JP2016102212A - Fluorine-based surfactant, resist composition, hardened product, and method for producing fluorine-based surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a fluorine-based surfactant that can produce a coat film in which the coat film is hard to be discolored (water stain is hard to occur) even when exposed to an alkaline solution or an acidic solution; a coating composition using the same; and a resist composition.SOLUTION: Provided are: a fluorine-based surfactant characterized to be a block copolymer comprising a polymer segment (A1) composed of a polymerizable monomer (a1) having a fluorinated alkyl group of 1 to 6 carbon atoms having the fluorine atom directly bonded thereto and a polymerizable unsaturated group, and a polymer segment (A2) composed of a polymerizable monomer containing a polymerizable monomer (a2) having a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group; a resist composition containing said fluorine-based surfactant; and a method for producing said fluorine-based surfactant.SELECTED DRAWING: None

Description

The present invention relates to a fluorosurfactant capable of obtaining a coating film in which the coating film is not easily discolored even when exposed to an alkaline solution or an acidic solution (a water stain is unlikely to occur), and a resist composition and a composition using the same. This invention relates to a method for producing a cured product and a fluorosurfactant .

  Color filters used in color liquid crystal display devices and organic EL display devices are generally red (R), green (G), and blue (B) pixels, and a black matrix (BM) for the purpose of improving display contrast therebetween. Has a basic structure formed. In the production of a color filter, a resist composition is generally applied on a glass substrate by a coating method such as spin coating or slit coating, and after drying, exposed using a mask and then developed to form a colored pattern.

  In the development, an alkaline developer is used as a developer, and unexposed portions are washed away by rinsing. At that time, there is also a problem that residues such as resin in the unexposed area present in the cleaning liquid adhere to the cured coating surface of the colored pattern in the exposed area, and the resist composition is also required to have characteristics that make it difficult for the residue to adhere to the colored pattern. It is done.

  Examples of the composition for forming a color filter pixel in which the residue is less likely to adhere to the colored pattern include, for example, a radical polymerizable monomer having a poly (perfluoroalkylene ether) chain and a radical polymerizable monomer having a polyalkylene glycol chain. Fluorine atom-containing surfactant obtained by reacting a copolymer having a reactive functional group obtained by copolymerizing a reactive functional group, a group having reactivity with the reactive functional group, and a compound having a radical polymerizable group A composition for forming a color filter pixel is disclosed (for example, see Patent Document 1). However, the color pattern obtained using the composition for forming a color filter pixel described in Patent Document 1 changes its color when exposed to an alkaline developer used in the development step. There is a problem that a phenomenon (water stain) occurs. Such water stain disappears after post-baking, so there is no problem as a product, but it is detected as unevenness in the appearance inspection of the patterning surface after development, and it is not possible to distinguish between normal products and abnormal products. It was happening. Therefore, if the inspection sensitivity of the inspection device is lowered in the appearance inspection, the yield of the final color filter product is reduced as a result, which becomes a problem. Accordingly, there is a need for a resist composition that can provide a cured coating film that is less likely to cause water stains in the development process and the washing process.

JP 2010-250256 A

The problem to be solved by the present invention is to use a fluorosurfactant and a fluorosurfactant that can obtain a coating film that is not easily discolored even when exposed to an alkaline solution or an acidic solution (i.e., does not easily cause water stain). It is in providing the manufacturing method of a resist composition, hardened | cured material, and fluorine-type surfactant .

  As a result of intensive studies, the present inventors have found that a polymer segment composed of a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group, a skeleton of a bridged ring hydrocarbon, and a polymerizable unsaturated group A polymerizable monomer having an adamantane ring and a polymerizable unsaturated group, a polymerizable monomer having a dicyclopentane ring and a polymerizable unsaturated group, , A polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group, a polymerizable monomer having a norbornane ring and a polymerizable unsaturated group, or a polymerization having a norbornene ring and a polymerizable unsaturated group The present inventors have found that a block copolymer composed of a polymer segment composed of a polymerizable monomer containing a polymerizable monomer becomes a fluorosurfactant that solves the above-mentioned problems, and has completed the present invention.

  That is, the present invention provides a polymerizable monomer comprising a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with fluorine atoms and a polymerizable unsaturated group. Polymer obtained by using a polymerizable monomer containing a polymer segment (A1) obtained by using the polymerizable monomer (a2) having a skeleton of a bridged ring hydrocarbon and a polymerizable unsaturated group The present invention provides a fluorosurfactant characterized by being a block copolymer containing a segment (A2).

The present invention also provides a resist composition containing the fluorine-based surfactant.

The present invention also provides a cured product of the resist composition.

Furthermore, the present invention provides a polymerizable monomer comprising a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded and a polymerizable unsaturated group. Polymer obtained by using a polymerizable monomer containing a polymer segment (A1) obtained by using the polymerizable monomer (a2) having a skeleton of a bridged ring hydrocarbon and a polymerizable unsaturated group A method for producing a fluorosurfactant, which is a block copolymer containing a segment (A2), wherein the block copolymer is produced by living radical polymerization. It is to provide.

By using a fluorine-based surfactant of the present invention can be water stains to the cured product of such a coating film is to provide a pile resist composition occurred.

  The fluorine-based surfactant of the present invention is polymerizable containing a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded and a polymerizable unsaturated group. Using a polymerizable monomer including a polymer segment (A1) obtained by using a monomer, and a polymerizable monomer (a2) having a crosslinked cyclic hydrocarbon skeleton and a polymerizable unsaturated group It is a block copolymer containing the polymer segment (A2) obtained.

  In the present invention, the polymer segment (A1) constituting the block copolymer refers to a segment obtained by polymerizing two or more polymerizable monomers (a1). In order to obtain such a segment, a polymerizable monomer other than the polymerizable monomer (a1) can be used in combination as long as the effects of the present invention are not impaired. Examples of the polymerizable monomer that can be used in combination include a polysynthetic monomer having a polyoxyalkylene chain, a polysynthetic monomer having a linear alkyl group having 1 to 18 carbon atoms, and 1 to 1 carbon atoms. And a polysynthetic monomer having 18 branched alkyl groups.

