JP5682773B2 - Fluorosurfactant, coating composition using the same, and resist composition - Google Patents

Description

  The present invention can be applied to various coating fields where high surface smoothness is required, or coating fields that require precision coating and require high speed, high shearing coating methods such as spin coating and spray coating. Photolithography process using photoresist that is sensitive to radiation such as UV, far UV, excimer laser light, X-rays, in particular, semiconductor manufacturing process such as LSI and IC, manufacturing of substrates such as liquid crystal and thermal head, various magnetics The present invention relates to a fluorine-containing surfactant which can be suitably used in the production of recording media such as discs, CDs and DVDs, the production of PS plates, and other photofabrication processes, and has low accumulation in the environment and living body, and a composition thereof.

  In various coating fields, surfactants called various leveling agents such as hydrocarbons, silicones, and fluorines have been used for the purpose of improving the homogeneity and smoothness of the resulting coating film. . Among them, fluorine-based surfactants are widely used because of their high surface tension reducing ability and low contamination after coating.

  As such a fluorine-based surfactant, a method using a polymer having a polymer unit having an alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom has been proposed (for example, , See Patent Document 1). In particular, it has been shown that a surfactant using a perfluoroalkyl group having 8 or more carbon atoms is excellent in performance as a leveling agent due to its ability to lower the surface tension, but the number of carbon atoms is 6 or less. In the case of a surfactant having a perfluoroalkyl group, it is difficult to maintain its performance, and there is a problem that the surface tension reducing ability further decreases as the number of carbon atoms decreases.

  However, in recent years, compounds having a perfluoroalkyl group having 8 carbon atoms decompose to produce perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA) having high accumulation in the environment and living body. It became clear to get. It has also been clarified that a compound having a perfluoroalkyl group having more carbon atoms than 8 can produce a compound having higher accumulation in the environment and living body. Therefore, the market demands a fluorinated alkyl group having 6 or less carbon atoms and a chain length as short as possible, for example, 4 or less carbon atoms, which cannot generate them due to the structure. As described above, as the chain length becomes shorter, it becomes difficult to achieve both performance as a surfactant.

JP-A-10-230154

  The problem to be solved by the present invention is that a surfactant having a fluorinated alkyl group having 4 or less carbon atoms is as high as or higher than a surfactant having a fluorinated alkyl group having 8 or more carbon atoms. It is to provide a fluorosurfactant that can be used as a leveling agent having a surface tension reducing ability. Moreover, it is providing the coating composition and resist composition using this fluorine-type surfactant.

  As a result of diligent research, the present inventors have found that a fluorinated polymerizable monomer having a fluorinated alkyl group having 4 or less carbon atoms and an ethylenic double bond and a non-fluorinated polymerizable monomer are co-polymerized. In the polymer, a fluorosurfactant comprising a block copolymer having a polymer segment of the fluoropolymeric monomer and a polymer segment of the non-fluoropolymeric monomer, the fluorosurfactant The fluorine atom content in a specific range includes a fluorinated polymerizable monomer having a fluorinated alkyl group having 8 or more carbon atoms and an ethylenic double bond, and a non-fluorinated polymerizable monomer. The present invention has been completed by discovering that it has a surface tension reducing ability equivalent to or higher than that of a normal random copolymer and is effective as a low-level fluorine leveling agent in terms of accumulation in the environment and living body.

That is, the present invention relates to a polymer segment comprising a fluorinated polymerizable monomer (m1) having a fluorinated alkyl group having 4 or less carbon atoms and an ethylenic double bond, and a non-fluorinated polymerizable monomer ( a block copolymer comprising a polymer segment comprising m2) , wherein the block copolymer is an atom transfer radical using an alkyl ester of 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms those prepared by polymerization or one the block copolymer of the fluorine atom content is to provide a fluorine-based surfactant, which is a 4 to 40 wt%.

  Moreover, this invention provides the coating composition and resist composition containing the said fluorine-type surfactant.

  The fluorosurfactant of the present invention uses a short-chain perfluoroalkyl group having 4 or less carbon atoms and is a safe product with low accumulation in the environment and living body. In addition, when the fluorosurfactant of the present invention is used as an additive for a coating composition or a resist composition, in a coating field requiring a high-speed, high-shearing coating method such as spin coating or spray coating. High surface smoothness can be realized.

FIG. 1 is an IR spectrum of the fluorosurfactant (1) synthesized in Example 1. FIG. 2 is a ¹ H-NMR spectrum of the fluorosurfactant (1) synthesized in Example 1. FIG. 3 is a GPC chart of the fluorosurfactant (1) synthesized in Example 1.

  As the fluorine-based polymerizable monomer (m1) having a fluorinated alkyl group having 4 or less carbon atoms and an ethylenic double bond used in the present invention, a fluorinated alkyl group having 4 or less carbon atoms in the molecule and Any compound having an ethylenically unsaturated group can be used without particular limitation. The fluorinated alkyl group having 4 or less carbon atoms is a perfluoroalkyl group having 1 to 4 carbon atoms or a partially fluorinated alkyl group in which a part of hydrogen atoms are fluorine atoms. A perfluoroalkyl group is preferable because of its high effect. Furthermore, the greater the number of carbon atoms, the better, and those with 4 carbon atoms are particularly preferred.

