JP2021055004A - Curable composition, paint, cured matter, and coated matter - Google Patents

Abstract

To provide a curable composition, a paint, a cured matter, and a coated matter that may be a cured material excellent in water and oil repellency and persistence of the water and oil repellency.SOLUTION: A curable composition comprises: a fluorine-containing surface modifier (X) having a reactive group G1, a curable compound (Y1), or a curable compound (Y2) and a curable compound (Y3), and the fluorine-containing surface modifier (X) is a polymer containing a structural unit (A) derived from the fluorine-containing polymerizable compound represented by the following formula (a), and a structural unit (B) having the reactive group G1, the curable compound (Y1) has a reactive group G2 that reacts with the reactive group G1, the curable compound (Y2) has a reactive group G3 that reacts with the reactive group G1, and a reactive group G4, the curable compound (Y3) has a reactive group G5 that reacts with the reactive group G4, and the reactive group G3 may be the same as or different from the reactive group G4, and the reactive group G5 may be the same as or different from the reactive group G1. CH2=CR1-CONR4-CR2R3-(CH2)n-COO-Q1-Rf1 (a).SELECTED DRAWING: None

Description

The present invention relates to curable compositions, paints, cured products, and coated products.

Conventionally, compounds having a fluorine-containing alkyl group have been used as, for example, coating agents (paints) and surfactants.
When a compound having a fluorine-containing alkyl group is used as a coating agent, water and oil repellency can be imparted to the surface of the article by applying the coating agent to the article, and the compound is used in various fields.
In addition, a fluorine-containing compound having a fluorine-containing alkyl group as a hydrophobic group is used as a surfactant because it has a high ability to reduce surface tension, and exhibits excellent effects such as permeability, wettability, and leveling property. To do. Furthermore, since the fluorine-containing surfactant has surface transferability, by adding a small amount as a surface modifier to a paint or resin composition, it repels the surface without changing the characteristics of the coating film or resin molded product. It is known that water-based properties, oil repellency, mold releasability, antifouling properties, etc. can be imparted (for example, Patent Document 1).

On the other hand, the present inventor has a surface modifier composed of a polymerizable compound having two chains in one molecule such as a perfluoroalkyl group, which is superior in surface transferability even if the fluorine content is smaller than that consisting of one chain. It has been found that oil repellency and the like can be imparted to the surface of the film (Patent Document 2).

Japanese Unexamined Patent Publication No. 6-240201 Japanese Patent No. 5931758

On the other hand, the present inventor prepared and evaluated a composition containing a surface modifier formed from a polymerizable compound having two chains of a perfluoroalkyl group in one molecule with reference to Patent Document 2. However, it is clear that the cured product (including, for example, a film, a molded product, etc., the same applies hereinafter) obtained from such a composition may have poor water and oil repellency and sustainability of water and oil repellency. It became.

Therefore, an object of the present invention is to provide a curable composition which can be a cured product having excellent durability of water and oil repellency and water and oil repellency.
It is also an object of the present invention to provide paints, cured products and coated products.

As a result of diligent research to solve the above problems, the present inventor has found that a desired effect can be obtained by reacting a fluorine-containing surface modifier with a reactive compound, and has reached the present invention.
The present invention is based on the above findings and the like, and specifically solves the above problems by the following configurations.

[1]
A fluorine-containing surface modifier (X) having a reactive group G1 and
It contains a curable compound (Y1), or a curable compound (Y2) and a curable compound (Y3).
The fluorine-containing surface modifier (X) has a structural unit (A) derived from a fluorine-containing polymerizable compound represented by the following formula (a) and a structural unit (B) having the reactive group G1. It is a polymer contained and
The curable compound (Y1) has a reactive group G2 that reacts with the reactive group G1.
The curable compound (Y2) has a reactive group G3 and a reactive group G4 that react with the reactive group G1.
The curable compound (Y3) has a reactive group G5 that reacts with the reactive group G4.
The curable composition, wherein the reactive group G3 may be the same as or different from the reactive group G4, and the reactive group G5 may be the same as or different from the reactive group G1. However, the curable compound (Y3) does not contain the fluorine-containing surface modifier (X).
CH ₂ = CR ^1- CONR ^{4 -CR 2} R ^3- (CH ₂ ) _n- COO-Q ^1- Rf ¹ (a)
The symbols in the formula have the following meanings.
R ¹ : Hydrogen atom or methyl group,
R ² , R ³ , R ⁴ : Independent of each other, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r) (however, of R ² , R ³ , and R ⁴ ). At least one is a group represented by the formula (r).),
-(CH ₂ ) _m- COO-Q ^2- Rf ² (r)
n and m: Independent of each other, integers 0-4,
Q ¹ and Q ² : Independent of each other, a single bond or a divalent linking group,
Rf ¹ and Rf ² : Independently, a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms.
[2]
The ^{curable composition according to [1], wherein Rf 1} and Rf ² are linear perfluoroalkyl groups having 1 to 6 carbon atoms.
[3]
The curable composition according to [1] or [2], wherein ^{Q 1} and Q ^{2 are linear alkylene groups.}
[4]
The reactive group G1 is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, a vinyl group, an allyl group, a (meth) acryloyl group, an isocyanate group, and a ketone group. 1] The curable composition according to any one of [3].
[5]
The curable composition according to any one of [1] to [4], wherein the content of the structural unit (A) is 5 to 60% by mass with respect to the total amount of the fluorine-containing surface modifier (X). Stuff.
[6]
The curable composition according to any one of [1] to [5], wherein the content of the structural unit (B) is 1 to 90% by mass with respect to the total amount of the fluorine-containing surface modifier (X). Stuff.
[7]
The fluorine-containing surface modifier (X) further contains a structural unit (C) other than the structural unit (A) and the structural unit (B).
The curable composition according to any one of [1] to [6], wherein the content of the structural unit (C) is 80% by mass or less with respect to the total amount of the fluorine-containing surface modifier (X). ..
[8]
The curable composition according to [7], wherein the polymerizable compound (c) constituting the structural unit (C) is a polymerizable compound (c1) having a polysiloxane chain.
[9]
Contains the curable compound (Y1)
The reactive group G1 is at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and the reactive group G2 is an ethylenically unsaturated group. The curable composition according to any one of [1] to [8].
[10]
Contains the curable compound (Y1)
The curable composition according to any one of [1] to [9], wherein the reactive groups G1 to G2 are independent of each other and are (meth) acryloyl groups.
[11]
The content of the fluorine-containing surface modifier (X) is 0.1 to 10% by mass with respect to the content of the curable compound (Y1), according to any one of [1] to [10]. The curable composition according to description.
[12]
Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G1 is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group, and the reactive groups G3 to G4 are independent of each other. It is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, an amino group, an imino group, a hydrazide group, an alkoxy group, and an acid anhydride group [1]. The curable composition according to any one of [8].
[13]
Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G5 is the functional group of at least one selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group, of [1] to [8], and [12]. The curable composition according to any one.
[14]
Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G1 and the reactive group G5 are hydroxy groups and are
The curable composition according to any one of [1] to [8], [12], and [13], wherein the reactive group G3 and the reactive group G4 are isocyanate groups.
[15]
[1] to [8] and [12], wherein the content of the fluorine-containing surface modifier (X) is 0.05 to 10% by mass with respect to the content of the curable compound (Y3). The curable composition according to any one of [14].
[16]
The curable composition according to any one of [1] to [15], wherein the structural unit (B) having the reactive group G1 is a structural unit derived from a polymerizable compound represented by the following formula (b1). Stuff.
CH ₂ = CR ^21- COO-R ^22- G1 (b1)
The symbols in the formula have the following meanings.
R ²¹ : Hydrogen atom or methyl group,
R ²² : Linear or branched divalent alkylene group,
G1: Reactive group G1 contained in the structural unit (B).
[17]
The curable composition according to [16], wherein the alkylene group as ^{R 22} has 2 or more carbon atoms in the above formula (b1).
[18]
The curable composition according to [16] or [17] ^{, wherein G1 is bonded to the terminal of the alkylene group as R 22} in the above formula (b1).
[19]
A paint comprising the curable composition according to any one of [1] to [18].
[20]
A cured product obtained by curing the curable composition according to any one of [1] to [18].
[21]
A coated product coated with the curable composition according to any one of [1] to [18] or the paint according to [19].

The curable composition of the present invention can be a cured product having excellent durability of water and oil repellency and water and oil repellency.
In the present invention, the paint, the cured product and the coated product are excellent in sustainability of water and oil repellency and water and oil repellency.

The present invention will be described in detail below.
In addition, in this specification, a fluorine-containing polymerizable compound represented by the formula (a) is also referred to as a compound (a). Compounds or groups represented by other formulas may be expressed in the same manner.
In addition, acrylic and methacrylic may be collectively referred to as "(meth) acrylic".
The numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, unless otherwise specified, each component contained in the curable composition of the present invention may be used alone or in combination of two or more kinds of substances corresponding to the component. When a component contains two or more substances, the content of the component means the total content of the two or more substances.
In the present specification, it is said that the effect of the present invention is more excellent when at least one of the water-repellent oil-repellent property and the durability of the water-repellent oil-repellent property is more excellent.

[Curable composition]
The curable composition of the present invention (the composition of the present invention) is
A fluorine-containing surface modifier (X) having a reactive group G1 and
It contains a curable compound (Y1), or a curable compound (Y2) and a curable compound (Y3).
The fluorine-containing surface modifier (X) is a structural unit (A) derived from a fluorine-containing polymerizable compound represented by the formula (a) described later, and a structural unit (B) having the reactive group G1. It is a polymer containing
The curable compound (Y1) has a reactive group G2 that reacts with the reactive group G1.
The curable compound (Y2) has a reactive group G3 and a reactive group G4 that react with the reactive group G1.
The curable compound (Y3) has a reactive group G5 that reacts with the reactive group G4.
The reactive group G3 may be the same as or different from the reactive group G4, and the reactive group G5 may be the same as or different from the reactive group G1.

