JP6210309B2 - 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 that has low concern about the property, has low foaming properties, and defoams 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, the market has a low risk of generating PFOS or PFOA, which has a high concern for the environment and bioaccumulation in terms of structure. There is a need for a surfactant that has excellent leveling properties, low foaming properties (hard to foam), and defoams in a short time even when foamed.

  In response to such demands, a fluorine-containing curable resin having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group, specifically, a poly (perfluoroalkylene ether) chain and polymerizable at both ends thereof. A polymer obtained by copolymerizing a polymerizable monomer having an unsaturated group, a reactive functional group and a monomer having a polymerizable unsaturated group, and a functional group having reactivity with the reactive functional group. A fluorine-containing curable resin (fluorinated surfactant) obtained by reacting a compound having a group with a polymerizable unsaturated group has been 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 such a case, it takes about 10 minutes for the liquid surface to begin to be exposed due to the disappearance of the generated bubbles, and even the fluorosurfactant disclosed in Patent Document 1 still does not have sufficient antifoaming properties.

Japanese Patent Application No. 2009-532474

  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 little concern about accumulation in the environment and the living body, and has low foaming properties (hard to foam), The object is to provide a surfactant composition that defoams in a short time even when foamed, and a coating composition and a resist composition containing the composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the poly (perfluoroalkylene ether) chain, a polymerizable monomer having a polymerizable unsaturated group at both ends thereof, and a reactive functional group. A polymer obtained by copolymerizing a group and a monomer having a polymerizable unsaturated group is reacted with a compound having a reactive functional group, a reactive functional group, and a polymerizable unsaturated group. Fluorinated alkyl group having 1 to 6 carbon atoms in which fluorine atoms are directly bonded to the (meth) acryloyl group of polyfunctional (meth) acrylate in the resulting fluorinated curable resin (fluorinated surfactant) The present inventors have found that a composition obtained by mixing a compound obtained by adding a specific amount of a compound having active hydrogen with a compound having active hydrogen using the Michael addition reaction can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention comprises a poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, a reactive functional group (b) and a polymerizable unsaturated group. A compound (C) having a functional group (c) having reactivity with the functional group (b) and a polymerizable unsaturated group (C) obtained by copolymerizing the monomer (B) having Fluorine-containing curable resin (I) obtained by reacting
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 And a compound (II) obtained by Michael addition of 2 to 2 moles 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 is also less susceptible to environmental and biological accumulation. 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 poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, and a reactive functional group (b ) And a monomer (B) having a polymerizable unsaturated group, a polymer (P) obtained by copolymerization with the functional group (c) having a reactivity with the functional group (b) and a polymerizable unsaturated group. Obtained by reacting a compound (C) having a saturated group.

  Examples of the poly (perfluoroalkylene ether) chain used in the above production method and the poly (perfluoroalkylene ether) chain possessed by the compound (A) having a polymerizable unsaturated group at both ends thereof include 1 to 1 carbon atoms. 3 having a structure in which divalent fluorocarbon groups and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be a single type or a mixture of a plurality of types, and specifically, those represented by the following structural formula 1 may be mentioned. It is done.

（上記構造式１中、Ｘは下記構造式ａ〜ｄであり、構造式１中の全てのＸが同一構造のものであってもよいし、また、複数の構造がランダムに又はブロック状に存在していてもよい。また、ｎは繰り返し単位を表す１以上の数である。）

(In the above structural formula 1, X is the following structural formulas a to d, and all X in the structural formula 1 may have the same structure, or a plurality of structures are randomly or block-shaped. And n is a number of 1 or more representing a repeating unit.

  Among these, since the leveling property of the coating composition to which the surfactant composition of the present invention is added becomes good and a smooth coating film is obtained, the perfluoromethylene structure represented by the structural formula (a), What coexists with the perfluoroethylene structure represented by the structural formula (b) is preferable. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula (a) and the perfluoroethylene structure represented by the structural formula (b) is a molar ratio [structure (a) / structure (b )] Is preferably 1/10 to 10/1 because a surfactant composition having excellent leveling properties is obtained. Moreover, the value of n in the structural formula (1) is preferably in the range of 3 to 100, more preferably in the range of 6 to 70.

  The poly (perfluoroalkylene ether) chain is compatible with the leveling property of the coating composition and the solubility in the non-fluorine-based material in the coating composition, and therefore the fluorine contained in one poly (perfluoroalkylene ether) chain. The total number of atoms is preferably in the range of 18 to 200, and more preferably in the range of 25 to 150.

  The average molecular weight of the poly (perfluoroalkylene ether) chain in the fluorine-containing curable resin (I) of the poly (perfluoroalkylene ether) chain is 400 to 10,000, and has high leveling properties, which will be described later. It is preferable because the compatibility with other components in the coating composition is good, and 500 to 5,000 is more preferable. The average molecular weight of the poly (perfluoroalkylene ether) chain in the fluorine-containing curable resin (I) is 2,500 to 10,000, and a cured coating film having excellent antifouling properties and slipperiness can be obtained. Therefore, 3,000 to 4,500 is more preferable.

  Next, the polymerizable unsaturated group contained in the polymerizable monomer (A) is an ethylenic double bond that exhibits curability when irradiated with active energy rays. Specifically, the following structural formula U-1 -U-5 etc. are mentioned.

（構造式Ｕ−５中のｎは１〜２０である。）

(N in Structural Formula U-5 is 1 to 20)

  Examples of the monomer (A) used in the present invention include those represented by structural formulas (A-1) to (A-16). In the following structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  Among these polymerizable unsaturated groups, the structural formula U- is particularly preferred because of the ease of obtaining and producing the compound (A) itself, or excellent polymerizability with the polymerizable unsaturated monomer (B) described later. The acryloyloxy group represented by 1 and the methacryloyloxy group represented by Structural Formula U-2 are preferred. Moreover, since chemical resistance improves, the methacryloyloxy group represented by Structural formula U-2 and the styryl group represented by Structural formula U-5 are preferable.

  In order to produce the polymerizable monomer (A) used in the present invention, for example, a (meth) acrylic acid chloride or a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain is used. A method of obtaining styrene having a halogenated alkyl group by dehydrochlorination reaction, a method of obtaining (meth) acrylic acid by dehydration reaction, a method of obtaining 2- (meth) acryloyloxyethyl isocyanate by urethanation reaction, itaconic anhydride Which is obtained by esterification reaction;

A method obtained by esterifying 4-hydroxybutyl acrylate glycidyl ether with a compound having one carboxyl group at both ends of a poly (perfluoroalkylene ether) chain, a method obtained by esterifying glycidyl methacrylate ;

A method in which 2-hydroxyethylacrylamide is reacted with a compound having one isocyanate group at each end of a poly (perfluoroalkylene ether) chain;

Examples include a method of reacting (meth) acrylic acid with a compound having one epoxy group at each end of a poly (perfluoroalkylene ether) chain. Among these, a method of obtaining a compound having one hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain by dehydrochlorination of (meth) acrylic acid chloride or styrene having an alkyl halide group. And a method obtained by urethanizing 2- (meth) acryloyloxyethyl isocyanate is particularly preferable in terms of easy reaction in production.

