JP7255666B2 - Fluorine-containing curable composition and article - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fluorine-containing curable composition excellent in antifouling properties and slipperiness, and an article having a cured film of the composition on its surface.

2. Description of the Related Art Conventionally, hard coating treatment has been widely used as means for protecting the surface of resin moldings and the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded article to make it difficult to be damaged. As a material for forming the hard coat layer, a composition curable by active energy rays such as a thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin is often used.

On the other hand, along with the expansion of the application field of resin molded products and the trend toward higher added value, the demand for higher functionality of the cured resin layer (hard coat layer) is increasing. There is a demand for imparting antifouling properties. By imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, this makes it difficult to stain, or even if it stains, it can be easily removed.

As a method for imparting antifouling properties to the hard coat layer, a method of coating and/or fixing a fluorine-containing antifouling agent on the surface of the hard coat layer once formed is widely used. is added to a curable resin composition before curing, followed by coating and curing to simultaneously form a hard coat layer and impart antifouling properties. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling properties by adding fluoroalkyl acrylate to a curable acrylic resin composition and curing the composition. ing.

In recent years, active energy ray-curable compositions containing such fluorine-containing acrylic compounds and having excellent antifouling properties have been widely used, and new functions have been required.

Due to the widening of the range of applications, hard coatings, especially antifouling treatment on the surface of large displays, and surface treatment of displays and housings of portable information devices such as smartphones and tablets, are antifouling represented by water repellency. Higher performance is required for wear resistance represented by performance and slipperiness. One means of meeting these demands is to arrange more fluorine-modified components on the surface. However, when the fluorine content of a single structure fluorine-containing acrylic compound is increased, the solubility in other components of the non-fluorinated hard coating agent decreases, resulting in uneven coating such as defects on the coating surface. A defect occurs.
In addition to the documents mentioned above, the following documents can be cited as conventional techniques related to the present invention.

JP-A-6-211945 JP 2010-53114 A Japanese Unexamined Patent Application Publication No. 2010-138112 JP 2010-285501 A

The present invention has been made in view of the above circumstances. The purpose is to provide goods that have

The present inventors have been developing various fluorine compounds that can impart antifouling properties to such curable resin compositions. JP-A-138112 (Patent Document 3) and JP-A-2010-285501 (Patent Document 4) have proposed photocurable fluorine compounds. In order to improve these antifouling properties and slipperiness, it is conceivable to increase the content of the fluorine component in the compound. However, as mentioned above, when the solubility in non-fluorinated components is improved with a single-structure fluorine-containing acrylic compound, the concentration of fluorine components on the coated surface becomes difficult, and as a result, the antifouling performance is exhibited. It may become difficult to do so.

Therefore, as a result of further studies, the present inventors have found that a linear polymer having a fluoropolyether in the main chain, having one or two (meth)acrylic groups at the ends, The average number of (meth) acrylic groups contained in is 2 or less, and the component (A) made of a compound having a fluorine content of 48% by mass or more and less than 62% by mass, a straight chain having a fluoropolyether It has two or more (meth)acrylic groups at each end in one molecule of the chain polymer, has an average of 4 to 10 (meth)acrylic groups in one molecule, and has a fluorine content of 25. A component (B) composed of a compound with a mass % or more and less than 45 mass %, and a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of 2 or more (meth) acrylic groups in one molecule. It was found that a fluorine-containing curable composition containing component (C) in a predetermined blending ratio can form a cured film having excellent antifouling properties and water repellency and a low coefficient of dynamic friction. Arrived.

（式中、Ｒｆ²は上記と同じである。Ｑ¹は独立に少なくとも（ａ＋１）個のケイ素原子を含む（ａ＋１）価の連結基であり、環状構造をなしていてもよい。ａは２～５の整数である。Ｚ²はそれぞれ独立に酸素原子及び／又は窒素原子を含んでいてもよい炭素数１～１００の２価の炭化水素基であり、途中環状構造を含んでいてもよい。Ｒ¹は独立に水素原子又は炭素数１～８の１価の炭化水素基である。Ｒ²は独立に水素原子、又は酸素原子及び／又は窒素原子を含んでいてもよい（メタ）アクリル基を有する１価の有機基であり、但し、Ｒ²は１分子中のそれぞれの末端に２個以上、かつ１分子中に平均して４～１０個の前記１価の有機基を有する。Ｚ³は独立に酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも１種のヘテロ原子を含んでいてもよい炭素数１～２０の２価の炭化水素基からなる連結基であり、途中環状構造を含んでいてもよく、炭素原子に結合した水素原子の一部がフッ素原子に置換されていてもよい。）
で表される成分（Ｂ）、及び
フルオロポリエーテル構造を含まず、１分子中に平均して２個以上の（メタ）アクリル基を有する非フッ素化アクリル化合物からなる成分（Ｃ）を必須成分とし、成分（Ｃ）１００質量部に対して、成分（Ａ）と成分（Ｂ）の配合量の合計が０．１～１０質量部であり、かつ成分（Ｂ）１００質量部に対する成分（Ａ）の配合量が３～５０質量部である含フッ素硬化性組成物。
［２］
更に、光重合開始剤（Ｄ）を含有する［１］に記載の含フッ素硬化性組成物。
［３］
成分（Ｂ）１００質量部に対する成分（Ａ）の配合量が５．２６～２５質量部である［１］又は［２］に記載の含フッ素硬化性組成物。
［４］
成分（Ａ）において、一般式（１）又は（２）中のＺ¹が、下記のいずれかの構造である［１］～［３］のいずれかに記載の含フッ素硬化性組成物。
－Ｃ（＝Ｏ）－
－Ｃ（＝Ｏ）Ｏ－
－Ｃ（＝Ｏ）ＯＣＨ₂－
－Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂－
－ＣＨ₂－
－ＣＨ₂Ｏ－
－ＣＨ₂ＯＣＨ₂－
－ＣＨ₂ＣＨ₂－
－ＣＨ₂ＣＨ₂ＣＨ₂－
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－
－ＣＨ₂ＯＣ（＝Ｏ）ＮＨ－
－ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂－
［５］
成分（Ａ）において、一般式（１）又は（２）中のＸ¹が、下記のいずれかで示されるものである［１］～［４］のいずれかに記載の含フッ素硬化性組成物。
－ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
－ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ ₂
－ＣＨ［ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂］［ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂］
－Ｃ（ＣＨ₃）［ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂］ ₂
－Ｃ（ＣＨ₂ＣＨ₃）［ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂］₂
－Ｃ（ＣＨ₂ＣＨ₃）［ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂］₂
［６］
成分（Ａ）において、一般式（１）又は（２）で表される含フッ素アクリル化合物が、下記のいずれかで示されるものである［１］～［５］のいずれかに記載の含フッ素硬化性組成物。
Ｒｆ¹ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
Ｒｆ¹ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
Ｒｆ¹ＯＲｆ²ＣＦ₂Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
Ｒｆ¹ＯＲｆ²ＣＦ₂Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
Ｒｆ¹ＯＲｆ²ＣＦ₂Ｃ（＝Ｏ）ＯＣＨ［ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂］［ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂］
Ｒｆ¹ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
Ｒｆ¹ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＨＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣ（ＣＨ₃）［ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂］₂
ＣＨ₂＝Ｃ（ＣＨ₃）Ｃ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＣＨ₂＝ＣＨＣ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＣＨ₂＝ＣＨＣ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
ＣＨ₂＝ＣＨＣ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＮＨＣ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
ＣＨ₂＝Ｃ（ＣＨ₃）Ｃ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＮＨＣ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣＨ₂ＯＣ（＝Ｏ）Ｃ（ＣＨ₃）＝ＣＨ₂
ＣＨ₂＝ＣＨＣ（＝Ｏ）ＯＣＨ₂ＣＨ₂ＮＨＣ（＝Ｏ）ＯＣＨ₂ＣＦ₂ＯＲｆ²ＣＦ₂ＣＨ₂ＯＣ（＝Ｏ）ＮＨＣＨ₂ＣＨ₂ＯＣ（＝Ｏ）ＣＨ＝ＣＨ₂
（式中、Ｒｆ¹、Ｒｆ²は上記と同じである。）
［７］
成分（Ｂ）において、一般式（３）中のＺ³が、下記式のいずれかで表されるものである［１］～［６］のいずれかに記載の含フッ素硬化性組成物。
－ＣＨ₂ＣＨ₂－
－ＣＨ₂ＣＨ₂ＣＨ₂－
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－
－ＣＨ₂ＯＣＨ₂ＣＨ₂－
－ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂－
［８］
成分（Ｂ）において、一般式（３）中のＱ¹が、下記式で表されるものである［１］～［７］のいずれかに記載の含フッ素硬化性組成物。

（式中、ａ１は２又は３である。）
［９］
成分（Ｂ）において、一般式（３）で表される含フッ素アクリル化合物が、下記一般式（４）又は（５）で表される含フッ素アクリル化合物である［１］～［８］のいずれかに記載の含フッ素硬化性組成物。

（式中、Ｚ³、Ｑ¹、ａは上記の通りであり、Ｒｆ’は－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_m（ＣＦ₂ＣＦ₂Ｏ）_nＣＦ₂－であり、ｍは１～２００の整数、ｎは１～１７０の整数、ｍ＋ｎは６～２０１の整数であり、－（ＣＦ₂Ｏ）－と－（ＣＦ₂ＣＦ₂Ｏ）－の配列はランダムであり、Ｒ³は水素原子又はメチル基であり、ｄ１、ｅ１は０～１０の整数であり、かつ式（４）、（５）で表される化合物において、フッ素含有率は２５質量％以上４５質量％未満である。）
［１０］
成分（Ｃ）の非フッ素化アクリル化合物が、１分子中に２個以上の（メタ）アクリル基を有しウレタン結合を有さない多官能アクリル化合物、又はこの多官能アクリル化合物と脂肪族ポリイソシアネートと水酸基を有するアクリル化合物とを反応させて得られた１分子中に３個以上の（メタ）アクリル基を有する多官能ウレタンアクリレート類、又は前記多官能アクリル化合物とウレタンアクリレート類とを含む２種類以上のアクリル化合物の混合物である［１］～［９］のいずれかに記載の含フッ素硬化性組成物。
［１１］
［１］～［１０］のいずれかに記載の含フッ素硬化性組成物の硬化被膜を表面に有する物品。 Accordingly, the present invention provides the following fluorine-containing curable composition and an article having a cured film of the composition on its surface.
[1]
A linear polymer having a fluoropolyether as the main chain, having one or two (meth)acrylic groups at one or both ends of the molecular chain, and the (meth)acrylic group contained in one molecule The following general formula (1) or (2) consisting of a compound having an average number of 2 or less and a fluorine content of 48% by mass or more and less than 62% by mass
Rf ¹ -O-Rf ² -CF ₂ -Z ¹ -X ¹ (1)
X ² -Z ¹ -CF ₂ O-Rf ² -CF ₂ -Z ¹ -X ¹ (2)
(In the formula, Rf ¹ is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, and Rf ² is one of the following two types of repeating units —CF ₂ O—
_{-CF2CF2O- _}
is a randomly arranged divalent perfluoropolyether group with a molecular weight of 600 to 20,000. Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and - A linking group selected from C(=O)O—, the divalent hydrocarbon group may contain a cyclic structure in the middle, and some of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms. may X ¹ is independently a monovalent organic group having a (meth)acryl group optionally containing an oxygen atom and/or a nitrogen atom, and X ² is a hydroxyl group or X ¹ . )
Component (A) represented by
Each molecule of a linear polymer having a fluoropolyether as a main chain has two or more (meth)acrylic groups at each molecular chain end, and an average of 4 to 10 (meth)acrylic groups per molecule. ) The following general formula (3), which has an acrylic group and is composed of a compound having a fluorine content of 25% by mass or more and less than 45% by mass

