KR20160132829A - Fluorine-based surfactant, coating composition, resist composition, and cured product - Google Patents

Abstract

The present invention relates to a fluorinated surfactant which is capable of obtaining a coating film in which a coating film is hardly discolored even when exposed to an alkaline solution or an acidic solution (water hardly occurs), a composition using the fluorinated surfactant and a cured product, (A1) obtained by using a polymerizable monomer containing a fluorinated alkyl group having 1 to 6 carbon atoms and a polymerizable monomer (a1) having a polymerizable unsaturated group and a polymer segment (A1) having a polymerizable unsaturated group having a skeleton of a crosslinked ring hydrocarbon and a polymerizable unsaturated group A fluorine-based surfactant characterized by being a block copolymer comprising a polymer segment (A2) obtained by using a polymerizable monomer containing a monomer (a2).

Description

TECHNICAL FIELD [0001] The present invention relates to a fluorine-based surfactant, a coating composition, a resist composition, and a cured product,

The present invention relates to a fluorine-based surfactant which can obtain a coating film which is difficult to discolor (hardly causing water spots) even when exposed to an alkaline solution or an acidic solution, a coating composition, a resist composition and a cured product of these compositions using the same.

A color filter used in a color liquid crystal display device or an organic EL display device is generally composed of red (R), green (G), and blue (B) pixels and a black matrix BM) are 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, slit coating, etc., followed by exposure using a mask and then development to form a coloring pattern.

In the above-mentioned phenomenon, an alkaline developer is used as a developing solution, and the unexposed portions are rinsed by rinsing. At that time, there is also a problem that residues such as the resin of the unexposed portion present in the cleaning liquid adhere to the cured coating film surface of the colored pattern of the exposed portion, and the resist composition is also required to have characteristics that it is difficult to adhere to the coloring pattern of the residue.

As a composition for forming a color filter pixel in which the residue is difficult to adhere onto a coloring pattern, for example, a composition comprising a radical polymerizable monomer having a poly (perfluoroalkylene ether) chain and a radical polymerizable monomer having a polyalkylene glycol chain A fluorine atom-containing surfactant obtained by reacting a copolymer having a reactive functional group obtained by copolymerizing a reactive functional group with a compound having a reactive group with the reactive functional group and a compound having a radically polymerizable group (See Patent Document 1). However, the coloring pattern obtained by using the composition for forming a color filter pixel described in Patent Document 1 is a phenomenon (water stain) in which the coloring pattern (coating film) discolors when exposed to an alkaline developing solution used in the developing step There is a problem that arises. Such water spots disappear after post-baking, so there is no problem with the product. However, in the appearance inspection of the patterned surface after the development, the water spots are detected as irregularities, resulting in a problem that the regular product and the abnormal product can not be discriminated. Therefore, if the inspection sensitivity of the inspection apparatus is lowered in the visual inspection, the yield of the final color filter product is lowered as a result, which is a problem. Accordingly, there is a demand for a resist composition which can provide a cured coating film that is less prone to water spots in the developing process and the cleaning process.

Japanese Patent Application Laid-Open No. 2010-250256

A problem to be solved by the present invention is to provide a coating composition, a resist composition and a cured product of the fluorinated surfactant which can obtain a coating film which is difficult to discolor (hardly causing water spots) even when exposed to an alkaline solution or an acidic solution .

As a result of intensive studies, the present inventors have found that a polymer segment comprising a polymerizable monomer having a fluorinated alkyl group and a polymerizable unsaturated group, a polymer segment having a skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer having a polymerizable unsaturated group, A polymerizable monomer having a dicyclopentanone ring and a polymerizable unsaturated group, a polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group, a polymerizable monomer having a dicyclopentane ring and a polymerizable monomer having a polymerizable unsaturated group, Or a block copolymer comprising a polymer segment comprising a polymerizable monomer having a norbornene ring and a polymerizable monomer having a polymerizable unsaturated group as a fluorochemical surfactant for solving the above problems, I have come to completion.

That is, the present invention relates to a polymer segment (A1) obtained by using a polymerizable monomer comprising a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable monomer (a1) having a polymerizable unsaturated group, (A2) obtained by using a polymerizable monomer comprising a skeleton of a cyclic hydrocarbon and a polymerizable monomer (a2) having a polymerizable unsaturated group. The present invention also provides a fluorinated surfactant comprising the polymer segment (A2).

The present invention also provides a coating composition characterized by containing the above-mentioned fluorine-based surfactant.

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

The present invention also provides a cured product obtained by curing the coating composition or the resist composition.

By using the fluorine-based surfactant of the present invention, it is possible to provide a coating composition or a resist composition which is less likely to cause water stains on a cured product such as a coating film.

The fluorine-containing surfactant of the present invention comprises polymer segments (A1) and (2) obtained by using a polymerizable monomer containing a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable unsaturated group , And a polymer segment (A2) obtained by using a polymerizable monomer comprising a skeleton of a crosslinked ring hydrocarbon and a polymerizable monomer (a2) having a polymerizable unsaturated group.

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) may be used in combination as long as the effect of the present invention is not impaired. Examples of the polymerizable monomer that can be used in combination include a polymerizable monomer having a polyoxyalkylene chain, a polymerizable monomer having a straight chain alkyl group having 1 to 18 carbon atoms, and a branched alkyl group having 1 to 18 carbon atoms And the like.

In the present invention, as the polymerizable monomer containing the polymerizable monomer (a1), it is preferable to use a monomer having a high content of the polymerizable monomer (a1). When the content of the polymerizable monomer (a1) is 100% Is particularly preferable.

The polymerizable monomer (a1) having a fluorinated alkyl group and a polymerizable unsaturated group having 1 to 6 carbon atoms in which a fluorine atom is directly bonded in the present invention is not particularly limited as long as the compound has the fluorinated alkyl group and the polymerizable unsaturated group in the molecule Can be used.

Here, the fluorinated alkyl group having 1 to 6 carbon atoms in which the fluorine atoms are directly bonded is a perfluoroalkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded, or a partially fluorinated alkyl group in which a part of hydrogen atoms are fluorine atoms. Of these fluorinated alkyl groups, perfluoroalkyl groups are preferred because they are highly effective as surfactants. The number of the carbon atoms to which the fluorine atoms are directly bonded is more preferable, and the number of the carbon atoms to which the fluorine atoms are directly bonded is particularly preferably from 4 to 6.

Examples of the polymerizable unsaturated group of the polymerizable monomer (a1) include a (meth) acryloyl group, a vinyl group, and a maleimide group. Among these, the (meth) acryloyl group is preferable because it is easy to obtain the raw materials, ease of controlling various coating compositions, compatibility with the compounding components in the resist composition, or polymerization reactivity. As the sphere having the (meth) acryloyl group, for example, a monomer represented by the following general formula (1) can be preferably exemplified. The polymerizable monomer (a1) may be used singly or in combination of two or more.