  Compound having one hydroxyl group at both ends of the poly (perfluoroalkylene ether) chain, compound having one carboxyl group at both ends of the poly (perfluoroalkylene ether) chain, poly (perfluoroalkylene ether) Examples of the compound having one isocyanate group at both ends of the chain and the compound having one epoxy group at both ends of the poly (perfluoroalkylene ether) chain include compounds having the following structures.

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

  Here, the polymer (P) used in the present invention includes, for example, the polymerizable monomer (A), the reactive functional group (b), and the monomer (B) having a polymerizable unsaturated group, organically. It can be obtained by a polymerization method using a radical polymerization initiator in a solvent.

  Here, examples of the reactive functional group (b) of the monomer (B) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic acid anhydride group. Examples of the polymerizable unsaturated monomer (B) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meta) ) Acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, terminal hydroxyl group-containing lactone modification ( Data) hydroxyl group-containing unsaturated monomers such as acrylate; 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxy) ethyl isocyanate group-containing unsaturated monomers such as isocyanate;

Epoxy group-containing unsaturated monomers such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid And carboxyl group-containing unsaturated monomers such as itaconic acid; and carboxylic acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. These monomers (B) can be used alone or in combination of two or more.

  Examples of the organic solvent include ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. 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 molecular weight of the obtained polymer (P) needs to be within a range in which crosslinking insolubilization does not occur during polymerization, and crosslinking insolubilization may occur if the molecular weight is too high. Within that range, the polymer (P) has a number average molecular weight (Mn) of 800 in that the number of polymerizable unsaturated groups in one molecule of the finally obtained fluorine-containing curable resin (I) increases. Is preferably in the range of ˜3,000, particularly 1,000 to 2,000, and the weight average molecular weight (Mw) is in the range of 1,500 to 20,000, particularly 2,000 to 5,000. It is preferable.

  By reacting the polymer (P) thus obtained with the compound (C) containing the functional group (c) having reactivity with the functional group (b) and a polymerizable unsaturated group, The fluorine-containing curable resin (I) used in the invention is obtained.

  Here, examples of the functional group (c) present in the compound (C) include a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. In the present invention, the functional group (b) is one or more functional groups selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group, and the compound (C) Reactive functional group (c) contained in (C) is reactive with the reactive functional group (b), and a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxyl group. A combination that is one or more functional groups selected from the group consisting of acid anhydride groups is preferred.

  As a combination of the functional group (b) and the functional group (c), for example, when the reactive functional group (b) is a hydroxyl group, the functional group (c) is an isocyanate group, a carboxyl group, a carboxylic acid halide group, When a carboxylic anhydride group is mentioned and the reactive functional group (b) is an isocyanate group, a hydroxyl group is mentioned as the functional group (c), and when the reactive functional group (b) is an epoxy group Includes a carboxyl group and a hydroxyl group as the functional group (c), and an epoxy group and a hydroxyl group as the functional group (c) when the reactive functional group (b) is a carboxyl group. These may be a combination of a plurality of functional groups.

  The polymerizable unsaturated group of the compound (C) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, and the like. (Meth) acryloyl groups are more preferred from the viewpoint of good curability in the active energy ray-curable resin composition described below.

  Specific examples of the compound (C) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at the terminal Unsaturated monomer having a hydroxyl group such relations;

Unsaturated monomer having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate body;

Unsaturated monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, Examples thereof include carboxyl group-containing unsaturated monomers such as maleic acid and itaconic acid; carboxylic acid anhydrides having an unsaturated double bond such as maleic anhydride and itaconic anhydride. Moreover, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate etc. can also be used as what has a several polymerizable unsaturated group. These compounds (C) can be used alone or in combination of two or more.

  Among the specific examples of the compound (C), 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate are preferable. Hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N- (2-hydroxyethyl) acrylamide, 2-acryloyloxyethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 4-hydroxybutyl acrylate glycidyl Ether and acrylic acid are preferred.

  The compound (C) may be a compound having one polymerizable unsaturated group per molecule or a compound having two or more. Among compounds (C), a compound having two or more polymerizable unsaturated groups per molecule is more preferable because a cured coating film having excellent scratch resistance can be obtained.

  The method of reacting the polymer (P) with a compound (C) containing a functional group (c) reactive with the functional group (b) and a polymerizable unsaturated group is the same as in the compound (C). What is necessary is just to perform on the conditions which a polymerizable unsaturated group does not superpose | polymerize, for example, it is preferable to make it react by adjusting temperature conditions in the range of 30-120 degreeC. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor and, if necessary, in the presence of an organic solvent.

  When the functional group (b) is a hydroxyl group and the functional group (c) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methyl is used as a polymerization inhibitor. Preferable is a method of using phenol or the like, and using dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like as the urethanization reaction catalyst and reacting at a reaction temperature of 40 to 120 ° C., particularly 60 to 90 ° C. .

  When the functional group (b) is an epoxy group and the functional group (c) is a carboxyl group, or the functional group (b) is a carboxyl group and the functional group (c) is an epoxy group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and tertiary amines such as triethylamine are used as an esterification reaction catalyst. Using a quaternary ammonium such as tetramethylammonium, a tertiary phosphine such as triphenylphosphine, a quaternary phosphonium such as tetrabutylphosphonium chloride, etc., and a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it react with.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, 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 may be appropriately selected in consideration of the boiling point and compatibility.

  The fluorine-containing curable resin (I) used in the present invention may have a maleimide group as long as the effects of the present invention are not impaired. By having a maleimide group, the fluorine-containing curable resin (I) can impart excellent antifouling properties to the coating film surface, and even when cured in an air atmosphere (in the presence of oxygen), Since curability by energy rays is good, it can be expected that excellent antifouling properties can be exhibited.

The fluorine-containing curable resin having a maleimide group can be obtained, for example, by the following method.
Production method 1: Poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, a monomer having a reactive functional group (b) and a polymerizable unsaturated group The polymer (P1) obtained by copolymerizing the polymer (B) and the polymerizable monomer (D1) having a maleimide group having no radical polymerizability is functionally reactive with the functional group (b). The compound (C) having a group (c) and a polymerizable unsaturated group is reacted.