Since the composition of the present invention has such a structure, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed to be as follows.
The structural unit (A) contained in the fluorine-containing surface modifier (X) contained in the composition of the present invention is derived from the fluorine-containing polymerizable compound represented by the formula (a), and the above formula (a). Since the compound represented by ⁽¹ ) has ^two Rf 1 and Rf 2 (polyfluoroalkyl group or polyfluoroether group having 1 to 6 carbon atoms) per molecule, the composition of the present invention has excellent water and oil repellency. Can be expressed.
Further, in the present invention, the reactive group G1 contained in the fluorine-containing surface modifier (X) can react with the reactive group G2 contained in the curable compound (Y1), or the fluorine-containing surface modifier (Fluent-containing surface modifier (X)). The reactive group G1 contained in X) can react with the reactive group G3 contained in the curable compound (Y2), and the reactive group G4 contained in the curable compound (Y2) is the curable compound (Y3). Can react with the reactive group G5 possessed by.
As described above, the fluorine-containing surface modifier (X) reacts with the curable compound (Y1) or at least the curable compound (Y2), so that the fluorine-containing surface modifier (X) is a cured product after curing. Therefore, it is considered that the cured product obtained from the composition of the present invention has excellent durability of water and oil repellency.
Further, it is considered that the curable compound (Y2) and the curable compound (Y3) are reacted and cured, so that the cured product obtained from the composition of the present invention has excellent durability of water and oil repellency. The same applies when the curable compounds (Y1) react with each other and cure.
The above mechanism is speculative, and even a mechanism other than the above is within the scope of the present invention.

Regarding Examples 4 to 7 of Patent Document 2, the present inventor used the acrylic silicone resin paints (top) in each of the polymers (1) to (4) used in the above examples. I think that it does not react with the guard (manufactured by Campe Hapio). This is because the acrylic silicone resin paint does not have a reactive group.

Hereinafter, each component contained in the composition of the present invention will be described in detail.

<Fluorine-containing surface modifier (X)>
The composition of the present invention contains a fluorine-containing surface modifier (X) having a reactive group G1. The fluorine-containing surface modifier (X) has a structural unit (A) derived from a fluorine-containing polymerizable compound represented by the following formula (a) and a structural unit (B) having the reactive group G1. It is a polymer contained. In other words, the polymer has a repeating unit derived from a fluorine-containing polymerizable compound represented by the following formula (a).
CH ₂ = CR ^1- CONR ^{4 -CR 2} R ^3- (CH ₂ ) _n- COO-Q ^1- Rf ¹ (a)

The estimated structure of the structural unit (A) derived from the fluorine-containing polymerizable compound represented by the above formula (a) is as follows.
-[CH _2- C ^* R ¹ ]-
-CONR ^4- CR ² R ^3- (CH ₂ ) _n- COO-Q ^1- Rf ¹ is bound to the above C ^*.

(Constituent unit (A))
The structural unit (A) of the fluorine-containing surface modifier (X) is derived from the fluorine-containing polymerizable compound represented by the formula (a).
When the fluorine-containing surface modifier (X) has the structural unit (A), the cured product obtained from the composition of the present invention is excellent in water repellency, oil repellency, antifouling property, and surface smoothness.

(R ¹ )
In formula (a), R ¹ is a hydrogen atom or a methyl group. R ¹ may be either a hydrogen atom or a methyl group, but when R ⁴ is not a ^{hydrogen atom, it is preferable that R 1} is a hydrogen atom from the viewpoint of polymerizable properties.

(R ² , R ³ , R ⁴ )
In the formula (a), R ² , R ³ and R ⁴ are independent of each other, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r).
-(CH ₂ ) _m- COO-Q ^2- Rf ² (r)
However, ^{at least one of R 2} , R ³ and R ⁴ is a group represented by the formula (r). In particular, it is preferable that ^{any one of R 2} and R ³ is a group represented by the formula (r), the other one is a hydrogen atom, and R ^{4 is a hydrogen atom.}

When R ¹ is a methyl group, it is preferable that ^{R 4 is a hydrogen atom from the viewpoint of polymerizability.}

(Rf ² )
Rf ² is a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms. Specifically, it includes those similar to the following Rf ^1, may be the same or different and Rf ^1.

(Q ² )
Q ² is a single bond or a divalent linking group. Specifically, it includes those similar to the following Q ^1, may be the same or different and Q ^1.

(N, m)
n and m are mutually independent integers of 0 to 4, preferably 0 to 2. When R ⁴ is a group represented by the formula (r), m is preferably 1 to 4 from the viewpoint of easy synthesis.

(Rf ¹ )
In the formula (a), Rf ¹ is a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms.
The polyfluoroalkyl group means a partially fluoro-substituted or perfluoro-substituted alkyl group in which two or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The polyfluoroalkyl group may have either a linear structure or a branched structure. In the case of a branched structure, the number of carbon atoms of the polyfluoroalkyl group is the number including the branched structure.
Examples of the linear structure include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the branched structure include an isopropyl group, an s-butyl group, a t-butyl group, a 3-methylbutyl group, an isopentyl group, a neopentyl group and an isohexyl group.
The polyfluoroether group means a group in which an ethereal oxygen atom is inserted between one or more carbon-carbon atoms in the polyfluoroalkyl group.

The number of carbon atoms of the polyfluoroalkyl group shall be determined so as to include all the carbon atoms to which the fluorine atom is bonded and to minimize the number of carbon atoms contained in the group.
For example, in the formula (a), when "-Q ^1- Rf ¹ " is a group represented by _{"-C 2} H ₄ -C ₆ F ₁₃ ^{", Q 1} is "C ₂ H ₄ " and Rf. ¹ is "C ₆ F ₁₃ ". Similarly, ^- if the "Q 1 -Rf ^1" is the group represented by _{"-CH 2 -CHF-CH 2 -CF 2} H ", a ^{Q 1} is "CH _2", Rf ¹ is "CHF- CH _2- CF ₂ H ”.

Rf ^{1 and Rf 2} in the formula (r) (hereinafter, also collectively referred to as Rf group) may have either a linear structure or a branched structure, but the Rf group is linear from the viewpoint of increasing the packing of the Rf group. The structure is preferred. For the same reason, in the case of a branched structure, it is preferable that the branched portion is present at the terminal portion of the Rf group.
Further, as the Rf group, a polyfluoroalkyl group is preferable because it has an excellent ability to reduce surface tension. Further, the Rf group is preferably a perfluoroalkyl group (RF group) substantially totally fluorine-substituted, and more preferably a linear RF group.

In the above formula (a), the above Rf ¹ and Rf ² are excellent in the effect of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), and has 1 to 6 carbon atoms. It is preferably a linear perfluoroalkyl group, more preferably -C ₆ F ₁₃ and -C ₄ F ₉ .

(Q ¹ )
In formula (a), Q ¹ is a single bond or divalent linking group. Any single bond or divalent linking group can be appropriately selected, and the present invention is not limited to the following examples.

The divalent linking group includes a linear or branched divalent alkylene group or alkenylene group, a divalent oxyalkylene group, a 6-membered ring aromatic group, and a 4- to 6-membered ring saturated or unsaturated fat. Examples thereof include a group group, a heterocyclic group having a 5- to 6-membered ring, and a divalent linking group represented by the following formula (q). These divalent linking groups may be combined and the ring groups may be condensed.
-Y-Z- (q)
The symbols in the formula have the following meanings.
Y: Linear or branched divalent alkylene group, 6-membered ring aromatic group, 4- to 6-membered saturated or unsaturated aliphatic group, 5- to 6-membered ring heterocyclic group, or any of these. Condensed ring group.
Z: -O-, -S-, -CO-, _{-COO-, -COS-, -N (R)-, -SO 2-} , -PO _2- , -N (R) -COO-, -N (R) -CO-, -N (R) -SO _2- , -N (R) -PO _2- .
R: Hydrogen atom, alkyl group having 1 to 3 carbon atoms.

The divalent linking group may have a substituent, and examples of the substituent include a halogen atom (F, Cl, Br, I), a cyano group, and an alkoxy group (methoxy group, ethoxy group, butoxy group). , Octyloxy group, methoxyethoxy group, etc.), allyloxy group (phenoxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), acyl group (acetyl group, propionyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, etc.) , Benzenesulfonyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group, etc.), sulfonyloxy group (methanesulfonyloxy group, toluenesulfonyloxy group, etc.), phosphonyl group (diethylphosphonyl group, etc.), amide group (acetylamino) Group, benzoylamino group, etc.), carbamoyl group (N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, etc.) , Aryl group (phenyl group, toluyl group, etc.), heterocyclic group (pyridyl group, imidazolyl group, furanyl group, etc.), alkenyl group (vinyl group, 1-propenyl group, etc.), alkoxyacyloxy group (acetyloxy group, etc.), Examples thereof include an alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.) and a polymerizable group (vinyl group, acryloyl group, metachloroyl group, silyl group, cinnamic acid residue, etc.).
However, when Q ¹ and Q ² are alkylene groups or oxyalkylene groups and have a structure in which a fluorine atom is substituted, the structures of Q ¹ and Q ² are also based on the definition of determining the carbon number of the polyfluoroalkyl group. It is determined.

In the above formula (a), Q ¹ and Q ² can be appropriately selected as long as they are single-bonded or divalent linking groups, but among them, single-bonded, linear or branched alkylene groups are preferable, and straight-chain. The alkylene group in the form is more preferable.

（ａ１） The compound (a) is preferably the following compound (a1) from the viewpoint of being more excellent in the effects of the present invention. P and q in the formula are integers from 0 to 6, and n, m, R ¹ , Rf ¹ and Rf ² are the same as the definitions in the formula (a).

(A1)

Specific examples of the compound (a1) include the following compounds (a2), (a3), (a4) and (a5).

Among them, the compound (a1) is preferably the compound (a3) from the viewpoint of being more excellent in the effects of the present invention.

(Method for producing compound (a))
The method for producing the compound (a) is not particularly limited. Specifically, for example, a first step of obtaining a corresponding amino acid ester by an esterification reaction of various amino acids with a fluoroalkyl group-containing alcohol, and a compound (a) by (meth) acrylamide conversion of the amino acid ester obtained in the first step. A method comprising the second step of obtaining the ester can be mentioned.

(Content of constituent unit (A))
The content of the structural unit (A) contained in the polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is excellent due to the effect of the present invention, and the obtained cured product has antifouling property and surface. From the viewpoint of excellent smoothness (leveling property), it is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total amount of the fluorine-containing surface modifier (X). It is more preferably 15 to 40% by mass. When the content of the structural unit (A) is within the above range, the fluorine-containing surface modification for the curable compound (Y1) or the curable compound (Y3), which will be described later, when the composition of the present invention is produced. This is because the compatibility of the agent (X) is improved.
In the present invention, when the content of the structural unit (A) is indicated by the mass ratio (the percentage of the mass of the structural unit (A) contained therein to the total mass of the structural unit), it is substantially the structural unit ( The content of A) is determined as the ratio of the mass of the compound (a) used for polymerization to the total mass of the polymerization raw material compound. The mass ratio of other structural units in the polymer can be obtained in the same manner. When two or more types of structural units (A) are included, the total amount is within the above range.

