JP7077774B2 - Active energy ray-curable composition - Google Patents

Description

The present invention relates to an active energy ray-curable composition. Specifically, it can be applied to an active energy ray-curable composition containing a photocationic curable resin, particularly as a photocationic hard coat agent, and is useful as an ultraviolet curable antifouling surface-imparting agent. With respect to a certain active energy ray curable composition.

A hard coat agent (or a paint having a role as a hard coat) is applied to the surface of various articles represented by plastic resin and cured to protect the surface of the article and have a new function on the surface of the article. It is used in a very wide range of applications as a material that can be given.

These hardcoat agents have water- and oil-repellent properties, antifouling properties, and fingerprint resistance, in addition to the hardness, abrasion resistance, chemical resistance, durability, etc. that have been conventionally required, depending on the spread of their applications. Further high functions such as weather resistance, slipperiness, antistatic property, antifog property, anti-fog property, and anti-reflection property are required. In particular, in recent years, there has been a demand for improvements in stain prevention and stain wiping properties.

The active energy ray-curable hard coat agent includes an ultraviolet / electron beam curable hard coat agent and a thermosetting hard coat agent. Examples of the ultraviolet / electron beam curable hard coat agent include an acrylic group-containing hard coat agent that is cured by radical polymerization by ultraviolet rays. In recent years, by adding a very small amount to an ultraviolet curable hard coat agent, in addition to the characteristics that the hard coat agent had before the addition, the obtained cured surface has water and oil repellency, stain resistance, fingerprint resistance, etc. Fluorine-containing compounds that can be imparted are being investigated.

The present inventor can be suitably used as an additive for an ultraviolet or electron beam curable hard coat agent in Patent Documents 1 to 4, and the obtained cured product has good water and oil repellency, antifouling property, and fingerprint resistance. We are proposing a fluorine-containing compound that can impart properties.

Japanese Unexamined Patent Publication No. 2010-053114 Japanese Unexamined Patent Publication No. 2010-138112 Japanese Unexamined Patent Publication No. 2010-285501 Japanese Unexamined Patent Publication No. 2011-241190

Ultraviolet (UV) curable acrylic hard coat agents that cure by radical polymerization used for the above purposes cure quickly and have a wide variety of acrylic compounds and initiators that can be used as ingredients, and have a composition that suits the purpose. It has the advantage of being easy to adjust. On the other hand, there are essential problems caused by the characteristics of radical polymerization of acrylic groups, such as being affected by curing inhibition by oxygen and having a large curing shrinkage.

In particular, the inhibition of curing by oxygen is more susceptible to the air interface of the coating film by the hard coat composition, that is, the side closer to the outermost surface, which is a major obstacle in imparting antifouling properties to the outermost surface. In addition, the curing shrinkage due to the polymerization of acrylic groups is likely to be greatly affected by curling, cracking, etc. due to curing shrinkage when polyfunctionalized due to the increase in hardness, and the demand for higher hardness for hard coat agents has further increased in recent years. It is becoming more difficult to deal with this with the acrylic polymerization type.

On the other hand, an ultraviolet curable cationic polymerization type hard coat agent using a compound having an epoxy group, an oxetane group, a vinyl ether group, etc. has excellent surface curability because there is no polymerization inhibition by oxygen, and the volume shrinkage at the time of curing is also an acrylic type (radical polymerization). It has a big feature that it is smaller than the mold).

For this reason, the development of UV cation-curable hard coat agents has been greatly advanced in recent years, and there has been an increasing demand for imparting antifouling properties to cation-curable hard coat agents.

The present invention has been made in view of the above circumstances, and is used as a photocationic hard coat agent capable of providing a cured product having excellent water and oil repellency, stain resistance, and fingerprint resistance on the surface. Also applicable, it is an object of the present invention to provide an active energy ray-curable composition which is useful as an ultraviolet curable antifouling surface-imparting agent.

（Ｒｆ、Ｑ１、Ｑ２、Ｘ、ａ、ａ’、ｂ及びａ＋ｂは下記の通りである。） As a result of diligent studies to solve the above problems, the present inventor has an active energy containing a specific fluorine-containing epoxy-modified organic silicon compound (A) represented by the following general formula (1) and a photopolymerization initiator (B). We have found that a cured product of a linear curable composition (photocationic polymerization type composition) can have excellent water and oil repellency, antifouling property, and fingerprint resistance on the surface, and have reached the present invention.

(Rf, Q1, Q2, X, a, a', b and a + b are as follows.)

（式（１）中、Ｒｆは互いに独立にフルオロポリエーテル構造を有する数平均分子量４００～４０，０００の一価又は二価の基であって、Ｒｆが一価の基のとき、下記式

（上記式中、ｊは１～３の整数であり、ｋは０～２００の整数であり、ｋ’は１～２００の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。）
で表され、
Ｒｆが二価の基のとき、下記式

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）、

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数であり、但し、ｈ＋ｉは２～３００である。各繰り返し単位はランダムに結合されていてよい。）、

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）、又は

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）
で表される。
Ｒｆが一価の基のときにはａ’は１であり、ａは１～６の整数である。Ｒｆが二価の基のときにはａ’は２であり、ａは１であり、ｂは１～２０の整数であり、ａ＋ｂは３～２１の整数である。
Ｑ¹は、互いに独立に、少なくとも（ａ＋ｂ）個のＳｉ原子を有する（ａ＋ｂ）価の基であり、下記式

（式中、ａ及びｂは前記の通りであり、破線は結合手を示し、ａ個の繰り返しを有する括弧内に示される単位の各ケイ素原子は前記式（１）中のＲｆと結合し、ｂ個の繰り返しを有する括弧内に示される単位の各ケイ素原子は前記式（１）中のＱ²と結合し、括弧内に示される単位の並びはランダムであってよい。）
で表される。
Ｑ²は、互いに独立にエーテル結合又はエステル結合を含んでいてもよく、環状構造を有していてもよい炭素数１～２０の二価炭化水素基である。
Ｘは、互いに独立に、下記式（Ｉ）又は（ＩＩ）

（式（Ｉ）中、Ｒ¹は互いに独立に水素原子又は炭素数１～２０の非置換又は置換の一価炭化水素基であり、エーテル結合又はエステル結合を含んでいてもよく、環状構造を有していてもよい。）

（式（ＩＩ）中、Ｒ²は互いに独立に水素原子又は炭素数１～２０の非置換又は置換の一価炭化水素基である。）
で表される基である。）
で表される含フッ素エポキシ変性有機ケイ素化合物（Ａ）と、
光重合開始剤（Ｂ）とを含み、ラジカル重合型（メタ）アクリル基含有含フッ素有機ケイ素化合物を含まない活性エネルギー線硬化性組成物であって、表面の水接触角が１００°以上である硬化物を与えるものである活性エネルギー線硬化性組成物。
［２］
前記式（１）において、－Ｑ²－Ｘで表される構造が下記式（２）～（５）で示される基から選ばれるものである［１］に記載の活性エネルギー線硬化性組成物。

（上記式中、ｆは１～１０の整数であり、ｅは０～５の整数であり、ｇは０～１０の整数であり、ｆ＋２ｇ＋ｅは１～２０の範囲にあり、ｎは１～２０の整数である。Ｒ²は互いに独立に水素原子又は炭素数１～２０の非置換又は置換の一価炭化水素基である。）。
［３］
前記式（１）において、Ｑ²が互いに独立に下記式で示される基より選ばれるものである［１］又は［２］に記載の活性エネルギー線硬化性組成物。
－ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂－、
－ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂－、又は
－ＣＨ₂ＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂ＯＣＨ₂ＣＨ₂－
［４］
前記式（１）において、－Ｑ²－Ｘで表される構造が下記式