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, and Rf' X represents any one of groups represented by the following formulas (X-1) to (X-10), Rf represents a group represented by any one of the following formulas (Rf-1) to (Rf-1) to (Rf-4).

N in the formulas (X-1), (X-3), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. M in the 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 of the following formulas (Rf-1) to (Rf-

[N in the formulas (Rf-1) and (Rf-2) represents an integer of 1 to 6) N in the formula (Rf-3) represents an integer of 2 to 6. N in the 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 crosslinked ring hydrocarbon skeleton and a polymerizable unsaturated group. On the surface of the coating film of the resist composition or coating composition containing the fluorine-based surfactant of the present invention, a layer containing the fluorine-based surfactant of the present invention (hereinafter, sometimes referred to as a block layer) is localized on the surface. In the fluorine-based surfactant of the present invention, the glass transition temperature (Tg) is high due to the presence of the skeleton of the crosslinked ring hydrocarbon, and as a result, the block layer becomes a hard layer. That is, although the cured coating film is formed by irradiation of the active energy ray, a coating film that is sufficiently cured by the presence of the skeleton of the crosslinked ring hydrocarbon can be obtained even when a sufficient activation energy ray is not irradiated. As a result, the inventors of the present invention have conceived that a coating film obtained by using the fluorine-based surfactant of the present invention can obtain a coating film in which water stains rarely occur.

Examples of the skeleton of the crosslinked ring hydrocarbon include adamantane ring, perhydroindenylene ring, decalin ring, perhydrofluorene ring, perhydroanthracene ring, perhydrophenanthrene ring, dicyclopentane ring, dicyclopentane ring , Perhydro-acenaphthene ring, perhydrophenylene ring, norbornane ring, norbornene ring and the like. Among them, a block layer having a high Tg can be formed by the surface of the coating film, and as a result, a cured coating film which is less liable to be immersed in water is obtained, and therefore adamantane, dicyclopentane ring, norbornane ring and norbornene ring are preferable And an adamantane ring is more preferable.

Examples of the polymerizable unsaturated group include (meth) acryloyl group, vinyl group, maleimide group, and the like. Among them, the (meth) acryloyl group is preferable because it is easy to obtain raw materials, ease of control of compatibility with various coating compositions or compounding components in a resist composition, or polymerization reactivity is good.

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

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

(Wherein 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 them, a hydroxyl group is preferable because a fluorine-based surfactant having good compatibility with a coating composition can be obtained.

The bonding position of the organic group having a reactive functional group represented by -XL in the general formula (a2-1) and Y may be bonded to any carbon atom in the adamantaneminal ring, and two or more . The hydrogen atom bonded to the carbon atom constituting the adamantanemember may be partially or entirely substituted with a fluorine atom, an alkyl group, 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 a methylene group, a propyl group, an isopropylidene group and the like having 1 to 8 carbon atoms Alkylene group.

In the compound represented by the above formula (a2-2), the (meth) acryloyl group may be bonded to any carbon atom in the adamantyl group. The hydrogen atom bonded to the carbon atom constituting the adamantane structure in the general formula (a2-1) may be partially or entirely substituted with a fluorine atom, an alkyl group or the like.

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

Further, more specific examples of the polymerizable monomer represented by the general formula (a2-2) include, for example, the following compounds.

Among the polymerizable monomers having an adamantane ring and a (meth) acryloyl group, a fluorinated surfactant having good compatibility with other constituent components in the coating composition can be obtained, and therefore the compound represented by the above formula (a2-1) is preferable, The compounds represented by the above formulas (a2-1-1), (a2-1-3) and (a2-1-5) are more preferable.

Hereinafter, a polymerizable monomer having a dicyclopentanecane ring and a polymerizable unsaturated group which 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 a compound represented by the following formula (a2-3).

(Wherein R represents a hydrogen atom, a methyl group or CF ₃ )

In the compound represented by the above formula (a2-3), the (meth) acryloyl group may be bonded to any carbon atom in the dicyclopentanemal ring. The hydrogen atom bonded to the carbon atom constituting the dicyclopentanecane ring in the general formula (a2-3) may be partially or entirely 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, for example, the following compounds.

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

Hereinafter, a polymerizable monomer having a dicyclopentene ring and a polymerizable unsaturated group which 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 a compound represented by the following formula (a2-4).

(Wherein 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 dicyclopentane ring. The hydrogen atom bonded to the carbon atom constituting the dicyclopentane ring in the general formula (a2-3) may be partially or entirely substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-4) include, for example, the following compounds.

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

Hereinafter, a norbornane ring and a polymerizable monomer having a polymerizable unsaturated group, which 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).

(Wherein 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. The hydrogen atom bonded to the carbon atom constituting the norbornane ring in the general formula (a2-5) may be partially or entirely substituted with a fluorine atom, an alkyl group or the like.

More specific examples of the polymerizable monomer represented by the general formula (a2-5) include, for example, the following compounds.

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

Hereinafter, the norbornene ring and the polymerizable monomer having a polymerizable unsaturated group which 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).

(Wherein 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. The hydrogen atom bonded to the carbon atom constituting the norbornene ring in the general formula (a2-6) may be partially or entirely substituted with a fluorine atom, an alkyl group or the like.

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

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

As described above, the fluorine-containing surfactant of the present invention is a polymer segment obtained by using a polymerizable monomer containing a polymerizable monomer (a1) having a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable unsaturated group (A2) obtained by using a polymerizable monomer containing a crosslinkable ring hydrocarbon skeleton and a polymerizable monomer (a2) having a polymerizable unsaturated group. Here, the proportion of the polymer segment (A1) to the polymer segment (A2) is (A1) :( A2) = 5: 95 to 90: 10 in terms of mass ratio since a fluorochemical surfactant having good compatibility with the coating composition is obtained More preferably 10:90 to 80:20.

The polymer segment (A2) is obtained by polymerizing the polymerizable monomer (a2) in an amount of from 10 to 100 mass% based on the mass of the prepolymerizable monomer (constituting the polymer segment (A2)) used in obtaining the polymer segment 100% by mass is preferable because it is possible to obtain a fluorine-based surfactant capable of forming a more rigid layer on the surface of the coating film, more preferably 20 to 90% by mass.

As described above, when the polymer segment (A2) is obtained, a polymerizable monomer other than the polymerizable monomer (a2) may be used in combination within a range not to impair the effect of the present invention. Examples of the polymerizable monomer that can be used in combination include a polymerizable monomer having a polyoxyalkylene chain, a polymerizable monomer having a straight chain alkyl group having 1 to 18 carbon atoms, and a branched alkyl group having 1 to 18 carbon atoms And the like.

