JP5923878B2 - 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 are decomposed, so that perfluorooctane sulfonic acid (hereinafter abbreviated as “PFOS”) or perfluoro, which has high accumulation in the environment and living organisms. It was revealed that octanoic acid (hereinafter abbreviated as “PFOA”) can be produced. 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. In addition, a fluorosurfactant having a C8 perfluoroalkyl group is foamed by the action of the fluorosurfactant when blended in various paints and uniformly stirred and mixed, and the foam is long. There was also a problem that time did not disappear.

  Under the circumstances as described above, the market has no risk of producing PFOS or PFOA having a high accumulation property in the environment and living body, and has an excellent leveling property that is the inherent performance of the surfactant, and There has been a demand for a surfactant having a low defoaming property and having a high defoaming property that defoams in a short time even when foamed.

JP-A-10-230154

  The problem to be solved by the present invention is that even if the surfactant has a fluorinated alkyl group having 6 or less carbon atoms, the leveling is equal to or higher than the surfactant having a fluorinated alkyl group having 8 or more carbon atoms. It is to provide a fluorosurfactant having an anti-foaming property. 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 out from a copolymer obtained by copolymerizing a monomer having a fluorinated alkyl group having 6 or less carbon atoms and a non-fluorinated monomer by living radical polymerization in the coexistence. Fluorosurfactant is structurally free from the risk of producing PFOS or PFOA with high accumulation in the environment and living body, has excellent leveling properties that are the original performance of the surfactant, and has foaming properties. The present invention was completed by finding that it has a low defoaming property and has an excellent defoaming property that defoams in a short time even when foaming.

That is, the present invention essentially includes a monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond by an oxygen atom) and a non-fluorine monomer (m2). as a monomer component, a process for producing the monomer (m1) and fluorine-containing surface active agent for causing atom transfer radical polymerization engaged in the coexistence of (m @ 2).

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

  Since the fluorosurfactant of the present invention does not have a fluorinated alkyl group having 8 or more carbon atoms, it is a safe product with low accumulation in the environment and living body. Further, when the fluorosurfactant of the present invention is added as a leveling agent to a coating composition or resist composition, an effect as an excellent leveling agent is obtained, and since the defoaming property is high, the handling property is extremely excellent. In addition, it can be applied to various coating methods such as spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, gravure coating, etc., and a coating film with high surface smoothness can be obtained. .

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

  The fluorine-based surfactant of the present invention includes a monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond with an oxygen atom) and a non-fluorinated monomer (m2). ) As an essential monomer component, and is produced by living radical polymerization of the monomers (m1) and (m2) in the coexistence.

  The fluorine-based monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond with an oxygen atom) used in the present invention includes fluorine having 6 or less carbon atoms in the molecule. Any compound having an alkyl group (including those having an ether bond with an oxygen atom) and a polymerizable unsaturated group can be used without particular limitation. The fluorinated alkyl group having 6 or less carbon atoms is a perfluoroalkyl group having 1 to 6 carbon atoms or a partially fluorinated alkyl group in which a part of hydrogen atoms are fluorine atoms, and has 6 carbon atoms. The following means that the number of carbon atoms bonded to the fluorine atom is 6 or less. Of these fluorinated alkyl groups, perfluoroalkyl groups are preferred because of their high effect as surfactants. Furthermore, it is preferable that the number of carbon atoms is large, and those having 4 to 6 carbon atoms are particularly preferable.

  As a polymerizable unsaturated group which the said fluorine-type monomer (m1) has, a (meth) acryloyl group, a vinyl group, a maleimide group, etc. are mentioned. Among these, a (meth) acryloyl group is preferable because of easy availability of raw materials, ease of controlling compatibility with blending components in various coating compositions, and good polymerization reactivity. Specific examples having the (meth) acryloyl group include a monomer represented by the general formula (1). Moreover, the said fluorine-type monomer (m1) may use only 1 type, or may use 2 or more types together.

