JP6210295B2 - Surfactant composition, coating composition, and resist composition - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention can be particularly suitably used as a leveling agent for various coating materials and resist materials in various coating fields in which surface smoothness is required, or coating fields in which precision coating is required, and accumulates in the environment and living organisms. The present invention relates to a surfactant composition having a low foaming property and a low foaming property and defoaming in a short time even when foamed, and a coating composition and a resist composition containing the composition.

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

  As such a fluorosurfactant, a method using a polymer having a polymer unit having an alkyl group having 20 or less carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom has been proposed. Among the fluorosurfactants, it is known that a surfactant using a perfluoroalkyl group having 8 or more carbon atoms is particularly excellent in performance as a leveling agent due to its surface tension reducing ability.

  However, in recent years, compounds having a perfluoroalkyl group having 8 carbon atoms are decomposed, so that perfluorooctane sulfonic acid (hereinafter abbreviated as “PFOS”) or perfluoro, which has high accumulation in the environment and living organisms. It was revealed that octanoic acid (hereinafter abbreviated as “PFOA”) can be produced. In addition, a fluorosurfactant having a perfluoroalkyl group having 8 or more carbon atoms, in particular, a fluorosurfactant having a perfluoroalkyl group having 8 carbon atoms, can be blended uniformly in various paints. When stirring and mixing, there was also a problem that bubbles were generated by the action of the fluorosurfactant and the bubbles did not disappear for a long time.

  Under the circumstances as described above, there is no risk of generating PFOS or PFOA that has a high accumulation property in the environment and living body in the market, there is little concern about accumulation in the environment and living body, and the inherent performance of the surfactant There is a need for a surfactant that has certain excellent leveling properties, has low foaming properties, and defoams in a short time even when foamed.

  In response to such a demand, fluorine obtained by copolymerizing a polymerizable monomer having a fluorinated alkyl group having 4 to 6 carbon atoms and a polymerizable monomer having a polyoxyalkylene chain as essential monomers. A system surfactant is disclosed (for example, see Patent Document 1).

  However, the fluorosurfactant disclosed in Patent Document 1 is, for example, 50 g of a solvent solution containing 1% by mass in propylene glycol monomethyl ether acetate is added to a 100 ml glass bottle, and this glass bottle is immersed 10 times in a 20 cm width. In this case, it takes about 3 minutes for the liquid surface to begin to be exposed due to disappearance of the generated bubbles, and even the fluorosurfactant disclosed in Patent Document 1 still does not have sufficient antifoaming properties.

JP 2012-62433 A

  The problem to be solved by the present invention is that it can impart excellent smoothness (surface smoothness) to the surface of the coating film, has low accumulation in the environment and the living body, and has low foaming properties. The object is to provide a surfactant composition that defoams in a short time, and a coating composition and a resist composition containing the composition.

  As a result of diligent studies to solve the above problems, the present inventors have found that a polymerizable monomer having a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded is used as the fluorine-based surfactant. Carbon atom in which fluorine atom is directly bonded to (meth) acryloyl group of polyfunctional (meth) acrylate in fluorine-based surfactant copolymerized with monomer and polymerizable monomer having polyoxyalkylene chain It has been found that a composition obtained by mixing a compound obtained by adding a specific amount of a compound having 1 to 6 fluorinated alkyl groups and active hydrogen using a Michael addition reaction can solve the above-mentioned problems, etc. The present invention has been completed.

  That is, the present invention relates to a monomer (α) having a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded, and the following general formula (β1).

（式中、Ｒは水素原子又はメチル基であり、Ｘ及びＹはそれぞれ独立のアルキレン基である。ｍ及びｎはそれぞれ０または１以上の整数であり、かつｍとｎの合計は２以上である。Ｚは水素原子又は炭素原子数１〜６のアルキル基である。）
で表されるポリオキシアルキレン鎖を有する単量体（β）を必須の単量体として共重合させて得られるフッ素系界面活性剤（Ｉ）と、
１分子中にｋ個（ここで、ｋは２以上である。）の（メタ）アクリロイル基を有する化合物（ａ１）１モルに、フッ素原子が直接結合した炭素原子の数が１〜６のフッ素化アルキル基と活性水素とを有する化合物（ａ２）２〜ｋモルをマイケル付加反応させてなる化合物（ＩＩ）とを含有することを特徴とする界面活性剤組成物を提供するものである。

(In the formula, R is a hydrogen atom or a methyl group, X and Y are each an independent alkylene group. M and n are each 0 or an integer of 1 or more, and the sum of m and n is 2 or more. Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
A fluorosurfactant (I) obtained by copolymerizing a monomer (β) having a polyoxyalkylene chain represented by
Fluorine having 1 to 6 carbon atoms in which fluorine atoms are directly bonded to 1 mol of compound (a1) having k (wherein k is 2 or more) (meth) acryloyl group in one molecule A surfactant composition comprising a compound (II) obtained by Michael addition reaction of 2-kmol of a compound (a2) having an alkyl group and active hydrogen.

  Moreover, this invention provides the coating composition characterized by including the said surfactant composition.

  Furthermore, this invention provides the resist composition characterized by including the said surfactant composition.

  According to the present invention, there is provided a surfactant composition that provides a coating material that imparts excellent smoothness to the coating film surface, is less likely to foam (low foaming property), and defoams in a short time even when foamed. Can be provided. The surfactant composition of the present invention also has low accumulation in the environment and living organisms. The surfactant composition of the present invention that exhibits the effects as described above is used as a leveling agent for various coating materials and resist materials used in various coating fields where surface smoothness is required, or in coating fields where precise coating is required. It can be particularly preferably used.

The fluorosurfactant (I) used in the present invention comprises a monomer (α) having a fluorinated alkyl group having 4 to 6 carbon atoms and a polyoxyalkylene chain represented by the general formula (β1) described later. It is a copolymer obtained by copolymerizing the monomer (β) as an essential monomer. Here, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group), and one in which some hydrogen atoms in the alkyl group are substituted with fluorine atoms (For example, HCF ₂ CF ₂ CF ₂ CF ₂ -etc.) is a general term. Incidentally, those containing an oxygen atom in the fluorinated alkyl group _{(e.g., CF 3 - (OCF 2 CF} 2) 2 - , etc.) is also included in this definition.

In the present invention, “a fluorinated alkyl group having 4 to 6 carbon atoms” means “a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded”. Therefore, for example, “CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ —” is a “fluorinated alkyl group having 4 carbon atoms” in the present invention.

  Examples of the monomer (α) include those represented by the following general formula (α1).

（上記一般式（α１）中、Ｒは水素原子、フッ素原子、メチル基、シアノ基、フェニル基、ベンジル基又は−Ｃ_ｎＨ_２ｎ−Ｒｆ’（ｎは１〜８の整数を表し、Ｒｆ’は下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）を表し、Ｌは、下記式（Ｌ−１）〜（Ｌ−１０）のいずれか１つの基を表し、Ｒｆは下記式（Ｒｆ−１）〜（Ｒｆ−７）のいずれか１つの基を表す。）

(In the general formula (α1), R 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 one group of the following formulas (Rf-1) to (Rf-7)), and L represents any one group of the following formulas (L-1) to (L-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).

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

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

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

(In the formulas (Rf-1) to (Rf-4), n represents an integer of 4 to 6. In the formula (Rf-5), m is an integer of 1 to 5, and n is 0 to 4). And the sum of m and n is 4 to 5. In the formula (Rf-6), m is an integer of 0 to 4, n is an integer of 1 to 4, and p is 0. ) Is an integer of -4, and the sum of m, n, and p is 4-5.)

  Moreover, the following monomers ((alpha) -1)-((alpha) -15) etc. are mentioned as a more preferable specific example of the said monomer ((alpha)). These monomers (α) can be used alone or in combination of two or more.

  The monomer (β) used in the present invention is a monomer having a polyoxyalkylene chain and is represented by the following general formula (β1).