<Constituent unit (B) having a reactive group G1>
In the present invention, the fluorine-containing surface modifier (X) contains a structural unit (B) having a reactive group G1.

In the fluorine-containing surface modifier (X), the structural unit (B) has a reactive group G1.
The reactive G1 can react with the reactive group G2 contained in the curable compound (Y1) described later or the reactive group G3 contained in the curable compound (Y2).
When the reactive G1 reacts with the reactive group G2 or the like, the cured product obtained from the composition of the present invention is excellent in sustainability of water repellency and oil repellency.

(Reactive group G1)
The reactive group G1 is a hydroxy group, a carboxy group, an epoxy group, a vinyl group, an allyl group, a (meth) acryloyl group, or an isocyanate group from the viewpoint of excellent reactivity with the curable compound (Y1) or (Y2). , And at least one functional group selected from the group consisting of a ketone group is preferable, a hydroxy group, a (meth) acryloyl group and an isocyanate group are more preferable, and a hydroxy group and a (meth) acryloyl group are further preferable.

The method for introducing the reactive group G1 into the fluorine-containing surface treatment agent (X) is not particularly limited, and for example, the polymerizable compound (b) having the reactive group G1 is copolymerized with the compound (a) and contained. Either the method of introducing into the fluorine surface treatment agent (X) or the method of introducing the reactive group G1 into the compound after the polymerization reaction may be used.

-Polymerizable compound having a reactive group G1 (b)
The polymerizable compound (b) having the above-mentioned reactive group G1 (which is also simply referred to as “compound (b)”) has the above-mentioned reactive group G1 and further contains a compound (in addition to the above-mentioned reactive group G1). Any compound having a polymerizable group capable of polymerizing with a) may be used.
In the compound (b), examples of the polymerizable group capable of polymerizing (addition polymerization) with the compound (a) include an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include CH ₂ = CH-, CH ₂ = CR- (R represents a hydrocarbon group; the above hydrocarbon group is not particularly limited) or a group having −CH = CH−. Can be mentioned. Specific examples thereof include (meth) acryloyl group, vinyl group, allyl group, vinylene group and the like.
In the compound (b), the reactive group G1 can be bonded to the polymerizable group that can be polymerized with the compound (a) via an organic group. The organic group is not particularly limited.
The compound (b) may have one or more reactive groups G1 per molecule.

Examples of the polymerizable compound (b) having a hydroxy group as the reactive group G1 include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-. Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxyethylacrylamide, polytetramethylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate ε- Examples include caprolactone adducts.

Examples of the polymerizable compound (b) having a carboxy group as the reactive group G1 include acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl succinic acid, itaconic acid, maleic acid, fumaric acid, and maleic anhydride. Examples include acid.

Examples of the polymerizable compound (b) having an epoxy group as the reactive group G1 include glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.

Examples of the polymerizable compound (b) having a vinyl group as the reactive group G1 include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate.

Examples of the polymerizable compound (b) having an allyl group as the reactive group G1 include triallyl isocyanurate, diallylamine, diallylphthalate, diallyl ether, and triallylamine.

As the polymerizable compound (b) having a (meth) acryloyl group as the reactive group G1, for example, in the polymerizable compound represented by the formula (b1) described later, G1 of the formula (b1) is the (meth) acryloyl. Examples include the compound that is the group.

Examples of the polymerizable compound (b) having an isocyanate group as the reactive group G1 include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, and 1,1- (bisacryloyloxymethyl) ethyl isocyanate. Examples thereof include a partial reaction product of a hydroxy group-containing (meth) acrylate and a polyisocyanate. Further, as the polymerizable compound (b) having a blocked isocyanate group, for example, 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl) carbonyl Amino] ethyl methacrylate and the like can be mentioned.

Examples of the polymerizable compound (b) having a ketone group as the reactive group G1 include diacetone acrylamide and the like.

Further, the structural unit (B) having the reactive group G1 is excellent due to the effect of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property). It is preferable that the structural unit is derived from the polymerizable compound represented by.
CH ₂ = CR ^21- COO-R ^22- G1 (b1)

(R ²¹ )
In formula (b1), R ²¹ represents a hydrogen atom or a methyl group.

(R ²² )
In formula (b1), R ²² represents a linear or branched divalent alkylene group.
The hydrocarbon group is preferably a linear divalent alkylene group from the viewpoint that the effect of the present invention is excellent and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property).

In the above formula (b1), ^{the carbon number of the alkylene group as R 22} is excellent due to the effect of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property). It is preferably 6.

^{In the above formula (b1), the alkylene group as R 22} is a linear divalent from the viewpoint that the cured product obtained is excellent in antifouling property and surface smoothness (leveling property) due to the effect of the present invention. It is preferable that G1 is bonded to the terminal of the divalent alkylene group as ^{R 22.}

(G1)
In the formula (b1), G1 represents the reactive group G1 contained in the structural unit (B). G1 in the formula (b1) is the same as the reactive group G1 contained in the structural unit (B).

Specific examples of the polymerizable compound represented by the above formula (b1) include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-. Examples thereof include hydroxybutyl (meth) acrylate (4-hydroxybutyl acrylate has the following structure).

The polymerizable compound represented by the above formula (b1) is particularly excellent due to the effect of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), and is a curable compound (Y1) or. From the viewpoint of excellent reactivity with (Y2), 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable, 4-hydroxybutyl (meth) acrylate is more preferable, and 4-hydroxybutyl acrylate is more preferable. Is more preferable.

-Method of introducing the reactive group G1 after the polymerization reaction to obtain the fluorine-containing surface treatment agent (X) The method of introducing the reactive group G1 after the polymerization reaction to obtain the fluorine-containing surface treatment agent (X) is not particularly limited. For example, a polymerizable compound (b') having a reactive group G6 was polymerized with a fluorine-containing polymerizable compound (a) and a polymerizable compound (c) described later, which can be used as needed. A precursor is obtained, and then the precursor is reacted with a compound (e) having a reactive group G7 and a reactive group G1 that react with the reactive group G6 to cause a fluorine-containing surface treatment agent (). Examples thereof include a method of obtaining X).

Examples of the reactive group G6 include a hydroxy group, a carboxy group, an epoxy group, and an isocyanate group.
Further, the reactive group G6 can be the same or different functional group as the reactive group G1 of the compound (e).
Examples of the polymerizable compound (b') having the reactive group G6 include the same as the above-mentioned polymerizable compound (b). Specifically, for example, as the reactive group G1, the same as the above-mentioned polymerizable compound (b) in the case of having a hydroxy group, a carboxy group, an epoxy group or an isocyanate group can be mentioned.

As described above, compound (e) can have a reactive group G1 and a reactive group G7.
The reactive group G1 contained in the compound (e) is not particularly limited, but is selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, a vinyl group, an allyl group, a (meth) acryloyl group, an isocyanate group, and a ketone group. It is preferably at least one functional group, and more preferably at least one functional group selected from the group consisting of a vinyl group, an allyl group and a (meth) acryloyl group.

In the polymer as the fluorine-containing surface treatment agent (X) obtained by the above method, a part or all of the structural units derived from the polymerizable compound (b') having the reactive group G6 are the above compound (e). Can react with to become a structural unit (B) having a reactive group G1.
The reactive group G6 of the structural unit derived from the polymerizable compound (b') that did not react with the compound (e) is the same as or different from the reactive group G1 introduced by the compound (e). You may.
If the unreacted reactive group G6 in the structural unit derived from the polymerizable compound (b') does not react with the reactive group G2 or G3 without reacting with the compound (e), the unreacted group G2 or G3 is not reacted. Reactive group G6 does not correspond to reactive group G1.

Examples of the combination of the reactive group G6 of the polymerizable compound (b') and the reactive group G7 (reacting with the reactive group G6) of the compound (e) include a hydroxy group, an isocyanate group, and a hydroxy group. And carboxylated products, hydroxy groups and carboxylic acid anhydrides, carboxy groups and epoxy groups, epoxy groups and carboxylic acid anhydrides, epoxy groups and amino groups, and the like.

Specific examples of the polymerizable compound (b') and the compound (e) are shown below, but the present invention is not limited thereto.
When the reactive group G6 of the polymerizable compound (b') is a hydroxy group, the compound (e) is, for example, the polymerizable compound (b) having an isocyanate group (in the above-mentioned polymerizable compound having the reactive group G1). Examples of the compounds already mentioned as, acrylic acid chloride, methacrylate chloride, acrylic acid anhydride, methacrylate anhydride, succinic anhydride, polyisocyanate, (meth) acryloyloxyalkyl isocyanate such as 2-acryloyloxyethyl isocyanate, etc. Be done.
When the reactive group G6 of the polymerizable compound (b') is a carboxy group, the compound (e) is, for example, the polymerizable compound (b) having an epoxy group (in the above-mentioned polymerizable compound having the reactive group G1). Examples include the compounds already mentioned.
When the reactive group G6 of the polymerizable compound (b') is an epoxy group, the compound (e) is, for example, the polymerizable compound (b) having a carboxy group (in the above-mentioned polymerizable compound having the reactive group G1). Examples thereof include the compounds already mentioned, succinic anhydride, acrylic anhydride, carboxylic acid anhydride such as methacrylic anhydride, polyamine and the like.
When the reactive group G6 of the polymerizable compound (b') is an isocyanate group, the compound (e) is, for example, the polymerizable compound (b) having a hydroxy group (in the above-mentioned polymerizable compound having the reactive group G1). Examples thereof include the compounds already mentioned, pentaerythritol triacrylate, and the like.

(Content of constituent unit (B))
The content of the structural unit (B) contained in the polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is excellent due to the effect of the present invention, and the obtained cured product has antifouling properties and a surface surface. From the viewpoint of excellent smoothness (leveling property), the content is preferably 1 to 90% by mass, more preferably 10 to 60% by mass, based on the total amount of the fluorine-containing surface modifier (X). When the content of the structural unit (B) in the polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is within the above range, the fluorine-containing surface modifier (X) will be described later. This is because it binds firmly to the curable compound (Y1) or the curable compound (Y3), and the durability of water and oil repellency becomes better.
Even in the above-mentioned method of introducing the reactive group G1 after the polymerization reaction to obtain the fluorine-containing surface treatment agent (X), the preferable range of the content of the structural unit (B) contained in the polymer is the same as described above. is there.

The polymer as the fluorine-containing surface modifier (X) has one or more reactive groups G1 per molecule, and preferably has a plurality of reactive groups.
The polymer as the fluorine-containing surface modifier (X) can have the reactive group G1 as one type or a plurality of types.