（上記一般式（１）中、Ｒ^１は水素原子、フッ素原子、メチル基、シアノ基、フェニル基、ベンジル基又は−Ｃ_ｎＨ_２ｎ−Ｒｆ’（ｎは１〜８の整数を表し、Ｒｆ’は下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）を表し、Ｘは、下記式（Ｘ−１）〜（Ｘ−１０）のいずれか１つの基を表し、Ｒｆは下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or —C _n H _2n —Rf ′ (n represents an integer of 1 to 8, Rf 'Represents any one group of the following formulas (Rf-1) to (Rf-7)), and X represents any one group of the following formulas (X-1) to (X-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).

（上記式（Ｘ−１）、（Ｘ−３）、（Ｘ−５）、（Ｘ−６）及び（Ｘ−７）中のｎは１〜８の整数を表す。上記式（Ｘ−８）、（Ｘ−９）及び（Ｘ−１０）中のｍは１〜８の整数を表し、ｎは０〜８の整数を表す。上記式（Ｘ−６）及び（Ｘ−７）中のＲｆ’’は下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the above formulas (X-1), (X-3), (X-5), (X-6) and (X-7), n represents an integer of 1 to 8. The above formula (X-8 M in (X-9) and (X-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (X-6) and (X-7) Rf ″ represents any one of the following formulas (Rf-1) to (Rf-7).)

（上記式（Ｒｆ−１）及び（Ｒｆ−２）中のｎは１〜６の整数を表す。上記式（Ｒｆ−３）中のｎは２〜６の整数を表す。上記式（Ｒｆ−４）中のｎは４〜６の整数を表す。上記式（Ｒｆ−５）中のｍは１〜５の整数であり、ｎは０〜４の整数であり、かつｍ及びｎの合計は１〜５である。上記式（Ｒｆ−６）中のｍは０〜４の整数であり、ｎは１〜４の整数であり、ｐは０〜４の整数であり、かつｍ、ｎ及びｐの合計は１〜５である。）

(In the formulas (Rf-1) and (Rf-2), n represents an integer of 1 to 6. In the formula (Rf-3), n represents an integer of 2 to 6. The formula (Rf- N in 4) represents an integer of 4 to 6. m in the above formula (Rf-5) is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is M in the above formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and m, n and The total of p is 1-5.)

  More specific examples of the fluorine-based monomer (m1) include compounds represented by the following formulas (m1-1) to (m1-15).

  In addition, the fluorine-based monomer (m1) used in the present invention has a good balance between leveling properties and antifoaming properties, so that it has a fluorinated alkyl group having 4 carbon atoms and 6 carbon atoms. It is preferable to use a monomer having a fluorinated alkyl group.

  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.

  As a non-fluorine-type monomer (m2) used by this invention, the monomer (m2-1) which has an oxyalkylene group, the monomer (m2-2) which has an alkyl group, etc. are mentioned, for example. Here, examples of the polymerizable unsaturated group possessed by the non-fluorinated monomer (m2) include a (meth) acryloyl group, a vinyl group, and a maleimide group. In the case where the polymerizable unsaturated group is a (meth) acryloyl group, the copolymerizability is good, so the polymerizable unsaturated group of the non-fluorinated monomer (m2) is also a (meth) acryloyl group. It is preferable that

  Examples of the monomer (m2-1) having an oxyalkylene group include monomers represented by the following general formula (2).

（式中、Ｒ^２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、Ｒ^３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 ² 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 R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  X and Y in the general formula (2) are alkylene groups, and the alkylene groups include those having a substituent. Specific examples of the -O- (XO) n- (YO) m- moiety include an ethylene glycol residue in which the number of repeating units n is 1, m is 0, and X is ethylene, and the number of repeating units n is 1. A propylene glycol residue in which m is 0 and X is propylene, a repeating unit number n is 1 and m is 0, and a butylene glycol residue in which X is butylene, and the repeating unit number n is 2 or more Polyethylene glycol residue in which m is 0 and X is ethylene, polypropylene glycol residue in which repeating unit number n is an integer of 2 or more and m is 0, and X is propylene, repeating unit number n And m is an integer of 1 or more, and X or Y is ethylene, and the other is propylene oxide. Group, and the like.

  The polymerization degree of the polyalkylene glycol, that is, the total of n and m in the general formula (2) is preferably in the range of 1-100, more preferably in the range of 2-80, and in the range of 3-50. Is more preferable. In addition, the repeating unit containing X and the repeating unit containing Y may be arrange | positioned at random or a block shape.