である［２］又は［３］に記載の活性エネルギー線硬化性組成物。
［５］
光重合開始剤（Ｂ）が、光酸発生剤である［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］
光重合開始剤（Ｂ）がジアゾニウム塩、ヨードニウム塩、スルホニウム塩のいずれかである［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］
カチオン硬化性を有する化合物が（Ａ）成分のみの場合、（Ａ）成分１００質量部に対して（Ｂ）成分を０．０１～２０質量部含むものである［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］
更に、（Ａ）成分以外の１種類以上のカチオン硬化性を有する化合物からなる（Ｃ）成分を含有し、（Ａ）成分と（Ｃ）成分の合計１００質量部に対して（Ｂ）成分を０．０１～２０質量部含むものである［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。
［９］
（Ｃ）成分が１分子中に１つ以上のエポキシ基、ビニルエーテル基、オキセタン基、カルボニル基のいずれかを有する化合物、脂肪族不飽和炭化水素化合物、スチレン誘導体、ビシクロオルトエステル、スピロオルトカーボネート、スピロオルトエステル又はカチオン重合性窒素含有化合物である［８］に記載の活性エネルギー線硬化性組成物。
［１０］
（Ｃ）成分１００質量部に対し、（Ａ）成分が０．０１～１０質量部含まれ、硬化後の硬化物表面の水接触角が１００°以上である［８］又は［９］に記載の活性エネルギー線硬化性組成物。
［１１］
（Ａ）成分が一般式（１）においてａ’が２であり、Ｒｆが二価の基の含フッ素エポキシ変性有機ケイ素化合物である［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。
［１２］
（Ａ）成分が一般式（１）においてａ’が１であり、Ｒｆが下記式

（上記式中、ｊは１～３の整数であり、ｋは０～２００の整数であり、ｋ’は１～２００の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。）
で表される一価の基の含フッ素エポキシ変性有機ケイ素化合物である［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。
［１３］
Ｒｆが下記式

（上記式中、ｊは１～３の整数であり、ｋ’は１～２００の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。）
のいずれかで表される一価の基である［１２］記載の活性エネルギー線硬化性組成物。 That is, the present invention provides the following active energy ray-curable composition.
[1]
The following general formula (1)

(In the formula (1), when Rf is a monovalent or divalent group having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other and Rf is a monovalent group, the following formula

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
Represented by
When Rf is a divalent group, the following formula

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.),.

(In the equation, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, respectively, and h + i is an integer of 2 to 300. Each repeating unit may be randomly combined. .),

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.) Or.

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.)
It is represented by.
When Rf is a monovalent group, a'is 1 and a is an integer of 1 to 6. When Rf is a divalent group, a'is 2, a is 1, b is an integer of 1 to 20, and a + b is an integer of 3 to 21.
Q ¹ is a (a + b) valence group having at least (a + b) Si atoms independently of each other, and has the following formula.

(In the formula, a and b are as described above, the broken line indicates a bond, and each silicon atom of the unit shown in parentheses having a repetition is bonded to Rf in the formula (1). Each silicon atom of the unit shown in parentheses having b repetitions may be bonded to Q ² in the above formula (1), and the sequence of units shown in parentheses may be random.)
It is represented by.
Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond independently of each other and may have a cyclic structure.
X is independent of each other and has the following formula (I) or (II).

(In formula (I), R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and may contain an ether bond or an ester bond, and has a cyclic structure. You may have it.)

(In formula (II), R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other.)
It is a group represented by. )
Fluorine-containing epoxy-modified organosilicon compound (A) represented by
An active energy ray-curable composition containing a photopolymerization initiator (B) and not containing a radically polymerized (meth) acrylic group-containing fluorine-containing organic silicon compound, at a surface water contact angle of 100 ° or more. An active energy ray-curable composition that provides a cured product.
[2]
The active energy ray-curable composition according to [1], wherein the structure represented by −Q2 ^- X in the above formula (1) is selected from the groups represented by the following formulas (2) to (5). ..

(In the above equation, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, f + 2g + e is in the range of 1 to 20, and n is 1 to 20. R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other.)
[3]
The active energy ray-curable composition according to [1] or [2], wherein Q ² is independently selected from the groups represented by the following formulas in the above formula (1).
-CH ₂ CH _2- ,
-CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ 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 CH ₂ OCH ₂ CH ₂ OCH ₂ -or-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2-
[4]
In the above formula (1), the structure represented by ^−Q2 −X is the following formula.

The active energy ray-curable composition according to [2] or [3].
[5]
The active energy ray-curable composition according to any one of [1] to [4], wherein the photopolymerization initiator (B) is a photoacid generator.
[6]
The active energy ray-curable composition according to any one of [1] to [5], wherein the photopolymerization initiator (B) is any one of a diazonium salt, an iodonium salt, and a sulfonium salt.
[7]
When the compound having cation curability is only the component (A), any of [1] to [6] containing 0.01 to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). The active energy ray-curable composition according to the above.
[8]
Further, the component (C) composed of one or more kinds of compounds having cation curability other than the component (A) is contained, and the component (B) is added to a total of 100 parts by mass of the component (A) and the component (C). The active energy ray-curable composition according to any one of [1] to [6], which contains 0.01 to 20 parts by mass.
[9]
(C) A compound having one or more epoxy group, vinyl ether group, oxetane group, or carbonyl group in one molecule, an aliphatic unsaturated hydrocarbon compound, a styrene derivative, a bicycloorthoester, a spirolotocarbonate, The active energy ray-curable composition according to [8], which is a spiroletoester or a cationically polymerizable nitrogen-containing compound.
[10]
[8] or [9], wherein the component (A) is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (C), and the water contact angle of the surface of the cured product after curing is 100 ° or more. Active energy ray-curable composition.
[11]
(A) The active energy ray according to any one of [1] to [10], wherein a'is 2 in the general formula (1) and Rf is a fluorine-containing epoxy-modified organosilicon compound having a divalent group. Curable composition.
[12]
(A) The component is 1 in the general formula (1), and Rf is the following formula.

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
The active energy ray-curable composition according to any one of [1] to [10], which is a fluorine-containing epoxy-modified organosilicon compound having a monovalent group represented by.
[13]
Rf is the following formula

(In the above formula, j is an integer of 1 to 3, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
The active energy ray-curable composition according to [12], which is a monovalent group represented by any of the above.

The active energy ray-curable composition of the present invention can impart excellent water and oil repellency, stain resistance, and fingerprint resistance to the surface of the cured product. Therefore, the active energy ray-curable composition can also be applied as a photocationic hard coat agent, and is useful as an ultraviolet curable antifouling surface-imparting agent that can be cured by a photocationic polymerization reaction.

Hereinafter, the present invention will be described in detail.
The active energy ray-curable composition according to the present invention is characterized by containing the following fluorine-containing epoxy-modified organosilicon compound (A) and a photopolymerization initiator (B).

（式（１）中、Ｒｆは互いに独立にフルオロポリエーテル構造を有する数平均分子量４００～４０，０００の一価又は二価の後述する特定の基であり、Ｑ¹は互いに独立に、少なくとも（ａ＋ｂ）個のＳｉ原子を有する（ａ＋ｂ）価の後述する特定の基であり、Ｑ²は互いに独立にエーテル結合又はエステル結合を含んでいてもよく、環状構造を有していてもよい炭素数１～２０の二価炭化水素基であり、Ｘは後述する式（Ｉ）又は（ＩＩ）で示される基である。また、Ｒｆが一価の基のときにはａ’は１であり、ａは１～６の整数である。Ｒｆが二価の基のときにはａ’は２であり、ａは１であり、ｂは１～２０の整数であり、ａ＋ｂは３～２１の整数である。） The fluorine-containing epoxy-modified organosilicon compound (A), which is the first component of the present invention, is a cationically curable compound represented by the following general formula (1).

(In formula (1), Rf is a monovalent or divalent group described below having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other, and Q ¹ is independent of each other, at least ( It is a specific group having a + b) Si atom (a + b) valence, which will be described later, and Q ² may contain an ether bond or an ester bond independently of each other, and may have a cyclic structure. It is a divalent hydrocarbon group of 1 to 20, X is a group represented by the formula (I) or (II) described later, and when Rf is a monovalent group, a'is 1 and a is 1. It is an integer of 1 to 6. When Rf is a divalent group, a'is 2, a is 1, b is an integer of 1 to 20, and a + b is an integer of 3 to 21.)

In the formula (1), X is a group represented by the following formula (I) or (II) independently of each other.

In formula (I), R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms independently of each other. It may contain an ether bond or an ester bond, and may have a cyclic structure. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group and a decyl group, and a vinyl group. Examples thereof include an alkenyl group such as an allyl group, a propenyl group, a butenyl group and a hexenyl group, and a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Further, it is a halogen-substituted monovalent hydrocarbon group such as a fluoromethyl group, a bromoethyl group or a trifluoropropyl group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine and bromine. May be good.
Preferably, R ¹ is a hydrogen atom.