(Constituent unit (C))
The fluorine-containing surface modifier (X) can further contain a structural unit (C) other than the structural unit (A) and the structural unit (B).
The structural unit (C) does not include the structural unit (A).
Further, the structural unit (C) basically does not have a reactive group G1 that reacts with the reactive group G2 or G3. In this respect, the structural unit (C) is different from the structural unit (B).

The purpose of introducing the structural unit (C) into the fluorine-containing surface modifier (X) is to improve compatibility with a curable compound (Y1) or a curable compound (Y2), improve slipperiness, and so on. Improvement of releasability, improvement of antifouling property, etc. can be mentioned. The structural unit (C) may be one type or two or more types.

-Polymerizable compound (c)
The polymerizable compound (c) that can constitute the structural unit (C) is a compound having copolymerizability with the compound (a) and the compound (b) (that is, copolymerizing with the compounds (a) and (b)). It has a polymerizable group). Examples of the polymerizable group that can be copolymerized with the compounds (a) and (b) include the same polymerizable groups that can be polymerized with the compound (a) in the compound (b) described above. In the polymerizable compound (c), the number of the polymerizable groups may be one per molecule.
As the polymerizable compound (c), various compounds can be appropriately selected depending on the intended purpose. The above-mentioned polymerizable compound (c) may be one kind or two or more kinds.

Examples of the polymerizable compound (c) include compounds (CC1) to (CC2), which will be described later.

.. Compound (CC1)
The polymerizable compound (c) that can constitute the structural unit (C) is, for example, other than the compound (a) and the compound (b), and the copolymerizability between the compound (a) and the compound (b) can be determined. Examples include the compound (CC1) having. The compound (CC1) basically has no reactive group G1 that reacts with the reactive group G2 or G3.

Examples of the compound (CC1) include a polymerizable compound (c1) having a polysiloxane chain in addition to the above-mentioned polymerizable group, a (meth) acrylic acid-based compound (c2), a styrene-based compound (c3), and other compounds. Polymerizable compounds (c4) can be mentioned. Specific examples of the above compound (CC1) are shown below, but the above compound (CC1) is not limited thereto.

... A polymerizable compound having a polysiloxane chain (c1)
When the polymerizable compound (c) contains the compound (CC1), the polymerizable compound (c) preferably contains a polymerizable compound (c1) having a polysiloxane chain.
The polymerizable compound (c1) having a polysiloxane chain can be a structural unit having a polysiloxane chain in the fluorine-containing surface modifier (X).
When a polymerizable compound (c1) having a polysiloxane chain is used as the polymerizable compound (c), slipperiness, releasability, and antifouling property are effectively imparted to the cured product obtained from such a curable composition. can do. Specific examples of the polymerizable compound (c1) having a polysiloxane chain include one-terminal (meth) acryloyl-modified silicone oil and both-terminal (meth) acryloyl-modified silicone oil.
The polymerizable compound (c1) having a polysiloxane chain is excellent in the effect of the present invention, has surface smoothness (leveling property), is compatible with a curable compound (Y1) or a curable compound (Y2), and is obtained to be cured. From the viewpoint of excellent antifouling property, one-terminal (meth) acryloyl-modified silicone oil is preferable.
The polymerizable compound (c1) having a polysiloxane chain does not have a reactive group that can be a reactive group G1. Examples of the polysiloxane chain, which is the main chain of the polymerizable compound (c1) having the polysiloxane chain, include polyorganosiloxane. Further, the polymerizable compound (c1) having a polysiloxane chain has a reactive group capable of becoming a reactive group G1 at a terminal different from the polymerizable group capable of copolymerizing with the compounds (a) and (b). Otherwise, the present invention is not particularly limited, and examples thereof include the case where the other terminal is sealed with a trialkylsilyl group.

Specific examples of the polymerizable compound (c1) are shown below, but the polymerizable compound (c1) is not limited thereto. Examples of the polymerizable compound (c1) include silaplane FM-0711, FM-0721, FM-0725, FM-7711, FM-7721, FM-7725, and Shin-Etsu Chemical Co., Ltd. manufactured by JNC Co., Ltd. X-22-174ASX, X-22-174BX, X-22-174DX, KF-2012, X-22-2426, X-22-2404, X-22-2445 and the like.

... (Meta) acrylic acid compound (c2)
Examples of the (meth) acrylic acid-based compound (c2) include (meth) acrylate and (meth) acrylamide represented by the following formula (c-1).
CH ₂ = C (R ^c1 ) -COX ^c1- Q ^c1- R ^c2 (c-1)
In the formula, R ^c1 : is a hydrogen atom or a methyl group, X ^c1 : -O- or -NR ^c3- , Q ^c1 : is a single-bonded or divalent linking group, and R ^c2 : -H, -Si. (OAk) ₃ (Ak is a linear or branched alkyl group having 1 to 3 carbon atoms), -CH _{3 , -CH 2} CH ₂ N (CH ₃ ) ₂ , -CH ₂ CH ₂ N (C ₂ H) ₅ ) ₂ ,-(CH ₂ ) _m H (m = 2 to 24), -CH ₂ CH (CH ₃ ) ₂ , -CH _2- C (CH ₃ ) _2- OCO-Ph, -CH ₂ Ph,- CH ₂ CH ₂ OPh,-(CH ₂ CH ₂ O) _m Ph (m = 2-45),-(CH ₂ CH ₂ O) _m Ph-C _n H _{2n + 1} (m = 2-45) (n = 1 to 24), −CH ₂ N ⁺ (CH ₃ ) ₃ Cl ⁻ , − (CH ₂ CH ₂ O) _m CH ₃ (m = 2 to 45), −SO ₃ H
However, (meth) acrylic acid is excluded from the formula (c-1).

Examples of -R ^{c3 in -NR c3} as X ^c1 include a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Further, as the divalent linking group of ^{Q c1} , the same structure as that ^{of Q 1} and Q ^{2 of compound (a) can be mentioned.} As Q ^c1 , a single bond, linear or branched alkylene group is preferable.
Further, polyvalent (meth) acrylate compounds such as diacrylate and dimethacrylate can also be mentioned. Since almost all of the polyvalent (meth) acrylate reacts during the polymerization of the compounds (a) and (b), the polyvalent (meth) acrylate is contained in the polymer as the fluorine-containing surface modifier (X). ) It is considered that no unreacted (meth) acryloyloxy group derived from the acrylate compound remains.
Further, (meth) acrylate or (meth) acrylamide having a polyfluoroalkyl group or a polyfluoroether group can be mentioned. As described above, the fluorine-containing polymerizable compound represented by the above formula (a) is excluded from the above polymerizable compound (c).

... Styrene compound (c3)
Examples of the styrene-based compound (c3) include styrene-based compounds represented by the following formula (c-2).

（ｃ−２）

(C-2)

Wherein _{^{(c-2), R c5}} : -H, -CH 3, -CH 2 N (CH 3) 2, -CH 2 N + (CH 3) 3 Cl -, -CH 2 N + H 3 Cl - , -CH ₂ SO ₃ Na or -CH ₂ OCOCH ₃ .

... yet another polymerizable compound (c4)
Still other polymerizable compounds (c4) include vinyl compounds other than the above (meth) acrylic acid-based compound (c2) and styrene-based compound (c3), for example, vinyl chloride (CH ₂ = CHCl) and acrylonitrile (CH _2). = CHCN), a large number of polymerizable compounds such as maleic acid dialkyl ester.

The compound (CC1) can be used as the polymerizable compound (c) even in the case of the proviso described later (when the compound described as the compound (b) can be the polymerizable compound (c)). ..

However, in the present invention, the compound described as the above compound (b) may be a polymerizable compound (c).
For example, when the reactive group G1 and the reactive group G2 or G3 are ethylenically unsaturated groups and they react by addition polymerization, the structural unit (C) is a structural unit composed of the compound (CC1). In addition, a structural unit having another functional group other than the ethylenically unsaturated group that performs addition polymerization with the compounds (a) and (b) can be mentioned. Examples of the functional group other than the ethylenically unsaturated group include a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, a ketone group, a halogen, an amino group, a cyano group, a mercapto group, a phosphoric acid group and the like. Among them, from the viewpoints of being excellent in the effect of the present invention, surface smoothness (leveling property), compatibility with a curable compound (Y1) or a curable compound (Y2), and antifouling property of the obtained cured product. , Hydroxy group, carboxy group is preferable.
In the above case (when the reactive groups G1 and G2 or G3 are addition-polymerized with an ethylenically unsaturated group), the above-mentioned hydroxy group or the like as a functional group other than the ethylenically unsaturated group in the structural unit (C) is reacted. It does not correspond to the sex group G1.

・ ・ Compound (CC2)
Therefore, when the reactive group G1 and the reactive group G2 or G3 react by addition polymerization with an ethylenically unsaturated group, the polymerizable compound (c) that can form the structural unit (C) is the compound. In addition to (CC1), for example, a compound (CC2) having a polymerizable group capable of copolymerizing with the compound (a) and the compound (b) and a functional group other than the ethylenically unsaturated group can be mentioned.
In the compound (CC2), the polymerizable group capable of copolymerizing with the compounds (a) and (b) is the same as the polymerizable group capable of polymerizing with the compound (a) in the compound (b) described above. Be done. In the compound (CC2), the number of the polymerizable groups may be one per molecule.
In the compound (CC2), the polymerizable group and the functional group other than the ethylenically unsaturated group can be bonded via an organic group. The organic group is not particularly limited.
The compound (CC2) may have one or more functional groups other than the ethylenically unsaturated group per molecule.

Examples of the compound (CC2) include (meth) acrylic acid, (meth) acrylate represented by the following formula (c-3), or (meth) acrylamide CH ₂ = C (R ^c1 ) -COX ^c1- Q ^c1. -R ^c2 (c-3)
(In formula (c-3), R ^c1 : is a hydrogen atom or a methyl group, X ^c1 : -O- or -NR ^c3- , and Q ^c1 : is a single bond or a divalent linking group, R ^c2. : -OH,-(CH ₂ CH ₂ O) _m H (m = 2-45),-(CH ₂ ) ₂ -NCO, -CH ₂ CH (OH) CH ₂ Cl, -P (O) (OH) ₂ , -CH ₂ CH (CH ₂ Cl) OP (O) (OH) ₂ , or -COOH. In addition, R ^c1 , X ^c1 , and Q ^c1 in the formula (c-3) are the above formula (c-1). ),
Examples thereof include styrene compounds represented by the following formula (c-4).