（式中、Ｒは水素原子又はメチル基であり、Ｘ及びＹはそれぞれ独立のアルキレン基である。ｍ及びｎはそれぞれ０または１以上の整数であり、かつｍとｎの合計は２以上である。Ｚは水素原子又は炭素原子数１〜６のアルキル基である。）

(In the formula, R is a hydrogen atom or a methyl group, X and Y are each an independent alkylene group. M and n are each 0 or an integer of 1 or more, and the sum of m and n is 2 or more. Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  In addition, although X and Y in the said general formula ((beta) 1) are alkylene groups, this alkylene group may have a substituent. Specific examples of the —O— (XO) m— (YO) n— moiety include polyoxyethylene in which the number of repeating units m is an integer of 2 or more, n is 0, and X is ethylene, and the number of repeating units m Is an integer of 2 or more, n is 0, and X is propylene, polyoxypropylene having a repeating unit number m of 2 or more, n is 0, and X is butylene, polyoxybutylene, repeating unit The number m is an integer of 2 or more, n is 0, and X is tetramethylene, the number of repeating units m and n is an integer of 1 or more, and X or Y is ethylene and the other is Polyoxyalkylene which is a copolymer of propylene oxide and propylene oxide, the number of repeating units m and n are both integers of 1 or more, and X or Y is propylene and the other is butylene A polyoxyalkylene which is a copolymer of propylene oxide and butylene oxide, ethylene oxide and tetrahydrofuran wherein the number of repeating units m and n are both integers of 1 or more and X or Y is ethylene and the other is tetramethylene And polyoxyalkylene which is a copolymer of In addition, the degree of polymerization of these polyoxyalkylenes, that is, the sum of m and n in the general formula (β1) is preferably 2 to 50. In addition, the repeating unit containing X and the repeating unit containing Y may be arrange | positioned at random or a block shape. In the present invention, “butylene” refers to a branched alkylene having 4 carbon atoms, and “tetramethylene” refers to a linear alkylene having 4 carbon atoms.

  Among the polyoxyalkylene chains of the monomer (β), those having at least one chain selected from the group consisting of a polyoxypropylene chain, a polyoxybutylene chain and a polyoxytetramethylene chain are those of the present invention. When a fluorosurfactant composition is added to a coating material such as a coating composition or a resist composition, it is preferable because it exhibits excellent leveling properties and a coating film having extremely high surface smoothness can be obtained. As those having at least a polyoxypropylene chain, a polyoxybutylene chain or a polyoxytetramethylene chain, these polyoxyalkylene chains may be used alone or they may be copolymers with other polyoxyalkylene chains. I do not care.

  When the number of repeating units m is an integer of 2 or more and n is 0, the monomer (β) is a monoalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, or polytetramethylene glycol. Examples thereof include (meth) acrylic acid esters, and poly (alkylene glycol) mono (meth) acrylic acid esters whose ends that are not (meth) acrylic acid esters are sealed with alkyl groups having 1 to 6 carbon atoms.

  More specific examples of the monomer (β) include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, and poly (ethylene glycol / propylene glycol) mono. (Meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetra) Methylene glycol) mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, poly (propylene) Glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono (meth) acrylate, polyethylene glycol / polybutylene glycol mono (meth) acrylate, Poly (tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / trimethylene glycol) mono (meta) ) Acrylate, polyethylene glycol polytrimethylene glycol mono (meth) acrylate, poly (propylene glycol tri Methylene glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol / polytetramethylene glycol mono (meta) ) Acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, polybutylene glycol / polytrimethylene glycol mono (meth) acrylate, and the like. These monomers (β) can be used alone or in combination of two or more.

  “Poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a block copolymer of ethylene glycol and propylene glycol. Meaning, and so on. Among the polyoxyalkylene chains of these monomers (β), the compatibility with other components in the coating composition of the present invention is improved, so that the polyoxypropylene chain, the polyoxybutylene chain or the polyoxyalkylene chain is excellent. An oxytetramethylene chain is preferable, and a polyoxybutylene chain or a polyoxytetramethylene chain is more preferable.

  Moreover, as a commercial item of the said monomer ((beta)), Shin-Nakamura Chemical Co., Ltd. make "NK ester M-90G", "NK ester M-230G", "NK ester AMP-10G", " "NK ester AMP-20G", "NK ester AMP-60G", "Blemmer PE-200", "Blemmer PE-350", "Blemmer PME-100", "Blemmer PME-200", manufactured by NOF Corporation "Blemmer PME-400", "Blemmer PME-4000", "Blemmer PP-1000", "Blemmer PP-500", "Blemmer PP-800", "Blemmer 70PEP-350B", "Blemmer 55 PET-800", "Blemmer 50POEP-800B "," Blemmer 10PPB-500B "," Blemmer N H-5050 "," Blemmer AP-400 ", include the Sartomer Co., Ltd." SR604 ", and the like. These monomers (β) can be used alone or in combination of two or more.

  The fluorosurfactant (I) used in the present invention contains the monomer (α) and the monomer (β) as essential components as raw materials, but a single monomer having an alkyl group as the other monomer. The body (γ) may be used in combination. Examples of the monomer (γ) include those represented by the following general formula (γ1).

（式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^２は炭素原子数１〜１８の直鎖状、分岐状又は環構造を有するアルキル基である。）

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)

Note that R ² in the general formula (γ1) is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms, and this alkyl group is an aliphatic or aromatic hydrocarbon. It may have a substituent such as a group or a hydroxyl group. Specific examples of the ethylenically unsaturated monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Alkyl having 1 to 18 carbon atoms of (meth) acrylic acid such as octyl acid, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid stearyl Esters: dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate , Dicyclopentenyl (meth) acryl Such as chromatography bets, etc. (meth) bridging cyclic alkyl ester having 1 to 18 carbon atoms of acrylic acid. These monomers (γ1) can be used alone or in combination of two or more.

  Furthermore, as a raw material for the fluorosurfactant of the present invention, as a monomer other than the monomer (α), monomer (β) and monomer (γ), styrene, α-methylstyrene, p -Aromatic vinyls such as methylstyrene and p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Etc. can also be used.

  In order to improve the leveling performance of the surfactant composition of the present invention, the mass ratio of the monomer (α) and the monomer (β) as the raw material of the fluorosurfactant (I) [ (Α) / (β)] is preferably in the range of 10/90 to 70/30, more preferably in the range of 15/85 to 60/40, and still more preferably in the range of 25/75 to 50/50. Moreover, when using monomers other than the said monomer ((alpha)) and monomer ((beta)), it is preferable to set it as 50 mass% or less in all the monomers.

  The method for producing the fluorosurfactant (I) used in the present invention is not particularly limited, but the fluoromonomer (α) and the monomer (β), and optionally a monomer ( Examples thereof include a method of polymerizing monomers other than these such as γ) in an organic solvent using a radical polymerization initiator. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These are appropriately selected in consideration of boiling point, compatibility, and polymerizability. Examples of the radical polymerization initiator include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid and the like can be used as necessary.

  The number average molecular weight (Mn) of the fluorosurfactant (I) used in the present invention has good compatibility with other compounding components when added to a resin composition such as a coating composition, and has high leveling. Therefore, the range of 2,000 to 100,000 is preferable, and the range of 2,500 to 50,000 is more preferable. The number average molecular weight (Mn) is a value in terms of 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 Oltec)
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 filtered in terms of resin solids through a microfilter (100 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

  In addition, the fluorine content in the fluorosurfactant (I) used in the present invention can make the leveling property of the coating composition sufficient, and the compatibility with other components in the coating composition is good. Therefore, the range of 2 to 40% by mass is preferable, the range of 5 to 30% by mass is more preferable, and the range of 10 to 25% by mass is more preferable. The fluorine content in the fluorosurfactant used in the present invention is calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

  The compound (II) used in the present invention contains fluorinated alkyl group and activity in 1 mol of compound (a1) having k (wherein k is 2 or more) (meth) acryloyl groups in one molecule. It is formed by Michael addition reaction of 2 to k mol of the compound (a2) having hydrogen. When the compound (a2) is added to the compound (a1) by Michael, even if less than 2 mol of (a2) is added to 1 mol of the compound (a1), the defoaming of the surfactant (I) -derived foam This is not preferable because the compound is not sufficiently effective.