  Production method 2: Poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, a reactive functional group (b) and a monomer having a polymerizable unsaturated group A compound (C) having a functional group (c) reactive with the functional group (b) and a polymerizable unsaturated group, and a polymer (P) obtained by copolymerizing the body (B); A functional group (d2) having reactivity with the functional group (b) is reacted with a compound (D2) having a maleimide group.

  The maleimide group having no radical polymerizability of the polymerizable monomer (D) is a carbon-carbon of the maleimide group by a copolymerization reaction of the polymerizable monomer (A) and the monomer (B). Any unsaturated double bond that does not participate in the copolymerization reaction, that is, has no radical polymerizability in the copolymerization reaction, can be used without particular limitation, but is represented by the following general formula (d1). A disubstituted maleimide group in which a substituent such as an alkyl group is bonded to carbon of such a carbon-carbon unsaturated double bond is preferable. By using the radically polymerizable unsaturated monomer (D1) having such a disubstituted maleimide group, when the polymerizable monomer (A) and the monomer (B) are copolymerized, a maleimide group This maleimide group, which can suppress consumption of the double bond in the copolymerization reaction, causes photodimerization reaction by irradiation with active energy rays even in the absence of a photopolymerization initiator described later. Possible functional groups.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素原子数１〜６のアルキル基、又はＲ^１とＲ^２とが１つとなって５員環もしくは６員環を形成する炭化水素基を表す。）

(In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, or a hydrocarbon in which R ¹ and R ² are combined to form a 5-membered or 6-membered ring. Represents a group.)

Specific examples of the maleimide group represented by the general formula (1) include the following formulas (d1-1) to (d1-3).

  Further, specific examples of the polymerizable monomer (D1) include monomers represented by the following formulas (D1-1) to (D1-6).

  The maleimide group of the compound (D2) having a functional group (d2) and a maleimide group having reactivity with the functional group (b) used in the production method 2 is represented by the following general formula (d2), for example. Groups and the like.

（式中、Ｒ^３及びＲ^４は、それぞれ独立して、水素原子もしくは炭素原子数１〜６のアルキル基、又はＲ^３とＲ^４とが１つとなって５員環もしくは６員環を形成する炭化水素基を表す。）

(Wherein R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ³ and R ⁴ are combined to form a 5-membered or 6-membered ring. Represents a hydrocarbon group.)

  Specific examples of the maleimide group represented by the general formula (2) include the following formulas (D2-1) to (D2-5).

  Further, specific examples of the polymerizable monomer (D2) include monomers represented by the following formulas (D2-1) to (D1-11).

  The fluorine-containing curable resin (I) used in the present invention may have an oxyalkylene group as long as the effects of the present invention are not impaired. By having an oxyalkylene group, the fluorine-containing curable resin has good compatibility with the main agent (polymerizable monomer or polymerizable oligomer) and solvent contained in the coating composition and resist composition described later, and a uniform composition. As a result, it is expected that a cured coating film with less repellency can be obtained.

Among the fluorine-containing curable resins (I), the fluorine-containing curable resin having an oxyalkylene group can be obtained, for example, by the following method.
Production method 3: Poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, a monomer having a reactive functional group (b) and a polymerizable unsaturated group The polymer (P2) obtained by copolymerizing the polymer (B), the oxyalkylene group and the polymerizable monomer (E) having a polymerizable unsaturated group has reactivity with the functional group (b). The compound (C) having a functional group (c) and a polymerizable unsaturated group is reacted.

  Examples of the polymerizable unsaturated group possessed by the polymerizable monomer (E) include a (meth) acryloyl group, a vinyl group, and a maleimide group. A (meth) acryloyl group is preferable because copolymerization with the body (B) is easy.

  Specific examples of the polymerizable monomer (E) include a monomer represented by the following general formula (E1).

（式中、Ｒ^５は水素原子又はメチル基であり、Ｘ、Ｙ及びＺはそれぞれ独立のアルキレン基であり、ｐ、ｑ及びｒはそれぞれ０又は１以上の整数であり、かつｐ、ｑ及びｒの合計は１以上の整数であり、Ｒ^６は水素原子又は炭素原子数１〜６のアルキル基である。）

(Wherein R ⁵ is a hydrogen atom or a methyl group, X, Y and Z are each independently an alkylene group, p, q and r are each 0 or an integer of 1 or more, and p, q and The total of r is an integer of 1 or more, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  In the general formula (E1), X, Y and Z are alkylene groups, and the alkylene groups include those having a substituent. Specific examples of the -O- (XO) p- (YO) q- (ZO) r- moiety include ethylene glycol residues in which the number of repeating units p is 1, q and r are 0, and X is ethylene A propylene glycol residue in which the number of repeating units p is 1, q and r are 0, and X is propylene, butylene glycol in which the number of repeating units p is 1, q and r are 0, and X is butylene Residue, repeating unit number p is an integer of 2 or more, q and r are 0, and X is an ethylene glycol residue, repeating unit number p is an integer of 2 or more, and q and r are 0, And a polypropylene glycol residue in which X is 1-methylethylene (propylene), the number of repeating units p and q are both integers of 1 or more, r is 0, and X or Y is ethylene and the other is 1-methylethylene ( Propire ) Is a residue of a copolymer of ethylene oxide and propylene oxide, the number of repeating units p, q and r are both integers of 1 or more, and X and Z are ethylene and Y is 1-methylethylene (propylene) Examples include residues of polyalkylene glycol such as residues of a copolymer of ethylene oxide and propylene oxide.

  The polymerization degree of the polyalkylene glycol, that is, the total of p, q and r in the general formula (E1) is preferably 1 to 80, more preferably 3 to 50. In addition, the repeating unit containing X, the repeating unit containing Y, and the repeating unit containing Z may be arrange | positioned at random or a block shape.

R ⁶ in the general formula (E1) is hydrogen or an alkyl group having 1 to 6 carbon atoms. When R ⁶ is hydrogen, the polymerizable monomer (E) is a mono (meth) acrylate ester of alkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc., and R ⁶ has 1 to 6 carbon atoms. In this case, the end of the alkylene glycol mono (meth) acrylate that is not a (meth) acrylate is sealed with an alkyl group having 1 to 6 carbon atoms.

  More specific examples of the monomer (E1) include polypropylene glycol mono (meth) acrylate, polyethylene 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 (pro Lenglycol / 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 Limethylene glycol) mono (meth) acrylate, polypropylene glycol / polytrimethylene glycol mono (meth) acrylate, poly (trimethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylene glycol / polytetramethylene glycol mono ( And (meth) acrylate, poly (butylene glycol / trimethylene glycol) mono (meth) acrylate, polybutylene glycol / polytrimethylene glycol mono (meth) acrylate, and the like. “Poly (ethylene glycol / propylene glycol)” means a random copolymer of ethylene glycol and propylene glycol, and “polyethylene glycol / polypropylene glycol” means a block copolymer of ethylene glycol and propylene glycol. means. The same applies to other items. Among these monomers (E), since compatibility with other components in the coating composition of the present invention is improved, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene Glycol / polypropylene glycol mono (meth) acrylate is preferred.