  The fluorine-based polymerizable monomer (m1) is a (meth) acrylic ester from the viewpoints of availability of raw materials, ease of controlling compatibility with blending components in various coating compositions, or polymerization reactivity. A compound having a group is suitable, and specific examples include fluorinated (meth) acrylates represented by the general formula (1).

  More preferable examples of the fluorine-based polymerizable monomer (m1) include compounds represented by the following formulas (1-1) to (1-4).

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid.

  Examples of the non-fluorinated monomer (m2) used in the present invention include an ethylenically unsaturated monomer having an oxyalkylene group and an ethylenically unsaturated monomer having an alkyl group. Examples of the ethylenically unsaturated monomer having an oxyalkylene group include a monomer having an oxyalkylene group represented by the following general formula (2).

（式中、Ｒ^３は水素原子又はメチル基であり、Ｘ及びＹはそれぞれ独立のアルキレン基であり、ｎ及びｍはそれぞれ０または１以上の整数であり、かつｎとｍとの合計は１以上であり、Ｚは水素原子又は炭素原子数１〜６のアルキル基である。）

(Wherein R ³ is a hydrogen atom or a methyl group, X and Y are each independently an alkylene group, n and m are each 0 or an integer of 1 or more, and the sum of n and m is 1) And Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In addition, although X and Y in the said General formula (2) are alkylene groups, this alkylene group may have a substituent. Specific examples of the —O— (XO) _n — (YO) _m — moiety include, for example, ethylene glycol in which the number of repeating units n is 1 and m is 0, and X is ethylene, and the number of repeating units n is 1. In which m is 0 and X is propylene, the number of repeating units n is 1 and m is 0 and X is butylene glycol in which X is butylene, the number of repeating units n is an integer of 1 or more and m is Polyethylene glycol in which X is 0 and X is ethylene, polypropylene glycol in which the repeating unit number n is an integer of 1 or more and m is 0, and X is 1-methylethylene (propylene), repeating unit number n and Copolymerization of ethylene oxide and propylene oxide in which m is an integer of 1 or more and X or Y is ethylene and the other is 1-methylethylene (propylene) Examples include polyalkylene glycols such as coalescence. In addition, the thing of 1-100 of the polymerization degree of these polyalkylene glycols, ie, the sum total of n and m in General formula (2), is preferable.

  When the number of repeating units n is 1 and m is 0, the ethylenically unsaturated monomer having an oxyalkylene group is a mono (meth) acrylic alkylene glycol such as ethylene glycol, propylene glycol, or butylene glycol. Acid ester, mono (meth) acrylic acid ester of alkylene glycol whose non- (meth) acrylic acid ester is capped with an alkyl group having 1 to 6 carbon atoms, and the total number of repeating units n and m is When it is an integer of 2 or more, the end of the poly (alkylene glycol) mono (meth) acrylate, which is not the (meth) acrylate ester of the poly (alkylene glycol) mono (meth) acrylate, has 1 to 6 carbon atoms. And the like sealed with an alkyl group. Examples of commercially available ethylenically unsaturated monomers having an oxyalkylene group include “NK Ester M-20G”, “NK Ester M-40G”, and “NK Ester M-” manufactured by Shin-Nakamura Chemical Co., Ltd. "90G", "NK ester M-230G", "NK ester AM-90G", "NK ester AMP-10G", "NK ester AMP-20G", "NK ester AMP-60G", " "Blemmer PE-90", "Blemmer PE-200", "Blemmer PE-350", "Blemmer PME-100", "Blemmer PME-200", "Blemmer PME-400", "Blemmer PME-4000", "Blemmer PP-1000 "," Blemmer PP-500 "," Blemmer PP-800 "," Blemmer 70 " EP-350B "," Blemmer 55PET-800 "," Blemmer 50POEP-800B "," Blemmer 10PPB-500B "," Blemmer NKH-5050 "," Blemmer AP-400 "," Blemmer AE-350 "and the like. . These ethylenically unsaturated monomers having an oxyalkylene group can be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer having an alkyl group that can be used as the non-fluorinated monomer (m2) include monomers represented by the following general formula (3).

（式中、Ｒ^４は水素原子又はメチル基であり、Ｒ^５は炭素原子数１〜１８の直鎖状、分岐状又は環構造を有するアルキル基である。）

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)

The above general formula (3) in R ⁵ is a straight-chain having 1 to 18 carbon atoms, is an alkyl group having a branched or cyclic structure, the alkyl group, an aliphatic or aromatic hydrocarbon It may have a substituent such as a group or a hydroxyl group. Specific examples of the ethylenically unsaturated monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Alkyl having 1 to 18 carbon atoms in (meth) acrylic acid such as octyl acid, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate Esters: dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acryl Such as chromatography bets, etc. (meth) bridging cyclic alkyl ester having 1 to 18 carbon atoms of acrylic acid. These ethylenically unsaturated monomers having an alkyl group can be used alone or in combination of two or more.