  The k is preferably 2 to 40 because a coating material that can be removed in a short time even when foamed is obtained, and a surfactant composition excellent in compatibility with the main agent in the coating material is obtained. 2 to 20 are more preferable. Here, when a mixture of compounds having various k values is used as the compound (a1), the average value of (meth) acryloyl groups possessed by one molecule in the mixture is defined as k.

In the present invention, the (meth) acryloyl group is a generic term for an acryloyl group and a methacryloyl group. In addition, the fluorinated alkyl group is one in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms (perfluoroalkyl group), and one in which some hydrogen atoms in the alkyl group are substituted with fluorine atoms ( For example, HCF ₂ CF ₂ CF ₂ CF ₂ — and the like. Incidentally, those containing an oxygen atom in the fluorinated alkyl group _{(e.g., CF 3 - (OCF 2 CF} 2) 2 - , etc.) is also included in this definition.

  The compound (II) used in the present invention utilizes a Michael addition reaction of an active hydrogen-containing group to a (meth) acryloyl group, and specifically, k per molecule (where k is 2 or more). A compound (a2) 2 having 1 mole of the compound (a1) having a (meth) acryloyl group, a fluorinated alkyl group having 1 to 6 carbon atoms to which fluorine atoms are directly bonded, and active hydrogen. ~ Kmol is obtained by reacting with Michael addition reaction. Since this reaction is an addition reaction, there is no compound by-produced by the reaction, and the reaction conditions described below can be allowed to proceed under mild conditions.

  The compound (a1) used in the present invention is not particularly limited as long as it contains two or more (meth) acryloyl groups in the molecule, and is appropriately selected depending on the intended use. From the viewpoint of easy availability and the choice of mild reaction conditions, the following general formula (3)

〔式中、Ｒ’は炭素原子数１〜２４のアルキル基、炭素原子数１〜２４のアルキルカルボニルオキシ基、ＣＨ_２＝ＣＨＣＯ_２ＣＨ_２−、ＣＨ_２＝Ｃ（ＣＨ_３）ＣＯ_２ＣＨ_２−、繰り返し数が１以上で末端が水素原子或いは炭素原子数１〜１８のアルキル基で封鎖された（ポリ）オキシアルキレン基、炭素原子数１〜１２のアルキロール基、カルボキシル基、又は下記一般式（４）

[Wherein, R ′ is an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ -, A (poly) oxyalkylene group having 1 or more repeats and a terminal end blocked with a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkylol group having 1 to 12 carbon atoms, a carboxyl group, or the following general Formula (4)

（式中、Ｒ^３は（メタ）アクリロイル基であり、Ｒ^４は水素原子、炭素原子数１〜１８アルキル基、炭素原子数１〜１８のアルキルエステル基又はカルボキシル基であり、ｔは０〜３の整数であり、ｕは０〜３の整数であって且つｔ＋ｕ＝３である。）で表される基であり、Ｒ^１は（メタ）アクリロイル基であり、Ｒ^２は水素原子又は炭素原子数１〜１８のアルキルカルボニル基であり、ｒは２又は３であり、ｓは０又は１であって且つｒ＋ｓ＝３である。〕で表される化合物（ａ１−１）、下記一般式（５）

(In the formula, R ³ is a (meth) acryloyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl ester group having 1 to 18 carbon atoms, or a carboxyl group, and t is 0 to 0. is 3 integer, u is a group represented by an integer from 0 to 3 and a and t + u = 3.), R 1 is a (meth) acryloyl group, R ² represents a hydrogen atom or a carbon An alkylcarbonyl group having 1 to 18 atoms; r is 2 or 3; s is 0 or 1; and r + s = 3. ] Compound (a1-1) represented by the following general formula (5)

〔式中、R^６、Ｒ^７はそれぞれ（メタ）アクリロイル基であり、Ｌは炭素原子数１〜１８のアルキル基、繰り返し単位数が１〜３０である炭素原子数１〜４のアルキレンオキシ基、炭素原子数３〜１００の環状炭化水素基または炭素原子数６〜１００の芳香族炭化水素基である。〕で表される化合物（ａ１−２）、ウレタン（メタ）アクリレート（ａ１−３）、シアヌレート環含有トリ（メタ）アクリレート（ａ１−４）、又はリン酸トリ（メタ）アクリレート（ａ１−５）であるであることが好ましい。

[Wherein R ⁶ and R ⁷ are each a (meth) acryloyl group, L is an alkyl group having 1 to 18 carbon atoms, and an alkyleneoxy group having 1 to 4 carbon atoms having 1 to 30 repeating units. , A cyclic hydrocarbon group having 3 to 100 carbon atoms or an aromatic hydrocarbon group having 6 to 100 carbon atoms. ] Compound (a1-2), urethane (meth) acrylate (a1-3), cyanurate ring-containing tri (meth) acrylate (a1-4), or phosphoric acid tri (meth) acrylate (a1-5) It is preferable that it is.

  Here, when an alkyleneoxy group is selected as “L” in the general formula (5), the alkyleneoxy group may be used alone or in combination of two or more. Here, when the “L” has two or more types of alkyleneoxy groups, the number of repeating units means the total number of repeating units of each alkyleneoxy group. Examples of the alkyleneoxy group having 1 to 4 carbon atoms include an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and a tetramethyleneoxy group.

Among these, the compound (a1) having two or more (meth) acryloyl groups is represented by the general formula (3) [wherein R ′ is a linear alkyl group having 1 to 4 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, or an alkylol group having 1 to 3 carbon atoms, or a group represented by the general formula (4), and R ³ Is a hydrogen atom or an alkylcarbonyl group having 1 to 12 carbon atoms. It is especially preferable that it is a compound represented by this.

  Specific examples of the compound (a1) used in the present invention include the following compounds.