  In the present invention, it is preferable to use a monomer having a high content of the polymerizable monomer (a1) as the polymerizable monomer containing the polymerizable monomer (a1). ) Is particularly preferable.

  As the polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded with fluorine atoms and a polymerizable unsaturated group used in the present invention, the fluorinated alkyl in the molecule Any compound having a group and a polymerizable unsaturated group can be used without particular limitation.

  Here, the fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded is a perfluoroalkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded or a part of hydrogen atoms. It is a partially fluorinated alkyl group having a fluorine atom. Among these fluorinated alkyl groups, a perfluoroalkyl group is preferable because of its high effect as a surfactant. Furthermore, the larger the number of carbon atoms to which fluorine atoms are directly bonded, the better. The number of carbon atoms to which fluorine atoms are directly bonded is particularly preferably 4 to 6.

  As a polymerizable unsaturated group which the said polymerizable monomer (a1) has, a (meth) acryloyl group, a vinyl group, a maleimide group etc. are mentioned, for example. Among these, the (meth) acryloyl group is available because of the availability of raw materials, the ease of controlling the compatibility with the various components in the coating composition and the resist composition, and the good polymerization reactivity. preferable. As a specific example having this (meth) acryloyl group, for example, a monomer represented by the following general formula (1) can be preferably exemplified. Moreover, the said polymerizable monomer (a1) 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−４）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−４）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-4)), and X represents any one group of the following formulas (X-1) to (X-10). Rf represents any one of the following formulas (Rf-1) to (Rf-4). ]

〔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−４）のいずれか１つの基を表す。〕

[N in the above formulas (X-1), (X-3), (X-5), (X-6) and (X-7) represents an integer of 1-8. M in the above formulas (X-8), (X-9) and (X-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. Rf ″ in the above formulas (X-6) and (X-7) represents any one group of the following formulas (Rf-1) to (Rf-4). ]

〔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。〕

[N in the above formulas (Rf-1) and (Rf-2) represents an integer of 1-6. N in the above formula (Rf-3) represents an integer of 2 to 6. N in the above formula (Rf-4) represents an integer of 4 to 6. ]

  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.

  The polymerizable monomer (a2) used in the present invention has a bridged cyclic hydrocarbon skeleton and a polymerizable unsaturated group. On the surface of the coating film of the resist composition or coating composition containing the fluorosurfactant of the present invention, a layer containing the fluorosurfactant of the present invention (hereinafter sometimes referred to as a block layer) is the surface. Is unevenly distributed. The fluorosurfactant of the present invention has a high glass transition temperature (Tg) due to the presence of the skeleton of the crosslinked ring hydrocarbon, and as a result, the block layer becomes a hard layer. In other words, a cured coating film is formed by irradiation with active energy rays, but even when sufficient active energy rays are not irradiated, a sufficiently cured coating film can be obtained due to the presence of a bridged cyclic hydrocarbon skeleton. . As a result, the present inventors consider that a coating film obtained by using the fluorosurfactant of the present invention can be a coating film that hardly causes water stain.

  Examples of the skeleton of the bridged ring hydrocarbon include an adamantane ring, perhydroindene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, dicyclopentane ring, dicyclopentene ring, perhydro Examples include acenaphthene ring, perhydrophenalene ring, norbornane ring, norbornene ring. Among them, an adamantane ring, a dicyclopentane ring, a norbornane ring, and a norbornene ring are preferable, because a block layer having a high Tg can be formed on the surface of the coating film, and as a result, a cured coating that is less likely to saturate is obtained. A ring is more preferred.

  Examples of the polymerizable unsaturated group include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, the (meth) acryloyl group is available because of the availability of raw materials, the ease of controlling the compatibility with the various components in the coating composition and the resist composition, and the good polymerization reactivity. preferable.

  Hereinafter, a polymerizable monomer having an adamantane ring and a polymerizable unsaturated group that can be preferably used as the polymerizable monomer (a2) in the present invention will be described.

  Examples of the polymerizable monomer having an adamantane ring and a (meth) acryloyl group include compounds represented by the following formulas (a2-1) and (a2-2).

（式中、Ｌは反応性官能基を表し、Ｘ及びＹは２価の有機基又は単結合を表し、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, L represents a reactive functional group, X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group, or CF ₃ ).

  Examples of the reactive functional group include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and an acid anhydride group. Among these, a hydroxyl group is preferable because a fluorosurfactant having good compatibility with the coating composition can be obtained.

  In the general formula (a2-1), the organic functional group having the reactive functional group represented by -XL and the bonding position of Y may be bonded to any carbon atom in the adamantane ring. , -X-L may have two or more. Furthermore, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane ring may be substituted with fluorine atoms, alkyl groups, or the like. In the general formula (a2-1), X and Y are a divalent organic group or a single bond. Examples of the divalent organic group include carbon atoms such as a methylene group, a propyl group, and an isopropylidene group. The alkylene group of number 1-8 is mentioned.

  In the compound represented by the formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantane ring. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the adamantane structure in the said general formula (a2-1) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  More specific examples of the polymerizable monomer represented by the general formula (a2-1) include compounds represented by the following.

  Moreover, as a more specific example of the polymerizable monomer represented by the general formula (a2-2), for example, a compound represented by the following can be given.

  Among the polymerizable monomers having an adamantane ring and a (meth) acryloyl group, a fluorine-based surfactant having good compatibility with other components in the coating composition can be obtained. ) Is preferable, and compounds represented by the formula (a2-1-1), the formula (a2-1-3) and the formula (a2-1-5) are more preferable.

  Hereinafter, a polymerizable monomer having a dicyclopentane ring and a polymerizable unsaturated group that can be preferably used as the polymerizable monomer (a2) in the present invention will be described.

