JP2017190429A - Fluorine-containing acryl composition and method for producing the same, fluorine-containing active energy ray-curable composition and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing acryl composition that can impart liquid-repellent and antifouling properties without increasing a volatile organic compound free of a group that reacts with an acrylic group, its production method, a fluorine-containing active energy ray-curable composition, and an article having a cured product layer thereof on the base material surface.SOLUTION: A fluorine-containing acryl composition contains (A) a fluorine-containing acryl compound of the following formula: X-Rf-Z-Q-[ZOR](Rfis a divalent perfluoropolyether group, Qis an Si-containing (a+1) valent linking group, Zis a divalent linking group, Zis a divalent hydrocarbon group, Ris H, or an (α-substituted) acrylic group-containing monovalent organic group, X is a fluorine atom or a -Z-Q-[ZOR]group. a is 1-10) and (B) an acryl compound having a viscosity at 25°C of 100 mPa s or less and containing a (meth) acrylic group, with a mass ratio between them being 0.03<(A)/(B)<10, where the fluorine-containing acryl composition does not contain a volatile organic compound free of a group that reacts with an acrylic group.SELECTED DRAWING: None

Description

  The present invention relates to a fluorine-containing acrylic composition that can be provided with liquid repellency and antifouling property by being added to an active energy ray-curable composition such as an ultraviolet ray or an electron beam, and production of the fluorine-containing acrylic composition The present invention relates to a method, a fluorine-containing active energy ray-curable composition having the composition, and an article having a cured layer of the composition on a substrate surface.

  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.

  On the other hand, the hard coat treatment is widely handled with a coating solution diluted with an organic solvent in order to improve the coating property and coating performance. In recent years, however, there has been an increasing trend to suppress the use of volatile organic compounds (VOC) such as volatile organic solvents due to concerns about the environment and the human body. There is a strong demand for the system. Along with this, volatile organic compounds having no reactive groups such as volatile organic solvents are also added to the additive composition added to impart liquid repellency and antifouling properties to the hard coat coating liquid as described above. There is a need for a composition that does not contain.

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, and by suppressing the content of volatile organic compounds having no reactive groups, when added to the curable composition, the acrylic group as a whole curable composition and Liquid repellency and prevention without increasing (non-reactive) volatile organic compounds that do not have reactive groups (especially non-reactive volatile organic compounds that do not contain (meth) acrylic groups in the molecule) Fluorine-containing acrylic composition capable of imparting dirtiness, method for producing the fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition having the composition, and a cured product layer of the composition It aims at providing the article which has on the material surface.

  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 No.-138112 (Patent Document 3), JP 2010-285501 (Patent Document 4), and the like have been proposed.

  These have a structure having a fluoropolyether structure and a plurality of acrylic groups in one molecule, and can impart high antifouling properties to the curable resin composition, but on the other hand, a highly viscous liquid that is difficult to handle by itself. Therefore, in order to facilitate the handling and to improve the mixing property with the resin composition, it was necessary to handle it as a solution diluted with a highly volatile organic solvent. For this reason, there is a problem that it cannot be blended as it is in a solventless hard coat agent or paint.

  As a result of further studies, the inventor has (A) a fluorine-containing acrylic compound represented by the formula (1) described later, and (B) a viscosity at 25 ° C. of 100 mPa · s or less, An acrylic compound containing one or two (meth) acrylic groups, and the mass ratio of the component (A) to the component (B) is within the range of 0.03 <(A) / (B) <10 A fluorinated organic compound that does not contain a volatile organic compound that does not react with an acrylic group (particularly, a non-reactive volatile organic compound that does not contain a (meth) acrylic group in the molecule). When the acrylic composition is added to the active energy ray-curable composition, it becomes a fluorine-containing active energy ray-curable composition that has liquid repellency and antifouling properties and suppresses the content of volatile organic compounds. To achieve the present invention. It was.

（但し、（ ）で括られた繰り返し単位の配列はランダムであり、ｐは１〜２００の整数、ｑは１〜１７０の整数、ｐ＋ｑは６〜２０１である。ｓは０〜６の整数、ｔ、ｕはそれぞれ１〜１００の整数、ｔ＋ｕは２〜１２０の整数である。ｖは１〜１２０の整数である。）
で表される２価パーフルオロポリエーテル基のいずれかである［１］〜［４］のいずれかに記載の含フッ素アクリル組成物。
［６］
（Ａ）成分において、一般式（１）中のＺ¹が下記式
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂−

で表されるいずれかの構造である［１］〜［５］のいずれかに記載の含フッ素アクリル組成物。
［７］
（Ａ）成分において、一般式（１）中のＱ¹が下記式

（式中、ａは独立に１〜１０の整数である。）
で表される構造である［１］〜［６］のいずれかに記載の含フッ素アクリル組成物。
［８］
（Ａ）成分が、下記式で表される含フッ素アクリル化合物から選ばれるものである［１］〜［７］のいずれかに記載の含フッ素アクリル組成物。

（式中、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である。ｅ１は１〜３０の整数である。Ｒ’は水素原子、

又は

であり、これらは一つの分子中に混在していてもよい。但し、Ｒ’は１分子中に平均して少なくとも１個の上記（メタ）アクリル基を含有する１価の有機基である。ｖ１は２〜１２０の整数である。）
［９］
（Ｂ）２５℃における粘度が１００ｍＰａ・ｓ以下で、１分子中に（メタ）アクリル基を１個又は２個含むアクリル化合物の存在下において、
（Ｃ）下記一般式（４）で表される含フッ素多官能アルコール化合物と、
Ｘ¹−Ｒｆ¹−Ｚ¹−Ｑ¹−［Ｚ²ＯＨ］_a （４）
（式中、Ｘ¹はフッ素原子又は−Ｚ¹−Ｑ¹−［Ｚ²ＯＨ］_aで表される基であり、Ｒｆ¹は炭素数１〜６のパーフルオロアルキレン基と酸素原子によって構成される分子量８００〜２０，０００の２価のパーフルオロポリエーテル基であり、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から選ばれる少なくとも１種を含んでいてもよい２価の連結基であり、Ｑ¹は独立に少なくとも（ａ＋１）個のケイ素原子を含む（ａ＋１）価の連結基であり、環状構造をなしていてもよく、酸素原子、窒素原子及びフッ素原子から選ばれる少なくとも１種を含んでいてもよい。Ｚ²は独立に炭素数１〜２００の、酸素原子、窒素原子及びケイ素原子から選ばれる少なくとも１種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。ａは１〜１０の整数である。）
（Ｄ）１分子中に一つのイソシアネート基と少なくとも一つの（メタ）アクリル基を有する化合物とを反応させて、
（Ａ）下記一般式（１）で表される含フッ素アクリル化合物
Ｘ−Ｒｆ¹−Ｚ¹−Ｑ¹−［Ｚ²ＯＲ¹］_a （１）
（式中、Ｒｆ¹、Ｚ¹、Ｑ¹、Ｚ²、ａは上記と同じである。Ｒ¹は独立に水素原子、又は酸素原子及び窒素原子から選ばれる少なくとも１種を含んでいてもよいアクリル基もしくはα置換アクリル基を含有する１価の有機基であり、但し、Ｒ¹は１分子中に平均して少なくとも１個の前記アクリル基もしくはα置換アクリル基を含有する１価の有機基を有する。Ｘはフッ素原子又は−Ｚ¹−Ｑ¹−［Ｚ²ＯＲ¹］_aで表される１価の基である。）
を生成させる工程を有し、上記（Ａ）成分と（Ｂ）成分の質量比が０．０３＜（Ａ）／（Ｂ）＜１０の範囲内であって、なおかつ、アクリル基と反応する基を持たない揮発性有機化合物が配合されていない含フッ素アクリル組成物を得ることを特徴とする含フッ素アクリル組成物の製造方法。
［１０］
（Ｂ）成分の一部又は全部として、下記一般式（２）
ＣＨ₂＝ＣＲ⁶ＣＯＯＲ⁵ （２）
（式中、Ｒ⁵は炭素数１〜２０のアルキル基、アリール基又はアラルキル基であり、分岐していても環状をなしていてもよく、脂肪族不飽和結合、ウレタン結合、エーテル結合、イソシアネート基、水酸基を含んでいてもよい。Ｒ⁶は水素原子又はメチル基、フッ素原子、炭素数１〜６のフルオロアルキル基である。）
で表されるアクリル化合物及び／又は下記一般式（３）
ＣＨ₂＝ＣＲ²ＣＯＯＺ³Ｒｆ² （３）
（但し、式中、Ｒ²は独立に水素原子、Ｆ、Ｃｌ、Ｂｒ又は炭素数１〜８の１価の炭化水素基であり、炭化水素基中の水素原子はＦ、Ｃｌ、Ｂｒで置換されていてもよい。Ｚ³は独立に炭素数１〜８の２価の炭化水素基であり、分岐していてもよく、途中に酸素原子、水酸基を含んでいてもよい。Ｒｆ²はフッ素原子数２〜２０のフルオロアルキル基であり、水素原子、酸素原子を含んでいてもよく、分岐していてもよい。）
で表される含フッ素アクリル化合物を含み、
（Ｃ）成分の一般式（４）及び（Ａ）成分の一般式（１）において、Ｒｆ¹が以下３種類の構造式
−ＣＦ₂Ｏ−（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_q−ＣＦ₂−