In formula (II), R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms independently of each other. .. Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group and a decyl group, and a vinyl group. Examples thereof include an alkenyl group such as an allyl group, a propenyl group, a butenyl group and a hexenyl group. Further, it is a halogen-substituted monovalent hydrocarbon group such as a fluoromethyl group, a bromoethyl group or a trifluoropropyl group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as chlorine, fluorine and bromine. May be good. Preferably, R ² is a hydrogen atom or a methyl group.

（式中、Ｒ²は上記の通りである。） Examples of the structure represented by the above formula (I) or (II) include the following.

(In the formula, R ² is as described above.)

In the above formula (1), Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms independently of each other, and may have a cyclic structure, and may have an ether bond (—O) in the middle. -) Or an ester bond (-COO-) may be contained.

（上記式中、ｆは１～１０の整数であり、ｅは０～５の整数であり、ｇは０～１０の整数であり、ｆ＋２ｇ＋ｅは１～２０の範囲にある。好ましくは、ｆは１～６の整数であり、ｅは１又は２であり、ｇは０～４の整数であり、ｆ＋２ｇ＋ｅは３～１０の範囲にある。ｎは１～２０の整数、好ましくは２～１５の整数である。） In the above formula (1), Q ² includes, for example, the following.

(In the above formula, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, and f + 2g + e is in the range of 1 to 20. Preferably, f is. It is an integer of 1 to 6, e is 1 or 2, g is an integer of 0 to 4, f + 2g + e is in the range of 3 to 10. n is an integer of 1 to 20, preferably 2 to 15. It is an integer.)

Examples of the Q ² include those having the following structure.
-CH ₂ CH _2- ,
-CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ 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 CH ₂ OCH ₂ CH ₂ OCH _2- ,
-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2-

In the above formula (1), examples of the structure represented by ^−Q2 −X include structures represented by the following formulas (2) to (5).

In the above formula, f, e, g, f + 2g + e, n are as described above. R ² is as described above, preferably a hydrogen atom or a methyl group.

であることが特に好ましい。 In the above formula (1), the structure represented by ^−Q2 −X is the following formula.

Is particularly preferable.

In the above formula (1), Q ¹ is a (a + b) valence group having at least (a + b) Si atoms independently of each other.
In the above formula (1), when Rf is monovalent, a'is 1, a is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably 1. When Rf is divalent, a'is 2 and a is 1. b is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 2 to 4. Further, a + b is an integer of 3 to 21, preferably an integer of a + b = 3 to 10, more preferably an integer of a + b = 3 to 6, and even more preferably a + b = 4 or 5.

The above Q ¹ has a cyclic siloxane structure having a (a + b) valence represented by the following formula.

In the above formula, a and b are as described above, a broken line indicates a bond, and each silicon atom of the unit shown in parentheses having a repetition is bonded to Rf in the above formula (1). Each silicon atom of the unit shown in parentheses having b repetitions is bonded to Q ² in the above formula (1). The sequence of each unit shown in parentheses may be random.

In the above formula (1), Rf is a monovalent or divalent group having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. The number average molecular weight of Rf is preferably in the range of 500 to 20,000. In the present invention, the number average molecular weight is a value calculated from the ratio of the terminal structure to the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

（上記式中、ｊは１～３の整数であり、ｋは０～２００の整数、好ましくは０～１００の整数であり、ｋ’は１～２００の整数、好ましくは１～６０の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。） Rf, which is the basis of monovalence, is expressed by the following formula.

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, and k'is an integer of 1 to 200, preferably an integer of 1 to 60. Yes, l and m are integers from 1 to 100, respectively.)

（上記式中、ｊは１～３の整数であり、ｋは０～２００の整数、好ましくは０～１００の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。） Of these, the one represented by the following formula is preferable.

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, and l and m are integers of 1 to 100, respectively.)

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数であり、但し、ｈ＋ｉは２～３００である。各繰り返し単位はランダムに結合されていてよい。）

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。） Rf, which is a divalent group, is expressed by the following formula.

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.)

(In the equation, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, respectively, and h + i is an integer of 2 to 300. Each repeating unit may be randomly combined. .)

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.)

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.)

（式中、ｊは１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数であり、但し、ｈ＋ｉは２～３００である。各繰り返し単位はランダムに結合されていてよい。） Of these, the one expressed by the following formula is particularly desirable.

(In the formula, j is an integer of 1 to 3, h and i are integers of 0 to 200, respectively, and h + i is an integer of 2 to 300. Each repeating unit may be randomly combined.)

The compound represented by the general formula (1) (fluorine-containing epoxy-modified organosilicon compound) can be produced, for example, by the following method.
First, the organic silicon compound (b) (siloxane or two or more thereof) having two or more, preferably three or more SiH groups in the molecule, with respect to the fluorine-containing compound (a) having an olefin group at the terminal. (Organic silicon compound consisting of the above combination) is subjected to an addition reaction under the condition that the SiH group becomes excessive. By this reaction, a fluorine-containing compound (c) having a plurality of SiH groups is synthesized.

The compound (a) can be particularly represented by the following formula (6).
Rf ^0- (CH = CH ₂ ) _x (6)
(In the above formula (6), x is 1 when Rf ⁰ is monovalent and 2 when Rf 0 is divalent.)

Rf ⁰ is a monovalent group represented by the following formula (7) or a divalent group represented by the following formula (8).
Rf ² -Q ^6- (7)
-Q ⁶ -Rf ¹ -Q ^6- (8)

（上記式中、ｊは１～３の整数であり、ｋは０～２００の整数、好ましくは０～１００の整数であり、ｋ’は１～２００の整数、好ましくは１～６０の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。）
で表される。 In the above formula (7), Rf ² is the following formula

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, preferably an integer of 0 to 100, and k'is an integer of 1 to 200, preferably an integer of 1 to 60. Yes, l and m are integers from 1 to 100, respectively.)
It is represented by.

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数であり、但し、ｋ＋ｔは２～２００である。ｓは０～６の整数である。）、

（式中、ｊは１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数であり、但し、ｈ＋ｉは２～３００である。）
で表される。 Further, in the above equation (8), Rf ¹ is the following equation.

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.),.

(In the formula, j is an integer of 1 to 3, h and i are integers of 0 to 200, respectively, and h + i is an integer of 2 to 300.)
It is represented by.

Further, in the above formulas (7) and ( ⁸ ), Q6 may contain an oxygen atom, a nitrogen atom or a silicon atom independently of each other, and is a divalent organic having 2 to 10 carbon atoms, preferably 2 carbon atoms. It is the basis.

As the above ^Q6 , the one expressed by the following formula can be mentioned.

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｊは１～３の整数であり、ｋ’は１～２００の整数、好ましくは１～６０の整数である。）

（上記式中、ｊは１～３の整数であり、ｌ、ｍはそれぞれ１～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。） Examples of the compound (a) having a monovalent Rf ⁰ include the following.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, j is an integer of 1 to 3, k'is an integer of 1 to 200, preferably an integer of 1 to 60.)

(In the above formula, j is an integer of 1 to 3, and l and m are integers of 1 to 100, respectively.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数、好ましくは０～１００の整数であり、但し、ｋ＋ｔは２～２００、好ましくは３～１５０である。ｓは０～６の整数である。）

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数、好ましくは２～１００の整数であり、但し、ｈ＋ｉは２～３００、好ましくは４～２００である。各繰り返し単位はランダムに結合されていてよい。）

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数、好ましくは０～１００の整数であり、但し、ｋ＋ｔは２～２００、好ましくは３～１５０である。ｓは０～６の整数である。）

（式中、ｒは２～６の整数であり、ｋ、ｔはそれぞれ０～２００の整数、好ましくは０～１００の整数であり、但し、ｋ＋ｔは２～２００、好ましくは３～１５０である。ｓは０～６の整数である。） Examples of the compound (a) having a divalent Rf ⁰ include the following.

(In the formula, r is an integer of 2 to 6, k and t are integers of 0 to 200, preferably 0 to 100, respectively, where k + t is an integer of 2 to 200, preferably 3 to 150. .S is an integer from 0 to 6.)

(In the formula, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, preferably 2 to 100, respectively, where h + i is 2 to 300, preferably 4 to 200. Each repeating unit may be randomly combined.)

(In the formula, r is an integer of 2 to 6, k and t are integers of 0 to 200, preferably 0 to 100, respectively, where k + t is an integer of 2 to 200, preferably 3 to 150. .S is an integer from 0 to 6.)