  The method for producing the fluorosurfactant of the present invention is not particularly limited, and includes a polymer segment composed of a fluoropolymerizable monomer (m1) and a non-fluorine polymerizable monomer (m2). Living radical polymerization is preferred from the viewpoint of easy control of the polymerization reaction for obtaining a block copolymer comprising polymerized segments.

  In general, in living radical polymerization, a dormant species whose active polymerization end is protected by an atom or an atomic group reversibly generates a radical and reacts with the monomer, whereby the growth reaction proceeds and the first monomer is consumed. However, the growth terminal can react with the second monomer added sequentially without losing the activity, and the block polymer can be obtained. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavage radical polymerization (RAFT), radical polymerization via nitroxide (NMP), radical polymerization using organic tellurium (TERP), etc. Is mentioned. There is no particular restriction as to which of these methods is used, but the above ATRP is preferable from the viewpoint of ease of control. ATRP is polymerized using an organic halide or a sulfonyl halide compound as an initiator, and a metal complex composed of a transition metal compound and a ligand as a catalyst.

  An organic halogenated compound can be used for the polymerization initiator used in the ATRP. Specifically, 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α, α′-dichloroxylene, α, α′-dibromoxylene, hexakis (α- 1 to 6 carbon atoms of bromomethyl) benzene, a 2-halogenated carboxylic acid having 1 to 6 carbon atoms (for example, 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) Examples include alkyl esters. Moreover, as a more specific example of a C1-C6 alkyl ester of a C1-C6 2-halogenated carboxylic acid, for example, methyl 2-chloropropionate, ethyl 2-chloropropionate, Examples include methyl 2-bromopropionate and ethyl 2-bromoisobutyrate.

The transition metal compound used in the ATRP is represented by M ^{n +} X _n . Transition metal M ^{n +} is Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ³⁺ , W ²⁺ , W ³⁺ , Rh ³⁺ , Rh ⁴⁺ , Co ⁺ , Co ²⁺ , Re ²⁺ , Re ³⁺ , Ni ⁰ , Ni ⁺ , Mn ³⁺ , Mn ⁴⁺ , V ²⁺ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ And Ag ²⁺ . X is a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, (S0 ₄ ) _1/2 , (P0 ₄ ) _1/3 , (HP0 ₄ ) _1/2 , (H ₂ P0 ₄ ), triflate , Hexafluorophosphate, methane sulfonate, aryl sulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents aryl, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R ² is 1 to 5 hydrogen atom or halogen. It represents a linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) which may be substituted once (preferably 1 to 3 times with fluorine or chlorine). Further, n represents a formal charge on the metal and is an integer of 0 to 7.

  Although it does not specifically limit as said transition metal complex, As a preferable thing, the transition metal complex of 7,8,9,10,11 is still more preferable as zero valent copper, monovalent copper, divalent ruthenium. A complex of divalent iron or divalent nickel may be mentioned.

  The compound having a ligand capable of coordinating with a transition metal is a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom that can be coordinated with the transition metal via a σ bond. A compound having two or more carbon atoms capable of coordinating with a transition metal via a π bond, a compound having a ligand capable of coordinating with a transition metal via a μ bond or η bond Is mentioned.

  Specific examples of the compound having a ligand include, for example, when the central metal is copper, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexa And a complex with a ligand such as polyamine such as methyltris (2-aminoethyl) amine. Examples of the divalent ruthenium complex include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzeneruthenium, dichlorop-cymenruthenium, dichloro (norbornadiene) ruthenium, Examples include cis-dichlorobis (2,2′-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium, and carbonylchlorohydridotris (triphenylphosphine) ruthenium. Furthermore, examples of the divalent iron complex include a bistriphenylphosphine complex and a triazacyclononane complex.

  In the living radical polymerization, it is preferable to use a solvent. Examples of the solvent used include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; toluene, Aromatic solvents such as xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methanol, ethanol and isopropanol; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. These solvents can be used alone or in combination of two or more.

  In the production of the fluorosurfactant of the present invention, in the presence of a polymerization initiator, a transition metal compound, a compound having a ligand capable of coordinating with the transition metal, and a solvent, a fluoropolymeric monomer. After subjecting the body (m1) to living radical polymerization, the non-fluorinated polymerizable monomer (m2) is added and further living radical polymerized, or the non-fluorinated polymerizable monomer (m2) is living radically polymerized. After that, it is preferable to take one of the methods of living radical polymerization of the fluorine-based polymerizable monomer (m1).

  The polymerization temperature in the living radical polymerization is preferably in the range of room temperature to 120 ° C.

  Further, when the fluorosurfactant of the present invention is produced by living radical polymerization, the metal resulting from the transition metal compound used in the polymerization may remain in the fluorosurfactant. Therefore, when used in semiconductor applications such as a photoresist composition that causes a problem when the metal remains, it is preferable to remove the residual metal using activated alumina or the like after the polymerization reaction.