  Examples of the polymerizable monomer having a dicyclopentane ring and a (meth) acryloyl group include compounds represented by the following formula (a2-3).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  In the compound represented by the formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentane ring. In addition, a part or all of the hydrogen atoms bonded to the carbon atoms constituting the dicyclopentane ring in the general formula (a2-3) may be substituted with a fluorine atom, an alkyl group, or the like. .

  More specific examples of the polymerizable monomer represented by the general formula (a2-3) include compounds represented by the following.

  Among the polymerizable monomers having a dicyclopentane ring and a (meth) acryloyl group, the compound represented by the formula (a2-3-2) is preferable because the Tg of the coating film is high.

  Hereinafter, the polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group that can be preferably used as the polymerizable monomer (a2) in the present invention will be described.

  Examples of the polymerizable monomer having a dicyclopentene ring and a (meth) acryloyl group include compounds represented by the following formula (a2-4).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  In the compound represented by the formula (a2-4), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentene ring. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the dicyclopentene ring in the said general formula (a2-3) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  Specific examples of the polymerizable monomer represented by the general formula (a2-4) include compounds represented by the following.

  Among the polymerizable monomers having a dicyclopentene ring and a (meth) acryloyl group, the compound represented by the formula (a2-4-2) is preferable because the Tg of the coating film is increased.

  Hereinafter, the polymerizable monomer having a norbornane ring and a polymerizable unsaturated group that can be preferably used as the polymerizable monomer (a2) in the present invention will be described.

  Examples of the polymerizable monomer having a norbornane ring and a (meth) acryloyl group include a compound represented by the following formula (a2-5).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  In the compound represented by the formula (a2-5), the (meth) acryloyl group may be bonded to any carbon atom in the norbornane ring. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the norbornane ring in the said general formula (a2-5) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  Specific examples of the polymerizable monomer represented by the general formula (a2-5) include compounds represented by the following.

  Among the polymerizable monomers having a norbornane ring and a (meth) acryloyl group, the compound represented by the formula (a2-5-2) is preferable because the Tg of the coating film is increased.

  Hereinafter, the polymerizable monomer having a norbornene ring and a polymerizable unsaturated group that can be preferably used as the polymerizable monomer (a2) in the present invention will be described.

  Examples of the polymerizable monomer having a norbornene ring and a (meth) acryloyl group include compounds represented by the following formulas (a2-6) and (a2-7).

（式中、Ｒは水素原子、メチル基又はＣＦ_３を表す。）

(In the formula, R represents a hydrogen atom, a methyl group or CF _3. )

  In the compound represented by the formula (a2-6), the (meth) acryloyl group may be bonded to any carbon atom in the norbornene ring. Moreover, the hydrogen atom couple | bonded with the carbon atom which comprises the norbornene ring in the said general formula (a2-6) may substitute the one part or all part by the fluorine atom, the alkyl group, etc.

  More specific examples of the polymerizable monomer represented by the general formula (a2-6) include compounds represented by the following.

  Among the polymerizable monomers having a norbornene ring and a (meth) acryloyl group, the compound represented by the formula (a2-6-2) is preferable because the Tg of the coating film is increased.

  As described above, the fluorosurfactant of the present invention is a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded and a polymerizable unsaturated group. Polymeric monomer comprising a polymer segment (A1) obtained by using a polymerizable monomer containing, and a polymerizable monomer (a2) having a crosslinked cyclic hydrocarbon skeleton and a polymerizable unsaturated group It is a block copolymer containing the polymer segment (A2) obtained using a body. Here, the ratio of the polymer segment (A1) and the polymer segment (A2) is (A1) :( A2) in mass ratio because a fluorosurfactant having good compatibility with the coating composition is obtained. = 5: 95 to 90:10 is preferable, and 10:90 to 80:20 is more preferable.

  The polymer segment (A2) is a polymerizable monomer (a2) that is used for obtaining the polymer segment (A2) [constituting the polymer segment (A2)]. What is obtained using 10 to 100% by mass based on the mass is preferable because a fluorosurfactant capable of forming a firm layer on the coating film surface is obtained, and more preferably obtained using 20 to 90% by mass. preferable.

  As described above, when the polymer segment (A2) is obtained, a polymerizable monomer other than the polymerizable monomer (a2) may be used in combination as long as the effects of the present invention are not impaired. Examples of the polymerizable monomer that can be used in combination include a polysynthetic monomer having a polyoxyalkylene chain, a polysynthetic monomer having a linear alkyl group having 1 to 18 carbon atoms, and 1 to 1 carbon atoms. And a polysynthetic monomer having 18 branched alkyl groups.

  The method for producing the fluorosurfactant of the present invention is not particularly limited, but the polymer segment (A1) obtained by using a polymerizable monomer containing the polymerizable monomer (a1), and polymerization Living radical polymerization is preferred from the viewpoint of easy control of the polymerization reaction for obtaining a block copolymer comprising a polymer segment (A2) obtained using a polymerizable monomer containing a polymerizable monomer (a2).

  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 producing the fluorosurfactant of the present invention, the following methods can be preferably exemplified.
Method 1: A polymerizable monomer containing a polymerizable monomer (a1) 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 Living radical polymerization, preferably atom transfer radical polymerization, to obtain a polymer segment (A1), and then a polymerizable monomer containing a polymerizable monomer (a2) is added to further polymerize the polymer segment (A1). A method of subjecting a polymerizable monomer containing the polymerizable monomer (a2) to living radical polymerization, preferably atom transfer radical polymerization.