R ³ in the general formula (2) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ³ is hydrogen, the monomer is a mono (meth) acrylic ester of alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., and when R ³ has 1 to 6 carbon atoms, alkylene The terminal which is not the (meth) acrylic acid ester of the mono (meth) acrylic acid ester of glycol is sealed with an alkyl group having 1 to 6 carbon atoms.

  Among the monomers (m2-1) having an oxyalkylene group, a monomer having a poly (oxyalkylene) group composed of a plurality of oxyalkylene groups is preferable. As a specific example, polypropylene glycol mono (meta) ) Acrylate, polyethylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene glycol / polypropylene glycol Mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate , Poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate, Polypropylene glycol / polytetramethylene glycol mono (meth) acrylate, Poly (propylene glycol / butylene glycol) mono (meth) acrylate, Polypropylene glycol / polybutylene glycol mono (Meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene glycol mono (meth) acrylate, poly (tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol・ Polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly ( Tylene glycol / trimethylene glycol) mono (meth) acrylate, polyethylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol / trimethylene glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono ( (Meth) acrylate, poly (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, Examples include polybutylene glycol and polytrimethylene glycol mono (meth) acrylate. “Poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a block copolymer of ethylene glycol and propylene glycol. means. The same applies to other items. Among these monomers having an oxyalkylene group, compatibility with other components in the coating composition of the present invention is improved, so that polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Polyethylene glycol / polypropylene glycol mono (meth) acrylate is preferable.

  Moreover, as a commercial item of the monomer (m2-1) which has an oxyalkylene group, for example, “NK ester M-20G”, “NK ester M-40G”, “NK ester” manufactured by Shin-Nakamura Chemical Co., Ltd. M-90G, NK ester M-230G, NK ester AM-90G, NK ester AMP-10G, NK ester AMP-20G, NK ester AMP-60G, manufactured by NOF Corporation “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 70P” P-350B "," Blemmer 55PET-800 "," Blemmer 50POEP-800B "," Blemmer 10PPB-500B "," Blemmer NKH-5050 "," Blemmer AP-400 "," Blemmer AE-350 "and the like. . These monomers having an oxyalkylene group (m2-1) can be used alone or in combination of two or more.

  Examples of the alkyl group-containing monomer (m2-2) that can be used as the non-fluorine-based 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 monomer (m2-2) having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2 An alkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid, such as ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; dicyclopentanyloxylethyl ( (Meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( (Meth) bridging cyclic alkyl ester having 1 to 18 carbon atoms of acrylic acid motor) acrylate. These monomers having an alkyl group (m2-2) can be used alone or in combination of two or more.

  The fluorosurfactant of the present invention contains the above monomers (m1) and (m2) together with the fluoromonomer (m1) and the non-fluorine monomer (m2) as essential monomer components. It can be obtained by living radical polymerization under.

  Here, in general, in living radical polymerization, a dormant species whose active polymerization end is protected by an atom or atomic group reversibly generates a radical and reacts with the monomer, whereby the growth reaction proceeds, and the first monomer becomes The block copolymer can be obtained by reacting with the second monomer added successively without losing the activity of the growing end even if consumed. However, the present invention is characterized in that living radical polymerization is performed in the coexistence of the first monomer and the second monomer, and living radical polymerization is used. The resulting copolymer is a random copolymer having disordered regularity. It is a coalescence.

  Examples of the above-mentioned living radical polymerization include atom transfer radical polymerization (hereinafter abbreviated as “ATRP”), reversible addition-cleavage radical polymerization (RAFT), radical polymerization via nitroxide (NMP), and organic tellurium. Examples include radical polymerization (TERP) to be used. 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, a fluoromonomer (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) It is preferable to add m1) and the non-fluorinated monomer (m2) to carry out living radical polymerization.

  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 weight average molecular weight (Mw) and the number average molecular weight (Mn) of the fluorosurfactant of the present invention are preferably 3,000 or more, and more preferably from 4,000 to 4,000, since the leveling property and defoaming property can be further improved. The range of 100,000 is more preferable, and the range of 5,000 to 50,000 is more preferable. Further, the dispersity (Mw / Mn) of the fluorosurfactant of the present invention is preferably 3 or less, more preferably in the range of 1.0 to 2.5, in order to be excellent in leveling properties and antifoaming properties. The range of 1.0 to 2.2 is more preferable.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[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-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltech Japan Co., Ltd.)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“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
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

  The fluorine atom content in the fluorosurfactant of the present invention is preferably in the range of 4 to 40% by mass, and preferably in the range of 4 to 40% by mass, because good leveling properties with less coating unevenness are obtained and excellent defoaming properties. % Is more preferable, and the range of 6 to 30% by mass is more preferable. The fluorine atom content can be measured by combustion ion chromatography.

