Fluorine-containing polymer, composition for forming fluorine-containing resin film, fluorine-containing resin film, composition for forming resist pattern, method for forming resist pattern, composition for forming resist upper layer film, method for decomposing fluorine-containing polymer, fluorine-containing polymerizable monomer, compound, and method for producing fluorine-containing polymerizable monomer

Abstract

Provided is a fluorine-containing polymer having water repellency and photosensitivity equivalent to those of a conventional fluorine-containing polymer and capable of being decomposed at a lower temperature.　A fluorine-containing polymer according to the present disclosure contains a repeating unit represented by general formula (1) or (1)'. (In general formula (1), R1 is a hydrogen atom, a fluorine atom, a chlorine atom, or a C1-10 straight-chain or C3-10 branched alkyl group. Some or all of hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. In general formula (1), R2 is a single bond, an alkylene group which may have a straight-chain, branched, or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part thereof may be fluorinated and / or chlorinated. In general formula (1)', R1a is a C1-10 straight-chain or C3-10 branched alkyl group. Some or all of hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. In general formula (1)', R2a is an alkylene group which may have a straight-chain, branched, or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part thereof may be fluorinated and / or chlorinated. In general formula (1)', R2b is an alkylene group which may have a straight-chain, branched, or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part thereof may be fluorinated and / or chlorinated. In general formulae (1) and (1)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulae (1) and (1)', n is a natural number of 1-3.)

Description

Fluorine-containing polymer, composition for forming fluorine-containing resin film, fluorine-containing resin film, composition for forming resist pattern, method for forming resist pattern, composition for forming resist upper layer film, method for decomposing fluorine-containing polymer, fluorine-containing polymerizable monomer, compound, and method for producing fluorine-containing polymerizable monomer

[0001] The present disclosure relates to a fluorine-containing polymer, a composition for forming a fluorine-containing resin film, a fluorine-containing resin film, a composition for forming a resist pattern, a method for forming a resist pattern, a composition for forming a resist upper layer film, a method for decomposing a fluorine-containing polymer, a fluorine-containing polymerizable monomer, a compound, and a method for producing a fluorine-containing polymerizable monomer.

[0002] Fluorine-containing polymers (fluorine-containing compounds) are being used or developed in a wide range of applications, primarily in the field of advanced materials, due to the properties of fluorine, such as water repellency, oil repellency, low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, photosensitivity, low refractive index, and low dielectric constant. With regard to coating applications in particular, active research and development is underway in fields such as anti-reflective films that utilize low refractive index and transparency for visible light, optical devices that utilize transparency in the high wavelength range (optical communication wavelength range), and resist materials that utilize transparency in the ultraviolet range (particularly the vacuum ultraviolet wavelength range). A common polymer design in these application fields is to incorporate as much fluorine as possible to achieve transparency at each wavelength used, while also achieving adhesion to substrates and a high glass transition temperature (hardness).

[0003] As a monomer for synthesizing such a fluorine-containing polymer, Patent Document 1 describes a polymerizable monomer represented by the following general formula (12):

[0004] (In general formula (12), R １ｐ represents a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, and a fluorine-containing alkyl group (the fluorine-containing alkyl group is linear or branched and may contain a cyclic structure). ２ｐR is a divalent or trivalent organic group, and the organic group is a group selected from an aliphatic hydrocarbon group (the aliphatic hydrocarbon group is linear or branched and may contain a cyclic structure), an aromatic ring group, or a composite substituent thereof, and some or all of the hydrogen atoms may be substituted with fluorine atoms or hydroxyl groups. ３ｐ represents a hydrogen atom, a hydrocarbon group, a fluorine-containing alkyl group (the fluorine-containing alkyl group is linear or branched and may contain a cyclic structure), or an aromatic ring group, and the hydrocarbon group or the fluorine-containing alkyl group may contain a divalent linking group selected from an ether group (—O—) and a carbonyl group (—(C═O)—). m represents an integer of 1 to 2. When m is 2, two R ３ｐ can be identical to each other or different from each other.)

[0005] The polymerizable monomer represented by the general formula (12) is derived from hexafluoroacetone (CF ３ ) ２ (OR ３ｐ ) C-moieties, and has a high fluorine content while successfully possessing polar groups in a well-balanced manner within the same molecule. This polymerizable monomer also has excellent polymerizability, and a fluorine-containing polymer obtained by polymerizing this polymerizable monomer combines the transparency provided by the fluorine atoms with the adhesion and processability provided by the polar groups, and is known to have excellent physical properties as an anti-reflection film material, an optical device material, a resist material, etc.

[0006] On the other hand, since resist materials become used substances after the photolithography process, material design that takes into consideration the disposal method of the material is also required. Patent Document 2 teaches that a polymer containing a repeating unit consisting of a monomer represented by the following general formula (13) has the following properties: "When resist waste liquid is treated after device fabrication, the (meth)acrylic acid ester moiety is alkaline hydrolyzed, making it possible to convert it into a compound with a lower molecular weight and less accumulation, and when disposed of by combustion, the fluorine substitution rate is low, so it has high combustibility."

[0007]

[0008] Japanese Patent No. 4083399 Japanese Patent Application Laid-Open No. 2012-107151

[0009] In photolithography processes, photosensitive compositions containing a fluorine-containing polymer as a main component are often used as resist films and / or top layer films that protect the resist film. The resist film and the top layer film are removed from the substrate in an alkaline development process or a resist removal process. The resist film and the top layer film (used material) are decomposed so as not to affect the environment. The fluorine-containing polymer is the main component of the used material, and therefore, examining the decomposition of the used material essentially amounts to examining the decomposition of the fluorine-containing resin. Thermal decomposition is a simple and convenient method for decomposing the used material, and is therefore preferred. Furthermore, it is preferable that the amount of energy required for the thermal decomposition be small.

[0010] According to the teaching of Patent Document 2, a low fluorine substitution rate is thought to be the key to thermal decomposition of the compound. On the other hand, multiple fluorines impart polarity to the compound, making it useful in resist materials and the like. In Patent Document 2, it is thought that by distributing fluorine unevenly in specific groups, a balance is achieved between flammability and usefulness in resist materials and the like. According to this teaching, it can be concluded that the compound disclosed in Patent Document 1 has a good balance between flammability and usefulness in resist materials and the like. Therefore, a breakthrough is needed in designing a compound that can reduce the amount of energy required for thermal decomposition of fluorine-containing polymers that have become waste materials after the photolithography process.

[0011] An object of the present disclosure is to provide a fluoropolymer that has water repellency and photosensitivity equivalent to those of conventional fluoropolymers and can be decomposed at a lower temperature.

[0012] As shown in the Examples of the present specification, the present inventors have newly synthesized a fluorine-containing polymer having a skeleton to which chlorodifluoro groups are bonded at specific positions.

[0013] The present disclosure (1) is a fluorine-containing polymer containing a repeating unit represented by the following general formula (1) or (1)'.

[0014] (In general formula (1), R １is 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. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. In general formula (1), R ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formulas (1) and (1)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulas (1) and (1)', n is a natural number from 1 to 3.

[0015] The present disclosure (2) is the fluorine-containing polymer according to the present disclosure (1), wherein the repeating units represented by the general formulae (1) and (1)′ contain repeating units represented by the following general formulae (2) and (2)′, respectively:

[0016]

[0017] The present disclosure (3) is a fluorine-containing polymer according to the present disclosure (2), which contains a repeating unit represented by the following general formula (3):

[0018] (In general formula (3), R ３represents a single bond, an alkylene group which may have a linear, branched or cyclic structure, or an aromatic ring, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these.

[0019] The present disclosure (4) is a fluorine-containing polymer according to any one of the present disclosures (1) to (3), wherein the repeating units represented by the general formulae (1) and (1)′ contain repeating units represented by the following general formulae (4) and (4)′, respectively:

[0020]

[0021] The present disclosure (5) is the fluorine-containing polymer according to the present disclosure (4), which contains a repeating unit represented by the following general formula (5):

[0022] (In general formula (5), R ４ represents a single bond, an alkylene group which may have a linear, branched or cyclic structure, or an aromatic ring, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these. L represents an acid-dissociable group.

[0023] The present disclosure (6) is the fluorine-containing polymer according to any one of the present disclosures (1) to (4), wherein the repeating units represented by the general formulae (1) and (1)′ contain repeating units represented by the following general formulae (2) and (2)′, respectively:

[0024] The present disclosure (7) is a fluorine-containing polymer according to the present disclosure (6), which contains a repeating unit represented by the following general formula (5): (In general formula (5), R ４ represents a single bond, an alkylene group which may have a linear, branched or cyclic structure, or an aromatic ring, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these. L represents an acid-dissociable group.

[0025] The present disclosure (8) is a composition for forming a fluorine-containing resin film, characterized by containing the fluorine-containing polymer according to any one of the present disclosures (1) to (7).

[0026] The present disclosure (9) is a fluororesin film characterized by comprising a coating film of the fluororesin film-forming composition according to the present disclosure (8). In this specification, the term "coating film" includes a cured product obtained by curing a fluoropolymer with a polymerization initiator, and a film-like material obtained by drying a fluororesin film-forming composition containing a fluoropolymer and a solvent.

[0027] The present disclosure (10) is a composition for forming a resist pattern, comprising the fluorine-containing polymer according to any one of the present disclosures (1) to (7), an acid generator, and a solvent.

[0028] The present disclosure (11) is a method for forming a resist pattern, comprising: a step of preparing the composition for forming a resist pattern according to the present disclosure (10); a film-forming step of applying the composition for forming a resist pattern onto a substrate to form a film; an exposure step of irradiating and exposing the film with electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer a pattern of the photomask to the film; and a development step of developing the film with a developer to obtain a pattern.

[0029] The present disclosure (12) is a composition for forming a resist upper layer film, comprising the fluorine-containing polymer according to any one of the present disclosures (1) to (7) and a solvent.

[0030] The present disclosure (13) is a method for forming a resist pattern, comprising: a step of preparing the composition for forming a resist upper layer film according to the present disclosure (12); a film-forming step of applying the composition for forming a resist upper layer film onto a resist film to form a resist upper layer film; an exposure step of irradiating and exposing the resist upper layer film and the resist film with electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer a pattern of the photomask to the resist film; and a development step of removing the resist upper layer film with a developer and developing the resist film to obtain a pattern.

[0031] The present disclosure (14) is a method for decomposing a fluoropolymer according to any one of the present disclosures (1) to (7), comprising heating the fluoropolymer at 50°C to 200°C.

[0032] The present disclosure (15) is a fluorine-containing polymerizable monomer represented by the following general formula (6) or (6)'.

[0033] (In general formula (6), 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. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. In general formula (6), R ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formulas (6) and (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulas (6) and (6)', n is a natural number from 1 to 3.

[0034] The present disclosure (16) is a compound represented by the following general formula (7).

[0035] (In general formula (7), R ２represents a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X represents a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n represents a natural number from 1 to 3.

[0036] The present disclosure (17) is a method for producing a fluorine-containing polymerizable monomer represented by the following general formula (6), comprising the steps of: preparing a compound represented by the following general formula (7); and reacting the compound represented by the general formula (7) with at least one selected from the group consisting of acid halides, acid anhydrides, esters, and carboxylic acids.

[0037] (In general formula (7), R ２ represents a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X represents a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n represents a natural number from 1 to 3.