（但し、（ ）で括られた繰り返し単位の配列はランダムであり、ｐは１〜２００の整数、ｑは１〜１７０の整数、ｐ＋ｑは６〜２０１である。ｓは０〜６の整数、ｔ、ｕはそれぞれ１〜１００の整数、ｔ＋ｕは２〜１２０の整数である。ｖは１〜１２０の整数である。）
で表される２価パーフルオロポリエーテル基のいずれかであり、Ｚ¹が下記式
−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−
−ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂−

で表されるいずれかの構造であり、Ｑ¹が下記式

（式中、ａは独立に１〜１０の整数である。）
で表される構造である［９］に記載の含フッ素アクリル組成物の製造方法。
［１１］
活性エネルギー線硬化性組成物（Ｅ）１００質量部に対し、［１］〜［８］のいずれかに記載の含フッ素アクリル組成物を０．００５〜４０質量部含むことを特徴とする含フッ素活性エネルギー線硬化性組成物。
［１２］
活性エネルギー線硬化性組成物（Ｅ）が、
（Ｅａ）アクリル化合物：１００質量部、
（Ｅｂ）光重合開始剤：０．１〜１５質量部
を含有してなるものである［１１］に記載の含フッ素活性エネルギー線硬化性組成物。
［１３］
［１１］又は［１２］に記載の含フッ素活性エネルギー線硬化性組成物の硬化物層を表面に有する物品。 Accordingly, the present invention provides the following fluorine-containing acrylic composition and method for producing the same.
[1]
(A) a fluorine-containing acrylic compound represented by the following general formula (1),
^{X-Rf 1 -Z 1 -Q 1} - [Z 2 OR 1] a (1)
(In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 800 to 20,000 composed of a C 1-6 perfluoroalkylene group and an oxygen atom, and Q ¹ is independently at least (a + 1 ) is a number of containing a silicon atom (a + 1) -valent linking group may optionally form a cyclic structure, an oxygen atom, a nitrogen atom and optionally .Z ¹ also include at least one selected from fluorine atoms A divalent linking group having 1 to 20 carbon atoms, which may contain at least one selected from an oxygen atom, a nitrogen atom and a silicon atom, may contain a cyclic structure, and is branched; And some hydrogen atoms may be substituted with fluorine atoms, and Z ² independently contains at least one selected from an oxygen atom, a nitrogen atom and a silicon atom having 1 to 200 carbon atoms. Also A There divalent hydrocarbon group, the middle ring structure may contain a .R ¹ is independently a hydrogen atom, or an oxygen atom and at least one optionally containing an acryl group or be α selected from nitrogen atom A monovalent organic group containing a substituted acrylic group, provided that R ¹ has an average of at least one monovalent organic group containing the above-mentioned acrylic group or α-substituted acrylic group in one molecule. a fluorine atom or a -Z ¹ -Q ¹ - is a monovalent group represented by [Z ² oR ^1] _a .a is an integer of 1 to 10).
(B) The viscosity at 25 ° C. is 100 mPa · s or less, contains an acrylic compound containing one or two (meth) acrylic groups in one molecule as an essential component, and the mass of component (A) and component (B) The ratio is within a range of 0.03 <(A) / (B) <10, and a volatile organic compound having no group that reacts with an acrylic group is not blended. Fluorine-containing acrylic composition.
[2]
As part or all of the component (B), the following general formula (2)
CH ₂ = CR ⁶ COOR ⁵ (2)
(In the formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, which may be branched or cyclic, an aliphatic unsaturated bond, a urethane bond, an ether bond, an isocyanate. R ⁶ may be a hydrogen atom, a methyl group, a fluorine atom, or a C 1-6 fluoroalkyl group.
The fluorine-containing acrylic composition according to [1], comprising an acrylic compound represented by the formula:
[3]
(B) The fluorine-containing acrylic composition according to [1] or [2], which includes an acrylic compound in which part of the hydrogen atoms is substituted with a halogen atom selected from F, Cl, and Br.
[4]
As part or all of the component (B), the following general formula (3)
CH ₂ = CR ² COOZ ³ Rf ² (3)
(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group is substituted with F, Cl, or Br. Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, may be branched, and may contain an oxygen atom or a hydroxyl group, and Rf ² is fluorine. (It is a fluoroalkyl group having 2 to 20 atoms, may contain a hydrogen atom or an oxygen atom, and may be branched.)
The fluorine-containing acrylic composition according to [3], which contains a fluorine-containing acrylic compound represented by the formula:
[5]
In the fluorine-containing acrylic compound represented by the general formula (1) of the component (A), Rf ¹ has the following three structural formulas: —CF ₂ O— (CF ₂ O) _p (CF ₂ CF ₂ O) _q —CF ₂ −

(However, the arrangement of the repeating units enclosed in () is random, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6 to 201. s is an integer of 0 to 6, (t and u are each an integer of 1 to 100, t + u is an integer of 2 to 120, and v is an integer of 1 to 120.)
The fluorine-containing acrylic composition according to any one of [1] to [4], which is any one of divalent perfluoropolyether groups represented by:
[6]
In the component (A), Z ¹ in the general formula (1) is represented by the following formula: —CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 OCH 2 CH 2 CH 2} -

The fluorine-containing acrylic composition according to any one of [1] to [5], which is any structure represented by:
[7]
In the component (A), Q ¹ in the general formula (1) is represented by the following formula:

(In the formula, a is an integer of 1 to 10 independently.)
The fluorine-containing acrylic composition according to any one of [1] to [6], which has a structure represented by:
[8]
(A) The fluorine-containing acrylic composition in any one of [1]-[7] whose component is chosen from the fluorine-containing acrylic compound represented by a following formula.

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6) E1 is an integer of 1 to 30. R 'is a hydrogen atom,

