of (4-methoxyphenyl)diphenylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of tri(4-tert-butyl)phenylsulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of diphenyl(l-(4-methoxy)naphthyl)sulfonium; a trifluoromethanesulfonic acid salt, a heptafluoropropylsulfonic acid salt or a nonafluorobutanesulfonic acid salt of di(l-naphthyl)phenylsulfonium, and the like. In addition, an onium salt in which the anion portion of the onium salt is replaced with a methanesulfonate, a n-propanesulfonate, a n-butenesulfonate or a n-octanesulfonate can also be used.

[0305] As the oxime sulfonate-based acid generators, specifically, α-(p-toluenesulfonyloxyimino)-benzyl cyanide, α-(p-chlorobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-benzyl cyanide, α-(benzenesulfonyloxyimino)-4-chlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-2,4-dichlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-2,6-dichlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(benzenesulfonyloxyimino)-thiophen-2-ylethanenitrile, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]ethanenitrile, α-[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl]ethanenitrile, α-(toluene- sulfonyloxyimino)-4-thienyl cyanide, α-(methylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylethanenitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylethanenitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylethanenitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(trifluoromethylsulfonyloxyimino)-cyclohexylethanenitrile, α-(ethylsulfonyloxyimino)-ethyl ethanenitrile, α-(propylsulfonyloxyimino)-propyl ethanenitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylethanenitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylethanenitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylethanenitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylethanenitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylethanenitrile, α-(n-butylsulfonyloxyimino)-1-cyclohexenylethanenitrile, α-(methylsulfonyloxyimino)-phenylethanenitrile, α-(methylsulfonyloxyimino)-p-methoxyphenylethanenitrile, α-(trifluoromethylsulfonyloxyimino)-phenylethanenitrile, α-(trifluoromethylsulfonyloxyimino)-p-methoxyphenylethanenitrile, α-(ethylsulfonyloxyimino)-p-methoxyphenylethanenitrile, α-(propylsulfonyloxyimino)-p-methylphenylethanenitrile, α-(methylsulfonyloxyimino)-p-bromophenylethanenitrile, and the like can be mentioned.

[0306] As specific examples of the bisalkyl or bisaryl sulfonyl diazomethane type, the following can be given: bis(isopropylsulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane, bis(l, 1-dimethylethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, and the like.

[0307] As examples of the solvent, the following can be given: methanol, ethanol, 1-propanol, isopropanol, n-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, n-hexanol, cyclohexanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-methyl-l-butanol, 3-methyl-l-butanol, 2-methyl-l-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-l-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-l-pentanol, 4-methyl-2-pentanol, ethylene glycol, propylene glycol, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol, ethyl acetate, butyl acetate, 2-hydroxypropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, 2-hydroxy-2-methylpropionic acid ethyl ester, ethoxyacetic acid ethyl ester, hydroxyacetic acid ethyl ester, 2-hydroxy-3-methylbutyric acid methyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, water, and the like.

[0308] Note that, in the case where the water-repellent film-forming composition of the third embodiment of the present application is used to form a resist film having no surface coating layer, the water-repellent film-forming composition of the third embodiment of the present application can contain a basic compound.

[0309] As examples of the basic compound, the following can be given: monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and the like; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine, and the like; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, and the like; alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, and the like; piperidine, piperazine, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, and the like.

[0310] Further, in the case where the water repellent film-forming composition of the third embodiment of the present application is used for forming a resist film having no top coat layer, the water repellent film-forming composition of the third embodiment of the present application can contain a base resin other than the copolymer of the first embodiment or the water repellent agent-use polymer of the second embodiment, or a weak acid photoacid generator (weak acid PAG).

[0311] As the base resin, a resin containing a structure represented by the following formula can be given.

[0312]

[0313] (In General Formulae (a) and (b), R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z B is a single bond, a phenylene group, a naphthylene group, or (main chain)-C(=0)-0-Z'-, Z' is an alkanediyl group having a carbon number of 1 to 10 which can contain a hydroxyl group, an ether bond, an ester bond, or a lactone ring, or a phenylene group or a naphthylene group. X B is an acid-labile group. Y B is a hydrogen atom, or a polar group containing at least one or more structures selected from a hydroxyl group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate ester bond, a lactone ring, a sultone ring, and a carboxylic anhydride (-C(=0)-0-C(=0)-).

[0314] The alkandiyl group can be any of linear, branched, or cyclic, and as specific examples, methylene, ethane-1, 1-diyl, ethane-1, 2-diyl, propane-1, 2-diyl, propane-2, 2-diyl, propane-1, 3-diyl, 2-methylpropane-1, 3-diyl, butane-1, 3-diyl, butane-2, 3-diyl, butane-1, 4-diyl, pentane-1, 3-diyl, pentane-1, 4-diyl, 2, 2-dimethylpropane-1, 3-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, cyclopentane-1, 2-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 6-diyl, and the like can be mentioned.

[0315] As the Z in the formula (a) is changed to B The structure of the acid-labile group represented by X B and X B are the same as described above.

[0316]

[0317] As the acid-labile group represented by X B is not particularly limited, and for example, a tertiary alkyl group having 4 to 20 carbons, a trialkylsilyl group in which each alkyl group has 1 to 6 carbons, a side oxygen-containing alkyl group having 4 to 20 carbons, and the like can be mentioned.

[0318] As the acid-labile group, a group represented by the following general formula (xa), (xb), or (xc) is particularly preferred.

[0319]

[0320] (In the general formula (xa), (xb), and (xc), R X is a monovalent hydrocarbon group having 1 to 10 carbons which can contain a hetero atom. k is 1 or 2. The dotted line is a bond.)

[0321] In the case where the tertiary alicyclic hydrocarbon group represented by the general formula (xa), (xb), or (xc) is bonded to the ester oxygen, the acid decomposition ability is improved due to steric repulsion as compared with other tertiary alkyl groups such as a tert-butyl group or a tert-pentyl group.

[0322] As the repeating unit represented by the general formula (a), the following repeating units can be mentioned, but are not limited thereto. Note that in the following general formula, R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0323]

[0324]

[0325]

[0326] Note that the above specific examples are Z B In the case of a single bond, Z B In the case other than a single bond, it can also be combined with the same acid-labile group.

[0327] As the repeating unit represented by General Formula (b), the following can be exemplified, but is not limited thereto. Note that in the following formulae, R B is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0328]

[0329]

[0330]

[0331] The water-repellent film-forming composition of the 3rd embodiment of the present application can contain one of the above structures as a base resin, or can contain two or more of the above structures as a base resin.

[0332] In the case where the base resin contains two or more of the above structures, R B , X B , Y B , Z B , R X may be the same or different.

[0333] As the weak acid PAG, a photodegradable base that generates a weak acid by being photosensitive to exposure can also be used.

[0334] As the photodegradable base, for example, an onium salt compound that is decomposed by exposure can be exemplified. As the onium salt compound, for example, a sulfonium salt compound represented by the following Formula (9-1), an iodonium salt compound represented by the following Formula (9-2), or the like can be exemplified.

[0335]

[0336] (In the Formulae (9-1) and (9-2), R 5 ~R 9 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or a halogen atom.

[0337] E - and Q - are each independently OH - , R β -COO - , R β -SO3 -or an anion represented by the following formula (9-3). In the formula (9-3), R β is an alkyl group, an aryl group, or an aralkyl group.