The method for producing the fluorine-based surfactant of the present invention is not particularly limited, but it is preferable to use a polymer segment (A1) obtained by using a polymerizable monomer containing a polymerizable monomer (a1) and a polymer segment Living radical polymerization is preferable because the polymerization reaction for obtaining a block copolymer composed of the polymer segment (A2) obtained by using a monomer is easy to control.

Generally, in the living radical polymerization, a dormant species (species) protected by an active polymerization terminal atom or atomic group reversibly reacts with a monomer by reacting with the monomer, so that the growth reaction proceeds, and even if the first monomer is consumed, The block polymer can be obtained by reacting with the second monomer which is added in sequence without losing the activity. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-cleavable radical polymerization (RAFT), radical polymerization through nitroxide (NMP), radical polymerization using organic tellurium . No particular limitation is imposed on which method to use, but ATRP is preferable for ease of control and the like. ATRP is polymerized using an organic halide, a halogenated sulfonyl compound or the like as a catalyst as a catalyst, a metal complex comprising an initiator, a transition metal compound and a ligand.

As the polymerization initiator used in the ATRP, an organic halogenated compound can be used. Specific examples thereof include 1-phenylethyl chloride and 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile,?,? '- dichloro xylene,?,?' - dibromohydrin, hexakis (Such as 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid, 2-bromoisobutyric acid, etc.) of 2-halogenated carboxylic acid having 1 to 6 carbon atoms Alkyl esters having a number of 1 to 6, and the like. More specific examples of the alkyl esters having 1 to 6 carbon atoms in the 2-halogenated carboxylic acid having 1 to 6 carbon atoms include methyl 2-chloropropionate, ethyl 2-chloropropionate, methyl 2-bromopropionate , Ethyl 2-bromoisobutyrate, and the like.

The transition metal compound used for ATRP is represented by M ^{n +} X _n . The transition metal is 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+, Z n +,} Zn 2+, Au +, Au 2 +, can be selected from the group consisting of Ag ⁺ and Ag ^{+ 2.} X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ) Plate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an alkyl group of 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) in the aryl, straight-chain or branched chain, and R ² represents a hydrogen atom, Or an alkyl group having 1 to 6 carbon atoms (preferably a methyl group), which may be substituted, which may be substituted one to three times by fluorine or chlorine. In addition, n represents a formal charge on the metal, and is an integer of 0 to 7.

The transition metal complex is not particularly limited but is preferably a transition metal complex of group 7, 8, 9, 10 or 11, more preferably a transition metal complex of 0 valent copper, monovalent copper, divalent ruthenium, Nickel complexes of nickel and silver.

As the compound having a ligand capable of coordinating with the transition metal described above, a compound having a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with a transition metal via a sigma bond, A compound having a ligand containing two or more carbon atoms capable of coordinating via a π bond, and a compound having a ligand capable of coordinating with a transition metal via a μ-bond or an η-bond.

Specific examples of the compound having a ligand include, for example, 2,2'-bipyridyl and its derivatives when the central metal is copper, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyl And polyamines such as diethylenetriamine, hexamethyltris (2-aminoethyl) amine, and the like. Examples of divalent ruthenium complexes include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichloro p-cymene ruthenium, Ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium and carbonylchlorohydrid tris (triphenylphosphine) ruthenium . Examples of the divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

In the living radical polymerization, a solvent is preferably used. Examples of the solvent to be 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-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohol solvents such as methanol, ethanol and isopropanol; And aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. These solvents may be used alone or in combination of two or more.

In the production of the fluorine-based surfactant of the present invention, the following methods can be preferably exemplified.

Method 1: In the presence of a polymerization initiator, a transition metal compound, a ligand capable of coordinating with the transition metal, and a solvent, the polymerizable monomer containing the polymerizable monomer (a1) is subjected to living radical polymerization, preferably atom transfer To obtain a polymer segment (A1), and then a polymerizable monomer containing a polymerizable monomer (a2) is added to obtain a polymerizable monomer containing a polymerizable monomer (a2) in addition to the polymer segment (A1) Polymerization, preferably atom transfer radical polymerization.

Method 2: A method of polymerizing a polymerizable monomer containing a polymerizable monomer (a2) in the presence of a polymerization initiator, a transition metal compound, a ligand capable of coordinating with the transition metal, and a solvent to a living radical polymerization, (A1) is added to the reaction system to obtain a polymer segment containing the polymerizable monomer (a1) in addition to the polymer segment (A2) 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 캜.

Further, when the fluorine-based surfactant of the present invention is produced by living radical polymerization, a metal originating from the transition metal compound used in the polymerization may remain in the fluorine-based surfactant. Therefore, when the metal is used for a semiconductor such as a photoresist composition which causes a problem when it remains, it is preferable to remove the residual metal by 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 fluorine-based surfactant of the present invention are preferably 500 to 200,000, more preferably 1,000 to 150,000, since they are fluorine- , And more preferably in the range of 1,500 to 100,000. The dispersion degree (Mw / Mn) of the fluorine-based surfactant of the present invention is preferably 1.5 or less, more preferably in the range of 1.00 to 1.40, further preferably in the range of 1.05 to 1.30 Range is more preferable.

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

[Conditions for measuring GPC]

Measurement apparatus: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 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 Tokushu Kika Kogyo Co., TSK-GEL GMHHR-N "(7.8 mm ID x 30 cm)

Detector: ELSD ("ELSD2000" manufactured by Orthek Japan Co., Ltd.)

Data processing: "GPC-8020 Model II Data Interpretation Version 4.30" manufactured by Tosoh Corporation

Measuring conditions : Column temperature 40 ℃

Developing solvent Tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid matter was filtered with a microfilter (5)).

Standard samples: 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".

(Monodisperse polystyrene)

&Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

&Quot; F-128 " manufactured by Tosoh Corporation

&Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

The content of fluorine atoms in the fluorine-based surfactant of the present invention is preferably in the range of 4 to 40 mass%, more preferably in the range of 5 to 35 mass%, more preferably in the range of 6 to 30 mass% % Is more preferable. The content of fluorine atoms can be measured by combustion ion chromatography.

The coating composition of the present invention uses the above-mentioned fluorine-based surfactant of the present invention as an additive. The amount of the fluorinated surfactant to be added in the coating composition varies depending on the kind of the coating resin, the coating method, and the intended thickness, but is preferably from 0.0001 to 10 parts by mass, more preferably from 0.001 to 5 parts by mass And more preferably 0.01 to 2 parts by mass. When the amount of the fluorochemical surfactant is within this range, the surface tension can be sufficiently lowered, and the aimed leveling property can be obtained, and occurrence of problems such as foam generation during coating can be suppressed.