(In the formula, Rf ² is the same as above. Q ¹ is an (a+1)-valent linking group that independently contains at least (a+1) silicon atoms and may have a cyclic structure. a is 2 is an integer of up to 5. Z ² is each independently a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain an oxygen atom and/or a nitrogen atom, and which may contain a cyclic structure in the middle; R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a hydrogen atom, or a (meth)acryl optionally containing an oxygen atom and/or a nitrogen atom; with the proviso that R ² has 2 or more at each end in one molecule and 4 to 10 of the above-mentioned monovalent organic groups on average in one molecule. Z ³ is a linking group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and has a cyclic structure in the middle; may contain, and some of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms.)
A component (B) represented by and a component (C) consisting of a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups in one molecule (C) as an essential component and the total amount of component (A) and component (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of component (C), and component (A ) in an amount of 3 to 50 parts by mass.
[2]
The fluorine-containing curable composition according to [1], further comprising a photopolymerization initiator (D).
[3]
The fluorine-containing curable composition according to [1] or [2], wherein the amount of component (A) is 5.26 to 25 parts by mass per 100 parts by mass of component (B).
[4]
The fluorine-containing curable composition according to any one of [1] to [3], wherein in component (A), Z ¹ in general formula (1) or (2) has any of the following structures.
-C(=O)-
-C(=O)O-
-C(=O) _OCH2-
-C ₍ =O) _{OCH2CH2-
-CH2-}
-CH ₂ O-
_{-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC} (=O)NH-
_{-CH2OC (} =O) _NHCH2CH2-
[5]
The fluorine-containing curable composition according to any one of [1] to [4], wherein in component (A), X ¹ in general formula (1) or (2) is any of the following: .
-OC(=O)CH= _CH2
-OC(=O)C( _CH3 )= _CH2
- CH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (=O)C( _CH3 )= _CH2 ]
-C( _CH3 )[ _CH2OC (=O)CH= _CH2 ] ₂
- C( _CH2CH3 )[ _CH2OC (=O)CH _{= CH2} ] ₂
-C( _CH2CH3 )[ _CH2OC ( ₌ O)C( _CH3 )= _CH2 ] ₂
[6]
The fluorine-containing acryl compound represented by formula (1) or (2) in component (A) is any one of the following: Curable composition.
^{Rf1ORf2CF2CH2OC} (= _O ) _{CH =} ^{CH2
Rf1ORf2CF2CH2OC} (= _O ) _C ( _CH3 ) ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC ( =} ^O )CH _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( _{= O} )C ⁽ _CH3 ) _{= CH2}
^Rf1ORf2CF2C ( ₌ O) _OCH2CH2OC (= ^O )CH _{= CH2}
^Rf1ORf2CF2C ₍ =O) _OCH2CH2OC ( ⁼ _O )C( _CH3 )= _{CH2
HOCH2CF2ORf2CF2C} ( ₌ O) ^OCH2CH2OC ₍ = _O )CH _{= CH2
HOCH2CF2ORf2CF2C} ( ₌ O) ^OCH2CH2OC ₍ = _O )C( _CH3 ) _{= CH2}
^Rf1ORf2CF2C (=O)OCH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (= _O ) _C ( ^CH3 )= _CH2 ]
^{Rf1ORf2CF2CH2OC} ( ₌ O) _NHCH2CH2OC ( ₌ ^O )CH _{= CH2}
^{Rf1ORf2CF2CH2OC} ( ₌ O) _NHCH2CH2OC ( ₌ ^O )C( _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC ( =} O) _NHCH2CH2OC (= _{O )} CH ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC} (=O) _NHCH2CH2OC ( _{= O )} C ⁽ _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( ₌ O)NHC ⁽ _CH3 )[ _{CH2OC (} = _O )CH= _CH2 ] _2
CH2 =C( _{CH3 )} ^C ₍ =O)OCH2CF2ORf2CF2CH2OC(= _O )C( _{CH3 )} = _{CH2
CH2 =} ^CHC (= _O ) _{OCH2CF2ORf2CF2CH2OC} (=O)C( _CH3 ) _{= CH2
CH2 = CHC (} =O) _{OCH2CF2ORf2CF2CH2OC} (=O)CH ₌ ^CH2
_CH2 = _CHC ⁽ _{= O ) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC( ₌ O) _CH = _CH2
CH2 =C _{( CH3} ) ^C ( ₌ O _{) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC(= _O )C( _{CH3 ) = CH2
CH2} = _CHC (=O) _OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( ⁼ _O ) _{NHCH2CH2OC (} = _{O )} CH _{= CH2}
(In the formula, Rf ¹ and Rf ² are the same as above.)
[7]
The fluorine-containing curable composition according to any one of [1] to [6], wherein in component (B), Z ³ in general formula (3) is represented by any one of the following formulae.
_{-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _}
[8]
The fluorine-containing curable composition according to any one of [1] to [7], wherein in component (B), Q ¹ in general formula (3) is represented by the following formula.

(In the formula, a1 is 2 or 3.)
[9]
Any of [1] to [8], wherein the fluorine-containing acrylic compound represented by the general formula (3) in the component (B) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5) The fluorine-containing curable composition according to 1.

(wherein Z ³ , Q ¹ and a are as defined above, Rf′ is —CF ₂ O(CF ₂ O) _m (CF ₂ CF ₂ O) _n CF ₂ —, m is 1 to 200 n is an integer of 1 to 170, m+n is an integer of 6 to 201, the arrangement of -(CF ₂ O)- and -(CF ₂ CF ₂ O)- is random, and R ³ is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and the fluorine content in the compounds represented by formulas (4) and (5) is 25% by mass or more and less than 45% by mass.)
[10]
The non-fluorinated acrylic compound of component (C) is a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or this polyfunctional acrylic compound and an aliphatic polyisocyanate. Polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule obtained by reacting with an acrylic compound having a hydroxyl group, or two types including the polyfunctional acrylic compound and urethane acrylates The fluorine-containing curable composition according to any one of [1] to [9], which is a mixture of the above acrylic compounds.
[11]
An article having on its surface a cured film of the fluorine-containing curable composition according to any one of [1] to [10].

The fluorine-containing curable composition of the present invention has stable solubility and can provide a cured film having high antifouling properties, stain-wiping properties and slipperiness.

The fluorine-containing curable composition of the present invention is a linear polymer having a fluoropolyether as a main chain, and has one or two (meth)acrylic groups at one or both ends of the molecular chain, The average number of (meth)acrylic groups contained in one molecule is 2 or less, and the component (A) made of a compound having a fluorine content of 48% by mass or more and less than 62% by mass, and a fluoropolyether as a main chain It has two or more (meth)acrylic groups at each molecular chain end (that is, both molecular chain ends) in one molecule of the linear polymer having an average of 4 to 10 in one molecule A component (B) comprising a compound having a (meth) acrylic group and having a fluorine content of 25% by mass or more and less than 45% by mass, and a component (B) containing no fluoropolyether structure and having an average of 2 or more in one molecule It is composed of a component (C) comprising a non-fluorinated acrylic compound having a (meth)acrylic group, and the components (A), (B) and (C) are essential components.

In the present invention, "acrylic compound" is a general term for compounds having an acrylic group and a methacrylic group, and "(meth)acrylic group" indicates one or both of an acrylic group and a methacrylic group, and "( “Meth)acrylic acid” refers to one or both of acrylic acid and methacrylic acid, and “(meth)acrylate” refers to one or both of acrylate and methacrylate. Furthermore, "acrylates" is a general term for compounds having acrylates and methacrylates.

In the present invention, each component of components (A), (B), and (C) does not need to be a single compound. The total amount of a mixture of a plurality of compounds that meet the respective conditions of (C) may be considered as the amount of each component.

[Component (A)]
Component (A), which is the first essential component in the fluorine-containing curable composition of the present invention, is a linear polymer having a fluoropolyether as a main chain, and has one or both ends of the molecular chain. It has two (meth)acrylic groups, and the average number of (meth)acrylic groups contained in one molecule is 2 or less (1 to 2) (that is, the molecular chain of the linear polymer one (meth)acrylic group at each end of the molecular chain, or one or two (meth)acrylic groups at one end of the molecular chain), with a fluorine content of 48% by mass or more and 62% by mass % of compounds.

Here, the fluorine content of the compound of component (A) is 48% by mass or more and less than 62% by mass, preferably 55% by mass or more and 61.5% by mass or less, more preferably 57% by mass or more and 61% by mass. % or less. If the fluorine content is less than 48% by mass, the antifouling performance is insufficient compared to the case where the component (A) is not used, and if it is 62% by mass or more, the solubility in the component (C) is insufficient. However, it is difficult to obtain a smooth coated surface of the cured film. In the present invention, the fluorine content is the mass % value of fluorine atoms in the molecule with respect to the number average molecular weight calculated from the molecular formula of the compound obtained from ¹⁹ F-NMR and ¹ H-NMR (hereinafter the same).

Examples of such compounds include fluorine-containing acrylic compounds represented by the following general formula (1) or (2).
Rf ¹ -O-Rf ² -CF ₂ -Z ¹ -X ¹ (1)
X ² -Z ¹ -CF ₂ O-Rf ² -CF ₂ -Z ¹ -X ¹ (2)

In the above formula (1), Rf ¹ is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom. , a fluorine atom, a trifluoromethyl group, a pentafluoroethyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, and a CF ₃ OCF ₂ CF ₂ −
_{CF3OCF2CF2CF2- _ _ _
CF3CF2OCF2CF2- _ _ _
( CF3 ) 2CFOCF2CF2-
CF3OCF2CF2CF2CF2- _ _ _ _
CF3CF2OCF2CF2CF2- _ _ _ _
CF3CF2CF2OCF2CF2- _ _ _ _
( CF3 ) 2CFCF2OCF2CF2- _
CF3CF2CF2CF2OCF2CF2 - _ _ _ _
CF3CF2CF2OCF2CF2CF2 - _ _ _ _}
Among these, CF ₃ — and CF ₃ CF ₂ — are particularly preferred.

In the above formulas (1) and (2), Rf ² is the following two types of repeating units -CF ₂ O-
_{-CF2CF2O- _}
is a randomly arranged divalent perfluoropolyether group having a molecular weight of 600 to 20,000, preferably 1,200 to 10,000, and can be represented, for example, as follows.
-( _{CF2O ) m} ( _CF2CF2O ) _n-

m is an integer of 1 to 200, preferably an integer of 6 to 50, n is an integer of 1 to 170, preferably an integer of 6 to 50, m+n is an integer of 6 to 201, preferably an integer of 12 to 100 If the values of m, n, and m+n, which are integers, are too small, the effect of imparting antifouling properties to the cured composition will be small, and if they are too large, compatibility with non-fluorinated components will be poor, It causes turbidity of the coating liquid and poor coating. The values of m and n may have a distribution, and if they have a distribution, it is preferable that the value of m+n determined by ¹⁹ F-NMR or the like satisfies the above range as a number average.

In the above formulas (1) and (2), Z ¹ is a divalent hydrocarbon having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom. A linking group selected from -C(=O)- and -C(=O)O-, wherein the divalent hydrocarbon group may contain a cyclic structure in the middle, hydrogen bonded to a carbon atom A part of the atoms may be substituted with fluorine atoms. Examples of suitable structures for such Z ¹ include the following structural groups.