Or

These may be mixed in one molecule. However, R ′ is a monovalent organic group containing at least one (meth) acryl group on average in one molecule. v1 is an integer of 2 to 120. )
[9]
(B) In the presence of an acrylic compound having a viscosity at 25 ° C. of 100 mPa · s or less and containing one or two (meth) acrylic groups in one molecule,
(C) a fluorine-containing polyfunctional alcohol compound represented by the following general formula (4);
^{X 1 -Rf 1 -Z 1 -Q 1} - [Z 2 OH] a (4)
(In the formula, X ¹ is a fluorine atom or a group represented by —Z ¹ —Q ¹ — [Z ² OH] _a , and Rf ¹ is composed of _a C 1-6 perfluoroalkylene group and an oxygen atom. A divalent perfluoropolyether group having a molecular weight of 800 to 20,000, and Z ¹ independently contains at least one selected from an oxygen atom, a nitrogen atom and a silicon atom having 1 to 20 carbon atoms. A good divalent linking group, Q ¹ is an (a + 1) valent linking group containing at least (a + 1) silicon atoms, may have a cyclic structure, and may be an oxygen atom, a nitrogen atom, or fluorine. The divalent carbon may optionally contain at least one selected from atoms, and Z ² may independently contain at least one selected from oxygen, nitrogen and silicon atoms having 1 to 200 carbon atoms. Hydrogen group, cyclic on the way May contain a granulation .a is an integer of from 1 to 10.)
(D) reacting a compound having one isocyanate group and at least one (meth) acryl group in one molecule;
(A) represented by the following general formula (1) a fluorine-containing acrylic compound X-Rf ¹ is represented by ^{-Z 1 -Q 1 - [Z 2} OR 1] a (1)
(In the formula, Rf ¹ , Z ¹ , Q ¹ , Z ² and a are the same as above. R ¹ may independently contain at least one selected from a hydrogen atom, an oxygen atom and a nitrogen atom. A monovalent organic group containing an acrylic group or an α-substituted acrylic group, wherein R ¹ is an average of at least one monovalent organic group containing the acrylic group or α-substituted acrylic group in one molecule; .X having a fluorine atom or a -Z ¹ -Q ¹ - is a monovalent group represented by _{^{[Z 2 oR 1] a)}} .
A group in which the mass ratio of the component (A) to the component (B) is in the range of 0.03 <(A) / (B) <10, and which reacts with an acrylic group. A method for producing a fluorine-containing acrylic composition, which comprises obtaining a fluorine-containing acrylic composition not containing a volatile organic compound having no odor.
[10]
As part or all of the component (B), the following general formula (2)
CH ₂ = CR ⁶ COOR ⁵ (2)
(In the formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, which may be branched or cyclic, an aliphatic unsaturated bond, a urethane bond, an ether bond, an isocyanate. R ⁶ may be a hydrogen atom, a methyl group, a fluorine atom, or a C 1-6 fluoroalkyl group.
And / or the following general formula (3)
CH ₂ = CR ² COOZ ³ Rf ² (3)
(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group is substituted with F, Cl, or Br. Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, may be branched, and may contain an oxygen atom or a hydroxyl group, and Rf ² is fluorine. (It is a fluoroalkyl group having 2 to 20 atoms, may contain a hydrogen atom or an oxygen atom, and may be branched.)
Including a fluorine-containing acrylic compound represented by
In the general formula (4) of the component (C) and the general formula (1) of the component (A), Rf ¹ is the following three structural formulas: —CF ₂ O— (CF ₂ O) _p (CF ₂ CF ₂ O) _q −CF ₂ −

(However, the arrangement of the repeating units enclosed in () is random, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6 to 201. s is an integer of 0 to 6, (t and u are each an integer of 1 to 100, t + u is an integer of 2 to 120, and v is an integer of 1 to 120.)
In which Z ¹ is represented by the following formula —CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 OCH 2 CH 2 CH 2} -

In which Q ¹ is represented by the following formula:

(In the formula, a is an integer of 1 to 10 independently.)
[9] The method for producing a fluorine-containing acrylic composition according to [9].
[11]
Fluorine-containing fluorinated composition comprising 0.005 to 40 parts by mass of the fluorinated acrylic composition according to any one of [1] to [8] with respect to 100 parts by mass of the active energy ray-curable composition (E). An active energy ray-curable composition.
[12]
The active energy ray-curable composition (E)
(Ea) Acrylic compound: 100 parts by mass,
(Eb) Photopolymerization initiator: The fluorine-containing active energy ray-curable composition according to [11], comprising 0.1 to 15 parts by mass.
[13]
An article having on its surface a cured product layer of the fluorinated active energy ray-curable composition according to [11] or [12].

  According to the fluorine-containing acrylic composition of the present invention, a volatile organic compound that does not have a group that reacts with an acrylic group (particularly, a non-reactive volatile organic compound that does not contain a (meth) acrylic group in the molecule). A fluorine-containing active energy ray-curable composition that can be added to the active energy ray-curable composition without increasing the content to impart liquid repellency and antifouling property can be provided.

  The fluorine-containing acrylic composition of the present invention comprises (A) a fluorine-containing acrylic compound represented by formula (1) described later, and (B) a viscosity at 25 ° C. of 100 mPa · s or less (meth) in one molecule. An acrylic compound containing one or two acrylic groups, and the mass ratio of the component (A) to the component (B) is in the range of 0.03 <(A) / (B) <10, and A volatile organic compound that does not have a group that reacts with an acrylic group (particularly, a non-reactive volatile organic compound that does not contain a (meth) acrylic group in the molecule) is not blended.

The fluorine-containing acrylic compound of the component (A) that is the first essential component in the fluorine-containing acrylic composition of the present invention is represented by the following general formula (1). In the present invention, the “acrylic compound” is a general term for compounds having an acrylic group and an α-substituted acrylic group, and urethane acrylates having a urethane bond in the molecule, and any side chain or terminal of various polymers. Also included are compounds in which two or more acrylic groups and α-substituted acrylic groups have been introduced by the method. In the present invention, “(meth) acrylate” refers to one or both of acrylate and methacrylate.
^{X-Rf 1 -Z 1 -Q 1} - [Z 2 OR 1] a (1)

In the above formula (1), Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 800 to 20,000 and comprising a perfluoroalkylene group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms and an oxygen atom. . Particularly preferred are linear perfluoropolyether groups having a molecular weight of 1,000 to 10,000. 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.

As Rf ¹ , the repeating unit group —CF ₂ O— whose main structure is particularly shown below
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
Those consisting of any one or a combination of these are preferred. Here, examples of the portion not corresponding to the main structure include a binding portion with Z ¹ , an initiator fragment and a by-product structure at the time of construction of the main chain structure.

Of these, those in which Rf ¹ has any ^one of the following structures are preferred.
_{-CF 2 O- (CF 2 O)} p (CF 2 CF 2 O) q -CF 2 -

Here, p and q represent the total number of each of the —CF ₂ O— structure and —CF ₂ CF ₂ O— structure enclosed in parentheses, and the individual —CF ₂ O— structure and —CF ₂ CF ₂ O -The arrangement of structures is random. At this time, it is preferable that p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is an integer of 6 to 201.
S is an integer of 0 to 6, t and u are each an integer of 1 to 100, t + u is an integer of 2 to 120, and v is preferably an integer of 1 to 120.

When the value of p + q, t + u or v is small, it is difficult to obtain the characteristics required as a fluorine compound, and when these values are too large, the compatibility with other components is deteriorated. The values of p, q and p + q, t, u and t + u or v in the composition may be single or have a distribution, and in the case of having a distribution, the number average molecular weight determined from ¹⁹ F-NMR or the like is in the above range. It is preferable to satisfy.

In the above formula (1), Z ¹ is a divalent linking group that may contain at least one selected from an oxygen atom having 1 to 20 carbon atoms, a nitrogen atom and a silicon atom, and has a cyclic structure in the middle. It may be included, may be branched, and some hydrogen atoms may be substituted with fluorine atoms.

Preferred examples of Z ¹ include the following structures.
—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 them, particularly preferred Z ¹ structures include the following.
—CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 OCH 2 CH 2 CH 2} -

In the above formula (1), Q ¹ is independently a (a + 1) -valent linking group containing at least (a + 1) silicon atoms, may have a cyclic structure, and is formed from an oxygen atom, a nitrogen atom and a fluorine atom. It may contain at least one selected. Preferred examples of such Q ¹ include a (a + 1) valence comprising a siloxane structure having (a + 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, a is the same as a of the said Formula (1), is an integer of 1-10 each independently, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-4. Moreover, b is an integer of 1-5, Preferably it is an integer of 3-5. The arrangement of each unit is random, and (a + 1) bonds such as units are connected to one Z ¹ end (CH ₂ etc.) and a Z ² end (CH ₂ ) surrounded by []. ₂ etc.).

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

Among these, particularly preferred Q ¹ is as follows.

In the above formula (1), Z ² is a divalent hydrocarbon having 1 to 200 carbon atoms, preferably 2 to 80, which may contain at least one selected from an oxygen atom, a nitrogen atom and a silicon atom. It is a group and may contain a ring structure in the middle.