By using the fluorine-based surfactant of the present invention as an additive for the coating composition, compared with the conventional fluorine-based surfactant having a perfluoroalkyl group having 8 or more carbon atoms, the accumulation property to the environment and the living body is low, It is possible to provide a coating composition which exhibits high leveling property even in a coating method accompanied by equivalent or superiority of a fluorinated surfactant having a perfluoroalkyl group having at least 8 atoms, that is, a high speed and a high shear force. As such a coating composition, useful coating compositions include, for example, compositions for various paints and photosensitive resin compositions.

Examples of the composition for paints include paints using natural resins such as petroleum resin paints, shellac paints, rosin paints, cellulose paints, rubber paints, paint paints, cashew resin paints, oil based vehicle paints and the like; Paints using synthetic resins such as phenol resin 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, fluoric resin paints, etc. .

In addition, the above-mentioned composition for paints may contain colorants such as pigments, dyes, and carbon, if necessary; Inorganic powders such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate; Organic fine powders such as higher fatty acids, polyacrylic resins, and polyethylene; Various additives such as a light resistance improving agent, a weather resistance improving agent, a heat resistance improving agent, an antioxidant, a thickener, and an anti-settling agent can be appropriately added. As the coating method, any method can be used as long as it is a publicly known coating method. For example, methods such as roll coater, electrostatic coating, bar coater, gravure coater, knife coater, dipping coating, have.

The above-mentioned photosensitive resin composition changes physical properties such as solubility, viscosity, transparency, refractive index, conductivity, and ion permeability of the resin by irradiating light such as visible light or ultraviolet light. Among these photosensitive resin compositions, resist compositions (such as a photoresist composition, a color resist composition for a color filter, and the like) require high leveling properties. Generally, in photolithography for semiconductors or liquid crystals, a resist composition is generally applied onto a silicon wafer or a glass substrate on which various metals are deposited by spin coating accompanied by a high shear force so as to have a thickness of about 1 to 2 mu m . At this time, if the thickness of the coating film is uneven or coating irregularity generally called striping occurs, the linearity and reproducibility of the pattern are lowered, and there arises a problem that a resist pattern having the desired degree (accuracy) can not be obtained . In addition, in recent years, problems related to various leveling such as drop marks, total irregularities, and bead phenomenon in which the edge portion becomes thicker than the center portion are being close up. It is an important problem to suppress the occurrence of unevenness of thickness of the coating film and the occurrence of stretching at the present time as the resist pattern becomes finer or the size of the silicon wafer becomes larger and the glass substrate for liquid crystal becomes larger. In addition, from the viewpoints of improvement in the productivity of the semiconductor and the liquid crystal device, and high functionality, it is necessary to strictly control the unevenness of the coating film thickness and the suppression of occurrence of striping.

Here, the fluorine-based surfactant of the present invention exhibits a high leveling property and can form a uniform coating film (cured product) by using the fluorine-containing surfactant as an additive for the photosensitive resin composition, particularly, the resist composition. I can solve the problem.

In general, in a resist composition, a color resist composition is composed of a surfactant and a photoresist agent. Examples of the photoresist agent include (1) an alkali-soluble resin, (2) a polymerizable compound and have.

The (1) alkali-soluble resin used in the present invention is not particularly limited as long as it is soluble in an alkali developer, but resins having at least one acid group selected from the group of a carboxyl group, a phenolic hydroxyl group and a sulfonic acid group or a salt thereof are preferable Do.

More specifically, the alkali-soluble resin (1) is obtained by polymerizing a monomer having an acidic group. (1) As the monomer having a carboxyl group as an acidic group serving as a raw material of the alkali-soluble resin, for example, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, .

(1) Examples of the monomer having a phenolic hydroxyl group as an acidic group serving as a raw material of the alkali-soluble resin include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene and the like. Further, compounds in which at least one hydrogen atom other than a phenolic hydroxyl group and a vinyl group bonded to the aromatic rings of these monomers are substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group or an amide group may be mentioned.

(1) Examples of the monomer having a sulfonic acid group as an acidic group serving as a raw material of the alkali-soluble resin include vinylsulfonic acid, styrenesulfonic acid, (meth) allylsulfonic acid, 2-hydroxy- (Meth) acryloxypropane sulfonic acid, 2- (meth) acrylamide-2 (meth) acrylate, 2- -Methylpropanesulfonic acid or their salts, and the like.

The above-mentioned monomer having an acidic group may be polymerized singly to (1) an alkali-soluble resin, but it may be copolymerized with other monomers. Examples of such other monomers include hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth) acrylic esters, (meth) acrylamides, Chloroolefins, conjugated dienes, and the like. Of these, (meth) acrylic acid esters are preferred.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (Meth) acrylate, n-pentyl (meth) acrylate, isobutyl acrylate, sec-butyl (meth) acrylate, t- (Meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, , Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclo Hexyl, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono Acrylate, 2-methoxyethyl (meth) acrylate, 1,1-dimethyl-3-oxobutyl (meth) acrylate, 2-acetoacetoxyethyl , And benzyl (meth) acrylate.

(1) Monomers having an acidic group as a raw material of the alkali-soluble resin and the above-mentioned other monomers may be used alone or in combination of two or more.

The above-mentioned (2) polymerizable compound is not particularly limited as long as it is a compound having a photopolymerizable functional group capable of undergoing polymerization or crosslinking by irradiation with active energy rays such as ultraviolet rays. Specific examples thereof include, for example, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) (Meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (Meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and the like (Meth) acrylate.