-C(=O)-
-C(=O)O-
-C(=O) _OCH2-
-C ₍ =O) _{OCH2CH2-
-CH2-}
-CH ₂ O-
_{-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC} (=O)NH-
_{-CH2OC (} =O) _NHCH2CH2-

Among these, -CH ₂ -
_-CH2OC (=O)NH-
_{-CH2OC (} =O) _NHCH2CH2-
is preferred.

In the above formulas (1) and (2), X ¹ is a monovalent organic group having preferably one or two (meth)acrylic groups which may independently contain an oxygen atom and/or a nitrogen atom. However, it has 1 or 2 said monovalent organic groups in 1 molecule. Moreover, in said formula (2), ^X2 is a hydroxyl group or ^X1 .

Preferred structures of X ¹ are specifically exemplified by the following structures.
-OC(=O)CH= _CH2
-OC(=O)C( _CH3 )= _CH2
- CH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (=O)C( _CH3 )= _CH2 ]
-C( _CH3 )[ _CH2OC (=O)CH= _CH2 ] ₂
- C( _CH2CH3 )[ _CH2OC (=O)CH _{= CH2} ] ₂
-C( _CH2CH3 )[ _CH2OC ( ₌ O)C( _CH3 )= _CH2 ] ₂

-OC(=O)CH=CH ₂ is particularly preferred
-OC(=O)C( _CH3 )= _CH2
is.

Preferred structures of X ² are specifically exemplified by the following structures.
HO-
_CH2 =C( _CH3 )C(=O)O-
_CH2 =CHC(=O)O-

More specific examples of such component (A) include compounds represented by the following structural groups.
^{Rf1ORf2CF2CH2OC} (= _O ) _{CH =} ^{CH2
Rf1ORf2CF2CH2OC} (= _O ) _C ( _CH3 ) ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC ( =} ^O )CH _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( _{= O} )C ⁽ _CH3 ) _{= CH2}
^Rf1ORf2CF2C (=O) _OCH2CH2OC (= ^O ) _{CH = CH2}
^Rf1ORf2CF2C _{( =} O) _OCH2CH2OC (= ^O )C( _CH3 )= _{CH2
HOCH2CF2ORf2CF2C} ( ₌ O) ^OCH2CH2OC ₍ = _O )CH _{= CH2
HOCH2CF2ORf2CF2C} ( ₌ O) ^OCH2CH2OC ₍ = _O )C( _CH3 ) _{= CH2}
^Rf1ORf2CF2C (=O)OCH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (= _O ) _C ( ^CH3 )= _CH2 ]
^{Rf1ORf2CF2CH2OC} ( ₌ O) _{NHCH2CH2OC (} = ^O )CH _{= CH2}
^{Rf1ORf2CF2CH2OC} ₍ =O) _NHCH2CH2OC ( ₌ ^O )C( _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC ( =} O) _NHCH2CH2OC (= _{O )} CH ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC} (=O) _NHCH2CH2OC ( _{= O )} C ⁽ _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( ₌ O)NHC ⁽ _CH3 )[ _{CH2OC (} = _O )CH= _CH2 ] _2
CH2 =C( _{CH3 )} ^C ₍ =O)OCH2CF2ORf2CF2CH2OC(= _O )C( _{CH3 )} = _{CH2
CH2 =} ^CHC (= _O ) _{OCH2CF2ORf2CF2CH2OC} (=O)C( _CH3 ) _{= CH2
CH2 = CHC (} =O) _{OCH2CF2ORf2CF2CH2OC} (=O)CH ₌ ^CH2
_CH2 = _CHC ⁽ = _{O ) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC( _{= O} ) _CH = _CH2
CH2 =C _{( CH3} ) ^C ( ₌ O _{) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC(= _O )C( _{CH3 ) = CH2
CH2} = _CHC (=O) _OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( ⁼ _O ) _{NHCH2CH2OC (} = _{O )} CH _{= CH2}
(In the formula, Rf ¹ and Rf ² are as described above, but compounds having an average fluorine content of 55% by mass or more and less than 62% by mass are particularly preferred as compounds corresponding to component (A).)

The following general formula (1) or (2), which is the component (A)
Rf ¹ -O-Rf ² -CF ₂ -Z ¹ -X ¹ (1)
X ² -Z ¹ -CF ₂ O-Rf ² -CF ₂ -Z ¹ -X ¹ (2)
(In the formula, Rf ¹ , Rf ² , Z ¹ , X ¹ and X ² are the same as above.)
As a suitable method for synthesizing the fluorine-containing acrylic compound represented by, for example, the following general formula (6) or (7)
^Rf1 -O-Rf2- ^CF2 _{- CH2} -OH (6)
HO--CH ₂ --CF ₂ O--Rf ² --CF ₂ --CH ₂ --OH (7)
(In the formula, Rf ¹ and Rf ² are the same as above.)
One of the fluorine-containing alcohol compounds represented by the following general formula (8)
_CH2 = ^CR3C (=O)X (8)
(In the formula, ^R3 is the same as above, and X is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom.)
A method of forming an ester by reacting a (meth)acrylic acid halide represented by the following general formula (9)
_CH2 = ^CR3C (=O) _{OCH2CH2 -} N=C=O (9)
(In the formula, R ³ is the same as above.)
A method of reacting an isocyanate compound containing a (meth)acrylic group represented by can be used to obtain a fluorine-containing acrylic compound represented by the above formula (1) or (2).

Here, examples of the (meth)acrylic acid halide represented by formula (8) include those shown below.
_CH2 =CHC(=O)X
_CH2 =C( _CH3 )C(=O)X
(In the formula, X is the same as above.)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.

Examples of the (meth)acrylic group-containing isocyanate compound represented by formula (9) include those shown below.
_CH2 =CHC(=O) _{OCH2CH2 -} N=C=O
_CH2 =C( _CH3 )C(=O) _{OCH2CH2 -} N=C=O

These (meth)acrylic acid halides or (meth)acrylic group-containing isocyanate compounds may be reacted in an equimolar amount or more with respect to the total amount of hydroxyl groups in the fluorine-containing alcohol compound, and all the hydroxyl groups may be reacted. In the compound of the formula (7), it suffices to introduce an average of 1 mol or more (meth)acrylic groups per 1 mol of the fluorine-containing alcohol compound. ) The isocyanate compound containing acrylic acid halide or (meth)acrylic group may not remain. Specifically, when the amount of fluorine-containing alcohol compound in the reaction system is x mol, and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is y mol, (meth)acrylic acid halide or isocyanate containing (meth)acrylic group The amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less. If the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may become low. If the amount is too large, it becomes difficult to remove unreacted (meth)acrylic acid halides or residual isocyanate compounds containing (meth)acrylic groups.

These reactions may be carried out by diluting with a suitable solvent as necessary. As such a solvent, any solvent that does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth)acrylic acid halide, or the isocyanate group of the isocyanate compound containing the (meth)acrylic group can be used without particular limitation. Specifically, hydrocarbon solvents such as toluene, xylene and isooctane; ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether; Fluorine-modified aromatic hydrocarbon solvents such as ketone solvents, m-xylene hexafluoride (also known as hexafluorometa-xylene) and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution depending on the intended use.
The amount of the solvent to be used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If too much solvent is used, there is a danger that the reaction rate will be greatly reduced.

Moreover, you may add a polymerization inhibitor as needed in the case of reaction. The polymerization inhibitor is not particularly limited, but those commonly used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
The amount of the polymerization inhibitor to be used may be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000,000,000,000,000,000,000,000, or 000 ppm, particularly preferably 0.1 to 500 ppm.

When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester formation reaction is carried out by dropping the (meth)acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor. Usable acid acceptors include triethylamine, pyridine, and urea. The amount of the acid acceptor used is desirably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If it is too small, a large amount of untrapped acid will remain, and if it is too large, it will be difficult to remove the surplus acid acceptor.

The dropwise addition of the (meth)acrylic acid halide is carried out over 20-60 minutes while maintaining the temperature of the reaction mixture at 0-35°C. Stirring is then continued for an additional 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by a method such as distillation, adsorption, filtration, washing, etc. to obtain the above formula (1) or (2). A fluorine-containing acrylic compound represented by can be obtained.

Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The produced acrylic acid esters can be removed by the same method as for removing unreacted (meth)acrylic acid halides, but they can also be used as they remain.

In the case of the reaction between the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group are stirred together with a solvent if necessary to initiate the reaction. proceed.

In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of catalysts include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctoate, tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, and other titanate esters or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelate compounds and the like are exemplified. These are not limited to one type, and can be used as a mixture of two or more types. The reaction rate can be increased by adding 0.01 to 2% by weight, preferably 0.05 to 1% by weight, of these catalysts relative to the total weight of the reactants.

The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.

After completion of the reaction, the unreacted isocyanate compound and reaction solvent are removed by distillation, adsorption, filtration, washing, or the like to obtain the fluorine-containing acrylic compound represented by the above formula (1) or (2). be able to.

Also, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.

[Component (B)]
Component (B), which is the second essential component in the fluorine-containing curable composition of the present invention, is each molecular chain end in one molecule of a linear polymer having a fluoropolyether as a main chain (that is, both molecular chain ends). terminal) each have 2 or more, preferably 2 to 4 (meth)acrylic groups, and an average of 4 to 10, preferably 4 to 8 (meth)acrylic groups per molecule and a compound having a fluorine content of 25% by mass or more and less than 45% by mass.

Here, the fluorine content of the compound of component (B) is 25% by mass or more and less than 45% by mass, preferably 28% by mass or more and 43% by mass or less, more preferably 33% by mass or more and 42% by mass or less. is. If the fluorine content is less than 25% by mass, the solubility in component (A) is reduced, and if it is 45% by mass or more, the solubility in component (C) is reduced, so that the composition as a whole can be coated smoothly. becomes difficult.

Specific examples of such compounds include fluorine-containing acrylic compounds represented by the following general formula (3).

In formula (3) above, Rf ² is the same as Rf ² in formulas (1) and (2) above.

In the above formula (3), R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and the monovalent hydrocarbon group is specifically methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, alkyl group such as octyl group, cycloalkyl group such as cyclohexyl group, vinyl group, allyl alkenyl groups such as propenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group and phenylethyl group. R ¹ is preferably a hydrogen atom or a methyl group.

In the above formula (3), R ² is independently a hydrogen atom or a monovalent organic group having a (meth)acrylic group which may contain an oxygen atom and/or a nitrogen atom. The monovalent organic group is preferably a group having at least one, preferably one or two (meth)acrylic groups at its terminals. Moreover, it may have an amide bond, an ether bond, an ester bond, or the like in the middle of the structure.

Examples of such structures include the following.
_CH2 =CHC(=O)-
_CH2 =C( _CH3 )C(=O)-
_CH2 =CHC(=O) _{OCH2CH2 -} NHC(=O)-
_CH2 =C( _CH3 )C(=O) _{OCH2CH2 -} NHC(=O)-
_CH2 =C _{( CH3} )C(=O) _{OCH2CH2OCH2CH2 - NHC} (=O)-
( _CH2 =CHC(= _{O)OCH2CH2)2C ( CH3 )} -NHC(=O)-

Among these, the following are particularly preferred.
_CH2 =CHC(=O) _{OCH2CH2 -} NHC(=O)-
_CH2 =C( _CH3 )C(=O) _{OCH2CH2 -} NHC(=O)-

In the above formula (3), a is independently an integer of 2-5, preferably an integer of 2-4, more preferably 2 or 3. If a is less than 2, the solubility in component (C) may be lowered, and if it is greater than 5, the solubility in component (A) may be lowered.

