JP2017002216A - Active energy ray curable composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable composition capable of providing a surface having stable solubility and excellent antifouling property after curing and further capable of adjusting slipperiness of a surface after curing and an article having a cured coated film of the composition.SOLUTION: There is provided a non-fluorinated acrylic compound having (A) a fluorine-containing acrylic compound represented by the formula (1), (B) a fluorine-containing acrylic compound represented by the formula (2) and (C) a non-fluorinated acrylic compound having 2 or more acrylic groups in a molecule.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composition having excellent antifouling properties, and an article having a cured film of the composition.

  Conventionally, hard coat treatment has been widely used as a means for protecting the surface of a resin molded body or the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded body, making it difficult to be damaged. As a material constituting the hard coat layer, many curable compositions using active energy rays such as thermosetting resins, ultraviolet rays, or electron beam curable resins are used.

  On the other hand, with the expansion of the application field of resin molded products and the trend toward higher added value, there is an increasing demand for higher functionality for the cured resin layer (hard coat layer). There is a demand for imparting dirtiness. This imparts water repellency, oil repellency and the like to the surface of the hard coat layer so that it is difficult to stain or can be easily removed even when soiled.

  As a method for imparting antifouling properties to the hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent to the surface of the hard coat layer once formed is widely used. A method for simultaneously forming a hard coat layer and imparting antifouling properties by adding to the cured resin composition before curing and coating and curing the same has also been studied. For example, JP-A-6-221945 (Patent Document 1) discloses the production of a hard coat layer imparted with antifouling property by adding and curing a fluoroalkyl acrylate to an acrylic curable resin composition. ing.

In recent years, the active energy ray-curable composition excellent in antifouling properties containing such a fluorine-containing acrylic compound has been greatly expanded in use, and a new function has been demanded.
In this way, the range of applications greatly expands the range of non-fluorinated components to be blended, and it has become necessary to dissolve in a wider range of non-fluorinated components than in the past. However, when the solubility in non-fluorinated components is improved with a fluorine-containing acrylic compound having a single structure, the concentration of fluorine components on the coating surface is less likely to occur, resulting in less antifouling performance. Problem occurs.

  For example, when only antifouling and dirt wiping properties are required for display surface treatment, etc., it is desirable that the cured surface should be slippery with as little friction as possible. In the case of antifouling surface treatment on the housing side, the higher the slipperiness, the higher the risk that the device will be removed, and the lower the slipperiness, the worse the tactile feel when holding it in the hand and the smoothness when wiping off the dirt. Therefore, a method for adjusting to an appropriate slipperiness according to the use is desired.

JP-A-6-221945 JP 2010-53114 A JP 2010-138112 A JP 2010-285501 A

  The present invention has been made in view of the above circumstances, has a stable solubility, can give a surface excellent in antifouling properties after curing, and further enables adjustment of slipperiness on the surface after curing. An object of the present invention is to provide an active energy ray-curable composition and an article having a cured film of the composition.

The present inventor has been developing various fluorine compounds that can impart antifouling properties to such a curable resin composition. For example, JP 2010-53114 A (Patent Document 2) and JP 2010 A In addition to JP-A-138112 (Patent Document 3) and JP-A 2010-285501 (Patent Document 4), a photo-curable fluorine compound shown in Japanese Patent Application No. 2014-074365 is proposed. As a method for synthesizing these photocurable fluorine compounds, a method of reacting a fluorine-containing alcohol with an acrylic acid halide or an acrylic compound having an isocyanate group is excellent. However, as described above, when the solubility in non-fluorinated components is improved with a fluorine-containing acrylic compound having a single structure, it is difficult for the fluorine component to concentrate on the coating surface, resulting in the appearance of antifouling performance. The problem that it becomes difficult to do occurs.
As a result of further studies, (A) a fluorine-containing acrylic compound represented by formula (1) described later, (B) a fluorine-containing acrylic compound represented by formula (2) described later, and (C ) A cured film in which an active energy ray-curable composition containing at least one non-fluorinated acrylic compound having two or more acrylic groups in one molecule has excellent antifouling property and enables control of the dynamic friction coefficient As a result, the present invention has been made.

（式中、Ｒｆ¹は独立にフッ素原子又は炭素数１〜６の酸素原子を含んでいてもよい１価の含フッ素アルキル基であり、ｎは独立に２〜１２０の正の整数であり、Ｚ¹は独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい２価の連結基であり、途中環状構造を含んでいてもよく、一部の水素原子がフッ素原子に置換されていてもよい。Ｑ¹は少なくとも（ａ＋ｂ）個のケイ素原子を含む（ａ＋ｂ）価の連結基であり、Ｚ²は独立に炭素数１〜２００の酸素原子及び窒素原子を含んでいてもよい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り、Ｒ²は独立に炭素数１〜８の１価の炭化水素基であり、Ｚ²とＲ¹及び／又はＺ²とＲ²はそれぞれ結合してＲ¹，Ｒ²と結合する炭素原子と共に環状構造をなしていてもよく、またＲ¹とＲ²が結合してそれぞれに結合する炭素原子と共にＺ²を含んだ環状構造をなしていてもよい。Ｒ³は独立に水素原子、又は酸素原子及び窒素原子を含んでいてもよいアクリル基もしくはα置換アクリル基を有する１価の有機基であり、但し、Ｒ³は分子中に平均して少なくとも１個の前記１価の有機基を有する。ａ、ｂはそれぞれ１〜１０の整数である。）
（Ｂ）下記一般式（２）で表される含フッ素アクリル化合物と、

（式中、Ｒ¹、Ｒ³、ｂは上記の通りである。Ｒｆ²は以下の２種類の繰り返し単位
−ＣＦ₂Ｏ−
−ＣＦ₂ＣＦ₂Ｏ−
がランダムに配列した分子量８００〜２０，０００の２価のパーフルオロポリエーテル基であり、Ｚ³は独立に炭素数１〜２０の酸素原子、窒素原子及びケイ素原子を含んでいてもよい２価の連結基であり、途中環状構造を含んでいてもよく、一部の水素原子がフッ素原子に置換されていてもよい。Ｑ²は独立に少なくとも（ｂ＋１）個のケイ素原子を含む（ｂ＋１）価の連結基であり、環状構造をなしていてもよい。Ｚ⁴は独立に炭素数１〜２００の酸素原子及び窒素原子を含んでいてもよい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とＺ⁴は結合してＲ¹と結合する炭素原子と共に環状構造をなしていてもよい。）
（Ｃ）１分子中に２個以上のアクリル基を有する非フッ素化アクリル化合物の少なくとも１種と
を含むことを特徴とする活性エネルギー線硬化性組成物。
〔２〕
（Ａ）成分と（Ｂ）成分の配合質量比が、以下の式
０．０１≦（Ｂ）／（Ａ）≦１００
で表される範囲内にあり、（Ａ）成分と（Ｂ）成分の合計質量が、（Ａ）〜（Ｃ）成分の合計質量に対して０．０５〜３０質量％であることを特徴とする〔１〕に記載の活性エネルギー線硬化性組成物。
〔３〕
（Ａ）成分において、式（１）中のＺ¹が、下記式

で表されるいずれかの構造であることを特徴とする〔１〕又は〔２〕に記載の活性エネルギー線硬化性組成物。
〔４〕
（Ａ）成分において、式（１）中のＱ¹が、下記式

（式中、ａ１、ｂ１はそれぞれ１〜１０の整数であり、ａ１＋ｂ１は３〜２０の整数である。）
で表される構造であることを特徴とする〔１〕〜〔３〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔５〕
（Ａ）成分が、下記一般式（３）

（式中、Ｚ¹、Ｑ¹、ａ、ｂ、ｎは上記の通りであり、ｅ１は０〜３０の整数であり、Ｒ⁴は水素原子又はメチル基である。）
で表される含フッ素アクリル化合物である〔１〕〜〔４〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔６〕
（Ｂ）成分において、式（２）中のＺ³が、下記式
−ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂−
で表されるいずれかの構造であることを特徴とする〔１〕〜〔５〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔７〕
（Ｂ）成分において、式（２）中のＱ²が、下記式