  Method 2: A polymerizable monomer containing a polymerizable monomer (a2) 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 After living radical polymerization, preferably atom transfer radical polymerization, to obtain a polymer segment (A2), a polymerizable monomer containing a polymerizable monomer (a1) is added to the reaction system to form a polymer segment (A2). Further, a method in which a polymerizable monomer containing the polymerizable monomer (a1) is subjected to living radical polymerization, preferably atom transfer 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 500 to 200,000, since it becomes a fluorosurfactant that provides a firmer coating surface. The range of 1,000 to 150,000 is more preferable, and the range of 1,500 to 100,000 is more preferable. Further, the dispersity (Mw / Mn) of the fluorosurfactant of the present invention is preferably 1.5 or less, since it becomes a fluorosurfactant that can obtain a firmer coating surface. The range of 1.40 is more preferable, and the range of 1.05 to 1.30 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” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
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: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through 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 more preferably in the range of 5 to 35% by mass because good leveling properties with less coating unevenness are obtained. 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 is used as an additive for this photosensitive resin composition, particularly a resist composition, thereby exhibiting a high leveling property and forming a uniform coating film (cured product). Therefore, the above problems can be solved.

  Usually, among the resist compositions, the color resist composition comprises a surfactant and a photoresist agent, and this photoresist agent contains (1) an alkali-soluble resin, (2) a polymerizable compound, and (3) a colorant. What can be illustrated.

  The alkali-soluble resin (1) used in the present invention is not particularly limited as long as it is soluble in an alkali developer, but at least one acidic group selected from the group of carboxyl group, phenolic hydroxyl group and sulfonic acid group. Or the resin which has the salt is preferable.

  The (1) alkali-soluble resin will be described more specifically. Examples include those obtained by polymerizing monomers having acidic groups. (1) Examples of the monomer having a carboxyl group as an acid group as a raw material for the alkali-soluble resin include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid or These salts are mentioned.

  (1) As a monomer which has a phenolic hydroxyl group as an acidic group used as the raw material of alkali-soluble resin, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene etc. are mentioned, for example. In addition, one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring of these monomers were substituted with an alkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or an amide group. A compound etc. are also mentioned.

  (1) Examples of the monomer having a sulfonic acid group as an acidic group used as a raw material for the alkali-soluble resin include vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, and 2-hydroxy-3- (meth). Allyloxypropanesulfonic acid, (meth) acrylic acid-2-sulfoethyl, (meth) acrylic acid-2-sulfopropyl, 2-hydroxy-3- (meth) acryloxypropanesulfonic acid, 2- (meth) acrylamide-2 -Methylpropanesulfonic acid or a salt thereof.

  Moreover, although the monomer which has said acidic group can superpose | polymerize independently and can be set as (1) alkali-soluble resin, you may copolymerize with another monomer. Such other monomers include hydrocarbon olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides. , Aromatic vinyl compounds, chloroolefins, conjugated dienes and the like. Among these, (meth) acrylic acid esters are preferable.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, (meth) acrylic acid n-hexyl, 2-ethyl- (meth) acrylate-n-hexyl, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) a 4-hydroxybutyl toluate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, (meth) acryl Acid 3-chloro-2-hydroxypropyl, glycerin mono (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, (meth) acrylic acid 2-acetoacetoxyethyl, (meth) acrylic acid 2- Examples include methoxyethyl, 2-ethoxyethyl (meth) acrylate, and benzyl (meth) acrylate.

  (1) The monomer having an acidic group that is a raw material for the alkali-soluble resin and the other monomer may be used alone or in combination of two or more.

  The polymerizable compound (2) is not particularly limited as long as it is a compound having a photopolymerizable functional group that can be polymerized or crosslinked by irradiation with active energy rays such as ultraviolet rays. Specific examples include, for example, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, Glycerin tri (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate (Meth) acrylate compounds such relations are exemplified.

  Also, N, N′-ethylene dimaleimide, N, N′-hexamethylene dimaleimide, N, N′-dodecamethylene dimaleimide, N, N′-m-phenylene dimaleimide, N, N′-p-pheny Rangemaleimide, N, N ′-(oxydi-p-phenylene) dimaleimide, N, N ′-(methylenedi-p-phenylene) dimaleimide, N, N′-2,4-tolylenemaleimide, N, N′-2 , 6-Tolylenedimaleimide, N, N′-dimaleimide, N, N′-m-xylylenedimaleimide, N, N′-p-xylylenedimaleimide, N, N′-oxydipropylenemaleimide, ethylenedioxy -Bis-N-ethylmaleimide, N, N'-p, p'-diphenylsulfone bismaleimide, N, N'-p, p'-diphenyl ether bismaleimide N, N'-dicyclohexylmethane bismaleimide, N, N '-(3,3'-dichloro-p, p'-bisphenylene) bismaleimide, 1,1,1,3,3,3-hexafluoro -2,2-bis (4-maleimidophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, ethoxy (3 -Maleimidopropioxy) ethane, ethoxy (3-maleimidopropoxy) butane, diethylene glycol (3-maleimidopropyl) methyl ether, methyl (3-maleimidopropyl) ether of polyethylene glycol with Mn = 400, trimethylolpropane tri (3- Maleimidopropyl ether), polyethylene glycol bis (3- Ether compounds such as (reimidopropyl) ether, polyethylene glycol mono (3-maleimidopropyl) vinylether with Mn = 400; methylmaleimide acetate, ethylmaleimide capronate, ethylene glycol monomethylethermaleimide acetate, polyethylene glycol with Mn = 400 Monomethyl ether maleimide acetate, tetrahydrofurfuryl maleimide acetate, diethylene glycol bismaleimide acetate, diethylene glycol monomaleimide acetate acrylate, bismaleimide acetate of polyethylene glycol with Mn = 400, bismaleimide acetate of polytetramethylene glycol with Mn = 250, Mn = 400 Polyethylene glycol monomaleimide capro Nate acrylate, trimethylolpropane trimaleimide acetate, ethylene oxide modified trimethylolpropane trimaleimide acetate, ethylene oxide modified trimethylolpropane dimaleimide acetate monoacrylate, pentaerythritol tetramaleimide acetate, ethylene oxide modified pentaerythritol dimaleimide acetate, ethylene oxide modified pentaerythritol trimaleimide Maleimide ester compounds such as acetate, ethylene oxide modified pentaerythritol tetramaleimide acetate, ethylene oxide modified pentaerythritol dimaleimide acetate diacrylate; N-ethyl- (2-maleimidoethyl) carbamate; sophorone diisocyanate and (poly) alkylene Urethane compounds obtained by reacting an equivalent mixture with ol with 2-maleimidoethanol; maleimide carbonate compounds such as 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-isopropyl carbonate, tetraethylene glycol bis (3-maleimidopropyl carbonate), etc. And maleimide derivatives of These (2) polymerizable compounds can be used alone or in combination of two or more.