  The coating composition of the present invention uses the above-described fluorosurfactant of the present invention as an additive. The addition amount of the fluorosurfactant in the coating composition varies depending on the type of coating resin, the coating method, the target film thickness, and the like, but is 0.1% relative to 100 parts by mass of the solid content in the coating composition. 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-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltech Japan Co., Ltd.)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids with a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

(Monodispersed polystyrene)
“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
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation

Example 1
A reaction vessel purged with nitrogen was charged with 67 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl and 0.305 parts by mass of cuprous chloride and stirred at room temperature for 60 minutes. Then, 2- (nonafluorobutyl) ethyl methacrylate (hereinafter abbreviated as “NFMA”) 3.37 parts by mass, 2- (tridecafluorohexyl) ethyl methacrylate (hereinafter abbreviated as “TFMA”) 3 .33 parts by mass, poly (1,2-oxybutylene) oxypropylene monomethacrylate (manufactured by NOF Corporation "Blenmer 10PPB-500B"; average number of repetitions of oxybutylene 6), 13.3 parts by mass, polyethylene glycol monomethacrylate ( “Blenmer PE-200” manufactured by NOF Corporation; average oxyethylene repeating number 4.5) 20 parts by mass and 0.6 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 60 ° C. for 10 hours in a nitrogen stream. It was. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (1) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (1) by GPC, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 13,000, and the dispersity (Mw / Mn) was 1.31. It was. Moreover, it was 9.1 mass% when the fluorine atom content in the obtained fluorosurfactant (1) was measured by combustion ion chromatography.

(Example 2)
A reaction vessel purged with nitrogen was charged with 26.68 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl and 0.305 parts by mass of cuprous chloride and stirred at room temperature for 60 minutes. Thereafter, 7.04 parts by mass of NFMA, 13.2 parts by mass of poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blenmer 10PPB-500B” manufactured by NOF Corporation), polyethylene glycol monomethacrylate (manufactured by NOF Corporation) “Blemmer PE-200”; average number of repetitions of oxyethylene 4.5) 19.76 parts by mass and 0.6 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 60 ° C. for 10 hours in a nitrogen stream. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (2) as a random copolymer. As a result of measuring the molecular weight of this fluorosurfactant (2) by GPC, the weight average molecular weight (Mw) was 34,300, the number average molecular weight (Mn) was 16,600, and the degree of dispersion (Mw / Mn) was 2.07. It was. Further, the fluorine atom content of the obtained fluorosurfactant (2) was measured by combustion ion chromatography and found to be 9.1% by mass.

(Example 3)
A reaction vessel purged with nitrogen was charged with 26.68 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl and 0.305 parts by mass of cuprous chloride and stirred at room temperature for 60 minutes. Thereafter, 6.36 parts by mass of TFMA, 13.46 parts by mass of poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blenmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions of oxybutylene 6), polyethylene glycol Monomethacrylate (“Blenmer PE-200” manufactured by NOF Corporation; average number of oxyethylene repeats: 4.5) 20.18 parts by mass and ethyl 2-bromoisobutyrate 0.6 parts by mass were added, and the mixture was heated at 60 ° C. under a nitrogen stream. For 10 hours. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (3) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (3) by GPC, the weight average molecular weight (Mw) was 27,800, the number average molecular weight (Mn) was 15,400, and the dispersity (Mw / Mn) was 1.81. It was. Further, the fluorine atom content of the obtained fluorosurfactant (3) was measured by combustion ion chromatography and found to be 9.1% by mass.