[0038] (In general formula (6), R １ R 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. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. ２ represents a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X represents a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n represents a natural number from 1 to 3.

[0039] The present disclosure (18) is a method for producing a fluorine-containing polymerizable monomer represented by the following general formula (6)', comprising the steps of preparing a compound represented by the following general formula (8) and reacting the compound represented by the general formula (8) with a compound represented by the following general formula (9):

[0040] (In general formula (8), R ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formula (8), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (8), n is a natural number from 1 to 3.

[0041] (In general formula (9), R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (9), A is a leaving group.

[0042] (In general formula (6)′, R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂis an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and a portion of which may be fluorinated and / or chlorinated. In general formula (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (6)', n is a natural number from 1 to 3.

[0043] The present disclosure (19) is a method for producing a fluorine-containing polymerizable monomer represented by the following general formula (6)', comprising the steps of preparing a compound represented by the following general formula (10), and reacting the compound represented by the general formula (10) with a compound represented by the following general formula (11):

[0044] (In general formula (10), R ２ｂ is an alkylene group, aromatic ring, ester, carbonyl, ether, amide, amine, or composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formula (10), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (10), A is a leaving group. In general formula (10), n is a natural number from 1 to 3.

[0045] (In general formula (11), R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated.

[0046] (In general formula (6)′, R １ａis a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and a portion of which may be fluorinated and / or chlorinated. In general formula (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (6)', n is a natural number from 1 to 3.

[0047] The fluorine-containing polymer of the present disclosure has water repellency and photosensitivity equivalent to those of conventional fluorine-containing polymers and can be decomposed at lower temperatures. The fluorine-containing polymer of the present disclosure can be used for photolithography resists, etc., and used materials derived from the fluorine-containing polymer of the present disclosure can be treated by precipitation, adsorption, activated sludge method, etc., which are simpler than combustion, and can contribute to energy saving in semiconductor processes.

[0048] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0049] In the "Form for Carrying Out the Invention" section of this specification, items indicated by "[" and "]", "<" and ">" are merely symbols and have no meaning in themselves.

[0050] <Fluorine-containing polymerizable monomer> First, the fluorine-containing polymerizable monomer of the present disclosure will be described. The fluorine-containing polymerizable monomer of the present disclosure is a fluorine-containing polymerizable monomer represented by the following general formula (6) or (6)'.

[0051] (In general formula (6), 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 some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formulas (6) and (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulas (6) and (6)', n is a natural number from 1 to 3.

[0052] The R １ Examples of the alkyl group exemplified by R include a methyl group, an ethyl group, and a propyl group such as a 1-propyl group or a 2-propyl group. １ａ Examples of the alkyl group exemplified above include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and a propyl group such as a 1,3-dichloro-1,1,3,3-tetrafluoroisopropyl group.

[0053] The R ２ , R ２ａand R ２ｂ Examples of the alkylene group exemplified by the formula (I) include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-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, an isarene 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, Examples of such hydrocarbon groups include saturated chain hydrocarbon groups such as a 4-butylene group, a methylidene group, an ethylidene group, a propylidene group, or a 2-propylidene group; monocyclic hydrocarbon ring groups such as cycloalkylene groups having 3 to 10 carbon atoms, such as cyclobutylene groups such as a 1,3-cyclobutylene group, cyclopentylene groups such as a 1,3-cyclopentylene group, cyclohexylene groups such as a 1,4-cyclohexylene group, and cyclooctylene groups such as a 1,5-cyclooctylene group; and bridged cyclic hydrocarbon ring groups such as bicyclic to tetracyclic hydrocarbon ring groups, such as norbornylene groups such as a 1,4-norbornylene group or a 2,5-norbornylene group, and adamantylene groups such as a 1,5-adamantylene group or a 2,6-adamantylene group.

[0054] R ２ , R ２ａ and R ２ｂ The amide exemplified by (—C(═O)NB １ -) (B １ represents a hydrogen atom or a monovalent organic group). ２ , R ２ａ and R ２ｂ The ether exemplified by R has a structure represented by (—O—). ２ , R ２ａ and R ２ｂ The amine exemplified by (-NB ２ -) (B ２ represents a hydrogen atom or a monovalent organic group).

[0055] In general formula (6)', R２ａ and R ２ｂ may be the same or different.

[0056] In the general formulas (6) and (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. Among these, a hydroxyl group or a hydrogen atom is preferred. When X is a hydroxyl group, there is a tendency that a polymer that can have properties such as water repellency, adhesion, and alkali solubility can be more suitably provided. Furthermore, when X is an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, or an oxycarboxy group, there is a tendency that a polymer that can have properties such as water repellency, water resistance, and polarity conversion by an acid or the like can be more suitably provided. Furthermore, when X is a hydrogen atom, there is a tendency that a polymer that can have properties such as water repellency and water resistance can be more suitably provided.

[0057] The oxycarbonyl group of X is (—O—C(═O)B ３ is a group represented by (B ３ represents a hydrogen atom or a monovalent organic group), for example, —O—C(═O)CH ３ etc. B ３ The monovalent organic group in the above means a group having one or more carbon atoms, preferably having 1 to 30 carbon atoms, more preferably having 1 to 8 carbon atoms, even more preferably having 1 to 3 carbon atoms, and particularly preferably having 1 or 2 carbon atoms. Examples of such monovalent organic groups include monovalent hydrocarbon groups.

[0058] B ３ The monovalent organic group (preferably a monovalent hydrocarbon group) in may have a heteroatom. Examples of the heteroatom include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a phosphorus atom, and a silicon atom. ３ The monovalent organic group (preferably a monovalent hydrocarbon group) in may have a plurality of these heteroatoms.

[0059] Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, a cycloalkyl group, a heterocyclic group, etc. Among these, an alkyl group is preferred.

[0060] Examples of the alkyl group may be linear or branched, and include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. Since the alkyl group may be linear or branched, a propyl group means an n-propyl group or an isopropyl group, and a butyl group means an n-butyl group, a sec-butyl group or a tert-butyl group, and the same applies to other groups that may be linear or branched.

[0061] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, and a methylethenyl group, which may be linear or branched.

[0062] The alkynyl group may be, for example, linear or branched, and includes an ethynyl group, a propargyl group, and the like.

[0063] The alkylidene group may be, for example, linear or branched, and includes a methylidene group, an ethylidene group, and the like.

[0064] Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0065] Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0066] Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

[0067] Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0068] B ３ Examples of the halogen atom that the monovalent organic group may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0069] The oxysulfonyl group of X is (—O—SO ２ -B ３ is a group represented by (B ３represents a hydrogen atom or a monovalent organic group), for example, —O—SO ２ -CH ３ etc.

[0070] The oxycarboxy group of X is (—O—C(═O)—O—B ３ is a group represented by (B ３ represents a hydrogen atom or a monovalent organic group), for example, —O—C(═O)—O—CH ３ , -OC(=O)-OC(CH ３ ) ３ etc.

[0071] The fluorine-containing polymerizable monomer represented by the above general formula (6) can be produced, for example, by the following method.

[0072] A method for producing the fluorine-containing polymerizable monomer represented by the above general formula (6) includes the steps of preparing a compound represented by the following general formula (7), and reacting the compound represented by the general formula (7) with at least one selected from the group consisting of acid halides, acid anhydrides, esters, and carboxylic acids:

[0073] (In general formula (7), R ２ represents a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. X represents a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n represents a natural number from 1 to 3.

[0074] The compound represented by the general formula (7) is R ２ is a single bond and X is not a hydrogen atom. The compound represented by formula (7) can be synthesized by a known organic synthesis method.

[0075] Examples of the acid halides include methacrylic acid chloride, methacrylic acid bromide, methacrylic acid fluoride, acrylic acid chloride, acrylic acid bromide, and acrylic acid fluoride. Examples of the acid anhydrides include methacrylic acid anhydride and acrylic acid anhydride. Examples of the esters include methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate. Examples of the carboxylic acids include methacrylic acid and acrylic acid.

[0076] The reaction of the compound represented by formula (7) with these compounds may be carried out in the presence of an acid or a base, if necessary. The reaction conditions are preferably a temperature of 0 to 130° C. for 0.5 to 10 hours.

[0077] The reaction product may be separated and purified by a conventional method, such as concentration, distillation, extraction, recrystallization, filtration, column chromatography, etc. Two or more of these methods may be used in combination.

[0078] The fluorine-containing polymerizable monomer represented by the above general formula (6)' can be produced, for example, by the following method.

[0079] A method for producing a fluorine-containing polymerizable monomer represented by general formula (6)' includes a step of preparing a compound represented by the following general formula (8), and a step of reacting the compound represented by general formula (8) with a compound represented by the following general formula (9).

[0080] (In general formula (8), R ２ｂis an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formula (8), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (8), n is a natural number from 1 to 3.

[0081] (In general formula (9), R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (9), A is a leaving group.

[0082] The fluorine-containing polymerizable monomer represented by the above general formula (6)' can also be produced, for example, by the following method.

[0083] A method for producing a fluorine-containing polymerizable monomer represented by general formula (6)' includes a step of preparing a compound represented by the following general formula (10), and a step of reacting the compound represented by the general formula (10) with a compound represented by the following general formula (11).

[0084] (In general formula (10), R ２ｂ is an alkylene group, aromatic ring, ester, carbonyl, ether, amide, amine, or composite substituent thereof, which may have a linear, branched, or cyclic structure, and may be partially fluorinated and / or chlorinated. In general formula (10), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (10), A is a leaving group. In general formula (10), n is a natural number from 1 to 3.

[0085] (In general formula (11), R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated.

[0086] The compounds represented by general formula (8) and general formula (10) can be synthesized by known organic synthesis techniques. In general formula (9) and general formula (10), the leaving group exemplified by A is not particularly limited, and may be a halogen atom, a tosyl group, a mesyl group, a triflate group, or the like.

[0087] A base may be added to the reaction between the compound represented by general formula (8) and the compound represented by general formula (9), if necessary. The reaction conditions are preferably 0 to 130°C for 0.5 to 10 hours. The reaction conditions for the compound represented by general formula (10) and the compound represented by general formula (11) are similar. The product after this reaction can be separated and purified by a conventional method, such as concentration, distillation, extraction, recrystallization, filtration, column chromatography, or the like. Two or more methods may also be used in combination.

[0088] <Fluorine-Containing Polymer> Next, the fluorine-containing polymer of the present disclosure obtained by polymerizing the fluorine-containing polymerizable monomer represented by the above general formula (6) or (6)' will be described.

[0089] The fluoropolymer of the present disclosure is a fluoropolymer containing a crosslinking unit represented by the following general formula (1) or (1)'.

[0090] (In general formula (1), R １is 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. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. In general formula (1), R ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, and a part of the substituent may be fluorinated and / or chlorinated. ２ｂ is an alkylene group, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, which may have a linear, branched, or cyclic structure, and which may be partially fluorinated and / or chlorinated. In the general formulas (1) and (1)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom.

[0091] The fluorine-containing polymers containing repeating units represented by the general formulae (1) and (1)' can be obtained by a polymerization step of polymerizing polymerizable monomers represented by the general formulae (6) and (6)', respectively.

[0092] The fluorine-containing polymer of the present disclosure may contain both repeating units represented by general formula (1) and (1)'.

[0093] In the following description, the polymerizable monomers represented by general formulas (6) and (6)' will also be referred to as "first polymerizable monomers", and the repeating units represented by general formulas (1) and (1)' will also be referred to as "first repeating units".