  The mass ratio between the (1) alkali-soluble resin and the (2) polymerizable compound is preferably in the range of (1) :( 2) = 20: 80 to 90:10, and in the range of 30:70 to 80:20. More preferably, the range of 40:60 to 70:30 is even more preferable.

  (3) The colorant used in the present invention can be used without particular limitation as long as it can be colored. However, a pigment is preferred from the viewpoint of high heat resistance and light resistance, and any of organic pigments and inorganic pigments can be used. Can be used.

  As said organic pigment, it uses according to the color of each pixel of red (R), green (G), and blue (B). For red (R) pixels, for example, C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Gment Red 240, C.I. I. Cement red 254, C.I. I. Red pigments such as CI Pigment Red 48: 1 can be used.

  For green (G) pixels, for example, C.I. I. Pigment green 7, C.I. I. Green pigments such as CI Pigment Green 36 can be used. For blue (B) pixels, for example, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Blue pigments such as CI Pigment Blue 64 can be used.

  In addition, for the purpose of improving the color reproducibility of each of the red (R), green (G), and blue (B) pixels, organic pigments of other colors may be used for hue adjustment. Examples of such organic pigments for hue adjustment include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. Violet pigments such as CI Pigment Violet 50; I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. And yellow pigments such as CI Pigment Yellow 185.

  On the other hand, the (3) colorant used for forming the black matrix (BM) is not particularly limited as long as it is black, but is composed of carbon black, metal oxide, or two or more metal oxides. Pigments such as composite metal compounds are preferred. Further, a combination in which two or more organic pigments selected from pigments having hues of red, blue, green, purple, yellow, cyan, and magenta are mixed and made black by mixing colors may be used.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, and furnace black. Examples of the metal oxide include titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Usually, titanium black is represented by Ti _m O _2m-1 (m is a number of 1 or more). Moreover, metal oxides, such as copper, iron, chromium, manganese, cobalt, are mentioned as a metal oxide. Furthermore, as the composite metal compound composed of two or more kinds of metal oxides, for example, copper-chromium oxide, copper-chromium-manganese oxide, copper-iron-manganese oxide, or cobalt-iron-manganese An oxide etc. are mentioned.

  On the other hand, examples of organic pigments include quinacridone pigments, perylene pigments, pyrrolo-pyrrole pigments, anthraquinone pigments and the like as pigments having a red hue, and phthalocyanines as pigments having a blue hue. Pigments, indanthrene pigments, etc., pigments having a green hue include halogenated phthalocyanine pigments, and pigments having a purple hue include dioxazine violet, fast violet B, methyl Examples of pigments having a hue having a yellow hue include tetrachloroisoindolinone pigments, hansa yellow pigments, benzidine yellow pigments, and azo pigments. As a pigment having a cyan hue, metal-free phthalose Nin, merocyanine, and examples of the pigment having a magenta hue, dimethyl quinacridone, thioindigo, and the like.

  (3) The colorant used for forming each pixel of red (R), green (G), and blue (B) and the black matrix (BM) may be used alone or in accordance with the required hue. It can also be used in combination.

  The blending amount of the (3) colorant is preferably in the range of 10 to 80 parts by mass on the basis of 100 parts by mass in total of the (1) alkali-soluble resin and (2) the polymerizable compound. A range of 15 to 65 parts by mass is more preferable.

  In the resist composition of the present invention, when the (3) colorant is a pigment, it is preferable to prepare and use a pigment dispersion prepared by dispersing it in an organic solvent using a dispersant. Examples of the dispersant include surfactants; intermediates or derivatives of pigments; intermediates or derivatives of dyes; resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins. It is done. Among these pigment dispersants, a resin dispersant containing an acrylic polymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain is particularly preferable. Examples of such commercially available resin-type dispersants include “BYK-160”, “BYK-161”, “BYK-2001” manufactured by BYK Chemie, “Efka 46” manufactured by Fuka Chemicals, and Ajinomoto Fine. Examples include “Ajisper PB-814” manufactured by Techno Corporation. These dispersants can be used alone or in combination of two or more.

  Examples of the organic solvent used in the preparation of the pigment dispersion include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; toluene Aromatic solvents such as xylene, methoxybenzene; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic carbonization such as hexane Hydrogen-based solvents; nitrogen compound solvents such as N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; γ-butyrolacto Lactone solvents such as carbene; carbamates and the like. These solvents can be used alone or in combination of two or more.

  Examples of the method for preparing the pigment dispersion include (3) a method of undergoing a kneading and dispersing step and a fine dispersion step of a colorant, a method of performing only by a fine dispersion step, and the like. In the kneading and dispersing step, (3) the colorant, (1) part of the alkali-soluble resin, and, if necessary, the dispersing agent are mixed and kneaded. Examples of the machine used for kneading include two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, and single-screw or twin-screw extruders. The colorant can be dispersed by dispersing while applying force. Further, (3) the colorant is preferably refined in particle size by a salt milling method or the like before the kneading.

  On the other hand, in the fine dispersion step, (3) the composition containing the colorant obtained in the kneading and dispersion step is added with a solvent, or (3) the colorant, (1) the alkali-soluble resin, the solvent and necessary In accordance with the above, the dispersion agent is mixed and dispersed using a disperser together with a dispersion medium for fine particles of glass, zirconia or ceramic, so that (3) the fine particles are close to primary particles. Can be dispersed.

  Moreover, (3) The average particle diameter of the primary particles of the colorant is preferably 10 to 100 nm, and more preferably 10 to 60 nm. The average particle size of the colorant (3) was measured with a dynamic light scattering particle size distribution meter. For example, Nanotrac particle size distribution measuring device “UPA-EX150 manufactured by Nikkiso Co., Ltd.” ”,“ UPA-EX250 ”or the like.