In the above formula (3), Q ¹ is independently a (a+1)-valent linking group containing at least (a+1) silicon atoms and may form a cyclic structure. Preferred examples of such Q ¹ include a siloxane structure each having at least (a+1) silicon atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more of these (a+1) valent linking groups. At this time, the (a+1) bonds preferably each have (a+1) silicon atoms. As a particularly preferred structure, specifically, the following structure is shown.
However, in the structures below, a is the same as a in formula (3) above. Also, b is an integer of 1-5, preferably an integer of 1-3. The arrangement of each unit is random, and the bonds of each of the (a+1) units are bonded to any of Z ³ and a CH ₂ groups enclosed in [ ].

Here, T' is a (a+1)-valent linking group, and examples thereof are given below.

（式中、ａ１は２又は３である。）Among these, the following are particularly preferred.

(In the formula, a1 is 2 or 3.)

In the above formula (3), Z ² is each independently a divalent hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 40 carbon atoms, which may contain an oxygen atom and/or a nitrogen atom; It may contain a cyclic structure.

Preferred structures for Z ² include the following.
_{-CH2 [ OC2H4 ] d [ OC3H6 ] e} [ _{OC4H8 ] fOCcH2c-}
(Wherein, d is an integer of 0 to 29, preferably an integer of 0 to 10, e is an integer of 0 to 29, preferably an integer of 0 to 10, f is an integer of 0 to 14, preferably It is an integer of 0 to 7, and c is an integer of 2 to 4. The total number of carbon atoms in the above structure may be 3 to 100, preferably 3 to 30. The arrangement of repeating units is independent of the type. Each repeating unit may be a mixture of structural isomers instead of a single unit.)

As Z ² , particularly preferred structures include the following two structures, among which those in which d is an integer of 0-10 and e is an integer of 0-10 are preferred.
_{-CH2 [ OC2H4 ] dOC2H4- _
-CH2} [ _OC3H6 ] _{eOCH2CH ( CH3} ) _-

Z ² may also include the following structures.

In the above formula (3), Z ³ is a linkage consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom. A group, which may contain a cyclic structure in the middle, and a portion of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. Examples of suitable structures for such Z ³ include the following structural groups.
_{-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _}

Among these, -CH ₂ CH ₂ -
_{-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _}
is preferred.

（式中、Ｚ³、Ｑ¹、ａは上記の通りであり、Ｒｆ’は－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_m（ＣＦ₂ＣＦ₂Ｏ）_nＣＦ₂－であり、ｍ、ｎ、ｍ＋ｎは上記と同じであり、－（ＣＦ₂Ｏ）－と－（ＣＦ₂ＣＦ₂Ｏ）－の配列はランダムであり、Ｒ³は水素原子又はメチル基であり、ｄ１、ｅ１は０～１０の整数であり、かつ式（４）、（５）で表される化合物において、フッ素含有率は２５質量％以上４５質量％未満である。）As the fluorine-containing acrylic compound represented by the above formula (3), more preferable structures include those represented by the following general formulas (4) and (5).

(wherein Z ³ , Q ¹ and a are as defined above, Rf' is -CF ₂ O(CF ₂ O) _m (CF ₂ CF ₂ O) _n CF ₂ -, m, n, m+n is the same as above, the arrangement of -(CF ₂ O)- and -(CF ₂ CF ₂ O)- is random, R ³ is a hydrogen atom or a methyl group, d1 and e1 are 0 to 10 In the compounds represented by formulas (4) and (5), which are integers, the fluorine content is 25% by mass or more and less than 45% by mass.)

（式中、Ｒｆ’は上記と同じであり、例えばｎ／ｍ＝０．９、ｍ＋ｎ≒４５である。ｅ２は１～１０の整数であり、例えば４である。）Specific examples of component (B) include those shown below.

(Wherein, Rf' is the same as above, for example n/m = 0.9, m + n ≈ 45. e2 is an integer of 1 to 10, for example 4.)

Further, the fluorine-containing acrylic compound represented by the formula (3) of the component (B) can be synthesized, for example, by the methods disclosed in JP-A-2010-285501 and JP-A-2015-199910.

（式中、Ｒｆ²、Ｚ³、Ｑ¹、ａは上記と同じであり、［ ］で括られたａ個のＨはすべてＱ¹構造中のケイ素原子と結合している。）
で表される多官能Ｓｉ－Ｈ基を有するフルオロポリエーテル化合物と、下記一般式（１１）
ＣＨ₂＝ＣＲ¹－Ｚ²－ＯＨ （１１）
（式中、Ｒ¹、Ｚ²は上記と同じである。）
で表される末端不飽和基含有アルコール（分子末端にアルケニル基と水酸基を有する化合物）とをヒドロシリル化反応させることにより、中間体である含フッ素アルコール化合物を得ることができる。For example, the fluorine-containing acrylic compound represented by the above formula (3) is first represented by the following general formula (10)

(In the formula, Rf ² , Z ³ , Q ¹ , and a are the same as above, and all a Hs enclosed in brackets [ ] are bonded to silicon atoms in the Q ¹ structure.)
and a fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (11)
_CH2 = ^CR1 - ^Z2 -OH (11)
(In the formula, R ¹ and Z ² are the same as above.)
A fluorine-containing alcohol compound, which is an intermediate, can be obtained by hydrosilylating a terminally unsaturated group-containing alcohol represented by (a compound having an alkenyl group and a hydroxyl group at the molecular terminal).

（式中、Ｒｆ’は上記と同じである。）Here, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (10) include those shown below.

(In the formula, Rf' is the same as above.)

Examples of terminal unsaturated group-containing alcohols represented by the formula (11) are shown below.
_CH2 =CH- _{CH2 -OCH2CH2} - _OH
CH2 =CH- _CH2 - _OCH2CH ( _CH3 )-OH
_CH2 =CH- _CH2- ( _OC3H6 ) _{2- OCH2CH} ( _CH3 ) _{-OH
CH2 =} CH- _CH2- ( _OC3H6 ) _{4- OCH2CH} ( _CH3 )-OH
_CH2 =CH- _CH2- ( _OC3H6 ) _{9- OCH2CH} ( _CH3 ) _-OH

In this hydrosilylation (addition) reaction, a fluoropolyether compound having a polyfunctional Si—H group represented by formula (10) and a terminal unsaturated group-containing alcohol represented by formula (11) are mixed, and platinum It is desirable to carry out the reaction at a reaction temperature of 50 to 150° C., preferably 60 to 120° C., for 1 minute to 48 hours, particularly 10 minutes to 12 hours, in the presence of a group metal-based addition reaction catalyst. If the reaction temperature is too low, the reaction may stop before the reaction proceeds sufficiently. If it is too high, the temperature rises due to the reaction heat of hydrosilylation, making the reaction uncontrollable and causing bumping or decomposition of the raw materials. There is

In this case, the reaction ratio between the fluoropolyether compound having a polyfunctional Si—H group represented by formula (10) and the terminal unsaturated group-containing alcohol represented by formula (11) is represented by formula (10). With respect to the total number of moles of H enclosed in [ ] of the fluoropolyether compound having a multifunctional Si—H group represented, the terminal unsaturated group-containing alcohol represented by the formula (11) is preferably used in an amount of 0.5 to 5 mol, particularly 0.9 to 2 mol, for the reaction. If the terminal unsaturated group-containing alcohol represented by formula (11) is too less than this, it may be difficult to obtain a highly soluble fluorine-containing alcohol compound. When removing the terminal unsaturated group-containing alcohol represented by the formula (11) after the reaction, conditions such as heating, reduced pressure, and extraction are changed so that excess unreacted alcohol It becomes necessary to make it stricter as much as .

The addition reaction catalyst can be, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium. Among them, compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, Alternatively, platinum supported on activated carbon can be used.
The amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a multifunctional Si—H group represented by formula (10). is preferable, and more preferably the amount is 0.2 to 1,000 ppm by mass.

The above addition reaction can be carried out without a solvent, but may be diluted with a solvent if necessary. At this time, as the diluent solvent, widely used organic solvents such as toluene, xylene and isooctane can be used. The fluoroalcohol compound is preferably soluble at the above reaction temperature. Examples of such solvents include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and partially fluorine-modified solvents such as fluorine-modified ether solvents such as methyl perfluorobutyl ether. is desirable, and m-xylene hexafluoride is particularly preferred.
When using a solvent, the amount used is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by formula (10), More preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with the solvent will be weak, and if it is more than this, the degree of dilution will become too high, which may lead to a decrease in the reaction rate.

After completion of the reaction, the unreacted terminal unsaturated group-containing alcohol represented by formula (11) and the diluent solvent are preferably removed by a known method such as distillation under reduced pressure, extraction, or adsorption, but reactions involving these The mixture can also be used for the next reaction as it is.

（式中、Ｒｆ’、ｅは上記と同じである。）Examples of the fluorine-containing alcohol compound obtained in this manner include those shown below.

(Wherein, Rf′ and e are the same as above.)

Then, by introducing a (meth)acryl group into the fluorine-containing alcohol compound obtained above, a fluorine-containing acrylic compound can be obtained. As a method for introducing a (meth)acrylic group into a fluorine-containing alcohol compound, one is a method of reacting with a (meth)acrylic acid halide represented by the following formula (12) to form an ester, and the other is a method of forming an ester by the following formula: A method of reacting with an isocyanate compound containing a (meth)acrylic group represented by (13) can be mentioned, and by these methods, the fluorine-containing acrylic compound aimed at by the present invention can be obtained.

_CH2 = ^CR3C (=O)X (12)
_CH2 = ^CR3C (=O) _{OCH2CH2 -} N=C=O (13)
(In the formula, R ³ and X are the same as above.)

Here, examples of the (meth)acrylic acid halide represented by formula (12) include those shown below.
_CH2 =CHC(=O)X
_CH2 =C( _CH3 )C(=O)X
(In the formula, X is the same as above.)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.

Examples of the (meth)acrylic group-containing isocyanate compound represented by formula (13) include those shown below.
_CH2 =CHC(=O) _{OCH2CH2 -} N=C=O
_CH2 =C( _CH3 )C(=O) _{OCH2CH2 -} N=C=O

These (meth)acrylic acid halides or (meth)acrylic group-containing isocyanate compounds may be reacted in an equimolar amount or more with respect to the total amount of hydroxyl groups in the fluorine-containing alcohol compound, and all the hydroxyl groups may be reacted. It suffices to introduce an average of 1 mol or more (meth)acrylic groups per 1 mol of the fluorine-containing alcohol compound. The isocyanate compound containing an acrylic group may not remain. Specifically, when the amount of fluorine-containing alcohol compound in the reaction system is x mol, and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is y mol, (meth)acrylic acid halide or isocyanate containing (meth)acrylic group The amount of the compound is preferably x mol or more and 2 y mol or less, and particularly preferably 0.6 y mol or more and 1.4 y mol or less. If the amount is too small, there is a high possibility that the fluorine-containing alcohol compound in which no (meth)acrylic group is introduced remains, and the solubility of the product may become low. If the amount is too large, it becomes difficult to remove unreacted (meth)acrylic acid halides or residual isocyanate compounds containing (meth)acrylic groups.

These reactions may be carried out by diluting with a suitable solvent as necessary. As such a solvent, any solvent that does not react with the hydroxyl group of the fluorine-containing alcohol compound, the halogen atom of the (meth)acrylic acid halide, or the isocyanate group of the isocyanate compound containing the (meth)acrylic group can be used without particular limitation. Specifically, hydrocarbon solvents such as toluene, xylene and isooctane, ether solvents such as THF, diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone. , m-xylene hexafluoride, benzotrifluoride and other fluorine-modified aromatic hydrocarbon solvents, and methyl perfluorobutyl ether and other fluorine-modified ether solvents. This solvent may be removed by a known technique such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution depending on the intended use.
The amount of the solvent to be used is not particularly limited, but is preferably 10 times or less with respect to the total mass of the reaction components. If too much solvent is used, there is a danger that the reaction rate will be greatly reduced.