[0094] The fluorine-containing polymer may contain a second repeating unit other than the repeating units represented by general formulae (1) and (1)'. In this case, the second repeating unit may contain, for example, at least one repeating unit obtained from the following polymerizable monomer (second polymerizable monomer):

[0095] Examples of the second polymerizable monomer include a hexafluoroisopropanol group (—C(CF ３ ) ２ OH), acrylic acid esters, methacrylic acid esters, fluorine-containing acrylic acid esters, fluorine-containing methacrylic acid esters, styrenes, fluorine-containing styrenes, vinyl ethers, fluorine-containing vinyl ethers, allyl ethers, fluorine-containing allyl ethers, unsaturated amides, olefins, fluorine-containing olefins, norbornene compounds, fluorine-containing norbornene compounds, vinyl silanes, vinyl sulfonic acid or vinyl sulfonic acid ester acrylic acid, methacrylic acid maleic acid, maleic anhydride, fumaric acid, sulfur dioxide, and monomers having a lactone structure.

[0096] The fluorine-containing polymers represented by general formulas (1) and (1)' may also contain a repeating unit containing an acid-decomposable group as the third repeating unit. When the fluorine-containing polymer containing the third repeating unit is used as a resist, the acid-decomposable group is decomposed by exposure of a resist film formed on a substrate to high-energy rays such as electromagnetic waves or electron beams with a wavelength of 300 nm or less, thereby generating an acid in the resist film. This acid can improve the solubility of the resist film in an alkaline developer in the exposed areas during development.

[0097] These fluorine-containing polymers may be homopolymers consisting of only the first repeating unit, or may be heteropolymers containing the second repeating unit and / or the third repeating unit.

[0098] In the case of a fluoropolymer heteropolymer, when all repeating units contained in the fluoropolymer are taken as 100 mol %, the proportion of the first repeating unit may be 22 mol % or more and 99 mol % or less, or 30 mol % or more and 95 mol % or less, or further 40 mol % or more and 90 mol % or less.

[0099] The fluorine-containing polymer is obtained by a polymerization reaction of each polymerizable monomer. The polymerization reaction is not particularly limited, and may be a radical polymerization reaction, an ionic polymerization reaction, a coordination anionic polymerization reaction, a living anionic polymerization reaction, or a cationic polymerization reaction. Among these, a radical polymerization reaction is preferable. When the polymerization reaction is a radical polymerization reaction, the polymerization initiator is not particularly limited as long as it causes a polymerization reaction, and an azo compound, a peroxide compound, or a redox compound can be used.

[0100] Examples of azo compounds include azobisisobutyronitrile. Examples of peroxide compounds include t-butyl peroxypivalate, di-t-butyl peroxide, i-butyryl peroxide, lauroyl peroxide, succinic acid peroxide, dicinnamyl peroxide, di-n-propyl peroxydicarbonate, t-butyl peroxyallyl monocarbonate, benzoyl peroxide, hydrogen peroxide, and ammonium persulfate.

[0101] Examples of redox compounds are used in combination of an oxidizing agent and a reducing agent, and examples of the oxidizing agent include hydrogen peroxide, persulfate, and cumene hydroperoxide, while examples of the reducing agent include iron (II) ion salts, copper (I) ion salts, ammonia, and triethylamine.

[0102] Furthermore, a polymerization solvent may be used in the radical polymerization reaction. The polymerization solvent is not particularly limited as long as it does not inhibit the radical polymerization reaction, and may be an organic solvent or water. Examples of organic solvents include hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, ether solvents, cyclic ether solvents, fluorocarbon solvents, and aromatic solvents. These solvents may be used alone or in combination of two or more. Examples of ester solvents include acetic acid and n-butyl acetate. Examples of ketone solvents include acetone and methyl isobutyl ketone. Examples of hydrocarbon solvents include toluene and cyclohexane. Examples of alcohol solvents include methanol, isopropyl alcohol, and ethylene glycol monomethyl ether.

[0103] In the radical polymerization reaction, a molecular weight modifier such as mercaptan may be used.

[0104] The reaction temperature in the radical polymerization reaction may be appropriately changed depending on the radical polymerization initiator or the type of radical polymerization initiator, but is preferably 20°C or higher and 200°C or lower, and more preferably 30°C or higher and 140°C or lower.

[0105] After the polymerization step, the organic solvent or water serving as the medium can be removed from the solution or dispersion containing the synthesized fluorine-containing polymer by any known method. Specific examples include reprecipitation, filtration, distillation by heating under reduced pressure, etc.

[0106] Through the above steps, a fluoropolymer containing repeating units represented by general formulas (1) and (1)' can be produced. The weight-average molecular weight of the fluoropolymer of the present disclosure may be 5,000 to 20,000, or even 7,000 to 12,000. In this specification, the weight-average molecular weight of the fluoropolymer means a value measured by gel permeation chromatography (GPC) under the following conditions:

[0107] [GPC conditions] Apparatus: HLC-8320GPC, manufactured by Tosoh Corporation Column for polymerizable monomer analysis: TSKgel series, manufactured by Tosoh Corporation (G2500HXL, G2000HXL, G1000HXL, G1000HXL connected in series in this order) Column for polymer analysis: TSKgel series, manufactured by Tosoh Corporation (G2500HXL, G2000HXL, G1000HXL, G1000HXL connected in series in this order) Temperature program: 40°C (hold) Flow rate: 1 mL / min Detector: differential refractometer (RI) Eluent: tetrahydrofuran (THF) Reference material: polystyrene standard solution

[0108] <Specific examples of fluorine-containing polymers>

[0109] In the fluorine-containing polymer of the present disclosure, the repeating unit represented by the general formula (1) may contain a repeating unit represented by the following general formula (2). The fluorine-containing polymer of the present disclosure may be composed solely of a repeating unit represented by the following general formula (2). The fluorine-containing polymer of the present disclosure may be composed solely of a repeating unit represented by the following general formula (1)'. The fluorine-containing polymer of the present disclosure may also contain a repeating unit represented by the following general formula (2)'. Furthermore, the fluorine-containing polymer of the present disclosure may contain both a repeating unit represented by the following general formula (2) and a repeating unit represented by the following general formula (2)'. When the fluorine-containing polymer of the present disclosure contains repeating units represented by the following general formulas (2) and (2)', the terminals of the side chains are hydroxyl groups, and therefore the polymer may have properties such as water repellency, adhesion, and alkali solubility.

[0110]

[0111] In the fluorine-containing polymer of the present disclosure, when the repeating units represented by the general formulae (1) and (1)' contain repeating units represented by the general formulae (2) and (2)', respectively, the fluorine-containing polymer of the present disclosure may contain a repeating unit represented by the following general formula (3). The fluorine-containing polymer of this embodiment may have properties such as alkali solubility, making it suitable, for example, for use as a resin contained in a resist top layer film. In particular, it is preferably used for a resist top layer film used in an immersion lithography process.

[0112] (R ３ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated.

[0113] The R ３Examples of the alkylene group exemplified by the formula (I) include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-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, an isarene 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, Examples of such hydrocarbon groups include saturated chain hydrocarbon groups such as a 4-butylene group, a methylidene group, an ethylidene group, a propylidene group, or a 2-propylidene group; monocyclic hydrocarbon ring groups such as cycloalkylene groups having 3 to 10 carbon atoms, such as cyclobutylene groups such as a 1,3-cyclobutylene group, cyclopentylene groups such as a 1,3-cyclopentylene group, cyclohexylene groups such as a 1,4-cyclohexylene group, and cyclooctylene groups such as a 1,5-cyclooctylene group; and bridged cyclic hydrocarbon ring groups such as bicyclic to tetracyclic hydrocarbon ring groups, such as norbornylene groups such as a 1,4-norbornylene group or a 2,5-norbornylene group, and adamantylene groups such as a 1,5-adamantylene group or a 2,6-adamantylene group.

[0114] The R ３ Examples of the aromatic ring exemplified by include an o-phenylene group, an m-phenylene group, and a p-phenylene group.

[0115] In the fluorine-containing polymer of the present disclosure, the repeating unit represented by the general formula (1) may contain a repeating unit represented by the following general formula (4). The fluorine-containing polymer of the present disclosure may be composed solely of a repeating unit represented by the following general formula (4). In the fluorine-containing polymer of the present disclosure, the repeating unit represented by the general formula (1)' may contain a repeating unit represented by the following general formula (4)'. The fluorine-containing polymer of the present disclosure may be composed solely of a repeating unit represented by the following general formula (4)'. Furthermore, the fluorine-containing polymer of the present disclosure may contain both a repeating unit represented by the following general formula (4) and a repeating unit represented by the following general formula (4)'. When the fluorine-containing polymer of the present disclosure contains repeating units represented by the following general formulas (4) and (4)', the terminals of the side chains are hydrogen groups, and therefore the polymer may have properties such as water repellency and water resistance. Furthermore, when the fluorine-containing polymer of the present disclosure contains repeating units represented by the following general formulas (4) and (4)', the polymer is suitable for use as a resin contained in a resist upper layer film, for example. In particular, it is preferably used as a resist top layer film used in an immersion exposure process.

[0116]

[0117] When the fluorine-containing polymer of the present disclosure contains repeating units represented by the general formulae (4) and (4)', the fluorine-containing polymer of the present disclosure may contain repeating units represented by the general formulae (2) and (2)'. In this embodiment, the repeating units represented by the general formulae (2) and (2)' have hydroxyl groups at the ends of the side chains, and therefore the fluorine-containing polymer can be a fluorine-containing polymer that can have properties such as water repellency, adhesion, and alkali solubility.

[0118] When the fluorine-containing polymer of the present disclosure contains repeating units represented by the general formulas (4) and (4)', the fluorine-containing polymer of the present disclosure may contain a repeating unit represented by the following general formula (5): The fluorine-containing polymer of this embodiment can have properties such as water repellency, water resistance, elimination of acid-dissociable groups by acid generated by exposure, and alkali solubility associated therewith, and is therefore suitable for use as a resin contained in an additive for a resist film, for example.

[0119] (R ４ represents a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, some of which may be fluorinated and / or chlorinated. L represents an acid-dissociable group.

[0120] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group such as a 1,3-propylene group or a 1,2-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, an isalene 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- Examples of such hydrocarbon groups include saturated chain hydrocarbon groups such as butylene, methylidene, ethylidene, propylidene, and 2-propylidene groups; monocyclic hydrocarbon ring groups such as cycloalkylene groups having 3 to 10 carbon atoms, including cyclobutylene groups such as 1,3-cyclobutylene groups, cyclopentylene groups such as 1,3-cyclopentylene groups, cyclohexylene groups such as 1,4-cyclohexylene groups, and cyclooctylene groups such as 1,5-cyclooctylene groups; and bridged cyclic hydrocarbon ring groups such as bicyclic to tetracyclic hydrocarbon ring groups, including norbornylene groups such as 1,4-norbornylene or 2,5-norbornylene groups, and adamantylene groups such as 1,5-adamantylene and 2,6-adamantylene groups.

[0121] Examples of the aromatic ring include an o-phenylene group, an m-phenylene group, and a p-phenylene group.