  When irradiating active energy rays, such as an ultraviolet-ray, and hardening the resist composition of this invention, a polymerization initiator is mix | blended with the resist composition of this invention. Examples of the polymerization initiator include benzophenone, acetophenone, benzoin, benzoin ethyl ether, benzoin isobutyl ether, benzyl methyl ketal, azobisisobutyronitrile, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -Phenyl-1-one, 1- (4'-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4'-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -One, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4 "-diethylisophthalophen, 2,2-dimethoxy-1,2-diphenylethane-1- ON, benzoin isopropyl ether, thioxanthone, 2-chloro Thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) -phenylphosphine oxide 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and may be used alone or in combination of two or more. Of these, (3) the composition for forming a color filter pixel of the present invention is relatively unaffected by the colorant and exhibits high curability, but 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1 is preferred.

  Moreover, if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to promote photopolymerization.

  The blending amount of the polymerization initiator may be in the range of 0.01 to 15 parts by mass with respect to a total of 100 parts by mass of the (1) alkali-soluble resin, (2) polymerizable compound, and (3) colorant. Preferably, it is in the range of 0.3 to 7 parts by mass.

  Furthermore, the resist composition of the present invention is an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light resistance stable, within a range that does not impair the effects of the present invention, depending on purposes such as use and characteristics. Additives such as an agent stabilizer, a heat stabilizer, and an antioxidant can be blended.

  In addition, in order to impart coating suitability to the resist composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent that can be used here include acetate solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; propionate solvents such as ethoxypropionate; aromatics such as toluene, xylene, and methoxybenzene. Group solvents; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N- Nitrogen compound solvents such as dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone; Lactone solvents such as γ-butyrolactone; Examples thereof include bamic acid esters. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the intended use and the target film thickness and viscosity, but is 0.5 to A range of 6 times the amount is preferable.

  Examples of active energy rays for curing the resist composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific energy sources or curing devices include, for example, germicidal lamps, ultraviolet fluorescent lamps, carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc. Or an electron beam using a scanning type or curtain type electron beam accelerator. In addition, when making it harden | cure with an electron beam, the mixing | blending of the said polymerization initiator to the resist composition of this invention is unnecessary.

  Among these active energy rays, ultraviolet rays are particularly preferable. Further, it is preferable to irradiate in an inert gas atmosphere such as nitrogen gas since the surface curability of the coating film is improved. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with active energy rays.

  The application method of the resist composition of the present invention varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, curtain coater, shower coater, spin coater, slit coater, dipping, screen printing, spray, applicator, An application method using a bar coater or the like can be mentioned.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, unless otherwise indicated, parts and% are based on mass.

Example 1 (Synthesis of fluorosurfactant)
A flask substituted with nitrogen was charged with 47.5 g of 2-propanol and 25.6 g of 3-hydroxy-1-adamantyl methacrylate as solvents, and the temperature was raised to 40 ° C. while stirring under a nitrogen stream. Next, 5.3 g of 2,2′-bipyridyl and 1.9 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 40 ° C. Thereafter, 3.3 g of ethyl 2-bromoisobutyrate was added and reacted at 40 ° C. for 2 hours under a nitrogen stream to obtain a polymer segment containing a backbone of a bridged ring hydrocarbon. Next, 45.9 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 40 ° C. for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorinated surfactant (1) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (1) by GPC, they were the weight average molecular weight (Mw) 3,100 and the number average molecular weight (Mn) 2,700. Moreover, fluorine atom content was 14.5 mass%.

Example 2 (same as above)
Into a flask purged with nitrogen, 81.7 g of 2-propanol and 40.5 g of 3-hydroxy-1-adamantyl methacrylate were charged as solvents, and the temperature was raised to 40 ° C. while stirring under a nitrogen stream. Next, 7.3 g of 2,2′-bipyridyl and 1.5 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 40 ° C. Thereafter, 2.5 g of ethyl 2-bromoisobutyrate was added and reacted for 2 hours at 40 ° C. under a nitrogen stream to obtain a polymer segment containing a skeleton of a bridged ring hydrocarbon. Next, 13.7 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 40 ° C. for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorosurfactant (2) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (2) by GPC, they were the weight average molecular weight (Mw) 3,200 and the number average molecular weight (Mn) 2,700. Moreover, fluorine atom content was 37 mass%.

Example 3 (same as above)
Into a flask purged with nitrogen, 47.5 g of 2-propanol and 25.6 g of dicyclopentanyl methacrylate were charged as a solvent, and the temperature was raised to 40 ° C. while stirring under a nitrogen stream. Next, 5.3 g of 2,2′-bipyridyl and 1.9 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 40 ° C. Then, 3.3 g of ethyl 2-bromoisobutyrate was added, reacted under nitrogen flow at 40 ° C. for 2 hours, then charged with 25.6 g of dicyclopentanyl methacrylate, and reacted at 40 ° C. for 2 hours to bridge the ring carbonized. A polymer segment containing a hydrogen skeleton was obtained. Next, 45.9 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 40 ° C. for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorosurfactant (3) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (3) by GPC, they were the weight average molecular weight (Mw) 3,300 and the number average molecular weight (Mn) 2,900. Moreover, fluorine atom content was 14.5 mass%.

Example 4 (same as above)
Into a flask purged with nitrogen, 65 g of methyl ethyl ketone and 25.6 g of dicyclopentanyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. while stirring under a nitrogen stream. Subsequently, 3.1 g of 2,2′-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 60 ° C. Thereafter, 2.0 g of ethyl 2-bromoisobutyrate was added and reacted at 40 ° C. for 2 hours under a nitrogen stream to obtain a polymer segment containing a skeleton of a bridged ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 60 ° C. for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorosurfactant (4) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (4) by GPC, they were the weight average molecular weight (Mw) 4,200 and the number average molecular weight (Mn) 3,500. Moreover, fluorine atom content was 14.5 mass%.