Example 4
A nitrogen-substituted reaction vessel was charged with 60 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl and 0.305 parts by mass of cuprous chloride and stirred at room temperature for 60 minutes. Thereafter, 5.56 parts by mass of NFMA, 6.67 parts by mass of TFMA, poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blemmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions 6 of oxybutylene) 57 parts by mass, 16.21 parts by mass of polyethylene glycol monomethacrylate (“Blenmer PE-200” manufactured by NOF Corporation; average number of repetitions of oxyethylene 4.5) and 0.6 parts of ethyl 2-bromoisobutyrate were added, and nitrogen was added. The reaction was carried out at 60 ° C. for 10 hours under an air stream. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (4) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (4) by GPC, the weight average molecular weight (Mw) was 15,600, the number average molecular weight (Mn) was 12,300, and the dispersity (Mw / Mn) was 1.27. It was. Moreover, it was 15 mass% when the fluorine atom content of the obtained fluorosurfactant (4) was measured by combustion ion chromatography.

(Comparative Example 1)
In a nitrogen-substituted reaction vessel, 600 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) was charged and heated to 100 ° C. while stirring. Thereafter, NFMA 50.52 parts by mass, TFMA 49.98 parts by mass, poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blemmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions 6 of oxybutylene) 199. 5 parts by weight, 300 parts by weight of polyethylene glycol monomethacrylate (“Blenmer PE-200” manufactured by NOF Corporation; average number of repetitions of oxyethylene 4.5) and dimethyl-2,2′-azobisisobutyrate (Otsuka Chemical) A solution prepared by dissolving 6 parts by mass of “MAIB” manufactured by MIBK in 484.2 parts by mass was added dropwise over 3 hours and further reacted at 100 ° C. for 15 hours. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C1) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C1) by GPC, the weight average molecular weight (Mw) was 25,200, the number average molecular weight (Mn) was 3,500, and the dispersity (Mw / Mn) was 7.20. It was. Further, the fluorine atom content of the obtained fluorosurfactant (C1) was measured by combustion ion chromatography and found to be 9.1% by mass.

(Comparative Example 2)
A reaction vessel purged with nitrogen was charged with 100 parts by mass of MIBK and heated to 100 ° C. while stirring. Then, 27.79 parts by mass of NFMA, 27.49 parts by mass of TFMA, poly (1,2-oxybutylene) oxypropylene monomethacrylate (manufactured by NOF Corporation “Blenmer 10PPB-500B”; average number of repetitions of oxybutylene 6) 89 parts by mass, polyethylene glycol monomethacrylate (manufactured by NOF Corporation “Blenmer PE-200”; average number of repetitions of oxyethylene 4.5) 26.89 parts by mass and dimethyl-2,2′-azobisisobutyrate ( A solution prepared by dissolving 1 part by mass of “MAIB” (manufactured by Otsuka Chemical Co., Ltd.) in 80.7 parts by mass of MIBK was added dropwise over 3 hours, and further reacted at 100 ° C. for 15 hours. Subsequently, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C2) which was a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C2) by GPC, the weight average molecular weight (Mw) was 16,000, the number average molecular weight (Mn) was 4,700, and the dispersity (Mw / Mn) was 3.40. It was. Moreover, it was 30 mass% when the fluorine atom content of the obtained fluorosurfactant (C2) was measured by combustion ion chromatography.

(Comparative Example 3)
A reaction vessel purged with nitrogen was charged with 100 parts by mass of MIBK and heated to 100 ° C. while stirring. Thereafter, 37.05 parts by mass of NFMA, 36.65 parts by mass of TFMA, poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blemmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions of oxybutylene of 6) 10. 5 parts by weight, polyethylene glycol monomethacrylate (“Blenmer PE-200” manufactured by NOF Corporation; average number of repetitions of oxyethylene 4.5) 15.8 parts by weight and dimethyl-2,2′-azobisisobutyrate ( A solution prepared by dissolving 1 part by mass of “MAIB” (manufactured by Otsuka Chemical Co., Ltd.) in 80.7 parts by mass of MIBK was added dropwise over 3 hours, and further reacted at 100 ° C. for 15 hours. Subsequently, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C3) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C3) by GPC, the weight average molecular weight (Mw) was 17,300, the number average molecular weight (Mn) was 5,600, and the dispersity (Mw / Mn) was 3.09. It was. Moreover, it was 40 mass% when the fluorine atom content of the obtained fluorosurfactant (C3) was measured by combustion ion chromatography.