  The number average molecular weight (Mn) of the fluorosurfactant of the present invention is preferably 3,000 or more, and more preferably 5,000 to 100,000. When the number average molecular weight (Mn) is in this range, compatibility with other compounding components when the fluorosurfactant of the present invention is added to a resin composition such as a coating composition is good, Leveling can be achieved. In addition, the measurement conditions of a number average molecular weight (Mn) are described in an Example.

  The fluorine atom content in the fluorosurfactant of the present invention is in the range of 4 to 40% by mass, more preferably in the range of 5 to 35% by mass, and still more preferably in the range of 6 to 25% by mass. When the fluorine atom content is less than 4% by mass, sufficient leveling performance is not exhibited, and it is difficult to obtain a smooth coating film. On the other hand, when the fluorine atom content exceeds 40% by mass, the compatibility with other resins is lowered, and there are problems such as turbidity and unevenness in the coating film.

  The coating composition of the present invention uses the above-described fluorosurfactant of the present invention as an additive. The amount of the fluorosurfactant added in the coating composition varies depending on the type of coating resin, the coating method, the target film thickness, etc. 0001-10 mass parts is preferable, 0.001-5 mass parts is more preferable, 0.01-2 mass parts is further more preferable. If the amount of the fluorosurfactant added is within this range, the surface tension can be sufficiently lowered, the intended leveling property can be obtained, and the occurrence of problems such as foaming during coating can be suppressed.

  By using the fluorosurfactant of the present invention as an additive of the coating composition, it can accumulate to the environment and living organisms compared to conventional fluorosurfactants having a perfluoroalkyl group having 8 or more carbon atoms. A coating composition that exhibits a high leveling property even in a coating method that is low and equivalent to or higher than a conventional fluorosurfactant having a perfluoroalkyl group having 8 or more carbon atoms, that is, high speed and high shearing force. Can be provided. Examples of such a coating composition include various coating compositions and photosensitive resin compositions as useful coating compositions.

  Examples of the paint composition include petroleum resin paints, shellac paints, rosin paints, cellulose paints, rubber paints, rubber paints, lacquer paints, cashew resin paints, oil resin vehicle paints and the like; phenol resins Paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, paints using fluororesin paints, etc. It is done.

  In the coating composition, if necessary, colorants such as pigments, dyes, and carbon; inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; Organic fine powders such as fatty acids, polyacrylic resins, polyethylene; various additives such as light resistance improvers, weather resistance improvers, heat resistance improvers, antioxidants, thickeners, antisettling agents may be added as appropriate Is possible. Furthermore, as for the coating method, any method can be used as long as it is a publicly known and publicly used coating method, for example, a roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dipping coating, spray coating, etc. Is mentioned.

  The photosensitive resin composition changes its physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin when irradiated with light such as visible light and ultraviolet light. Among these photosensitive resin compositions, resist compositions (photoresist compositions, color resist compositions for color filters, etc.) are required to have a high leveling property. Usually, in photolithography relating to semiconductors or liquid crystals, a resist composition is applied onto a silicon wafer or a glass substrate on which various metals are vapor-deposited by spin coating with high shearing force so as to have a thickness of about 1 to 2 μm. Is common. At this time, if the coating film thickness fluctuates or coating unevenness commonly referred to as striation occurs, the linearity and reproducibility of the pattern deteriorates, resulting in a problem that a resist pattern having the desired accuracy cannot be obtained. . Recently, other problems related to various leveling such as dripping marks, overall unevenness, and a bead phenomenon in which the edge portion becomes thicker than the central portion have been highlighted. As resist patterns become finer, silicon wafers have larger diameters, and glass substrates for liquid crystals are becoming larger due to higher integration of semiconductor elements, it is important to suppress such fluctuations in coating thickness and the occurrence of striations. It is a difficult issue. In recent years, it has been necessary to strictly control the fluctuations in the coating film thickness and the occurrence of striations from the viewpoints of improving the productivity of semiconductors and liquid crystal elements and increasing the functionality.

  Here, the fluorosurfactant of the present invention can exhibit a high leveling property and form a uniform coating film by using it as an additive of this photosensitive resin composition, particularly a resist composition. Therefore, the above problems can be solved.

  In general, a resist composition is composed of a surfactant and a photoresist agent. The photoresist agent is composed of (1) an alkali-soluble resin, (2) a radiation-sensitive material (photosensitive material), (3) a solvent, and necessary. Depending on (4) other additives.