（式中、ｂ２は２〜１０の整数である。）
で表される構造であることを特徴とする〔１〕〜〔６〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔８〕
（Ｂ）成分が、下記一般式（４）又は（５）

（式中、Ｑ²、Ｚ³、ｂ、Ｒ⁴は上記の通りであり、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_qＣＦ₂−であり、ｐは１〜２００の整数、ｑは１〜１７０の整数、ｐ＋ｑは６〜２０１の整数であり、ｄ１、ｅ２は０〜２９の整数である。）
で表される含フッ素アクリル化合物である〔１〕〜〔７〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔９〕
更に、（Ｄ）光重合開始剤を、（Ａ）〜（Ｃ）成分の合計１００質量部に対して０．１〜１５質量部配合することを特徴とする〔１〕〜〔８〕のいずれかに記載の活性エネルギー線硬化性組成物。
〔１０〕
非フッ素化アクリル化合物（Ｃ）が、１分子中に２個以上のアクリル基又はα置換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つ以上のアクリル基又はα置換アクリル基を有する多官能ウレタンアクリレート類とを含む少なくとも２種類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活性エネルギー線硬化性組成物。
〔１１〕
〔１〕〜〔１０〕のいずれかに記載の活性エネルギー線硬化性組成物を表面に塗布し、硬化させた物品。 Accordingly, the present invention provides the following active energy ray-curable composition and article.
[1]
(A) a fluorine-containing acrylic compound represented by the following general formula (1);

(In the formula, Rf ¹ is independently a fluorine atom or a monovalent fluorine-containing alkyl group optionally containing an oxygen atom having 1 to 6 carbon atoms, n is independently a positive integer of 2 to 120, Z ¹ is a divalent linking group which may independently contain an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, may contain a cyclic structure, and some of the hydrogen atoms are fluorine. Q ¹ is an (a + b) -valent linking group containing at least (a + b) silicon atoms, and Z ² independently contains an oxygen atom having 1 to 200 carbon atoms and a nitrogen atom. R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² is independently a divalent hydrocarbon group which may be a divalent hydrocarbon group. to a monovalent hydrocarbon group having 1 to 8 carbon atoms, Z ² and R ¹ and / or Z ² and R ² it Is bonded to R ^1, may optionally form a cyclic structure together with the carbon atom bonded with R ^2, and R ¹ and R ² form a cyclic structure containing Z ² together with the carbon atom bonded to each bond R ³ is independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group that may contain an oxygen atom and a nitrogen atom, provided that R ³ is in the molecule. (On average, it has at least one monovalent organic group, a and b are each an integer of 1 to 10.)
(B) a fluorine-containing acrylic compound represented by the following general formula (2);

(Wherein R ¹ , R ³ and b are as described above. Rf ² represents the following two types of repeating units —CF ₂ O—
-CF ₂ CF ₂ O-
Is a bivalent perfluoropolyether group having a molecular weight of 800 to 20,000 arranged at random, and Z ³ may independently contain an oxygen atom, a nitrogen atom and a silicon atom having 1 to 20 carbon atoms. And may contain a cyclic structure in the middle, and some hydrogen atoms may be substituted with fluorine atoms. Q ² is independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms, and may have a cyclic structure. Z ⁴ is a divalent hydrocarbon group which may independently contain an oxygen atom having 1 to 200 carbon atoms and a nitrogen atom, and may contain an intermediate cyclic structure. R ¹ and Z ⁴ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ . )
(C) An active energy ray-curable composition comprising at least one non-fluorinated acrylic compound having two or more acrylic groups in one molecule.
[2]
The blending mass ratio of the component (A) and the component (B) is the following formula: 0.01 ≦ (B) / (A) ≦ 100
The total mass of the component (A) and the component (B) is 0.05 to 30% by mass with respect to the total mass of the components (A) to (C). The active energy ray-curable composition according to [1].
[3]
In the component (A), Z ¹ in the formula (1) is represented by the following formula:

The active energy ray-curable composition according to [1] or [2], which has any structure represented by
[4]
In component (A), Q ^{1 in} formula (1) is

(In the formula, a1 and b1 are each an integer of 1 to 10, and a1 + b1 is an integer of 3 to 20.)
The active energy ray-curable composition according to any one of [1] to [3], which has a structure represented by:
[5]
(A) component is the following general formula (3)

(In the formula, Z ¹ , Q ¹ , a, b, and n are as described above, e 1 is an integer of 0 to 30, and R ⁴ is a hydrogen atom or a methyl group.)
The active energy ray-curable composition according to any one of [1] to [4], which is a fluorine-containing acrylic compound represented by:
[6]
In the component (B), Z ³ in the formula (2) is represented by the following formula —CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -
The active energy ray-curable composition according to any one of [1] to [5], which is any one of structures represented by:
[7]
In the component (B), Q ² in the formula (2) is represented by the following formula:

(In the formula, b2 is an integer of 2 to 10.)
The active energy ray-curable composition according to any one of [1] to [6], which has a structure represented by:
[8]
(B) component is the following general formula (4) or (5)

(Wherein Q ² , Z ³ , b and R ⁴ are as described above, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, and p is (An integer of 1 to 200, q is an integer of 1 to 170, p + q is an integer of 6 to 201, and d1 and e2 are integers of 0 to 29.)
The active energy ray-curable composition according to any one of [1] to [7], which is a fluorine-containing acrylic compound represented by:
[9]
Furthermore, (D) 0.1-15 mass parts is mix | blended with respect to a total of 100 mass parts of (A)-(C) a photoinitiator, Any of [1]-[8] characterized by the above-mentioned. The active energy ray-curable composition according to claim 1.
[10]
The non-fluorinated acrylic compound (C) is a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond, or the polyfunctional acrylic compound and an aliphatic polyisocyanate. It is a mixture of at least two kinds of acrylic compounds containing 3 or more acrylic groups or polyfunctional urethane acrylates having an α-substituted acrylic group in one molecule obtained by reacting an acrylic compound having a hydroxyl group with each other [ The active energy ray-curable composition according to any one of 1] to [9].
[11]
[1] An article obtained by applying the active energy ray-curable composition according to any one of [10] to a surface and curing the composition.

  The active energy ray-curable composition of the present invention has a stable solubility at the time of coating, enables adjustment of slipperiness, and can provide a cured surface having high antifouling properties and dirt wiping properties. .

  The active energy ray-curable composition of the present invention comprises (A) a fluorine-containing acrylic compound represented by the following formula (1), (B) a fluorine-containing acrylic compound represented by the following formula (2), and ( C) A non-fluorinated acrylic compound having two or more acrylic groups in one molecule of at least one kind is an essential component.

The fluorine-containing acrylic compound of the component (A) that is the first essential component in the active energy ray-curable composition of the present invention is represented by the following general formula (1).

In the above formula (1), Rf ¹ is independently a fluorine atom or a monovalent fluorine-containing alkyl group optionally containing an oxygen atom having 1 to 6 carbon atoms. Specifically, in addition to the fluorine atom, Trifluoromethyl group, pentafluoroethyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, and CF ₃ OCF ₂ CF ₂ −
CF ₃ OCF ₂ CF ₂ CF ₂ −
CF ₃ CF ₂ OCF ₂ CF ₂ −
(CF ₃ ) ₂ CFOCF ₂ CF ₂ −
CF ₃ OCF ₂ CF ₂ CF ₂ CF ₂ −
CF ₃ CF ₂ OCF ₂ CF ₂ CF ₂ −
CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ −
(CF ₃ ) ₂ CFCF ₂ OCF ₂ CF ₂ −
CF ₃ CF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ −
CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ −
Among these, a fluorine atom is particularly preferable.