[0122] Examples of the acid-dissociable group include a tert-butyl group, a tert-amyl group, a 1,1-dimethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1-dimethylbutyl group, an allyl group, a 1-pyrenylmethyl group, a 5-dibenzosuberyl group, a triphenylmethyl group, a 1-ethyl-1-methylbutyl group, a 1,1-diethylpropyl group, a 1,1-dimethyl-1-phenylmethyl group, a 1-methyl-1-ethyl-1-phenylmethyl group, a 1,1-diethyl-1-phenylmethyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isobornyl group, 1-methyladamantyl group, 1-ethyladamantyl group, 1-isopropyladamantyl group, 1-isopropylnorbornyl group, 1-isopropyl-(4-methylcyclohexyl) group, tert-butoxycarbonyl group, tert-amyloxycarbonyl group, methoxycarbonyl group, ethoxy Carbonyl group, i-propoxycarbonyl group, methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group, ethoxybutyl group, ethoxyisobutyl group, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group a tri-i-propylsilyl group, a tert-butyldimethylsilyl group, a methyldi-tert-butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group, an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauryl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutar ... Examples of such groups include a thallyl group, adipoyl group, piperoyl group, suberoyl group, azelaoyl group, sebacoyl group, (meth)acryloyl group, propioloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, and isonicotinoyl group.

[0123] Furthermore, in the fluorine-containing polymer of the present disclosure, the repeating units represented by the general formula (1) and / or (1)' may contain repeating units represented by the general formula (2) and / or (2)' and repeating units represented by the general formula (4) and / or (4)'. The fluorine-containing polymer of this embodiment can have properties such as adhesion, alkali solubility, water repellency, water resistance, deprotection of acid-dissociable groups by acid, and consequent alkali solubility in exposed areas, and is therefore suitable for use as a resin contained in an additive for a resist film, for example.

[0124] When the fluorine-containing polymer of the present disclosure contains repeating units represented by the general formula (2) and / or (2)' and repeating units represented by the general formula (4) and / or (4)', it may further contain repeating units represented by the general formula (5). The fluorine-containing polymer of the present disclosure may be composed only of repeating units represented by the general formula (2) and / or (2)', repeating units represented by the general formula (4) and / or (4)', and repeating units represented by the general formula (5).

[0125] In the fluorine-containing polymer of the present disclosure, R １ may be the same in each repeating unit or may be different in each repeating unit. ２ Similarly, X in the repeating unit represented by general formula (1) may be the same in each repeating unit or may be different in each repeating unit. Similarly, n in the repeating unit represented by general formula (1) may be the same in each repeating unit or may be different in each repeating unit.

[0126] In the fluorine-containing polymer of the present disclosure, R １ａ may be the same in each repeating unit or may be different in each repeating unit.２ａ and R ２ｂ Similarly, X may be the same in each repeating unit or may be different in each repeating unit. Similarly, X in the repeating unit represented by general formula (1)' may be the same in each repeating unit or may be different in each repeating unit. Similarly, n in the repeating unit represented by general formula (1)' may be the same in each repeating unit or may be different in each repeating unit.

[0127] In the fluorine-containing polymer of the present disclosure, R ３ and R in the repeating unit represented by general formula (5) ４ Similarly, L in the repeating unit represented by general formula (5) may be the same in each repeating unit or may be different in each repeating unit. Similarly, L in the repeating unit represented by general formula (1) may be the same in each repeating unit or may be different in each repeating unit. １ , R in the repeating unit represented by formula (3) １ and R in the repeating unit represented by general formula (5) １ However, when the fluorine-containing polymer of the present disclosure contains two or more of these, R １ may be the same in each repeating unit or may be different in each repeating unit.

[0128] Next, a method for using the fluorine-containing polymer of the present disclosure will be described.

[0129] <Formation of Resist Film and Upper Layer Film> The fluorine-containing polymer of the present disclosure can be used as a component of a resist film and / or an upper layer film that protects the resist film.

[0130] The resist film and the upper layer film are obtained by applying a photosensitive resin composition containing the fluorine-containing polymer of the present disclosure to a substrate or the like. The photosensitive resin composition for forming the resist film is a composition for forming a resist pattern of the present disclosure, and contains the fluorine-containing polymer of the present disclosure, an acid generator, and a solvent. The photosensitive resin composition for forming the upper layer film is a composition for forming a resist upper layer film of the present disclosure, and contains the fluorine-containing polymer of the present disclosure and a solvent.

[0131] The resist film may be either negative or positive. The substrate is not particularly limited, and examples thereof include a silicon wafer, a compound semiconductor substrate, and an insulating substrate. The substrate may have an anti-reflection film formed thereon. When the upper layer film is formed, the photosensitive resin composition may be applied onto the resist film.

[0132] When the fluorine-containing polymer of the present disclosure is used to form a resist film, a resist pattern-forming composition may be applied to a substrate to form a resist film. The resist film may then be subjected to exposure or immersion exposure. When the fluorine-containing polymer of the present disclosure is used to form an upper layer film, a resist upper layer film-forming composition may be applied to the resist film and / or resist pattern to form an upper layer film. The upper layer film may then be subjected to exposure or immersion exposure.

[0133] <Composition for forming a resist pattern> As described above, when the fluorine-containing polymer of the present disclosure is used to form a resist film, the composition for forming a resist pattern may contain the fluorine-containing polymer of the present disclosure, an acid generator, and a solvent.

[0134] Examples of the acid generator include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisaryl sulfonyl diazomethanes and poly(bissulfonyl)diazomethanes, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

[0135] Specific examples of onium salt acid generators include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri(4-methylphenyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, dimethyl(4-hydroxynaphthyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, monophenyldimethylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenylmonomethylsulfonium trifluoromethanesulfonate, nitrate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri(4-tert-butyl)phenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl(1-(4-methoxy)naphthyl)sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, di(1-naphthyl)phenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, and the like. Furthermore, onium salts in which the anion moiety of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

[0136] Specific examples of oxime sulfonate acid generators include 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)-4-chlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-2,4-dichlorobenzyl cyanide, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-(benzenesulfonyloxyimino)-2,6-dichlorobenzyl cyanide, α-(benzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxybenzyl cyanide, α-(benzenesulfonyloxyimino)-thien-2-ylacetonitrile, α-(4-dodecylbenzenesulfonyloxyimino)-benzyl cyanide, α-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(dodecylbenzenesulfonyloxyimino)- 4-Methoxyphenyl]acetonitrile, α-(tosyloxyimino)-4-thienyl cyanide, α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenylacetonitrile α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile,α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methyl Examples thereof include α-(ethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-p-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-p-methylphenylacetonitrile, and α-(methylsulfonyloxyimino)-p-bromophenylacetonitrile.

[0137] With regard to diazomethane-based acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes, specific examples of the bisalkyl or bisarylsulfonyldiazomethanes include bis(isopropylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane.

[0138] Examples of the solvent include 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-1-butanol, 3-methyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-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 Examples of the solvent include ethylene 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, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, and water.

[0139] The composition for forming a resist pattern of the present disclosure may contain a basic compound. Examples of basic compounds include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, and tri-n-noniamine. trialkylamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine; alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine; 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.

[0140] Furthermore, the composition for forming a resist pattern of the present disclosure may contain a base resin other than the fluorine-containing polymer of the present disclosure, and a weak acid photoacid generator (weak acid PAG).

[0141] The base resin may be a resin containing a structure represented by the following chemical formula:

[0142] (In general formulas (a) and (b), R Ｂ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Ｂ represents a single bond, a phenylene group, a naphthylene group, or (main chain) -C(=O)-O-Z'-, and Z' represents an alkanediyl group having 1 to 10 carbon atoms which may contain a hydroxy group, an ether bond, an ester bond, or a lactone ring, or a phenylene group or a naphthylene group. Ｂ is an acid labile group. Ｂis a hydrogen atom, or a polar group containing at least one structure selected from a hydroxy group, a cyano group, a carbonyl group, a carboxyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, and a carboxylic anhydride (-C(=O)-O-C(=O)-).

[0143] The alkanediyl group may be linear, branched, or cyclic, and specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a propane-1,3-diyl group, a 2-methylpropane-1,3-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, a butane-1,4-diyl group, a pentane-1,3-diyl group, a pentane-1,4-diyl group, a 2,2-dimethylpropane-1,3-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a cyclopentane-1,2-diyl group, a cyclopentane-1,3-diyl group, and a cyclohexane-1,6-diyl group.

[0144] Z in formula (a) Ｂ Examples of structures in which R is changed include, but are not limited to, those shown below. Ｂ and X Ｂ is the same as above.

[0145]

[0146] X Ｂ The acid labile group represented by the formula (I) is not particularly limited, but examples thereof include a tertiary alkyl group having 4 to 20 carbon atoms, a trialkylsilyl group in which each alkyl group has 1 to 6 carbon atoms, and an oxoalkyl group having 4 to 20 carbon atoms.

[0147] As the acid labile group, those represented by the following general formula (xa), (xb) or (xc) are particularly preferred.

[0148] (In the general formulas (xa), (xb) and (xc), R Ｘis a monovalent hydrocarbon group having 1 to 10 carbon atoms which may contain a heteroatom. k is 1 or 2. The dashed line represents a bond.

[0149] When a tertiary alicyclic hydrocarbon group represented by the general formula (xa), (xb), or (xc) is bonded to an ester oxygen, the acid decomposition ability is higher than that of other tertiary alkyl groups, such as a tert-butyl group or a tert-pentyl group, due to steric repulsion.

[0150] Examples of the repeating unit represented by general formula (a) include, but are not limited to, those shown below. Ｂ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0151]

[0152]

[0153]

[0154] The above specific example is Z Ｂ is a single bond, but Z Ｂ When is other than a single bond, it can be combined with a similar acid labile group.

[0155] Examples of the repeating unit represented by general formula (b) include, but are not limited to, those shown below. Ｂ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0156]

[0157]

[0158]

[0159] The base resin in the composition for forming a resist pattern of the present disclosure may contain one of the above structures, or may contain two or more of the above structures. When the base resin contains two or more of the above structures, R Ｂ , X Ｂ , Y Ｂ , Z Ｂ , RＸ may be the same or different.

[0160] The weak acid PAG may also be a photodegradable base that is photosensitive upon exposure to generate a weak acid. Examples of the photodegradable base include onium salt compounds that decompose upon exposure to light. Examples of the onium salt compound include sulfonium salt compounds represented by the following formula (10-1) and iodonium salt compounds represented by the following formula (10-2).

[0161] (In the above formula (10-1) and formula (10-2), R ５ ~R ９ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom. － and Q － are each independently OH － , R β -COO － , R β -SO ３ － Or an anion represented by the following formula (10-3): β is an alkyl group, an aryl group, or an aralkyl group.

[0162] (In the above formula (10-3), R １０ represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms, or a linear or branched alkoxyl group having 1 to 12 carbon atoms; and u represents an integer of 0 to 2.

[0163] Specific examples of weak acid PAGs include the following compounds:

[0164]

[0165] The resist pattern can be obtained through a process including a step of preparing the composition for forming a resist pattern, a film-forming step of applying the composition onto a substrate to form a film, an exposure step of irradiating the film with electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer the pattern of the photomask onto the film, and a development step of developing the film using a developer to obtain a pattern.

[0166] <Composition for forming a resist upper layer film> As described above, the composition for forming a resist upper layer film of the present disclosure preferably contains the fluorine-containing polymer of the present disclosure and a solvent. Examples of the solvent include the same as the preferred examples of the solvent for the composition for forming a resist pattern of the present disclosure.