  Examples of the (1) alkali-soluble resin used in the resist composition of the present invention include resins that are soluble in an alkaline solution that is a developer used for patterning a resist. Examples of the alkali-soluble resin include at least one selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, phloroglicinol, and hydroquinone, and alkyl-substituted or halogen-substituted aromatic compounds, formaldehyde, acetaldehyde, Novolak resins obtained by condensing with aldehyde compounds such as benzaldehyde, vinylphenol compounds such as o-vinylphenol, m-vinylphenol, p-vinylphenol, α-methylvinylphenol, and polymers of these halogen-substituted compounds, or Copolymers, acrylic acids such as acrylic acid, methacrylic acid, and hydroxyethyl (meth) acrylate, or methacrylic acid polymers or copolymers, polyvinyl alcohol, and various other resins Quinonediazide group through a portion of the hydroxyl groups, naphthoquinone azido group, an aromatic azide group, modified resin obtained by introducing a radioactive-sensitive groups, such as aromatic cinnamoyl group. These alkali-soluble resins can be used alone or in combination of two or more.

  Furthermore, as the alkali-soluble resin, it is possible to use a urethane resin containing an acidic group such as carboxylic acid or sulfonic acid in the molecule, and this urethane resin can be used in combination with the above alkali-soluble resin. It is.

  (2) Radioactive substance (photosensitive substance) used in the resist composition of the present invention is mixed with the above alkali-soluble resin, and ultraviolet rays, far ultraviolet rays, excimer laser light, X-rays, electron beams, ion rays, Any substance that changes the solubility of an alkali-soluble resin in a developer by irradiation with molecular beam, γ-ray, or the like can be used.

  Examples of the radiation sensitive substances include quinonediazide compounds, diazo compounds, diazide compounds, onium salt compounds, halogenated organic compounds, mixtures of halogenated organic compounds and organometallic compounds, organic acid ester compounds, and organic acid amide compounds. , Organic acid imide compounds, and poly (olefin sulfone) compounds described in JP-A-59-152.

  Examples of the quinonediazide compounds include 1,2-benzoquinoneazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, 1-naphthoquinonediazide-4-sulfonic acid ester, 2,1-naphthoquinonediazide-5-sulfonic acid ester, other 1,2-benzoquinone azido-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 2,1-naphthoquinonediazide-4-sulfonic acid chloride, sulfonic acid chloride of quinonediazide derivatives such as 2,1-naphthoquinonediazide-5-sulfonic acid chloride, etc. It is done.

  Examples of the diazo compound include a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the condensate. Examples thereof include diazo resin inorganic salts which are reactive organisms, diazo resin organic salts which are reaction products of the above condensates and sulfonic acids, as described in USP 3,300,309.

  Examples of the azide compound and diazide compound include azidochalconic acid, diazidobenzalmethylcyclohexanones and azidocinnamylideneacetophenones described in JP-A No. 58-203438, Journal of Chemical Society of Japan No. 12, an aromatic azide compound or an aromatic diazide compound described in p1708-1714 (1983).

  Any halogenated organic compound can be used as the halogenated organic compound. Specific examples include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, and halogen-containing benzophenones. Compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing trizole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, Various compounds such as halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, sulfenyl halide compounds, and further, for example, tris (2,3-dibromopropyl) phosphate, tris (2, -Dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis (bromo Ethyl ether) tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, Compounds used as halogen-based flame retardants such as 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, organic chloro-based compounds such as dichlorophenyltrichloroethane Compounds which are used as drugs may also be used.

  Examples of the organic acid esters include carboxylic acid esters and sulfonic acid esters. Examples of the organic acid amide include carboxylic acid amides and sulfonic acid amides. Furthermore, examples of the organic acid imide include carboxylic acid imide and sulfonic acid imide. These radiation sensitive substances can be used alone or in combination of two or more.

  In the resist composition of the present invention, the blending ratio of the radiation sensitive substance is preferably in the range of 1 to 100 parts by mass and more preferably in the range of 3 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

  Examples of the (3) solvent used in the resist composition of the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone; methanol, ethanol, alcohols such as n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, pro Alcohol ethers such as lenglycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate , Esters such as propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionic acid Monocarboxylic such as propyl, butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate Esters: Cellosolve acetates such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propylene glycols such as butyl ether acetate; diethylene glycols such as diethyler glycol monomethyl ether, diethyler glycol monoethyl ether, diethyler glycol dimethyl ether, diethyler glycol diethyl ether, and diethyler glycol methyl ethyl ether; trichloroethylene; Freon solvent, Halogenated hydrocarbons such as HCFC and HFC; perfluorinated solvents such as perfluorooctane; aromatics such as toluene and xylene; dimethylacetamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone, etc. Examples of the solvent include polar solvents, and solvents described in the book "Solvent Pocket Handbook" (Organic Synthetic Chemistry Association, Ohmsha). These solvents can be used alone or in combination of two or more.

  Examples of the method for applying the resist composition of the present invention include spin coating, roll coating, dip coating, spray coating, blade coating, curtain coating, and gravure coating. The resist composition is filtered through a filter before application. Thus, solid impurities can be removed.