In said formula (1), n is a positive integer of 2-120 independently, The positive integer of 6-60 is especially suitable, More preferably, it is a positive integer of 10-40. When the value of n is small, the properties required as a fluorine compound are difficult to be obtained, and when the value of n is too large, the compatibility with non-fluorinated components in the composition is deteriorated. The value of n in the composition may be single or have a distribution, and in the case of having a distribution, the value of n obtained from ¹⁹ F-NMR or the like preferably satisfies the above range in terms of number average.

In the above formula (1), Z ¹ is a divalent linking group that may optionally contain an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, Some hydrogen atoms may be substituted with fluorine atoms. As such Z ¹ , preferred structures include the following structural groups.

—CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -

Among these, the following are particularly preferable.

In the above formula (1), Q ¹ is an (a + b) -valent linking group containing at least (a + b) silicon atoms, and preferable examples of such Q ¹ each have (a + b) Si atoms. (A + b) -valent linking groups comprising a siloxane structure, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more of these. Specifically, the following structures are specifically shown as preferable structures.

However, a and b are the same as a and b in the above formula (1), each independently an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 4. is there. Moreover, a1 is the same as a, b1 is the same as b, and a1 + b1 is an integer of 3-20. c is an integer of 1 to 5, and preferably an integer of 3 to 5. The arrangement of each unit is random, and a bond such as (a + b) units is bonded to any group of a Z ¹ and b CH ₂ enclosed in [].

Here, T is an (a + b) -valent linking group, and examples thereof include the following.

Among these, the following are particularly preferable.

In the above formula (1), Z ² is independently a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, preferably ^{2 to} 80 carbon atoms, and includes a cyclic structure in the middle. May be. Preferred examples of Z ² include the following.
—CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f OCH 2 -

  Here, d is an integer of 0 to 99, e is an integer of 0 to 66, and f is an integer of 0 to 50, and it is sufficient that the total number is 200 or less. The arrangement of repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers instead of a simple substance.

Examples of particularly preferred structures for Z ² include the following, and those having e of 0 to 30 are preferred.
—CH ₂ [OC ₃ H ₆ ] _e OCH ₂ —

In the above formula (1), 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 R ² is independently 1 to 8 carbon atoms, preferably 1 To 6 monovalent hydrocarbon groups. Specific examples of these monovalent hydrocarbon groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Alkyl groups such as pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, aryl groups such as phenyl group, tolyl group, xylyl group, Examples include aralkyl groups such as benzyl group and phenylethyl group. R ¹ is preferably a hydrogen atom or a methyl group, and R ² is preferably a methyl group.

Further, it may have an annular structure together with the carbon atom bonded respectively coupled Z ² and R ¹ and / or Z ² and R ² and R ^1, R ^2, also by bonding R ¹ and R ² together with the carbon atom bonded to each may form a ring structure containing Z ^2.

Examples of the case where Z ² and R ¹ or Z ² and R ² are combined to form a cyclic structure include the following structures. The bond is bonded to OR ³ and CHR ¹ or CHR ² and CH ₂ .

Further, examples of the cyclic structure containing Z ² together with the carbon atoms bonded to R ¹ and R ² can include the following structures. The bond indicated by the broken line is bonded to OR ³ and CH ₂ .

In the above formula (1), R ³ is independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group that may contain an oxygen atom and a nitrogen atom. The monovalent organic group is preferably a group having at least one, preferably 1 to 5 acryl group or α-substituted acryl group at the terminal, and examples of the substituent include a methyl group, an ethyl group, F, CF _3. , Cl, Br and the like. Moreover, you may have an amide bond, an ether bond, an ester bond, etc. in the middle of a structure.

Examples of such a structure include the following.
CH ₂ = CHCO-
_{CH 2 = C (CH 3)} CO-
_{CH 2 = C (C 2 H} 5) CO-
CH ₂ = CFCO-
CH ₂ = CClCO-
CH ₂ = CBrCO-
_{CH 2 = C (CF 3)} CO-
CH ₂ = CHCOOCH ₂ CH ₂ -NHCO-
_{CH 2 = C (CH 3)} COOCH 2 CH 2 -NHCO-
_{CH 2 = C (CH 3)} COOCH 2 CH 2 OCH 2 CH 2 -NHCO-
_{(CH 2 = CHCOOCH 2 CH 2} ) 2 C (CH 3) -NHCO-

Among these, the following are particularly preferable.
CH ₂ = CHCOOCH ₂ CH ₂ -NHCO-
_{CH 2 = C (CH 3)} COOCH 2 CH 2 -NHCO-

In the fluorine-containing acrylic compound represented by the formula (1), a part of R ³ may be a hydrogen atom, but not all are a hydrogen atom, and on average one or more acrylic groups and / or in one molecule. It contains an α-substituted acrylic group.

（式中、Ｚ¹、Ｑ¹、ａ、ｂ、ｎは前述の通りであり、ｅ１は０〜３０、好ましくは１〜１０の整数であり、Ｒ⁴は水素原子又はメチル基である。） As a more preferable structure as a fluorine-containing acrylic compound represented by the said Formula (1), what is represented by following General formula (3) can be illustrated.

(In the formula, Z ¹ , Q ¹ , a, b, and n are as described above, e 1 is an integer of 0 to 30, preferably 1 to 10, and R ⁴ is a hydrogen atom or a methyl group.)

（式中、ｅ１は上記と同じであり、ｎ１は６〜６０、好ましくは１０〜４０の整数、例えば２４である。） Specific examples of the component (A) include those shown below.

(Wherein e1 is the same as above, and n1 is an integer of 6 to 60, preferably 10 to 40, for example 24.)

The fluorine-containing acrylic compound as component (B), which is the second essential component in the active energy ray-curable composition of the present invention, is represented by the following general formula (2).

In the formula (2), R ^1, R ^3, b is the same as R ^1, R ^3, b in the formula (1) can be exemplified by the same manner as described above.

In the above formula (2), Rf ² represents the following two types of repeating units —CF ₂ O—
-CF ₂ CF ₂ O-
Is a bivalent perfluoropolyether group having a molecular weight of 800 to 20,000 arranged at random, and a linear perfluoropolyether group having a molecular weight of 1,000 to 10,000 is particularly preferable. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio between the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

The Rf ^2, preferably those shown below.
− (CF ₂ O) _p (CF ₂ CF ₂ O) _q −
(In the formula, p is an integer of 1 to 200, preferably 5 to 50, q is an integer of 1 to 170, preferably 5 to 50, p + q is an integer of 6 to 201, preferably 10 to 100, and (Repeating units may be combined randomly.)

In the above formula (2), Z ³ is a divalent linking group which may optionally contain an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, Some hydrogen atoms may be substituted with fluorine atoms. As such Z ³ , preferred structures include the following structural groups.
—CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -

Among these, in particular —CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -
Is preferred.

In the above formula (2), Q ² is independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms, and may have a cyclic structure. Preferred examples of such Q ² include a (b + 1) valence comprising a siloxane structure having (b + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof. Of the linking group. Specifically, the following structures are specifically shown as preferable structures.

However, b is the same as b of the said Formula (2), and is an integer of 1-10 independently, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-4. Moreover, b2 is an integer of 2-10, Preferably it is an integer of 2-8, More preferably, it is an integer of 2-4. c is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the bond of (b + 1) units or the like is bonded to any group of b CH ₂ surrounded by Z ³ and [].

Here, T ′ is a (b + 1) -valent linking group, and examples thereof include the following.

Among these, the following are particularly preferable.

In the above formula (2), Z ⁴ is a divalent hydrocarbon group which may contain an oxygen atom and a nitrogen atom having 1 to 200 carbon atoms, preferably 1 to 60 carbon atoms, and forms a cyclic structure in the middle. Alternatively, adjacent R ¹ and Z ⁴ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ . Preferred examples of the structure of Z ⁴ include the following.
_{-CH 2 [OC 2 H 4]} d [OC 3 H 6] e [OC 4 H 8] f -
(In the formula, d, e, and f are the same as described above. The arrangement of the repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers instead of a simple substance.)