Further, it is also possible to use N, N'-ethylenediimaleimide, N, N'-hexamethylene dimaleimide, N, N'-dodecamethylene dimaleimide, N, N'-methylene di-p-phenylene) dimaleimide, N, N '- (oxydi-p-phenylene) dimaleimide, N, N'-m-xylylenediimaleimide, N, N'-2,6-tolylene dimaleimide, N, N, N'-p, p'-diphenylsulfone bismaleimide, N, N'-oxydipropylene dimaleimide, ethylenedioxy-bis-N-ethyl maleimide, , 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-maleimidopropyl (3-maleimidopropyl) butane, diethylene glycol (3-maleimidopropyl) methyl ether, methyl (3-maleimidopropyl) ether of polyethylene glycol with Mn = 400, trimethylolpropane (3-maleimide propyl ether), Mn = 400 bis (3-maleimidopropyl) ether of polyethylene glycol, and Mn = 400 polyethylene glycol mono (3-maleimidopropyl) vinyl ether; Methylmaleimide acetate, ethylmaleimide caproate, ethylene glycol monomethyl ether maleimide acetate, monomethyl ether maleimide acetate of polyethylene glycol with Mn = 400, tetrahydrofurfuryl maleimide acetate, diethylene glycol bismaleimide acetate, Diethylene glycol monomaleimide acetate acrylate, bismaleimide acetate of polyethylene glycol of Mn = 400, bismaleimide acetate of polytetramethylene glycol of Mn = 250, monomaleimide capronate acrylate of polyethylene glycol of Mn = 400 , Trimethylolpropane trimaleimide acetate, ethylene oxide modified trimethylol propane trimaleimide acetate, ethylene oxide modified trimethylol propane dimaleimide acetate monoacrylate, pentaerythritol tetramale Ethylene oxide modified pentaerythritol dimaleimide acetate, ethylene oxide modified pentaerythritol trimaleimide acetate, ethylene oxide modified pentaerythritol tetramaleimide acetate, ethylene oxide modified pentaerythritol dimaleimide acetate diacrylate, etc. Maleimide ester compounds; N-ethyl- (2-maleimideethyl) carbamate; A urethane compound obtained by reacting an equivalent mixture of isophorone diisocyanate and (poly) alkylene polyol with 2-maleimide ethanol; Maleimide derivatives such as maleimide carbonate compounds such as 2-maleimide ethyl-ethyl carbonate, 2-maleimide ethyl-isopropyl carbonate and tetraethylene glycol bis (3-maleimidepropyl carbonate). These (2) polymerizable compounds may be used alone, or two or more of them may be used in combination.

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

The colorant (3) used in the present invention is not particularly limited as long as it can be colored, but a pigment is preferable from the viewpoint of heat resistance and light fastness, and organic pigments and inorganic pigments can be used.

The organic pigment is used in accordance with the color of each pixel of red (R), green (G), and blue (B). In the red pixel, for example, C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 217, C.I. Pigment Red 220, C.I. Pigment Red 223, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 227, C.I. Pigment Red 228, C. I. Pigment Red 240, C. I. Pigment Red 254, C.I. Pigment Red 48: 1 can be used.

In the pixel of green (G), for example, C.I. Pigment Green 7, C.I. Pigment Green 36 and the like can be used. In the blue (B) pixel, for example, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 6, C.I. Pigment Blue 22, C.I. Pigment Blue 60, C.I. Pigment Blue 64 and the like can be used.

Further, in order to improve the color reproducibility of each of the red (R), green (G) and blue (B) pixels, the organic pigments of other colors may be used as the color adjustment. As such an organic pigment for color adjustment, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 30, C.I. Pigment Violet 37, C.I. Pigment Violet 40, C.I. Violet pigments such as Pigment Violet 50; C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 117, C.I. Pigment Yellow 125, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. And Pigment Yellow 185, and the like.

On the other hand, the (3) coloring agent used for forming the black matrix (BM) is not particularly limited as long as it is black, but a pigment such as carbon black, a metal oxide, and a composite metal compound composed of two or more metal oxides is preferable. Further, it may be a combination of two or more organic pigments selected from pigments having colors of red, blue, green, purple, yellow, cyan and magenta, and black by mixing.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, furnace black and the like. 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 _{2 m -1} (m is a number of 1 or more). As the metal oxide, metal oxides such as copper, iron, chromium, manganese, and cobalt can also be used. Examples of the composite metal compound composed of two or more metal oxides include oxides of copper-chromium, oxides of copper-chromium-manganese, oxides of copper-iron-manganese, and oxides of cobalt-iron- .

Examples of the organic pigments include quinacridone pigments, perylene pigments, pyrrolo pyrrole pigments, anthraquinone pigments, and the like. Examples of pigments having a hue include red Phthalocyanine pigments, and indanthrene pigments. Examples of pigments having a rust hue include halogenated phthalocyanine pigments and pigments having a purple hue include dioxazine violet, fast violet B , Methyl violet lake, and indanthrene brilliant violet. Examples of pigments having a yellow color include tetrachloroisoindolinone type pigments, hansa yellow type pigments, benzidine yellow type pigments and azo type pigments. Examples of the pigment having a hue include nonmetal phthalocyanine and merocyanine, and as the pigment having a magenta hue, Creations can be money, thioindigo and the like.

The coloring agents used for forming red (R), green (G), and blue (B) and the black matrix (BM) may be used alone or in combination of two or more You may.

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

In the resist composition of the present invention, when the (3) coloring agent is a pigment, it is preferable to prepare the pigment dispersion prepared by dispersing in an organic solvent using a dispersing agent in advance. As the dispersing agent, for example, a surfactant; Intermediates or derivatives of pigments; Intermediates or derivatives of dyes; And resinous dispersants such as polyamide resins, polyurethane resins, polyester resins and acrylic resins. Among these pigment dispersants, a resinous 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 commercial products of such a resinous dispersant include BYK-160, BYK-161 and BYK-2001 manufactured by BICKEMI Co., Ltd., FUKA 46 manufactured by Fuka Chemicals, Ajinomoto Fine Techno AJI Super PB-814 " manufactured by Nippon Kayaku Co., Ltd., and the like. These dispersants may be used alone or in combination of two or more.

Examples of the organic solvent used in the preparation of the pigment dispersion include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Propionate-based solvents such as ethoxypropionate; Aromatic solvents such as toluene, xylene and 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 hydrocarbon solvents such as hexane; Nitrogen-based solvents such as N, N-dimethylformamide,? -Butyrolactam and N-methyl-2-pyrrolidone; lactone type solvents such as? -butyrolactone; And carbamic acid esters. These solvents may be used alone, or two or more of them may be used in combination.

Examples of the method for preparing the pigment dispersion include (3) a method in which a colorant is subjected to a kneading and dispersing step and a microdispersion step, and a method in which only a microdispersion step is performed. In the kneading and dispersing step, (3) a colorant, (1) a part of an alkali-soluble resin and, if necessary, the dispersing agent are mixed and kneaded. Examples of the machine used for kneading include 2 rolls, 3 rolls, a ball mill, a tron mill, a dispenser, a kneader, a coneizer, a homogenizer, a blender, a single or double shaft extruder, So that the coloring agent can be dispersed by dispersing while adding a strong shearing force. It is preferable that (3) the coloring agent is made finer by the salt milling method or the like before carrying out the above kneading.

(3) a colorant, (1) an alkali-soluble resin, a solvent and, if necessary, the above-mentioned dispersing agent, in the above- (3) the particles of the coloring agent can be dispersed in a minute state close to the primary particles by mixing and dispersing the mixture with a dispersion medium for fine particles of glass, zirconia or ceramics using a dispersing machine.