  First, as the bifunctional (meth) acrylate, for example, 1,3-butylene glycol di (meth) acrylate (for example, SR-212 manufactured by Kayaku Sartomer Co., Ltd.), 1,4-diol di (meth) acrylate ( For example, Osaka Organic Chemical Co., Ltd. biscoat # 195 etc.), 1,6-hexanediol di (meth) acrylate (for example, Kyoeisha Chemical Co., Ltd. 1,6HX-A), ethylene oxide (hereinafter abbreviated as EO) modified 1, 6-hexanediol di (meth) acrylate (for example, RCC 13-361 manufactured by Sannopco Corporation), epichlorohydrin (hereinafter abbreviated as ECH) modified 1,6-hexanediol di (meth) acrylate (for example, Nippon Kayaku Co., Ltd.) Kayarad R-167, etc.), 1,9-nonanediol di (meth) acrylate For example, Osaka Organic Chemical Co., Ltd. biscoat # 215, etc.), diethylene glycol di (meth) acrylate (for example, Bremer ADE-100 manufactured by Nippon Oil & Fats Co., Ltd.), ECH-modified hexahydrophthalic acid di (meth) acrylate (for example, Nagase Kasei) Denacol acrylate DA-722, etc.), neopentyl glycol di (meth) acrylate hydroxypivalate (light acrylate HPP-A, etc., manufactured by Kyoeisha Chemical Co., Ltd.), neopentyl glycol di (meth) acrylate (for example, Nippon Kayaku) Kayrad NPGDA manufactured by Yakuhin Co., Ltd.), EO-modified neopentyl glycol di (meth) acrylate (for example, Photomer 4160 manufactured by San Nopco Co., Ltd.), propylene oxide (hereinafter abbreviated as PO) modified neopentyl glycol di ( ) Acrylate (for example, SR-9003 manufactured by Kayaku Sartomer Co., Ltd.), stearic acid-modified pentaerythritol di (meth) acrylate (for example, Aronix M-233 manufactured by Toagosei Co., Ltd.), polyethylene glycol di (meth) acrylate (For example, Nippon Oil & Fat Co., Ltd. Blemmer ADE-200 etc.), Polypropylene glycol di (meth) acrylate (eg, Nippon Oil & Fat Co., Ltd. Blemmer ADP-200 etc.), polyethylene glycol-propylene glycol-polyethylene glycol di (meth) acrylate (For example, Nippon Oil & Fat Co., Ltd. Bremer ADC series etc.), polytetramethylene diglycol di (meth) acrylate (for example, Kyoeisha Chemical Co., Ltd. light acrylate PTMGA-250 etc.), poly Ethylene glycol di (meth) acrylate (for example, light acrylate 3EG-A manufactured by Kyoeisha Chemical Co., Ltd.), dimethylol dicyclopentane di (meth) acrylate (for example, IRR214 manufactured by Daicel UCB Corporation), tricyclodecane dimethanol Di (meth) acrylate (for example, LUMICURE DCA-200 manufactured by Dainippon Ink & Chemicals, Inc.), neopentyl glycol-modified trimethylolpropane di (meth) acrylate (for example, Kayrad R-604 manufactured by Nippon Kayaku Co., Ltd.), Examples include triglycerol di (meth) acrylate (for example, epoxy ester 80MFA manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the trifunctional (meth) acrylate include EO-modified glycerol acrylate (for example, New Frontier GE3A manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), PO-modified glycerol triacrylate (for example, Beam Set 720 manufactured by Arakawa Chemical Co., Ltd.), Pentaerythritol triacrylate (PETA) (for example, New Frontier PET-3 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), EO-modified phosphate triacrylate (for example, Biscoat 3A manufactured by Osaka Organic Chemical Co., Ltd.), trimethylolpropane triacrylate ( TMTPA) (for example, New Frontier TMTP manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), caprolactone-modified trimethylolpropane triacrylate (for example, Ebecryl 2047 manufactured by Daicel UCB Corporation), HPA-modified Limethylolpropane triacrylate (for example, Kayrad THE-330 manufactured by Nippon Kayaku Co., Ltd.), (EO) or (PO) modified trimethylolpropane triacrylate (for example, LUMICURE ETA-300 manufactured by Dainippon Ink & Chemicals, Inc., Daiichi Kogyo Seiyaku Co., Ltd. New Frontier TMP-3P, etc.), alkyl-modified dipentaerythritol triacrylate (eg, Kayrad D-330 produced by Nippon Kayaku Co., Ltd.), tris (acryloxyethyl) isocyanurate (eg, Hitachi) And the like.

  Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetraacrylate (DTMPTA) (for example, LUMICURE DTA-400 manufactured by Dainippon Ink & Chemicals, Inc.), pentaerythritol ethoxytetraacrylate (for example, Mitsubishi Rayon Co., Ltd.) Diabeam UK-4154 manufactured by the company), pentaerythritol tetraacrylate (PETTA) (for example, NK Ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  Examples of pentafunctional or hexafunctional (meth) acrylates include dipentaerythritol hydroxypentaacrylate (for example, SR-399E manufactured by Kayaku Sartomer Co., Ltd.), alkyl-modified dipentaerythritol pentaacrylate (for example, Nippon Kayaku Co., Ltd.) Company Kayrad D-310), dipentaerythritol hexaacrylate (for example, DAP-600 manufactured by Dainippon Ink & Chemicals, Inc.), dipentaerythritol penta and hexaacrylate base / multifunctional monomer mixture (for example, Dainippon Ink Chemical) LUMICURE DPA-620 manufactured by Kogyo Co., Ltd.) and the like.

  Needless to say, the present invention is not limited to these specific examples. These may be used alone, or may be a mixture of a plurality of compounds having different (meth) acryloyl group numbers, or a mixture of a plurality of compounds having different structures. Further, the compound (a1) that is generally commercially available is often a mixture of compounds having different numbers of (meth) acryloyl groups with respect to the target compound as the main component. In use, the compound having the desired number of (meth) acryloyl groups may be taken out and used by various purification methods such as chromatography and extraction, but may be used as a mixture.

  Moreover, as said compound (a1) used by this invention, it is also possible to use urethane (meth) acrylate (a1-2). There is no restriction | limiting in the manufacturing method of the said urethane (meth) acrylate (a1-2), For example, the hydroxyl-containing (meth) acrylate (x1) and isocyanate compound (x2) which have a 2 or more (meth) acryloyl group, It can be obtained by a polyaddition reaction or the like.

  The reaction can be performed without a catalyst, but a reaction aid such as a urethanization catalyst can be used from the viewpoint of reaction efficiency. Examples of the urethanization catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1 , 4-diazabicyclo [2.2.2] octane and the like, and 0.01 to 10% by weight is used with respect to the total weight of the hydroxyl group-containing (meth) acrylate (x1) and isocyanate compound used as a raw material. preferable.

  Examples of the hydroxyl group-containing (meth) acrylate (x1) include 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol hydroxypentaacrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate ( For example, Nippon Oil & Fat Co., Ltd. Blemmer GAM etc.) etc.

  As the isocyanate compound (x2), any of an aromatic isocyanate compound, an aliphatic isocyanate compound, and an alicyclic isocyanate compound can be used. For example, toluene diisocyanate, tolylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, hexa Examples include methylene diisocyanate, trimethylhexamethylene diisocyanate, and adamantyl diisocyanate. From the viewpoint of the glass transition temperature of the resulting cured product, the scratch resistance of the cured product, and the like, it is preferable to have an alicyclic structure. For example, norbornane diisocyanate, isophorone diisocyanate, and adamantyl diisocyanate are preferably used. That is, as urethane (meth) acrylate (a1-2), a hydroxyl group-containing (meth) acrylate (x1) having two or more (meth) acryloyl groups and an isocyanate compound (x2) having an alicyclic structure are reacted. It is preferable that it is urethane (meth) acrylate obtained. In addition, the compound obtained by introducing a fluorinated alkyl group into the urethane (meth) acrylate (a1-2) by Michael addition uses a compound having a hydroxyl group as the compound (a1-1), and this is a Michael addition reaction. It is also possible to synthesize by introducing a fluorinated alkyl group by the reaction with an isocyanate compound, and the reaction order is not particularly limited.

  The compound (a1) having two or more (meth) acryloyl groups used in the present invention has a high antifoaming effect and does not cause repellency or unevenness in the coating film. Therefore, dipentaerythritol hexaacrylate, pentaerythritol One or more compounds selected from the group consisting of triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, polyoxypropylene diacrylate and polyoxyethylene diacrylate are preferred.

  Next, the compound (a2) having a fluorinated alkyl group and active hydrogen will be described. The fluorinated alkyl group is preferably a perfluoroalkyl group from the viewpoint that the performance derived from a fluorine atom can be effectively expressed. When a fluorinated alkyl group other than a perfluoroalkyl group is used, it is preferable to select the structure and type of the fluorinated alkyl group depending on the required level of performance and application.

As the compound (a2), it is easy to obtain industrially, and from the viewpoint that mild reaction conditions can be selected, the following general formula (1)
Rf (CH ₂ ) mZH (1)
[Wherein, m is an integer of 0 to 20, Rf is —C _n F _{2n + 1} (n is an integer of 1 to 6), and Z is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. A nitrogen atom, an oxygen atom, a sulfur atom, or —SO ₂ —NR— (wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms). Or a compound represented by the following general formula (2)

〔式中、Ｙは酸素原子または硫黄原子であり、ｐとｑはそれぞれ１〜４の整数であり、ＲｆとＲｆ^１はそれぞれ−Ｃ_ｎＦ２_ｎ＋１（ｎは１〜６の整数である。）であり、ＬとＬ^１はそれぞれカルボニル基、カルボニル基を有する炭素原子数１〜４のアルキル基及び炭素原子数１〜４のアルキル基からなる群から選ばれる一種以上の基である〕で表される化合物が好ましい。

[In the formula, Y is an oxygen atom or a sulfur atom, p and q are each an integer of 1 to 4, and Rf and Rf ¹ are each —C _n F2 _{n + 1} (n is an integer of 1 to 6). L and L ¹ are each a carbonyl group, an alkyl group having 1 to 4 carbon atoms having a carbonyl group, and one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms.] Are preferred.