Moreover, you may add a polymerization inhibitor as needed in the case of reaction. The polymerization inhibitor is not particularly limited, but those commonly used as polymerization inhibitors for acrylic compounds can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.
The amount of the polymerization inhibitor to be used may be determined based on the reaction conditions, post-reaction purification conditions, and final use conditions, and is not particularly limited, but is usually 0.01 to 5,000,000,000,000,000,000,000,000, or 000 ppm, particularly preferably 0.1 to 500 ppm.

When a (meth)acrylic acid halide is reacted with a fluorine-containing alcohol compound, it is particularly preferable to react acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester formation reaction is carried out by dropping the (meth)acrylic acid halide while mixing and stirring the reaction intermediate (fluorine-containing alcohol compound) and the acid acceptor. Usable acid acceptors include triethylamine, pyridine, and urea. The amount of the acid acceptor used is desirably about 0.9 to 3 times the number of moles of the (meth)acrylic acid halide charged. If it is too small, a large amount of untrapped acid will remain, and if it is too large, it will be difficult to remove the surplus acid acceptor.

The dropwise addition of the (meth)acrylic acid halide is carried out over 20-60 minutes while maintaining the temperature of the reaction mixture at 0-35°C. Stirring is then continued for an additional 30 minutes to 10 hours. After completion of the reaction, the unreacted (meth)acrylic acid halide, the salt generated by the reaction, the reaction solvent, etc. are removed by a method such as distillation, adsorption, filtration, washing, etc., and the reaction represented by the above formula (3) is obtained. A fluorine-containing acrylic compound can be obtained.

Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The (meth)acrylic acid esters produced can be removed by the same method as for removing unreacted (meth)acrylic acid halides, but they can also be used as they remain.

In the case of the reaction between the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group, the fluorine-containing alcohol compound and the isocyanate compound containing the (meth)acrylic group are stirred together with a solvent if necessary to initiate the reaction. proceed.

In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of catalysts include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctoate, tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetona)titanium, titanium isopropoxyoctylene glycol, and other titanate esters or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium dibutoxybis(ethylacetoacetate), zirconium tetraacetylacetonate, zirconium chelate compounds and the like are exemplified. These compounds are not limited to one of them, and can be used as a mixture of two or more of them. Titanium compounds and tin compounds, which have a particularly low impact on the environment, are preferably used. The reaction rate can be increased by adding 0.01 to 2% by weight, preferably 0.05 to 1% by weight, of these catalysts relative to the total weight of the reactants.

The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may become too slow, and if the reaction temperature is too high, polymerization of (meth)acrylic groups may occur as a side reaction.

After completion of the reaction, the unreacted isocyanate compound and reaction solvent are removed by distillation, adsorption, filtration, washing, or the like to obtain the fluorine-containing acrylic compound represented by the above formula (3).

Also, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The produced urethane acrylates can be removed in the same manner as the unreacted isocyanate compound, but they can also be used as they remain.

[Component (C)]
Component (C), which is the third essential component in the fluorine-containing curable composition of the present invention, does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups per molecule. It is a fluorinated acrylic compound. Component (C) also includes urethane acrylates having urethane bonds in the molecule, and compounds obtained by introducing two or more (meth)acryl groups to the side chains or terminals of various polymers by any method.

Such a non-fluorinated acrylic compound (C) may have two or more (meth)acrylic groups in one molecule, for example, 1,6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanurate ethylene oxide-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) Acrylates, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl)ethyl, glycerol tri(meth)acrylate, pentaerythritol Bi- to hexafunctional (meth)acrylics such as tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, etc. compounds, these (meth)acrylic compounds ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding (meth)acrylic acid to epoxy resins, and (meth)acrylic acid ester copolymers Examples include those containing a copolymer having a (meth)acryloyl group introduced into the side chain of the coalescence.

In addition, urethane acrylates, those obtained by reacting polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyisocyanate and a polyester with a terminal diol with a (meth)acrylate having a hydroxyl group, an excess of polyol It is also possible to use those obtained by reacting a polyisocyanate obtained by reacting the diisocyanate of (1) with a (meth)acrylate having a hydroxyl group. Among them, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and (meth)acrylate having a hydroxyl group selected from pentaerythritol tri(meth)acrylate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5 - Urethane acrylates reacted with a polyisocyanate selected from diisocyanatocyclohexane and diphenylmethane diisocyanate are preferred.

Component (C) can be used alone, but can also be used by blending a plurality of corresponding compounds in order to improve coatability and properties of the cured film.
In particular, a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group It is preferable to use a mixture of at least two kinds of acrylic compounds, including polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule, which are obtained by the following methods.

Here, polyfunctional acrylic compounds having two or more (meth)acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and Compounds obtained by modifying these with ethylene oxide or propylene oxide are exemplified.

Polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, and isophorone diisocyanate. And these trimers and bifunctional or trifunctional isocyanates are reacted with aliphatic diols, aliphatic polyols and polyacrylates having hydroxyl groups in side chains to bifunctional or higher polyisocyanates, Trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, di Pentaerythritol penta (meth) acrylate and those obtained by reacting ethylene oxide and propylene oxide modified products thereof, aliphatic polyols and polyacrylates having hydroxyl groups in side chains and 2-isocyanatoethyl (meth) acrylate, 1, It can be obtained by reacting an acrylic compound having an isocyanate group such as 1-(bisacryloyloxymethyl)ethyl isocyanate.

In addition, the component (C) may include not only a liquid component but also those obtained by modifying the surface of fine particles of a high molecular weight substance or inorganic filler fine particles with a (meth)acrylic group.

In the fluorine-containing curable composition of the present invention, the composition ratio of each component is 0.05 to 50 mass parts of component (A) and component (B) per 100 mass parts of component (C). part, particularly preferably 0.1 to 10 parts by mass, and the amount of component (A) blended with respect to 100 parts by mass of component (B) is 1 to 100 parts by mass, particularly preferably 3 to 50 parts by mass. It is desirable to have If the total amount of components (A) and (B) is too large relative to component (C), the performance of the hard coat film will deteriorate, and if it is too small, sufficient antifouling performance cannot be exhibited. If the amount of component (A) is too large relative to component (B), the solubility in component (C) may become too poor, resulting in poor coating. No difference can be seen for use in

The fluorine-containing curable composition of the present invention essentially comprises the above-described three components (A), (B), and (C), and a mixture of these components alone is cured by heat, electron beams, or the like. However, it is also possible to contain components other than these three components depending on workability and necessity.
In particular, by containing a photopolymerization initiator as component (D), it is possible to obtain a curable composition having enhanced curability when ultraviolet rays are used as active energy rays.

[Component (D)]
The photopolymerization initiator of component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, but preferably includes, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2 -hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4 ,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O- benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4- [4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, etc., may be used alone or in combination of two or more.

The content of component (D) can be appropriately determined according to the curing conditions and the desired physical properties of the composition. In particular, it is desirable that the amount is 1 to 10 parts by mass. If the amount added is less than this, the curability may be lowered, and if the amount is more than this, there is a risk that the physical properties after curing will be greatly affected.

These components (A), (B), (C), and (D) can be used as a single type of compound or a mixture of multiple compounds whose structure corresponds to the definition of each compound. In the case of a mixture of a plurality of compounds, the total mass of each compound group should be considered as the mass of each compound when considering the blending amount.

The fluorine-containing curable composition of the present invention may further contain active energy ray-reactive compounds other than (meth)acrylic groups, such as monofunctional acrylic compounds, thiol compounds, and maleimide compounds, as reactive diluents, depending on the purpose. , organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymer and inorganic fillers. can also

Organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol and diacetone alcohol; methylpropylketone, diethylketone, methylethylketone, methylisobutylketone, cyclohexanone and the like. ketones; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; propyl acetate, butyl acetate, cyclohexyl acetate, etc. and aromatics such as toluene, xylene, triethylbenzene and alkylbenzenes. The above solvents may be used singly or in combination of two or more.
The amount of the solvent used is not particularly limited, but is preferably 20 to 10,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of components (A) to (C) in total. .

In addition, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and fillers are not particularly limited, and known ones can be used. It can be used as long as the object of the present invention is not impaired.

Furthermore, it may contain by-products generated in the production of the components (A) and (B) in the present invention, residual unreacted components, etc., as long as they do not impair the object and effect of the present invention. As such a component, for example, the fluorine-containing alcohol compounds represented by the formulas (6) and (7) may remain as unreacted components.

Various hard coating agents containing the component (C) and various additives are commercially available from various companies. The fluorine-containing curable composition of the present invention may be obtained by adding component (A) and component (B) to such a commercially available hard coating agent. Commercially available hard coating agents include, for example, Arakawa Chemical Industries Co., Ltd. "Beam Set", Ohashi Chemical Industry Co., Ltd. "Ubik", Origin Electric Co., Ltd. "UV Coat", Cashew Co., Ltd. "Cashew UV", JSR Corporation "Desolite", Dainichiseika Kogyo Co., Ltd. "Seika Beam", Nippon Synthetic Chemical Co., Ltd. "Shiko", Fujikura Kasei Co., Ltd. "Fuji Hard", Mitsubishi Rayon Co., Ltd. "Diabeam", Musashi Paint Co., Ltd. "Ultrabine" etc. are mentioned.

In addition, even if a commercially available hard coating agent is used as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, and a heat stabilizer may be used depending on the purpose. Agents, antioxidants, surfactants, colorants, fillers, and the like can be additionally incorporated.

Components (C) and (D) as described above, and other additives that can be arbitrarily blended, are described, for example, by Technonet Co., Ltd., "Light Curing Technology Data Book, Material Edition" (2000, Technonet Co.), Photopolymer Konwakai ed. "Photopolymer Handbook" (1989, Industrial Research Institute), Sogo Gijutsu Center ed. 2003, CMC), Technical Information Institute, "Cure Defective/Inhibition Causes and Countermeasures in UV Curing" (2003, Technical Information Institute), Technical Information Institute, "Composition Design, Characteristic Evaluation and New Applications of UV Curing Resins". (Technical Information Association, 2017), CMC Publishing, "Market Status and Prospects for UV/EB Curing Materials and Products" (2007, CMC Publishing), Science & Technology, "Optimization of UV Curing Process" (2008) , Science & Technology), etc., and these can be used in any combination.

The method of blending the fluorine-containing curable composition of the present invention may be any method depending on the application, and is not particularly limited. It is desirable to be well mixed, for example, components (A) and (B) are mixed in the required ratio, diluted with a solvent if necessary, and then mixed with component (C) and other components, or A method of mixing the component (A) diluted with a solvent and the component (B) diluted with a solvent and mixing with the component (C) and other components is suitable.

The method of curing the fluorine-containing curable composition of the present invention is not particularly limited. However, when the photopolymerization initiator of component (D) is further contained, it can be cured with ultraviolet rays. In the case of curing with ultraviolet rays, ultraviolet irradiation can be performed in the air, but it is preferable to suppress the oxygen concentration to 5,000 ppm or less in order to prevent inhibition of curing by oxygen, and inert gases such as nitrogen, carbon dioxide, and argon. Curing under atmosphere is particularly preferred.