  As described above, the fluorosurfactant of the present invention is useful as an additive for coating compositions (coating compositions, photosensitive resin compositions, etc.) and is particularly useful for resist compositions. Applications include single-layer or multi-layer coating compositions for the manufacture of halogenated photographic light-sensitive materials, the manufacture of lithographic printing plates, the manufacture of liquid crystal related products such as color filter materials, the manufacture of PS plates, and other photofabrication processes. It can be used as a leveling agent that exhibits excellent smoothness free from pinholes, yuzu skin, coating unevenness, repellency and the like.

  Further, when the fluorosurfactant of the present invention is blended with a paint or coating material containing a fluororesin, the dispersibility of the fluororesin is improved by the action of a fluorinated alkyl group, and not only leveling properties but also fluorine It can also be expected to function as a resin dispersant.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by GPC measurement under the following conditions.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml / min Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl).

(Example 1) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 300 parts by mass of methyl ethyl ketone (hereinafter referred to as “MEK”), 2,2′-bipyridyl 6 .26 parts by mass and 1.98 parts by mass of cuprous chloride were charged and stirred at room temperature for 30 minutes. Then, 63.3 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation) and 3.69 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours. . Subsequently, 3,6.7 parts of 3,3,4,4,5,5,6,6,6-nonafluorohexyl methacrylate (hereinafter referred to as “NFMA”) was added, and the temperature was raised to 60 ° C. for 12 hours. Reacted. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (1) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (1) by GPC, the weight average molecular weight (Mw) was 8,500, the number average molecular weight (Mn) was 7,200, and the degree of dispersion (Mw / Mn) was 1.18. It was. Further, the fluorine atom content of the obtained fluorosurfactant (1) was measured by a combustion ion chromatography method and found to be 18.2%.

(Example 2) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 133 parts by mass of MEK, 8.01 parts by mass of 2,2'-bipyridyl, and cuprous chloride 2 .54 parts by mass was charged and stirred at room temperature for 30 minutes. Thereafter, 14.5 parts by mass of polyethylene glycol monomethyl ether monomethacrylate (“NK Ester M-90G” manufactured by Shin-Nakamura Chemical Co., Ltd.), 15.8 parts by mass of stearyl methacrylate, 5.25 parts by mass of isobutyl methacrylate, 4. 22 parts by mass and 5.00 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours under a nitrogen stream. Next, 37.5 parts by mass of NFMA was added, and the temperature was raised to 60 ° C. and reacted for 12 hours. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (2) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (2) by GPC, the weight average molecular weight (Mw) was 6,800, the number average molecular weight (Mn) was 5,400, and the dispersity (Mw / Mn) was 1.27. It was. Further, the fluorine atom content of the obtained fluorosurfactant (2) was measured by a combustion ion chromatography method and found to be 24.3%.

(Example 3) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 300 parts by mass of MEK, 6.26 parts by mass of 2,2′-bipyridyl and cuprous chloride 1 .98 parts by mass was charged and stirred at room temperature for 30 minutes. Then, 89.8 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation) and 3.69 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours. . Next, 10.2 parts by mass of NFMA was added, and the temperature was raised to 60 ° C. and reacted for 12 hours. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (3) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (3) by GPC, the weight average molecular weight (Mw) was 8,700, the number average molecular weight (Mn) was 7,200, and the dispersity (Mw / Mn) was 1.21. It was. Moreover, it was 4.9% when the fluorine atom content of the obtained fluorosurfactant (3) was measured by the combustion ion chromatography method.

(Example 4) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 90 parts by mass of MEK, 6.26 parts by mass of 2,2′-bipyridyl, and cuprous chloride 1 .98 parts by mass was charged and stirred at room temperature for 30 minutes. Then, 30 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation) and 3.69 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours. Next, 210 parts by mass of MEK and 70 parts by mass of NFMA were added, and the temperature was raised to 60 ° C. and reacted for 12 hours. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (4) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (4) by GPC, the weight average molecular weight (Mw) was 8,200, the number average molecular weight (Mn) was 7,000, and the dispersity (Mw / Mn) was 1.17. It was. Moreover, it was 35.0% when the fluorine atom content of the obtained fluorosurfactant (4) was measured by the combustion ion chromatography method.

(Comparative Example 1) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 300 parts by mass of MEK, 6.26 parts by mass of 2,2′-bipyridyl and cuprous chloride 1 .98 parts by mass was charged and stirred at room temperature for 30 minutes. Then, 93.8 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation) and 3.69 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours. . Next, 6.2 parts by mass of NFMA was added, and the temperature was raised to 60 ° C. and reacted for 12 hours. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C1) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (C1) by GPC, the weight average molecular weight (Mw) was 8,900, the number average molecular weight (Mn) was 7,700, and the dispersity (Mw / Mn) was 1.16. It was. Further, the fluorine atom content of the obtained fluorosurfactant (C1) was measured by a combustion ion chromatography method and found to be 2.6%.