As Z ⁴ , the following two structures are particularly preferable. Among them, those in which d is 1 to 30 and e is 1 to 30 are preferable.
_{-CH 2 [OC 2 H 4]} d -
_{-CH 2 [OC 3 H 6]} e -

Moreover, as an example in which R ¹ and Z ⁴ are bonded to form a cyclic structure, the following structures can be exemplified. The bond is bonded to OR ³ and CH ₂ .

（式中、Ｑ²、Ｚ³、Ｒ⁴、ｂは上記の通りであり、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_qＣＦ₂−であり、ｐ、ｑ、ｐ＋ｑは上記と同じである。ｄ１、ｅ２は０〜２９の整数である。） As a more preferable structure as a fluorine-containing acrylic compound represented by the said Formula (2), what is represented by following General formula (4), (5) can be illustrated.

(Wherein Q ² , Z ³ , R ⁴ , b are as described above, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, p, q and p + q are the same as above, and d1 and e2 are integers from 0 to 29.)

（式中、Ｒｆ’は−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_qＣＦ₂−であり、ｐ、ｑ、ｐ＋ｑは上記と同じであり、例えばｑ／ｐ＝０．９、ｐ＋ｑ≒４５である。ｅ２は上記と同じであり、例えば４である。） Specific examples of the component (B) include those shown below.

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, and p, q and p + q are the same as described above. For example, q / p = 0. 9, p + q≈45, e2 is the same as above, for example, 4.

The fluorine-containing acrylic compound represented by the formula (1) of the component (A) can be synthesized, for example, by the technique shown in Japanese Patent Application No. 2014-074365.
The fluorine-containing acrylic compound represented by the formula (2) of the component (B) can be synthesized by, for example, a method disclosed in JP 2010-285501 A and Japanese Patent Application No. 2014-074365.

（式中、Ｒｆ¹、Ｚ¹、Ｑ¹、ｎ、ａ、ｂは上記と同じであり、［ ］で括られたａ個のＺ¹及びｂ個のＨはすべてそれぞれＱ¹構造中のケイ素原子と結合している。）

（式中、Ｒｆ²、Ｚ³、Ｑ²、ｂは上記と同じであり、［ ］で括られたｂ個のＨはすべてＱ²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（８）
ＣＨ₂＝ＣＲ¹−Ｚ²−ＣＨＲ²−ＯＨ （８）
（式中、Ｒ¹、Ｒ²、Ｚ²は上記と同じであり、Ｚ²とＲ¹及び／又はＺ²とＲ²はそれぞれ結合してＲ¹，Ｒ²と結合する炭素原子と共に環状構造をなしていてもよく、またＲ¹とＲ²が結合してそれぞれに結合する炭素原子と共にＺ²を含んだ環状構造をなしていてもよい。）
で表される末端不飽和基含有アルコール（分子中にアルケニル基と２級のアルコールを有する化合物）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 (1) or (2) is first represented by the following general formula (6) or (7).

(Wherein Rf ¹ , Z ¹ , Q ¹ , n, a, b are the same as above, and a Z ¹ and b H enclosed in [] are all silicon in the Q ¹ structure. It is bonded to an atom.)

(In the formula, Rf ² , Z ³ , Q ² , and b are the same as described above, and all b H's enclosed in [] are bonded to the silicon atom in the Q ² structure.)
A fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (8):
_{^{CH 2 = CR 1 -Z 2 -CHR}} 2 -OH (8)
(Wherein R ¹ , R ² and Z ² are the same as above, and Z ² and R ¹ and / or Z ² and R ² are bonded to each other to form a cyclic structure together with the carbon atoms bonded to R ¹ and R ^2. And R ¹ and R ² may be bonded to form a cyclic structure containing Z ² together with the carbon atoms bonded to each other.)
A fluorine-containing alcohol compound as an intermediate can be obtained by hydrosilylation reaction of a terminal unsaturated group-containing alcohol represented by the formula (a compound having an alkenyl group and a secondary alcohol in the molecule).

（式中、ｎ１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 (6) include those shown below.

(In the formula, n1 is the same as above.)

（式中、Ｒｆ’は上記と同じである。） Examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (7) include those shown below.

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

Moreover, what is shown below can be illustrated as terminal unsaturated group containing alcohol represented by the said Formula (8).
_{CH 2 = CH-CH 2 -OCH} 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 2 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 4 -OCH 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) 9 -OCH 2 CH (CH 3) -OH

  This hydrosilylation (addition) reaction comprises a fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7) and a terminal unsaturated group-containing alcohol represented by the formula (8). It is desirable to mix and carry out the reaction in the presence of a platinum group metal-based addition reaction catalyst 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. If the reaction temperature is too low, the reaction may stop without sufficiently progressing, and if it is too high, the reaction cannot be controlled due to the temperature rise due to the reaction heat of hydrosilylation, causing bumping or decomposition of raw materials. There is.

  In this case, the reaction ratio between the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7) and the terminal unsaturated group-containing alcohol represented by the formula (8) is expressed by the formula: The terminal unsaturation represented by the formula (8) with respect to the total number of moles of H surrounded by [] of the fluoropolyether compound having a polyfunctional Si—H group represented by (6) or (7) It is desirable that the terminal unsaturated group of the group-containing alcohol is reacted in an amount of 0.5 to 5.0 times mol, particularly 0.9 to 2.0 times mol. If the amount of the terminal unsaturated group-containing alcohol represented by formula (8) is too small, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility. The reaction rate becomes unstable due to a decrease in the properties, and when the terminal unsaturated group-containing alcohol represented by the formula (8) is removed after the reaction, the excess unreacted alcohol is subjected to the conditions such as heating, decompression and extraction. It becomes necessary to be stricter as much as increases.

As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferable. Hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, Alternatively, platinum supported on activated carbon can be used.
The compounding amount of the addition reaction catalyst is 0.1 to 5,000 mass ppm of metal contained with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7). The amount is preferably 1 to 1,000 ppm by mass.

The above addition reaction can be carried out without a solvent, but may be diluted with a solvent as necessary. At this time, a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluting solvent, but the boiling point is higher than the target reaction temperature and does not hinder the reaction, and is contained after the reaction. It is preferable that the fluoroalcohol compound is soluble at the reaction temperature. Examples of such solvents include partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. And m-xylene hexafluoride is particularly preferable.
When using a solvent, the amount used is preferably 5 to 2,000 masses with respect to 100 mass parts of the fluoropolyether compound having a polyfunctional Si—H group represented by formula (6) or (7). Part, more preferably 50 to 500 parts by weight. If it is less than this, the effect of dilution with a solvent will become thin, and if it is more, the degree of dilution will be too high and the reaction rate may be reduced.

  After completion of the reaction, it is preferable to remove the unreacted terminal unsaturated group-containing alcohol and diluent solvent represented by the formula (8) by a known method such as distillation under reduced pressure, extraction, adsorption, and the like. It can also be used for the next reaction as a mixture.

（式中、ｎ１、ｅ１は上記と同じである。） Examples of the fluorine-containing alcohol compound thus obtained include those shown below.

(In the formula, n1 and e1 are the same as above.)

（式中、Ｒｆ’、ｅ２は上記と同じである。）

(In the formula, Rf ′ and e2 are the same as above.)

  Subsequently, a fluorine-containing acrylic compound can be obtained by introduce | transducing an acrylic group into the fluorine-containing alcohol compound obtained above. As a method of introducing an acryl group into the fluorinated alcohol compound, one is a method of forming an ester by reacting with an acrylic acid halide represented by the following formula (9), and the other is represented by the following formula (10). The method of making it react with the isocyanate compound containing the acrylic group which can be mentioned, The fluorine-containing acrylic compound made into the objective of this invention can be obtained by these methods.