(Comparative Example 4)
Into a nitrogen-substituted reaction vessel, 49.44 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl, and 0.305 parts by mass of cuprous chloride were charged and stirred at room temperature for 60 minutes. Then, 13.2 parts by mass of poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blemmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions of oxybutylene of 6), polyethylene glycol monomethacrylate (NOF Corporation) "Blemmer PE-200" manufactured by company; average number of repetitions of oxyethylene 4.5) 19.76 parts by mass and 0.6 parts by mass of ethyl 2-bromoisobutyrate were added and reacted at 60 ° C for 5 hours in a nitrogen stream. Thereafter, 7.04 parts by mass of NFMA was added, and the mixture was further reacted for 12 hours. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C4) as a block copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C4) by GPC, the weight average molecular weight (Mw) was 16,300, the number average molecular weight (Mn) was 12,300, and the dispersity (Mw / Mn) was 1.33. It was. Further, the fluorine atom content of the obtained fluorosurfactant (C4) was measured by combustion ion chromatography and found to be 9.1% by mass.

(Comparative Example 5)
A nitrogen-substituted reaction vessel was charged with 50.46 parts by mass of methanol, 0.961 parts by mass of 2,2′-bipyridyl and 0.305 parts by mass of cuprous chloride, and stirred at room temperature for 60 minutes. Thereafter, 13.46 parts by mass of poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blenmer 10PPB-500B” manufactured by NOF Corporation; average number of repeating oxybutylenes 6), polyethylene glycol monomethacrylate (NOF Corporation) “Blemmer PE-200” manufactured by company; average number of repetitions of oxyethylene 4.5) 20.18 parts by mass and 0.6 part by mass of ethyl 2-bromoisobutyrate were added and reacted at 60 ° C. for 5 hours in a nitrogen stream. Thereafter, 6.36 parts by mass of TFMA was added, and the mixture was further reacted for 12 hours. Next, 30 parts by mass of activated alumina was added to the reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C5) as a block copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C5) by GPC, the weight average molecular weight (Mw) was 17,000, the number average molecular weight (Mn) was 12,700, and the dispersity (Mw / Mn) was 1.34. It was. Moreover, it was 9.1 mass% when the fluorine atom content of the obtained fluorochemical surfactant (C5) was measured by the combustion ion chromatography.

(Comparative Example 6)
In a reaction vessel purged with nitrogen, 352.6 parts by mass of isopropyl alcohol, 18.5 parts by mass of 2- (heptadecafluorooctyl) ethyl methacrylate (hereinafter abbreviated as “HFMA”), polyethylene glycol dimethacrylate (Shin Nakamura Chemical) “NK ester 4G” manufactured by Kogyo Co., Ltd .; average number of repetitions of oxyethylene 4) 4.4 parts by mass, polyethylene glycol / polypropylene glycol monoacrylate (average number of repetitions 22 of oxyethylene, average number of repetitions 22 of oxypropylene) 2 parts by mass, 12 parts by mass of 3-tris (trimethylsiloxy) silylpropyl methacrylate (“Silane Plan TM-0701” manufactured by Chisso Corporation; hereinafter abbreviated as “Si-MA”), methyl methacrylate (hereinafter, “MMA”) ". 7.8 parts by mass, 1.2 parts by mass of n-dodecyl mercaptan (“thiocalcol 20” manufactured by Kao Corporation) and 0.4 parts by mass of azobisisobutyronitrile were stirred and dissolved, and then 75 ° C. And then reacted at 80 ° C. for 12 hours. Subsequently, the solvent was distilled off under reduced pressure to obtain a fluorosurfactant (C6) as a random copolymer. As a result of measuring the molecular weight of the fluorosurfactant (C6) by GPC, the weight average molecular weight (Mw) was 37,400, the number average molecular weight (Mn) was 6,600, and the dispersity (Mw / Mn) was 5.67. It was. Further, the fluorine atom content of the obtained fluorosurfactant (C6) was measured by combustion ion chromatography and found to be 11.5% by mass.

  Types of monomers that are raw materials of the fluorosurfactants (1) to (4) and (C1) to (C6) obtained in Examples 1 to 4 and Comparative Examples 1 to 6, and the number average molecular weight Table 1 summarizes (Mn), weight average molecular weight (Mw), fluorine atom content, and bioaccumulation safety. The bioaccumulation safety was evaluated according to the following criteria.