(In the formula, r is an integer of 2 to 6, k and t are integers of 0 to 200, preferably 0 to 100, respectively, where k + t is an integer of 2 to 200, preferably 3 to 150. .S is an integer from 0 to 6.)

The compound (b) can be particularly represented by the following formula (9).
Q ¹ － (H) _{a + b} (9)
(In formula (9), ^Q1 , a, and b are as described above. H shown in parentheses is a hydrogen atom directly bonded to a Si atom in the ^Q1 structure.)

（上記式中、ａ、ｂは上述の通りである。） Examples of the compound (b) include the following.

(In the above formula, a and b are as described above.)

In particular, the following are preferable.

When Rf ⁰ in the compound (a) is a monovalent group, the number of olefin groups contained in the compound (a) is (a + b) relative to the number of SiH groups contained in one molecule of the compound (b) (a + b). It is preferable to react in an amount of less than a + b), preferably a. The structure of the obtained compound (c) can be represented by the following formula (10).
(Rf ⁰ -C ₂ H ₄ ) _a -Q ^1- (H) _b (10)
(In the above formula, Rf ⁰ , Q ¹ , a and b are as described above.)

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。） Examples of the compound (c) represented by the formula (10) include the following.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

（上記式中、Ｑ¹、Ｒｆ⁰及びｂは上述した通りである。括弧内に示されたＨは、Ｑ¹構造中のＳｉ原子に直接結合する水素原子である。） When Rf ⁰ in the compound (a) is a divalent group, it is desirable to react in a molar ratio of compound (a): compound (b) = 1: 2, and the structure of the obtained compound (c) is, for example, It can be expressed by the following equation (11). That is, the structure is such that one molecule of the compound (b) is introduced into both ends of the compound (a).

(In the above formula, Q ¹ , Rf ⁰ and b are as described above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q ¹ structure.)

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数、好ましくは２～１００の整数であり、但し、ｈ＋ｉは２～３００、好ましくは４～２００である。各繰り返し単位はランダムに結合されていてよい。） Examples of the compound (c) represented by the formula (11) include the following.

(In the formula, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, preferably 2 to 100, respectively, where h + i is 2 to 300, preferably 4 to 200. Each repeating unit may be randomly combined.)

The above addition reaction can be carried out without a solvent, but may be carried out in the presence of a solvent if necessary. As the solvent, a widely used organic solvent such as toluene, xylene, and isooctane may be used. However, it is preferable that the boiling point is equal to or higher than the target reaction temperature, the reaction is not inhibited, and the fluorine-containing compound (c) produced after the reaction is soluble at the reaction temperature. For example, a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluorolide and benzotrifloride, and a partially fluorine-modified solvent such as a fluorine-modified ether solvent such as methyl perfluorobutyl ether are desirable, and particularly m-. Xylene hexafluorolides are preferred.

As the addition reaction catalyst, a conventionally known one may be used. For example, compounds containing platinum, rhodium or palladium can be used. Of these, compounds containing platinum are preferable, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, etc. Alternatively, platinum carried on activated carbon can be used. The blending amount of the catalyst may be an effective amount. In particular, the amount of the metal contained in the compound (a) is preferably 0.1 to 5,000 mass ppm, more preferably 1 to 1,000 mass ppm.

In the addition reaction, the order of charging each component is not particularly limited. For example, a method of gradually heating a mixture of compound (a), compound (b) and a catalyst from room temperature to an addition reaction temperature, up to a reaction temperature for a mixture of compound (a), compound (b) and a diluting solvent. A method of adding a catalyst after heating, a method of dropping the compound (a) into a mixture of the compound (b) heated to the target reaction temperature and the catalyst, and a method of adding the compound (b) to the compound (b) heated to the target reaction temperature. A) and a method of dropping a mixture of the catalyst can be mentioned. Among them, a method of adding a catalyst after heating a mixture of the compound (a), the compound (b) and the diluting solvent to the target reaction temperature, or a method of adding the catalyst to the compound (b) heated to the target reaction temperature, the compound ( A method of dropping a mixture of a) and the catalyst is particularly preferable. The above-mentioned addition reaction conditions may follow a conventionally known method. In particular, in a dry atmosphere, in air or in an inert gas (N ₂ , Ar, etc.), the reaction temperature is 50 to 150 ° C., preferably 70 to 120 ° C., 0.5 to 96 hours, preferably 1 to 48 hours. It is desirable to do it.

The compounding amount of the compound (a) is such that the number of olefin groups of the compound (a) is less than (a + b), preferably a, with respect to one molecule of the compound (b) having (a + b) SiH groups. The amount should be. In particular, when Rf ⁰ in compound (a) is a divalent group, it is desirable to react in a molar ratio of compound (a): compound (b) = 1: 2. In particular, in order to prevent three-dimensional cross-linking, an addition reaction is carried out with respect to the terminal olefin group of the compound (a) using an excessive amount of the compound (b), and then the unreacted compound (b) is distilled off under reduced pressure or the like. It is desirable to remove it.

Next, the SiH group of the fluorine-containing compound (c) obtained above is subjected to an addition reaction with the compound (d) having a terminal olefin group and an epoxy group in one molecule, thereby being represented by the above formula (1). A fluorine-containing epoxy-modified organic silicon compound can be obtained.

Examples of the compound (d) include compounds represented by the following formulas (2a) to (5a).

In the above equation, f'is an integer of 0 to 8, e is an integer of 0 to 5, g is an integer of 0 to 10, and f'+ 2g + e is in the range of 2 to 18. Preferably, f is an integer of 0 to 6, e is 1 or 2, g is an integer of 0 to 4, and f'+ 2g + e is in the range of 2 to 8. n'is an integer of 0 to 18, preferably an integer of 0 to 13. R ² is as described above, preferably a hydrogen atom or a methyl group.

Examples of the compound (d) include the following. The compound may be used alone or in combination of two or more.

The addition reaction between the compound (c) and the compound (d) may be carried out according to a conventionally known method. Preferably, in the presence of the above-mentioned addition reaction catalyst, in a dry atmosphere, in air or in an inert gas (N ₂ , Ar, etc.), the reaction temperature is 50 to 150 ° C., preferably 50 to 120 ° C. for 0.5 to 96 hours. It may be carried out in 1 to 48 hours, preferably. The reaction may use a solvent, if necessary.

Any value can be used for the blending amount of the compound (d) with respect to the compound (c), but the number of terminal olefin groups of the compound (d) is relative to the number of SiH groups of the compound (c). It is desirable to carry out the addition reaction using an amount of equal or excessive number of terminal olefin groups, and then remove the unreacted compound (d) by distillation under reduced pressure or the like. In particular, the ratio of the number of terminal olefin groups of compound (d) to one SiH group of compound (c) is 1.0 to 5.0, preferably 1.0 to 2.0. It is desirable to carry out the reaction.

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｋは０～２００の整数、好ましくは０～１００の整数である。）

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数、好ましくは２～１００の整数であり、但し、ｈ＋ｉは２～３００、好ましくは４～２００である。各繰り返し単位はランダムに結合されていてよい。）

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数、好ましくは２～１００の整数であり、但し、ｈ＋ｉは２～３００、好ましくは４～２００である。各繰り返し単位はランダムに結合されていてよい。）

（式中、ｊは独立に１～３の整数であり、ｈ、ｉはそれぞれ０～２００の整数、好ましくは２～１００の整数であり、但し、ｈ＋ｉは２～３００、好ましくは４～２００である。各繰り返し単位はランダムに結合されていてよい。） Particularly preferably, the compound (A) represented by the general formula (1) can be mentioned below.

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, k is an integer of 0 to 200, preferably an integer of 0 to 100.)

(In the formula, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, preferably 2 to 100, respectively, where h + i is 2 to 300, preferably 4 to 200. Each repeating unit may be randomly combined.)

(In the formula, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, preferably 2 to 100, respectively, where h + i is 2 to 300, preferably 4 to 200. Each repeating unit may be randomly combined.)

(In the formula, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, preferably 2 to 100, respectively, where h + i is 2 to 300, preferably 4 to 200. Each repeating unit may be randomly combined.)

These compounds (A) may be used alone or in combination of a plurality of different compounds (A).

The present invention is an active energy ray-curable composition containing the above-mentioned compound (A) and at least one photopolymerization initiator (B). The photopolymerization initiator (B) is not particularly limited as long as it is a compound capable of initiating the polymerization of the epoxy group of the compound (A) by light (particularly ultraviolet rays), but is particularly widely used as a photoacid-generating agent. Examples of those used include various onium salts that photodecompose.