（ｃ−４）

(C-4)

In formula (c-4), R ^c5 : -Cl, -CHO, -COOH, -CH ₂ Cl, -CH ₂ NH ₂ , -CH ₂ COOH, -CH ₂ N (CH ₂ COOH) ₂ , or -CH ₂ SH

When the reactive group G1 and the reactive group G2 or G3 react by addition polymerization with an ethylenically unsaturated group, the structural unit (C) is superior to the effect of the present invention and has a surface smoothness (leveling property). Other than the structural unit and / or ethylenically unsaturated group composed of the above compound (CC1) from the viewpoint of excellent compatibility with the curable compound (Y1) or the curable compound (Y2) and the antifouling property of the obtained cured product. It is preferable to include a structural unit having a functional group of
It is more preferable to include a structural unit composed of a compound represented by the above formula (c-1), a structural unit having a polysiloxane chain, and / or a structural unit having a hydroxy group or an isocyanate group.
It is more preferable to include the structural unit composed of the compound represented by the above formula (c-1), the structural unit having the polysiloxane chain, and the structural unit having a hydroxy group.
Examples of the structural unit having a hydroxy group include a compound represented by the above formula (c-3), in which R ^c2 is −OH or −CH ₂ CH (OH) CH ₂ Cl, and the structural unit is represented by the above formula. In (c-3), the constituent unit of the compound in which ^{R c1} is a hydrogen atom or a methyl group, X ^c1 is −O−, Q ^c1 is a divalent linking group, and R ^{c2 is −OH is} preferable.
The compound (CC1) does not contain the compound (CC2).

(Content of constituent unit (C))
The content of the structural unit (C) contained in the polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is excellent due to the effect of the present invention, and the obtained cured product has antifouling property and surface. From the viewpoint of excellent smoothness (leveling property), the content is preferably 0 to 80% by mass, more preferably 0 to 50% by mass, based on the total amount of the fluorine-containing surface modifier (X). When the content of the structural unit (C) in the polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is within the above range, compatibility with the curable compound (Y1) and the like, This is because the antifouling property, slipperiness, and mold releasability can be improved.
When the polymer contained as the fluorine-containing surface modifier (X) further contains the structural unit (C), the lower limit of the content of the structural unit (C) may exceed 0 parts by mass.

The polymer contained as the fluorine-containing surface modifier (X) in the composition of the present invention is not particularly limited in terms of polymerization form and the like. The polymerization form may be random, block, graft or the like.

In order to obtain the above polymer (polymer as a fluorine-containing surface modifier (X); the same applies hereinafter), various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be adopted. The polymerization initiator is not particularly limited, but ordinary initiators such as organic peroxides, azo compounds, and persulfates can be used. In the case of emulsion polymerization in an aqueous medium, it is preferable to use a water-soluble azo initiator or peroxide-based initiator.

The molecular weight of the polymer (fluorine-containing surface modifier (X)) is not particularly limited, but the weight average molecular weight (Mw) is preferably 10 to 500,000, more preferably 20 to 100,000. When the weight average molecular weight is in such a range, the compatibility with the curable compound (Y1) and the like, the solubility in various media (solvents) are good, and the surface transferability is excellent.
The method for adjusting the molecular weight of the polymer (fluorine-containing surface modifier (X)) to the above range is not particularly limited, and a mercapto group-containing compound such as 1-dodecanethiol is added during the polymerization reaction and chained. Examples thereof include a method of adjusting the molecular weight by acting as a transfer agent.
In the present invention, the weight average molecular weight (Mw) of the polymer is a value converted to polymethyl methacrylate by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.

The fluorine-containing surface modifier (X) may be composed of only one type of the polymer, or may be composed of two or more types of the polymer. Specific examples of the two or more types of polymers include polymers containing two or more types of structural unit (A), and polymers having different structural units (B) and (C).

<Curable compound (Y1)>
The composition of the present invention contains a curable compound (Y1), or a curable compound (Y2) and a curable compound (Y3). The composition of the present invention has an embodiment containing a curable compound (Y1) and an embodiment containing a curable compound (Y2) and a curable compound (Y3).
As described above, the composition of the present invention can contain a curable compound (Y1). The curable compound (Y1) has a reactive group G2 that reacts with the reactive group G1.
In the curable compound (Y1), the reactive group G2 can be bonded to an organic group. The organic group is not particularly limited.
When the composition of the present invention contains a curable compound (Y1), the reactive group G1 reacts with the reactive group G2, so that the fluorine-containing surface treatment agent (X) cures the composition. It is fixed to a cured product (for example, a product obtained by reacting a curable compound (Y1) or a curable compound (Y1) with each other), and the obtained cured product has excellent water and oil repellency.
Further, when the reactive groups G2 react with each other between different curable compounds (Y1) (that is, when the curable compounds (Y1) react with each other), the durability of the water and oil repellency of the obtained cured product Excellent.

When the composition of the present invention contains a curable compound (Y1), the reactive group G2 is preferably an ethylenically unsaturated group.
Examples of the ethylenically unsaturated group include CH ₂ = CH-, CH ₂ = CR- (R represents a hydrocarbon group; the above hydrocarbon group is not particularly limited) or a group having −CH = CH−. Can be mentioned. Specific examples thereof include (meth) acryloyl group, vinyl group, allyl group, vinylene group and the like.

The curable compound (Y1) has one or more reactive groups G2 per molecule, and preferably has a plurality of reactive groups.

Examples of the curable compound (Y1) include curable compounds having a (meth) acryloyl group, styrene compounds, unsaturated polyester resins, vinyl ester resins and the like.
Examples of the curable compound having a (meth) acryloyl group include polyfunctional (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate;
Oligomers such as urethane acrylate (compound having (meth) acryloyloxy group and urethane bond), epoxy (meth) acrylate (ester of epoxy compound and (meth) acrylic acid);
The (meth) acrylate-based compound (c2) as the polymerizable compound (c) that can further form the structural unit (C) that the above-mentioned fluorine-containing surface modifier (X) can further contain (specifically, For example, the same as (meth) acrylate or (meth) acrylamide represented by the above formula (c-1) and (meth) acrylate or (meth) acrylamide represented by the above formula (c-3) can be mentioned. Be done.

As the styrene-based compound, the styrene-based compound (c3) as the polymerizable compound (c) that can further constitute the structural unit (C) that can be further contained by the above-mentioned fluorine-containing surface modifier (X) (specifically). Examples of the styrene-based compound represented by the above formula (c-2) and the same as the styrene-based compound represented by the above formula (c-4) can be mentioned.

The unsaturated polyester resin is not particularly limited as long as it is a polyester having an unsaturated bond. One of the preferred embodiments of the unsaturated polyester resin is that the unsaturated bond is incorporated in the main chain of the polyester.
Examples of the unsaturated polyester resin include unsaturated polyesters produced by polycondensation of an acid containing an unsaturated dibasic acid and a polyol.
The unsaturated polyester resin may be a mixture of the unsaturated polyester and a reactive monomer such as styrene.

Examples of the vinyl ester resin include a mixture of a vinyl ester produced by an addition reaction of an epoxy resin and (meth) acrylic acid and a reactive monomer such as styrene.

(Combination of G1 and G2)
When the composition of the present invention contains the curable compound (Y1),
The G1 is preferably at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group.
The G1 is at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and
The G2 is more preferably an ethylenically unsaturated group from the viewpoint of excellent reactivity with the G1.

When the curable compound (Y1) is a curable compound having a (meth) acryloyl group as G2, G1 is preferably a (meth) acryloyl group.
When the curable compound (Y1) is a curable compound having an ethylenically unsaturated group other than the (meth) acryloyl group as G2, G1 is selected from the group consisting of a vinyl group, an allyl group and a (meth) acryloyl group. It is preferably at least one functional group.

The reactive groups G1 to G2 are preferably (meth) acryloyl groups independently of each other from the viewpoint of excellent reactivity.

When the G2 is an ethylenically unsaturated group (excluding the (meth) acryloyl group), the G1 is composed of a group consisting of a vinyl group, an allyl group and a (meth) acryloyl group from the viewpoint of excellent reactivity. It is preferably at least one functional group of choice.

The curable compound (Y1) may be one type or two or more types, respectively.

<Curable compound (Y2) and curable compound (Y3)>
As described above, the composition of the present invention can contain a curable compound (Y2) and a curable compound (Y3).

(Curable compound (Y2))
The curable compound (Y2) has a reactive group G3 that reacts with the reactive group G1 and a reactive group G4. The reactive group G3 may be the same as or different from the reactive group G4.
The reactive group G3 reacts with the reactive group G1.
The reactive group G4 reacts with the reactive group G5 contained in the curable compound (Y3), which will be described later.

As described above, the curable compound (Y2) can react with the fluorine-containing surface treatment agent (X) and the curable compound (Y3), and thus can function as a so-called cross-linking agent (curing agent).

When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The reactive groups G3 to G4 are excellent in terms of the effects of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property). It is preferably at least one functional group selected from the group consisting of an epoxy group, an isocyanate group, an amino group, an imino group, a hydrazide group, an alkoxy group, and an acid anhydride group.
One of the preferred embodiments is that the hydroxy group or the alkoxy group does not bond to a silicon atom. The hydroxy group or the alkoxy group can be bonded to, for example, a carbon atom.

The curable compound (Y2) has one or more reactive groups G3 and G4 per molecule.

(Combination of reactive group G1 and reactive group G3)
When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The combination of the reactive group G1 and the reactive group G3 is not particularly limited as long as it is a combination in which the reactive group G1 and the reactive group G3 react.
When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The reactive group G1 is preferably at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group.
The reactive group G1 is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group, and the reactive groups G3 to G4 are independent of each other. More preferably, it is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, an amino group, an imino group, a hydrazide group, an alkoxy group, and an acid anhydride group. ..
Examples of the combination of the reactive group G1 and the reactive group G3 include a hydroxy group and an isocyanate group, an amino group and an isocyanate group, a hydroxy group and an acid anhydride group, an epoxy group and a carboxy group, and an epoxy group and an amino group. , Epoxy group and acid anhydride group, ketone group and hydrazide group and the like.

Examples of the curable compound (Y2) include polyisocyanate compounds such as diisocyanate and triisocyanate; polyamine compounds such as diamine and triamine; hydrazine compounds such as adipic acid dihydrazide; malonic acid, succinic acid and citric acid. Examples thereof include polycarboxylic acid compounds and their acid anhydride compounds; polyhydric alcohol compounds such as diols and triols; polyepoxy compounds such as diepoxy compounds; and amino resins such as melamine resins and urea resins.
The curable compound (Y2) may be one type or two or more types, respectively.

When the reactive group G1 is a hydroxy group, it is preferable that the reactive groups G3 and G4 are isocyanate groups as one of the preferred embodiments. In this case, the curable compound (Y2) is preferably a polyisocyanate compound.
The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups per molecule.
As the polyisocyanate compound, an isocyanurate-type polyisocyanate is mentioned as one of the preferred embodiments.