Example 5 (same as above)
65 g of methyl ethyl ketone and 31 g of 1-adamantyl methacrylate were charged as a solvent in a flask purged with nitrogen, and the temperature was raised to 60 ° C. while stirring under a nitrogen stream. Subsequently, 3.1 g of 2,2′-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 60 ° C. Thereafter, 2.0 g of ethyl 2-bromoisobutyrate was added and reacted at 60 ° C. for 3 hours under a nitrogen stream to obtain a polymer segment containing a skeleton of a bridged ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 60 ° C. for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorosurfactant (5) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (5) by GPC, they were the weight average molecular weight (Mw) 4,100 and the number average molecular weight (Mn) 3,500. Moreover, fluorine atom content was 14.5 mass%.

Example 5 (same as above)
To a flask purged with nitrogen, 65 g of methyl ethyl ketone and 31 g of isobornyl methacrylate were charged as solvents, and the temperature was raised to 60 ° C. while stirring under a nitrogen stream. Subsequently, 3.1 g of 2,2′-bipyridyl and 1.1 g of cuprous chloride were charged, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 60 ° C. Thereafter, 2.0 g of ethyl 2-bromoisobutyrate was added and reacted at 60 ° C. for 3 hours under a nitrogen stream to obtain a polymer segment containing a skeleton of a bridged ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and reacted at 60 ° C. for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorosurfactant (5) of the present invention. As a result of measuring the molecular weight of this fluorine-type surfactant (5) by GPC, they were the weight average molecular weight (Mw) 4,200 and the number average molecular weight (Mn) 3,600. Moreover, fluorine atom content was 14.5 mass%.

Comparative Example 1
Into a glass flask equipped with a stirrer, a condenser, a dripping device, and a thermometer, 133 parts by mass of methyl isobutyl ketone was added and heated to 90 ° C. while stirring in a nitrogen stream. Next, 32 parts by mass of 2- (tridecafluorohexyl) ethyl methacrylate, 68 parts by mass of propylene glycol / polybutylene glycol monomethacrylate having an oxypropylene moiety having a repeating unit number of 1 and an oxybutylene moiety having an average repeating unit number of 6 were added to methyl isobutyl. Two types of dripping solutions, a monomer solution dissolved in 80 parts by mass of ketone and a radical polymerization initiator solution in which 6 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 20 parts by mass of methyl isobutyl ketone, respectively It set in another dripping apparatus, and it was dripped over 2 hours simultaneously, keeping the inside of a flask at 90 degreeC. After completion of the dropwise addition, the mixture was stirred at 90 ° C. for 10 hours, and then the solvent was removed under reduced pressure to obtain a fluorosurfactant (1 ′). This fluorosurfactant (1 ′) had a number average molecular weight of 3,600 and a weight average molecular weight of 9,500. The fluorine content was 19% by mass.

Comparative Example 2
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50.4 g of methyl isobutyl ketone as a solvent and heated to 90 ° C. while stirring under a nitrogen stream. Subsequently, 44.1 g of 2- (tridecafluorohexyl) ethyl methacrylate, a monomer solution obtained by dissolving 59.1 g of 3-hydroxy-1-adamantyl methacrylate in 167.4 g of methyl isobutyl ketone, and t-butyl as a radical polymerization initiator Two kinds of dripping liquids, which are a polymerization initiator solution in which 6.2 g of peroxy-2-ethylhexanoate was dissolved in 23.2 g of methyl isobutyl ketone, were set in separate dripping apparatuses, and the flask was kept at 90 ° C. It was dripped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 90 ° C. for 9 hours, and then 172.0 parts of the solvent was distilled off under reduced pressure to obtain a polymer (P-1) solution.

  Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate 34. 4 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 8 hours to confirm the disappearance of the isocyanate group by IR spectrum measurement, methyl isobutyl ketone was added, and a fluorosurfactant A methyl isobutyl ketone solution containing 40% of (2 ′) was obtained. The molecular weight of the fluorosurfactant (2 ') was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 3,600 and the weight average molecular weight was 18,000. The fluorine atom content calculated from the raw material charge ratio was 18%, the adamantane content was 24%, and the radical polymerizable unsaturated group equivalent was 550 g / eq. Met.

Comparative Example 3
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (X-1), and diisopropyl ether 20 as a solvent A mass part, 0.02 part by mass of p-methoxyphenol as a polymerization inhibitor, and 3.1 parts by mass of triethylamine as a neutralizing agent, stirring was started under an air stream, and acrylic acid was maintained while maintaining the inside of the flask at 10 ° C. 2.7 parts by mass of chloride was added dropwise over 1 hour. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer, and washing was repeated 3 times. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. . Subsequently, the solvent was distilled off under reduced pressure to obtain a monomer represented by the following structural formula (d1-1-1).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

  In another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 63 parts by mass of methyl isobutyl ketone was charged as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Subsequently, 21.5 parts by mass of the monomer (d1-1-1) obtained above, 41.3 parts by mass of 2-hydroxyethyl methacrylate, t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 9.4 parts by weight and 135.4 parts by weight of an initiator solution obtained by mixing 126 parts by weight of methyl isobutyl ketone as a solvent were set in separate dropping devices, and the flask was kept at 105 ° C at the same time. It was dripped over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P1-1).

  Next, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, 0.06 part by mass of dibutyltin dilaurate as a urethanization catalyst, and stirring under an air stream were started. While maintaining the temperature, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours. As a result, the disappearance of the isocyanate group was confirmed by IR spectrum measurement. Next, 37.4 parts by mass of methyl ethyl ketone was added as a solvent, and a substance insoluble in the solution was separated by filtration to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorosurfactant (3 ') having a polymerizable group. The molecular weight of the fluorosurfactant (3 ') was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,400, the weight average molecular weight was 7,100, and the maximum molecular weight was 200,000.