[0338]

[0339] In the formula (9-3), R 10 is a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched alkoxy group having 1 to 12 carbon atoms, and a part or all of the hydrogen atoms of the alkyl group are optionally substituted with fluorine atoms. u is an integer of 0 to 2.

[0340] As a specific example of the weak acid PAG, for example, the following compound can be given.

[0341]

[0342] As described in detail below, the resist film without a surface coating layer can be formed by the following processes: a process of preparing a water repellent film-forming composition; a film formation process of applying the water repellent film-forming composition on a substrate to form a film; an exposure process of irradiating electromagnetic waves or high-energy rays having an exposure wavelength of 300 nm or less with an interval light mask to the film to transfer a pattern of the light mask to the film; and a development process of developing the film using a developing solution to obtain a pattern.

[0343] Water repellent film-forming composition for forming an upper layer film

[0344] As described above, in the case where the water repellent film-forming composition of the third embodiment of the present application is used to form an upper layer film, the water repellent film-forming composition of the third embodiment of the present application preferably contains a solvent in addition to the copolymer of the first embodiment or the water repellent agent polymer of the second embodiment.

[0345] As examples of the solvent, the same as the examples of the solvent used for forming the resist film without a surface coating layer can be given.

[0346] As described in detail below, the method of forming an upper layer film can be exemplified by a method including the following processes: a process of preparing a water repellent film-forming composition; a film formation process of applying the water repellent film-forming composition on a resist film to form an upper layer film; an exposure process of irradiating electromagnetic waves or high-energy rays having an exposure wavelength of 300 nm or less with an interval light mask to the upper layer film and the resist film to transfer a pattern of the light mask to the resist film; and a development process of removing the upper layer film and developing the resist film using a developing solution to obtain a pattern.

[0347] (4th Embodiment)

[0348] Next, a method of forming a resist pattern according to the fourth embodiment of the present application will be described.

[0349] The resist pattern forming method of the fourth embodiment of the present application includes: a film forming step of forming a resin film by applying the water repellent film forming composition of the third embodiment of the present application to the surface of a substrate or a primer film; and a liquid immersion exposure step of exposing the resin film by irradiating the resin film with electromagnetic waves having a wavelength of 300 nm or less or high energy rays in a state where water directly contacts the surface of the resin film.

[0350] Note that, in the resist pattern forming method of the fourth embodiment of the present application, a developing step of removing used substances using a developing solution and developing can be performed after the liquid immersion exposure step.

[0351] The so-called liquid immersion exposure refers to exposure processing performed with a liquid immersion liquid filled between a lens of an exposure apparatus and a substrate.

[0352] If the liquid immersion liquid is filled between the lens of the exposure apparatus and the substrate, the incident angle of exposure light incident to the substrate through the lens can be reduced compared to a case where air is filled between the lens of the exposure apparatus and the substrate. Thus, the numerical aperture of the lens can be increased to improve resolution.

[0353] In addition, exposure using a lens having an existing numerical aperture can also expand the depth of focus, thereby enabling stable yield to be ensured.

[0354] In addition, in the resist pattern formation in the case where liquid immersion exposure is performed, there are cases where resist pattern formation defects occur due to the liquid immersion liquid penetrating into the resist film (primer film). In addition, there are cases where resist pattern formation defects occur due to various components penetrating from the resist film (primer film) into the liquid immersion liquid. Furthermore, there are cases where pattern defects occur if droplets remain on the substrate after liquid immersion exposure.

[0355] In the case where liquid immersion exposure is performed, an upper layer film for preventing such pattern formation defects and the like is formed on the resist film (primer film).

[0356] In addition, a resist film having a higher water repellency is directly formed on the substrate without a surface coating layer.

[0357] As described above, the resin film of the coated film including the water repellent film forming composition of the third embodiment of the present application has a low receding angle and a low sliding angle with respect to the liquid immersion liquid in liquid immersion exposure.

[0358] Thus, in the resist pattern forming method of the fourth embodiment of the present application using the water repellent film forming composition of the third embodiment of the present application, it is difficult to cause pattern formation defects.

[0359] Hereinafter, each step is described.

[0360] Film forming step

[0361] In the film forming step, the water repellent film forming composition of the third embodiment of the present application is applied to the surface of a substrate or a primer film (resist film) to form a resin film.

[0362] In the case where the water repellent film forming composition of the third embodiment is applied to the surface of a substrate, the water repellent film forming composition becomes a resist film without a surface coating layer.

[0363] In the case where the water repellent film forming composition of the third embodiment is applied to the surface of a primer film (resist film), the water repellent film forming composition becomes an upper layer film.

[0364] The resin film can be subjected to a heat treatment after the resin film is formed.

[0365] The substrate is not particularly limited, and examples thereof include a silicon wafer, a compound semiconductor substrate, an insulating substrate, and the like. The substrate can be one on which an anti-reflection film is formed.

[0366] The primer film is not particularly limited, and examples thereof include conventional resist films.

[0367] The method of applying the water repellent film forming composition is not particularly limited, and a conventional method such as a spin coater or a bar coater can be used.

[0368] The thickness of the resin film formed is not particularly limited, and is preferably 5 to 500 nm.

[0369] <Immersion liquid exposure step>

[0370] The resin film is exposed by irradiating electromagnetic waves having a wavelength of 300 nm or less or high-energy rays in a state where water directly contacts the surface of the resin film.

[0371] By this, the resin film which is a resist film without a surface coating layer or the primer film (resist film) is photosensitive.

[0372] Note that a baking treatment can be performed after the immersion liquid exposure.

[0373] <Development step>

[0374] After the immersion liquid exposure step, a development treatment is performed using a developing solution. Development refers to a process in which a used substance is removed using an alkaline solution (for a positive pattern formation) or an organic solvent (for a negative pattern formation) as a developing solution to form a resist pattern.

[0375] [Positive pattern formation]

[0376] Positive pattern formation refers to a process in which an exposed portion is dissolved and removed by washing using an alkaline solution as a developing solution, thereby forming a pattern.

[0377] Generally, the developing solution can use an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.1 mass% or more and 10 mass% or less as a basic aqueous solution.

[0378] As other basic developing solutions, an aqueous solution in which sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonane, or the like is dissolved can be exemplified.

[0379] As the developing solution used, there is no particular limitation as long as the desired used substance can be removed with a prescribed developing method, and generally, an aqueous solution of an inorganic base, a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt, and a mixture thereof can be exemplified. In addition, a water-soluble organic solvent such as an alcohol such as methanol, ethanol, or the like, or a surfactant can be added in an appropriate amount to the developing solution.

[0380] In the case where developing is performed using the aqueous basic solution, the target pattern can be formed by washing, rinsing, drying, or the like as needed.

[0381] As the developing method, a known method such as an immersion method, a slurry method, a spray method, or the like can be used, and the developing time can be set to 0.1 minutes or more and 3 minutes or less. In addition, 0.5 minutes or more and 2 minutes or less are preferred.

[0382] [Negative pattern formation]

[0383] Negative pattern formation refers to a method in which an organic solvent is used as a developing solution, only the unexposed portion is dissolved and washed away, and thereby a pattern is formed.

[0384] Generally, butyl acetate can be used as an organic solvent in the developing solution.