The average particle diameter of (3) primary particles of the colorant is preferably 10 to 100 nm, more preferably 10 to 60 nm. The average particle diameter of the (3) colorant is measured by a particle size distribution meter of a dynamic light scattering type. For example, a particle size distribution measuring apparatus "UPA-EX150", a Nanotrac particle size distribution measuring apparatus manufactured by Nikkiso Co., &Quot; UPA-EX250 " or the like.

When an active energy ray such as ultraviolet rays is irradiated to cure the resist composition of the present invention, a polymerization initiator is added to the resist composition of the present 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 (4'-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4'-dodecylphenyl) 2-methylpropan-1-one, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylisophthalo 2-methylthioxanthone, 2-isopropylthioxanthone, 2-isopropylthioxanthone, 2-methylthioxanthone, -Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6- And diphenylphosphine oxide. These may be used singly or in combination of two or more. Among them, the effect of the (3) coloring agent contained in the composition for forming a color filter pixel of the present invention is relatively difficult to obtain, and although it exhibits high curability, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1 is preferred.

If necessary, a photosensitizer such as an amine compound or phosphorus compound may be added to promote photopolymerization.

The blending amount of the polymerization initiator is preferably in the range of 0.01 to 15 parts by mass, more preferably in the range of 0.3 to 7 parts by mass with respect to 100 parts by mass of the total of the above-mentioned (1) alkali-soluble resin, (2) polymerizable compound and (3) Is more preferable.

The resist composition of the present invention may contain an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity adjuster, a light stabilizer, a heat stabilizer, a heat stabilizer, An antioxidant and the like may be added.

In order to impart coating properties to the resist composition of the present invention, an organic solvent may be added to adjust the viscosity. Examples of the organic solvent usable herein include acetic acid ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Propionate-based solvents such as ethoxypropionate; Aromatic solvents such as toluene, xylene and 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 hydrocarbon solvents such as hexane; Nitrogen-based solvents such as N, N-dimethylformamide,? -Butyrolactam and N-methyl-2-pyrrolidone; lactone type solvents such as? -butyrolactone; And carbamic acid esters. These solvents may be used alone, or two or more of them may be used in combination.

Here, the amount of the organic solvent to be used varies depending on the intended use and the intended film thickness or viscosity. However, the amount of the organic solvent is preferably in the range of 0.5 to 6 times the mass of the total of the above-mentioned (1) alkali-soluble resin and (2) .

Examples of the active energy ray for curing the resist composition of the present invention include active energy rays such as light, electron beam, and radiation. Specific examples of the energy source or curing device include sterilizing lamps, fluorescent lamps for ultraviolet rays, carbon arc lamps, xenon lamps, high pressure mercury lamps for copying, medium pressure or high pressure mercury lamps, ultra high pressure mercury lamps, electrodeless lamps, metal halide lamps, Ultraviolet rays generated by a curtain type electron beam accelerator, or an electron beam by a scanning type or curtain type electron beam accelerator. In addition, when curing is carried out with an electron beam, the addition of the polymerization initiator to the resist composition of the present invention is unnecessary.

Among these active energy rays, ultraviolet rays are particularly preferable. Further, irradiation in an inert gas atmosphere such as nitrogen gas is preferable because the surface hardenability of the coating film is improved. Further, if necessary, heat may be used as an energy source, followed by curing with an active energy ray, followed by heat treatment.

The coating method of the resist composition of the present invention varies depending on the application, but may be applied to various coating methods such as a gravure coater, roll coater, comma coater, knife coater, curtain coater, shower coater, spin coater, slit coater, dipping, , A bar coater, and the like.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Unless otherwise noted, parts and percentages are by weight.

Example 1 (Synthesis of fluorine-containing surfactant)

47.5 g of 2-propanol as a solvent and 25.6 g of 3-hydroxy-1-adamantyl methacrylate were fed into a nitrogen-purged flask, and the mixture was heated to 40 캜 while stirring under a nitrogen stream. Next, 5.3 g of 2,2'-bipyridyl and 1.9 g of cuprous chloride were added, 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 the mixture was reacted at 40 DEG C for 2 hours in a nitrogen stream to obtain a polymer segment containing a crosslinked ring hydrocarbon skeleton. Next, 45.9 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and the reaction was carried out at 40 占 폚 for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorochemical surfactant (1) of the present invention. The molecular weight of this fluorine-containing surfactant (1) was measured by GPC and found to be 3, 100, and 2,700 in terms of weight average molecular weight (Mw) and number average molecular weight (Mn). The fluorine atom content was 14.5% by mass.

Example 2 (frozen phase)

Into a flask purged with nitrogen, 81.7 g of 2-propanol and 40.5 g of 3-hydroxy-1-adamantyl methacrylate were added as a solvent, and the mixture was heated to 40 DEG C while stirring under a nitrogen stream. Next, 7.3 g of 2,2'-bipyridyl and 1.5 g of cuprous chloride were added, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 40 占 폚. Then, 2.5 g of ethyl 2-bromoisobutyrate was added and the mixture was reacted at 40 DEG C for 2 hours under a nitrogen stream to obtain a polymer segment containing a crosslinked ring hydrocarbon skeleton. Then, 13.7 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment, and the reaction was carried out at 40 DEG C for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (2) of the present invention. The molecular weight of the fluorine-containing surfactant (2) was measured by GPC and found to be 3,200 in weight average molecular weight (Mw) and 2,700 in number average molecular weight (Mn). The fluorine atom content was 37% by mass.

Example 3 (frostbite (same as above))

47.5 g of 2-propanol and 25.6 g of dicyclopentyl methacrylate were added to a flask purged with nitrogen, and the temperature was raised to 40 占 폚 while stirring under a nitrogen stream. Next, 5.3 g of 2,2'-bipyridyl and 1.9 g of cuprous chloride were added, and the mixture was stirred for 30 minutes while maintaining the inside of the flask at 40 ° C. Subsequently, 3.3 g of ethyl 2-bromoisobutyrate was added, and the mixture was reacted at 40 DEG C for 2 hours in a nitrogen stream. Then, 25.6 g of dicyclopentyl methacrylate was added and reacted at 40 DEG C for 2 hours, A polymer segment containing the skeleton of the hydrocarbon was obtained. Next, 45.9 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment and the reaction was carried out at 40 占 폚 for 5 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-based surfactant (3) of the present invention. The molecular weight of this fluorine-containing surfactant (3) was measured by GPC and found to be 3,300 in weight average molecular weight (Mw) and 2,900 in number average molecular weight (Mn). The fluorine atom content was 14.5% by mass.