Examples of such are SbF _6- ^, AsF _6- ^, BF _4- ^, B (C ₆ F ₅ ) _4- ^, PF _6- ^, (Rf'''') _x PF _6-x- ⁽ Rf'''') as counter anions. In the formula, Rf'''' is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and carbon atoms of each group independently of each other. It is a group in which a hydrogen atom bonded to is substituted with a fluorine atom in an amount of 80 mol% or more, and x is an integer of 1 to 5). Examples thereof include a sulfonium salt (sulfonium salt), but from the viewpoint of toxicity, an onium salt having a boron or phosphorus-based counter anion is particularly preferable.

As the photopolymerization initiator (B), various compounds and mixtures thereof are commercially available, including the examples shown above. Specific product names include Sun Appro Co., Ltd. "CPI Series" (for example, CPI-100P, CPI-101A8, CPI-200K, CPI-210S, CPI-310B, CPI-400PG), ADEKA Corporation "ADEKA PTOMER SP". Series ”(eg SP150, SP152, SP170, ADEKA SP172), Sanshin Chemical“ Sun Aid SI Series ”(eg SI-60L, SI-80L, SI-100L), Fujifilm Wako Pure Chemical Industries, Ltd.“ Hikari "WPI series" (for example, PI-169, WPI-170, WPI-124, WPI-116, WPI-113), BASF "IRGACURE 250, IRGACURE 270, IRGACURE 290", etc. can be shown, and these can be used alone or. It is also possible to mix and use multiple. Further, in recent years, a polymerization initiator having both a photocation generation function and a thermal cation generation function has been commercially available, and such a polymerization initiator can also be used. For example, TA-100 of Sun Appro Co., Ltd. can be mentioned.

In the present invention, in addition to the component (A) and the component (B), a component (C) composed of one or more kinds of compounds having cationic curability other than the component (A) can also be contained.
Examples of the cationically curable compound include one or more epoxy groups in one molecule, a compound having a cyclic ether such as an oxetane group, a compound having a vinyl ether group, an aliphatic unsaturated hydrocarbon compound such as isobutene (IB), and styrene. Examples thereof include derivatives, compounds having a carbonyl group such as lactones and cyclic carbonates, and cationically polymerizable nitrogen-containing compounds (monomers) such as bicycloorthoesters, spirolotocarbonates, spirolotoesters, and N-vinylcarbazoles.

Among these, compounds having an epoxy group include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

Examples of the aromatic epoxide include monovalent or polyvalent phenol derivatives having at least one aromatic ring, such as phenol, bisphenol A, bisphenol F, bisphenol AF, and glycidyl ether of phenol novolac. In addition, compounds in which an alkyl ether or an ester structure is introduced into a part of the structure of these glycidyl ethers can also be used.

The alicyclic epoxide is a compound obtained by epoxidizing a compound having at least one cyclohexene ring and cyclopentene ring, and some of its structures include alkyl ethers, alkyl ether oligomers, ester structures, and ε-caprolactone oligomers. Can also be used with compounds introduced into the structure. Specifically, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, limonenedioxide, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide 1,4 -Cyclohexanedimethanol bis (3,4-epoxycyclocarboxylate) and the like can be mentioned.

Examples of the aliphatic epoxide include an aliphatic polyhydric alcohol or a polyglycidyl ether of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), and an aliphatic polybasic acid. Examples thereof include polyglycidyl esters (diglycidyl tetrahydrophthalate and the like) and epoxidates of long-chain unsaturated compounds (epoxidized polybutadiene, epoxidates of plant-derived unsaturated hydrocarbon compounds).

As the compound having an oxetane group, known compounds and the like can be used, for example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-hydroxyethyl). Ethyl-3-oxetanylmethyl) ethers, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ethers, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsilsesquioxetane and Examples thereof include phenol novolac oxetane. Specific product names include "Aron Oxetane Series" manufactured by Toagosei Co., Ltd.

Examples of the compound having a vinyl ether group include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, and aromatic vinyl ethers such as 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether. Further, bifunctional vinyl ethers such as butanediol-1,4-divinyl ether, triethylene glycol divinyl ether and dipropylene glycol divinyl ether can be mentioned.

Examples of the styrene derivative include derivatives such as α-methylstyrene, p-methoxystyrene and p-tert-butoxystyrene in addition to styrene.

Examples of the aliphatic unsaturated hydrocarbon compound include isobutylene, cyclopentadiene, norbornadiene, indene, tetrahydroindene and the like.

Examples of the cationically polymerizable nitrogen-containing monomer include cyclic amines such as ethyleneimine, oxazolines, N-vinylcarbazole, and N-vinylpyrrolidone.

Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] Octane and the like can be mentioned.

Examples of the spiro orthocarbonate include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. Be done.

In particular, those having an epoxy group, an oxetane group, and a vinyl ether group are preferable, and these polymerizable reactive groups are introduced into the terminal and side chains of the siloxane polymer (oligomer) in addition to the above-mentioned form of the monomer. A form can also be used.

The ratio of each component of the active energy ray-curable composition of the present invention takes into consideration various factors such as the properties of the cationically polymerizable compound, the type and irradiation amount of the energy ray, the temperature, the curing time, the humidity, and the thickness of the coating film. When the compound having cation curability is only the component (A), the component (B) is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A). Particularly preferably, it contains 0.05 to 10 parts by mass. If the amount of the component (B) is too small, the concentration of the initiator component is low, so that curing failure is likely to occur, and the reaction rate is lowered. If it is too large, the amount of the initiator fragment contained in the cured product after curing may be too large and may unintentionally affect the physical properties of the cured product.

When the active energy ray-curable composition of the present invention further contains the component (C), the component (B) is preferably 0. It contains 01 to 20 parts by mass, particularly preferably 0.05 to 10 parts by mass. In this case as well, if the amount of the component (B) is too small, the concentration of the initiator component is low, so that curing failure is likely to occur, and the reaction rate is lowered. If it is too large, the amount of the initiator fragment contained in the cured product after curing may be too large and may unintentionally affect the physical properties of the cured product.

Further, when the active energy ray-curable composition of the present invention contains the component (C), it is preferable that the component (A) is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (C), particularly 0. It is more preferable to contain 0.05 to 5 parts by mass.

If necessary, the active energy ray-curable composition of the present invention may contain a sensitizer as a supplement to the curability. As such a sensitizer, for example, the sensitizers disclosed in JP-A-11-279212 and JP-A-09-183960 can be used, and specifically, anthracene {anthracene, 9,10-dibutoxy. Anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthrene; perylene; tetrasen Anthracene; thioxanthone {thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; N-phenylphenanthrene, etc.}; Xantone; Naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, and 4-methoxy-1-naphthol, etc.}; Ketone {dimethoxy Acetphenone, Diethoxyacetphenone, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4'-methyldiphenylsulfide, etc. }; Carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidylcarbazole, etc.}; Anthracene {1,4-dimethoxycrisen and 1,4-di-α-methylbenzyloxychrysen Etc.}; Phenanthrene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like. When the sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass with respect to 100 parts by mass of the component (B).

Other known additives (pigments, fillers, antistatic agents, flame retardants, defoamers, flow modifiers, light stabilizers, antioxidants, adhesions, etc.) may be added to the curable composition of the present invention, if necessary. It can contain a sex-imparting agent, an ion-replenishing agent, an anti-coloring agent, a solvent, a non-reactive resin and oil, an oligomer, etc.).

For the above components (B), (C), and other additives that can be arbitrarily blended, for example, "Photocuring Technology Data Book Materials" edited by Technonet (2000, Technonet), Photo. "Photopolymer Handbook" edited by Polymer Association (1989, Industrial Research Council), "UV / EB Curing Technology" edited by Comprehensive Technology Center (1982, Comprehensive Technology Center), "UV / EB Curing Material" edited by Radtech Study Group (1982) 1992, CMC), Technical Information Association, "Causes of Curing Poorness / Inhibition in UV Curing and Countermeasures" (2003, Technical Information Association), Color Materials, 68, (5), 286-293 (1995), Fine Chemicals , 29, (19), 5-14 (2000), "Network Polymer" Vol. 30 No. 5 (2009), "Network Polymer" Vol. 30 No. 5 (2009), "Network Polymer" Vol. 31 No. 4 (2010), "UV Curable Resin Formulation Design, Characteristic Evaluation and New Applications" edited by Technical Information Association (2017, Technical Information Association), "Market Actual Conditions and Prospects of UV / EB Curing Materials and Products" edited by CMC Publishing. (2007, CMC Publishing), Science & Technology, "Optimization of UV Curing Process" (2008, Science & Technology), etc. show many known ones, and these can be used in any combination.