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 —
_{-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 CH ₂ CH ₂ OCH ₂ CH ₂ —
_{-CH 2 CH 2 CH 2 [OC} 2 H 4] d [OC 3 H 6] e [OC 4 H 8] f -

  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.

As Z ² , particularly preferred structures include the following, among which d is 1 to 30 and e is 1 to 30.
_{-CH 2 CH 2 CH 2 [OC} 2 H 4] d -
_{-CH 2 CH 2 CH 2 [OC} 3 H 6] e -

In the above formula (1), R ¹ is a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group that may contain at least one selected from an oxygen atom and a nitrogen atom. However, R ¹ has a monovalent organic group containing at least one acrylic group or α-substituted acrylic group on average in one molecule. 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. , Halogen atoms selected from Cl and Br. Further, it may have an amide bond, an ether bond, an ester bond or the like in the middle of the structure, and particularly includes a urethane bond (—NH (C═O) O—) as the R ¹ O— group. Also good.

Examples of such a structure of R ¹ 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 ¹ 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.

In the above formula (1), X is a fluorine atom or a -Z ¹ -Q ¹ - is a monovalent group represented by [Z ² OR ^1] _a. Here, Z ¹ , Q ¹ , Z ² , R ¹ and a are the same as described above.

（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。ｅ１は１〜３０の整数であり、例えば２、４、９である。Ｒ’は水素原子、

又は

であり、これらは一つの分子中に混在していてもよい。但し、Ｒ’は１分子中に平均して少なくとも１個の上記（メタ）アクリル基を含有する１価の有機基である。） Fluorine-containing acrylic compound represented by the above formula (1), X is -Z ¹ -Q ¹ - for the case where a [Z ² OR ^1] _a, more specifically, it is possible to indicate the following structure .

(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, e1 is an integer of 1 to 30, for example 2, 4, 9. R ′ is a hydrogen atom,

Or

These may be mixed in one molecule. However, R ′ is a monovalent organic group containing at least one (meth) acryl group on average in one molecule. )

（式中、ｖ１は２〜１２０の整数、好ましくは４〜６０の整数であり、ｅ１、Ｒ’は前述のとおりである。） As the preferred structure when X is a fluorine atom, the following structure can be specifically shown as the fluorine-containing acrylic compound represented by the above formula (1).

(In the formula, v1 is an integer of 2 to 120, preferably an integer of 4 to 60, and e1 and R ′ are as described above.)

  These (A) components may be single or a mixture of a plurality of compounds that meet the above definition. In the case of a mixture, the total content of compounds corresponding to (A) is calculated as the content of (A) component. do it.

  The second essential component in the fluorine-containing acrylic composition of the present invention is (B) an acrylic compound containing one or two (meth) acrylic groups in one molecule. The component (B) has a viscosity at 25 ° C. of 100 mPa · s or less, preferably 0.4 to 20 mPa · s, from the solubility with the component (A) and the miscibility with the component (C) described later. . In the acrylic compound of component (B), hydrogen atoms may be partially substituted with chlorine atoms (Cl), fluorine atoms (F), or bromine atoms (Br), and oxygen atoms and nitrogen atoms other than acrylic structures It may contain an ether bond, a urethane bond, an isocyanate group, or a hydroxyl group.

As a preferable example of the compound having one (meth) acryl group in the molecule among the component (B), a compound represented by the following general formula (2) is specifically shown.
CH ₂ = CR ⁶ COOR ⁵ (2)
(In the formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an aryl group or an aralkyl group, which may be branched or cyclic, and is aliphatic unsaturated (double ) Bond, urethane bond, ether bond, isocyanate group, hydroxyl group, R ⁵ may be, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group, dicyclopentanyl group, a dicyclopentenyl group, furfuryl group, tetrahydrofurfuryl Lil group, tetrahydropyranyl _{group, -CH 2 CH 2 -OH, -CH} 2 CH (CH 3) -OH, -CH 2 CH 2 -NCO, etc. R ⁶ is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, particularly a hydrogen atom, a methyl group, a fluorine atom, A trifluoromethyl group is preferred.)

  More specifically, as such a compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, isostearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate , Tetrahydrofluryl (meth) acrylate, isobornyl (meth) acrylate, phenoxyethyl acrylate, neopentyl glycol-acrylic acid-benzoic acid ester, and the like.

  Examples of acrylate compounds having a repeating unit structure such as ethylene oxide, propylene oxide, tetramethylene oxide, and lactone and having various alkoxy terminals include, for example, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene. Even a (meth) acryl compound commercially available under the names of glycol (meth) acrylate, nonylphenol EO adduct acrylate and the like can be used as long as the viscosity at 25 ° C. is 100 mPa · s or less.

  Further, as compounds having two acrylic groups in one molecule, specifically, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, dipropylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonanediol di (meth) acrylate, etc. be able to.

Furthermore, it is preferable that a part or all of the component (B) has a hydrogen atom partially substituted with F, Cl, or Br, and an acrylic compound represented by the following general formula (3) is particularly desirable.
CH ₂ = CR ² COOZ ³ Rf ² (3)

In the above formula (3), R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group is F, Cl, Br. May be substituted.
Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, include alkyl groups such as a methyl group and an ethyl group, and fluoroalkyl groups such as a trifluoromethyl group. R ² is preferably a hydrogen atom or a methyl group.

In the above formula (3), Z ³ is a divalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 4 carbon atoms, which may be branched, and contains an oxygen atom or a hydroxyl group in the middle. May be.
Particularly preferred Z ³ includes the following.
—CH ₂ —
—CH ₂ CH ₂ —
_{-CH 2 -CH (OH) -CH 2} -
—CH ₂ —CH ₂ —O—CH ₂ CH ₂ —

In the above formula (3), Rf ² is a fluoroalkyl group having 2 to 20, particularly 1 to 10 fluorine atoms, may contain a hydrogen atom, an oxygen atom, or may be branched.
Specific examples of Rf ² are as follows.
-CF ₃
-C ₂ F ₅
-C ₃ F ₇
-C ₄ F ₉
-C ₆ F ₁₃
-CF ₂ H
-C ₂ F ₄ H
-CF ₂ CF ₂ H
-CF ₂ CF ₂ CF ₂ CF ₂ H
-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ H
_{-CF 2 CF 2 CF (CF 3} ) 2
-CF (CF ₃ ) ₂
-CH (CF _{3) 2}
-CF ₂ CHFCF ₃
-CF ₂ CF ₂ OCF ₃

As the acrylic compound of the component (B) that satisfies the above conditions, the following can be exemplified.
CH ₂ = CHCOOCH ₂ CH ₂ C ₄ F ₉
CH ₂ = CHCOOCH ₂ CH ₂ C ₆ F _{13
CH 2 = C (CH 3)} COOCH 2 CH 2 C 4 F 9
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 6 F 13

  The component (B) may be a single component or a mixture of a plurality of compounds that meet the above definition. In the case of a mixture, the total content of compounds corresponding to (B) may be calculated as the content of component (B). . The compound corresponding to component (B) can be synthesized by a known method as necessary, but various compounds are commercially available from reagent manufacturers and the like, and these can be used as they are.

The fluorine-containing acrylic composition according to the first embodiment of the present invention has the components (A) and (B) as essential components, and the mass ratio of the components (A) and (B) is 0.03 <(A ) / (B) <10, preferably 0.05 ≦ (A) / (B) ≦ 8, more preferably 0.1 ≦ (A) / (B) ≦ 5, and acrylic. A volatile organic compound that does not have a group that reacts with a group (particularly, a non-reactive volatile organic compound that does not contain a (meth) acryl group in the molecule) is not blended.
As another embodiment of the present invention, the fluorine-containing acrylic composition is mixed with an active energy ray-curable composition (E) described later to form a fluorine-containing active energy ray-curable composition, which is applied and cured. In addition, a liquid repellent and antifouling cured product layer can be provided on the substrate, but this liquid repellency and antifouling property is dispersed in the components of the active energy ray curable composition (E). (A) It expresses because a component exists in the hardened | cured material layer surface. For this reason, when the mass ratio (A) / (B) is 0.03 or less, the content of the component (A) in the fluorine-containing acrylic composition becomes too small, and the final liquid repellency and antifouling properties are obtained. Expression becomes difficult. On the other hand, when the mass ratio (A) / (B) is 10 or more, workability is lowered due to the high viscosity of the component (A), and compatibility and mixing with the component (E) are reduced. descend.