CH ₂ = CR ⁴ COX (9)
^{_{CH 2 = CR 4 COOCH 2 CH}} 2 -N = C = O (10)
(In the formula, R ⁴ is the same as above, and X is a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.)

Here, what is shown below is mentioned as an acrylic acid halide represented by Formula (9).
CH ₂ = CHCOX
CH ₂ = C (CH ₃ ) COX
(Wherein X is the same as above)
Acrylic acid chloride and methacrylic acid chloride are particularly preferred.

Moreover, what is shown below is mentioned as an isocyanate compound containing the acrylic group represented by Formula (10).
_{CH 2 = CHCOOCH 2 CH 2 -N} = C = O
_{CH 2 = C (CH 3)} COOCH 2 CH 2 -N = C = O

  These isocyanates containing an acrylic acid halide or an acrylic group may be charged in an equimolar amount or more with respect to the total amount of hydroxyl groups of the fluorinated alcohol compound, and all the hydroxyl groups may be reacted. An average of 1 mole or more of an acrylic group may be introduced with respect to the mole, and by making the hydroxyl group excessive, an unreacted acrylic acid halide or an isocyanate compound containing an acrylic group may not be left. . Specifically, when the amount of the fluorinated alcohol compound in the reaction system is x mol and the total amount of hydroxyl groups of the fluorinated alcohol compound is y mol, the acrylic acid halide or the isocyanate compound containing an acryl group is at least x mol 2y. It is desirable that it is not more than mol, particularly preferably not less than 0.6 ymol and not more than 1.3 ymol. When the amount is too small, there is a high possibility that a fluorine-containing alcohol compound into which no acrylic group is introduced remains, and the solubility of the product may be lowered. When the amount is too large, it is difficult to remove unreacted acrylic acid halide or residual isocyanate compound containing an acrylic group.

  These reactions may be performed by diluting with an appropriate solvent as necessary. As such a solvent, any solvent that does not react with the isocyanate group of an isocyanate compound containing a hydroxyl group of a fluorine-containing alcohol compound, a halogen atom of an acrylic acid halide, or an acrylic group can be used without particular limitation. Hydrocarbon solvents such as toluene, xylene and isooctane, ether solvents such as tetrahydrofuran (THF), diisopropyl ether and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone and cyclohexanone, m- Examples thereof include fluorine-modified aromatic hydrocarbon solvents such as xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. This solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as it is as a diluted solution for the intended purpose.

  In the reaction, a polymerization inhibitor may be added as necessary. Although there is no restriction | limiting in particular as a polymerization inhibitor, Usually, what is used as a polymerization inhibitor of an acrylic compound can be used. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene and the like.

  When the fluorinated alcohol compound is reacted with acrylic acid halide, it is particularly preferable to react with acrylic acid chloride or methacrylic acid chloride to produce an ester. The ester forming reaction is performed by dropping acrylic acid halide while mixing and stirring the above reaction intermediate (fluorinated alcohol compound) and acid acceptor. As the acid acceptor, triethylamine, pyridine, urea or the like can be used.

The dropwise addition is carried out over 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ° C. Thereafter, stirring is continued for another 30 minutes to 10 hours. After completion of the reaction, the fluorine-containing acrylic compound of the present invention can be obtained by removing unreacted acrylic acid halide, salt generated by the reaction, reaction solvent and the like by a method such as distillation, adsorption, filtration and washing.
Moreover, when stopping the reaction, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted acrylic acid halide. The produced acrylic acid esters can be removed by the same method as the removal of unreacted acrylic acid halide, but can also be used while remaining.

  In the case of a reaction between a fluorinated alcohol compound and an isocyanate compound containing an acryl group, the fluorinated alcohol compound and an isocyanate compound containing an acryl group are stirred together with a solvent as necessary to advance the reaction.

  In this reaction, a suitable catalyst may be added to increase the rate of reaction. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, stannous dioctanoate, tin compounds such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and other titanates or titanium chelate compounds, zirconium tetraacetylacetonate, zirconium tributoxymonoacetyl Acetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate) G), zirconium tetra acetylacetonate, zirconium chelate compound and the like. These are not limited to one type, and can be used as a mixture of two or more types. Particularly, it is preferable to use a titanium compound or a zirconium compound having a low influence on the environment.

  The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants. The 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 be too slow. If the reaction temperature is too high, polymerization of acrylic groups may occur as a side reaction.

After completion of the reaction, the fluorine-containing acrylic compound of the present invention can be obtained by removing the unreacted isocyanate compound, the reaction solvent, and the like by a method such as distillation, adsorption, filtration and washing.
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 can also be used while remaining.

  The (C) component which is the third essential component in the active energy ray-curable composition of the present invention is a non-fluorinated acrylic compound having two or more acrylic groups in one molecule. In the present invention, “acrylic compound” is a general term for compounds having an acrylic group and an α-substituted acrylic group. Urethane acrylates having a urethane bond in the molecule and various methods on the side chains and terminals of various polymers. The compound which introduce | transduced the 2 or more acryl group and the alpha substituted acryl group is also included. In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate.

  Such a non-fluorinated acrylic compound (C) may be any compound having two or more acrylic groups or α-substituted acrylic groups in one molecule, such as 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate 2-6 functional groups such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, etc. (Meth) acrylic compounds, ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resins, and acrylic ester copolymers The thing containing the copolymer etc. which introduce | transduced the (meth) acryloyl group into the side chain is mentioned.

  Also, urethane acrylates, those obtained by reacting polyisocyanate with (meth) acrylate having hydroxyl group, those obtained by reacting polyisocyanate and terminal diol polyester with hydroxyl group (meth) acrylate, excess in polyol It is also possible to use a polyisocyanate obtained by reacting with a diisocyanate obtained by reacting a (meth) acrylate having a hydroxyl group. Among them, (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, 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-diisocyanate Urethane acrylates obtained by reacting polyisocyanate selected from natocyclohexane and diphenylmethane diisocyanate are preferred.

  Although (C) component can be used individually by 1 type, in order to improve the characteristic of a coating property and a film after hardening, it can also mix | blend and use the corresponding several compound.

  In particular, a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and having no urethane bond, or this polyfunctional acrylic compound, 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 those composed of polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by the reaction.

  Here, as a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and having no urethane bond, 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.

  Polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, Bifunctional or higher polyisocyanates obtained by reacting isophorone diisocyanates and their trimers, and these bifunctional and trifunctional isocyanates with aliphatic diols, aliphatic polyols and polyacrylates having hydroxyl groups in the side chains Trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditri Tyrololpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and those obtained by reacting these ethylene oxide and propylene oxide modified products, aliphatic polyols and polyacrylates having a hydroxyl group in the side chain and 2-isocyanate What reacted with acrylic compounds which have isocyanate groups, such as a natoethyl (meth) acrylate and 1, 1- (bis acryloyl oxymethyl) ethyl isocyanate, can be shown.

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

In the active energy ray-curable composition of the present invention, the blending amount of each component may be appropriately determined according to the desired properties of the cured product, the solubility of the composition, the curing conditions, etc., and the blending ratio is particularly limited. However, for example, the mass ratio of the component (A) to the component (B) is expressed by the following formula 0.01 ≦ (B) / (A) ≦ 100
In particular, the following formula 0.05 ≦ (B) / (A) ≦ 20
The total mass of the component (A) and the component (B) is 0.05 to 30% by mass with respect to the total mass of the components (A) to (C), particularly 0.1 to 0.1%. It is preferable that it is 10 mass%.
In the present invention, when the total mass of the components constituting the solid component after the composition is cured is 100 parts by mass, the sum of the masses of the components (A) and (B) is 0.05 to 20 masses. It is preferable that the amount be a part.

  The active energy ray-curable composition of the present invention essentially comprises the above-mentioned three components (A), (B), and (C), and can be cured with an electron beam or the like by blending only these components. However, it can also contain components other than these three components as required by workability.

  In particular, by containing a photopolymerization initiator as the component (D), a curable composition having improved curability when ultraviolet rays are used as active energy rays can be obtained.