Further, as a general form of use of the fluorine-containing curable composition of the present invention, the fluorine-containing curable composition layer of the present invention may be applied onto any substrate as long as it adheres or adheres after curing. can, but especially resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymers, cyclo Olefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluorine resin, Resins such as nylon and acrylic resins can be used. They can be used on the surfaces of films, plates, and moldings of any shape.

In the case of coating on a film base material, it may have a structure in which an adhesive is applied to the opposite side of the fluorine-containing curable composition layer coated and formed. A mold film may be placed.

Further, the film substrate may be a substrate consisting of only the above-mentioned resin film. It may be a film substrate provided with a layer. Examples of the primer layer include those made of polyester-based resins, urethane-based resins, acrylic-based resins, and the like.

The fluorine-containing curable composition of the present invention may be coated and cured on a cured or uncured curable composition layer that does not correspond to the present invention. For example, the fluorine-containing curable composition of the present invention can be overcoated on a cured product layer having higher hardness, durability, antistatic properties, and anti-curling properties.

For the purpose of improving the adhesion with the fluorine-containing curable composition of the present invention, the surface of the resin substrate may be subjected to roughening treatment such as sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, and flame treatment. Treatment, hot air treatment, ozone/ultraviolet irradiation treatment, oxidation treatment, or the like can also be applied.

The method of applying the fluorine-containing curable composition of the present invention to the substrate or article is not particularly limited, but examples include roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, and spin coating. , bar coating, screen printing, and other known coating methods can be used.

After coating, the coating film is irradiated with active energy rays to cure it. Here, as the active energy ray, an electron beam, ultraviolet rays, or any other rays can be used, but ultraviolet rays are particularly preferable. Mercury lamps, metal halide lamps, and LED lamps are suitable as ultraviolet light sources. The amount of UV irradiation is 10 to 10,000 mJ/ ^cm.sup.2 , especially 100 to 4,000 mJ/cm. It is desirable to be in the range of ² .

In addition, in order to prevent curing inhibition due to oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, argon, etc. during ultraviolet irradiation, and the coating film surface is treated with a UV-transmitting agent that has releasability. Cover with a protective layer and irradiate UV rays from above, or if the substrate has UV transparency, cover the coating surface with a protective layer that has releasability and then place it on the opposite side of the coated surface of the substrate You may irradiate an ultraviolet-ray from the side. In order to level the coating film or to effectively polymerize the (meth)acrylic groups in the coating film, the coating film and substrate are heated by any method such as infrared rays or a hot air drying furnace before and during UV irradiation. good too.

The thickness of the cured product layer of the fluorine-containing curable composition thus obtained is not particularly limited, but is preferably 0.01 to 5,000 μm, particularly 0.05 to 200 μm.

The cured product layer of the fluorine-containing curable composition of the present invention obtained in this manner was measured by measuring the angle formed by the liquid surface and the solid surface one second after contact with a 2 μL droplet of ion-exchanged water. A static water contact angle of 114° or more, particularly 115° or more, and a static oleic acid contact angle of 73° measured by the angle formed by the liquid surface and the solid surface one second after a 4 μL droplet of oleic acid comes into contact with the liquid. It is preferable to be able to have a water- and oil-repellent surface having an angle of 74° or more, particularly 74° or more. In addition, the cured product layer of the fluorine-containing curable composition of the present invention preferably has a water-repellent and oil-repellent surface with a low dynamic friction coefficient of 0.10 or less, particularly 0.09 or less. . In order to achieve the above contact angle and/or dynamic friction coefficient, the cured product layer of the fluorine-containing curable composition of the present invention must have an average thickness of 10 nm or more with respect to the total surface area of the cured product layer. It is preferable that it is an amount that can be made. In addition, it is preferable that no unreacted (meth)acrylic groups remain on the surface of the cured product layer. Therefore, it is preferable that the cured product layer is cured in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

As described above, the fluorine-containing curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and is excellent in water and oil repellency, antifouling properties, slipperiness and wear resistance on the surface of articles. A hardened resin layer can be formed.

Furthermore, the present invention provides an article having a cured film obtained by coating the surface of the fluorine-containing curable composition of the present invention and curing the composition. As described above, by using the fluorine-containing curable composition of the present invention, it is possible to form a cured film (cured resin layer) having excellent surface properties on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coat. As a result, fingerprints, sebum, human oils such as perspiration, dirt from cosmetics, etc., and machine oil are less likely to adhere, and a hard coat surface excellent in wiping properties can be provided to the substrate. For this reason, the fluorine-containing curable composition of the present invention is a substrate (article) that may be soiled by human oils, cosmetics, etc., when touched by a person, or may be soiled by workers' human oils, machine oils, etc. An antifouling coating or protective coating can be provided for surfaces such as process material films that are potentially used inside machinery.

The cured film (cured resin layer) formed using the fluorine-containing curable composition of the present invention can be used for tablet computers, notebook PCs, portable (communication) information terminals such as mobile phones and smart phones, digital media players, and electronic books. Casings for various devices such as readers, watch-type/glass-type wearable computers, head-mounted displays, liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, vacuum fluorescent display (VFD), field emission projection displays , CRT, toner-based displays, quantum dot (QD) displays and other flat panel displays, TV screens and other display operation device surfaces and various optical films used inside these, automobile exteriors, pianos and furniture Glossy surfaces, architectural stone surfaces such as marble, decorative building materials around water such as toilets, baths, washrooms, etc. Protective glass for displaying works of art, show windows, showcases, covers for photo frames, watches, exteriors and decorations for cosmetic containers Exterior of product containers, window glass for automobiles, window glass for trains, aircraft, etc., transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlights and tail lamps, automotive sensors such as millimeter wave radar It is useful as a coating film and a surface protective film for cover members of various mirror members.

In particular, various devices having a display input device such as a touch panel display for operating on the screen with a human finger or palm, such as tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, smart watches , Digital Media Players, Electronic Book Readers, Digital Photo Frames, Game Machines, Digital Cameras, Digital Video Cameras, GPS Display Recording Devices, Navigation Devices for Automobiles, etc., Control Panels for Automobiles, etc., Automatic Cash Drawer and Deposit Equipment, Cash Automatic It is useful as a surface protective film for payment machines, vending machines, digital signage (electronic signboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

Further, the cured film formed from the fluorine-containing curable composition of the present invention can be used for optical recording media such as magneto-optical discs and optical discs; It is also useful as a surface protective film for lenses, antireflection films, various camera lenses, protective filters for various lenses, and optical parts and optical devices such as optical fibers and optical couplers.

As described above, the fluorine-containing curable composition of the present invention can be repelled by disposing the fluoropolyether structure in the compounds of the components (A) and (B) according to the present invention on the surface of the target article. The essence is to provide excellent properties such as water resistance, oil repellency, slipperiness, antifouling properties, inconspicuous fingerprints, fingerprint wiping properties, abrasion resistance, low refractive index properties, solvent resistance, and chemical resistance. there is

When using such a fluorine-containing curable composition of the present invention, an appropriate usage method is known according to each application, depending on the combination of compounds, composition ratio, and what kind of characteristics are emphasized. can be selected based on the technology of Such known techniques can be included in the scope of examination including not only those for fluorine-containing compositions, but also methods used for existing active energy ray-curable compositions.

For example, when blending and preparing the fluorine-containing curable composition of the present invention, in addition to the components (A) and (B) according to the present invention, when combining various formulations in the above-described fluorine-containing curable composition In addition, when emphasizing low refractive index characteristics and low reflection characteristics using this, reactive hollow silica, hollow silica having no reactive group, or trifunctional or higher non-fluorine-based component (C) In the case of using a polyfunctional acrylic compound and improving the film strength and scratch resistance, two or more non-fluorine-based polyfunctional acrylic compounds are blended in a suitable amount as the component (C), or hardness In order to balance flexibility, it is possible to perform a combination of a non-fluorinated hexafunctional or higher polyfunctional acrylic compound and a trifunctional or lower acrylic compound as the component (C). Known acrylic curable compositions It can be easily inferred from knowledge of compounding.
When obtaining an article by applying the fluorine-containing curable composition of the present invention, for example, when applying the composition to a film substrate, the coating thickness is adjusted to prevent interference fringes. By adjusting the thickness of the film base material to make it easier to suppress curling, and by adjusting the elastic modulus of the base film, deformation and coating after curing of the fluorine-containing curable composition can be prevented. Suppression of film cracking, etc., can be achieved easily by combining the present invention and existing technology by performing screening work based on a combination of existing conditions according to each characteristic.

Synthesis examples, examples, and comparative examples are shown below to specifically describe the present invention, but the present invention is not limited to the following examples.

[Synthesis Example 1] Synthesis of fluorine-containing acrylic compound (A-1) In a 300 L four-necked flask equipped with a reflux device and a stirring device,
_{HOCH2CF2O ( CF2CF2O )20.1 ( CF2O} ) _21.6CF2CH2OH ( _{I )}
100 g (OH group: 0.0508 mol) of a compound represented by the following formula (II) (wherein the arrangement of repeating units of -CF ₂ CF ₂ O- and -CF ₂ O- is random)
_CH2 =CHC(=O) _{OCH2CH2 -} N=C=O (II)
7.17 g of the compound represented by and 200 g of hexafluorometaxylene were charged and heated to 40° C. while stirring in a dry air atmosphere. Then, 0.01 g of dioctyltin dilaurate was added, and heating and stirring were continued for 6 hours, after which the heating was stopped. According to ¹⁹ F-NMR of the reaction solution, the peaks (-81.1 ppm, -83.15 ppm) derived from CF ₂ of -OCF ₂ CH ₂ OH are all derived from -OCF ₂ CH ₂ OC(=O)-. It was confirmed that it changed to (-78.4 ppm, -80.4 ppm). 2 g of activated carbon was added to the obtained reaction solution, and the mixture was stirred at room temperature for 3 hours, and then filtered with a filter plate. The obtained filtrate was distilled off under reduced pressure at 50° C. to obtain 97.8 g of the desired compound having the following average structure (A-1) with a fluorine content of 57.5 mass %.
_CH2 =CHC( ₌ O) _{OCH2CH2NHC ( = O ) OCH2CF2O ( CF2CF2O ) 20.1} ( _CF2O ) _21.6CF2CH2OC (=O)NHCH2CH2OC (=O) CH=CH ₂ (A-1)

[Synthesis Example 2] Synthesis of fluorine-containing acrylic compound (A-2) In Synthesis Example 1, instead of the above formula (I), the following formula (III) as an average structure
_{HOCH2CF2O ( CF2CF2O ) 31.1 ( CF2O ) 30.5CF2CH2OH}
(III)
Using 100 g (OH group: 0.0345 mol) of the compound represented by the above formula (II) (wherein the arrangement of the repeating units of —CF ₂ CF ₂ O— and —CF ₂ O— is random), The same procedure as in Synthesis Example 1 was performed except that the amount was changed to 4.86 g, and 96.2 g of the following compound (A-2) having a fluorine content of 59.2% by mass as an average structure was obtained. .
_{CH2 =} CHC(=O) _OCH2CH2NHC (=O _{) OCH2CF2O ( CF2CF2O ) 31.1 ( CF2O} ) _30.5CF2CH2OC (= _O ) _NHCH2CH2OC (=O) CH=CH ₂ (A-2)