  In the fluorine-containing acrylic composition according to the first embodiment of the present invention, the production method is not particularly limited, and the component (A) and the component (B) produced by various methods may be mixed. However, the acrylic compound of component (A) tends to become a highly viscous compound with higher viscosity and difficult to remove volatile matter as its liquid repellency and antifouling properties are improved. Effective conditions such as reduced pressure and heating cause polymerization of acrylic groups in the structure of component (A), and there is a great risk of thickening and gelation. Therefore, more preferably, in the synthesis step before the introduction of the acrylic group, a raw material from which the volatile component (a volatile organic compound having no group that reacts with the acrylic group) has been removed is prepared and used in the presence of the component (B). It is desirable to synthesize the component (A) to obtain the desired fluorine-containing acrylic composition.

(A) As a manufacturing method of the fluorine-containing acrylic compound represented by Formula (1) of a component, first, following general formula (5) manufactured with a conventionally well-known method first, for example.
X′—Rf ¹ —Z ¹ —Q ¹ — [H] _a (5)
(In the formula, Rf ¹ , Z ¹ , Q ¹ , and a are the same as described above, and all a Hs enclosed in [] are bonded to the silicon atom in the Q ¹ structure. X ′ is fluorine. atoms or -Z ¹ -Q ¹ - is [H] _a).
A fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (6):
_{^{CH 2 = CR 4 -Z 3 -OH}} (6)
(Wherein, R ^4, Z ³ is, -CH ₂ -CHR ⁴ -Z ³ are formed after the hydrosilylation - structure, and (1) as long as it satisfies the requirements of Z ² in Formula, R ⁴ Z ³ may be bonded to form a cyclic structure.)
The terminal unsaturated group-containing alcohol represented by the formula (compound having an alkenyl group and an alcoholic hydroxyl group in the molecule) is subjected to a hydrosilylation reaction, whereby the fluorine-containing compound represented by the following general formula (4), which is an intermediate, is obtained. A functional alcohol compound is obtained.
^{X 1 -Rf 1 -Z 1 -Q 1} - [Z 2 OH] a (4)
(In the formula, X ¹ is a fluorine atom or a group represented by —Z ¹ -Q ^1- [Z ² OH] _a , and Rf ¹ , Z ¹ , Q ¹ , Z ² and a are as described above. .)

（式中、Ｒｆ’は前記と同じである。）

（式中、ｖ１は前記と同じである。） Here, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (5) include those shown below.

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

(Wherein v1 is the same as above)

（式中、ｄ１は１〜３０の整数であり、ｅ１は上記と同じである。） Moreover, what is shown below can be illustrated as terminal unsaturated group containing alcohol represented by the said Formula (6).
CH ₂ = CH-CH ₂ -OH
_{CH 2 = CH-CH 2 -OCH} 2 CH 2 -OH
_{CH 2 = CH-CH 2 -OCH} 2 CH 2 CH 2 -OH
_{CH 2 = CH-CH 2 -OCH} 2 CH (CH 3) -OH
_{CH 2 = CH-CH 2 -OCH} 2 CH 2 CH 2 CH 2 -OH
_{CH 2 = CH-CH 2 -} (OCH 2 CH 2) d1 -OH
_{CH 2 = CH-CH 2 -} (OC 3 H 6) e1-1 -OCH 2 CH (CH 3) -OH

(In the formula, d1 is an integer of 1 to 30, and e1 is the same as above.)

  In this hydrosilylation (addition) reaction, a fluoropolyether compound having a polyfunctional Si—H group represented by formula (5) and a terminal unsaturated group-containing alcohol represented by formula (6) are mixed, In the presence of a platinum group metal-based addition reaction catalyst, it is desirable to carry out the reaction at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. for 1 minute to 48 hours, particularly 10 minutes to 12 hours. 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 (5) and the terminal unsaturated group-containing alcohol represented by the formula (6) is represented by the formula (5). The terminal unsaturated group of the terminal unsaturated group-containing alcohol represented by the formula (6) with respect to the total number of moles of H surrounded by [] of the fluoropolyether compound having a polyfunctional Si—H group represented by Is preferably used in a reaction of 0.5 to 5.0 times mol, particularly 0.9 to 2.0 times mol. If the terminal unsaturated group-containing alcohol represented by formula (6) is too small, it may be difficult to obtain a fluorine-containing polyfunctional alcohol compound having high solubility. When the removal of the terminal unsaturated group-containing alcohol represented by the formula (6) is carried out after the reaction, the conditions such as heating, decompression and extraction are not excessively reacted. It becomes necessary to be strict as much as the alcohol 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 addition amount of the addition reaction catalyst is 0.1 to 5,000 mass ppm of metal contained in the addition reaction catalyst with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (5). 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 fluorine polyfunctional alcohol 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 of use is preferably 5 to 2,000 parts by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (5). More preferably, it is 50-500 mass parts. 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 represented by the formula (6) and the diluting solvent by a known method such as distillation under reduced pressure, extraction or adsorption. These methods can be carried out singly or in combination of a plurality of methods. In particular, in the final stage of removal, vacuum distillation or molecular distillation is used, for example, an internal temperature of 85 ° C. or higher and a vacuum of 0.133 kPa or lower. It is desirable to keep the content of the volatile organic compound corresponding to a boiling point of 260 ° C. or less at normal pressure to 1% by mass or less by performing distillation until distillation of the fraction stops depending on conditions.

（式中、Ｒｆ’、ｅ１、ｖ１は上記と同じである。） Examples of the fluorine-containing polyfunctional alcohol compound represented by the formula (4) thus obtained include those shown below.

(In the formula, Rf ′, e1, and v1 are the same as above.)

Subsequently, a fluorine-containing acrylic compound (A) can be obtained by introduce | transducing an acrylic group into the fluorine-containing polyfunctional alcohol compound obtained above.
In another embodiment of the present invention, the fluorine-containing polyfunctional alcohol compound represented by the above formula (4) obtained as described above is used as the component (C), and in the presence of the component (B), one molecule A component (A) is synthesized by reacting with a compound (D) having one isocyanate group and at least one (meth) acryl group therein to obtain a fluorine-containing acrylic composition according to the first embodiment of the present invention. Is the method.

Examples of the compound (D) having one isocyanate group and at least one (meth) acryl group in one molecule include those shown below.
_{CH 2 = CHCOOCH 2 CH 2 -N} = C = O
_{CH 2 = CCH 3 COOCH 2 CH} 2 -N = C = O
_{CH 2 = CCH 3 COOCH 2 CH} 2 OCH 2 CH 2 -N = C = O
_{[CH 2 = CCH 3 COOCH 2} ] 2 CH (CH 3) -N = C = O

Of these, the following two types are particularly preferred.
_{CH 2 = CHCOOCH 2 CH 2 -N} = C = O
_{CH 2 = CCH 3 COOCH 2 CH} 2 -N = C = O

  The component (D) may be urethanized by reacting all of the hydroxyl groups by reacting with an equimolar amount or more as an isocyanate group with respect to the total amount of hydroxyl groups in the component (C). In average, 1 mol or more of an acrylic group may be introduced, and the residual amount of the unreacted component (D) can be reduced by making the hydroxyl group and the isocyanate group equivalent or the hydroxyl group slightly excessive. Specifically, when the total amount of compounds corresponding to the component (C) in the reaction system is x mol, and the total amount of hydroxyl groups in the component (C) is y mol, the amount of the component (D) is x mol or more. It is desirable that it is 1.05 ymol or less, and particularly preferably 0.5 ymol or more and 1.0 ymol or less. When the component (D) is too small, there is a high possibility that the component (C) in which no acrylic group is introduced remains, and the curability of the final composition and the solubility of the product may be reduced. is there. When there are too many (D) components, the residual amount of (D) component will become large and may affect the antifouling performance of a final composition.