  The photopolymerization initiator of component (D) is not particularly limited as long as the acrylic compound can be cured by ultraviolet irradiation, but preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethane-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. One species may be used alone, or two or more species may be used in combination.

  Although content of (D) component can be suitably determined according to hardening conditions and the physical property of this target composition, for example with respect to a total of 100 mass parts of (A)-(C) component, it is 0. The amount is preferably 1 to 15 parts by mass, particularly 1 to 10 parts by mass. If the addition amount is less than this, the curability may be lowered, and if it is more than this, the influence on the physical properties after curing may be increased.

  These components (A), (B), (C), and (D) can be used as a single compound or a mixture of a plurality of compounds corresponding to the structure in the definition of each compound. In the case of a mixture of a plurality of compounds, the total mass of each compound group can be considered as the mass of each compound in order to consider the compounding amount.

  The active energy ray-curable composition of the present invention further includes an active energy ray-reactive compound other than an acrylic group, such as a monofunctional acrylic compound, a thiol compound or a maleimide compound as a reactive diluent, depending on the purpose. A solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, and a polymer or inorganic filler may also be blended. it can.

Examples of organic solvents include alcohols such as 1-propanol, 2-propanol, isopropyl alcohol, n-butanol, isobutanol, tert-butanol, diacetone alcohol; methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, 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. Esters, toluene, xylene, triethylbenzene, alkylbenzene aromatics, etc. It can gel. The said solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
Although the usage-amount of a solvent is not restrict | limited in particular, 20-10,000 mass parts are preferable with respect to a total of 100 mass parts of (A)-(C) component, and 100-1,000 mass parts are especially preferable. .

  The polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant, and filler are not particularly limited and may be known ones. It can be used as long as the object of the present invention is not impaired.

Various hard coat agents containing component (C) and various additives are commercially available from various companies. The active energy ray-curable composition of the present invention may be one obtained by adding the component (A) and the component (B) to such a commercially available hard coat agent. Examples of commercially available hard coat agents include Arakawa Chemical Industries, Ltd. “Beam Set”, Ohashi Chemical Industries, Ltd. “Ubic”, Origin Electric Co., Ltd. “UV Coat”, Cashew Co., Ltd., “Cashew UV” JSR Co., Ltd. “Desolite”, Dainichi Seika Kogyo Co., Ltd. “Seika Beam”, Nippon Synthetic Chemical Co., Ltd. “Shikou”, Fujikura Kasei Co., Ltd. “Fujihard”, Mitsubishi Rayon Co., Ltd. “Diabeam”, Musashi Paint "Ultravine" etc. are mentioned.
Moreover, even when using a commercially available hard coat agent as described above, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer An additive, an antioxidant, a surfactant, a colorant, a filler and the like can be added and blended.

  The blending method of the composition of the present invention may be carried out by any method depending on the application, and is not particularly limited. However, the components (A) and (B) are well mixed before mixing with other components. For example, (A) component and (B) component are mixed in the required ratio and diluted with solvent as necessary, and then mixed with (C) component and other components, or diluted with solvent A method in which the component (A) and the component (B) diluted with a solvent are mixed and mixed with the component (C) and other components is suitable.

  As mentioned above, if it is the active energy ray curable composition of this invention, compatibility of the sclerosing | hardenable component ((C) component) of a hard-coat agent and a fluorine-containing acrylic compound ((A), (B) component). And a curable composition that can be cured by active energy rays such as ultraviolet rays and can form a cured resin layer having excellent antifouling properties and scratch resistance.

  Furthermore, in this invention, the active energy ray curable composition of this invention mentioned above is apply | coated to the base-material surface, and the article | item hardened | cured is provided. As described above, when the active energy ray-curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency and antifouling properties to the surface of an acrylic hard coat. This makes it possible to give a substrate (article) a hard coat surface that is less likely to be contaminated with human fat such as fingerprints, sebum, sweat, and cosmetics, and that has excellent wiping properties. For this reason, the curable composition of this invention can provide the coating film or protective film with respect to the surface of the base material (article) which a human body may touch and may be polluted with human fat, cosmetics, etc.

  The cured film (cured resin layer) formed using the active energy ray-curable composition of the present invention is applied directly to the surface of an article to which properties are imparted and cured, or the activity of the present invention on various substrates. Properties can be imparted to various articles by applying a film obtained by coating the energy ray curable composition to produce a cured film on the surface of the target article.

  Examples of such articles include tablet computers, portable (communication) information terminals such as mobile phones and smartphones, notebook PCs, digital media players, watch-type / glasses-type wearable computers, digital cameras, digital video cameras, and electronic books. Cases of various devices carried by people such as readers; various flat panels such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes (VFD), field emission projection displays, CRTs, and toner-based displays Surfaces of display operation devices such as displays and TV screens, automobile exteriors, glossy surfaces of pianos and furniture, surfaces of building stones such as marble, decorative building materials around water such as toilets, baths, and washrooms, protection for art exhibitions Ga , Show windows, showcases, photo frame covers, watches, window glass for trains, window glass for trains, aircraft, etc., transparent glass or transparent plastics (acrylic, polycarbonate, etc.) such as automobile headlights and tail lamps It is useful as a coating film and surface protective film for various mirror members.

  In particular, various devices having a display input device that performs operations on the screen with a human finger or palm such as a touch panel display, such as a tablet computer, a notebook PC, a watch-type wearable computer, an activity meter, a mobile phone, a smartphone, etc. Communication) Information terminals, digital media players, electronic book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, automotive navigation devices, automatic cash withdrawal and deposit machines, cash dispensers, Useful as a surface protection film for vending machines, digital signage (digital signage), security system terminals, POS terminals, remote controllers, and other display controllers, and display input devices such as panel switches for in-vehicle devices. That.

  Further, the cured film formed by the active energy ray-curable composition of the present invention includes optical recording media such as magneto-optical disks and optical disks; eyeglass lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, It is also useful as a surface protective film for optical parts and optical devices such as Fresnel lenses, antireflection films, optical fibers and optical couplers.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

で表される化合物２００ｇ（Ｓｉ−Ｈ価０．０００６１モル／ｇ）、ポリプロピレングリコールの片末端アリルエーテル（日本油脂（株）製ユニルーブＭＡ−３５、分子量６３９、アルコールの２級含有率１００％）８９ｇ（アリル基量０．００１６モル／ｇ）、ｍ−キシレンヘキサフロライド３００ｇを仕込み、窒素雰囲気下で９０℃まで加熱攪拌した。ここに白金／１，３−ジビニル−テトラメチルジシロキサン錯体のトルエン溶液０．４４２ｇ（Ｐｔ単体として１．１×１０^-6モルを含有）を投入し、内温を９０℃以上に維持したまま４時間攪拌を継続し、¹Ｈ−ＮＭＲで原料のアリル基、Ｓｉ−Ｈ基に由来するピークが消失したのを確認した。次いで攪拌装置を備えた５Ｌのフラスコにヘキサン３Ｌを仕込み、攪拌しながら、室温まで冷却した前記反応溶液を滴下して更に１時間攪拌した。攪拌停止後に２時間静置して、上層のヘキサン層をデカントで取り除き、得られた沈殿物から残存した溶媒をエバポレーターで除去し、半透明淡黄色高粘稠液体の下記式で示される含フッ素アルコール化合物（ＩＩ）２７２ｇを得た。

[Synthesis Example 1] Synthesis of fluorinated acrylic compound (A-1) In a 1 L four-necked flask equipped with a reflux apparatus and a stirring apparatus, the following formula (I)

200 g of a compound represented by the formula (Si-H value 0.00061 mol / g), one-end allyl ether of polypropylene glycol (Uniluve MA-35 manufactured by NOF Corporation, molecular weight 639, secondary content of alcohol 100%) 89 g (allyl group amount 0.0016 mol / g) and m-xylene hexafluoride 300 g were charged, and the mixture was heated and stirred to 90 ° C. in a nitrogen atmosphere. Here, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours, and it was confirmed by ¹ H-NMR that peaks derived from the allyl group and Si—H group of the raw material disappeared. Next, 3 L of hexane was charged into a 5 L flask equipped with a stirrer, and while stirring, the reaction solution cooled to room temperature was added dropwise and further stirred for 1 hour. After the stirring was stopped, the mixture was allowed to stand for 2 hours, the upper hexane layer was removed by decantation, the remaining solvent from the resulting precipitate was removed by an evaporator, and a fluorine-containing fluorinated liquid represented by the following formula of a translucent pale yellow highly viscous liquid 272 g of alcohol compound (II) was obtained.