(Comparative Example 2) Synthesis of a block copolymer having a fluorinated alkyl group having 4 carbon atoms In a nitrogen-substituted reaction vessel, 30 parts by mass of MEK, 6.26 parts by mass of 2,2′-bipyridyl, and cuprous chloride 1 .98 parts by mass was charged and stirred at room temperature for 30 minutes. Thereafter, 15 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation) and 3.69 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 40 ° C. for 5 hours. Next, 270 parts by mass of MEK and 85 parts by mass of NFMA were added, and the temperature was raised to 60 ° C. and reacted for 12 hours. To this reaction mixture, 30 parts by mass of activated alumina was added and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C2) as a block polymer. As a result of measuring the molecular weight of the fluorosurfactant (C2) by GPC, the weight average molecular weight (Mw) was 8,200, the number average molecular weight (Mn) was 7,000, and the dispersity (Mw / Mn) was 1.17. It was. Moreover, it was 44.0% when the fluorine atom content of the obtained fluorosurfactant (C2) was measured by the combustion ion chromatography method.

(Comparative example 3) Synthesis of random copolymer having fluorinated alkyl group having 4 carbon atoms Into a nitrogen-substituted reaction vessel, 120 parts by mass of MIBK was charged and heated to 90 ° C while stirring. Thereafter, 63.3 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation), 36.7 parts by mass of NFMA, and tertiary butyl peroxy-2-ethylhexanoate (“NOF CORPORATION“ Perbutyl O ") 4.5 parts by mass in MIBK 80 parts by mass was dropped over 2 hours and further reacted at 90 ° C for 9 hours to obtain a fluorosurfactant (C3) as a random copolymer. It was. As a result of measuring the molecular weight of the fluorosurfactant (C3) by GPC, the weight average molecular weight (Mw) was 8,900, the number average molecular weight (Mn) was 7,600, and the dispersity (Mw / Mn) was 1.17. It was. Moreover, it was 19.0% when the fluorine atom content of the obtained fluorosurfactant (C3) was measured by the combustion ion chromatography method.

Comparative Example 4 Synthesis of Random Copolymer Having a C4 Fluorinated Alkyl Group Into a nitrogen-substituted reaction vessel, 230 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) was charged and stirred. The temperature was raised to 90 ° C. Thereafter, 14.5 parts by mass of NK ester M-90G, 15.8 parts by mass of stearyl methacrylate, 5.25 parts by mass of isobutyl methacrylate, 4.22 parts by mass of methyl methacrylate, 42.5 parts by mass of NFMA, and 2,2′- A solution prepared by dissolving 4 parts by mass of azobis (2-methylbutyronitrile) (hereinafter referred to as “ABNE”) in 110 parts by mass of PGMEA was added dropwise over 2 hours, and the mixture was further reacted at 95 ° C. for 10 hours. A combined fluorosurfactant (C4) was obtained. Moreover, it was 25.0% when the fluorine atom content of the obtained fluorosurfactant (C4) was measured by the combustion ion chromatography method.

(Comparative Example 5) Synthesis of random copolymer having fluorinated alkyl group having 8 carbon atoms Into a nitrogen-substituted reaction vessel, 120 parts by mass of MIBK was charged and heated to 100 ° C while stirring. Thereafter, 68.2 parts by mass of polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation), 3,3,4,4,5,5,6,6,7,7,8,8,9 , 9,10,10,10-heptadecafluorohexyl methacrylate (hereinafter referred to as “HFMA”) 31.8 parts by mass and tertiary butyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation “Perbutyl Oh”) ) A solution prepared by dissolving 4 parts by mass in 80 parts by mass of MIBK was added dropwise over 2 hours, and further reacted at 100 ° C. for 9 hours to obtain a fluorosurfactant (C5) as a random copolymer. Further, the fluorine atom content of the obtained fluorosurfactant (C5) was measured by a combustion ion chromatography method and found to be 18.7%.

(Comparative Example 6) Synthesis of random copolymer having fluorinated alkyl group having 8 carbon atoms In a nitrogen-substituted reaction vessel, 280 parts by mass of isopropyl alcohol, polyethylene glycol monomethyl ether monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “ NK ester M-90G ") 10.4 parts by weight, stearyl methacrylate 11.4 parts by weight, isobutyl methacrylate 3.68 parts by weight, methyl methacrylate 3.05 parts by weight, HFMA 28 parts by weight and azobisisobutyronitrile 10 parts by weight Was dissolved by stirring. The reaction was performed at 100 ° C. for 12 hours to obtain a fluorosurfactant (C6) which is a random copolymer. Moreover, it was 24.0% when the fluorine atom content of the obtained fluorosurfactant (C6) was measured by the combustion ion chromatography method.

  The following measurements and evaluations were performed using the fluorosurfactants (1) to (4) and (C1) to (C6) obtained in Examples 1 to 4 and Comparative Examples 1 to 6.

[Accumulation in the environment and living body]
Those with low possibility of accumulation in the environment and living body were evaluated as “◯”, and those with high possibility were evaluated as “x”.

[Measurement of static surface tension]
Using a self-balancing electro surface tension meter ESB-IV (manufactured by Kyowa Kagaku Co., Ltd.), the solid content of the fluorosurfactant is less than that of propylene glycol monomethyl ether acetate, which is a general solvent for resist compositions. The solution was prepared so that it might become 0.1 mass%, and static surface tension was measured by the Wilhelmy method using the platinum plate at 25 degreeC about the solution.