  Moreover, as a commercial item of the said monomer (E), Shin-Nakamura Chemical Co., Ltd. "NK ester M-20G", "NK ester M-40G", "NK ester M-90G", " "NK ester M-230G", "NK ester AM-90G", "NK ester AMP-10G", "NK ester AMP-20G", "NK ester AMP-60G", "Blemmer PE-90" manufactured by NOF Corporation ”,“ Blemmer PE-200 ”,“ Blemmer PE-350 ”,“ Blemmer PME-100 ”,“ Blemmer PME-200 ”,“ Blemmer PME-400 ”,“ Blemmer PME-4000 ”,“ Blemmer PP-1000 ” , “Blemmer PP-500”, “Blemmer PP-800”, “Blemmer 70PEP-350B”, “Blemma 55PET-800 "," Brenmer 50POEP-800B "," Blemmer 10PPB-500B "," Blemmer NKH-5050 "," Blemmer AP-400 ", such as" Blemmer AE-350 ", and the like. These monomers (E) can be used alone or in combination of two or more.

  Moreover, the fluorine-containing curable resin (I) used in the present invention may have an adamantyl group as long as the effects of the present invention are not impaired. By having an adamantyl group, it can be expected that a cured coating film having excellent scratch resistance can be obtained.

Among the fluorine-containing curable resins (I), the fluorine-containing curable resin having an adamantyl group can be obtained by, for example, the following method.
Production method 4: Poly (perfluoroalkylene ether) chain, a polymerizable monomer (A) having a polymerizable unsaturated group at both ends thereof, a monomer having a reactive functional group (b) and a polymerizable unsaturated group The polymer (P3) obtained by copolymerizing the polymer (B), a polymerizable monomer (F) having an adamantyl group and a polymerizable unsaturated group is functionally reactive with the functional group (b). The compound (C) having a group (c) and a polymerizable unsaturated group is reacted.

  The adamantyl group of the polymerizable monomer (F) is an organic group having the following adamantane structure.

  Examples of the polymerizable monomer (F) having an adamantyl group and a polymerizable unsaturated group include compounds represented by the following general formula.

In the formulas (F1) and (F2), L represents the reactive functional group (b). X and Y represent a divalent organic group or a single bond, and R represents a hydrogen atom, a methyl group or CF ₃ .

  The general formula (F1) has a reactive functional group (b) as described above. Since this reactive functional group (b) is reactive with the functional group (c) of the compound (C), the reactive functional group (b) is used to polymerize a fluorine-containing curable resin having an adamantyl group. It is also possible to introduce an unsaturated group.

  The organic group having the reactive functional group (b1) represented by -XL in the general formula (F1) and the bonding position of Y may be bonded to any carbon atom in the adamantane structure, Moreover, you may have 2 or more about -XL. Furthermore, part or all of the hydrogen atoms bonded to the carbon atoms constituting the adamantane structure may be substituted with fluorine atoms, alkyl groups, or the like. X and Y in the general formula (F1) are a divalent organic group or a single bond. Examples of the divalent organic group include carbon atoms such as a methylene group, a propyl group, and an isopropylidene group. The alkylene group of number 1-8 is mentioned.

  Specific examples of the compound represented by the general formula (F1) include the following formulas (F1-1) to (F1-5).

  Specific examples of the compound represented by the general formula (F2) include the following formulas (F2-1) to (F2-6).

  Moreover, the fluorine-containing curable resin (I) used in the present invention may have a silicone chain as long as the effects of the present invention are not impaired. By having a silicone chain, the slipperiness of the coating film surface is improved, and as a result, it can be expected that a cured coating film having excellent scratch resistance can be obtained.

Among the fluorine-containing curable resins (I), the fluorine-containing curable resin having the silicone chain can be obtained by, for example, the following method.
Production Method 5: Poly (perfluoroalkylene ether) chain, polymerizable monomer (A) having a polymerizable unsaturated group at both ends, a reactive functional group (b) and a monomer having a polymerizable unsaturated group The polymer (P3) obtained by copolymerizing the polymer (B), the silicone chain and the polymerizable monomer (G) having a polymerizable unsaturated group is functionally reactive with the functional group (b). The compound (C) having a group (c) and a polymerizable unsaturated group is reacted.

  Examples of the silicone chain of the polymerizable monomer (G) include those represented by the following general formula (S1) or (S2).

(In the formula, R, R ′, R ″ and R ′ ″ each independently represents an alkyl group having 1 to 18 carbon atoms or a phenyl group, and n is the number of repeating units. Represents an integer.)

  Moreover, as a polymerizable unsaturated group which the said polymerizable monomer (G) has, the carbon-carbon unsaturated double bond which has radical polymerizability is preferable, (meth) acryloyl group, a vinyl group, a maleimide group, etc. Can be mentioned. Among these, (meth) acryloyl is easy because of the availability of raw materials, the ease of controlling the compatibility with each compounding component in the active energy ray-curable composition described later, or the good polymerization reactivity. Groups are preferred.

  Specific examples of the polymerizable monomer (G) include monomers represented by the following general formulas (G1) to (G8). Moreover, these polymerizable monomers (G) can be used alone or in combination of two or more.

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and R ^{9 to} R ¹² , R ^{16 to} R ²⁰ , R ^{22 to} R ^23, and R ²⁵ are each independently an alkyl group having 1 to 18 carbon atoms or phenyl. R ⁸ , R ^{13 to} R ¹⁵ and R ²¹ , R ²⁴ and R ²⁶ each independently represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and m and l are each independently 1 And n represents an integer of 0 to 250, and r, s, t, v, w, x, y, and z each independently represents an integer of 1 to 250.)

  The fluorine-containing curable resin (I) of the present invention may contain the adamantyl group in addition to the silicone chain. The fluorine-containing polymerizable resin having a silicone chain and an adamantyl group can be expected to provide a cured coating film that is more excellent in scratch resistance than a fluorine-containing curable resin having a silicone chain or an adamantyl group alone.

  In the present invention, in addition to the polymerizable monomers (D) to (G), other polymerizable monomers may be used in combination to obtain the fluorinated curable resin (I). Examples of other polymerizable monomers include alkyl (meth) acrylate (H). As alkyl (meth) acrylate (H), what is represented by the following general formula (H1) can be illustrated, for example.