[0385] Other organic solvents that can be listed include: 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl valerate, methyl butenoate, ethyl butenoate. Esters, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, ethyl formate, phenyl ethyl formate, methyl 3-phenylpropionate, benzyl propionate, 2-phenylethyl acetate, etc.

[0386] The developer used is not particularly limited as long as the used substances can be removed by the prescribed developing method. Water-soluble organic solvents such as methanol, ethanol, or surfactants may also be added to the developer in appropriate amounts.

[0387] When developing with the organic solvent, cleaning, rinsing, drying, etc., can be performed as needed to form a negative pattern of the target.

[0388] As a developing method, known methods such as immersion, paste, and spray can be used, and the developing time can be set to 0.1 minutes or more and 3 minutes or less. In addition, 0.5 minutes or more and 2 minutes or less is preferred.

[0389] The above processes can be used to form anti-corrosion patterns.

[0390] It should be noted that the waste liquid generated in the developing process contains resin derived from the repeating unit represented by the general formula (1) of the resin dichlorofluoromethyl (-CF2Cl).

[0391] The resin contained in this type of waste liquid is easily decomposed, thus making waste liquid treatment easy.

[0392] Example

[0393] The present invention will now be described in detail with reference to specific embodiments. However, the present invention is not limited to the following embodiments.

[0394] In the embodiments, unless otherwise specified, some of the compounds are described below.

[0395] Diisobutyl ketone: IPE

[0396] Butyl methacrylate (BMA)

[0397] Tetramethylammonium hydroxide: TMAH

[0398] propylene glycol monomethyl ether acetate: PGMEA

[0399] methyl ethyl ketone: MEK

[0400] MA-4FHB-OH: a compound represented by the following formula

[0401]

[0402] 4FIP-M: a compound represented by the following formula

[0403]

[0404] i-4FHK-OH: a compound represented by the following formula

[0405]

[0406] 4FIP: a compound represented by the following formula

[0407]

[0408] MA-BTHB-OH: a compound represented by the following formula

[0409]

[0410] HFIP-M: a compound represented by the following formula

[0411]

[0412] The apparatuses or the assay conditions for various assays are described.

[0413] [Analysis of fluorine-containing polymerizable monomer]

[0414] Using a nuclear magnetic resonance apparatus (hereinafter referred to as NMR, manufactured by JEOL Ltd., machine name JNM-ECA400) with a resonance frequency of 400 MHz, the following were measured. 19 F-NMR, 1 H-NMR.

[0415] [Analysis of polymer]

[0416] The composition of the repeating unit in the polymer was determined from the measured values of H-NMR and 1 F-NMR. 19

[0417] [Analysis of weight average molecular weight]

[0418] ​The weight average molecular weight (Mw) of the resin composition and the like described below was determined in the following manner. The number average molecular weight Mn of the polymer and the molecular weight dispersion (ratio of the number average molecular weight Mn to the mass average molecular weight Mw = Mw / Mn) were determined using a high-performance gel permeation chromatograph (hereinafter, sometimes referred to as GPC. Manufactured by Tosoh Corporation, Model HLC-8320GPC), connecting one each of an ALPHA-M column and an ALPHA-2500 column manufactured by Tosoh Corporation in series, and using tetrahydrofuran as the developing solvent. The detector used was a refractive index difference measurement detector.

[0419] The synthesis of fluorine-containing polymerizable monomers and intermediates for fluorine-containing polymerizable monomers will be described.

[0420] [Synthesis Example 1: Synthesis of i-4FHK-OH and MA-4FHB-OH]

[0421] To a 1 L three-necked flask was added concentrated sulfuric acid (0.31 g, 3.16 mmol), acetone (307 g, 5.28 mol), 1,3-dichlorotetrafluoroacetone (manufactured by Synquest Laboratories, Inc., 210 g, 1.06 mol), and stirred at 30°C overnight. The reaction liquid was concentrated with an evaporator at a bath temperature of 30°C and 100 hPa, and the resulting concentrated liquid was washed with ion exchange water. Thereafter, it was concentrated with an evaporator to obtain concentrated liquid 1 (245 g).

[0422] To a 1 L three-necked flask was added tetrahydrofuran (super-dehydrated grade, 551 g), and sodium borohydride (32.5 g, 857 mmol) was dispersed and immersed in an ice bath to cool. Thereafter, the concentrated liquid 1 was added dropwise over 30 minutes, and the reaction was stopped with hydrochloric acid water after 1.5 hours. The reaction liquid was extracted with IPE (551 g), and ion exchange water was washed once. While the washed IPE solution was solvent-exchanged with toluene, it was concentrated with an evaporator at a bath temperature of 42°C and 20 hPa to obtain concentrated liquid 2 containing i-4FHK-OH (215 g).

[0423] To a 1 L three-necked flask, the concentrate 2, methanesulfonic acid (5.97 g, 62.1 mmol), Nonflex MBP (manufactured by KANTO CHEMICAL CO., INC., 0.96 g) were added and mixed, and then methyl methacrylate anhydride (hereinafter, MAAH, Tokyo Chemical Industry Co., Ltd., 105 g, 683 mmol) was added dropwise at a bath temperature of 38°C. Thereafter, the reaction was stirred for 1.5 hours at a bath temperature of 47°C and for 3 hours at a bath temperature of 57°C, and then the reaction was stopped. The reaction solution was extracted with IPE (322 g), and then washed with sodium hydroxide water and ion exchange water each once. Thereafter, a small amount of 2-methoxyphenothiazine was added, and then the concentrate was concentrated with an evaporator at a bath temperature of 42°C and at 20 hPa. The obtained concentrate was distilled at 0.2 kPa and at an inner temperature of 125 to 136°C to obtain MA-4FHB-OH (123 g, yield 36% (3-step yield), GC purity > 99%). The following shows this reaction.

[0424]

[0425] <NMR analysis results>

[0426] The results of NMR are shown below.

[0427] 1 H-NMR (CDCI3, reference material: TMS): 6.36 ppm (s, 1H), 6.18 ppm (m, 1H), 5.65 ppm (quin, J = 1.6 Hz, 1H), 5.22 ppm (m, 1H), 2.43 ppm (dd, J = 4.8 Hz, 0.8 Hz, 2H), 1.95 ppm (m, 3H), 1.46 ppm (d, J = 6.4 Hz, 3H)

[0428] 19 F-NMR (CDCI3, reference material: C6F6): -60.1 ppm (q, 15.2 Hz, 2F), -79.6 ppm (m, 2F)

[0429] [Synthesis Example 2: Synthesis of 4FIP and 4FIP-M]

[0430] To a 1 L three-necked flask was added sodium borohydride (22.8 g, 603 mmol), IPE (300 g), and immersed in an ice bath to cool. Thereafter, after slowly dropping 1,3-dichlorotetrafluoroacetone (manufactured by Synquest Laboratories, Inc., 100 g, 503 mmol), it was set to room temperature and stirred for 17 hours. After being immersed in an ice bath to cool, the reaction was stopped with hydrochloric acid water 200 g. Thereafter, it was subjected to liquid separation, and the obtained organic layer was subjected to normal pressure distillation (oil bath 120 to 150°C) to thereby obtain an IPE solution of 4FIP 129 g. The purity was 64 wt% and the yield was 82%. The following shows this reaction.

[0431]

[0432] <NMR analysis results>

[0433] The results of NMR are shown below. Only the results of 4FIP are shown.