[Synthesis Example 3] Synthesis of fluorine-containing acrylic compound (A-3) In a 300 L four-necked flask equipped with a reflux device and a stirrer, 100 g of the compound of formula (I) (OH group: 0.0508 mol) and 7.20 g of triethylamine were added. , 150 g of hexafluorometa-xylene was added dropwise over 30 minutes while stirring at room temperature in a dry air atmosphere. Stirring was continued for 6 hours and then stopped, followed by filtration with filter paper. The resulting filtrate was poured into 1,000 g of hexane, the generated precipitate was recovered, dissolved in 100 g of hexafluorometa-xylene, the solvent was distilled off under reduced pressure at 50° C., and the desired product was obtained by ¹⁹ F-NMR. It was confirmed that 90.5 g of compound (A-3) having a fluorine content of 60.0% by mass and having the following average structure was obtained.
_{CH2 =CHC(=O)OCH2CF2O(CF2CF2O)20.1 ( CF2O ) 21.6CF2CH2OC ( =} O)CH= _{CH2 (} A _- 3)

[Synthesis Example 4] Synthesis of fluorine-containing acrylic compound (A-4) In Synthesis Example 1, instead of the above formula (I), the following formula (IV) as an average structure
_{CF3O ( CF2CF2O} ) _20.1 ( _CF2O ) _{19.2CF2CH2OH (} IV ₎
Using 100 g (0.0264 mol of OH groups) of the compound represented by the above formula (II) (wherein the arrangement of repeating units of —CF ₂ CF ₂ O— and —CF ₂ O— is random), The same procedure as in Synthesis Example 1 was repeated except that the amount was changed to 4.11 g and 0.2 g of tetrakis(2-ethylhexyl) orthotitanate was used instead of dioctyltin dilaurate. 97.5 g of compound (A-4) having a fluorine content of 60.2% by mass was obtained.
_CF3O ( _{CF2CF2O ) 20.1} ( _CF2O ) _19.2CF2CH2OC (=O) _{NHCH2CH2OC (} =O)CH= _CH2 (A _- 4 ₎

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_20.9（ＣＦ₂Ｏ）_21.2ＣＦ₂－
乾燥空気雰囲気下で、上記で得られた化合物（Ｖ）５０．０ｇ（Ｓｉ－Ｈ基量０．０６５７ｍｏｌ）に対して、２－アリルオキシエタノール７．０５ｇ（０．０６９０ｍｏｌ）、ｍ－キシレンヘキサフロライド５０．０ｇ、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０４４２ｇ（Ｐｔ単体として１．１×１０^-7ｍｏｌを含有）を混合し、１００℃で４時間攪拌した。¹Ｈ－ＮＭＲ及びＩＲでＳｉ－Ｈ基が消失したのを確認した後、溶剤と過剰の２－アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物（ＶＩ）５４．９ｇを得た。

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_20.9（ＣＦ₂Ｏ）_21.2ＣＦ₂－
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物（ＶＩ）５０．０ｇ（水酸基量０．０５８ｍｏｌ）に対して、ＴＨＦ５０．０ｇとアクリロイルオキシエチルイソシアネート９．００ｇ（０．０６３８ｍｏｌ）を混合し、５０℃に加熱した。そこにオルトチタン酸テトラキス（２－エチルヘキシル）０．１５ｇを添加し、５０℃下２４時間攪拌した。加熱終了後、８０℃／０．２６６ｋＰａで減圧留去を行い、淡黄色のペースト状物質５８．５ｇを得た。¹Ｈ－ＮＭＲ及びＩＲの結果から下記に示す、フッ素含有率４１．０質量％の含フッ素アクリル化合物であることを確認した。

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_20.9（ＣＦ₂Ｏ）_21.2ＣＦ₂－[Synthesis Example 5] Synthesis of fluorine-containing acrylic compound (B-1) In a 5,000 mL three-necked flask equipped with a reflux device and a stirrer under a dry nitrogen atmosphere, the following formula CH ₂ ═CH—CH ₂ —O was added. _-CH2 -Rf'-CH2 _- O- _CH2 -CH= _CH2
Rf ': _{-CF2O ( CF2CF2O} ) _20.9 ( _CF2O ) _21.2CF2-
1,000 g (0.245 mol) of perfluoropolyether represented by , 1,400 g of m-xylene hexafluoride, and 722 g (3.00 mol) of tetramethylcyclotetrasiloxane were charged and heated to 90°C while stirring. heated. 0.884 g of a toluene solution of a platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 2.2×10 ⁻⁶ mol as Pt alone) was added thereto, and the internal temperature was maintained at 90° C. or higher. Stirring was continued for 4 hours. After confirming the disappearance of the starting allyl group by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, the mixture was treated with activated carbon to obtain 993 g of a colorless and transparent liquid compound (V) represented by the following formula.

_Rf ': _{-CF2O ( CF2CF2O} ) _20.9 ( _CF2O ) _21.2CF2-
In a dry air atmosphere, 7.05 g (0.0690 mol) of 2-allyloxyethanol, m-xylene hexa 50.0 g of fluoride and 0.0442 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 1.1×10 ⁻⁷ mol as Pt alone) were mixed and stirred at 100° C. for 4 hours. After confirming the disappearance of the Si—H group by ¹ H—NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and the residue was treated with activated carbon to give a pale yellow transparent liquid represented by the following formula. 54.9 g of fluorine-containing alcohol compound (VI) was obtained.

_Rf ': _{-CF2O ( CF2CF2O} ) _20.9 ( _CF2O ) _21.2CF2-
In a dry air atmosphere, 50.0 g of the obtained fluorine-containing alcohol compound (VI) (0.058 mol of hydroxyl group) was mixed with 50.0 g of THF and 9.00 g (0.0638 mol) of acryloyloxyethyl isocyanate, Heated to 50°C. 0.15 g of tetrakis(2-ethylhexyl) orthotitanate was added thereto and stirred at 50° C. for 24 hours. After completion of heating, distillation under reduced pressure was carried out at 80° C./0.266 kPa to obtain 58.5 g of a pale yellow pasty substance. From the results of ¹ H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound with a fluorine content of 41.0% by mass as shown below.

_Rf ': _{-CF2O ( CF2CF2O} ) _20.9 ( _CF2O ) _21.2CF2-

Ｒｆ”：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_9.8（ＣＦ₂Ｏ）_9.1ＣＦ₂－
乾燥空気雰囲気下で、上記で得られた化合物（ＶＩＩ）５０．０ｇ（Ｓｉ－Ｈ基量０．１２１ｍｏｌ）に対して、２－アリルオキシエタノール１５．１ｇ（０．１４９ｍｏｌ）、ｍ－キシレンヘキサフロライド１００．０ｇ、及び塩化白金酸／ビニルシロキサン錯体のトルエン溶液０．０８８４ｇ（Ｐｔ単体として２．２×１０^-7ｍｏｌを含有）を混合し、１００℃で４時間攪拌した。¹Ｈ－ＮＭＲ及びＩＲでＳｉ－Ｈ基が消失したのを確認した後、溶剤と過剰の２－アリルオキシエタノールを減圧溜去し、活性炭処理を行い、下記式で示される淡黄色透明の液体含フッ素アルコール化合物（ＶＩＩＩ）６０．２ｇを得た。

Ｒｆ”：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_9.8（ＣＦ₂Ｏ）_9.1ＣＦ₂－
乾燥空気雰囲気下で、得られた含フッ素アルコール化合物（ＶＩＩＩ）５０．０ｇ（水酸基量０．０９７ｍｏｌ）に対して、ＴＨＦ５０．０ｇとアクリロイルオキシエチルイソシアネート１７．7ｇ（０．１２５ｍｏｌ）を混合し、５０℃に加熱した。そこにジオクチル錫ジラウレート０．０５ｇを添加し、５０℃下２４時間攪拌した。加熱終了後、８０℃／０．２６６ｋＰａで減圧留去を行い、淡黄色の高粘調液体６３．５ｇを得た。¹Ｈ－ＮＭＲ及びＩＲの結果から下記に示す、フッ素含有率２９．７質量％の含フッ素アクリル化合物であることを確認した。

Ｒｆ”：－ＣＦ₂Ｏ（ＣＦ₂ＣＦ₂Ｏ）_9.8（ＣＦ₂Ｏ）_9.1ＣＦ₂－[Synthesis Example 6] Synthesis of fluorine-containing acrylic compound (B-2) In a 500 mL three-necked flask equipped with a reflux device and a stirrer under a dry nitrogen atmosphere, the following formula CH ₂ ═CH—CH ₂ —O—CH ₂ -Rf" _-CH2- O- _CH2 -CH= _CH2
Rf": -CF ₂ O (CF ₂ CF ₂ O) _9.8 (CF ₂ O) _9.1 CF ₂ -
100 g (0.0501 mol) of perfluoropolyether represented by , 100 g of m-xylene hexafluoride, and 121 g (0.502 mol) of tetramethylcyclotetrasiloxane were added and heated to 90°C while stirring. 0.442 g of a toluene solution of a platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ⁻⁶ mol as Pt alone) was added thereto, and the internal temperature was maintained at 90° C. or higher. Stirring was continued for 4 hours. After confirming the disappearance of the starting allyl group by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed to obtain 112 g of a colorless and transparent liquid compound (VII) represented by the following formula.

Rf": -CF ₂ O (CF ₂ CF ₂ O) _9.8 (CF ₂ O) _9.1 CF ₂ -
In a dry air atmosphere, 15.1 g (0.149 mol) of 2-allyloxyethanol, m-xylenehexa 100.0 g of fluoride and 0.0884 g of a toluene solution of a chloroplatinic acid/vinylsiloxane complex (containing 2.2×10 ⁻⁷ mol of Pt alone) were mixed and stirred at 100° C. for 4 hours. After confirming the disappearance of the Si—H group by ¹ H—NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure, and the residue was treated with activated carbon to give a pale yellow transparent liquid represented by the following formula. 60.2 g of fluorine-containing alcohol compound (VIII) was obtained.

Rf": -CF ₂ O (CF ₂ CF ₂ O) _9.8 (CF ₂ O) _9.1 CF ₂ -
In a dry air atmosphere, 50.0 g of THF and 17.7 g (0.125 mol) of acryloyloxyethyl isocyanate were mixed with 50.0 g of the obtained fluorine-containing alcohol compound (VIII) (0.097 mol of hydroxyl group), Heated to 50°C. 0.05 g of dioctyltin dilaurate was added thereto and stirred at 50° C. for 24 hours. After completion of heating, distillation under reduced pressure was carried out at 80° C./0.266 kPa to obtain 63.5 g of a pale yellow highly viscous liquid. From the results of ¹ H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound with a fluorine content of 29.7 mass % shown below.

Rf": -CF ₂ O (CF ₂ CF ₂ O) _9.8 (CF ₂ O) _9.1 CF ₂ -

[Examples 1 to 11, Comparative Examples 1 to 7]
Raw material components of the fluorine-containing curable composition of the present invention are shown below.
(A) Fluorine-containing acrylic compound (A-1) Fluorine-containing acrylic compound obtained in Synthesis Example 1 (A-2) Fluorine-containing acrylic compound obtained in Synthesis Example 2 (A-3) Obtained in Synthesis Example 3 Fluorine-containing acrylic compound (A-4) Fluorine-containing acrylic compound obtained in Synthesis Example 4 (B) Fluorine-containing acrylic compound (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 5 (B-2) Synthesis Fluorine-containing acrylic compound obtained in Example 6 (C) Non-fluorinated acrylic compound (C-1) Pentaerythritol ethoxy tetraacrylate [EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.]
(C-2) Pentaerythritol triacrylate (C-3) Polyfunctional acrylate composed of a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]
(D) Photopolymerization initiator (D-1) 1-hydroxycyclohexylphenyl ketone (trade name: IRGACURE 184, manufactured by BASF Japan)
(D-2) 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: IRGACURE 127, BASF Japan) made)

[Preparation of fluorine-containing curable composition]
All components (A) and (B) were diluted with methyl ethyl ketone to 20% by mass, and component (C) was diluted with butyl acetate to 40% by mass. In addition, 2-propanol was used instead of butyl acetate as the diluting solvent of (C-1) and diluted to 40% by mass was blended as (C-4).
Components (A) to (D) were mixed so as to have the compounding ratio shown in Table 1 below, excluding the solvent component, to obtain a fluorine-containing curable composition.