（式中、Ｒ^３１は水素原子又はメチル基であり、Ｒ^３２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 ³¹ is a hydrogen atom or a methyl group, and R ³² is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)

Note that R ³² in the general formula (H1) is an alkyl group having a linear, branched, or cyclic structure having 1 to 18 carbon atoms. The alkyl group includes an aliphatic or aromatic carbon group. Those having a substituent such as a hydrogen group or a hydroxyl group are also included. More specific examples of the alkyl (meth) acrylate (C) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2- C1-C18 alkyl esters of (meth) acrylic acid such as ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; dicyclopentanyloxylethyl (meth) ) Acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopente Le (meth) (meth) bridging cyclic alkyl ester having 1 to 18 carbon atoms of acrylic acid such as acrylates and the like. These polymerizable monomers (H1) can be used alone or in combination of two or more.

  Moreover, as a raw material of the fluorine-containing curable resin (I) used in the present invention, aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmaleimide, ethylmaleimide, Maleimide compounds such as propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like can also be used. Further, a polymerizable monomer having a fluorinated alkyl group having 1 to 6 carbon atoms may be used.

  The number average molecular weight (Mn) and weight average molecular weight (Mw) of the fluorinated curable resin (I) used in the present invention are compatible with other compounding components when added to a resin composition such as a coating composition. The number average molecular weight (Mn) is preferably in the range of 500 to 20,000, more preferably in the range of 1,500 to 10,000, since it is good and can achieve high leveling properties. The weight average molecular weight (Mw) is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 50,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + “TSK− manufactured by Tosoh Corporation” GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by 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 fluorine-containing curable resin (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. In addition, the fluorine content rate in fluorine-containing curable resin (I) used by this invention is computed from the mass ratio of the fluorine atom with respect to the total amount of the used raw material.

  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 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.

  Here, when the compound (a1) used in the present invention is a mixture of compounds having various numbers of (meth) acryloyl groups, the number of (meth) acryloyl groups that the compound (a1) has is the average of the compounds. The number of (meth) acryloyl groups.

  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. 2-20 are more preferable, 3-20 are still more preferable, and 4-20 are especially 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 is obtained by using a Michael addition reaction of an active hydrogen-containing group to a (meth) acryloyl group. Specifically, k compounds (here, k Is a compound having a fluorinated alkyl group having 1 to 6 carbon atoms in which a fluorine atom is directly bonded to 1 mol of the compound (a1) having a (meth) acryloyl group and an active hydrogen ( a2) It is obtained by adding 2 to kmol using the 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 DIC Corporation), neopentyl glycol-modified trimethylolpropane di (meth) acrylate (for example, Kayarad R-604 manufactured by Nippon Kayaku Co., Ltd.), triglycerol di ( And (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 DIC Corporation, Daiichi Kogyo Seiyaku) New Frontier TMP-3P manufactured by Co., Ltd.), alkyl-modified dipentaerythritol triacrylate (for example, Kayrad D-330 manufactured by Nippon Kayaku Co., Ltd.), tris (acryloxyethyl) isocyanurate (for example, manufactured by Hitachi Chemical Co., Ltd.) Funkrill FA-731A etc.).

  Examples of the tetrafunctional (meth) acrylate include ditrimethylolpropane tetraacrylate (DTMPTA) (for example, LUMICURE DTA-400 manufactured by DIC Corporation), pentaerythritol ethoxytetraacrylate (for example, Diabeam manufactured by Mitsubishi Rayon Co., Ltd.). UK-4154), 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 DIC Corporation), dipentaerythritol penta and hexaacrylate base / polyfunctional monomer mixture (for example, LUMICURE DPA-620 manufactured by DIC Corporation) Etc.).

  Furthermore, (meth) acrylates exceeding 6 functionalities, for example, Unidic V-4000BA (an acrylate compound having an average functional group number of 9 manufactured by DIC Corporation), NK Oligo UA-53H (average functionality manufactured by Shin-Nakamura Chemical Co., Ltd.) An acrylate compound having a group number of 15), NK Oligo U-15HA (an acrylate compound having an average functional group number of 15 manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can also be used as the compound (a1).

  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.

  Examples of the cyanurate ring-containing (meth) acrylate (a1-4) include those having 3 to 40 (meth) acryloyl groups. Moreover, what has 3-12 phosphoric acid tri (meth) acrylate (a1-5), for example, (meth) acryloyl group, etc. are mentioned.

  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 from 1 to 6.), Z is a nitrogen atom having an alkyl group of 1 to 24 carbon atoms , 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のアルキル基または炭素原子数１〜４のアルキル基である〕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). And L and L ¹ are each a carbonyl group, an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a carbonyl group].

Among the general formula (1), Z is a nitrogen atom, a sulfur atom, or —NR—SO ₂ — (R is an alkyl group having 1 to 6 carbon atoms) having an alkyl group having 1 to 6 carbon atoms. A certain compound 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 resist composition varies depending on the type of the resist composition, the coating method, the target film thickness, etc., but is 0.0001 based on 100 parts by mass of the solid content in 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)]
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 20 g of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a1-1), 20 g of diisopropyl ether as a solvent, polymerization prohibited 0.02 g of p-methoxyphenol as an agent and 3.1 g of triethylamine as a neutralizer were added, stirring was started under an air stream, and 2.7 g of acrylic acid chloride was added over 1 hour while maintaining the inside of the flask at 10 ° C. It was dripped. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 g of diisopropyl ether as a solvent, 80 g of ion-exchanged water was mixed and stirred, and then allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Next, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off.

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣによる数平均分子量は１，５００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC is 1,500.)

  Subsequently, the solvent was distilled off under reduced pressure to obtain 21.5 g of a polymerizable monomer having a poly (perfluoroalkylene ether) chain represented by the following formula (A1) and an acryloyl group at both ends thereof. .

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

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

  In another glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 63 g of methyl isobutyl ketone as a solvent was charged and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 g of monomer (A1), 41.3 g of 2-hydroxyethyl methacrylate, 9.4 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, and 126 g of methyl isobutyl ketone as a solvent were mixed. Three types of dropping solutions of 135.4 g of the initiator solution were set in separate dropping devices, respectively, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain 67.5 g of a polymer (P1).

  Next, 74.7 g of methyl ethyl ketone as a solvent, 0.1 g of p-methoxyphenol as a polymerization inhibitor, and 0.06 g of dibutyltin dilaurate as a urethanization catalyst were charged, stirring was started in an air stream, 44.8 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement. Thereafter, 37.4 g of methyl ethyl ketone was added as a solvent, and 224.6 parts by mass of a methyl ethyl ketone solution containing 50% of the fluorinated curable resin (I-1) was added. Obtained. As a result of measuring the molecular weight of fluorine-containing curable resin (I-1) by GPC (polystyrene conversion molecular weight), it was number average molecular weight 2,400, weight average molecular weight 7,100, and maximum molecular weight 200,000.