[0434] 1 H-NMR (CDCI3, reference material: TMS): 4.42 ppm (m, 1H)

[0435] 19 F-NMR (CDCI3, reference material: C6F6): -58.7 ppm (m, 2F), -63.4 ppm (m, 2F)

[0436] To a 500 mL three-necked flask was added an IPE solution of 4FIP (120 g, 410 mmol), triethylamine (46 g, 454 mmol), IPE (150 g), and immersed in an ice bath to cool. Thereafter, after slowly dropping methacryloyl chloride (45 g, 45.2 mmol), it was set to room temperature and stirred for 3 hours, and then the reaction was stopped with saturated sodium bicarbonate solution 200 g. Thereafter, it was subjected to liquid separation, and the obtained organic layer was washed once with saturated sodium bicarbonate solution 200 g and twice with distilled water 200 g, and then the organic layer was subjected to reduced pressure distillation (reduced pressure degree 0.6 kPa, oil bath 50 to 100°C) to thereby obtain 4FIP-M 86 g. The yield was 80% and the GC purity was >99%. The following shows this reaction.

[0437]

[0438] <NMR analysis results>

[0439] The results of NMR are shown below.

[0440] 1H-NMR (CDCI3, reference substance: TMS): 6.36 ppm (m, 1H), 5.89 ppm (m, 1H), 5.84 ppm (m, 1H), 2.03 ppm (m, 3H)

[0441] 19 F-NMR (CDCI3, reference substance: C6F6): -58.5 ppm (m, 2F), -60.1 ppm (m, 2F)

[0442] Next, the synthesis of the polymers will be described.

[0443] [Example 1-1: Synthesis of Copolymer 1-1]

[0444] To a 300 mL three-necked flask, MEK (75.6 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixed solution of MA-4FHB-OH (8.2 g, 25 mmol) and BMA (10.7 g, 75 mmol) and MEK (18.9 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) to perform reprecipitation, filtered, and the resulting polymer was dried under reduced pressure to obtain a white powder of 14.2 g. In this way, the copolymer 1-1 of Example 1-1 was synthesized.

[0445] [Example 1-2 and Example 1-3: Synthesis of Copolymer 1-2 and Copolymer 1-3]

[0446] The ratio (molar ratio) of MA-4FHB-OH and BMA used was changed as shown in Table 1, and otherwise, the copolymer 1-2 and copolymer 1-3 of Example 1-2 and Example 1-3 were synthesized in the same manner as Example 1-1.

[0447] [Example 1-4: Synthesis of Copolymer 1-4]

[0448] MEK (83.3 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80°C. Then, a mixture of MA-4FHB-OH (8.2 g, 25 mmol), 1-methylcyclopentyl methacrylate (12.6 g, 75 mmol), and MEK (20.8 g) was added dropwise over 30 minutes, and the mixture was stirred at 80°C for 5 hours. After returning to room temperature, MEK was removed by vacuum distillation to prepare a 50 wt% solution, and then MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation and filtration. The resulting polymer was dried under reduced pressure to obtain 16.0 g of a white powder. The copolymers 1-4 of Examples 1-4 were synthesized through the above steps.

[0449] [Examples 1-5 and Examples 1-6: Synthesis of Copolymers 1-5 and 1-6]

[0450] As shown in Table 1, the ratio (molar ratio) of MA-4FHB-OH to 1-methylcyclopentyl methacrylate used was changed. Otherwise, copolymers 1-5 and 1-6 of Examples 1-5 and 1-6 were synthesized in the same manner as in Examples 1-4.

[0451] [Examples 1-7: Synthesis of copolymers 1-7]

[0452] MEK (87.5 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80 °C. Then, a mixture of MA-4FHB-OH (8.2 g, 25 mmol), 1-ethylcyclopentyl methacrylate (13.7 g, 75 mmol), and MEK (21.9 g) was added dropwise over 30 minutes, and the mixture was stirred at 80 °C for 5 hours. After returning to room temperature, MEK was removed by vacuum distillation to prepare a 50 wt% solution, and then MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation and filtration. The resulting polymer was dried under reduced pressure to obtain 17.3 g of a white powder. Through the above steps, copolymer 1-7 of Examples 1-7 was synthesized.

[0453] [Examples 1-8 and Examples 1-9: Synthesis of Copolymers 1-8 and 1-9]

[0454] As shown in Table 1, the ratio (molar ratio) of MA-4FHB-OH to 1-ethylcyclopentyl methacrylate used was changed. Otherwise, copolymers 1-8 and 1-9 of Examples 1-8 and 1-9 were synthesized in the same manner as in Examples 1-7.

[0455] [Examples 1-10: Synthesis of copolymers 1-10]

[0456] To a 300 mL three-necked flask was added MEK (103.1 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (8.2 g, 25 mmol) and methyl methacrylate (17.5 g, 175 mmol) and MEK (25.8 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 19.3 g. The copolymer 1-10 of Example 1-10 was synthesized by the above procedure.

[0457] [Examples 1-11 and 1-12: Synthesis of copolymer 1-11 and copolymer 1-12]

[0458] The ratio (molar ratio) of MA-4FHB-OH to methyl methacrylate used was changed as shown in Table 1, and otherwise, the copolymer 1-11 and 1-12 of Examples 1-11 and 1-12 were synthesized in the same manner as Example 1-10.

[0459] [Example 1-13: Synthesis of copolymer 1-13]

[0460] To a 300 mL three-necked flask was added MEK (104.0 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (8.2 g, 25 mmol) and methyl methacrylate (17.5 g, 175 mmol) and MEK (25.8 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 19.3 g. The copolymer 1-10 of Example 1-10 was synthesized by the above procedure.

[0461] [Examples 1-14 and 1-15: Synthesis of copolymer 1-14 and copolymer 1-15]

[0462] The ratio (molar ratio) of MA-4FHB-OH to methyl methacrylate used was changed as shown in Table 1, and otherwise, the copolymer 1-11 and 1-12 of Examples 1-11 and 1-12 were synthesized in the same manner as Example 1-10.

[0463] [Examples 1-16: Synthesis of Copolymer 1-16]

[0464] To a 300 mL three-necked flask was added MEK (58.6 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (8.2 g, 25 mmol) and methyl methacrylate (6.5 g, 75 mmol) and MEK (14.7 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 8.8 g. The copolymer 1-16 of Example 1-16 was synthesized by the above procedure.

[0465] [Examples 1-17 and 1-18: Synthesis of Copolymer 1-17 and Copolymer 1-18]

[0466] The ratio (molar ratio) of MA-4FHB-OH to methyl methacrylate used was changed as shown in Table 1, and otherwise, the copolymer 1-17 and 1-18 of Examples 1-17 and 1-18 were synthesized in the same manner as in Example 1-16.

[0467] [Comparative Example 1-1: Synthesis of Comparative Copolymer 1-1]

[0468] To a 300 mL three-necked flask was added MEK (72.4 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (7.4 g, 25 mmol) and BMA (10.7 g, 75 mmol) and MEK (18.1 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (200 g) was added. Thereafter, the resulting solution was added dropwise to heptane (20 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 13.2 g. The comparative copolymer 1-1 of Comparative Example 1-1 was synthesized by the above procedure.