Further, the active energy ray-curable composition of the present invention may contain a solvent, if necessary. Preferred solvents include alcohols such as isopropanol and butanol, ethers such as tetrahydrofuran and diethylene glycol dimethyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and ethyl lactate, and propylene glycol monomethyl ether acetate. Examples thereof include esterified products of glycol ether. The blending amount of the solvent is not particularly limited, but preferably the total of 100 parts by mass of the above-mentioned components (A) and (B) (when the component (C) is contained, the total of the components (A), (B) and (C)). It is preferably 20 to 900 parts by mass, particularly 50 to 400 parts by mass with respect to 100 parts by mass.

The method for preparing the active energy ray-curable composition of the present invention is not particularly limited. The curable composition of the present invention can be obtained by mixing the above-mentioned component (A) and component (B), if necessary, component (C), any other additive and solvent according to a conventionally known method. can.

Further, as a general usage form of the active energy ray-curable composition of the present invention, it is applied on any substrate as long as the active energy ray-curable composition layer of the present invention adheres or adheres after curing. It is also possible, but in particular 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. , Cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyetherimide, polyimide, fluorine Examples thereof include resins such as resins, nylons, and acrylic resins. These can be used on the surface of any form such as a film, a plate, and a molded member.

Further, when applied to a film substrate, it may have a structure in which a pressure-sensitive adhesive is applied to the surface opposite to the surface on which the fluorine-containing active energy ray-curable composition layer is applied and formed, further protecting the pressure-sensitive adhesive. A release film for the purpose may be arranged.

Further, the film base material may be a base material consisting of only the resin film mentioned above, but in order to improve the adhesion to the active energy ray-curable composition of the present invention, a primer is applied to the resin film. It may be a film substrate provided with a layer. Examples of the primer layer include those made of polyester-based resin, urethane-based resin, acrylic-based resin, and the like.

Further, the active energy ray-curable composition of the present invention may be applied and cured on a cured / uncured curable composition layer which does not correspond to the present invention. For example, the active energy ray-curable composition of the present invention can be overcoated on a cured product layer having higher deformation resistance such as hardness, durability, antistatic property, and curl.

Further, for the purpose of improving the adhesion to the active energy ray-curable composition of the present invention, the surface of the resin film is subjected to surface unevenness treatment by sandblasting method, solvent treatment method, etc., corona discharge treatment, chromic acid treatment, flame. It can also be treated by treatment, hot air treatment, ozone / ultraviolet irradiation treatment, oxidation treatment and the like.

The method for applying the active energy ray-curable composition of the present invention to the substrate or the article is not particularly limited, but for example, roll coat, gravure coat, flow coat, curtain coat, dip coat, spray coat, spin. Known coating methods such as coating, bar coating, inkjet printing, and screen printing can be used.

After coating, the coating film is irradiated with active energy rays to cure it. Here, as the active energy ray, any beam such as an electron beam and ultraviolet rays can be used, but ultraviolet rays are particularly preferable. As the ultraviolet source, a mercury lamp, a metal halide lamp, and an LED lamp are suitable. If the amount of ultraviolet irradiation is too small, uncured components will remain, and if it is too large, the coating film and the base material may deteriorate. Therefore, 10 to 10,000 mJ / cm 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 moisture, the irradiation atmosphere may be replaced with a gas such as air, nitrogen, carbon dioxide, or argon in which the amount of water in the gas is controlled during ultraviolet irradiation, or the surface of the coating film may be releasable. Cover with a protective layer that is transparent to ultraviolet rays and irradiate ultraviolet rays from above, or if the base material has ultraviolet rays, cover the surface of the coating film with a protective layer that has a releasable property and then use the base material. Ultraviolet rays may be irradiated from the side opposite to the coated surface. In addition, in order to effectively perform the leveling of the coating film or the reaction of the cationically polymerizable group in the coating film, even if the coating film and the base material are heated by any method such as infrared rays or a hot air drying oven before and during irradiation with ultraviolet rays. good.

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

Further, the cured product layer of the active energy ray-curable composition of the present invention thus obtained is measured by the angle formed by the liquid surface and the solid surface of 2 μL droplets of ion-exchanged water 1 second after contact with the liquid. The surface has a static water contact angle (also simply referred to as a water contact angle) of 100 ° or more, particularly 105 ° or more. In addition, the static oleic acid contact angle (also simply referred to as oleic acid contact angle) measured by the angle formed by the liquid surface and the solid surface of 4 μL of oleic acid droplets 1 second after contact with the liquid is 60 ° or more, particularly 65. It is preferable that the surface can have a water-repellent and oil-repellent surface of ° or more. In order to obtain the contact angle, the cured product layer of the fluorine-containing active energy ray-curable composition of the present invention is formed to 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 the amount is sufficient. Further, it is preferable that no unreacted cationically polymerizable group remains on the surface of the cured product layer. Therefore, the active energy ray curing treatment under a moisture-controlled atmosphere and heating conditions, and a photopolymerization initiator (B) It is possible to arbitrarily adjust the blending amount of the polymer, maintain it for the progress of the dark reaction in a clean environment after irradiation with active energy rays, and the like.

As described above, the active energy ray-curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and has water and oil repellency, stain resistance, fingerprint resistance, and slipperiness on the surface of the article. A cured resin layer having excellent wear resistance can be formed.

Further, the present invention provides an article having a cured film obtained by applying and curing the above-mentioned active energy ray-curable composition of the present invention on a surface thereof. As described above, by using the active energy ray-curable composition of the present invention, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of a base material (article). In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of a cation-curable hard coat. This makes it difficult for fingerprints, sebum, human oil such as sweat, stains caused by cosmetics, machine oil, etc. to adhere to the substrate, and a hard coat surface having excellent wiping property can be provided to the base material. Therefore, the active energy ray-curable composition of the present invention is contaminated with a base material (article) that may be contaminated by human fat, cosmetics, etc., and worker's human fat, machine oil, etc. It is possible to provide an antifouling coating film or a protective film for the surface of a process material film or the like used inside a machine which may be used.

The cured film (cured resin layer) formed by using the active energy ray-curable composition of the present invention is a portable (communication) information terminal such as a tablet computer, a notebook PC, a mobile phone / smartphone, a digital media player, and an electronic device. Cases of various devices such as book readers, watch-type and eyeglass-type wearable computers; liquid crystal display, plasma display, organic EL (electroluminescence) display, rear projection type display, fluorescent display tube (VFD), field emission projection display, CRT, Various flat panel displays such as toner-based displays, display operation equipment surfaces such as TV screens, various optical films used inside these, automobile exteriors, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, etc. , Decorative building materials around water such as toilets, baths, washrooms, protective glass for art exhibitions, show windows, showcases, photo frame covers, watches, automobile window glass, trains, aircraft window glass, automobile headlights, etc. It is useful as a coating film and a surface protective film for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as tail lamps, and various mirror members.

In particular, various devices such as touch panel displays that have display input devices that operate on the screen with human fingers or palms, such as tablet computers, notebook PCs, smartphones, mobile phones, other mobile (communication) information terminals, and smart watches. , Digital media player, electronic book reader, digital photo frame, game machine, digital camera, digital video camera, GPS display recording device, navigation device for automobiles, control panel for automobiles, automatic cash withdrawal deposit device, automatic cash It is useful as a surface protective film for various controllers such as payment machines, vending machines, digital signage (electronic signboards), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices.

Further, the cured film formed by the active energy ray-curable composition of the present invention is an optical recording medium such as a photomagnetic disk or an optical disk; It is also useful as a surface protective film for optical components and optical devices such as Fresnel lenses, antireflection films, lenses for various cameras, protective filters for various lenses, optical fibers and optical couplers.

In the active energy ray-curable composition of the present invention as described above, the perfluoropolyether structure of the fluorine-containing epoxy-modified organic silicon compound (A) according to the present invention is arranged on the surface of the target article. Its essence is to provide excellent properties such as water repellency, oil repellency, slipperiness, stain resistance, fingerprint inconspicuousness, fingerprint wiping resistance, wear resistance, low refractive index characteristics, solvent resistance, and chemical resistance. It is supposed to be.