Synthesis example 2 (same as above)
91.1 g of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 20 g of monomer (A1), 211.3 g of a monomer solution obtained by dissolving 19.2 g of 2-hydroxyethyl methacrylate and 40 g of N-acryloyloxyethyl tetrahydrophthalimide in 152.1 g of methyl isobutyl ketone, and a radical polymerization initiator Three types of dropping solutions with 42 g of radical polymerization initiator solution in which 11.9 parts by mass of t-butylperoxy-2-ethylhexanoate were dissolved in 30.1 g of methyl isobutyl ketone were set in separate dropping devices, respectively. While keeping the inside at 105 ° C., it was added dropwise over 2 hours at the same time. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P2).

  Next, 101.2 g of methyl ethyl ketone as a solvent, 0.1 g of p-methoxyphenol as a polymerization inhibitor, and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P2), and stirring was started under an air stream. While maintaining 60 ° C., 20.8 g of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 4 hours to be reacted. The disappearance of the isocyanate group by this reaction was confirmed by IR spectrum measurement, and then methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (I-2). As a result of measuring the molecular weight of the fluorine-containing curable resin (I-2) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000 and the weight average molecular weight was 13,600. The fluorine content was 11% by mass.

Synthesis example 3 (same as above)
Methyl isobutyl ketone 78.4 was charged as a solvent in another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, 20 g of monomer (A1), polypropylene glycol monomethacrylate (“Blenmer PP-1000” manufactured by NOF Corporation, number of repeating oxypropylene units: average 6) 58.4 g, t-butylperoxy as a radical polymerization initiator Three types of dripping liquids of 38.3 g of initiator solution mixed with 11.3 g of 2-ethylhexanoate and 26.5 g of methyl isobutyl ketone as a solvent were set in separate dripping apparatuses, respectively, and the inside of the flask was heated to 105 ° C. While maintaining, it was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P3).

  Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of dibutyltin dilaurate as a urethanization catalyst were charged, stirring was started under an air stream, and 21.6 g of 2-acryloyloxyethyl isocyanate was maintained while maintaining 60 ° C. Was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement to obtain a methyl ethyl ketone solution containing 50% of the fluorinated curable resin (I-3). As a result of measuring the molecular weight of the fluorine-containing curable resin (I-3) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,500 and the weight average molecular weight was 6,100.

Synthesis example 4 (same as above)
100 g of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Then, 20 g of monomer (A1), a monomer solution obtained by dissolving 50.1 g of 3-hydroxy-1-adamantyl methacrylate in 120 g of methyl isobutyl ketone, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator Three types of dripping liquid with a radical polymerization initiator solution in which 10.5 g was dissolved in 80 g of methyl isobutyl ketone were set in separate dripping apparatuses, respectively, and dripped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P4).

  Next, 0.1 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of tin octylate as a urethanization catalyst were charged into the polymer (P4), and stirring was started under an air stream. 29.9 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement, and then methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 50% by mass of the fluorinated curable resin (I-4). As a result of measuring the molecular weight of the fluorine-containing curable resin (I-4) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 1,500 and the weight average molecular weight was 3,900. The fluorine content was 11% by mass.

Synthesis example 5 (same as above)
96.7 g of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 74 g of monomer (A1), 37 g of polymerizable unsaturated monomer having a silicone chain represented by the following formula (G4-1) and 45.4 g of 2-hydroxyethyl methacrylate are dissolved in 126 g of methyl isobutyl ketone. Three types of dropping solutions of the monomer solution and a radical polymerization initiator solution obtained by dissolving 23.5 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator in 67.8 g of methyl isobutyl ketone were separately used. It set to the dripping apparatus and it dripped over 2 hours simultaneously, keeping the inside of a flask at 105 degreeC. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P5).

（式中、ｖは平均６５である。）

(Wherein v is an average of 65)

  Next, 0.2 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of tin octylate as a urethanization catalyst were charged into the polymer (P5), and stirring was started under an air stream. 49.1 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement, and then methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 40% by mass of the fluorine-containing curable resin (I-5). The molecular weight of the fluorine-containing curable resin (I-5) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,700 and the weight average molecular weight was 8,000.

Synthesis example 6 (same as above)
69.3 g of methyl isobutyl ketone was added as a solvent to a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Next, 74 g of monomer (A1), 59.2 g of 3-hydroxy-1-adamantyl methacrylate and 37 g of polymerizable unsaturated monomer having a silicone chain represented by the above formula (G4-1) were converted into methyl isobutyl ketone. Three dripping liquids, a monomer solution dissolved in 100 g, and a radical polymerization initiator solution in which 25.5 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator were dissolved in 38.7 g of methyl isobutyl ketone were used. Each was set in a separate dropping device and dropped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain a polymer (P6).

  Next, 0.2 g of p-methoxyphenol as a polymerization inhibitor and 0.06 g of tin octylate as a urethanization catalyst were charged into the polymer (P6), and stirring was started under an air stream. 35.4 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement, and then methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 40% by mass of the fluorinated curable resin (I-6). The molecular weight of the fluorine-containing curable resin (I-6) was measured by GPC (polystyrene equivalent molecular weight). As a result, the number average molecular weight was 2,900 and the weight average molecular weight was 14,000.

Synthesis example 7 (same as above)
In a glass flask equipped with a stirrer, thermometer, condenser, and dropping device, 20 g of a compound having hydroxyl groups at both ends represented by the following formula (a1-2), 10 g of metaxylene hexafluoride as a solvent, a polymerization inhibitor P-methoxyphenol 0.02 g and triethylamine 1.5 g as a neutralizing agent were added, stirring was started in an air stream, and 1.3 g of methacrylic acid chloride was added dropwise over 1 hour while maintaining the inside of the flask at 10 ° C. did. After completion of dropping, the mixture was stirred at 10 ° C. for 1 hour, heated, stirred at 30 ° C. for 1 hour, further heated to 50 ° C. and stirred for 10 hours, and then disappearance of methacrylic acid chloride by gas chromatography measurement. The reaction was terminated. Next, after adding 70 g of metaxylene hexafluoride as a solvent, 80 g of ion-exchanged water was mixed and stirred and then allowed to stand, and washing by a method of separating and removing the aqueous layer was repeated three times. Next, 0.02 g of p-methoxyphenol was added as a polymerization inhibitor, 8 g of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off.