[0469] [Comparative Examples 1-2 and 1-3: Synthesis of Comparative Copolymer 1-2 and Comparative Copolymer 1-3]

[0470] The ratio (molar ratio) of MA-BTHB-OH to BMA used was changed as shown in Table 1, and otherwise, the comparative copolymer 1-2 and 1-3 of Comparative Examples 1-2 and 1-3 were synthesized in the same manner as in Comparative Example 1-1.

[0471] [Comparative Example 1-4: Synthesis of Comparative Copolymer 1-4]

[0472] To a 300 mL three-necked flask was added MEK (80.1 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (7.4 g, 25 mmol) and 1-methylcyclopentyl methacrylate (12.6 g, 75 mmol) and MEK (20.0 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 15.9 g. Comparative Copolymer 1-4 of Comparative Example 1-4 was synthesized through the above procedure.

[0473] [Comparative Example 1-5 and Comparative Example 1-6: Synthesis of Comparative Copolymer 1-5 and Comparative Copolymer 1-6]

[0474] The ratio (molar ratio) of MA-BTHB-OH to 1-methylcyclopentyl methacrylate used was changed as shown in Table 1, and otherwise, Comparative Copolymer 1-5 and Comparative Copolymer 1-6 of Comparative Example 1-5 and Comparative Example 1-6 were synthesized in the same manner as Comparative Example 1-4.

[0475] [Comparative Example 1-7: Synthesis of Comparative Copolymer 1-7]

[0476] To a 300 mL three-necked flask was added MEK (84.4 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (7.4 g, 25 mmol) and 1-ethylcyclopentyl methacrylate (13.7 g, 75 mmol) and MEK (21.1 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 17.2 g. Comparative Copolymer 1-7 of Comparative Example 1-7 was synthesized through the above procedure.

[0477] [Comparative Example 1-8 and Comparative Example 1-9: Synthesis of Comparative Copolymer 1-8 and Comparative Copolymer 1-9]

[0478] The ratio (molar ratio) of MA-BTHB-OH to 1-ethylcyclopentyl methacrylate used was changed as shown in Table 1, and otherwise, Comparative Copolymer 1-8 and Comparative Copolymer 1-9 of Comparative Example 1-8 and Comparative Example 1-9 were synthesized in the same manner as Comparative Example 1-7.

[0479] [Comparative Examples 1-10: Synthesis of Comparative Copolymers 1-10]

[0480] To a 300 mL three-necked flask, MEK (99.9 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (7.4 g, 25 mmol) and 2-ethyl-2-adamantyl methacrylate (17.8 g, 75 mmol) and MEK (26.0 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon returning to room temperature, MEK was removed by distillation under reduced pressure, and after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) to perform reprecipitation, filtration, and the resulting polymer was dried under reduced pressure to obtain a white powder of 19.5 g. Comparative Copolymer 1-13 of Comparative Example 1-13 was synthesized through the above procedures.

[0481] [Comparative Examples 1-11 and 1-12: Synthesis of Comparative Copolymer 1-11 and Comparative Copolymer 1-12]

[0482] The ratio (molar ratio) of MA-BTHB-OH and 2-methyl-2-adamantyl methacrylate used was changed as shown in Table 1, and otherwise, Comparative Copolymer 1-11 and Comparative Copolymer 1-12 of Comparative Examples 1-11 and 1-12 were synthesized in the same manner as Comparative Example 1-10.

[0483] [Comparative Example 1-13: Synthesis of Comparative Copolymer 1-13]

[0484] To a 300 mL three-necked flask, MEK (99.9 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (7.4 g, 25 mmol) and 2-ethyl-2-adamantyl methacrylate (17.8 g, 75 mmol) and MEK (26.0 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon returning to room temperature, MEK was removed by distillation under reduced pressure, and after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) to perform reprecipitation, filtration, and the resulting polymer was dried under reduced pressure to obtain a white powder of 19.5 g. Comparative Copolymer 1-13 of Comparative Example 1-13 was synthesized through the above procedures.

[0485] [Comparative Examples 1-14 and 1-15: Synthesis of Comparative Copolymer 1-14 and Comparative Copolymer 1-15]

[0486] As shown in Table 1, the ratio (molar ratio) of MA-BTHB-OH to 2-ethyl-2-adamantyl methacrylate used was changed. Otherwise, comparative copolymers 1-14 and 1-15 of comparative examples 1-14 and 1-15 were synthesized in the same manner as comparative examples 1-13.

[0487] [Comparative Examples 1-16: Synthesis of Comparative Copolymers 1-16]

[0488] MEK (55.4 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80 °C. Then, a mixture of MA-BTHB-OH (7.4 g, 25 mmol), methacrylic acid (6.5 g, 75 mmol), and MEK (13.9 g) was added dropwise over 30 minutes, and the mixture was stirred at 80 °C for 5 hours. After returning to room temperature, MEK was removed by vacuum distillation to prepare a 50 wt% solution, and then MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation, filtered, and the resulting polymer was dried under reduced pressure to obtain 7.5 g of a white powder. Comparative copolymer 1-16 of Comparative Example 1-16 was synthesized through the above steps.

[0489] [Comparative Examples 1-17 and 1-18: Synthesis of Comparative Copolymers 1-17 and 1-18]

[0490] As shown in Table 1, the ratio (molar ratio) of MA-BTHB-OH to methacrylic acid used was changed. Otherwise, comparative copolymers 1-17 and 1-18 of comparative examples 1-17 and 1-18 were synthesized in the same manner as comparative examples 1-16.

[0491] [Table 1]

[0492]

[0493] [Example 2-1: Synthesis of copolymer 2-1]

[0494] MEK (69.6 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80 °C. Then, a mixture of 4FIP-M (6.7 g, 25 mmol) and BMA (10.7 g, 75 mmol) was added dropwise over 30 minutes, and the mixture was stirred at 80 °C for 5 hours. After returning to room temperature, the MEK was removed by vacuum distillation to prepare a 50 wt% solution, and then MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation and filtration. The resulting polymer was dried under reduced pressure to obtain 12.2 g of a white powder. The copolymer 2-1 of Example 2-1 was synthesized through the above steps.

[0495] [Example 2-2 and Example 2-3: Synthesis of Copolymer 2-2 and Copolymer 2-3]

[0496] The copolymer 2-2 and the copolymer 2-3 of Example 2-2 and Example 2-3 were synthesized in the same manner as Example 2-1 except that the ratio (molar ratio) of 4FIP-M to BMA used was changed as shown in Table 2.

[0497] [Example 2-4: Synthesis of Copolymer 2-4]

[0498] To a 300 mL three-necked flask, MEK (73.2 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of 4FIP-M (6.7 g, 25 mmol) and 1-methylcyclopentyl methacrylate (12.6 g, 75 mmol) and MEK (19.3 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 14.1 g. The copolymer 2-4 of Example 2-4 was synthesized through the above procedures.

[0499] [Example 2-5 and Example 2-6: Synthesis of Copolymer 2-5 and Copolymer 2-6]

[0500] The copolymer 2-5 and the copolymer 2-6 of Example 2-5 and Example 2-6 were synthesized in the same manner as Example 2-4 except that the ratio (molar ratio) of 4FIP-M to 1-methylcyclopentyl methacrylate used was changed as shown in Table 2.

[0501] [Example 2-7: Synthesis of Copolymer 2-7]

[0502] To a 300 mL three-necked flask, MEK (81.6 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of 4FIP-M (6.7 g, 25 mmol) and 1-ethylcyclopentyl methacrylate (13.7 g, 75 mmol) and MEK (20.4 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 15.1 g. The copolymer 2-7 of Example 2-7 was synthesized through the above procedures.