When such a fluorine-containing active energy ray-curable composition of the present invention is used, an appropriate usage method is applied to each application according to the combination of formulations, the composition ratio, and what characteristics are emphasized. It may be selected based on the known technique according to the situation. Such known techniques can be included in the scope of study, including not only for compositions containing fluorine, but also for techniques used in existing active energy ray-curable compositions.

For example, when the active energy ray-curable composition of the present invention is blended and prepared, in addition to the fluorine-containing epoxy-modified organic silicon compound (A) according to the present invention, various formulations in the above-mentioned curable composition are combined. When emphasizing low refractive index characteristics and low reflection characteristics using these, reactive hollow silica, hollow silica having no reactive group, and various polyfunctional compounds as compound (C) should be used. When improving the film strength and scratch resistance, various polyfunctional compounds are blended in an appropriate amount as the compound (C), and an epoxy group-containing compound having a slow curing rate is used as the compound (C). It is a method that can be easily inferred from the knowledge of known cationically curable composition formulations, such as improving the curing rate by blending an oxetane group-containing compound or a vinyl ether-containing compound.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

（式中Ｒｆ''は下記の基である。繰返し単位の数は分布を有し、５．２は平均値である。

）
で表される含フッ素環状シロキサン３０．０ｇと、ｍ－キシレンヘキサフロライド３０．０ｇを仕込み、攪拌しながら９０℃まで加熱した。ここにアリルグリシジルエーテル８．０ｇと白金／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０．０１０ｇ（白金換算で２．４９×１０^-8ｍｏｌ）の混合溶液を３０分かけて滴下し、９０℃で８時間攪拌した。この場合、上記含フッ素環状シロキサンが有するＳｉＨ基１個に対するアリルグリシジルエーテルが有する末端オレフィン基の個数の比は１．０２である。¹Ｈ－ＮＭＲで原料のＳｉ－Ｈが消失したのを確認した後、活性炭処理を行った。その後溶剤や過剰のアリルグリシジルエーテルを減圧溜去し、下記式で表される化合物（Ａ－１）３４．２ｇを得た。

[Synthesis Example 1]
-Production of compound (A-1) Under a dry nitrogen atmosphere, the following formula was placed in a 100 ml three-necked flask equipped with a reflux device and a stirrer.

(Rf'' in the equation is the following group. The number of repeating units has a distribution, and 5.2 is an average value.

)
30.0 g of a fluorine-containing cyclic siloxane represented by (1) and 30.0 g of m-xylene hexafloride were charged and heated to 90 ° C. with stirring. A mixed solution of 8.0 g of allyl glycidyl ether and 0.010 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (2.49 × 10 ^-8 mol in terms of platinum) was added dropwise over 30 minutes. Then, the mixture was stirred at 90 ° C. for 8 hours. In this case, the ratio of the number of terminal olefin groups contained in the allyl glycidyl ether to one SiH group contained in the fluorine-containing cyclic siloxane is 1.02. After confirming that the raw material Si—H had disappeared by ¹ H-NMR, activated carbon treatment was performed. Then, the solvent and excess allyl glycidyl ether were distilled off under reduced pressure to obtain 34.2 g of the compound (A-1) represented by the following formula.

Ｒｆ’：－ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂－
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 2]
-Production of compound (A-2) Under a dry nitrogen atmosphere, in a 2000 ml three-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 (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-
(P / q = 0.9, p + q≈45)
500 g of perfluoropolyether having an α-unsaturated bond, 700 g of m-xylenehexafluorolide, and 361 g of tetramethylcyclotetrasiloxane were added to both ends represented by (1) and heated to 90 ° C. with stirring. Toluene solution 0.442 g of 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. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 498 g of a colorless and transparent liquid compound (P-1) represented by the following formula.

Rf': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-
(P / q = 0.9, p + q≈45)

Ｒｆ’：－ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂－
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） 60.0 g of the above compound (P-1), 10.0 g of allyl glycidyl ether and 60.0 g of m-xylene hexafloride were mixed and heated to 80 ° C. under a nitrogen atmosphere with stirring. In this case, the ratio of the number of terminal olefin groups contained in the allyl glycidyl ether to one SiH group contained in the compound (P-1) is 1.15. 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone) was added thereto, and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that the raw material Si—H had disappeared by ¹ H-NMR, activated carbon treatment was performed. Then, the solvent and excess allyl glycidyl ether were distilled off under reduced pressure to obtain 66.2 g of a translucent grease-like compound (A-2) represented by the following formula.

Rf': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-
(P / q = 0.9, p + q≈45)

Ｒｆ’：－ＣＦ₂（ＯＣＦ₂ＣＦ₂）_p（ＯＣＦ₂）_qＯＣＦ₂－
（ｐ／ｑ＝０．９、ｐ＋ｑ≒４５） [Synthesis Example 3]
-Production of compound (A-3) 60.0 g of the above compound (P-1), 10.9 g of 3-vinylcyclohexene oxide and 60.0 g of m-xylenehexafloride are mixed and stirred in a nitrogen atmosphere. It was heated to 80 ° C. In this case, the ratio of the number of terminal olefin groups of 3-vinylcyclohexene oxide to one SiH group of the compound (P-1) is 1.14. 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone) was added thereto, and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that the raw material Si—H had disappeared by ¹ H-NMR, activated carbon treatment was performed. Then, the solvent and excess 3-vinylcyclohexene oxide were distilled off under reduced pressure to obtain 66.1 g of a translucent grease-like compound (A-3) represented by the following formula.

Rf': -CF ₂ (OCF ₂ CF ₂ ) _p (OCF ₂ ) _q OCF _2-
(P / q = 0.9, p + q≈45)

Ｒｆ'''：－ＣＦ₂（ＯＣＦ₂ＣＦ₂）_h’（ＯＣＦ₂）_i’ＯＣＦ₂－
（ｈ’＝６．８、ｉ’＝５．７、ｈ’及びｉ’はそれぞれの平均値） [Synthesis Example 4]
-Production of compound (A-4) Under a dry nitrogen atmosphere, in a 2000 ml three-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 (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i'OCF 2} －
(H'= 6.8, i'= 5.7, h'and i'are the average values of each)
500 g of perfluoropolyether having an α-unsaturated bond, 700 g of m-xylene hexafloride, and 865 g of pentamethylcyclopentasiloxane were added to both ends represented by (1) and heated to 90 ° C. with stirring. Toluene solution 0.442 g of 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. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 538 g of a colorless and transparent liquid compound (P-2) represented by the following formula.

Rf''': －CF ₂ (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i'OCF 2} －
(H'= 6.8, i'= 5.7, h'and i'are the average values of each)

Ｒｆ'''：－ＣＦ₂（ＯＣＦ₂ＣＦ₂）_h’（ＯＣＦ₂）_i’ＯＣＦ₂－
（ｈ’＝６．８、ｉ’＝５．７、ｈ’及びｉ’はそれぞれの平均値） 100.0 g of the above compound (P-2), 41.0 g of allyl glycidyl ether and 100.0 g of m-xylene hexafloride were mixed and heated to 80 ° C. under a nitrogen atmosphere with stirring. In this case, the ratio of the number of terminal olefin groups contained in the allyl glycidyl ether to one SiH group contained in the compound (P-2) is 1.2. 0.0221 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 5.6 × 10 ^-8 mol as Pt alone) was added thereto, and the internal temperature was maintained at 90 to 120 ° C. Stirring was continued for 6 hours. After confirming that the raw material Si—H had disappeared by ¹ H-NMR, activated carbon treatment was performed. Then, the solvent and excess allyl glycidyl ether were distilled off under reduced pressure to obtain 134 g of a colorless transparent liquid compound (A-4) represented by the following formula.

Rf''': －CF ₂ (OCF ₂ CF ₂ ) _h' (OCF ₂ ) _{i'OCF 2} －
(H'= 6.8, i'= 5.7, h'and i'are the average values of each)

[Examples and Comparative Examples]
(Preparation of active energy ray-curable composition)
Each component was mixed according to the composition shown in Table 1 below to prepare an active energy ray-curable composition.