Among the general formula (1), Z is a hydrogen atom or a nitrogen atom having a C 1-6 alkyl group, a sulfur atom, or —NR—SO ₂ — (R is a C 1-6 alkyl group. .) Is preferable because compound (II) can be obtained under milder reaction conditions. Among the general formula (2), those in which Y is a sulfur atom are preferable because the compound (II) can be obtained under milder reaction conditions.

  Among Rf and Rf1 in the compounds represented by the general formula (1) and the general formula (2), those having n of 2 to 6 are less likely to foam (low foaming property) and may foam. It is preferable because it becomes a surfactant composition from which a coating material capable of defoaming in a short time can be obtained.

  Among the compounds (II), those obtained by using the compound represented by the general formula (1) or the general formula (2) are necessary for an application viewpoint, that is, when applied to a photocurable composition. Accordingly, compatibility with other components used in combination, transparency of the resulting cured product, surface characteristics derived from fluorine atoms, and optical characteristics are also advantageous.

Examples of the compound represented by the general formula (1) include the following compounds, which may be used alone or as a mixture of two or more.
_{C 4 F 9 SO 2 N (} CH 3) H (a2-1)
_{C 4 F 9 SO 2 N (} C 3 H 7) H (a2-2)
_{C 4 F 9 CH 2 CH 2} N (C 8 H 17) H (a2-3)
_{C 4 F 9 CH 2 CH 2} SH (a2-4)
_{C 6 F 13 CH 2 CH 2} SO 2 N (C 8 H 17) H (a2-5)
_{C 6 F 13 CH 2 CH 2} SH (a2-6)
_{C 6 F 13 CH 2 CH 2} N (C 4 H 9) H (a2-7)

  Examples of the method for producing the compound represented by the general formula (2) include 2-hydroxysuccinic acid (hereinafter referred to as malic acid) and 2-mercaptosuccinic acid (hereinafter referred to as thiomalic acid). And a method in which a fluorinated alkyl group-containing alcohol or a fluorinated alkyl group-containing mercaptan is reacted to form a diester, specifically, the following compounds may be mentioned.

  The reaction between the compound (a1) and the compound (a2) may be carried out in accordance with the usual Michael addition reaction method, and special consideration by having a fluorine atom is not particularly required. Can be manufactured. When a solvent is used, it is appropriately selected in consideration of the solubility, boiling point, equipment used, etc. of the compound (a1) and the compound (a2). Esters such as ethyl and butyl acetate, halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone (hereinafter abbreviated as MEK), methyl Ketones such as isobutyl ketone (hereinafter abbreviated as MIBK), alcohols such as methanol, ethanol and isopropanol, aprotic polar compounds such as dimethylformamide, dimethylformacetamide and dimethylsulfoxide, ethers such as diethyl ether and tetrahydrofuran , Aliphatic hydrocarbons such as hexane and heptane Etc., and it may be used by mixing two or more solvents in combination. Among these, it is preferable to use esters, aromatic hydrocarbons, ketones, alcohols, ethers, dimethylformacetamide, dimethyl sulfoxide, and the like, and esters, ketones, alcohols, ethers are preferably used. Particularly preferred.

  This reaction can be performed without a catalyst, but from the viewpoint of reaction efficiency, a reaction aid such as a catalyst can be appropriately selected and used. Examples of the reaction aid include metal alcoholates such as sodium methoxide and sodium ethoxide; amines such as trimethylamine, triethylamine and 1,4-diazabicyclo- [2.2.2] -octane; sodium hydride, hydrogen Metal hydrides such as lithium iodide; ammonium salts such as benzyltrimethylammonium hydroxide, tetraammonium fluoride and the like; peroxides such as peracetic acid, and the like, preferably metal alcoholates, amines and ammonium salts Particularly preferred are amines. The amount of the reaction aid used is not particularly limited, but is 0.01 to 50 mol%, preferably 0.1 to 20 mol%, based on 1 mol of the compound (a1) used as a raw material. is there.

  Furthermore, depending on the compound (a1) and the compound (a2) to be used, heat can be used alone or in combination as a reaction activation energy source. The reaction temperature is usually 0 ° C. to reflux temperature, preferably 20 to 100 ° C., particularly preferably 20 to 70 ° C. When a solvent or the like is used during the reaction, the solute concentration is usually 2 to 90% by weight, preferably 20 to 80% by weight. There is no particular limitation on the order of the reaction materials. The product thus obtained can be used after being purified by extraction, column chromatography, or the like, but can also be used as it is. In particular, in the case of using a compound having a large k value among the compound (a1) [having a large number of (meth) acryloyl groups], it is usually difficult to control the place where the compound (a2) is added, and thus obtained. Compound (II) is a mixture consisting of various compounds with different addition sites, but even in this case, it is not necessary to take out a single substance by isolation and purification, and from various compounds with different positions of the Michael addition reaction. Can be used as a mixture.

  As described above, by passing through the Michael addition reaction between the compound (a1) and the compound (a2), the present compound can be obtained under a simpler and milder condition without undergoing a condensation reaction that requires a strong acid catalyst. Compound (II) used in the invention can be produced. In addition, since various polyfunctional (meth) acrylates that are currently available as commercially available products or can be easily synthesized can be used as starting materials, coating compositions containing compound (II) It is easy to change the structure or the fluorine atom content in one molecule with respect to the purpose, application and required characteristics of the resist composition, and it can be said that this is a more effective production method.

  As a weight average molecular weight of compound (II) used by this invention, 300-20,000 are preferable from the high antifoaming improvement effect and compatibility, and 500-10,000 are more preferable. Moreover, as a number average molecular weight, 300-20,000 are preferable and 500-10,000 are more preferable.

  The fluorine content in the compound (II) used in the present invention is preferably in the range of 20 to 80% by mass and more preferably in the range of 25 to 70% by mass because the antifoaming effect is high and the compatibility is good. The range of 30 to 60% by mass is more preferable. In addition, the said fluorine content rate of this invention is computed from the mass ratio of the fluorine atom with respect to the total amount of the raw material used for preparation of compound (II) used by this invention.

  The surfactant composition of the present invention is characterized by containing the fluorosurfactant (I) and the compound (II). The surfactant composition of the present invention may contain a surfactant other than the fluorosurfactant (I). Examples of such a surfactant include Megafac F-171 and F- 172, F-173, F-176, F-177, F-141, F-142, F-142, F-143, F-144, R-30, F-437, F- 475, F-479, F-482, F-560, F-561, F-780, F-780, F-781 (manufactured by DIC Corporation), Florard FC430, FC431, FC171 ( Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393 , KH-40 [above, Asahi Glass Co., Ltd.)], and the like.

  The content of the compound (II) in the surfactant composition of the present invention is 0.01 to 80 parts by mass per 100 parts by mass of the fluorosurfactant (I). It is preferable because the state of the film surface is not deteriorated, and more preferably 0.1 to 50 parts by mass.

  The coating composition of the present invention contains the surfactant composition of the present invention. The content of the compound (II) in the coating composition varies depending on the type of coating resin, the coating method, the target film thickness, etc., but it has a high defoaming effect and does not deteriorate the coating state. 0.000001-10 mass parts is preferable with respect to 100 mass parts of solid content among compositions, 0.00001-5 mass parts is more preferable, 0.01-2 mass parts is further more preferable.

  The content of the fluorosurfactant (I) in the coating composition varies depending on the type of coating resin, the coating method, the target film thickness, etc., but with respect to 100 parts by mass of the solid content in the coating composition. 0.0001-10 mass parts is preferable, 0.001-5 mass parts is more preferable, and 0.01-2 mass parts is still more preferable. If the content of the fluorosurfactant (I) is within this range, the surface tension can be sufficiently reduced, the desired leveling properties can be obtained, and problems such as foaming during coating can occur. Can be suppressed.

  By using the surfactant composition of the present invention as an additive for the coating composition, a coating composition having excellent smoothness (leveling property) and low foaming property can be obtained. Examples of such a coating composition include various coating compositions and photosensitive resin compositions.