Two-necked 100 mL eggplant flask equipped with 10.0 g of the obtained fluorinated alcohol compound (II) (hydroxyl amount 0.0040 mol), 10.0 g of methyl ethyl ketone and 0.01 g of 4-methoxyhydroquinone each equipped with a reflux device and a stirrer. In addition, 0.62 g (0.0043 mol) of 2-isocyanatoethyl acrylate was further added and heated to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C.
After confirming the disappearance of the 2,280 cm ⁻¹ peak derived from the isocyanate group in the reaction solution by IR spectrum measurement, the reaction solution was cooled to room temperature, 100 g of hexane was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered with filter paper, the components remaining on the filter paper were dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 80 ° C./0.13 kPa for 2 hours. The fluorine-containing acrylic compound 9 shown below 0.1 g was obtained.

[Synthesis Example 2] Synthesis of fluorinated acrylic compound (A-2) Instead of Unilub MA-35, 64 g of pentapropylene glycol monoallyl ether having a secondary alcohol terminal (allyl group amount 0.0029 mol / g) was used. In the same manner as in Synthesis Example 1, 228 g of a fluorinated alcohol compound (III) represented by the following formula as a translucent pale yellow highly viscous liquid was obtained.

Two-necked 100 mL eggplant flask equipped with 10.0 g of the obtained fluorinated alcohol compound (III) (hydroxyl amount 0.0043 mol), 10.0 g of methyl ethyl ketone and 0.01 g of 4-methoxyhydroquinone each equipped with a reflux device and a stirrer In addition, 0.62 g (0.0043 mol) of 2-isocyanatoethyl acrylate was further added and heated to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C.
After confirming the disappearance of the 2,280 cm ⁻¹ peak derived from the isocyanate group in the reaction solution by IR spectrum measurement, the reaction solution was cooled to room temperature, 100 g of hexane was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered with filter paper, the components remaining on the filter paper were dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 80 ° C./0.13 kPa for 2 hours. The fluorine-containing acrylic compound 9 shown below .3 g was obtained.

[Synthesis Example 3] Synthesis of fluorinated acrylic compound (A-3) 22 g (vinyl) of linalool oxide (pyranoid) (3-hydroxy-2,2,6-trimethyl-6-vinyltetrahydropyran) instead of UNILUBE MA-35 Except for using a base amount of 0.0059 mol / g), 201 g of a fluorinated alcohol compound (IV) represented by the following formula of a translucent light yellow highly viscous liquid was obtained in the same manner as in Synthesis Example 1.

Two-necked 100 mL eggplant flask equipped with 10.0 g of the obtained fluorinated alcohol compound (IV) (hydroxyl amount 0.0045 mol), 10.0 g of methyl ethyl ketone and 0.01 g of 4-methoxyhydroquinone each equipped with a reflux device and a stirrer. In addition, 0.55 g (0.0039 mol) of 2-isocyanatoethyl acrylate was further added and heated to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C.
After confirming the disappearance of the 2,280 cm ⁻¹ peak derived from the isocyanate group in the reaction solution by IR spectrum measurement, the reaction solution was cooled to room temperature, 100 g of hexane was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered with filter paper, the components remaining on the filter paper were dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 80 ° C./0.13 kPa for 2 hours. The fluorine-containing acrylic compound 8 shown below 0.2 g was obtained.

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） In Synthesis dry nitrogen atmosphere Synthesis Example 4] The fluorine-containing acrylic compound (B-1), in 2,000mL necked flask equipped with a reflux device and a stirrer, the following formula CH ₂ = CH-CH ₂ -O —CH ₂ —Rf′—CH ₂ —O—CH ₂ —CH═CH ₂
Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)
500 g (0.125 mol) of perfluoropolyether represented by the formula, 700 g of m-xylene hexafluoride and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. . Here, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1 × 10 ⁻⁶ mol as Pt alone) was added, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. After confirming disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (V) represented by the following formula.

Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Under a dry air atmosphere, 7.05 g (0.0690 mol) of 2-allyloxyethanol, 5% of compound (V) obtained above (Si-H group content: 0.0669 mol), m- 50.0 g of xylene hexafluoride and 0.0442 g of a toluene solution of chloroplatinic acid / vinyl siloxane 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, treated with activated carbon, and a pale yellow transparent liquid represented by the following formula 55.2 g of fluorine-containing alcohol compound (VI) was obtained.

Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） 50.0 g of THF and 9.00 g (0.063 mol) of acryloyloxyethyl isocyanate are mixed with 50.0 g (hydroxyl group amount 0.058 mol) of the obtained fluorinated alcohol compound (VI) in a dry air atmosphere. And heated to 50 ° C. Dioctyltin laurate 0.05g was added there, and it stirred at 50 degreeC for 24 hours. After completion of the heating, vacuum distillation was performed at 80 ° C./0.266 kPa to obtain 58.7 g of a pale yellow pasty substance. ^From the results of ¹ H-NMR and IR, it was confirmed to be the following fluorinated acrylic compound.

Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） [Synthesis Example 5] Synthesis of fluorinated acrylic compound (B-2) Under a dry air atmosphere, the compound (V) obtained in Synthesis Example 4 was 50.0 g (Si-H group content: 0.0669 mol). 27.5 g (0.0789 mol) of pentapropylene glycol monoallyl ether having a secondary alcohol terminal, 50.0 g of m-xylene hexafluoride, and 0.0442 g of a chloroplatinic acid / vinylsiloxane complex toluene solution (Pt 1.1 × 10 ⁻⁷ mol as a simple substance) was mixed and stirred at 100 ° C. for 4 hours. After confirming disappearance of the Si—H group by ¹ H-NMR and IR, the reaction solution was cooled to room temperature. Next, 500 mL of hexane was charged into a 2 L flask equipped with a stirrer, and the reaction solution cooled to room temperature was added dropwise with stirring, followed by further stirring for 1 hour. After the stirring was stopped, the mixture was allowed to stand for 2 hours, the upper hexane layer was removed by decantation, the remaining solvent from the resulting precipitate was removed by an evaporator, and a fluorine-containing fluorinated liquid represented by the following formula of a translucent pale yellow highly viscous liquid 45.1 g of alcohol compound (VII) was obtained.

Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Two-necked 100 mL eggplant flask equipped with 10.0 g of the obtained fluorinated alcohol compound (VII) (hydroxyl amount 0.0091 mol), methyl ethyl ketone 10.0 g and 4-methoxyhydroquinone 0.01 g, each equipped with a reflux device and a stirrer In addition, 1.30 g (0.0092 mol) of 2-isocyanatoethyl acrylate was further added and heated to 40 ° C. in a dry atmosphere. Next, 0.2 g of a 10% by mass methyl ethyl ketone solution of tetraoctyl titanate was added thereto, and heating was continued at 40 ° C.
After confirming the disappearance of the 2,280 cm ⁻¹ peak derived from the isocyanate group in the reaction solution by IR spectrum measurement, the reaction solution was cooled to room temperature, poured into 100 g of hexane, and stirred for 1 hour. After stirring, the mixture was filtered with filter paper, the components remaining on the filter paper were dissolved with m-xylene hexafluoride, and distilled under reduced pressure at 50 ° C./0.13 kPa for 2 hours. The fluorine-containing acrylic compound 9 shown below .4 g was obtained.