〔式中、ｐは平均１７、ｑは平均１９であり、ポリ（パーフルオロアルキレンエーテル）鎖部分の平均分子量は３，４４２である。なお、オキシパーフルオロメチレン単位とオキシパーフルオロエチレン単位との結合はランダムである。以下同じ。〕

[Wherein, p is an average of 17, q is an average of 19, and the average molecular weight of the poly (perfluoroalkylene ether) chain portion is 3,442. The bond between the oxyperfluoromethylene unit and the oxyperfluoroethylene unit is random. same as below. ]

  Subsequently, the solvent was distilled off under reduced pressure to obtain a polymerizable monomer having a poly (perfluoroalkylene ether) chain represented by the following formula (A2) and a matacryloyl group at both ends thereof.

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 146.1 g of metaxylene hexafluoride as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 g of the monomer (A2), 160 g of 2-hydroxyethyl methacrylate, 9.4 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, and 306.2 g of metaxylene hexafluoride as a solvent. The three types of dripping liquids mixed with the polymerization initiator solution were set in separate dripping apparatuses, and dripped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 5 hours to obtain a polymer (P7).

  Next, 0.17 g of p-methoxyphenol as a polymerization inhibitor and 0.13 g of tin octylate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate 169. 9 g was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, further heated to 80 ° C. and stirred for 4 hours to be reacted. The disappearance of the isocyanate group due to this reaction was confirmed by IR spectrum measurement, and then metaxylene hexafluoride was added as a solution to add metaxylene hexafluoride containing 50% by mass of the fluorine-containing polymerizable resin (I-7). Obtained. As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (I-7) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,200 and a weight average molecular weight 6,300. The fluorine content was 12% by mass.

Synthesis example 8 (same as above)
In another glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 48 g of methyl isobutyl ketone was charged as a solvent, and the temperature was raised to 105 ° C. while stirring in a nitrogen stream. Next, an initiator solution 135.4 g in which 20 g of monomer (A1), 35 g of 2-hydroxyethyl methacrylate, 8 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and 117 g of methyl isobutyl ketone as a solvent are mixed. These three types of dripping liquids were set in separate dripping apparatuses, respectively, and were dripped simultaneously over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain 53.5 g of a polymer (P8).

  Next, 74.7 g of methyl ethyl ketone as a solvent, 0.1 g of p-methoxyphenol as a polymerization inhibitor, and 0.06 g of dibutyltin dilaurate as a urethanization catalyst were charged, stirring was started in an air stream, 15 g of 1- (bisacryloyloxymethyl) ethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to be reacted. The disappearance of the isocyanate group by this reaction was confirmed by IR spectrum measurement, and then 123 g of methyl ethyl ketone was added as a solvent to obtain a methyl ethyl ketone solution containing 20% of the fluorinated curable resin (I-8). As a result of measuring the molecular weight of fluorine-containing curable resin (I-8) by GPC (polystyrene conversion molecular weight), it was a number average molecular weight 2400 and a weight average molecular weight 4500.

Synthesis example 9 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 g of a compound having a hydroxyl group at both ends represented by the following formula (a1-3), 10 g of diisopropyl ether as a solvent, p- as a polymerization inhibitor 0.006 g of methoxyphenol and 3.3 g of triethylamine as a neutralizing agent were added, stirring was started under an air stream, and 3.1 g of methacrylic acid chloride was added dropwise over 2 hours while maintaining the inside of the flask at 10 ° C. After completion of dropping, the mixture was stirred at 10 ° C. for 1 hour, heated, stirred at 30 ° C. for 1 hour, further heated to 50 ° C. and stirred for 10 hours, and then disappearance of methacrylic acid chloride by gas chromatography measurement. The reaction was terminated.

〔式中、ａは平均５、ｂは平均８であり、フッ素原子の数が４６である。以下同じ。〕

[Wherein, a is 5 on average, b is 8 on average, and the number of fluorine atoms is 46. same as below. ]

  Next, 72 g of diisopropyl ether was added as a solvent, and then 72 g of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer three times. Next, 8 g of magnesium sulfate was added as a dehydrating agent and left to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. Thereafter, the solvent was distilled off under reduced pressure to obtain a polymerizable monomer having a poly (perfluoroalkylene ether) chain represented by the following formula (A3) and methacryloyl groups at both ends thereof.

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 57.3 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 19.6 g of the monomer (A3), 37.7 g of 2-hydroxyethyl methacrylate, 8.6 g of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and 115 g of methyl isobutyl ketone as a solvent are mixed. Three kinds of dropping solutions with the polymerization initiator solution thus prepared were set in separate dropping devices, respectively, and dropped simultaneously over 2 hours while maintaining the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer (P9).

  Next, 97.3 g of methyl ethyl ketone as a solvent, 0.05 g of p-methoxyphenol as a polymerization inhibitor, and 0.04 g of tin octylate as a urethanization catalyst were charged, and stirring was started in an air stream. -39.7 g of acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour, further heated to 80 ° C. and stirred for 5 hours to be reacted. The disappearance of the isocyanate group by this reaction was confirmed by IR spectrum measurement, and then methyl ethyl ketone was added as a solution to obtain a methyl ethyl ketone solution containing 50% by mass of the fluorine-containing polymerizable resin (I-9). As a result of measuring the molecular weight of the obtained fluorine-containing polymerizable resin (I-9) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,200 and a weight average molecular weight 6,200. The fluorine content was 11% by mass.

Synthesis example 10 (same as above)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 200 g of a perfluoropolyether compound having hydroxyl groups at both ends represented by the above formula (a1-1), and 123.4 g of p-chloromethylstyrene. , 0.06 g of p-methoxyphenol, 32.3 g of 50% by weight aqueous solution of benzyltriethylammonium chloride and 1.35 g of potassium iodide were charged. Next, stirring was started under an air stream, the temperature in the flask was raised to 45 ° C., and 9.2 parts by mass of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 2 hours. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 1 hour. Thereafter, 37.1 g of a 49% by mass aqueous solution of sodium hydroxide was added dropwise over 4 hours, and the reaction was further continued for 15 hours.

  After completion of the reaction, the produced salt was filtered off, the filtrate was allowed to stand, and the supernatant was removed. Further, 500 mL of water was added and washed with water three times. After washing with water, it was further washed 3 times with 500 mL of methanol. Thereafter, 0.06 g of p-methoxyphenol and 0.2 g of 3,5-t-dibutyl-4-hydroxytoluene were added to the liquid as a polymerization inhibitor, and then a water bath and a rotary evaporator set at 45 ° C. were used. By distilling off methanol while concentrating, a poly (perfluoroalkylene ether) chain represented by the following formula (A4) and a polymerizable monomer having styryl groups at both ends were obtained.

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個である。）

(In the formula, X represents a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups per molecule.)