[Evaluation of bioaccumulation safety]
The bioaccumulation safety of each fluorosurfactant was evaluated according to the following criteria.
○: It does not contain a perfluoroalkyl group having 8 or more carbon atoms, has a low possibility of accumulating in a living body, and is highly safe.
X: It contains a perfluoroalkyl group having 8 or more carbon atoms, has a high possibility of accumulating in a living body, and has low safety.

The abbreviations “BO-PO”, “EO”, “EO-DMA”, and “EO-PO” in Table 1 mean the following.
BO-PO: poly (1,2-oxybutylene) oxypropylene monomethacrylate (“Blenmer 10PPB-500B” manufactured by NOF Corporation; average number of repetitions of oxybutylene of 6)
EO: Polyethylene glycol monomethacrylate (“Blemmer PE-200” manufactured by NOF Corporation; average number of repetitions of oxyethylene 4.5)
EO-DMA: Polyethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd. “NK ester 4G”; average number of oxyethylene repeats 4)
EO-PO: Polyethylene glycol / polypropylene glycol monoacrylate (average number of repetitions of oxyethylene 22 and average number of repetitions of oxypropylene 22)

(Example 5)
Using the fluorine-based surfactant (1) obtained in Example 1 above, a resist composition was prepared as follows, and coating unevenness evaluation and an antifoaming test were performed. The defoaming test was carried out by preparing a propylene glycol monomethyl ether acetate solution of a fluorosurfactant, measuring the time until defoaming after foaming the solution.

  100 parts by mass of cresol novolac resin obtained by condensing 27 parts by mass of a condensate of 2,3,4-trihydroxybezophenone and orthonaphthoxydiazide-5-sulfonyl chloride with cresol and formaldehyde A solution is prepared by dissolving 400 parts by mass of propylene glycol monomethyl ether acetate (hereinafter abbreviated as “PGMEA”), and the fluorosurfactant (1) obtained in Example 1 is added to the above. A resist composition was prepared by adding 0.1 parts by mass with respect to a total of 100 parts by mass of the condensate and the cresol-novolak resin, and performing microfiltration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm.

[Evaluation of coating unevenness]
The resist composition obtained above was spin-coated on a glass substrate having a diameter of 8 inches on a chrome-treated surface at 500 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. The surface of the obtained resist film was visually observed using a sodium lamp to observe unevenness of the coating film surface, and coating unevenness was evaluated according to the following criteria.
A: Uneven coating was not observed.
○: Slight application unevenness is observed (the area where the application unevenness is less than 10% of the whole).
Δ: Some coating unevenness is observed (the area where the coating unevenness is 10% or more and less than 30% of the whole).
X: Many coating unevenness is observed (the area which became the coating unevenness is 30% or more of the whole).

[Defoaming test and evaluation]
50 g of PGMEA solution added so that the content of the fluorosurfactant (1) obtained in Example 1 was 1% by mass was placed in a 100 ml sample tube, shaken for 20 seconds, and then the liquid level was generated. The time until 90% or more of the liquid surface area was exposed due to the disappearance of bubbles was measured as the defoaming time. From the measured defoaming time, the defoaming property was evaluated according to the following criteria. The measurement time was up to 600 seconds, and no further measurement was performed for those in which 90% or more of the liquid surface area was not exposed even after 600 seconds had elapsed.
A: Time required for exposing 90% or more of the liquid surface area is less than 60 seconds.
○: The time required to expose 90% or more of the liquid surface area is 60 seconds or more and less than 360 seconds.
Δ: The time required for 90% or more of the liquid surface area to be exposed is 360 seconds or more and less than 600 seconds.
X: Time required for exposing 90% or more of the area of the liquid surface is 600 seconds or more.

(Examples 6-8 and Comparative Examples 7-12)
In the same manner as in Example 5, using the fluorosurfactants (2) to (4) and (C1) to (C6) obtained in Examples 2 to 4 and Comparative Examples 1 to 6, uneven coating was performed. Evaluation and antifoaming property test were conducted.

  Table 2 shows the evaluation and test results obtained in Examples 5-8 and Comparative Examples 7-12. In addition, the expression “> 600” of the defoaming time means that 90% or more of the liquid surface area was not exposed even after 600 seconds had elapsed.