(Curable compound (Y3))
The curable compound (Y3) has a reactive group G5 that reacts with the reactive group G4. The reactive group G5 may be the same as or different from the reactive group G1. However, the curable compound (Y3) does not contain the fluorine-containing surface modifier (X).

The curable compound (Y3) has one or more reactive groups G5 per molecule, and preferably has a plurality of reactive groups.

When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The reactive group G5 is excellent due to the effect of the present invention, and from the viewpoint that the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone are used. It is preferably at least one functional group selected from the group consisting of groups.

The main skeleton of the curable compound (Y3) is not particularly limited.
Examples of the main skeleton of the curable compound (Y3) include (meth) acrylic resin, acrylic urethane resin, urethane resin, epoxy resin, polyester resin, melamine resin, fluororesin, silicone resin, and phenol resin. Not limited to these.
The reactive group G5 can be attached to the main skeleton directly or via an organic group. The organic group is not particularly limited.
The curable compound (Y3) may be one type or two or more types, respectively.

When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The combination of the reactive group G4 and the reactive group G5 is not particularly limited as long as it is a combination in which the reactive group G4 and the reactive group G5 react.
Examples of the combination of the reactive group G4 and the reactive group G5 include an isocyanate group and a hydroxy group, an isocyanate group and an amino group, an acid anhydride group and a hydroxy group, a carboxy group and an epoxy group, and an amino group and an epoxy group. , Acid anhydride group and epoxy group, hydrazide group and ketone group and the like.

When the composition of the present invention contains a curable compound (Y2) and a curable compound (Y3),
The combination of the reactive groups G1 and G3 to G5 is excellent due to the effect of the present invention, and the obtained cured product is excellent in antifouling property and surface smoothness (leveling property). A combination in which the reactive group G5 is a hydroxy group and the reactive group G3 and the reactive group G4 are isocyanate groups is preferable.

(Content of fluorine-containing surface modifier (X))
When the composition of the present invention contains the curable compound (Y1) When the composition of the present invention contains the curable compound (Y1), the content of the fluorine-containing surface modifier (X) is The curable compound (Y1) is excellent in terms of the effects of the present invention, the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), and properties such as strength of the obtained cured product can be maintained. It is preferably 0.1 to 10% by mass with respect to the content of.
The composition of the present invention has excellent water and oil repellency even if the content of the fluorine-containing surface modifier (X) is small with respect to (Y1) as described above or (Y3) as described later. Can produce the effect of.
When the composition of the present invention contains the curable compound (Y1), the content of the fluorine-containing surface modifier (X) is even smaller than the above range, and the content of the curable compound (Y1). On the other hand, it may be about 0.1 to 5% by mass, and further, about 0.1 to 2.5% by mass.

When the composition of the present invention contains the curable compounds (Y2) and (Y3) When the composition of the present invention contains the curable compounds (Y2) and (Y3), the fluorine-containing surface modification The content of the agent (X) is excellent from the viewpoint of the effect of the present invention, the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), and properties such as strength of the cured product can be maintained. It is preferably 0.05 to 10% by mass with respect to the content of the curable compound (Y3).
When the composition of the present invention contains the curable compound (Y3), the content of the fluorine-containing surface modifier (X) is even smaller than the above range, and the content of the curable compound (Y3). On the other hand, it may be about 0.1 to 5% by mass, and further, about 0.1 to 2% by mass.

When the composition of the present invention contains the curable compounds (Y2) and (Y3) When the composition of the present invention contains the curable compounds (Y2) and (Y3), the curable compound (Y2) ) Is excellent due to the effect of the present invention, the obtained cured product is excellent in antifouling property and surface smoothness (leveling property), and the above-mentioned curable compound can maintain properties such as strength of the cured product. It is preferably 1 to 300% by mass, more preferably 10 to 200% by mass, based on the content of (Y3).

When the composition of the present invention contains the curable compounds (Y2) and (Y3), the amounts of the reactive groups G3 and G4 of the curable compound (Y2) are more excellent than the effects of the present invention. From the viewpoint that the obtained cured product has excellent antifouling property and surface smoothness (leveling property) and can maintain properties such as strength of the cured product, it is contained as a fluorine-containing surface modifier (X) in the composition of the present invention. The molar ratio [(G3 + G4) / (G1 + G5)] is 0.5 to 1. It is preferably 0.

The composition of the present invention may further contain additives in addition to the above essential components.
Examples of the additive include various polymerization initiators, curing agents, curing catalysts, solvents, fillers (fillers), pigments, dyes, polymerization inhibitors, and release agents that can be used to cure the curable compound (Y1) and the like. Molding agents, thickeners, thickeners, defoaming agents, foaming agents, anti-separation agents, leveling agents, plasticizers, emulsifiers, desiccants, glass fibers, reinforcing fibers such as carbon fibers, surfactants, low shrinkage agents , Colorants and the like.

The solvent is not particularly limited as long as the composition of the present invention can be dissolved and / or dispersed, and various solvents such as water, hydrocarbon solvents, and fluorine solvents can be used. It may be a single solvent or a mixed solvent.

The method for producing the composition of the present invention is not particularly limited. For example, the fluorine-containing surface modifier (X) and the curable compound (Y1), or the curable compound (Y2) and the curable compound (Y3) can be used as needed. It can be produced by mixing with an additive.

Applications of the composition of the present invention include, for example, paints, coating agents, and surface treatment agents.
The composition of the present invention can be used as it is as a paint, a coating agent, or a surface treatment agent.

The method of using the composition of the present invention is not particularly limited. For example, a method of curing the composition of the present invention to obtain a cured product can be mentioned.
Specifically, for example, a method of applying the composition of the present invention to a substrate and curing the composition of the present invention to obtain, for example, a film as a cured product, a method of molding and curing the composition of the present invention and curing the cured product. A method of obtaining (for example, a molded product) can be mentioned.

When the composition of the present invention is applied to a base material, the method of applying the composition of the present invention to the base material is not particularly limited.
Examples of the material of the base material include glass, plastic, rubber, metal, and ceramic.

When the composition of the present invention is molded and cured, the method of molding the composition of the present invention is not particularly limited.

The method for curing the composition of the present invention is not particularly limited, and examples thereof include thermosetting, active energy ray curing such as ultraviolet rays, and room temperature curing.

By curing the composition of the present invention, a cured product (for example, a film or a molded product) can be obtained (formed).

[Cured product]
The cured product of the present invention is a cured product obtained by curing the curable composition of the present invention.
Since the cured product of the present invention is a cured product of the curable composition of the present invention, it is excellent in water and oil repellency and durability of water and oil repellency. Moreover, the cured product of the present invention is excellent in antifouling property.
The curable composition used for the cured product of the present invention is not particularly limited as long as it is the curable composition of the present invention.
The method of mixing the curable composition with the other materials and the method of molding the mixture are not particularly limited. The method of curing the molded product after molding is the same as the method of curing the composition of the present invention described above.
Examples of the cured product of the present invention include molded products around water such as bathroom members, washbasin members, and kitchen members. As the cured product of the present invention, for example, the above-mentioned molded product around water, which requires antifouling property, is mentioned as a preferable embodiment.

[paint]
The paint of the present invention is a paint containing the curable composition of the present invention.
The paint of the present invention is excellent in sustainability of water-repellent oil-repellent property and water-repellent oil-repellent property of a cured product (specifically, for example, a film) obtained from the paint. Further, the coating material of the present invention is excellent in antifouling property of the cured product.
The curable composition contained in the coating material of the present invention is not particularly limited as long as it is the curable composition of the present invention.

As the paint of the present invention, the curable composition of the present invention can be used as it is as a paint.

The objects (articles) to which the paint of the present invention is applied include, for example, exterior-related buildings such as piers, roofs, and outer walls; interior-related products such as floors and inner walls; housing products such as furniture, home appliances, and water supply products; ships. , Vehicle bodies of airplanes, automobiles, etc. (including exterior materials and interior materials).

[Coated product]
The coated product of the present invention is a coated product coated with the curable composition of the present invention or the paint of the present invention.
Since the coated product of the present invention has a cured product (specifically, for example, a film) obtained by curing the curable composition or paint of the present invention, the water and oil repellency and the water and oil repellency are maintained. Excellent in sex. Further, the coated product of the present invention is excellent in antifouling property.
The curable composition or paint used in the coated product of the present invention is not particularly limited as long as it is the curable composition or paint of the present invention.

Examples of the article to which the curable composition or the coating material is applied include the same articles as those to which the coating material of the present invention is applied (article) described above.
The method of applying the curable composition or paint to an article is not particularly limited. For example, a conventionally known method can be mentioned.
The method for curing the curable composition or paint is the same as the method for curing the composition of the present invention.
In the coated product of the present invention, at least a part of the surface of the object (article) may be covered with the cured product (for example, a film).

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. In the following, unless otherwise specified, what is indicated by "parts" and "%" are "parts by mass" and "% by mass".

(Preparation of Fluorine-Containing Surface Modulator (X))
Fluorine-containing surface modifier having a hydroxy group as the reactive group G1 Each component shown in the "Polymerization composition of fluorine-containing surface modifier (X)" column of Table 1 below is at the ratio (parts by mass) shown in the same table. It was charged in a pressure-resistant airtight container, purged with nitrogen, and then reacted at 70 ° C. for 18 hours to obtain a MEK (methylethylketone) solution having a solid content concentration of about 41%.
Each of the above MEK solutions contains fluorine-containing surface modifiers (X-1) to (X-5) and (X-7) to (X-9) as solids (solutes) at the above concentrations.

The fluorine-containing surface modifiers (X-1) to (X-5) are a constituent unit (A) derived from a fluorine-containing polymerizable compound (compound (a3)) represented by the formula (a), and 4-. It is a polymer having at least a structural unit derived from hydroxybutyl acrylate (the above structural unit corresponds to the structural unit (B) because it has a hydroxy group as the reactive group G1). Therefore, the fluorine-containing surface modifiers (X-1) to (X-5) correspond to the fluorine-containing surface modifiers (X) contained in the composition of the present invention.
The fluorine-containing surface modifiers (X-7) to (X-8) have a structural unit having a hydroxy group as the reactive group G1, but do not have a structural unit derived from the compound (a3). Therefore, the fluorine-containing surface modifiers (X-7) to (X-8) do not correspond to the fluorine-containing surface modifiers (X) contained in the composition of the present invention.
The fluorine-containing surface modifier (X-9) has a structural unit derived from the compound (a3), but does not have a structural unit having a reactive group G1. Therefore, the fluorine-containing surface modifier (X-9) does not correspond to the fluorine-containing surface modifier (X) contained in the composition of the present invention.