  Examples of the coating 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 addition to the coating composition exemplified above, the surfactant composition of the present invention can also be used as an active energy ray-curable composition as a coating composition. This active energy ray curable composition contains an active energy ray curable resin or an active energy ray curable monomer as a main component. The active energy ray curable resin and the active energy ray curable monomer may be used alone or in combination.

  Examples of the active energy ray-curable resin include urethane (meth) acrylate resins, unsaturated polyester resins, epoxy (meth) acrylate resins, polyester (meth) acrylate resins, acrylic (meth) acrylate resins, and maleimide group-containing resins. In the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. Etc.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  Examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,5 -Monohydric alcohols such as pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalic acid neopentyl glycol mono (meth) acrylate ) Acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate Mono- or di (meth) acrylates of trivalent alcohols such as relate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some of these alcoholic hydroxyl groups with ε-caprolactone Containing mono- and di (meth) acrylates; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and more than trifunctional (meth) acryloyl groups Or a hydroxyl group-containing polyfunctional (meth) acrylate further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene (Meth) acrylate compounds having an oxyalkylene chain such as glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) acrylate (Meth) acrylate compounds having a block structure oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate, etc. Examples thereof include (meth) acrylate compounds having an oxyalkylene chain.

  The reaction of the aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing acrylate compound can be performed by a conventional method in the presence of a urethanization catalyst, for example. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, and octyl. Organic tin compounds such as tin diacetate, dibutyltin diacetate and tin octylate; and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned.

  As the maleimide group-containing resin, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like. These active energy ray-curable resins can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene having a number average molecular weight in the range of 150 to 1,000. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) having a number average molecular weight in the range of 150 to 1000 Acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, propyl ( (Meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate Rate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, aliphatic alkyl (meth) acrylate such as isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydipropy Glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexylmaleimide, N -Octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, N-ethyl- (2-maleimidoethyl) Carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-dimale And maleimides such as midcyclohexane.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( Bifunctional or more polyfunctional (meth) acrylates such as (meth) acrylate are preferred. These active energy ray-curable monomers can be used alone or in combination of two or more.

  The said active energy ray hardening-type composition can be made into a cured coating film by irradiating an active energy ray after apply | coating to a base material. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator to the active energy ray curable composition to improve curability. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α ray, β ray, and γ ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. There is no need to add a photosensitizer.

  Examples of the photopolymerization initiator include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone compounds such as methylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;

Benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoin diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; benzyl And methylphenylglyoxyester.

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; 10-butyl-2 Chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the above photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone is excellent in compatibility with the active energy ray-curable resin and the active energy ray-curable monomer in the active energy ray-curable coating composition. And benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluenesulfonate, and the like. And sulfur compounds.

  These photopolymerization initiators and photosensitizers are preferably used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the nonvolatile component in the active energy ray-curable composition. % Is more preferable, and 0.3 to 7 parts by mass is more preferable.

  In the coating composition, if necessary, organic solvents; colorants such as pigments, dyes, and carbon; inorganics such as silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, and calcium carbonate Powder: Higher fatty acid, acrylic resin, phenol resin, polyester resin, polystyrene resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin (PTFE (polytetrafluoroethylene) ), Etc.), various resin fine powders such as polyethylene and polypropylene; antistatic agents, viscosity modifiers, light stabilizers, weathering stabilizers, heat stabilizers, antioxidants, rust inhibitors, slip agents, waxes, gloss modifiers , Mold release agent, compatibilizer, conductivity modifier, dispersant, dispersion stabilizer, thickener, anti-settling Agent, it is possible to add various additives such as a silicone-based or hydrocarbon-based surfactant as appropriate.

  The organic solvent is useful in appropriately adjusting the solution viscosity of the coating composition, and it is easy to adjust the film thickness, particularly for thin film coating. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

  In addition, although the coating method of the coating composition varies depending on the application, for example, gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater, dipping, Examples thereof include screen printing, spraying, applicators, bar coaters, coating methods using electrostatic coating, and molding methods using various molds.

  The above-mentioned photosensitive resin composition changes its physical properties such as resin solubility, viscosity, transparency, refractive index, conductivity, and ion permeability 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 generally applied by spin coating onto a silicon wafer or a glass substrate on which various metals are deposited so as to have a thickness of about 1 to 2 μm. . At this time, the fluctuation of the coating film thickness can be a deterioration or defect of the quality of the semiconductor or the liquid crystal element, but the surfactant composition of the present invention is high when used as an additive of the photosensitive resin composition. Since a uniform coating film can be formed due to leveling properties, it becomes possible to improve the productivity of semiconductors and liquid crystal elements, to enhance the functions, and the like.

  Next, the resist composition of the present invention will be described. The resist composition of the present invention is characterized by containing the surfactant composition of the present invention. Usually, the resist composition comprises the surfactant composition of the present invention and a photoresist agent. The photoresist agent comprises (1) an alkali-soluble resin, (2) a radiation sensitive substance (photosensitive substance), (3 ) A solvent, and optionally (4) other additives.

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

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

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

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

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

  Examples of the diazo compound include a salt of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as hexafluorophosphate, tetrafluoroborate, perchlorate or periodate and the above condensate. Inorganic salts of diazo resins that are reactive organisms with diazo resins, organic salts of diazo resins that are reaction products of the above condensates and sulfonic acids as described in US Pat. No. 3,300,309, and the like.

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

  As the halogenated organic compound, for example, any halide of an organic compound can be used. Specific examples include halogen-containing oxadiazole compounds, halogen-containing triazine compounds, halogen-containing acetophenone compounds, halogens. Containing benzophenone compounds, halogen containing sulfoxide compounds, halogen containing sulfone compounds, halogen containing thiazole compounds, halogen containing oxazole compounds, halogen containing trizole compounds, halogen containing 2-pyrone compounds, halogen containing aliphatic hydrocarbons Various compounds such as compounds, halogen-containing aromatic hydrocarbon compounds, other halogen-containing heterocyclic compounds, sulfenyl halide compounds, and further, for example, tris (2,3-dibromopropyl) phosphate, tri (2,3-dibromo-3-chloropropyl) phosphate, chlorotetrabromomethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A Bis (bromoethyl ether) tetrabromobisphenol A, bis (chloroethyl ether) tetrachlorobisphenol A, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromo Phenyl) propane, compounds used as halogen flame retardants such as 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, organics such as dichlorophenyltrichloroethane Rollo compounds are used as agricultural chemicals, etc. can be mentioned.

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

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

  Examples of the (3) solvent used in the resist composition of the present invention include ketones such as acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, cycloheptanone, 2-heptanone, methyl isobutyl ketone, butyrolactone; methanol, ethanol, alcohols such as n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-butyl alcohol, pentanol, heptanol, octanol, nonanol, decanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ethers such as dioxane;

Alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether; ethyl formate, propyl formate, butyl formate, methyl acetate , Ethyl acetate, butyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, propyl butyrate, ethyl lactate, butyl lactate, 2- Methyl oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2-methoxypropionic acid Chill, 2-methoxy ethyl propionate, 2-methoxy-propionic acid propyl, 2-methoxy-propionic acid monocarboxylic acid esters such as butyl;

Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, etc. Propylene glycols; Diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, Diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, Diethylene glycol methyl ethyl ether, and other diethylene glycols; Trichlorethylene, Freon solvent, HCFC, H Halogenated hydrocarbons such as C; perfluorinated solvents such as perfluorooctane; aromatics such as toluene and xylene; polar solvents such as dimethylacetamide, dimethylformamide, N-methylacetamide, and N-methylpyrrolidone The solvent described in the book “Solvent Pocket Handbook” (edited by the Society of Synthetic Organic Chemistry, Ohm Co., Ltd.). These solvents can be used alone or in combination of two or more.