[0503] [Example 2-8 and Example 2-9: Synthesis of Copolymer 2-8 and Copolymer 2-9]

[0504] The copolymer 2-8 and the copolymer 2-9 of Example 2-8 and Example 2-9 were synthesized in the same manner as Example 2-7, except that the ratio (molar ratio) of the 4FIP-M used to 1- ethylcyclopentyl methacrylate was changed as shown in Table 2.

[0505] [Example 2-10: Synthesis of Copolymer 2-10]

[0506] To a 300 mL three-necked flask was added MEK (92.8 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of 4FIP-M (6.7 g, 25 mmol) and 2-methyl-2-adamantyl methacrylate (17.5 g, 75 mmol) and MEK (24.2 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 18.3 g. The copolymer 2-10 of Example 2-10 was synthesized through the above procedures.

[0507] [Example 2-11 and Example 2-12: Synthesis of Copolymer 2-11 and Copolymer 2-12]

[0508] The copolymer 2-11 and the copolymer 2-12 of Example 2-11 and Example 2-12 were synthesized in the same manner as Example 2-10, except that the ratio (molar ratio) of the 4FIP-M used to 2-methyl-2-adamantyl methacrylate was changed as shown in Table 2.

[0509] [Example 2-13: Synthesis of Copolymer 2-13]

[0510] To a 300 mL three-necked flask was added MEK (101.6 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of 4FIP-M (6.7 g, 25 mmol) and 2-ethyl-2-adamantyl methacrylate (17.8 g, 75 mmol) and MEK (25.4 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 17.8 g. The copolymer 2-13 of Example 2-13 was synthesized through the above procedures.

[0511] [Example 2-14 and Example 2-15: Synthesis of Copolymer 2-14 and Copolymer 2-15]

[0512] The copolymer 2-14 and the copolymer 2-15 of Example 2-14 and Example 2-15 were synthesized in the same manner as Example 2-13, except that the ratio (molar ratio) of 4FIP-M to 2-ethyl-2-adamantyl methacrylate used was changed as shown in Table 2.

[0513] [Example 2-16: Synthesis of Copolymer 2-16]

[0514] To a 300 mL three-necked flask was added MEK (52.7 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of 4FIP-M (6.7 g, 25 mmol) and methyl acrylate (6.5 g, 75 mmol) and MEK (13.2 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 8.8 g. The copolymer 2-16 of Example 2-16 was synthesized through the above procedures.

[0515] [Example 2-17 and Example 2-18: Synthesis of Copolymer 2-17 and Copolymer 2-18]

[0516] The copolymer 2-17 and the copolymer 2-18 of Example 2-17 and Example 2-18 were synthesized in the same manner as Example 2-16, except that the ratio (molar ratio) of 4FIP-M to methyl acrylate used was changed as shown in Table 2.

[0517] [Comparative Example 2-1: Synthesis of Comparative Copolymer 2-1]

[0518] To a 300 mL three-necked flask was added MEK (66.3 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of HFIP-M (5.9 g, 25 mmol) and BMA (10.7 g, 75 mmol) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 12.0 g. The comparative copolymer 2-1 of Comparative Example 2-1 was synthesized through the above procedures.

[0519] [Comparative Example 2-2 and Comparative Example 2-3: Synthesis of Comparative Copolymer 2-2 and Comparative Copolymer 2-3]

[0520] As shown in Table 2, the ratio (molar ratio) of HFIP-M to BMA used was changed. Otherwise, comparative copolymers 2-2 and 2-3 of Comparative Examples 2-2 and 2-3 were synthesized in the same manner as Comparative Example 2-1.

[0521] [Comparative Examples 2-4: Synthesis of Comparative Copolymer 2-4]

[0522] MEK (76.8 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80 °C. Then, over 30 minutes, a mixture of HFIP-M (5.9 g, 25 mmol), 1-methylcyclopentyl methacrylate (12.6 g, 75 mmol), and MEK (18.5 g) was added dropwise, and the mixture was stirred at 80 °C for 5 hours. After returning to room temperature, MEK was removed by vacuum distillation to prepare a 50 wt% solution, and MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation and filtration. The resulting polymer was dried under reduced pressure to obtain 14.9 g of a white powder. Comparative copolymer 2-4 of Comparative Example 2-4 was synthesized through the above steps.

[0523] [Comparative Examples 2-5 and 2-6: Synthesis of Comparative Copolymers 2-5 and 2-6]

[0524] As shown in Table 2, the ratio (molar ratio) of HFIP-M to 1-methylcyclopentyl methacrylate used was changed. Otherwise, comparative copolymers 2-5 and 2-6 of comparative examples 2-5 and 2-6 were synthesized in the same manner as comparative examples 2-4.

[0525] [Comparative Examples 2-7: Synthesis of Comparative Copolymers 2-7]

[0526] MEK (80.8 g) was added to a 300 mL three-necked flask, and the temperature was raised to 80 °C. Then, a mixture of HFIP-M (5.9 g, 25 mmol), 1-ethylcyclopentyl methacrylate (13.7 g, 75 mmol), and MEK (19.6 g) was added dropwise over 30 minutes, and the mixture was stirred at 80 °C for 5 hours. After returning to room temperature, MEK was removed by vacuum distillation to prepare a 50 wt% solution, and MeOH (20 g) was added. The resulting solution was then added dropwise to heptane (200 g) for reprecipitation and filtration. The resulting polymer was dried under reduced pressure to obtain 17.1 g of a white powder. Comparative copolymer 2-7 of Comparative Example 2-7 was synthesized through the above steps.

[0527] [Comparative Examples 2-8 and 2-9: Synthesis of Comparative Copolymers 2-8 and 2-9]

[0528] Comparative Copolymer 2-8 and Comparative Copolymer 2-9 of Comparative Examples 2-8 and 2-9 were synthesized in the same manner as Comparative Examples 2-7, except that the ratio (molar ratio) of HFIP-M to 1-ethylcyclopentyl methacrylate used was changed as shown in Table 2.

[0529] [Comparative Example 2-10: Synthesis of Comparative Copolymer 2-10]

[0530] To a 300 mL three-necked flask was added MEK (96.8 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of HFIP-M (5.9 g, 25 mmol) and 2-methyl-2-adamantyl methacrylate (16.8 g, 75 mmol) and MEK (22.7 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 19.0 g. Comparative Copolymer 2-10 of Comparative Example 2-10 was synthesized through the above procedures.

[0531] [Comparative Example 2-11 and Comparative Example 2-12: Synthesis of Comparative Copolymer 2-11 and Comparative Copolymer 2-12]

[0532] Comparative Copolymer 2-11 and Comparative Copolymer 2-12 of Comparative Examples 2-11 and 2-12 were synthesized in the same manner as Comparative Example 2-10, except that the ratio (molar ratio) of HFIP-M to 2-methyl-2-adamantyl methacrylate used was changed as shown in Table 2.

[0533] [Comparative Example 2-13: Synthesis of Comparative Copolymer 2-13]

[0534] To a 300 mL three-necked flask was added MEK (100.8 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of HFIP-M (5.9 g, 25 mmol) and 2-ethyl-2-adamantyl methacrylate (17.8 g, 75 mmol) and MEK (23.7 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After returning to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 19.2 g. Comparative Copolymer 2-13 of Comparative Example 2-13 was synthesized through the above procedures.