The mixing ratio of each component (B), (C), (D) during the reaction is such that the blending amount of the component (D) is 1.0y or less, and the component (D) does not remain after the reaction, the mass ratio It is preferable that the following is satisfied.
0.03 <[(C) + (D)] / (B) <5

Moreover, when the compounding quantity of (D) component is larger than 1.0y and (D) component remains after reaction, the remaining (D) component can be considered as a part of (B) component. That is, the component (B) contained in addition to the remaining component (D) is (B1), the mass of the component (D) corresponding to 1.0y is (d1), and the mass of all blended (D) components is (d1 ) Is subtracted from (d2), the following conditions are preferably satisfied.
0.03 <[(C) + (d1)] / [(B1) + (d2)] <5

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.
These blending amounts are desirably 1 to 3,000 ppm, more preferably 1 to 500 ppm of the total mass of the components (B), (C), and (D).

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 titanate 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 is increased by adding 0.01 to 2% by mass, preferably 0.05 to 1% by mass of these catalysts with respect to the total mass of the reactants (total mass of the components (C) and (D)). Can be made.

In the reaction, the components (B), (C), and (D) are stirred and mixed with the above-described polymerization inhibitor and catalyst as necessary, and heated as necessary to advance the reaction.
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, if necessary, the coloring component and the insoluble component can be removed by a method such as adsorption treatment or filtration washing to obtain the fluorine-containing acrylic composition of the present invention.
The fluorinated acrylic composition thus obtained does not contain a volatile organic compound.

The fluorine-containing acrylic composition of the present invention can be added to the active energy ray-curable composition (E) described later to obtain a fluorine-containing active energy ray-curable composition.
The active energy ray-curable composition (E) used in one embodiment of the present invention is not particularly limited as long as it gives a cured product by irradiation with active energy rays such as ultraviolet rays and electron beams. It is preferable that a compound (Ea) and a photoinitiator (Eb) are included.

  The acrylic compound (Ea) can be used regardless of monofunctional or polyfunctional. For example, the above-mentioned monofunctional and bifunctional acrylic compounds as the component (B) can be used, but the (Ea) component includes a non-fluorinated acrylic compound having two or more acrylic groups in one molecule. It is preferable.

  Such a non-fluorinated acrylic compound may be any compound having two or more acrylic groups or α-substituted acrylic groups in one molecule. For example, 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 (meta) such as intererythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate ) Acrylic compounds, ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl modified products of these (meth) acrylic compounds, epoxy acrylates obtained by adding acrylic acid to epoxy resins, and side chains of acrylic ester copolymers And those containing a copolymer having a (meth) acryloyl group introduced therein.

  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.

  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 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 can be mentioned.

  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 difunctional 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-isocyanato What reacted with acrylic compounds which have isocyanate groups, such as ethyl (meth) acrylate and 1, 1- (bis acryloyloxymethyl) ethyl isocyanate, can be shown.

  Furthermore, as the component (Ea), not only a liquid component but also a surface obtained by modifying the surface of a particulate high molecular weight body or the surface of an inorganic filler particulate with an acrylic group may be included.

  Although the above (Ea) component can be used alone, it can also be used in combination with a plurality of corresponding compounds in order to improve the coating properties and the properties of the coating after curing.

  Moreover, it can be set as the curable composition which improved the sclerosis | hardenability at the time of using an ultraviolet-ray as an active energy ray by containing a photoinitiator as (Eb) component.

  The photopolymerization initiator of the component (Eb) is not particularly limited as long as the acrylic compound can be cured by irradiation with ultraviolet rays. Preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2- Diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-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-morpholino Phenyl) butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Ruphorinyl) 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-acetyl) Oxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, and the like. May be used in combination.

  The content of the component (Eb) can be appropriately determined according to the curing conditions and the physical properties of the cured product of the target active energy ray-curable composition (E). For example, the total amount of the component (Ea) is 100 parts by mass. It is desirable that the amount be 0.1 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.

  In addition to the active energy ray-curable composition (E), active energy ray-reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity An adjusting agent, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, a polymer or an inorganic filler, and the like can also be blended. These structures are not particularly limited, and known ones can be used as long as the object of the present invention is not impaired.

  In addition, as the active energy ray curable composition (E), the active energy ray curable composition in which the components (Ea) and (Eb) and various additives have been blended, paints, inks, hard coat agents, etc. The existing composition marketed by the classification of (E) may be used as a part or all of the component (E). Thus, even when using a commercially available hard coat agent, depending on the purpose, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an oxidation agent An inhibitor, a surfactant, a colorant, a filler, and the like can be added and blended.

  In one embodiment of the present invention, the fluorine-containing acrylic composition according to the first embodiment of the present invention is 0.005 to 40 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition (E). The fluorine-containing active energy ray-curable composition is preferably contained in an amount of 0.01 to 20 parts by mass. The blending amount of the fluorine-containing acrylic composition is not particularly limited as long as it is within the above range, but the blending amount as the component (A) in the fluorine-containing acrylic composition is preferably 0.00% in the fluorine-containing active energy ray-curable composition. It is desirable that it is 005-10 mass%. When the amount of the component (A) is less than this, when the cured product is formed, the component (A) cannot be sufficiently disposed on the surface, and the expected liquid repellency and antifouling properties cannot be exhibited, and larger than this. If it becomes, the influence of the (A) component with respect to the intensity | strength and hardness of a hardened | cured material layer will become large too much, and the hardened | cured material characteristic of the original active energy ray-curable composition (E) will be lost.

  With the fluorine-containing active energy ray-curable composition of the present invention obtained as described above, it is possible to suppress the inclusion of a volatile organic compound that is not incorporated into the structure of the cured product. In addition, a curable composition with extremely little generation of volatile organic compounds capable of forming a cured resin layer having excellent antifouling properties and liquid repellency is obtained.

  Furthermore, in this invention, the fluorine-containing 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 fluorine-containing 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 fluorine-containing active energy ray-curable composition of the present invention provides a coating film or a protective film on the surface of a substrate (article) that may be touched by a human body and contaminated by human fat, cosmetics, or the like. Can do.

  The cured film (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention is directly applied to the surface of an article to which properties are imparted and cured, or the present invention is applied to various substrates. Properties can be imparted to various articles by applying a film prepared by coating the fluorine-containing active energy ray-curable composition of 1 to the surface of the target article.

Here, the coating method of the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, and examples thereof include roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, and bar coating. A known coating method such as 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 one such as an electron beam and ultraviolet rays can be used, but ultraviolet rays are particularly preferable. As the ultraviolet ray source, a mercury lamp, a metal halide lamp, and an LED lamp are suitable. If the amount of UV irradiation is too small, an uncured component remains, and if it is too large, the coating film and the substrate may be deteriorated, so 10 to 10,000 mJ / cm ² , especially 20 to 4,000 mJ / cm. It is desirable to be in the range of ² . In order to prevent curing inhibition by oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon during UV irradiation, or the surface of the coating film is UV transparent. Cover with a protective layer and then irradiate with UV rays, or if the substrate is UV transparent, cover the surface of the coating with a releasable protective layer and then reverse the coating surface of the substrate Ultraviolet rays may be irradiated from the side. In order to effectively perform leveling of the coating film or polymerization of acrylic groups in the coating film, the coating film and the substrate may be heated by an arbitrary method such as a hot air drying furnace before and during irradiation with ultraviolet rays.

  Moreover, the thickness of the cured film (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but when the obtained film thickness is too thin Sufficient surface hardness cannot be obtained, and if it is too thick, the mechanical strength of the hard coat film is lowered and cracks are likely to occur, and therefore it is usually preferably 5 nm to 100 μm, particularly preferably 1 μm to 20 μm.

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

  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.