Ｂ－１：光カチオン重合開始剤ＣＰＩ－２００Ｋ（リン系アニオン型トリアリールスルホニウム塩、溶媒希釈品、サンアプロ株式会社製）
Ｂ－２：光カチオン重合開始剤ＣＰＩ－２１０Ｓ（リン系アニオン型トリアリールスルホニウム塩、粉体、サンアプロ株式会社製）
Ｂ－３：光・熱カチオン重合開始剤ＴＡ－１００（スルホニウム塩、粉体、サンアプロ株式会社製）
Ｃ－１：液状エポキシ樹脂 エポトート ＺＸ－１０５９（下記式のビスフェノールＡ、ビスフェノールＦモノマー混合物、新日鉄住金化学株式会社）

Ｃ－２：下記式の４官能エポキシ化合物

Ｄ－１：メチルエチルケトン
Ｄ－２：酢酸ブチル

B-1: Photocationic polymerization initiator CPI-200K (phosphorus anionic triarylsulfonium salt, solvent diluted product, manufactured by San-Apro Co., Ltd.)
B-2: Photocationic polymerization initiator CPI-210S (phosphorus anionic triarylsulfonium salt, powder, manufactured by San-Apro Co., Ltd.)
B-3: Photo-thermal cationic polymerization initiator TA-100 (sulfonium salt, powder, manufactured by Sun Appro Co., Ltd.)
C-1: Liquid epoxy resin Epototo ZX-1059 (Bisphenol A, bisphenol F monomer mixture of the following formula, Nippon Steel & Sumikin Chemical Co., Ltd.)

C-2: The tetrafunctional epoxy compound of the following formula

D-1: Methyl ethyl ketone D-2: Butyl acetate

(Formation of cured film)
Each composition of Formulation Examples 1 to 14 was coated on a polycarbonate plate having a thickness of about 12 μm (wet film thickness) with a spin coater, and dried with a hot air dryer. The dry film thickness after drying was about 5 μm. Then, using a conveyor-type metal halide UV irradiator (manufactured by Panasonic Electric Works Co., Ltd., 80 w / cm), the film was irradiated with ultraviolet rays having a predetermined integrated light intensity in a nitrogen atmosphere under the conditions shown in Table 2 to obtain a cured film.
Further, each composition of Formulation Examples 6 to 8 and 12 to 14 is coated on a polycarbonate plate having a thickness of about 12 μm (wet film thickness) with a spin coater, and dried with a hot air dryer. Carried out. The dry film thickness after drying was about 5 μm. Then, using a conveyor-type metal halide UV irradiator (manufactured by Panasonic Electric Works Co., Ltd., 80 w / cm), ultraviolet rays of a predetermined integrated amount of light were irradiated in the air under the conditions shown in Table 3 and cured to obtain a cured film.

(Evaluation method)
[Evaluation of water and oil repellency]
Using the contact angle meter DropMaster (manufactured by Kyowa Surface Science Co., Ltd.), the contact angle (water contact angle) of the cured film surface obtained above with water and the contact angle with oleic acid at 25 ° C. are measured (oleic acid contact angle). did. The measurement was performed 30 minutes after UV irradiation.
The water contact angle was measured by the angle formed by the liquid surface and the cured film surface 1 second after the droplet of 2 μL of ion-exchanged water came into contact with the liquid. The contact angle of oleic acid was measured by the angle formed by a droplet of 4 μL of oleic acid between the liquid surface and the cured film surface 1 second after contact with the liquid.

[Magic ink repellent]
An oil-based marker (manufactured by Zebra Co., Ltd., bold in Hi-McKee) was applied to the surface of the cured product, and the repellent property of the ink was visually evaluated using the following indexes. The measurement was performed 45 minutes after UV irradiation.
A: Repel quickly.
B: Repel.
C: It doesn't repel at all.

[Fingerprint wiping property]
The sebum on the forehead was transferred to the surface of the cured product with fingers by five panelists, and the wiping property when wiped with Bencot (manufactured by Asahi Kasei Corporation) was evaluated according to the following evaluation criteria. The evaluation was performed between 1 hour and 2 hours after UV irradiation.
A: Fingerprints can be easily wiped off.
B: Fingerprints can be wiped off.
C: Fingerprints cannot be wiped off.
The above evaluation results are shown in Tables 2 and 3, respectively.

Claims (13)

The following general formula (1)

(In the formula (1), Rf is a monovalent or divalent group having a number average molecular weight of 400 to 40,000 having a fluoropolyether structure independently of each other.
When Rf is a monovalent group, the following formula

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
Represented by
When Rf is a divalent group, the following formula

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.),.

(In the equation, j is an independent integer of 1 to 3, h and i are integers of 0 to 200, respectively, and h + i is an integer of 2 to 300. Each repeating unit may be randomly combined. .),

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.) Or.

(In the equation, r is an integer of 2 to 6, k and t are integers of 0 to 200, respectively, where k + t is an integer of 2 to 200. S is an integer of 0 to 6.)
It is represented by.
When Rf is a monovalent group, a'is 1 and a is an integer of 1 to 6. When Rf is a divalent group, a'is 2, a is 1, b is an integer of 1 to 20, and a + b is an integer of 3 to 21.
Q ¹ is a (a + b) valence group having at least (a + b) Si atoms independently of each other, and has the following formula.

(In the formula, a and b are as described above, the broken line indicates a bond, and each silicon atom of the unit shown in parentheses having a repetition is bonded to Rf in the formula (1). Each silicon atom of the unit shown in parentheses having b repetitions may be bonded to Q ² in the above formula (1), and the sequence of units shown in parentheses may be random.)
It is represented by.
Q ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond independently of each other and may have a cyclic structure.
X is independent of each other and has the following formula (I) or (II).

(In formula (I), R ¹ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and may contain an ether bond or an ester bond, and has a cyclic structure. You may have it.)

(In formula (II), R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other.)
It is a group represented by. )
Fluorine-containing epoxy-modified organosilicon compound (A) represented by
An active energy ray-curable composition containing a photopolymerization initiator (B) and not containing a radically polymerized (meth) acrylic group-containing fluorine-containing organic silicon compound, at a surface water contact angle of 100 ° or more. An active energy ray-curable composition that provides a cured product. The active energy ray-curable composition according to claim 1, wherein in the formula (1), the structure represented by ^−Q2 −X is selected from the groups represented by the following formulas (2) to (5).

(In the above equation, f is an integer of 1 to 10, e is an integer of 0 to 5, g is an integer of 0 to 10, f + 2g + e is in the range of 1 to 20, and n is 1 to 20. R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other.) The active energy ray-curable composition according to claim 1 or 2, wherein in the formula (1), Q ² is independently selected from the groups represented by the following formulas.
-CH ₂ CH _2- ,
-CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ,
-CH ₂ 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 CH ₂ OCH ₂ CH ₂ OCH ₂ -or-CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH _2- In the above formula (1), the structure represented by ^−Q2 −X is the following formula.

The active energy ray-curable composition according to claim 2 or 3. The active energy ray-curable composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (B) is a photoacid generator. The active energy ray-curable composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (B) is any one of a diazonium salt, an iodonium salt, and a sulfonium salt. 17. Active energy ray-curable composition. Further, the component (C) composed of one or more kinds of compounds having cation curability other than the component (A) is contained, and the component (B) is added to a total of 100 parts by mass of the component (A) and the component (C). The active energy ray-curable composition according to any one of claims 1 to 6, which comprises 0.01 to 20 parts by mass. (C) A compound having one or more epoxy group, vinyl ether group, oxetane group, or carbonyl group in one molecule, an aliphatic unsaturated hydrocarbon compound, a styrene derivative, a bicycloorthoester, a spirolotocarbonate, The active energy ray-curable composition according to claim 8, which is a spiroletoester or a cationically polymerizable nitrogen-containing compound. The active energy according to claim 8 or 9, wherein the component (A) is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (C), and the water contact angle of the surface of the cured product after curing is 100 ° or more. Linear curable composition. The active energy ray curing according to any one of claims 1 to 10, wherein the component (A) is a fluorine-containing epoxy-modified organosilicon compound in which a'is 2 in the general formula (1) and Rf is a divalent group. Sex composition. (A) The component is 1 in the general formula (1), and Rf is the following formula.

(In the above formula, j is an integer of 1 to 3, k is an integer of 0 to 200, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
The active energy ray-curable composition according to any one of claims 1 to 10, which is a fluorine-containing epoxy-modified organosilicon compound having a monovalent group represented by. Rf is the following formula

(In the above formula, j is an integer of 1 to 3, k'is an integer of 1 to 200, and l and m are integers of 1 to 100, respectively.)
The active energy ray-curable composition according to claim 12, which is a monovalent group represented by any of the above.