Details of each component shown in the "Polymerization composition of fluorine-containing surface modifier (X)" column of Table 1 are as follows. The details of each component shown in the “Polymerization composition (precursor) of fluorine-containing surface modifier (X)” column in Table 2 are the same as below.

（ａ３） -Compound (a3): A compound represented by the following formula. Compound (a3) corresponds to a fluorine-containing polymerizable compound represented by the above formula (a).

(A3)

C6FMA: CH ₂ = C (CH ₃ ) -COO- (CH ₂ ) _2- C ₆ F ₁₃ . C6FMA does not correspond to the fluorine-containing polymerizable compound represented by the above formula (a).

-Methyl methacrylate: CH ₂ = C (CH ₃ ) -COO-CH ₃ . Methyl methacrylate corresponds to the (meth) acrylic acid-based compound (c2) constituting the structural unit (C).
Butyl methacrylate: CH ₂ = C (CH ₃ ) -COO-C ₄ H ₉ . Butyl methacrylate corresponds to the (meth) acrylic acid-based compound (c2) constituting the structural unit (C).

4-Hydroxybutyl acrylate: CH ₂ = CH-COO- (CH ₂ ) _4- OH. The compound becomes a structural unit (B) having a reactive group G1 (hydroxy group) contained in the fluorine-containing surface modifier (X).

-CH ₂ = CH-COO- (CH ₂ CH ₂ O) _n- CH ₃ (n ≒ 9): Product name AM-90G Manufactured by Shin Nakamura Chemical Industry Co., Ltd. The above compound does not have a reactive group that can be a reactive group G1. Further, the above compound does not have fluorine and does not correspond to the above formula (a).

Compound (c-1): One-ended methacryloyl-modified silicone oil (molecular weight 4600). Product name X-22-174DX, manufactured by Shin-Etsu Chemical Co., Ltd. Compound (c-1) corresponds to the above-mentioned polymerizable compound (c1) having a polysiloxane chain. The compound (c-1) does not have a reactive group that can be a reactive group G1. Further, the compound (c-1) does not have fluorine and does not correspond to the above formula (a).
-Compound (c-2): One-ended methacryloyl-modified silicone oil. Product name Silaplane FM-0721, manufactured by JNC Corporation. (Molecular weight 5000). Compound (c-2) corresponds to the above-mentioned polymerizable compound (c1) having a polysiloxane chain. The compound (c-2) does not have a reactive group that can be a reactive group G1. Further, the compound (c-2) does not correspond to the formula (a).

V-601: Dimethyl 2,2'-azobis (2-methylpurpionate)
・ MEK: Methyl ethyl ketone

Fluorine-containing surface modifier having an acryloyl group as the reactive group G1 The ratio of each component shown in the "Polymerization composition (precursor) of fluorine-containing surface modifier (X)" column in Table 2 below ( It was charged in a pressure-resistant airtight container (by mass), purged with nitrogen, and reacted at 70 ° C. for 18 hours to obtain a MEK (methylethylketone) solution having a solid content concentration of about 41%.
Each of the above MEK solutions contains precursors of fluorine-containing surface modifiers (X-10) to (X-11) as solids (solutes) at the above concentrations. The precursor has, as its structural unit, a structural unit having a hydroxy group (corresponding to the reactive group G6) formed of 4-hydroxybutyl acrylate and the like.
Next, to 100 parts by mass of each of the above MEK solutions, each component shown in the "Post-polymerization acryloyl introduction" column of Table 2 was added at the ratio (parts by mass) shown in the same table, and reacted at 50 ° C. to obtain a solid content concentration of about. A 41% MEK (methyl ethyl ketone) solution was obtained.
Each of the above MEK solutions contains fluorine-containing surface modifiers (X-10) to (X-11) as solids (solutes) at the above concentrations.
The fluorine-containing surface modifiers (X-10) to (X-11) have a structural unit (A) derived from the fluorine-containing polymerizable compound represented by the formula (a) and an acryloyl group as the reactive group G1. It is a polymer having at least a structural unit having a structural unit (the above structural unit corresponds to the structural unit (B)) and a structural unit having a hydroxy group. Therefore, the fluorine-containing surface modifiers (X-10) to (X-11) correspond to the fluorine-containing surface modifiers (X) contained in the composition of the present invention.
The fluorine-containing surface modifiers (X-10) to (X-11) are a curable compound (Y1-1) having an acryloyl group as the reactive group G2, and the reactive groups G1 and G2 by irradiation with ultraviolet rays. The hydroxy groups of the fluorine-containing surface modifiers (X-10) to (X-11) do not correspond to the reactive group G1 because they react with the addition polymerization of the double bond.

Details of each component shown in the "Introduction of acryloyl after polymerization" column in Table 2 are as follows. As described above, the details of each component shown in the “Polymerization composition (precursor) of fluorine-containing surface modifier (X)” column in Table 2 are the same as those shown in Table 1.
-2-Acryloyloxyethyl isocyanate: Brand name Calends AOI, manufactured by Showa Denko KK. NCO group-containing acrylate. The compound has a reactive group G7 (isocyanate group) and a reactive group G1 (acryloyl group) that react with the reactive group G6 (hydroxy group) of each of the precursors, and the compound (e) has Applicable.
-Polymerization inhibitor: p-methoxyphenol-Catalyst: 1,4-diazabicyclo [2.2.2] octane

(Manufacturing of curable composition)
A curable composition (XYY) containing a fluorine-containing surface modifier (X), a curable compound (Y2), and a curable compound (Y3).
The MEK solution containing the fluorine-containing surface modifier (X) prepared as described above shown in the "Curable composition (XYY)" column of Table 1 below, and the curable compound (Y3) (main agent). The curable compound (Y3-1), the curable compound (Y2-1) as the curable compound (Y2) (curing agent), and MEK (methyl ethyl ketone) are mixed in the composition (part by mass) shown in the table. , Each curable composition was produced at a solid content concentration of about 30% by mass.
The values in the upper row of the "MEK solution containing the fluorine-containing surface modifier (X)" column of the "curable composition (XYY)" in Table 1 indicate the amount of the MEK solution used, and the values in the lower row. Indicates the amount of the fluorine-containing surface modifier (X) as a solid content (solute) in the MEK solution.

The details of the curable compound (Y2-1) and the curable compound (Y3-1) shown in the “Curable composition (XYY)” column of Table 1 below are as follows.
-Curable compound (Y3-1): Aclinal TZ # 4599 (manufactured by Toei Kasei Co., Ltd.). Tg95 ° C., OHV81. Acrylic polyol (main chain is acrylic resin). Solid content concentration 36.9%. The curable compound (Y3-1) has a hydroxy group as the reactive group G5 and corresponds to the curable compound (Y3).
-Cursable compound (Y2-1): Duranate TPA-100 (isocyanate-based curing agent manufactured by Asahi Kasei Corporation, NCO 23.1%). The curable compound (Y2-1) has an isocyanate group as the reactive groups G3 and G4, and corresponds to the curable compound (Y2). Isocyanurate-form polyisocyanate.

A curable composition (XY) containing a fluorine-containing surface modifier (X) and a curable compound (Y1).
Polymerization of the MEK solution containing the fluorine-containing surface modifier (X) prepared as described above shown in the "Curable composition (XY)" column of Table 2 below and the curable compound (Y1-1). The initiator and MEK (methyl ethyl ketone) were mixed in the composition (part by mass) shown in the same table to prepare each curable composition.
The values in the upper row of the "MEK solution containing the fluorine-containing surface modifier (X)" column of the "curable composition (XY)" in Table 2 indicate the amount of the MEK solution used, and the values in the lower row. Indicates the amount of the fluorine-containing surface modifier (X) as a solid content (solute) in the MEK solution.

The details of the curable compound (Y1-1) and the polymerization initiator shown in the “Curable composition (XY)” column of Table 2 below are as follows.
-Curable compound (Y1-1): DPHA (dipentaerythritol hexaacrylate) curable compound (Y1-1) has an acryloyl group as the reactive group G2 and corresponds to the curable compound (Y1).
-Polymerization initiator: Irgacure 184 (1-hydroxycyclohexylphenyl ketone)

(Formation of cured product (film))
Curing Conditions for Curable Composition (XYY) in Table 1 Each curable composition (XYY) in Table 1 produced as described above was applied to a glass plate using bar coater # 48, and 1 at 120 ° C. It was heated for an hour and cured to obtain a test piece (coated product).

Curing conditions of the curable composition (XY) in Table 2 Each curable composition (XY) in Table 2 produced as described above was applied to a glass plate using a bar coater # 48, and 800 mJ / cm ² A test piece (coated product) was obtained by irradiating with ultraviolet rays and curing.

[Evaluation]
Various tests were performed on each test piece obtained as described above. The test method is shown below. The test results are shown in Tables 1 and 2.

[Leveling property]
The membrane of each test piece was visually observed and evaluated according to the following criteria.
When the film of each test piece was smooth as a whole, it was evaluated as having excellent leveling property and was marked with "○".
When streaks or unevenness were partially observed on the membrane, it was evaluated as having a slightly excellent leveling property, and this was indicated as "Δ".
When streaks or unevenness were observed on the membrane as a whole, it was evaluated as inferior in leveling property and marked with "x".

[Evaluation of water and oil repellency]
In the present invention, the water and oil repellency of the obtained cured product (film) was evaluated using the results of the initial water and oil repellency after curing.
Water (n-HD) was dropped on the membrane of each test piece at 5 points each, and the contact angle of water was measured using an automatic contact angle meter OCA-20 [manufactured by dataphysics], and the average value of the 5 points was calculated. ("Initial contact angle water" column in each table. Unit: °).
In addition, water was replaced with n-hexadecane (n-HD), the contact angle of n-HD was measured in the same manner as above, and the average value of 5 points was calculated (“Initial contact angle n-HD” column of each table). . Unit: °).

-Evaluation Criteria for Water and Oil Repellent (Initial) In the present invention, when the average value of the initial contact angles of the water is 100 ° or more and the average value of the initial contact angles of the n-HD is 70 ° or more. , The obtained cured product shall be excellent in water repellency and oil repellency (initial stage).
The more the average value of the initial contact angles of water is larger than 100 °, and / or the more the average value of the initial contact angles of n-HD is larger than 70 °, the more water and oil repellency of the obtained cured product (initial). To be better.
When the average value of the initial contact angles of the water is less than 100 °, or the average value of the initial contact angles of the n-HD is less than 70 °, the water and oil repellency (initial) of the obtained cured product is determined. It shall be inferior.