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） [Synthesis Example 1] fluoroalcohol compound (C-1) Under a dry nitrogen atmosphere, and the 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 (I) 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, 28.20 g (0.276 mol) of 2-allyloxyethanol, m- 200.0 g of xylene hexafluoride and 0.0884 g of toluene solution of chloroplatinic acid / vinyl siloxane complex (containing 2.2 × 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 216.1 g of fluorine-containing alcohol compound (C-1) 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）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂−
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） [Synthesis Example 2] fluoroalcohol compound (C-2) Synthesis dry nitrogen atmosphere, and the 3,000mL 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) _p2 (CF ₂ CF ₂ O) _{q 2} CF ₂ —
(Q2 / p2 = 1.2, p2 + q2≈18.5)
500 g (0.272 mol) of perfluoropolyether represented by the formula, 1,000 g of m-xylene hexafluoride and 660 g (2.72 mol) of tetramethylcyclotetrasiloxane are added, and the mixture is stirred to 90 ° C. Heated. Here, 0.884 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.2 × 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 581 g of a colorless and transparent liquid compound (II) represented by the following formula.

Rf ′: —CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _{q 2} CF ₂ —
(Q2 / p2 = 1.2, p2 + q2≈18.5)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂−
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） Under a dry air atmosphere, 205.8 g (Si-H group content: 0.518 mol) of the compound (II) obtained above, 105.8 g (1.04 mol) of 2-allyloxyethanol, m- 400.0 g of xylene hexafluoride and 1.77 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 4.4 × 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 240.4 g of fluorine-containing alcohol compound (C-2) was obtained.

Rf ′: —CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _{q 2} CF ₂ —
(Q2 / p2 = 1.2, p2 + q2≈18.5)

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂−
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） [Example 1] Preparation of fluorine-containing acrylic composition (F-1) 50.0 g of fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 (hydroxyl amount 0.058 mol) in a dry air atmosphere (B-1) 2- (perfluorohexyl) ethyl acrylate [viscosity 4 mPa · s / 25 ° C.] 57.9 g and (D) acryloyloxyethyl isocyanate 7.87 g (0.055 mol) were mixed. The mixture was heated to 50 ° C. and stirred for 1 hour. Dioctyltin (di) laurate 0.05g was added there, and it stirred at 50 degreeC for 8 hours. ^From the result of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate was completely changed to the 4.1 ppm methylene peak after urethane bond formation. The disappearance of the peak of the isocyanate group at 260 cm ⁻¹ was confirmed. After completion of the heating, the obtained reaction solution was treated with activated carbon to obtain 100.3 g of a pale yellow liquid. As a result, the following fluorine-containing acrylic compound (A-1) and 2- (perfluorohexyl) ethyl acrylate (B-1), which are the reaction products of (C-1) and (D), are converted into (A-1) / A fluorine-containing acrylic composition (F-1) mixed at a mass ratio of (B-1) = 1 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)

[Example 2] Preparation of fluorine-containing acrylic composition (F-2) 50.0 g of fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 under a dry air atmosphere (hydroxyl amount 0.058 mol) (B-2) 2- (perfluorohexyl) ethyl methacrylate [viscosity 5 mPa · s / 25 ° C.] 57.9 g, (B-3) isobutyl acrylate [viscosity 1 mPa · s / 25 ° C.] 115.8 g (D) 7.87 g (0.055 mol) of acryloyloxyethyl isocyanate was mixed, heated to 50 ° C. and stirred for 1 hour. Dioctyltin (di) laurate 0.05g was added there, and it stirred at 50 degreeC for 8 hours. ^From the result of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate was completely changed to the 4.1 ppm methylene peak after urethane bond formation. The disappearance of the peak of the isocyanate group at 260 cm ⁻¹ was confirmed. After the heating, the obtained reaction solution was treated with activated carbon to obtain 170.1 g of a pale yellow liquid. As a result, the following fluorine-containing acrylic compound (A-1), 2- (perfluorohexyl) ethyl methacrylate (B-2) and isobutyl acrylate (B-3), which are reaction products of (C-1) and (D), are shown below. ), And a fluorine-containing acrylic composition (F-2) having a mass ratio of (A-1) / [(B-2) + (B-3)] = 0.33 was obtained.

[Example 3] Preparation of fluorine-containing acrylic composition (F-3) 50.0 g of fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 (hydroxyl amount 0.058 mol) in a dry air atmosphere M-xylene hexafluoride (50.0 g) and (D) acryloyloxyethyl isocyanate 7.87 g (0.055 mol) were mixed, heated to 50 ° C., and stirred for 1 hour. Dioctyltin (di) laurate 0.05g was added there, and it stirred at 50 degreeC for 8 hours. ^From the result of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate was completely changed to the 4.1 ppm methylene peak after urethane bond formation. After confirming the disappearance of the 260 cm ⁻¹ isocyanate group peak, heating was terminated. The obtained reaction solution was treated with activated carbon to obtain 98.2 g of a pale yellow liquid. The obtained pale yellow liquid was distilled off under reduced pressure at 60 ° C. and 133.32 Pa for 3 hours using a rotary evaporator to isolate (A-1) as 55.2 g of a pale yellow ointment-like component. The obtained (A-1) was confirmed to be 0.01% by mass or less by mass drying at 105 ° C. for 3 hours.

  10 g of (A-1) obtained above was charged into a glass vial with a lid, and (B-4) 2- (perfluorobutyl) ethyl acrylate [viscosity 3 mPa · s / 25 ° C.] 10 g, (B-5) ) Add 30 g of tetrahydrofurryl acrylate [viscosity 3 mPa · s / 25 ° C.], shake with a shaker until evenly dissolved, (A-1) / [(B-4) + (B-5)] = Fluorine-containing acrylic composition (F-3) having a mass ratio of 0.25 was obtained.

Ｒｆ’：−ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂−
（ｑ２／ｐ２＝１．２、ｐ２＋ｑ２≒１８．５） [Example 4] Preparation of fluorine-containing acrylic composition (F-4) 50.0 g of fluorine-containing alcohol compound (C-2) obtained in Synthesis Example 2 under a dry air atmosphere (hydroxyl amount 0.102 mol) (B-3) 254.8 g of isobutyl acrylate and (D) acryloyloxyethyl isocyanate 13.7 g (0.097 mol) were mixed, heated to 50 ° C. and stirred for 1 hour. Dioctyltin (di) laurate 0.10g was added there, and it stirred at 50 degreeC for 8 hours. ^From the result of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted acryloyloxyethyl isocyanate was completely changed to the 4.1 ppm methylene peak after urethane bond formation. The disappearance of the peak of the isocyanate group at 260 cm ⁻¹ was confirmed. After completion of the heating, the obtained reaction solution was treated with activated carbon to obtain 318.7 g of a pale yellow liquid. As a result, the fluorine-containing acrylic compound (A-2) and (B-3) isobutyl acrylate shown below, which are reaction products of (C-2) and (D), are (A-2) / (B-3) = 0. A fluorine-containing acrylic composition (F-4) mixed at a mass ratio of .25 was obtained.

Rf ′: —CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _{q 2} CF ₂ —
(Q2 / p2 = 1.2, p2 + q2≈18.5)

  In addition, the volatile organic compound is not contained in the fluorine-containing acrylic composition obtained in the said Examples 1-4.

[Comparative Example 1]
In Example 3, instead of (B-5) tetrahydrofurryl acrylate, an attempt was made to prepare a composition using trimethylolpropane triacrylate [viscosity 110 mPa · s / 25 ° C.], which is a trifunctional acrylic compound. Separated without dissolving.

[Examples 5 to 10, Comparative Examples 2 to 5]
An active energy ray-curable composition (E) was prepared using the following acrylic compound (Ea) and photopolymerization initiator (Eb).
(Ea-1) Dipentaerythritol penta / hexaacrylate
[Shin Nakamura Chemical Co., Ltd. A-9550]
(Ea-2) Pentaerythritol triacrylate
[A-TMM-3 manufactured by Shin-Nakamura Chemical Co., Ltd.]
(Ea-3) Pentaerythritol ethoxytetraacrylate
[EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.]
(Ea-4) Tetrahydrofurryl acrylate (Eb-1) 1-hydroxycyclohexyl phenyl ketone
[IRGACURE 184 manufactured by BASF Japan Ltd.]
(Eb-2) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropiyl)
Onyl) benzyl] phenyl} -2-methylpropan-1-one
[IRGACURE 127 manufactured by BASF Japan Ltd.]