  The content of the surfactant composition in the resist composition of the present invention varies depending on the type of resist composition, the coating method, the target film thickness, etc., but has a high defoaming effect and deteriorates the coating state. Therefore, 0.000001 to 10 parts by mass is preferable with respect to 100 parts by mass of the solid content of the resist composition, more preferably 0.00001 to 5 parts by mass, and still more preferably 0.0001 to 2 parts by mass.

  The content of the surfactant composition in the coating composition varies depending on the type of the coating composition, the coating method, the target film thickness, etc., but is 0.0001 with respect to 100 parts by mass of the solid content of the coating composition. 10 mass parts is preferable, 0.001-5 mass parts is more preferable, 0.001-2 mass parts is further more preferable. If content of surfactant composition is this range, surface tension can fully be reduced, the target leveling property will be acquired, and generation | occurrence | production of malfunctions, such as foaming at the time of coating, can be suppressed.

  Examples of the coating method of the resist composition of the present invention include spin coating, roll coating, dip coating, spray coating, blade coating, slit coating, curtain coating, and gravure coating. The resist composition is filtered before coating. To remove solid impurities.

  As described above, the surfactant composition of the present invention is useful as an additive for coating compositions (coating compositions, photosensitive resin compositions, etc.) and resist compositions. Examples of application of the surfactant composition of the present invention include, for example, hard coat materials for gravure printing inks for various display screens such as liquid crystal displays, plasma displays, and organic EL displays (PDPs), inkjet inks; Paint or hard coat material; Hard coat material for mobile phone screen; Hard coat material for optical recording media such as CD, DVD, Blu-ray disc; Hard coat material for transfer film for insert mold (IMD, IMF); Printing inks or paints for various building materials; coating materials for window glass of houses; wood coating materials for furniture, etc .; coating materials for artificial and synthetic leathers; paints or coating materials for various plastic molded products such as housings for home appliances; Paint or coating material; RGB pixels used in color filters for liquid crystal displays Color resist for forming or black resist for forming black matrix; Photoresist used for semiconductor production; Photosensitive material for lithographic printing plate (PS plate); Single layer or multilayer coating for other photofabrication processes Examples thereof include compositions. By adding the fluorosurfactant of the present invention to these coating compositions, excellent smoothness free from pinholes, yuzu skin, coating unevenness, cissing and the like can be expressed.

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

  Examples of the present invention will be described below, and the present invention will be described in detail while comparing with comparative examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

Synthesis Example 1 [Preparation of Fluorosurfactant (I)]
133 g of methyl isobutyl ketone was added to a glass flask equipped with a stirrer, a condenser and a thermometer, and the temperature was raised to 110 ° C. while stirring in a nitrogen stream. Then, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate 32 g, oxypropylene moiety having 1 repeating unit and 6 repeating units Droplets prepared by dissolving 68 g of propylene glycol / polybutylene glycol monomethacrylate having an oxybutylene moiety and 6 g of t-butylperoxy-2-ethylhexanoate in 100 g of methyl isobutyl ketone were set in separate dropping devices, respectively. Was simultaneously added dropwise over 6 hours while maintaining at 110 ° C. After completion of the dropwise addition, the mixture was stirred at 110 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain fluorinated surfactant (I-1). The fluorine-based surfactant (I-1) had a number average molecular weight of 4200 and a weight average molecular weight of 9,500. The fluorine content was 18.7% by mass.

Synthesis example 2 (same as above)
To a glass flask equipped with a stirrer, a condenser, and a thermometer, 102 g of methyl isobutyl ketone was added, and the temperature was raised to 95 ° C. while stirring in a nitrogen stream. Next, 37 g of 2- [bis (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl) methoxycarbonylamino] ethyl methacrylate, average repeat A dripping solution prepared by dissolving 64 g of 5 units of polypropylene glycol monomethacrylate and 1 g of t-butylperoxy-2-ethylhexanoate in 120 g of methyl isobutyl ketone was set in a dropping device, and the flask was kept at 88 ° C. for 6 hours. It was dripped over. After completion of dropping, the mixture was stirred at 95 ° C. for 8 hours. Then, it stirred at 110 degreeC for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain fluorinated surfactant (I-2). The fluorine-based surfactant (I-2) had a number average molecular weight of 5700 and a weight average molecular weight of 27100. Further, the fluorine content was 19.3 mass%.

Synthesis Example 3 [Preparation of Compound (II)]
In a glass flask equipped with a stirrer, a condenser and a thermometer, 40 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 10 g of dipentaerythritol hexaacrylate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-1) having a solid content of 100%. The number average molecular weight of the compound (II-1) was 3,022 and the weight average molecular weight was 3,107. The fluorine content was 51.8% by mass.

Synthesis example 4 (same as above)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 40 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. Ten grams of pentaerythritol triacrylate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-2) having a solid content of 100%. Compound (II-2) had a number average molecular weight of 1,713 and a weight average molecular weight of 1,773. The fluorine content was 51.5% by mass.

Synthesis example 5 (same as above)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 41 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 9 g of pentaerythritol tetraacrylate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-3) having a solid content of 100%. The number average molecular weight of the compound (II-3) was 2,048, and the weight average molecular weight was 2,084. The fluorine content was 52.8% by mass.

Synthesis example 6 (same as above)
In a glass flask equipped with a stirrer, condenser and thermometer, 38 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 12 g of ditrimethylolpropane tetraacrylate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-4) having a solid content of 100%. The number average molecular weight of the compound (II-4) was 2,260, and the weight average molecular weight was 2,299. The fluorine content was 49.7% by mass.

Synthesis example 7 (same as above)
In a glass flask equipped with a stirrer, condenser and thermometer, 36 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 14 g of polyoxyethylene diacrylate having 4 repeating units was set in a dropping device and dropped over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 12 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-5) having a solid content of 100%. The number average molecular weight of the compound (II-5) was 1,157, and the weight average molecular weight was 1,165. The fluorine content was 46.2% by mass.

Synthesis example 8 (same as above)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 35 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 15 g of polyoxybutylene diacrylate having 4 repeating units was set in a dropping device and dropped over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 12 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-6) having a solid content of 100%. Compound (II-6) had a number average molecular weight of 1,283 and a weight average molecular weight of 1,306. The fluorine content was 44.9% by mass.

Synthesis example 9 (same as above)
In a glass flask equipped with a stirrer, condenser and thermometer, 38 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 12 g of polyoxypropylene diacrylate having 2 repeating units was set in a dropping device and dropped over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 12 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-7) having a solid content of 100%. The number average molecular weight of the compound (II-7) was 1,080, and the weight average molecular weight was 1,084. The fluorine content was 49.3 mass%.

Synthesis example 10 (same as above)
In a glass flask equipped with a stirrer, condenser and thermometer, 33 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 16 g of dipentaerythritol hexaacrylate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-8) having a solid content of 100%. The number average molecular weight of the compound (II-8) was 1551, and the weight average molecular weight was 2,123. The fluorine content was 43.5% by mass.

Synthesis example 11 (same as above)
In a glass flask equipped with a stirrer, a condenser and a thermometer, 35 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctanethiol in an air stream And 1 g of triethylamine was added. 15 g of Unidic V-4000BA manufactured by DIC Corporation was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 85 ° C. for 6 hours. After completion of the reaction, the unreacted raw material was distilled off under reduced pressure to obtain Compound (II-9) having a solid content of 100%. The number average molecular weight of the compound (II-9) was 4520 and the weight average molecular weight was 4,830. The fluorine content was 46.0% by mass.

Examples 1 to 10 (Preparation of surfactant composition)
The surfactants (1) to (10) of the present invention were obtained by mixing the fluorosurfactant and the compound in the formulation shown in Table 1. The obtained surfactant composition was used to evaluate defoaming properties and applicability. The evaluation method is shown below. The evaluation results are shown in Table 1.