[0167] Examples of a method for forming a resist pattern using such a composition for forming a resist upper layer film include a method comprising the steps of: preparing the composition for forming a resist upper layer film; a film-forming step of applying the composition for forming a resist upper layer film onto a resist film to form a resist upper layer film; an exposure step of irradiating and exposing the resist upper layer film and the resist film with electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer the pattern of the photomask to the resist film; and a development step of removing the resist upper layer film using a developer and developing the resist film to obtain a pattern.

[0168] <Formation of the resist film or top layer material (used material)> After baking the exposed substrate, it is developed using a developer. Development involves forming a resist pattern using an alkaline solution (forming a positive pattern) or an organic solvent (forming a negative pattern) as the developer.

[0169] [Positive Pattern Formation] Positive pattern formation is a process in which an alkaline solution is used as a developer to dissolve and wash away only the exposed area, thereby forming a pattern. Typically, an alkaline aqueous solution of tetramethylammonium hydroxide having a concentration of 0.1% by mass or more and 10% by mass or less can be used as the developer.

[0170] Other alkaline developers include alkaline aqueous solutions 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.

[0171] The developer used is not particularly limited as long as it can remove the desired resist and resist upper layer film by a predetermined developing method, and generally includes an aqueous alkaline solution using an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium salt, or a mixture thereof. These developers may also contain an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant.

[0172] When development is performed using the alkaline aqueous solution, washing, rinsing, drying, etc. can be performed as necessary to form the desired pattern. Known development methods such as immersion boron, puddling, and spraying can be used, and the development time may be 0.1 minutes or more and 3 minutes or less. It is preferably 0.5 minutes or more and 2 minutes or less. During development, the upper layer film dissolves, and only the exposed portion of the lower layer resist film dissolves.

[0173] In the alkali development step or the resist removal step, the fluorine-containing polymer is removed from the substrate. The resist film or the upper layer film removed from the substrate becomes a used material. The used material includes the fluorine-containing polymer of the present disclosure.

[0174] [Negative Pattern Formation] Negative pattern formation is a process in which a pattern is formed by dissolving and washing away only the unexposed areas using an organic solvent as a developer. Typically, butyl acetate can be used as the organic solvent for the developer.

[0175] Other organic solvents include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, propionate, Examples of the lactone derivative include methyl lactate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, ethyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, and 2-phenylethyl acetate.

[0176] The developer to be used is not particularly limited as long as it can remove the desired resist and resist upper layer film by a predetermined developing method, and these developers may also contain an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant.

[0177] When development is performed using the organic solvent, washing, rinsing, drying, etc. can be performed as necessary to form the desired negative pattern. Known development methods such as immersion boron, puddling, and spraying can be used, and the development time may be 0.1 minutes or more and 3 minutes or less. It is preferably 0.5 minutes or more and 2 minutes or less. During development, the upper layer film dissolves, and only the exposed portion of the lower resist film dissolves.

[0178] In the development step or resist removal step, the fluorine-containing polymer is removed from the substrate. The resist film or upper layer film removed from the substrate becomes a used material. The used material includes the fluorine-containing polymer of the present disclosure.

[0179] Waste liquid containing the fluoropolymer of the present disclosure, generated in the development process or the subsequent rinsing process, is treated by heating through total combustion. Alternatively, it is treated by heating during distillation to recover water from the waste liquid. These heating processes decompose the monochloro-difluoroalkyl groups in the fluoropolymer, leading to decomposition of the fluoropolymer. Since it has been confirmed that fluoride ions and chloride ions are generated by the heat treatment, it is expected that the monochloro-difluoroalkyl groups are decomposed and converted to carboxy groups. The heating temperature is preferably 50°C to 200°C, more preferably 55 to 160°C, and even more preferably 60 to 120°C. The upper limit of the temperature may be set low, such as 100°C or lower, or even 95°C or lower. Examples of treatment methods using such low heating temperatures include precipitation, adsorption, and activated sludge processes. These methods are simpler than combustion, and disposal of waste materials derived from the fluoropolymer of the present disclosure is easy. Therefore, use of the fluoropolymer of the present disclosure can contribute to energy reduction in semiconductor processes.

[0180] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.

[0181] In the examples, unless otherwise specified, some compounds are represented as follows:

[0182] Methyl ethyl ketone: MEK Diisobutyl ketone: IPE Tetrahydrofuran: THF Tetramethylammonium hydroxide: TMAH Propylene glycol monomethyl ether acetate: PGMEA

[0183] MA-4FHB-OH: A compound represented by the following chemical formula

[0184]

[0185] 4FIP-M: A compound represented by the following chemical formula

[0186]

[0187] i-4FHK-OH: A compound represented by the following chemical formula

[0188]

[0189] 4FIP: A compound represented by the following chemical formula

[0190]

[0191] MA-BTHB-OH: a compound represented by the following chemical formula

[0192]

[0193] HFIP-M: A compound represented by the following chemical formula

[0194]

[0195] 4FHB-NB: A compound represented by the following chemical formula

[0196]

[0197] MA-4FHB-NB: A compound represented by the following chemical formula

[0198]

[0199] MA-4FHP-OH: A compound represented by the following chemical formula

[0200]

[0201] 4F-Iee: A compound represented by the following chemical formula

[0202]

[0203] MA-MIP-4FA: a compound represented by the following chemical formula

[0204]

[0205] Bis-4FIP: a compound represented by the following chemical formula

[0206]

[0207] The equipment used for various measurements and the measurement conditions will be explained.

[0208] [Analysis of Fluorine-Containing Polymerizable Monomer] A nuclear magnetic resonance apparatus (hereinafter referred to as NMR, manufactured by JEOL Ltd., equipment name JNM-ECA400) with a resonance frequency of 400 MHz was used. １９F-NMR, １ H-NMR was measured.

[0209] [Polymer Analysis] The composition of the repeating units in the polymer was analyzed by NMR. １ H-NMR and １９ It was determined by F-NMR measurements.

[0210] [Analysis of Weight-Average Molecular Weight] The weight-average molecular weight (Mw) of the resin compositions and the like described below was measured as follows. The number-average molecular weight Mn and molecular weight distribution (ratio of number-average molecular weight Mn to mass-average molecular weight Mw = Mw / Mn) of the polymer were measured using high-performance gel permeation chromatography (hereinafter sometimes referred to as GPC, manufactured by Tosoh Corporation, model HLC-8320GPC) with one ALPHA-M column and one ALPHA-2500 column, both manufactured by Tosoh Corporation, connected in series, using tetrahydrofuran as the developing solvent. A refractive index difference detector was used as the detector.

[0211] The synthesis of the fluorine-containing polymerizable monomer and the intermediate for the fluorine-containing polymerizable monomer will be described below.

[0212] Synthesis Example 1 Synthesis of i-4FHK-OH and MA-4FHB-OH Concentrated sulfuric acid (0.31 g, 3.16 mmol), acetone (307 g, 5.28 mol), and 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 210 g, 1.06 mol) were added to a 1 L three-necked recovery flask and stirred overnight at 30°C. The reaction solution was concentrated using an evaporator at a bath temperature of 30°C and 100 hPa, and the resulting concentrate was washed with ion-exchanged water. The mixture was then concentrated using an evaporator to obtain Concentrate 1 (245 g). Tetrahydrofuran (ultra-dehydrated grade, 551 g) and sodium borohydride (32.5 g, 857 mmol) were added to a 1 L three-necked recovery flask, dispersed, and then immersed in an ice bath to cool. Thereafter, the above-mentioned concentrated solution 1 was added dropwise over 30 minutes, and the reaction was stopped after 1.5 hours with aqueous hydrochloric acid. The reaction solution was extracted with IPE (551 g) and washed with ion-exchanged water once. The washed IPE solution was concentrated in an evaporator under conditions of a bath temperature of 42 ° C and 20 hPa while solvent substitution with toluene was performed to obtain concentrated solution 2 (215 g) containing i-4FHK-OH. The above-mentioned concentrated solution 2, methanesulfonic acid (5.97 g, 62.1 mmol), and Nonflex MBP (Seiko Chemical Co., Ltd., 0.96 g) were added to a 1 L three-necked eggplant flask and mixed. Under conditions of a bath temperature of 38 ° C, methacrylic anhydride (hereinafter referred to as MAAH, Tokyo Chemical Industry Co., Ltd., 105 g, 683 mmol) was added dropwise. The mixture was then stirred at a bath temperature of 47 ° C for 1.5 hours and a bath temperature of 57 ° C for 3 hours, and the reaction was stopped. The reaction solution was extracted with IPE (322 g), washed once with aqueous sodium hydroxide, and once with ion-exchanged water. Thereafter, a small amount of 2-methoxyphenothiazine was added, and the mixture was concentrated in an evaporator at a bath temperature of 42°C and 20 hPa. The resulting concentrate was distilled at 0.2 kPa and an internal temperature of 125-136°C to obtain MA-4FHB-OH (123 g, yield 36% (yield over three steps), GC purity >99%). This reaction is shown below.

[0213]

[0214] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３, reference material: TMS): 6.36ppm (s, 1H), 6.18ppm (m, 1H), 5.65ppm (quin, J = 1.6Hz, 1H), 5.22ppm (m, 1H), 2.43ppm (dd, J=4.8Hz, 0.8Hz, 2H), 1.95ppm (m, 3H), 1.46ppm (d, J=6.4Hz, 3H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): -60.1ppm (q, 15.2Hz, 2F), -79.6ppm (m, 2F)

[0215] Synthesis Example 2: Synthesis of 4FIP and 4FIP-M Sodium borohydride (22.8 g, 603 mmol) and IPE (300 g) were added to a 1 L three-necked eggplant flask and cooled in an ice bath. 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 100 g, 503 mmol) was then slowly added dropwise, and the mixture was allowed to cool to room temperature and stirred for 17 hours. After cooling in an ice bath, the reaction was quenched with 200 g of aqueous hydrochloric acid. The organic layer obtained after separation was then subjected to atmospheric distillation (oil bath 120-150°C) to obtain 129 g of an IPE solution of 4FIP. The purity was 64 wt %, and the yield was 82%. The reaction is shown below.

[0216]

[0217] <NMR Analysis Results> The NMR results are shown below. The results for 4FIP only are shown. １ H-NMR (CDCl ３ , Reference substance: TMS): 4.42 ppm (m, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): -58.7ppm (m, 2F), -63.4ppm (m, 2F)

[0218] A 500 mL three-necked eggplant flask was charged with a solution of 4FIP in IPE (120 g, 410 mmol), triethylamine (46 g, 454 mmol), and IPE (150 g), and the mixture was cooled in an ice bath. Then, methacrylic acid chloride (45 g, 45.2 mmol) was slowly added dropwise. The mixture was then allowed to warm to room temperature and stirred for 3 hours. The reaction was then quenched with 200 g of saturated aqueous sodium bicarbonate. The resulting organic layer was washed once with 200 g of saturated aqueous sodium bicarbonate and twice with 200 g of distilled water. The organic layer was then distilled under reduced pressure (0.6 kPa, oil bath at 50-100°C) to obtain 86 g of 4FIP-M. The yield was 80%, and the GC purity was >99%. The reaction is shown below.