[0535] [Comparative Example 2-14 and Comparative Example 2-15: Synthesis of Comparative Copolymer 2-14 and Comparative Copolymer 2-15]

[0536] The ratio (molar ratio) of HFIP-M to 2-ethyl-2-adamantyl methacrylate used was changed as shown in Table 2, and otherwise, comparative copolymer 2-14 and comparative copolymer 2-15 of Comparative Examples 2-14 and 2-15 were synthesized in the same manner as Comparative Examples 2-13.

[0537] [Comparative Example 2-16: Synthesis of Comparative Copolymer 2-16]

[0538] To a 300 mL three-necked flask, MEK (49.4 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of HFIP-M (5.9 g, 25 mmol) and methyl acrylate (6.5 g, 75 mmol) and MEK (12.4 g) was added dropwise over 30 minutes, and stirred at an internal temperature of 80°C for 5 hours. After cooling to room temperature, the MEK was distilled off under reduced pressure, and after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g), and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure were performed to obtain a white powder of 6.2 g. Comparative copolymer 2-16 of Comparative Example 2-16 was synthesized through the above procedures.

[0539] [Comparative Example 2-17 and Comparative Example 2-18: Synthesis of Comparative Copolymer 2-17 and Comparative Copolymer 2-18]

[0540] The ratio (molar ratio) of HFIP-M to methyl acrylate used was changed as shown in Table 2, and otherwise, comparative copolymer 2-17 and comparative copolymer 2-18 of Comparative Examples 2-17 and 2-18 were synthesized in the same manner as Comparative Example 2-16.

[0541] [Table 2]

[0542]

[0543] [Example 3-1 and Synthesis of Copolymer 3-1]

[0544] To a 300 mL three-necked flask was added MEK (96.4 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (6.6 g, 20 mmol) and 4FIP-M (10.8 g, 40 mmol) and 1 -methylcyclopentyl methacrylate (6.7 g, 40 mmol) and MEK (24.1 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 20.1 g. The copolymer 3-1 of Example 3-1 was synthesized by the above procedure.

[0545] [Synthesis of Example 3-2 and copolymer 3-2]

[0546] To a 300 mL three-necked flask was added MEK (99.7 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (6.6 g, 20 mmol) and 4FIP-M (10.8 g, 40 mmol) and 1 -methylcyclopentyl methacrylate (6.7 g, 40 mmol) and MEK (24.1 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 20.1 g. The copolymer 3-1 of Example 3-1 was synthesized by the above procedure.

[0547] [Synthesis of Example 3-3 and copolymer 3-3]

[0548] To a 300 mL three-necked flask was added MEK (99.7 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (6.6 g, 20 mmol) and 4FIP-M (10.8 g, 40 mmol) and 1 -methylcyclopentyl methacrylate (6.7 g, 40 mmol) and MEK (24.1 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 20.1 g. The copolymer 3-1 of Example 3-1 was synthesized by the above procedure.

[0549] [Synthesis of Example 3-4 and copolymer 3-4]

[0550] To a 300 mL three-necked flask was added MEK (109.7 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (6.6 g, 20 mmol) and 4FIP-M (10.8 g, 40 mmol) and 2-ethyl-2-adamantyl methacrylate (9.9 g, 40 mmol) and MEK (27.3 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon return to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 24.8 g. The copolymer 3-4 of Example 3-4 was synthesized through the above procedure.

[0551] [Synthesis of Example 3-5 and Copolymer 3-5]

[0552] To a 300 mL three-necked flask was added MEK (83.1 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-4FHB-OH (6.6 g, 20 mmol) and 4FIP-M (10.8 g, 40 mmol) and methacrylic acid (3.4 g, 40 mmol) and MEK (20.8 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon return to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 17.5 g. The copolymer 3-5 of Example 3-5 was synthesized through the above procedure.

[0553] [Synthesis of Comparative Example 3-1 and Comparative Copolymer 3-1]

[0554] To a 300 mL three-necked flask was added MEK (96.4 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (5.9 g, 20 mmol) and HFIP-M (9.4 g, 40 mmol) and 1-methylcyclopentyl methacrylate (6.7 g, 40 mmol) and MEK (22.0 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon return to room temperature, the MEK was removed by distillation under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration, and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 16.1 g. The comparative copolymer 3-1 of Comparative Example 3-1 was synthesized through the above procedure.

[0555] [Synthesis of Comparative Example 3-2 and Comparative Copolymer 3-2]

[0556] To a 300 mL three-necked flask was added MEK (90.4 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (5.9 g, 20 mmol) and HFIP-M (9.4 g, 40 mmol) and 1- ethylcyclopentyl methacrylate (7.3 g, 40 mmol) and MEK (22.6 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 16.4 g. The comparative copolymer 3-2 of Comparative Example 3-2 was synthesized by the above procedure.

[0557] [Synthesis of Comparative Example 3-3 and Comparative Copolymer 3-3]

[0558] To a 300 mL three-necked flask was added MEK (98.7 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (5.9 g, 20 mmol) and HFIP-M (9.4 g, 40 mmol) and 2-methyl-2-adamantyl methacrylate (9.4 g, 40 mmol) and MEK (24.7 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 18.0 g. The comparative copolymer 3-3 of Comparative Example 3-3 was synthesized by the above procedure.

[0559] [Synthesis of Comparative Example 3-4 and Comparative Copolymer 3-4]

[0560] To a 300 mL three-necked flask was added MEK (100.9 g) and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (5.9 g, 20 mmol) and HFIP-M (9.4 g, 40 mmol) and 2-ethyl-2-adamantyl methacrylate (9.9 g, 40 mmol) and MEK (25.2 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. Upon cooling to room temperature, the MEK was removed by distillation under reduced pressure and a 50 wt% solution was prepared by adding MeOH (20 g). Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitation, filtration and drying of the resulting polymer under reduced pressure was performed to obtain a white powder of 18.9 g. The comparative copolymer 3-4 of Comparative Example 3-4 was synthesized by the above procedure.

[0561] [Synthesis of Comparative Copolymer 3-5 and Comparative Example 3-5]

[0562] To a 300 mL three-necked flask, MEK (75.2 g) was added and warmed to an internal temperature of 80°C. Thereafter, a mixture of MA-BTHB-OH (5.9 g, 20 mmol) and HFIP-M (9.4 g, 40 mmol) and methacrylic acid (3.4 g, 40 mmol) and MEK (18.8 g) was added dropwise over 30 minutes and stirred at an internal temperature of 80°C for 5 hours. After cooling to room temperature, MEK was distilled off under reduced pressure and, after making a 50 wt% solution, MeOH (20 g) was added. Thereafter, the resulting solution was added dropwise to heptane (200 g) and reprecipitated, filtered, and the resulting polymer was dried under reduced pressure to obtain a white powder, 14.5 g. Comparative Copolymer 3-5 of Comparative Example 3-5 was synthesized through the above procedure.

[0563] [Table 3]

[0564]

[0565] Each of the resulting copolymers was subjected to GPC measurement. The results are shown in Tables 1, 2 and 3.