[Preparation of resist composition]
27 parts by mass of a condensate of 2,3,4-trihydroxybezophenone and orthonaphthoxydiazide-5-sulfonyl chloride and 100 parts by mass of a novolac resin obtained by condensing cresol and formaldehyde A solution is prepared by dissolving in 400 parts by mass of glycol monomethyl ether acetate, and 0.1 parts by mass of a fluorosurfactant is added to 100 parts by mass of the above condensate and novolak resin. A resist composition was prepared by microfiltration with a polytetrafluoroethylene (PTFE) filter. As Comparative Example 7, a resist composition to which no fluorosurfactant was added was also prepared.

[Compatibility with resin]
The appearance of the resist composition obtained above was visually observed, and the compatibility of each fluorosurfactant with the resin was evaluated according to the following criteria.
○: Uniform and not turbid.
X: Turbidity occurs.

[Evaluation of coating properties]
The resist composition obtained above was spin-coated on a chrome-treated glass substrate having a diameter of 8 inches at a rotational speed of 500 rpm or 3,000 rpm, and then heat-dried at 110 ° C. for 3 minutes to obtain a film thickness of 1.5 μm. A wafer having a resist film was obtained. As a result of visual observation of the surface of the obtained resist film using a sodium lamp, the presence or absence of occurrence of irregularities (coating unevenness) on the coating film surface and streaks (radiation) that can be radiated from the center of the wafer are evaluated as applicability. Were evaluated according to the following criteria. In addition, about the striation, only what was spin-coated at 3,000 rpm was evaluated.

(Applicability: uneven application)
○: Application unevenness was not observed.
Δ: Some coating unevenness is observed, but it is an acceptable level.
X: Many coating unevenness is observed and is an unacceptable level.

(Applicability: striation)
○: The occurrence of a story is not recognized.
Δ: Slightly recognized storage
X: The striation is recognized remarkably.

  Table 1 shows the measurement and evaluation results obtained above.

  From the results shown in Table 1, it was found that the static surface tension of the fluorinated surfactants of Examples 1 to 4 of the present invention was greatly reduced and the leveling property was improved. Moreover, it turned out that the resist composition using the fluorinated surfactant of Examples 1-4 of this invention has favorable applicability | paintability, and can also suppress generation | occurrence | production of a coating nonuniformity and striation.

  On the other hand, it was found that the fluorinated surfactants of Comparative Examples 1 and 3 to 6 have a slight decrease in static surface tension and cannot be expected to improve leveling properties. Moreover, it turned out that the resist composition using the fluorinated surfactant of Comparative Examples 1 and 3 to 6 has poor applicability and cannot sufficiently suppress the occurrence of coating unevenness and striation. Furthermore, although the static surface tension of the fluorinated surfactant of Comparative Example 2 was greatly reduced, when added to the resist composition, the compatibility with the resin in the composition was poor, resulting in turbidity and uneven coating. Also found to occur.

Claims (8)

A polymer segment comprising a fluorinated polymerizable monomer (m1) having a fluorinated alkyl group having 4 or less carbon atoms and an ethylenic double bond, and a polymer segment comprising a non-fluorinated polymerizable monomer (m2) The block copolymer is produced by atom transfer radical polymerization using an alkyl ester having 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms as a polymerization initiator. fluorosurfactant having been either one fluorine atom content of the block copolymer is characterized by a 4 to 40 wt%. An alkyl ester of 1 to 6 carbon atoms of a 2-halogenated carboxylic acid having 1 to 6 carbon atoms is methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate or 2-bromoisobutyric acid 2. The fluorosurfactant according to claim 1, which is ethyl. The fluorine-based surfactant according to claim 1, wherein the alkyl ester having 1 to 6 carbon atoms of the 2-halogenated carboxylic acid having 1 to 6 carbon atoms is ethyl 2-bromoisobutyrate. The fluorine-based surfactant according to claim 1, wherein the fluorine-based polymerizable monomer (m1) is a monomer selected from at least one of the following general formula (1).

The fluorine-free polymerizable monomer (m2) is a fluorocarbon surfactant of claim 1 Symbol placement is a monomer having an oxyalkylene group represented by the following general formula (2).

(Wherein R ³ is a hydrogen atom or a methyl group, X and Y are each independently an alkylene group, n and m are each 0 or an integer of 1 or more, and the sum of n and m is 1) And Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) The non-fluorine-containing polymerizable monomer (m2) is a monomer having an oxyalkylene group represented by the general formula (2) and a monomer represented by the following general formula (3). 5. The fluorosurfactant according to 5 .

(In the formula, R ⁴ is a hydrogen atom or a methyl group, and R ⁵ is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)   A coating composition comprising the fluorosurfactant according to any one of claims 1 to 6.   A resist composition containing the fluorosurfactant according to any one of claims 1 to 6.

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