  A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 80 g of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, a monomer solution in which 20 g of monomer (A4) is dissolved in 20 g of methyl isobutyl ketone, a monomer solution in which 38.4 g of 2-hydroxyethyl methacrylate is dissolved in 38 g of methyl isobutyl ketone, and t-butylperoxy as a radical polymerization initiator. Two kinds of dropping solutions of a polymerization initiator solution in which 8.8 g of 2-ethylhexanoate was dissolved in 26 g of methyl isobutyl ketone were set in separate dropping apparatuses, and simultaneously kept for 2 hours while keeping the inside of the flask at 105 ° C. It was dripped over. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then a part of the solvent was distilled off under reduced pressure to obtain a polymer (P10).

Next, 0.3 g of p-methoxyphenol as a polymerization inhibitor and 0.03 g of dibutyltin dilaurate as a urethanization catalyst were charged, stirring was started under an air stream, and 2-acryloyloxyethyl isocyanate 41. 6 g was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to confirm the disappearance of the absorption peak near 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement. A methyl isobutyl ketone solution containing 50% by mass of the fluorine curable resin (I-10) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (I-10) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 2,200 and the weight average molecular weight was 7,000.

Synthesis Example 11 [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. Here, 10 g of dipentaerythritol hexaacrylate was dropped 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.

  According to the analysis by NMR, the compound (II-1) was obtained by adding 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca to 1 mol of dipentaerythritol hexaacrylate. It was a compound with an average addition of 5.7 moles of fluorooctanethiol.

The analysis by ¹³ C-NMR was performed under the following conditions.
[ ^13C -NMR measurement conditions]
Apparatus: AL-400 manufactured by JEOL Ltd.
Solvent: chloroform-d1

Synthesis example 12 (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. Here, 10 g of dipentaerythritol pentaacrylate monopropionate was dropped 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 1,055 and a weight average molecular weight of 1,830. The fluorine content was 51.5% by mass.

According to the analysis by ¹³ C-NMR, the compound (II-2) was obtained by adding 3,3,4,4,5,5,6,6,7,7,8 to 1 mol of dipentaerythritol pentaacrylate monopropionate. , 8,8-tridecafluorooctanethiol was added in an average of 4.8 mol.

Synthesis example 14 (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. Here, 15 g of urethane acrylate (Unidic V-4000BA manufactured by DIC Corporation) having an average of 9 acrylate groups per molecule and a number average molecular weight of 877 was dropped 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%. Compound (II-3) had a number average molecular weight of 2,318 and a weight average molecular weight of 7,068. The fluorine content was 46.0% by mass.

According to the analysis by ¹³ C-NMR, the compound (II-3) was found to be 3,3,4,4,5,5,6,6,7,7,8 per 1 mol of Unidic V-4000BA (urethane acrylate). , 8,8-tridecafluorooctanethiol was added in an average of 8.2 mol.

Synthesis example 15 (same as above)
In a glass flask equipped with a stirrer, condenser and thermometer, 30 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. 20 g of polyoxyethylene diacrylate having 7 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-4) having a solid content of 100%. Compound (II-4) had a number average molecular weight of 1,157 and a weight average molecular weight of 1,165. The fluorine content was 46.2% by mass.

According to the analysis by ¹³ C-NMR, compound (II-4) was found to be 3,3,4,4,5,5,6,6,7,7,8,8,8 per mole of polyoxyethylene diacrylate. -It was a compound to which 2.0 mol of tridecafluorooctanethiol was added on average.

Synthesis example 16 (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-5) having a solid content of 100%. The number average molecular weight of the compound (II-5) was 1,551 and the weight average molecular weight was 2,123. The fluorine content was 43.5% by mass.

According to the analysis by ¹³ C-NMR, the compound (II-5) was found to be 3,3,4,4,5,5,6,6,7,7,8,8,8 in 1 mol of dipentaerythritol hexaacrylate. -It was a compound with an average of 4.3 mol of tridecafluorooctanethiol added.

Examples 1-14 (Preparation of surfactant composition)
The surfactants (1) to (14) of the present invention were obtained by mixing the fluorosurfactant and the compound in the formulations shown in Tables 1 and 2. The obtained surfactant composition was used to evaluate defoaming properties and applicability. The evaluation method is shown below. The evaluation results are shown in Tables 1 and 2.

[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 1-10
Comparative comparative fluorosurfactants (1 ′) to (10 ′) 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 (19)

A polymerizable monomer (A) having a poly (perfluoroalkylene ether) chain and a polymerizable unsaturated group at both ends thereof, a monomer having a reactive functional group (b) and a polymerizable unsaturated group (B And a compound (C) having a functional group (c) reactive with the functional group (b) and a polymerizable unsaturated group (C). A fluorine-containing curable resin (I),
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 of 2 to k mol 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 1 to 24 carbon atoms , 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). And L and L ¹ are each a carbonyl group, a C1-C4 alkyl group having a carbonyl group, or a C1-C4 alkyl group]. Surfactant composition. Z in the general formula (1) is a nitrogen atom, sulfur atom, or —SO ₂ —NR— (R is an alkyl group having 1 to 6 carbon atoms) having an alkyl group having 1 to 6 carbon atoms. 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 reactive functional group (b) contained in the polymerizable unsaturated monomer (B) is selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide group, and a carboxylic anhydride group. One or more types of functional groups, the reactive functional group (c) contained in the compound (C) is reactive with the reactive functional group (b), and is a hydroxyl group, isocyanate group, epoxy The surfactant composition according to claim 1, wherein the surfactant composition is at least one functional group selected from the group consisting of a group, a carboxyl group, a carboxylic acid halide group, and a carboxylic acid anhydride group.   The surfactant composition according to claim 1, wherein the fluorine-containing curable resin (I) further has a maleimide group.   The surfactant composition according to claim 1, wherein the fluorine-containing curable resin (I) further has a polyalkylene ether chain.   The surfactant composition according to claim 1, wherein the fluorine-containing curable resin (I) further has an adamantyl group.   The surfactant composition according to claim 1, wherein the fluorine-containing curable resin (I) further has a silicone chain.   The surfactant composition according to claim 1, wherein the fluorine-containing curable resin (I) further has an adamantyl group and a silicone chain.   The surfactant composition according to any one of claims 1 to 12, wherein an average molecular weight of the poly (perfluoroalkylene ether) chain in the fluorine-containing curable resin (I) is 400 to 10,000.   The surfactant composition according to any one of claims 1 to 13, wherein the compound (C) is a compound having two or more polymerizable unsaturated groups per molecule.   The surfactant composition according to claim 1, wherein the polymerizable unsaturated group of the polymerizable monomer (A) is a methacryloyloxy group.   The surfactant composition according to any one of claims 1 to 13, wherein the polymerizable unsaturated group of the polymerizable monomer (A) is a styryl group.   The surfactant composition according to any one of claims 1 to 16, 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.