[0566] <Water repellency evaluation>

[0567] Each of the copolymers 1 g was added to PGMEA (3 g) to prepare a composition. Thereafter, the prepared composition was applied on a 4-inch silicon substrate by a spin coater and dried on a hot plate heated to 80°C for 3 minutes to form a film having a film thickness of 2 to 3 μm. Note that the film thickness is the thickness of the film to be evaluated for water repellency, and in fact, a resist film or a film having a top layer of a thicker film is formed.

[0568] [Measurement of static contact angle]

[0569] A water droplet was placed on the film on the silicon substrate and a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the static contact angle by the drop method. In this specification, the static contact angle refers to the angle formed with the film surface when a water droplet is dropped and placed on the film surface. The results are shown in Tables 1, 2 and 3.

[0570] [Measurement of hysteresis angle (dynamic advancing angle - dynamic receding angle)]

[0571] A water droplet was placed on the film on the silicon substrate and a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the hysteresis angle (dynamic advancing angle - dynamic receding angle) by the expansion and contraction method. In this specification, the dynamic receding angle refers to the contact angle when a water droplet is contracted by suction with a needle or the like, the dynamic advancing angle refers to the contact angle when a water droplet is expanded by ejection with a needle or the like, and the hysteresis angle refers to the difference between the dynamic contact angle and the dynamic receding angle. The results are shown in Tables 1, 2 and 3.

[0572] [Determination of slip angle]

[0573] A water droplet (50 μL) was placed on a film on a silicon substrate, and the slip angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The slip angle refers to the angle at which the water droplet moves when the silicon substrate is tilted. The results are shown in Tables 1, 2, and 3.

[0574] As shown in Table 1, it is clear that if copolymers 1-1 to 1-18 of Examples 1-1 to 1-18 are used, the hysteresis angle and slip angle are lower relative to water (immersion liquid) compared to comparative copolymers 1-1 to 1-18 of Comparative Examples 1-1 to 1-18.

[0575] Furthermore, as shown in Table 2, it is clear that compared to the comparative copolymers 2-1 to 2-18 of Comparative Examples 2-1 to 2-18, the copolymers 2-1 to 2-18 of Examples 2-1 to 2-18 have lower hysteresis angles and lower slip angles.

[0576] Furthermore, as shown in Table 3, it is clear that compared to the comparative copolymers 3-1 to 3-5 of Comparative Examples 3-1 to 3-5, the copolymers 3-1 to 3-5 of Examples 3-1 to 3-5 have lower hysteresis angles and lower slip angles.

[0577] When performing high-efficiency exposure using an exposure apparatus, the resulting film has a low hysteresis angle (advancing contact angle - receding contact angle) and a low slip angle relative to the immersion liquid. This results in good liquid removal properties of the immersion liquid during exposure, making it less prone to poor pattern formation. In other words, it is clear that the copolymers of each embodiment can be used as films formed during immersion exposure.

[0578] <Evaluation of solubility in alkaline developing solution>

[0579] Copolymers 1-1 to 1-18 and comparative copolymers 1-1 to 1-18 (1 g each) were added to PGMEA (3 g) to prepare compositions. Subsequently, the prepared compositions were coated onto a 4-inch silicon substrate using a spin coater and dried on a hot plate heated to 80°C for 3 minutes to form a film with a thickness of 3 μm. The film was then immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution for 1 minute, and the dissolution of the film on the silicon substrate in the TMAH aqueous solution was observed. The results are shown in Table 1.

[0580] As shown in Table 1, the films formed using copolymers 1-1 to 1-18 exhibited the same degree of solubility in alkaline developer as the films formed using comparative copolymers 1-1 to 1-18.

Claims

1. A copolymer having repeating units represented by the following general formula (1) and repeating units derived from compounds having polymerizable carbon-carbon double bonds, In general formula (1), R 1 It is a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, wherein some or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally replaced with fluorine atoms. R 2 It is a single bond, straight chain, branched chain, or optionally cyclic alkylene ring, aromatic ring, ester, carbonyl group, ether, amide, amine, or complex substituent thereof, a portion of which is optionally fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

2. The copolymer according to claim 1, wherein, The repeating unit represented by the general formula (1) includes the repeating unit represented by the following general formula (2). 。 3. The copolymer according to claim 2, wherein, The repeating unit represented by the general formula (2) includes the repeating unit represented by the following general formula (2-1). 。 4. The copolymer according to claim 1, wherein, The repeating unit represented by the general formula (1) includes the repeating unit represented by the following general formula (3). 。 5. The copolymer according to claim 4, wherein, The repeating unit represented by the general formula (3) includes the repeating unit represented by the following general formula (3-1). 。 6. The copolymer according to claim 1, wherein, The repeating unit derived from compounds having polymerizable carbon-carbon double bonds comprises repeating units represented by the following general formula (4). In general formula (4), R A Y is a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, wherein some or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally replaced with fluorine atoms. A It is a monovalent organic group.

7. The copolymer according to claim 6, wherein, The repeating unit represented by the general formula (4) includes repeating units that do not have fluorine atoms.

8. The copolymer according to claim 6, wherein, The repeating unit represented by the general formula (4) comprises a repeating unit derived from at least one compound having a polymerizable carbon-carbon double bond selected from the group consisting of: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, amyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, the compound represented by formula (4'-1), the compound represented by formula (4'-2), and the compound represented by formula (4'-3). Compounds represented by the following formulas (4'-4), (4'-5), (4'-6), (4'-7), (4'-8), (4'-9), (4'-10), (4'-11), (4'-12), (4'-13), (4'-14), (4'-15), and (4'-16). 。 9. A polymer for use as a water repellent, comprising repeating units represented by the following general formula (1), In general formula (1), R 1 It is a hydrogen atom, a fluorine atom, a chlorine atom, or a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, wherein some or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group are optionally replaced with fluorine atoms. R 2 It is a single bond, straight chain, branched chain, or optionally cyclic alkylene ring, aromatic ring, ester, carbonyl group, ether, amide, amine, or complex substituent thereof, a portion of which is optionally fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, or a hydrogen atom.

10. The polymer for water repellency according to claim 9, wherein, The repeating unit represented by the general formula (1) includes the repeating unit represented by the following general formula (2). 。 11. The polymer for water repellency according to claim 10, wherein, The repeating unit represented by the general formula (2) includes the repeating unit represented by the following general formula (2-1). 。 12. The polymer for water repellency according to claim 9, wherein, The repeating unit represented by the general formula (1) includes the repeating unit represented by the following general formula (3). 。 13. The polymer for water repellency according to claim 12, wherein, The repeating unit represented by the general formula (3) includes the repeating unit represented by the following general formula (3-1). 。 14. A composition for forming a water-repellent film, comprising the copolymer of any one of claims 1 to 8 or the polymer for water repellency of any one of claims 9 to 13.

15. The composition for forming a water-repellent film according to claim 14, comprising two or more copolymers according to any one of claims 1 to 8 or polymers for water repellency according to any one of claims 9 to 13.

16. The composition for forming a water-repellent film according to claim 14, further comprising an acid-generating agent.

17. A resin film comprising a coating of the water-repellent film-forming composition of claim 14.

18. The resin film according to claim 17, used for immersion exposure.

19. A method for forming a resist pattern, comprising: The film-forming process involves coating the water-repellent film-forming composition of claim 14 onto the surface of a substrate or a bottom film to form a resin film; and The immersion exposure process involves exposing the resin film to electromagnetic waves or high-energy rays with a wavelength of less than 300 nm while water is in direct contact with the surface of the resin film.

Images