Example 7 (Preparation of resist composition)
42 g of green pigment dispersion using FASTOGEN Green A110 manufactured by DIC Corporation as a colorant, 15 g of Unidic RS20-160 manufactured by DIC Corporation as a binder resin, and NK ester manufactured by Shin-Nakamura Chemical Co., Ltd. as a photopolymerizable monomer 6 g of A-200, 0.5 g of Irgacure # 369 manufactured by BASF Japan Ltd. as a photopolymerization initiator, 0.06 g of the fluorosurfactant (1) of the present invention in terms of solid content, and 37 g of PGMEA are mixed. Thus, a color resist composition (1) was prepared.

  A cured coating film was obtained using the color resist composition (1). The water stain was evaluated using this cured coating film. A method for creating a cured coating film and a method for evaluating water stain are shown below. The evaluation results are shown in Table 1.

<Method for creating cured coating film>
The color resist composition (1) was spin-coated on a 7 cm × 7 cm glass plate at 1000 rpm for 10 seconds, and then exposed to a high-pressure mercury lamp at 200 mJ / cm ² to form a coating film.

<Evaluation method of water stain>
The glass plate on which the coating film was formed was stood against a cylindrical container, ion-exchanged water was added until about half of the substrate was immersed, and then allowed to stand for 5 minutes, and then taken out. The following evaluation was performed according to the degree of white line-like spots generated on the water line portion of the substrate. Evaluation is as follows.
○: White line-like spots are hardly seen. Δ: White line-like spots are seen thin. ×: White line-like spots are seen thick.

Example 8 (same as above)
A color resist composition (2) was obtained in the same manner as in Example 7 except that the fluorosurfactant (2) was used in place of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Example 9 (same as above)
A color resist composition (3) was obtained in the same manner as in Example 7 except that the fluorosurfactant (3) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Example 10 (same as above)
A color resist composition (4) was obtained in the same manner as in Example 7 except that the fluorosurfactant (4) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Example 11 (same as above)
A color resist composition (5) was obtained in the same manner as in Example 7 except that the fluorosurfactant (5) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Example 12 (same as above)
A color resist composition (6) was obtained in the same manner as in Example 7 except that the fluorosurfactant (6) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Comparative Example 1 (Preparation of resist composition for comparison)
A comparative color resist composition (1 ′) was obtained in the same manner as in Example 7 except that the comparative fluorosurfactant (1 ′) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Comparative Example 2 (same as above)
A comparative color resist composition (2 ′) was obtained in the same manner as in Example 7 except that the comparative fluorosurfactant (2 ′) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Comparative Example 3 (same as above)
A comparative color resist composition (3 ′) was obtained in the same manner as in Example 7 except that the comparative fluorosurfactant (3 ′) was used instead of the fluorosurfactant (1). The same evaluation as in Example 7 was performed, and the results are shown in Table 1.

Claims (12)

  Polymer obtained by using polymerizable monomer including polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded and a polymerizable unsaturated group A polymer segment (A2) obtained by using a polymerizable monomer including a segment (A1) and a polymerizable monomer (a2) having a backbone of a bridged ring hydrocarbon and a polymerizable unsaturated group A fluorine-based surfactant, which is a block copolymer.   2. The fluorine-based surfactant according to claim 1, wherein the skeleton of the bridged ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentene ring, a norbornane ring or a norbornene ring.   The fluorinated surfactant according to claim 1, wherein the skeleton of the bridged cyclic hydrocarbon of the polymerizable monomer (a2) is an adamantane ring.   The fluorinated surfactant according to claim 2 or 3, wherein the skeleton of the bridged cyclic hydrocarbon of the polymerizable monomer (a2) has a hydroxyl group.   The polymer segment (A2) is obtained by using the polymerizable monomer (a2) in an amount of 10 to 100% by mass based on the mass of all polymerizable monomers constituting the polymer segment (A2). The fluorinated surfactant according to claim 1. The fluorine-based surfactant according to claim 1, wherein the polymerizable monomer (a1) is a monomer represented by 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-4)), and X represents any one group of the following formulas (X-1) to (X-10). Rf represents any one of the following formulas (Rf-1) to (Rf-4). ]

[N in the above formulas (X-1), (X-3), (X-5), (X-6) and (X-7) represents an integer of 1-8. M in the above formulas (X-8), (X-9) and (X-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. Rf ″ in the above formulas (X-6) and (X-7) represents any one group of the following formulas (Rf-1) to (Rf-4). ]

[N in the above formulas (Rf-1) and (Rf-2) represents an integer of 1-6. N in the above formula (Rf-3) represents an integer of 2 to 6. N in the above formula (Rf-4) represents an integer of 4 to 6. ]   A resist composition comprising the fluorosurfactant according to any one of claims 1 to 6.   A cured product of the resist composition according to claim 7. Polymer obtained by using polymerizable monomer including polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded and a polymerizable unsaturated group A polymer segment (A2) obtained by using a polymerizable monomer including a segment (A1) and a polymerizable monomer (a2) having a backbone of a bridged ring hydrocarbon and a polymerizable unsaturated group A process for producing a fluorosurfactant which is a block copolymer, wherein the block copolymer is produced by living radical polymerization. The method for producing a fluorosurfactant according to claim 7, wherein the living radical polymerization is atom transfer radical polymerization. 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, the polymerizable monomer containing the polymerizable monomer (a1) is converted into an atom transfer radical. After polymerizing to obtain a polymer segment (A1), a polymerizable monomer containing a polymerizable monomer (a2) is added, and a polymerizable monomer (a2) is further added to the polymer segment (A1). The method for producing a fluorosurfactant according to claim 9, wherein the polymerizable monomer is atom transfer radical polymerized. 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, the polymerizable monomer containing the polymerizable monomer (a2) is converted into an atom transfer radical. After polymerizing to obtain a polymer segment (A2), a polymerizable monomer containing a polymerizable monomer (a1) is added, and a polymerizable monomer (a1) is further added to the polymer segment (A2). The method for producing a fluorosurfactant according to claim 9, wherein the polymerizable monomer is atom transfer radical polymerized.