[Method for evaluating defoaming property]
A surfactant composition was added to propylene glycol monomethyl ether acetate to a concentration of 1.0% to prepare a solvent solution containing the surfactant composition. 50 g of this solvent solution was added to a 100 ml glass bottle and sealed, and this glass bottle was left in a constant temperature layer at 25 ° C. for 30 minutes. Thereafter, the glass bottle was shaken 10 times with a width of 20 cm to generate bubbles on the liquid surface of the solvent solution. The glass bottle was allowed to stand immediately after the foam was generated, and the time (T0) until the liquid surface of the solvent solution began to be exposed due to the disappearance of the foam was measured from the time when the glass bottle was left still. It shows that it is a surfactant composition from which the solvent solution which is excellent in defoaming property is obtained, so that these time is short.

[Method for evaluating applicability]
<Preparation of coating composition>
27 parts of a condensate of 2,3,4-trihydroxybenzophenone and o-naphthoxydiazide-5-sulfonyl chloride and 100 parts of a novolak resin obtained by condensing cresol and formaldehyde were mixed with propylene glycol methyl ether acetate. A solution was prepared by dissolving in 400 parts by weight. To this solution, a surfactant composition was added to a concentration of 0.5% and mixed uniformly, and then finely filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain a coating composition. . The occurrence of unevenness and streaks on the surface of the coating film obtained using this coating composition was observed. A method for preparing a coating film for observing the occurrence of unevenness and streaks on the surface of the coating film and evaluation criteria are shown below.

<Method for creating coating film and evaluation criteria for observing unevenness of coating film surface>
The coating composition was spin-coated on a chromium-deposited glass substrate having a side of 10 cm square at a rotation speed of 500 rpm to form a coating film of the coating composition on the glass substrate. Thereafter, the glass substrate on which the coating film was formed was left in an environment of 110 ° C. for 1 minute to dry the coating film.

About the obtained dried coating film, the degree of unevenness (coating unevenness) on the coating surface was visually observed using a sodium lamp, and the coating film surface smoothness was evaluated according to the following criteria.
○: Coating film unevenness is hardly observed on the coating film surface.
Δ: Some coating film unevenness is observed on the coating film surface.
X: Many coating film nonuniformities are observed on the coating film surface.

<Method for creating coating film and evaluation criteria for observing streaks on coating film surface>
The coating composition was spin-coated on a chromium-deposited glass substrate having a side of 10 cm square at a rotation speed of 500 rpm to form a coating film of the coating composition on the glass substrate. Thereafter, the glass substrate on which the coating film was formed was allowed to settle for 5 minutes at room temperature, and then was left to stand in an environment of 110 ° C. for 1 minute to dry the coating film.

About the obtained dry coating film, the generation | occurrence | production condition of the stripe which generate | occur | produces on the application | coating surface was observed visually using the sodium lamp, and the coating film surface smoothness was evaluated on the following judgment criteria.
○: Less than 5 streaks generated on the surface of the coating film.
Δ: 5 or more and less than 10 streaks generated on the coating film surface.
X: 10 or more streaks generated on the surface of the coating film.

Comparative Examples 1-2
Comparative comparative fluorosurfactants (1 ′) to (2 ′) were obtained in the same manner as in Example 1 except that the antifoaming agent was not used. In the same manner as in the examples, the defoaming property and the coating property were evaluated. The evaluation results are shown in Table 1.

Claims (11)

Monomer (α) having a fluorinated alkyl group having 4 to 6 carbon atoms to which fluorine atoms are directly bonded, and the following general formula (β1)

(In the formula, R is a hydrogen atom or a methyl group, X and Y are each an independent alkylene group. M and n are each 0 or an integer of 1 or more, and the sum of m and n is 2 or more. Z is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
A fluorosurfactant (I) obtained by copolymerizing a monomer (β) having a polyoxyalkylene chain represented by
Fluorine having 1 to 6 carbon atoms in which fluorine atoms are directly bonded to 1 mol of compound (a1) having k (wherein k is 2 or more) (meth) acryloyl group in one molecule A surfactant composition comprising a compound (II) obtained by Michael addition reaction of 2-kmol of a compound (a2) having an alkyl group and active hydrogen.   The surfactant composition according to claim 1, wherein k is 2 to 40. The compound (a2) having a fluorinated alkyl group having 1 to 6 carbon atoms to which the fluorine atom is directly bonded and active hydrogen is represented by the following general formula (1)
Rf (CH ₂ ) _m ZH (1)
Wherein, m is an integer of 0 to 20, Rf is _-C n _{F 2n +} 1 (n is an integer from 1 to 6.), Z is a nitrogen atom having an alkyl group of carbon number 1 to 24 , An oxygen atom, a sulfur atom, or —SO ₂ —NR— (wherein R is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms). Or a compound represented by the following general formula (2)

[In the formula, Y is an oxygen atom or a sulfur atom, p and q are each an integer of 1 to 4, and Rf and Rf ¹ are each —C _n F2 _{n + 1} (n is an integer of 1 to 6). L and L ¹ are each a carbonyl group, an alkyl group having 1 to 4 carbon atoms having a carbonyl group, and one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms.] The surfactant composition according to claim 1, which is a compound to be produced. Z in the general formula (1) is a nitrogen atom having an alkyl group having 1 to 6 carbon atoms, a sulfur atom, or (R is an alkyl group having 1 to 6 carbon atoms.) _-SO 2 -NR- in The surfactant composition according to claim 3. The compound (a1) having k (meth) acryloyl groups (wherein k is 2 or more) in one molecule is represented by the following general formula (3)

[Wherein, R ′ is an alkyl group having 1 to 24 carbon atoms, an alkylcarbonyloxy group having 1 to 24 carbon atoms, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ -, A (poly) oxyalkylene group having 1 or more repeats and a terminal end blocked with a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkylol group having 1 to 12 carbon atoms, a carboxyl group, or the following general Formula (4)

(In the formula, R ³ is a (meth) acryloyl group, R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl ester group having 1 to 18 carbon atoms, or a carboxyl group, and t is 0 to 0. is 3 integer, u is a group represented by an integer from 0 to 3 and a and t + u = 3.), R 1 is a (meth) acryloyl group, R ² represents a hydrogen atom or a carbon An alkylcarbonyl group having 1 to 18 atoms; r is 2 or 3; s is 0 or 1; and r + s = 3. ] Compound (a1-1) represented by the following general formula (5)

[Wherein R ⁶ and R ⁷ are each a (meth) acryloyl group, L is an alkyl group having 1 to 18 carbon atoms, and an alkyleneoxy group having 1 to 4 carbon atoms having 1 to 30 repeating units. , A cyclic hydrocarbon group having 3 to 100 carbon atoms or an aromatic hydrocarbon group having 6 to 100 carbon atoms. ] The compound (a1-2), urethane (meth) acrylate (a1-3), cyanurate ring-containing tri (meth) acrylate (a1-4) and phosphoric acid tri (meth) acrylate (a1-5) represented by The surfactant composition according to claim 1, which is one or more compounds selected from the group consisting of: Compound (a1) having k (meth) acryloyl groups (wherein K is 2 or more) in one molecule has the above general formula (3) [wherein R ′ has 1 to 4 carbon atoms. A linear alkyl group, CH ₂ ═CHCO ₂ CH ₂ —, CH ₂ ═C (CH ₃ ) CO ₂ CH ₂ —, or an alkylol group having 1 to 3 carbon atoms, or the general formula (4) And R ³ is a hydrogen atom or an alkylcarbonyl group having 1 to 12 carbon atoms. Or a urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate (x1) having two or more (meth) acryloyl groups with an isocyanate compound (x2). 5. The surfactant composition according to 5.   The polyoxyalkylene chain of the fluorosurfactant (I) is at least one chain selected from the group consisting of a polyoxypropylene chain, a polyoxybutylene chain and a polyoxytetramethylene chain. Surfactant composition.   In the range in which the fluorosurfactant (I) makes the monomer (α) and the monomer (β) 10/90 to 70/30 at a mass ratio [(α) / (β)]. The surfactant composition according to claim 1, which is obtained by use. The surfactant composition according to any one of claims 1 to 8 , wherein the content of the compound (II) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the fluorosurfactant (I). .   A coating composition comprising the surfactant composition according to claim 1.   A resist composition comprising the surfactant composition according to claim 1.