[Dissolution state of composition]
The dissolution state (appearance of coating liquid) of each composition was visually observed. Further evaluation was not performed for the composition in which a precipitate was generated. Table 2 shows the results.

Coating and preparation of cured product Each composition of Examples and Comparative Examples was coated on a polycarbonate substrate with a wire bar No. 1. 7 (wet film thickness: 16.0 µm). After drying at 100°C for 1 minute after coating, the coated surface was irradiated with UV rays with an accumulated irradiation dose of 400 mJ/cm ² in a nitrogen atmosphere using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works). The composition was cured with a mortar to obtain a cured film having a thickness of 5 μm.

[Evaluation of water and oil repellency]
1) Measurement of Water Contact Angle Using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.), a water droplet of 2 μL was dropped on the cured film, and the water contact angle was measured one second later. The average value of N=5 was used as the measured value. Table 2 shows the results.
2) Oleic acid contact angle measurement Using a contact angle meter (DropMaster, manufactured by Kyowa Interface Science Co., Ltd.), a droplet of 4 μL of oleic acid was dropped on the cured film, and the oleic acid contact angle was measured one second after. The average value of N=5 was used as the measured value. Table 2 shows the results.

[Measurement of dynamic friction coefficient]
The dynamic friction coefficient of the cured film against BEMCOT (manufactured by Asahi Kasei Corp.) was measured under the following conditions using a surface property tester 14FW (manufactured by Shinto Kagaku Corp.). Table 2 shows the results.
Contact area: 10mm x 35mm
Load: 100g

[Evaluation of magic repellency]
A straight line was drawn on the surface of the cured film with a magic pen (Himakkie bold type, manufactured by Zebra), and the degree of repelling was evaluated by visual observation. Table 2 shows the results.

[Evaluation of magic wiping performance]
Draw a straight line on the surface of the cured film with a magic pen (Himackey Bold by Zebra), and after 1 minute, lightly rub it 3 times with a tissue paper. was evaluated as "cannot be wiped off". Table 2 shows the results.

As is clear from the above results, the compositions of Comparative Examples 1 to 3, in which only the components (A) and (C) were blended without blending the component (B), had a poor dissolution state of the composition and formed precipitates. However, the compositions of Examples 1 to 11 of the present invention, in which components (A), (B), and (C) are blended, can prepare a transparent and uniform coating liquid, and the The compositions of Examples 1 to 11 did not contain the component (A) and had higher liquid repellency than the compositions of Comparative Examples 4, 5 and 7 containing only the components (B) and (C). A slippery surface can be formed.

Claims (11)

A linear polymer having a fluoropolyether as the main chain, having one or two (meth)acrylic groups at one or both ends of the molecular chain, and the (meth)acrylic group contained in one molecule The following general formula (1) or (2) consisting of a compound having an average number of 2 or less and a fluorine content of 48% by mass or more and less than 62% by mass
Rf ¹ -O-Rf ² -CF ₂ -Z ¹ -X ¹ (1)
X ² -Z ¹ -CF ₂ O-Rf ² -CF ₂ -Z ¹ -X ¹ (2)
(In the formula, Rf ¹ is a fluorine atom or a monovalent fluorine-containing alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, and Rf ² is one of the following two types of repeating units —CF ₂ O—
_{-CF2CF2O- _}
is a randomly arranged divalent perfluoropolyether group with a molecular weight of 600 to 20,000. Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and - A linking group selected from C(=O)O—, the divalent hydrocarbon group may contain a cyclic structure in the middle, and some of the hydrogen atoms bonded to the carbon atoms are substituted with fluorine atoms. may X ¹ is independently a monovalent organic group having a (meth)acryl group optionally containing an oxygen atom and/or a nitrogen atom, and X ² is a hydroxyl group or X ¹ . )
Component (A) represented by
Each molecule of a linear polymer having a fluoropolyether as a main chain has two or more (meth)acrylic groups at each molecular chain end, and an average of 4 to 10 (meth)acrylic groups per molecule. ) The following general formula (3), which has an acrylic group and is composed of a compound having a fluorine content of 25% by mass or more and less than 45% by mass

(In the formula, Rf ² is the same as above. Q ¹ is an (a+1)-valent linking group that independently contains at least (a+1) silicon atoms and may have a cyclic structure. a is 2 is an integer of up to 5. Z ² is each independently a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain an oxygen atom and/or a nitrogen atom, and which may contain a cyclic structure in the middle; R ¹ is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, R ² is independently a hydrogen atom, or a (meth)acryl optionally containing an oxygen atom and/or a nitrogen atom; with the proviso that R ² has 2 or more at each end in one molecule and 4 to 10 of the above-mentioned monovalent organic groups on average in one molecule. Z ³ is a linking group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one heteroatom independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and has a cyclic structure in the middle; may contain, and some of the hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms.)
A component (B) represented by and a component (C) consisting of a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of two or more (meth)acrylic groups in one molecule (C) as an essential component and the total amount of component (A) and component (B) is 0.1 to 10 parts by mass with respect to 100 parts by mass of component (C), and component (A ) in an amount of 3 to 50 parts by mass. 2. The fluorine-containing curable composition according to claim 1, further comprising a photopolymerization initiator (D). 3. The fluorine-containing curable composition according to claim 1, wherein the amount of component (A) is 5.26 to 25 parts by mass per 100 parts by mass of component (B). 4. The fluorine-containing curable composition according to any one of claims 1 to 3, wherein in component (A), Z ¹ in general formula (1) or (2) has any of the following structures.
-C(=O)-
-C(=O)O-
-C(=O) _OCH2-
-C ₍ =O) _{OCH2CH2-
-CH2-}
-CH ₂ O-
_{-CH2OCH2- _
-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OC} (=O)NH-
_{-CH2OC (} =O) _NHCH2CH2- 5. The fluorine-containing curable composition according to any one of claims 1 to 4, wherein in component (A), X ¹ in general formula (1) or (2) is represented by any one of the following: .
-OC(=O)CH= _CH2
-OC(=O)C( _CH3 )= _CH2
- CH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (=O)C( _CH3 )= _CH2 ]
-C( _CH3 )[ _CH2OC (=O)CH= _CH2 ] ₂
- C( _CH2CH3 )[ _CH2OC (=O)CH _{= CH2} ] ₂
-C( _CH2CH3 )[ _CH2OC ( ₌ O)C( _CH3 )= _CH2 ] ₂ 6. The fluorine-containing acrylic compound according to any one of claims 1 to 5, wherein in component (A), the fluorine-containing acrylic compound represented by general formula (1) or (2) is represented by any one of the following: Curable composition.
^{Rf1ORf2CF2CH2OC} (= _O ) _{CH =} ^{CH2
Rf1ORf2CF2CH2OC} (= _O ) _C ( _CH3 ) ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC ( =} ^O )CH _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( _{= O} )C ⁽ _CH3 ) _{= CH2}
^Rf1ORf2CF2C (=O) _OCH2CH2OC (= ^O ) _{CH = CH2}
^Rf1ORf2CF2C _{( =} O) _OCH2CH2OC (= ^O )C( _CH3 )= _{CH2
HOCH2CF2ORf2CF2C ( =} O) ^OCH2CH2OC (= _O )CH _{= CH2
HOCH2CF2ORf2CF2C} ( ₌ O) ^OCH2CH2OC ₍ = _O )C( _CH3 ) _{= CH2}
^Rf1ORf2CF2C (=O)OCH[ _CH2OC (=O)CH= _CH2 ][ _CH2OC (= _O ) _C ( ^CH3 )= _CH2 ]
^{Rf1ORf2CF2CH2OC} ( ₌ O) _NHCH2CH2OC ( ₌ ^O )CH _{= CH2}
^{Rf1ORf2CF2CH2OC} (=O) _{NHCH2CH2OC ( =} ^O )C( _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC ( =} O) _NHCH2CH2OC (= _{O )} CH ₌ ^CH2
_{HOCH2CF2ORf2CF2CH2OC} (=O) _NHCH2CH2OC ( _{= O )} C ⁽ _CH3 ) _{= CH2
HOCH2CF2ORf2CF2CH2OC} ( ₌ O)NHC ⁽ _CH3 )[ _{CH2OC (} = _O )CH= _CH2 ] _2
CH2 =C( _{CH3 )} ^C ₍ =O)OCH2CF2ORf2CF2CH2OC(= _O )C( _{CH3 )} = _{CH2
CH2 =} ^CHC (= _O ) _{OCH2CF2ORf2CF2CH2OC} (=O)C( _CH3 ) _{= CH2
CH2 = CHC (} =O) _{OCH2CF2ORf2CF2CH2OC} (=O)CH ₌ ^CH2
_CH2 = _CHC ⁽ = _{O ) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC( _{= O} ) _CH = _CH2
CH2 =C _{( CH3} ) ^C ( ₌ O _{) OCH2CH2NHC} (=O)OCH2CF2ORf2CF2CH2OCH2OC(= _O )C( _{CH3 ) = CH2
CH2} = _CHC (=O) _OCH2CH2NHC (=O)OCH2CF2ORf2CF2CH2OC( ⁼ _O ) _{NHCH2CH2OC (} = _{O )} CH _{= CH2}
(In the formula, Rf ¹ and Rf ² are the same as above.) 7. The fluorine-containing curable composition according to any one of claims 1 to 6, wherein in component (B), Z ³ in general formula (3) is represented by any one of the following formulae.
_{-CH2CH2- _
-CH2CH2CH2- _ _
-CH2CH2CH2CH2- _ _ _
-CH2OCH2CH2- _ _
-CH2OCH2CH2CH2- _ _ _} 8. The fluorine-containing curable composition according to any one of claims 1 to 7, wherein in component (B), Q ¹ in general formula (3) is represented by the following formula.

(In the formula, a1 is 2 or 3.) 9. Any one of claims 1 to 8, wherein in the component (B), the fluorine-containing acrylic compound represented by the general formula (3) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5). Fluorine-containing curable composition according to the item.

(wherein Z ³ , Q ¹ and a are as defined above, Rf′ is —CF ₂ O(CF ₂ O) _m (CF ₂ CF ₂ O) _n CF ₂ —, m is 1 to 200 n is an integer of 1 to 170, m+n is an integer of 6 to 201, the arrangement of -(CF ₂ O)- and -(CF ₂ CF ₂ O)- is random, and R ³ is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and the fluorine content in the compounds represented by formulas (4) and (5) is 25% by mass or more and less than 45% by mass.) The non-fluorinated acrylic compound of component (C) is a polyfunctional acrylic compound having two or more (meth)acrylic groups in one molecule and no urethane bond, or this polyfunctional acrylic compound and an aliphatic polyisocyanate. Polyfunctional urethane acrylates having 3 or more (meth)acrylic groups in one molecule obtained by reacting with an acrylic compound having a hydroxyl group, or two types including the polyfunctional acrylic compound and urethane acrylates The fluorine-containing curable composition according to any one of claims 1 to 9, which is a mixture of the above acrylic compounds. An article having on its surface a cured film of the fluorine-containing curable composition according to any one of claims 1 to 10.