  From the results of Examples 5 to 8 shown in Table 2, the resist composition using the fluorinated surfactants (1) to (4) of the present invention obtained in Examples 1 to 4 has little coating unevenness. Since a smooth coating film was obtained, it turned out that it is excellent in leveling property. Moreover, it turned out that the defoaming property in a PGMEA solution is also excellent. In particular, the fluorosurfactant (2) obtained in Example 2 had very good antifoaming properties.

  From the results of Comparative Example 7 shown in Table 2, the fluorinated surfactant (C1) of Comparative Example 1 produced not by living radical polymerization but by free radical polymerization has a fluorine atom content obtained in Examples 1 to 3. It was found to be the same level as the obtained fluorinated surfactants (1) to (3) of the present invention, but uneven coating occurred and the leveling property was insufficient.

  From the results of Comparative Examples 8 and 9 shown in Table 2, the fluorinated surfactants (C2) and (C3) of Comparative Examples 2 and 3 produced not by living radical polymerization but by free radical polymerization had a fluorine atom content. However, the foamed foam does not immediately defoam but there is a problem with defoaming properties, although there was little coating unevenness and good leveling properties. I understood.

  From the results of Comparative Examples 10 and 11 shown in Table 2, the fluorinated surfactants of Comparative Examples 4 and 5 were prepared by living radical polymerization in the same manner as in the present invention, but not by random copolymerization but by block copolymerization ( Although C4) and (C5) had excellent leveling properties with little coating unevenness, it was found that the foamed foam was not immediately defoamed and there was a problem in defoaming properties.

  From the results of Comparative Example 12 shown in Table 2, the fluorinated surfactant (C6) of Comparative Example 6 produced using a monomer having a fluorinated alkyl group having 8 carbon atoms has a slight coating unevenness. The resulting leveling property was not good, and it was found that the foamed foam did not immediately disappear and there was a problem with the defoaming property.

Claims (6)

As an essential monomer component, a monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond with an oxygen atom) and a non-fluorine monomer (m2) production method of the monomer (m1) and fluorine-containing surface active agent for causing atom transfer radical polymerization engaged in the coexistence of (m @ 2). The method for producing a fluorosurfactant according to claim 1, wherein the fluoromonomer (m1) is a monomer selected from at least one of the following general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or —C _n H _2n —Rf ′ (n represents an integer of 1 to 8, Rf 'Represents any one group of the following formulas (Rf-1) to (Rf-7)), and X represents any one group of the following formulas (X-1) to (X-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).

(In the above formulas (X-1), (X-3), (X-5), (X-6) and (X-7), n represents an integer of 1 to 8. The above formula (X-8 M in (X-9) and (X-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (X-6) and (X-7) Rf ″ represents any one of the following formulas (Rf-1) to (Rf-7).)

(In the formulas (Rf-1) and (Rf-2), n represents an integer of 1 to 6. In the formula (Rf-3), n represents an integer of 2 to 6. The formula (Rf- N in 4) represents an integer of 4 to 6. m in the above formula (Rf-5) is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is M in the above formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and m, n and The total of p is 1-5.) The method for producing a fluorine-based surfactant according to claim 1 or 2, wherein the non-fluorine-based monomer (m2) is a monomer having an oxyalkylene group represented by the following general formula (2).

(Wherein R ² 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 R ³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) The non-fluorine 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). Of producing a fluorosurfactant.

(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.) As an essential monomer component, a monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond with an oxygen atom) and a non-fluorine monomer (m2) Including a step of obtaining a fluorosurfactant by atom transfer radical polymerization in the presence of the monomers (m1) and (m2), and a step of mixing the fluorosurfactant and an alkali-soluble resin. A method for producing a resist composition. As an essential monomer component, a monomer (m1) having a fluorinated alkyl group having 6 or less carbon atoms (including those having an ether bond with an oxygen atom) and a non-fluorine monomer (m2) A step of obtaining a fluorosurfactant by atom transfer radical polymerization in the presence of the monomers (m1) and (m2), and a step of mixing the fluorosurfactant, an alkali-soluble resin and a solvent. A method for producing a resist composition according to claim 5.

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