[0219]

[0220] <NMR Analysis Results> The NMR results are shown below. １ H-NMR (CDCl ３ , reference material: TMS): 6.36ppm (m, 1H), 5.89ppm (m, 1H), 5.84ppm (m, 1H), 2.03ppm (m, 3H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): -58.5ppm (m, 2F), -60.1ppm (m, 2F)

[0221] [Synthesis Example 3: Synthesis of 4FHB, 4FHB-NB, and MA-4FHB-NB] 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 50 g, 0.25 mol) was charged into a pressure-resistant vessel (500 ml) equipped with a stirrer, and the reactor was sealed. Next, the reactor was degassed with a vacuum pump, and then 10.5 g (0.25 mol) of propylene was introduced while stirring the contents with a stirrer. Next, the temperature inside the reactor was raised to 100 ° C., and stirring was continued for 80 hours. After completion of the reaction, the mixture was distilled under reduced pressure at an absolute pressure of 3.0 kPa and a temperature of 68 ° C. to 69 ° C. to obtain 36.5 g of 1-chloro-2-(chlorodifluoromethyl)-1,1-difluoro-3-buten-1-ol (hereinafter 4FHB) represented by the following formula, in a yield of 60%. The reaction is shown below.

[0222]

[0223] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ5.89 (m, 1H), 5.40 (ddt, 1H), 5.34 (dq, 1H), 3.20 (brs, 1H), 2.88 (dd, 2H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.7 (s, 4F)

[0224] Dicyclopentadiene (13.22 g, 0.1 mol) and 4FHB (24.3 g, 0.1 mol) were charged into a 100 mL SUS autoclave. The reaction mixture was stirred for 1 hour and heated at 150°C for 10 hours. After cooling the reaction mixture, each component was fractionated. The fraction distilled at a pressure of 0.1 kPa and a temperature of 85°C to 90°C was collected to obtain 15 g of 4FHB-NB shown below in a 40% yield. This reaction is shown below.

[0225]

[0226] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ6.20 (dd, 1H), 5.98 (dd, 1H), 3.05 (m, 1H), 2.92 (m, 1H), 2.81 (m, 1H), 2.00 (dd, 2H), 1.80 (d, 1H), 1.35 (m, 2H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-59.9 (m, 2F), -60.5 (m, 2F)

[0227] 4FHB-NB (10 g, 31.7 mmol) and formic acid (30 g, 653 mmol) were added to a 100 mL three-necked recovery flask and stirred at 65°C for 2 hours. IPE (100 g) was then added, and the organic layer was washed once with 100 g of ion-exchanged water, twice with 100 g of saturated sodium bicarbonate water, and once with 100 g of ion-exchanged water. The organic layer obtained after separation was concentrated using an evaporator to obtain Concentrated Solution 3 (10.5 g). This reaction is shown below.

[0228]

[0229] Concentrated Solution 3 (10.5 g), methanol (30 g), and ion-exchanged water (30 g) were placed in a 300 mL three-necked recovery flask, followed by the addition of trifluoroacetic acid (0.3 g, 2.6 mmol) and stirring at 60°C for 8 hours. IPE (100 g) was then added, and the organic layer was washed once with 100 g of ion-exchanged water, once with 100 g of saturated sodium bicarbonate water, and once with 100 g of ion-exchanged water. The organic layer separated was concentrated in an evaporator to give Concentrated Solution 4 (9.5 g). This reaction is shown below.

[0230]

[0231] Concentrated solution 4 (9.5 g), toluene (20 g), and methacrylic anhydride (4.7 g, 30.8 mmol) were added to a 100 mL three-necked recovery flask, followed by the addition of methanesulfonic acid (0.4 g, 4.4 mmol) and stirring at 80°C for 1 hour. IPE (20 g) was then added, and the organic layer was washed once with 50 g of saturated sodium bicarbonate water and once with 50 g of ion-exchanged water. The organic layer obtained after separation was concentrated in an evaporator. Kugelrohr distillation was then performed to obtain 5.1 g of MA-4FHB-NB. The purity was 98%, and the yield from 4FHB-NB was 50%. The reaction is shown below.

[0232]

[0233] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３, reference material: TMS) δ6.05 (m, 1H), 5.52 (m, 1H), 4.64 (m, 1H), 3.55 (m, 1H), 2.33 (m, 2H), 2.15 (m, 2H), 1.95 (m, 1H), 1.90 (m, 3H), 1.88 (m, 1H), 1.53 (m, 2H), 1.30 (m, 2H), 1.15 (m, 1H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-60.3 (m, 4F)

[0234] Synthesis Example 4: Synthesis of 4FHP-OH and MA-4FHP-OH 1,3-Dichlorotetrafluoroacetone (Synquest Laboratories, 50 g, 252 mmol) and butyl vinyl ether (40.2 g, 400 mmol) were added to a 300 mL three-necked recovery flask and stirred at room temperature for 18 hours. Simple distillation was then performed to obtain 50.9 g of the target oxetane with a GC purity of 95% and a yield of 83%. This reaction is shown below.

[0235]

[0236] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ5.56 (t, 1H), 3.79 (dt, 1H), 3.55 (dt, 1H), 3.11 (dd, 1H), 2.93 (dd, 1H), 1.60 (m, 2H), 1.40 (m, 2H), 0.93 (t, 3H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-62.2 (m, 4F)

[0237] The above oxetane (49 g, 252 mmol), ion-exchanged water (72 g), and formic acid (180 g) were added to a 300 mL three-necked recovery flask and stirred at 70°C for 4 hours. IPE (200 g) was then added and the mixture was separated. The resulting organic layer was concentrated using an evaporator and subjected to simple distillation to obtain 34 g of the target aldehyde with a GC purity of 98% and a yield of 54%. This reaction is shown below.

[0238]

[0239] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ9.88 (s, 1H), 3.12 (s, 2H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-60.8 (d, 2F), -62.6 (d, 2F)

[0240] The above aldehyde (33 g, 252 mmol), IPE (100 g), and sodium borohydride (51 g, 135 mmol) were added to a 300 mL three-necked recovery flask and stirred at room temperature for 7 hours. Then, IPE (200 g) and 1 N aqueous hydrochloric acid solution (200 g) were added and the mixture was separated. The organic layer was concentrated and distilled using an evaporator to obtain 30 g of 4FHP-OH with a GC purity of 99% and a yield of 90%. The reaction is shown below.

[0241]

[0242] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ6.10 (brs, 1H), 4.15 (t, 2H), 2.43 (brs, 1H), 2.38 (t, 2H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-61.1 (s, 2F), -61.5 (s, 2F)

[0243] 4FHP-OH (4.2 g, 17.1 mmol), toluene (15 g), methacrylic anhydride (2.8 g, 18.0 mmol), and methanesulfonic acid (0.4 g, 4.4 mmol) were added to a 50 mL three-necked recovery flask and stirred at 70°C for 7 hours. IPE (20 g) was then added, and the mixture was washed with saturated sodium bicarbonate water and ion-exchanged water. The resulting organic layer was concentrated using an evaporator and subjected to simple distillation to obtain 3.1 g of MA-4FHP-OH with a GC purity of 99% and a yield of 69%. This reaction is shown below.

[0244]

[0245] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ6.14 (m, 1H), 5.63 (m, 1H), 4.88 (brs, 1H), 4.46 (t, 2H), 2.48 (t, 2H), 1.93 (m, 3H) １９ F-NMR (CDCl): δ-61.0 (m, 4F)

[0246] Synthesis Example 5: Synthesis of 4F-Iee 4FHP-OH (8.1 g, 33 mmol), dichloromethane (30 g), and triethylamine (4.0 g, 39.3 mmol) were placed in a 50 mL three-necked recovery flask and cooled in an ice bath. Ethyl 2-bromomethylacrylate (6.4 g, 33 mmol) was then added, and the mixture was allowed to warm to room temperature and stirred for 3 hours. The reaction mixture was filtered under reduced pressure, and the filtrate was washed with 1 N aqueous hydrochloric acid solution (50 g), ion-exchanged water (50 g), and saturated saline. The resulting organic layer was concentrated using an evaporator and subjected to simple distillation to obtain 12.8 g of 4F-Iee with a GC purity of 99% and a yield of 80%. This reaction is shown below.

[0247]

[0248] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS) δ6.35 (m, 1H), 5.88 (brs, 1H), 5.81 (m, 1H), 4.23 (q, 2H), 4.22 (brs, 2H), 3.91 (t, 2H), 2.41 (t, 2H), 1.30 (t, 3H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): δ-61.0 (d, 4F)

[0249] Synthesis Example 6: Synthesis of MA-MIP-4FA MA-MIP-4FA was synthesized in the same manner as in Synthesis Example 1, except that acetone was replaced with isopropyl methyl ketone. The yield was 110 g, 30% (yield over three steps), and GC purity was >99%. The reaction is shown below.

[0250]

[0251] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS): 6.39ppm (s, 1H), 6.19ppm (m, 1H), 5.70ppm (dt, 1H), 5.20ppm m (m, 1H), 2.45ppm (dd, 2H), 2.04 (m, 1H), 1.93ppm (m, 3H), 1.24ppm (d, 6H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): -60.0ppm (q, 2F), -79.6ppm (m, 2F)

[0252] Synthesis Example 7: Synthesis of bis-4FIP derivative Trifluoroacetic acid (0.14 g, 1.2 mmol), acetone (1.5 g, 25.1 mol), and 1,3-dichlorotetrafluoroacetone (Synquest Laboratories, 14.0 g, 70.4 mol) were added to a 100 mL autoclave and stirred overnight at 80°C. The reaction solution was concentrated using an evaporator at a bath temperature of 30°C and 100 hPa, and the resulting concentrate was washed with ion-exchanged water. The mixture was then concentrated using an evaporator to obtain concentrate 5 (10 g). Tetrahydrofuran (ultra-dehydrated grade, 30 g) and sodium borohydride (0.9 g, 22 mmol) were added to a 100 mL three-necked recovery flask, dispersed, and then cooled in an ice bath. The concentrate 5 was then added dropwise, and the reaction was stopped after 1.5 hours with aqueous hydrochloric acid. The reaction solution was extracted with IPE (50 g) and washed once with ion-exchanged water. The washed IPE solution was concentrated in an evaporator at a bath temperature of 42 ° C and 20 hPa while solvent substitution with toluene was performed to obtain concentrate 6 (9 g). The concentrate 6, methacrylic acid (3.2 g, 37 mmol), concentrated sulfuric acid (0.4 g, 37 mmol), and Topanol A (0.1 g) were added to a 100 mL three-necked eggplant flask and stirred overnight at 80 ° C. The reaction solution was extracted with IPE (30 g) and washed once with saturated sodium bicarbonate water and once with ion-exchanged water. The mixture was then concentrated in an evaporator. The resulting concentrate was distilled to obtain bis-4FIP (6 g, yield 30% (3-step yield), GC purity > 99%). This reaction is shown below.

[0253]

[0254] <NMR Analysis Results> The results of nuclear magnetic resonance analysis (hereinafter sometimes referred to as NMR) are shown below. １ H-NMR (CDCl ３ , reference material: TMS): 6.21ppm (t, 1H), 5.74ppm (t, 1H), 5.51ppm (m, 1H), 4.90 (brt, 1H), 2.55ppm (m, 4H), 1.96ppm (t, 3H) １９ F-NMR (CDCl ３ , Reference material: C ６ F ６ ): -61.5ppm (m, 8F)

[0255] Next, the synthesis of the polymer will be described.