Example 4 (frozen phase)

65 g of methyl ethyl ketone and 25.6 g of dicyclopentyl methacrylate were put in a nitrogen-purged flask, and the temperature was raised to 60 캜 while stirring in a nitrogen stream. Next, 3.1 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were added, 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 the reaction was carried out at 40 DEG C for 2 hours under a nitrogen gas stream to obtain a polymer segment containing a skeleton of the crosslinked ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment, and the reaction was carried out at 60 DEG C for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (4) of the present invention. The molecular weight of this fluorine-containing surfactant (4) was measured by GPC and found to be 4,200 in weight average molecular weight (Mw) and 3,500 in number average molecular weight (Mn). The fluorine atom content was 14.5% by mass.

Example 5 (frozen phase)

65 g of methyl ethyl ketone as a solvent and 31 g of 1-adamantyl methacrylate were fed into a nitrogen-purged flask, and the mixture was heated to 60 캜 while stirring under a nitrogen stream. Next, 3.1 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were added, 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 the mixture was reacted at 60 DEG C for 3 hours under a nitrogen stream to obtain a polymer segment containing a skeleton of the crosslinked ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment, and the reaction was carried out at 60 DEG C for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (5) of the present invention. The molecular weight of this fluorine-containing surfactant (5) was measured by GPC, and found to be 4,100, and 3,500, respectively, as a weight average molecular weight (Mw) and a number average molecular weight (Mn). The fluorine atom content was 14.5% by mass.

Example 5 (frozen phase)

65 g of methyl ethyl ketone as a solvent and 31 g of isobornyl methacrylate were fed into a nitrogen-purged flask, and the mixture was heated to 60 캜 while stirring under a nitrogen stream. Next, 3.1 g of 2,2'-bipyridyl and 1.1 g of cuprous chloride were added, 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 the mixture was reacted at 60 DEG C for 3 hours under a nitrogen stream to obtain a polymer segment containing a skeleton of the crosslinked ring hydrocarbon. Next, 10.5 g of 2- (tridecafluorohexyl) ethyl methacrylate was added to the reaction system containing the polymer segment, and the reaction was carried out at 60 DEG C for 8 hours to obtain a reaction product. Next, 30 g of activated alumina was added to the obtained reaction product and the mixture was stirred. After filtration of the activated alumina, the solvent was distilled off under reduced pressure to obtain the fluorine-containing surfactant (5) of the present invention. The molecular weight of this fluorine-containing surfactant (5) was measured by GPC and found to be 4,200 in weight average molecular weight (Mw) and 3,600 in number average molecular weight (Mn). The fluorine atom content was 14.5% by mass.

Comparative Example 1

A glass flask equipped with a stirrer, a condenser, a dropping device and a thermometer was charged with 133 parts by mass of methyl isobutyl ketone and heated to 90 DEG C while stirring in a nitrogen stream. Subsequently, 32 parts by mass of 2- (tridecafluorohexyl) ethyl methacrylate, propylene glycol-polybutylene glycol monomethacrylate having an oxypropylene portion having a number of repeating units of 1 and an oxybutylene portion having an average number of repeating units of 6 A monomer solution in which 68 parts by mass of acrylate was dissolved in 80 parts by mass of methyl isobutyl ketone and 2 parts by mass of a radical polymerization initiator solution in which 6 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 20 parts by mass of methyl isobutyl ketone The kinds of the dropping liquids were set in different dropping apparatuses, and dropped in the flask at the same time while maintaining the inside of the flask at 90 DEG C over 2 hours. After completion of dropwise addition, the mixture was stirred at 90 占 폚 for 10 hours, and then the solvent was removed under reduced pressure to obtain a fluorochemical surfactant (1 '). The fluorine-containing surfactant (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

50.4 g of methyl isobutyl ketone as a solvent was added to a glass flask equipped with a stirrer, a thermometer, a cooling tube and a dropping device, and the mixture was heated to 90 DEG C while stirring under a nitrogen stream. Next, a monomer solution prepared by dissolving 44.1 g of 2- (tridecafluorohexyl) ethyl methacrylate and 59.1 g of 3-hydroxy-1-adamantyl methacrylate in 167.4 g of methyl isobutyl ketone, And a polymerization initiator solution in which 6.2 g of t-butyl peroxy-2-ethylhexanoate as an initiator was dissolved in 23.2 g of methyl isobutyl ketone were set in different dropping apparatuses, and the inside of the flask was maintained at 90 DEG C While dropping over two hours at the same time. After completion of the dropwise addition, the mixture was stirred at 90 占 폚 for 9 hours, and 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 octyl as a urethanization catalyst were introduced, stirring was started in an air stream, and 2-acryloyloxyethyl isocyanate 34.4 g for 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 spectroscopy and methyl isobutyl ketone was added thereto to prepare a fluorochemical surfactant (2 ' To obtain a solution of methyl isobutyl ketone containing 40%. The molecular weight of the fluorine-containing surfactant (2 ') was measured by GPC (polystyrene reduced 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 was 18%, the adamantane content was 24%, and the radical polymerizable unsaturated group equivalent was 550 g / eq., Calculated from the raw material charging ratio.

Comparative Example 3

In a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 20 parts by mass of a perfluoropolyether compound having hydroxyl groups at both terminals and represented by the following formula (X-1), 20 parts by mass of diisopropyl ether , 0.02 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 3.1 parts by mass of triethylamine as a neutralizing agent were introduced into a flask, and stirring was started in an air stream. 2.7 parts by mass of acrylic acid chloride Over a period of time. After completion of the dropwise addition, the mixture was stirred at 10 ° C for 1 hour, elevated to room temperature, stirred at 30 ° C for 1 hour, heated to 50 ° C and stirred for 10 hours, and disappearance of acrylic acid chloride was confirmed by gas chromatography measurement. Subsequently, 40 parts by mass of diisopropyl ether was added as a solvent, and 80 parts by mass of ion-exchanged water was mixed and stirred. After that, the aqueous layer was separated and removed, followed by washing three times. Next, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, and 8 parts by mass of magnesium sulfate as a dehydrating agent was added. After complete dehydration by standing for one day, the dehydrating agent was filtered off. Next, the solvent was distilled off under reduced pressure to obtain a monomer represented by the following structural formula (d1-1-1).