Rf ′: —CF ₂ O (CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF ₂ —
(Q1 / p1 = 0.9, p1 + q1≈45)

[Examples 1 to 9, Comparative Examples 1 to 4]
The raw material components of the active energy ray-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

(B) Fluorine-containing acrylic compound (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 4 (B-2) Fluorine-containing acrylic compound obtained in Synthesis Example 5

(C) Non-fluorinated polyfunctional acrylate (C-1) Pentaerythritol ethoxytetraacrylate [Daicel Ornex Co., Ltd. EBECRYL 40]
(C-2) Pentaerythritol triacrylate (C-3) Multifunctional acrylate consisting of a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]

(D) Photopolymerization initiator (D-1) 1-hydroxycyclohexyl phenyl ketone (trade name: IRGACURE
1841, manufactured by BASF Japan Ltd.)
(D-2) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: IRGA
CURE 127, manufactured by BASF Japan Ltd.)

[Preparation of active energy ray-curable composition]
(A) and (B) were all diluted to 20% by mass with methyl ethyl ketone, and (C) was diluted to 40% by mass with toluene. Moreover, what diluted the dilution solvent of (C-1) from toluene to 2-propanol and diluted to 40 mass% was mix | blended as (C-4).
(A)-(D) were mixed so that it may become the following Table 1 as a compounding ratio except the solvent component of each component, and the active energy ray-curable composition was obtained.

  The following measurement and evaluation were performed about the obtained active energy ray curable composition and its hardened | cured material. These results are shown in Table 2.

[Dissolved state of composition]
The dissolution state of each composition was visually observed. In addition, subsequent evaluation was not performed about the composition in which the deposit generate | occur | produced.

Preparation of Coating and Cured Products Each composition of Examples and Comparative Examples was placed on a polycarbonate substrate with a wire bar No. 7 (wet film thickness 16.0 μm). After coating, after drying at 100 ° C for 1 minute, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works), in the nitrogen atmosphere, UV light with an integrated irradiation amount of 1,600 mJ / cm ² is applied to the coated surface. The composition was cured by irradiation to obtain a cured film.

[Evaluation of water and oil repellency]
1) Water contact angle measurement Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.
2) Measurement of oleic acid contact angle Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 7 μL droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was taken as the measured value.

[Measurement of dynamic friction coefficient]
The dynamic friction coefficient of the cured film with respect to Bencott (Asahi Kasei Co., Ltd.) was measured using a surface property tester 14FW (Shinto Kagaku Co., Ltd.) under the following conditions.
Contact area: 10mm x 35mm
Load: 100g

[Evaluation of magic repellent properties]
A straight line was drawn on the surface of the cured film with a magic pen (Himackey Bold, manufactured by Zebra Corporation), and the repellency was evaluated by visual observation.

Claims (11)

(A) a fluorine-containing acrylic compound represented by the following general formula (1);

(In the formula, Rf ¹ is independently a fluorine atom or a monovalent fluorine-containing alkyl group optionally containing an oxygen atom having 1 to 6 carbon atoms, n is independently a positive integer of 2 to 120, Z ¹ is a divalent linking group which may independently contain an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, may contain a cyclic structure, and some of the hydrogen atoms are fluorine. Q ¹ is an (a + b) -valent linking group containing at least (a + b) silicon atoms, and Z ² independently contains an oxygen atom having 1 to 200 carbon atoms and a nitrogen atom. R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R ² is independently a divalent hydrocarbon group which may be a divalent hydrocarbon group. to a monovalent hydrocarbon group having 1 to 8 carbon atoms, Z ² and R ¹ and / or Z ² and R ² it Is bonded to R ^1, may optionally form a cyclic structure together with the carbon atom bonded with R ^2, and R ¹ and R ² form a cyclic structure containing Z ² together with the carbon atom bonded to each bond R ³ is independently a hydrogen atom, or a monovalent organic group having an acrylic group or an α-substituted acrylic group that may contain an oxygen atom and a nitrogen atom, provided that R ³ is in the molecule. (On average, it has at least one monovalent organic group, a and b are each an integer of 1 to 10.)
(B) a fluorine-containing acrylic compound represented by the following general formula (2);

(Wherein R ¹ , R ³ and b are as described above. Rf ² represents the following two types of repeating units —CF ₂ O—
-CF ₂ CF ₂ O-
Is a bivalent perfluoropolyether group having a molecular weight of 800 to 20,000 arranged at random, and Z ³ may independently contain an oxygen atom, a nitrogen atom and a silicon atom having 1 to 20 carbon atoms. And may contain a cyclic structure in the middle, and some hydrogen atoms may be substituted with fluorine atoms. Q ² is independently a (b + 1) -valent linking group containing at least (b + 1) silicon atoms, and may have a cyclic structure. Z ⁴ is a divalent hydrocarbon group which may independently contain an oxygen atom having 1 to 200 carbon atoms and a nitrogen atom, and may contain an intermediate cyclic structure. R ¹ and Z ⁴ may be bonded to form a cyclic structure together with the carbon atom bonded to R ¹ . )
(C) An active energy ray-curable composition comprising at least one non-fluorinated acrylic compound having two or more acrylic groups in one molecule. The blending mass ratio of the component (A) and the component (B) is the following formula: 0.01 ≦ (B) / (A) ≦ 100
The total mass of the component (A) and the component (B) is 0.05 to 30% by mass with respect to the total mass of the components (A) to (C). The active energy ray-curable composition according to claim 1. In the component (A), Z ¹ in the formula (1) is represented by the following formula:

The active energy ray-curable composition according to claim 1, wherein the active energy ray-curable composition is any one of the structures represented by: In component (A), Q ^{1 in} formula (1) is

(In the formula, a1 and b1 are each an integer of 1 to 10, and a1 + b1 is an integer of 3 to 20.)
The active energy ray-curable composition according to claim 1, wherein the active energy ray-curable composition is represented by the formula: (A) component is the following general formula (3)

(In the formula, Z ¹ , Q ¹ , a, b, and n are as described above, e 1 is an integer of 0 to 30, and R ⁴ is a hydrogen atom or a methyl group.)
The active energy ray-curable composition according to claim 1, which is a fluorine-containing acrylic compound represented by the formula: In the component (B), Z ³ in the formula (2) is represented by the following formula —CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ —
—CH ₂ CH ₂ CH ₂ CH ₂ —
-CH ₂ OCH ₂ CH ₂ -
_{-CH 2 OCH 2 CH 2 CH 2} -
The active energy ray-curable composition according to any one of claims 1 to 5, wherein the active energy ray-curable composition is any one of the structures represented by: In the component (B), Q ² in the formula (2) is

(In the formula, b2 is an integer of 2 to 10.)
The active energy ray-curable composition according to any one of claims 1 to 6, wherein the active energy ray-curable composition is represented by the following formula. (B) component is the following general formula (4) or (5)

(Wherein Q ² , Z ³ , b and R ⁴ are as described above, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, and p is (An integer of 1 to 200, q is an integer of 1 to 170, p + q is an integer of 6 to 201, and d1 and e2 are integers of 0 to 29.)
The active energy ray-curable composition according to claim 1, which is a fluorine-containing acrylic compound represented by the formula:   Furthermore, (D) 0.1-15 mass parts of photoinitiators are mix | blended with respect to a total of 100 mass parts of (A)-(C) component, The any one of Claims 1-8 characterized by the above-mentioned. The active energy ray-curable composition according to Item.   The non-fluorinated acrylic compound (C) is a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and having no urethane bond, or this polyfunctional acrylic compound and an aliphatic poly It is a mixture of at least two kinds of acrylic compounds containing polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting isocyanate and an acrylic compound having a hydroxyl group. The active energy ray-curable composition according to any one of claims 1 to 9.   The article | item which apply | coated the active energy ray curable composition of any one of Claims 1-10 on the surface, and was made to harden | cure.