[0256] Synthesis Example 8 Synthesis of Fluoropolymer 1 Into a 100 mL glass flask were placed 8.0 g (24 mmol) of MA-4FHB-OH and 32 g of MEK at room temperature, and 0.6 g (2.4 mmol) of 2,2'-azobis(isobutyrate)dimethyl (hereinafter referred to as V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was further added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 80 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 6.4 g of fluoropolymer 1 having the following repeating unit in a yield of 80%.

[0257]

[0258] As a result of GPC measurement, Mw was 13,000 and Mw / Mn was 1.9.

[0259] Synthesis Example 9 Synthesis of Fluorine-Containing Polymer 2 5 g (19 mmol) of 4FIP-M and 2.5 g of butyl acetate were placed in a 100 mL glass flask at room temperature, and 0.2 g (0.9 mmol) of V-601 was further added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 70 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 4.1 g of fluorine-containing polymer 2 having the following repeating unit in a yield of 82%.

[0260]

[0261] As a result of GPC measurement, Mw was 9,000 and Mw / Mn was 2.1.

[0262] Synthesis Example 10 Synthesis of Fluoropolymer 3 Into a 100 mL glass flask, 8.0 g (24 mmol) of MA-4FHB-OH, 6.3 g (24 mmol) of 4FIP-M, and 60 g of MEK were placed at room temperature, and 1.2 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd., 4.8 mmol) was further added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 100 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 12.0 g of fluoropolymer 3 having the following repeating units in a yield of 84%.

[0263]

[0264] As a result of GPC measurement, Mw was 10,800 and Mw / Mn was 1.8.

[0265] As a result of NMR measurement, the composition ratio of the structural units of Fluoropolymer 3, expressed in mol %, was structural units derived from MA-4FHB-OH:structural units derived from 4FIP-M=52:48.

[0266] Synthesis Example 11 Synthesis of Fluorine-Containing Polymer 4 Into a 100 mL glass flask, 8.0 g (24 mmol) of MA-4FHB-OH, 1.7 g (16 mmol) of vinyl sulfonic acid, and 40 g of MEK were placed at room temperature, and 1.2 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd., 4.8 mmol) was further added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 100 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 8.0 g of fluorine-containing polymer 4 having the following repeating units in a yield of 81%.

[0267]

[0268] As a result of GPC measurement, Mw was 9,800 and Mw / Mn was 1.9.

[0269] As a result of NMR measurement, the composition ratio of the structural units of Fluoropolymer 4, expressed in mol %, of structural units derived from MA-4FHB-OH:structural units derived from vinylsulfonic acid was 59:41.

[0270] Synthesis Example 12 Synthesis of Fluorine-Containing Polymer 5 Into a 100 mL glass flask were placed 6.3 g (24 mmol) of 4FIP-M, 6.0 g (24 mmol) of 2-ethyl-2-methacryloyloxyadamantane (hereinafter referred to as EMOE), and 50 g of MEK at room temperature, and 1.2 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 4.8 mmol) was further added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 100 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 10.5 g of fluorine-containing polymer 5 having the following repeating units in a yield of 85%.

[0271]

[0272] As a result of GPC measurement, Mw was 9900 and Mw / Mn was 2.1.

[0273] As a result of NMR measurement, the composition ratio of the structural units of the fluoropolymer 5, expressed in mol %, of structural units derived from 4FIP-M:structural units derived from EMOA was 55:45.

[0274] Synthesis Example 13 Synthesis of Fluorine-Containing Polymer 6 Into a 200 mL glass flask at room temperature were placed 8.0 g (24 mmol) of MA-4FHB-OH, 6.3 g (24 mmol) of 4FIP-M, 6.0 g (24 mmol) of 2-ethyl-2-methacryloyloxyadamantane (hereinafter referred to as EMOE), and 80 g of MEK, and then 1.2 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 4.8 mmol) was added. The flask was then degassed with stirring. Thereafter, the atmosphere in the flask was replaced with nitrogen gas, and the internal temperature was raised to 78°C, followed by reaction for 18 hours. The reaction solution was added dropwise to 150 g of heptane to cause reprecipitation, followed by decantation. The resulting polymer was dried in a vacuum dryer to obtain 18.1 g of fluorine-containing polymer 6 having the following repeating units in a yield of 89%.

[0275]

[0276] As a result of GPC measurement, Mw was 12,000 and Mw / Mn was 2.3.

[0277] As a result of NMR measurement, the compositional ratio of the structural units of fluoropolymer 6, expressed in mol %, (structural unit derived from MA-4FHB-OH: structure derived from 4FIP-M: structural unit derived from EMOA) was 35:33:32.

[0278] Synthesis Example 14 Synthesis of Fluoropolymer 7 A fluoropolymer was synthesized in the same manner as in Synthesis Example 8, except that MA-4FHB-OH was changed to MA-BTHB-OH, to obtain 6.0 g of fluoropolymer 7 having the following repeating unit in a yield of 76%.

[0279]

[0280] As a result of GPC measurement, Mw was 12,000 and Mw / Mn was 2.0.

[0281] Synthesis Example 15 Synthesis of Fluorine-Containing Polymer 8 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 9, except that 4FIP-M was changed to HFIP-M, to obtain 3.9 g of fluorine-containing polymer 8 having the following repeating unit in a yield of 80%.

[0282]

[0283] As a result of GPC measurement, Mw was 9,800 and Mw / Mn was 2.2.

[0284] Synthesis Example 16 Synthesis of Fluorine-Containing Polymer 9 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 10, except that MA-4FHB-OH was changed to MA-BTHB-OH and 4FIP-M was changed to HFIP-M, to obtain 10.0 g of fluorine-containing polymer 9 having the following repeating unit in a yield of 78%.

[0285]

[0286] As a result of GPC measurement, Mw was 10,000 and Mw / Mn was 1.9.

[0287] As a result of NMR measurement, the composition ratio of the structural units of the fluorine-containing polymer 9, expressed in mol %, was structural units derived from MA-BTHB-OH:structural units derived from HFIP-M=53:47.

[0288] Synthesis Example 17 Synthesis of Fluoropolymer 10 A fluoropolymer was synthesized in the same manner as in Synthesis Example 11, except that MA-4FHB-OH was changed to MA-BTHB-OH, to obtain 7.0 g of fluoropolymer 10 having the following repeating unit in a yield of 75%.

[0289]

[0290] As a result of GPC measurement, Mw was 11,000 and Mw / Mn was 1.9.

[0291] As a result of NMR measurement, the composition ratio of the structural units of the fluoropolymer 10, expressed in mol %, structural units derived from MA-BTHB-OH:structural units derived from vinylsulfonic acid=58:42.

[0292] Synthesis Example 18 Synthesis of Fluorine-Containing Polymer 11 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 12, except that MA-4FHB-OH was changed to MA-BTHB-OH, to obtain 9.5 g of a fluorine-containing polymer 11 having the following repeating unit in a yield of 80%.

[0293]

[0294] As a result of GPC measurement, Mw was 9,000 and Mw / Mn was 2.2.

[0295] As a result of NMR measurement, the composition ratio of the structural units of the fluoropolymer 11, expressed in mol %, of the structural units derived from MA-BTHB-OH:the structural units derived from EMOA was 54:46.

[0296] Synthesis Example 19 Fluorine-containing polymer 12 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 13, except that MA-4FHB-OH was changed to MA-BTHB-OH and 4FIP-M was changed to HFIP-M, to obtain 17.1 g of a fluorine-containing polymer 12 having the following repeating unit in a yield of 85%.

[0297]

[0298] As a result of GPC measurement, Mw was 11,000 and Mw / Mn was 2.3.

[0299] As a result of NMR measurement, the composition ratio of the structural units of the fluoropolymer 12, expressed in mol %, (structural unit derived from MA-BTHB-OH:structure derived from HFIP-M:structural unit derived from EMOA) was 36:33:31.

[0300] Synthesis Example 20 Synthesis of Fluorine-Containing Polymer 13 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 8, except that MA-4FHB-OH was changed to MA-4FHB-NB, to obtain 5.1 g of fluorine-containing polymer 13 having the following repeating unit in a yield of 70%.

[0301]

[0302] As a result of GPC measurement, Mw was 27,200 and Mw / Mn was 2.0.

[0303] Synthesis Example 21 Synthesis of Fluoropolymer 14 A fluoropolymer was synthesized in the same manner as in Synthesis Example 8, except that MA-4FHB-OH was changed to MA-4FHP-OH, to obtain 5.6 g of fluoropolymer 14 having the following repeating unit in a yield of 75%.

[0304]

[0305] As a result of GPC measurement, Mw was 11,600 and Mw / Mn was 2.1.

[0306] Synthesis Example 22 Synthesis of Fluoropolymer 15 A fluoropolymer was synthesized in the same manner as in Synthesis Example 10, except that MA-4FHB-OH was changed to 4F-Iee, to obtain 5.1 g of fluoropolymer 15 having the following repeating unit in a yield of 40%.

[0307]

[0308] As a result of GPC measurement, Mw was 10,800 and Mw / Mn was 1.8.

[0309] As a result of NMR measurement, the composition ratio of the structural units of the fluoropolymer 3, expressed in mol %, of structural units derived from 4F-Iee:structural units derived from 4FIP-M was 52:48.

[0310] Synthesis Example 23 Synthesis of Fluorine-Containing Polymer 16 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 8, except that MA-4FHB-OH was changed to MA-MIB-4FA, to obtain 5.5 g of fluorine-containing polymer 16 having the following repeating unit in a yield of 72%.

[0311]

[0312] As a result of GPC measurement, Mw was 10,000 and Mw / Mn was 2.0.

[0313] Synthesis Example 24 Synthesis of Fluorine-Containing Polymer 17 A fluorine-containing polymer was synthesized in the same manner as in Synthesis Example 8 except that MA-4FHB-OH was changed to a bis-4FIP form, thereby obtaining 4.6 g of fluorine-containing polymer 17 having the following repeating unit in a yield of 65%.

[0314]

[0315] As a result of GPC measurement, Mw was 18,200 and Mw / Mn was 2.6.

[0316] Table 1 shows the yield, Mw and molecular weight distribution (Mw / Mn) of fluorine-containing polymers 1 to 17.

[0317]

[0318] <Degradability Evaluation 1> The degradability of fluoropolymers 1 to 17 was confirmed by the following method using NMR. 2.38 wt % TMAH aqueous solution (20 g) was added to 1 g of each fluoropolymer. １９ F-NMR was measured after stirring for 24 hours at room temperature or after stirring for 24 hours at 90°C. １９ F-NMR was measured to confirm the １９ The chlorodifluoro group was judged to have decomposed when 50% or more of the peak area in F-NMR was replaced by a new peak with a different chemical shift value. The results are shown in Table 2.

[0319]

[0320] It was confirmed that the fluoropolymers containing MA-BTHB-OH or HFIP-M having a trifluoromethyl group as a repeating unit (Comparative Examples 1 to 6) did not decompose at room temperature under heating conditions, but the fluoropolymers containing MA-4FHB-OH or 4FIP-M having a chlorodifluoro group as a repeating unit (Examples 1 to 11) showed decomposition of the chlorodifluoro group at 90° C. From these results, a fluoropolymer that can be decomposed at a lower temperature is provided, and in the photolithography step, the fluoropolymer can be decomposed at a lower temperature after development, which is thought to contribute to lowering the energy consumption of semiconductor processes.