(Wherein X is a perfluoromethylene group and a perfluoroethylene group, an average of 7 perfluoromethylene groups per molecule and an average of 8 perfluoroethylene groups, and the average number of fluorine atoms is 46 to be)

In another glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device, 63 parts by mass of methyl isobutyl ketone as a solvent was charged, and the mixture was heated to 105 DEG C while stirring under a nitrogen stream. Next, 21.5 parts by mass of the monomer (d1-1-1) obtained above, 41.3 parts by mass of 2-hydroxyethyl methacrylate, 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, And 135.4 parts by mass of an initiator solution obtained by mixing 126 parts by mass of methyl isobutyl ketone as a solvent were set in different dropping apparatuses and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 占 폚. After completion of the dropwise addition, the mixture was stirred at 105 DEG 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, and 0.06 parts by mass of dibutyltin dilaurate as a urethanation catalyst were introduced, stirring was started in an air stream, And 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 占 폚 for 1 hour, elevated to 80 占 폚 and stirred for 10 hours, and the disappearance of the isocyanate group was confirmed by IR spectroscopy. Next, 37.4 parts by mass of methyl ethyl ketone as a solvent was added and the solution insoluble in the filtrate was filtered to obtain a methyl ethyl ketone solution containing 50% by mass of a fluorine surfactant (3 ') having a polymerizable group. The molecular weight of the fluorochemical surfactant (3 ') was measured by GPC (polystyrene reduced 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)

As a binder resin, 15 g of Unidic RS20-160 manufactured by DIC Co., Ltd. was added to 42 g of a green pigment dispersion liquid using FASTOGEN Green A110 manufactured by DIC Corporation as a coloring agent, 15 g of Unidic RS20-160 manufactured by DIC Kabushiki Kaisha, 0.5 g of Irgacure # 369 manufactured by BASF Japan Ltd. as a photopolymerization initiator, 0.06 g of the fluorine-based surfactant (1) of the present invention in terms of solid content and 37 g of PGMEA were mixed to prepare a color To thereby prepare a resist composition (1).

A cured coating film was obtained using the color resist composition (1). Water stains were evaluated using this cured coating film. The preparation method of the cured coating film and the evaluation method of the water stain are shown below. The evaluation results are shown in Table 1.

≪ Preparation method of cured coating film &

The color resist composition (1) was spin-coated on a 7 cm x 7 cm glass plate at a number of revolutions of 1000 rpm for 10 seconds and exposed to light under a condition of 200 mJ / cm 2 using a high-pressure mercury lamp to form a coating film.

<Evaluation method of water stain>

A glass plate on which a coated film was formed was placed on a cylindrical container, and ion-exchanged water was added until about half of the substrate was immersed, and after standing for 5 minutes, it was taken out. The following evaluations were carried out according to the degree of white line water stains occurring in the portion of the humid water line (draft line) of the substrate. The evaluation is as follows.

○: Water spots on the white line are hardly visible

?: Water stains on the white line appear narrow

X: Water stain on the white line appears thick

Example 8 (frozen phase)

A color resist composition (2) was obtained in the same manner as in Example 7 except that the fluorinated surfactant (2) was used instead of the fluorinated surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Example 9 (frozen phase)

A color resist composition (3) was obtained in the same manner as in Example 7 except that the fluorinated surfactant (3) was used instead of the fluorinated surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Example 10 (frozen phase)

A color resist composition (4) was obtained in the same manner as in Example 7 except that the fluorinated surfactant (4) was used instead of the fluorinated surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Example 11 (frozen phase)

A color resist composition (5) was obtained in the same manner as in Example 7 except that the fluorinated surfactant (5) was used instead of the fluorinated surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Example 12 (frozen phase)

A color resist composition (6) was obtained in the same manner as in Example 7 except that the fluorinated surfactant (6) was used instead of the fluorinated surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Comparative Example 1 (Preparation of resist composition for comparison control)

A comparative color resist composition (1 ') was obtained in the same manner as in Example 7 except that the fluorine-containing surfactant (1') for comparison control was used in place of the fluorine-containing surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Comparative Example 2 (frost phase)

A color resist composition (2 ') for comparison control was obtained in the same manner as in Example 7 except that the fluorine-containing surfactant (2') for comparison control was used in place of the fluorine-containing surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

Comparative Example 3 (frost phase)

A color resist composition (3 ') for comparison control was obtained in the same manner as in Example 7 except that the fluorine-containing surfactant (3') for comparison control was used in place of the fluorine-containing surfactant (1). Evaluation was conducted in the same manner as in Example 7, and the results are shown in Table 1.

[Table 1]

Claims (14)

A polymer segment (A1) obtained by using a polymerizable monomer comprising a fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded and a polymerizable monomer (a1) having a polymerizable unsaturated group, and a polymer segment A fluorocarbon surfactant characterized by being a block copolymer comprising a polymer segment (A2) obtained by using a polymerizable monomer containing a polymerizable monomer (a2) having a unsaturated group. The method according to claim 1,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring, a dicyclopentane ring, a dicyclopentane ring, a norbornane ring, or a norbornene ring. The method according to claim 1,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) is an adamantane ring. The method according to claim 2 or 3,
Wherein the skeleton of the crosslinked ring hydrocarbon of the polymerizable monomer (a2) has a hydroxyl group. The method according to claim 1,
Wherein the polymer segment (A2) is obtained by using the polymerizable monomer (a2) in an amount of 10 to 100 mass% based on the mass of the polymerizable monomer constituting the polymer segment (A2). The method according to claim 1,
Wherein the polymerizable monomer (a1) is a monomer represented by the following 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, and Rf' X represents any one of groups represented by the following formulas (X-1) to (X-10), Rf represents a group represented by any one of the following formulas (Rf-1) to (Rf-1) to (Rf-4).

N in the formulas (X-1), (X-3), (X-5), (X-6) and (X-7) represents an integer of 1 to 8. M in the 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 &quot; in the above formulas (X-6) and (X-7) represents any one of the following formulas (Rf-1) to (Rf-

[N in the formulas (Rf-1) and (Rf-2) represents an integer of 1 to 6) N in the formula (Rf-3) represents an integer of 2 to 6. N in the formula (Rf-4) represents an integer of 4 to 6) 7. The method according to any one of claims 1 to 6,
Wherein the block copolymer is prepared by living radical polymerization. 8. The method of claim 7,
Wherein the living radical polymerization is an atom transfer radical polymerization. 8. The method of claim 7,
The block copolymer is subjected to atom transfer radical polymerization of 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, After obtaining the polymer segment (A1), a polymerizable monomer containing the polymerizable monomer (a2) is added to the polymer segment (A1) to further transfer the polymerizable monomer containing the polymerizable monomer (a2) Fluorine-containing surfactant. 9. The method of claim 8,
The block copolymer is subjected to atom transfer radical polymerization of 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 the polymer segment (A2) is obtained, a polymerizable monomer containing the polymerizable monomer (a1) is added to the polymer segment (A2) to further transfer the polymerizable monomer containing the polymerizable monomer (a1) Fluorine-containing surfactant. A coating composition comprising the fluorosurfactant according to any one of claims 1 to 10. A resist composition comprising the fluorosurfactant according to any one of claims 1 to 10. A cured product obtained by curing the coating composition according to claim 11. A cured product obtained by curing the resist composition according to claim 12.