[Evaluation of abrasion resistance]
Using the surface measuring machine Tribo Station Type32 (manufactured by Shinto Kagaku Co., Ltd.), attach a professional wiper soft wiper (industrial wipe, manufactured by Daio Paper Corporation; the same applies hereinafter) to the surface indenter, and each test piece 30 times with a load of 100 g. A friction test was performed to rub the surface of the film.
The water and oil repellency after the friction test was evaluated by the same method as in the above [evaluation of water and oil repellency].
The results are shown in the "Post-friction contact angle water" column and the "Post-friction contact angle n-HD" column of each table (unit: °).

-Evaluation Criteria for Friction Resistance In the present invention, the durability of the water and oil repellency of the obtained cured product (film) was evaluated using the results of the water and oil repellency after the friction test.
In the above evaluation of water and oil repellency (initial), when the water and oil repellency (initial) is excellent, the average value of the contact angles of water after the friction test is 110 ° or more, and after the friction test, the average value is 110 ° or more. When the average value of the contact angles of n-HD is 60 ° or more, the durability of the water and oil repellency of the obtained cured product is considered to be excellent.
Further, in the above case, the more the average value of the contact angles of water after the friction test is larger than 110 °, and / or the more the average value of the contact angles of n-HD after the friction test is larger than 60 °. The durability of the water and oil repellency of the obtained cured product shall be improved.
Regardless of the evaluation result of water repellency and oil repellency (initial), the average value of the contact angle of water after the friction test is less than 110 °, or the average value of the contact angle of n-HD after the friction test. If is less than 60 °, the durability of the water and oil repellency of the obtained cured product shall be inferior.

[Evaluation of reactivity]
A wiping test was performed in which the surface of each test piece was lightly wiped 10 times with a pro-wipe impregnated with methyl ethyl ketone (MEK).
The water and oil repellency after the MEK wiping test was evaluated by the same method as in the above [evaluation of water and oil repellency].
The results are shown in the "contact angle after wiping MEK water" column and the "contact angle n-HD after wiping MEK" column of each table (unit: °).

-Reactivity Evaluation Criteria In the present invention, the reactivity of the curable composition (particularly, the fluorine-containing surface treatment agent (X) and the curable compound (Y1)) is used by using the result of the water and oil repellency after the MEK friction test. Alternatively, the reactivity with the curable compound (Y2)) was evaluated.
When the average value of the contact angle of water after the MEK friction test is 90 ° or more and the average value of the contact angle of n-HD after the MEK friction test is 50 ° or more, the reactivity is excellent. And.
The more the average value of the contact angle of water after the MEK friction test is larger than 90 °, and / or the more the average value of the contact angle of n-HD after the MEK friction test is larger than 50 °, the more the reactivity It shall be excellent.
If the average value of the contact angle of water after the MEK friction test is less than 90 °, or the average value of the contact angle of n-HD after the MEK friction test is less than 50 °, the reactivity is inferior. And.

[Anti-fouling property]
-Evaluation method of antifouling property Oil-based magic (McKee extra-fine manufactured by Zebra) was applied to the cured product (film) of each test piece, and after drying, the oil-based magic was wiped off with a pro wipe and visually observed.

-Evaluation criteria for antifouling property When the oil-based magic was completely wiped off by rubbing each test piece lightly, it was evaluated as having excellent antifouling property and marked with "◎".
When the oil-based magic was completely wiped off with force, it was evaluated as having a little excellent antifouling property, and this was displayed as "○".
The oil-based magic can be wiped off, but if traces of the oil-based magic remain, it is evaluated as being slightly inferior in antifouling property and marked with "△".
If the oil-based magic could not be wiped off at all, it was evaluated as being extremely inferior in antifouling property, and this was marked as "x".

As is clear from the results shown in Tables 1 and 2, Comparative Examples 1 and 2 in which the fluorine-containing surface modifier does not have a predetermined structural unit (A) have water- and oil-repellent properties and durability of water- and oil-repellent properties. , The antifouling property was inferior.
Comparative Example 3 in which the fluorine-containing surface modifier did not have a predetermined structural unit (B) was inferior in water and oil repellency, durability of water and oil repellency, reactivity, and antifouling property.
Comparative Examples 4 and 5 which did not contain the predetermined fluorine-containing surface modifier (X) were inferior in water repellency, oil repellency, durability of water repellency, reactivity, and antifouling property.

On the other hand, the composition of the present invention was excellent in sustainability of water and oil repellency and water and oil repellency. Moreover, the composition of the present invention was excellent in reactivity.

In Table 1, the cured products obtained in Examples 1 to 4 showed better water and oil repellency, persistence of water and oil repellency, and reactivity than the cured products obtained in Comparative Example 1.
Further, in Examples 1 to 4, although the fluorine content was lower than that in Comparative Example 2, the leveling property was excellent, and good water and oil repellency, sustainability of water and oil repellency, and reactivity were exhibited.
The cured product obtained in Example 5 exhibited good water and oil repellency, longevity of water and oil repellency, reactivity, and good antifouling property.

In Table 2, the cured product obtained in Example 6 showed good water and oil repellency, persistence of water and oil repellency, and reactivity.
Further, the cured product obtained in Example 7 exhibited good water and oil repellency, durability of water and oil repellency, reactivity, and good antifouling property.

Claims (21)

A fluorine-containing surface modifier (X) having a reactive group G1 and
It contains a curable compound (Y1), or a curable compound (Y2) and a curable compound (Y3).
The fluorine-containing surface modifier (X) has a structural unit (A) derived from a fluorine-containing polymerizable compound represented by the following formula (a) and a structural unit (B) having the reactive group G1. It is a polymer contained and
The curable compound (Y1) has a reactive group G2 that reacts with the reactive group G1.
The curable compound (Y2) has a reactive group G3 and a reactive group G4 that react with the reactive group G1.
The curable compound (Y3) has a reactive group G5 that reacts with the reactive group G4.
The curable composition, wherein the reactive group G3 may be the same as or different from the reactive group G4, and the reactive group G5 may be the same as or different from the reactive group G1. However, the curable compound (Y3) does not contain a fluorine-containing surface modifier (X).
CH ₂ = CR ^1- CONR ^{4 -CR 2} R ^3- (CH ₂ ) _n- COO-Q ^1- Rf ¹ (a)
The symbols in the formula have the following meanings.
R ¹ : Hydrogen atom or methyl group,
R ² , R ³ , R ⁴ : Independent of each other, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group represented by the following formula (r) (however, of R ² , R ³ , and R ⁴ ). At least one is a group represented by the formula (r).),
-(CH ₂ ) _m- COO-Q ^2- Rf ² (r)
n and m: Independent of each other, integers 0-4,
Q ¹ and Q ² : Independent of each other, a single bond or a divalent linking group,
Rf ¹ and Rf ² : Independently, a polyfluoroalkyl group or a polyfluoroether group having 1 to 6 carbon atoms. The curable composition according to claim 1, wherein Rf ¹ and Rf ² are linear perfluoroalkyl groups having 1 to 6 carbon atoms. The curable composition according to claim 1 or 2, wherein Q ¹ and Q ^{2 are linear alkylene groups.} Claimed that the reactive group G1 is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, a vinyl group, an allyl group, a (meth) acryloyl group, an isocyanate group, and a ketone group. Item 2. The curable composition according to any one of Items 1 to 3. The curable composition according to any one of claims 1 to 4, wherein the content of the structural unit (A) is 5 to 60% by mass with respect to the total amount of the fluorine-containing surface modifier (X). Stuff. The curable composition according to any one of claims 1 to 5, wherein the content of the structural unit (B) is 1 to 90% by mass with respect to the total amount of the fluorine-containing surface modifier (X). Stuff. The fluorine-containing surface modifier (X) further contains a structural unit (C) other than the structural unit (A) and the structural unit (B).
The curable composition according to any one of claims 1 to 6, wherein the content of the structural unit (C) is 80% by mass or less with respect to the total amount of the fluorine-containing surface modifier (X). .. The curable composition according to claim 7, wherein the polymerizable compound (c) constituting the structural unit (C) is a polymerizable compound (c1) having a polysiloxane chain. Contains the curable compound (Y1)
The reactive group G1 is at least one functional group selected from the group consisting of a vinyl group, an allyl group, and a (meth) acryloyl group, and the reactive group G2 is an ethylenically unsaturated group. The curable composition according to any one of claims 1 to 8. Contains the curable compound (Y1)
The curable composition according to any one of claims 1 to 9, wherein the reactive groups G1 to G2 are independent of each other and are (meth) acryloyl groups. According to any one of claims 1 to 10, the content of the fluorine-containing surface modifier (X) is 0.1 to 10% by mass with respect to the content of the curable compound (Y1). The curable composition according to description. Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G1 is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group, and the reactive groups G3 to G4 are independent of each other. The first functional group is selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, an amino group, an imino group, a hydrazide group, an alkoxy group, and an acid anhydride group. The curable composition according to any one of 8 to 8. Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G5 is any one of claims 1 to 8 and 12, which is at least one functional group selected from the group consisting of a hydroxy group, a carboxy group, an epoxy group, an isocyanate group, and a ketone group. The curable composition according to. Containing the curable compound (Y2) and the curable compound (Y3),
The reactive group G1 and the reactive group G5 are hydroxy groups and are
The curable composition according to any one of claims 1 to 8, 12 and 13, wherein the reactive group G3 and the reactive group G4 are isocyanate groups. Any of claims 1 to 8 and 12 to 14, wherein the content of the fluorine-containing surface modifier (X) is 0.05 to 10% by mass with respect to the content of the curable compound (Y3). The curable composition according to item 1. The curable composition according to any one of claims 1 to 15, wherein the structural unit (B) having the reactive group G1 is a structural unit derived from a polymerizable compound represented by the following formula (b1). Stuff.
CH ₂ = CR ^21- COO-R ^22- G1 (b1)
The symbols in the formula have the following meanings.
R ²¹ : Hydrogen atom or methyl group,
R ²² : Linear or branched divalent alkylene group,
G1: Reactive group G1 contained in the structural unit (B). The curable composition according to claim 16, wherein in the formula (b1), the ^{alkylene group as R 22 has 2 or more carbon atoms.} The curable composition according to claim 16 or 17, wherein ^{G1 is bonded to the terminal of the alkylene group as R 22} in the formula (b1). A coating material comprising the curable composition according to any one of claims 1 to 18. A cured product obtained by curing the curable composition according to any one of claims 1 to 18. A coated product coated with the curable composition according to any one of claims 1 to 18 or the paint according to claim 19.