[0321] <Degradability Evaluation 2> Fluoropolymers 1 to 17 were treated under the following conditions, and the concentrations of fluorine ions and chloride ions generated were measured to evaluate the degradability of each fluoropolymer. 20 g of a 2.38 wt % aqueous TMAH solution was added to 1 g of each fluoropolymer and stirred at 90°C for 24 hours to obtain a solution. 20 g of diisopropyl ether (IPE) was added to 21 g of each solution and stirred for 5 minutes, then allowed to stand and separated to remove organic matter, and the fluorine ions and chloride ions contained in the aqueous layer were measured by ion chromatography. The ion chromatography apparatus used was a Thermo Fisher Scientific "ICS-2100," the column used was a Thermo Fisher Scientific IonPac CS16 RFIC (5 x 250 mm), the eluent was a KOH aqueous solution, and the detector was an electrical conductivity detector (under these conditions, fluoride ions were detected at 8.8 min and chloride ions at 13.3 min). The concentrations of fluoride ions and chloride ions were measured using calibration curves from the measurement results. The results are shown in Table 3.

[0322]

[0323] As shown in Table 3, it was confirmed that in the fluoropolymers (Examples 1 to 11) containing MA-4FHB-OH or 4FIP-M having chlorodifluoro groups as repeating units, the chlorodifluoro groups were decomposed into fluorine ions and chloride ions under basic conditions at 90°C.

[0324] From the above results, it was found that the fluoropolymers according to the examples of the present disclosure are fluoropolymers that can be decomposed at a lower temperature than conventional fluoropolymers.

[0325] Next, in order to confirm whether the fluorine-containing polymer of the present disclosure can be used for a resist film, an upper layer film, etc. in photolithography, the following <evaluation of water repellency>, <evaluation of insolubility in water>, <evaluation of solubility in an alkaline developer> and <evaluation of transmittance at 193 nm> were carried out.

[0326] <Evaluation of water repellency> A composition was prepared by adding 1 g of each fluoropolymer to 3 g of PGMEA. The prepared composition was then applied to a 4-inch silicon substrate using a spinner and dried for 3 minutes on a hot plate heated to 80°C to form a film with a thickness of 2 to 3 µm.

[0327] [Measurement of static contact angle] A water droplet was placed on the film on the silicon substrate, and the static contact angle was measured by the sessile drop method using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). In the present invention, the static contact angle refers to the angle formed by a water droplet placed on the film surface when it lands on the film surface. The results are shown in Table 4.

[0328] [Measurement of hysteresis (dynamic advancing angle - dynamic receding angle)] A water droplet was placed on a film on a silicon substrate, and hysteresis (dynamic advancing angle - dynamic receding angle) was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) by the expansion / contraction method. In the present invention, the dynamic receding angle refers to the contact angle when a water droplet is sucked in with a needle or the like and the water droplet contracts, the dynamic advancing angle refers to the contact angle when a water droplet is ejected with a needle or the like and the water droplet expands, and hysteresis refers to the difference between the dynamic contact angle and the dynamic receding angle. The results are shown in Table 4.

[0329] [Measurement of sliding angle] A water droplet (50 μL) was placed on the film on the silicon substrate, and the sliding angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The sliding angle is the angle at which the water droplet moves when the angle of the silicon substrate is tilted. The results are shown in Table 4.

[0330]

[0331] Examples 1 to 11 had static contact angles, sliding angles, and hysteresis comparable to those of Comparative Examples 1 to 6, and it was confirmed that the fluoropolymers containing MA-4FHB-OH having chlorodifluoro groups or 4FIP-M as repeating units also had similar levels of water repellency.

[0332] <Evaluation of insolubility in water> A composition was prepared by adding fluoropolymer 1 (1 g) to PGMEA (3 g). The prepared composition was then applied to a 4-inch silicon substrate using a spinner and dried for 3 minutes on a hot plate heated to 80°C to form a film with a thickness of 3 µm. The substrate was then immersed in ion-exchanged water for 1 minute, and the film thickness on the silicon substrate was measured. The film thickness was found to be 3 µm, confirming that the composition was insoluble in ion-exchanged water.

[0333] <Evaluation of Solubility in Alkaline Developer> A composition was prepared by adding fluoropolymer 1 (1 g) to PGMEA (3 g). The prepared composition was then applied to a 4-inch silicon substrate using a spinner and dried for 3 minutes on a hot plate heated to 80°C to form a film with a thickness of 3 µm. The substrate was then immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, and it was confirmed that the film on the silicon substrate was removed and dissolved in the TMAH solution.

[0334] <Evaluation of 193 nm Transmittance> A composition was prepared by adding fluoropolymer 1 (1 g) to PGMEA (19 g). The prepared composition was then applied to a 4-inch quartz glass plate using a spinner and dried for 3 minutes on a hot plate heated to 80°C to form a film with a thickness of 225 nm. The transmittance was then measured by irradiating the plate with 193 nm light using an ArFES-3500LDLS (manufactured by Litho Tech Japan Co., Ltd.) in transmittance measurement mode. The transmittance at 193 nm was 97%, confirming that the film sufficiently transmitted 193 nm light. The film thickness after irradiation was measured, and the film thickness remained unchanged before and after irradiation at 225 nm, confirming that the film was inactive to 193 nm light.

[0335] From the above results, it was found that the fluorine-containing polymer of the present disclosure can be suitably used for resist films, upper layer films, etc. in photolithography.

[0336]

[0013] Summarizing the above results, it has been found that the present disclosure provides a fluoropolymer that can be decomposed at a lower temperature than conventional fluoropolymers. Furthermore, it has been found that the fluoropolymer of the present disclosure can be suitably used for resist films, upper layer films, etc. in photolithography, and that used substances derived from the fluoropolymer of the present disclosure can be treated by precipitation, adsorption, activated sludge method, etc., which are simpler than combustion, and therefore can contribute to energy saving in semiconductor processes.

Claims

1. A fluorine-containing polymer comprising a repeating unit represented by the following general formula (1) or (1)': (In 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. A part or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formulas (1) and (1)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulas (1) and (1)', n is a natural number from 1 to 3.

2. The fluorine-containing polymer according to claim 1, wherein the repeating units represented by the general formulae (1) and (1)' contain repeating units represented by the following general formulae (2) and (2)', respectively.

3. The fluorine-containing polymer according to claim 2, which contains a repeating unit represented by the following general formula (3): (In general formula (3), R ３is an alkylene group or aromatic ring which may have a single bond, a straight chain, a branched or a cyclic structure, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these.

4. The fluorine-containing polymer according to claim 1, wherein the repeating units represented by the general formulae (1) and (1)' contain repeating units represented by the following general formulae (4) and (4)', respectively.

5. The fluorine-containing polymer according to claim 4, which contains a repeating unit represented by the following general formula (5): (In general formula (5), R ４ is an alkylene group or aromatic ring which may have a single bond, a straight chain, a branched or a cyclic structure, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these. L is an acid-dissociable group.

6. The fluorine-containing polymer according to claim 4, wherein the repeating units represented by the general formulae (1) and (1)' contain repeating units represented by the following general formulae (2) and (2)', respectively.

7. The fluorine-containing polymer according to claim 6, which contains a repeating unit represented by the following general formula (5): (In general formula (5), R ４ is an alkylene group or aromatic ring which may have a single bond, a straight chain, a branched or a cyclic structure, and may partially contain an ester bond, a carbonyl bond, an ether bond, an amide bond, an acetal bond, a hydroxyl group, an amino group, a fluorine atom or a chlorine atom, or may be a composite substituent of these. L is an acid-dissociable group.

8. A composition for forming a fluorine-containing resin film, comprising the fluorine-containing polymer according to any one of claims 1 to 7.

9. A fluorine-containing resin film comprising a coating of the composition for forming a fluorine-containing resin film according to claim 8.

10. A composition for forming a resist pattern, comprising the fluorine-containing polymer according to any one of claims 1 to 7, an acid generator, and a solvent.

11. A method for forming a resist pattern, comprising: a step of preparing a composition for forming a resist pattern according to claim 10; a film-forming step of applying the composition for forming a resist pattern onto a substrate to form a film; an exposure step of irradiating and exposing the film to electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer the pattern of the photomask to the film; and a development step of developing the film with a developer to obtain a pattern.

12. A composition for forming a resist upper layer film, comprising the fluorine-containing polymer according to any one of claims 1 to 7 and a solvent.

13. A method for forming a resist pattern, comprising: a step of preparing a composition for forming a resist upper layer film according to claim 12; a film-forming step of applying the composition for forming a resist upper layer film onto a resist film to form a resist upper layer film; an exposure step of irradiating and exposing the resist upper layer film and the resist film with electromagnetic waves or high-energy rays having a wavelength of 300 nm or less through a photomask to transfer a pattern of the photomask onto the resist film; and a development step of removing the resist upper layer film with a developer and developing the resist film to obtain a pattern.

14. A method for decomposing a fluoropolymer according to any one of claims 1 to 7, which comprises heating the fluoropolymer at 50°C to 200°C.

15. A fluorine-containing polymerizable monomer represented by the following general formula (6) or (6)': (In general formula (6), 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. A part or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. ２ is a single bond, an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. １ａis a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formulas (6) and (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formulas (6) and (6)', n is a natural number from 1 to 3.

16. A compound represented by the following general formula (7): (In general formula (7), R ２ is a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n is a natural number from 1 to 3.

17. A method for producing a fluorine-containing polymerizable monomer represented by the following general formula (6), comprising the steps of: preparing a compound represented by the following general formula (7); and reacting the compound represented by the general formula (7) with at least one selected from the group consisting of acid halides, acid anhydrides, esters and carboxylic acids. (In general formula (7), R ２is a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n is a natural number from 1 to 3. (In general formula (6), R １ R 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. Some or all of the hydrogen atoms bonded to carbon atoms in the alkyl group may be substituted with fluorine atoms. ２ is a single bond, an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. n is a natural number from 1 to 3.

18. A method for producing a fluorine-containing polymerizable monomer represented by the following general formula (6)', comprising the steps of: preparing a compound represented by the following general formula (8); and reacting the compound represented by the general formula (8) with a compound represented by the following general formula (9). (In general formula (8), R ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (8), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (8), n is a natural number from 1 to 3. (In general formula (9), R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａis an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In the general formula (9), A is a leaving group. (In general formula (6)′, R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (6)', n is a natural number from 1 to 3.

19. A method for producing a fluorine-containing polymerizable monomer represented by general formula (6)' below, comprising the steps of: preparing a compound represented by general formula (10) below; and reacting the compound represented by general formula (10) with a compound represented by general formula (11) below. (In general formula (10), R ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (10), X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (10), A is a leaving group. In general formula (10), n is a natural number from 1 to 3.) (In general formula (11), R １ａis a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. (In general formula (6)′, R １ａ is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. A part or all of the hydrogen atoms bonded to the carbon atoms in the alkyl group may be substituted with fluorine atoms and / or chlorine atoms. ２ａ is an alkylene group which may have a linear, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. ２ｂ is an alkylene group which may have a straight-chain, branched or cyclic structure, an aromatic ring, an ester, a carbonyl, an ether, an amide, an amine, or a composite substituent thereof, a part of which may be fluorinated and / or chlorinated. In general formula (6)', X is a hydroxyl group, an alkoxy group, an oxycarbonyl group, an oxysulfonyl group, an oxycarboxy group, or a hydrogen atom. In general formula (6)', n is a natural number from 1 to 3.

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