Active energy ray-curable composition (E1):
(Ea-1) 70 parts by mass (Ea-4) 30 parts by mass (Eb-1) 3 parts by mass

Active energy ray-curable composition (E2):
(Ea-1) 70 parts by mass (Ea-2) 30 parts by mass (Eb-1) 3 parts by mass

Active energy ray-curable composition (E3):
(Ea-1) 30 parts by mass (Ea-2) 70 parts by mass (Eb-1) 3 parts by mass

Active energy ray-curable composition (E4):
(Ea-3) 100 parts by mass (Eb-2) 3 parts by mass

Preparation of Comparative Composition Comparative compositions (G-1) and (G-2) were prepared at the following ratios.
(G-1): (B-1) 50 parts by mass, (B-2) 100 parts by mass (G-2): (B-1) 50 parts by mass, (B-2) 150 parts by mass

Preparation of fluorine-containing active energy ray-curable composition The fluorine-containing acrylic compositions (F-1) to (F-4) obtained in the above examples, the fluorine-containing acrylic compound ( A-1), 2- (perfluorohexyl) ethyl acrylate (B-1) or the comparative compositions (G-1) and (G-2), and the active energy ray-curable composition (E1) to (E4) was mixed to prepare a fluorine-containing active energy ray-curable composition. The appearance of the resulting composition was measured and shown in Table 1.

Coating and Preparation of Cured Film Each fluorine-containing active energy ray-curable composition of Examples and Comparative Examples was applied onto a polycarbonate substrate by spin coating. After coating, after leveling at room temperature for 10 minutes, using a conveyor type metal halide UV irradiation device (manufactured by Panasonic Electric Works), irradiate the coated surface with ultraviolet rays with an integrated dose of 1,600 mJ / cm ² in a nitrogen atmosphere. The composition was cured to obtain a cured film having a thickness of 9 μm. About Example 10, it heated at 100 degreeC for 1 minute instead of leveling for 10 minutes at room temperature.

Evaluation of Cured Film The appearance (transparency) of the cured film obtained above was measured visually, and the water contact angle and magic resistance were evaluated by the methods described below. These results are shown in Table 1.

[Water contact angle measurement]
Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 2 μL of a 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.

[Evaluation of magic resistance]
A straight line was drawn on the surface of the cured film with a magic pen (Magic Ink, manufactured by Teranishi Chemical Industry Co., Ltd.).

Claims (13)

(A) a fluorine-containing acrylic compound represented by the following general formula (1),
^{X-Rf 1 -Z 1 -Q 1} - [Z 2 OR 1] a (1)
(In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 800 to 20,000 composed of a C 1-6 perfluoroalkylene group and an oxygen atom, and Q ¹ is independently at least (a + 1 ) is a number of containing a silicon atom (a + 1) -valent linking group may optionally form a cyclic structure, an oxygen atom, a nitrogen atom and optionally .Z ¹ also include at least one selected from fluorine atoms A divalent linking group having 1 to 20 carbon atoms, which may contain at least one selected from an oxygen atom, a nitrogen atom and a silicon atom, may contain a cyclic structure, and is branched; And some hydrogen atoms may be substituted with fluorine atoms, and Z ² independently contains at least one selected from an oxygen atom, a nitrogen atom and a silicon atom having 1 to 200 carbon atoms. Also A There divalent hydrocarbon group, the middle ring structure may contain a .R ¹ is independently a hydrogen atom, or an oxygen atom and at least one optionally containing an acryl group or be α selected from nitrogen atom A monovalent organic group containing a substituted acrylic group, provided that R ¹ has an average of at least one monovalent organic group containing the above-mentioned acrylic group or α-substituted acrylic group in one molecule. a fluorine atom or a -Z ¹ -Q ¹ - is a monovalent group represented by [Z ² oR ^1] _a .a is an integer of 1 to 10).
(B) The viscosity at 25 ° C. is 100 mPa · s or less, contains an acrylic compound containing one or two (meth) acrylic groups in one molecule as an essential component, and the mass of component (A) and component (B) The ratio is within a range of 0.03 <(A) / (B) <10, and a volatile organic compound having no group that reacts with an acrylic group is not blended. Fluorine-containing acrylic composition. As part or all of the component (B), the following general formula (2)
CH ₂ = CR ⁶ COOR ⁵ (2)
(In the formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, which may be branched or cyclic, an aliphatic unsaturated bond, a urethane bond, an ether bond, an isocyanate. R ⁶ may be a hydrogen atom, a methyl group, a fluorine atom, or a C 1-6 fluoroalkyl group.
The fluorine-containing acrylic composition according to claim 1, comprising an acrylic compound represented by the formula:   The fluorine-containing acrylic composition according to claim 1 or 2, wherein the component (B) comprises an acrylic compound in which a part of hydrogen atoms is substituted with a halogen atom selected from F, Cl, and Br. As part or all of the component (B), the following general formula (3)
CH ₂ = CR ² COOZ ³ Rf ² (3)
(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group is substituted with F, Cl, or Br. Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, may be branched, and may contain an oxygen atom or a hydroxyl group, and Rf ² is fluorine. (It is a fluoroalkyl group having 2 to 20 atoms, may contain a hydrogen atom or an oxygen atom, and may be branched.)
The fluorine-containing acrylic composition according to claim 3, comprising a fluorine-containing acrylic compound represented by the formula: In the fluorine-containing acrylic compound represented by the general formula (1) of the component (A), Rf ¹ has the following three structural formulas: —CF ₂ O— (CF ₂ O) _p (CF ₂ CF ₂ O) _q —CF ₂ −

(However, the arrangement of the repeating units enclosed in () is random, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6 to 201. s is an integer of 0 to 6, (t and u are each an integer of 1 to 100, t + u is an integer of 2 to 120, and v is an integer of 1 to 120.)
The fluorine-containing acrylic composition according to any one of claims 1 to 4, wherein the fluorine-containing acrylic composition is any one of divalent perfluoropolyether groups represented by: In the component (A), Z ¹ in the general formula (1) is represented by the following formula: —CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 OCH 2 CH 2 CH 2} -

The fluorine-containing acrylic composition according to any one of claims 1 to 5, which has a structure represented by: In the component (A), Q ¹ in the general formula (1) is

(In the formula, a is an integer of 1 to 10 independently.)
The fluorine-containing acrylic composition according to any one of claims 1 to 6, which has a structure represented by: (A) A component is chosen from the fluorine-containing acrylic compound represented by a following formula, The fluorine-containing acrylic composition of any one of Claims 1-7.

(In the formula, Rf ′ is —CF ₂ O (CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ —, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6) E1 is an integer of 1 to 30. R 'is a hydrogen atom,

Or

These may be mixed in one molecule. However, R ′ is a monovalent organic group containing at least one (meth) acryl group on average in one molecule. v1 is an integer of 2 to 120. ) (B) In the presence of an acrylic compound having a viscosity at 25 ° C. of 100 mPa · s or less and containing one or two (meth) acrylic groups in one molecule,
(C) a fluorine-containing polyfunctional alcohol compound represented by the following general formula (4);
^{X 1 -Rf 1 -Z 1 -Q 1} - [Z 2 OH] a (4)
(In the formula, X ¹ is a fluorine atom or a group represented by —Z ¹ —Q ¹ — [Z ² OH] _a , and Rf ¹ is composed of _a C 1-6 perfluoroalkylene group and an oxygen atom. A divalent perfluoropolyether group having a molecular weight of 800 to 20,000, and Z ¹ independently contains at least one selected from an oxygen atom, a nitrogen atom and a silicon atom having 1 to 20 carbon atoms. A good divalent linking group, Q ¹ is an (a + 1) valent linking group containing at least (a + 1) silicon atoms, may have a cyclic structure, and may be an oxygen atom, a nitrogen atom, or fluorine. The divalent carbon may optionally contain at least one selected from atoms, and Z ² may independently contain at least one selected from oxygen, nitrogen and silicon atoms having 1 to 200 carbon atoms. Hydrogen group, cyclic on the way May contain a granulation .a is an integer of from 1 to 10.)
(D) reacting a compound having one isocyanate group and at least one (meth) acryl group in one molecule;
(A) represented by the following general formula (1) a fluorine-containing acrylic compound X-Rf ¹ is represented by ^{-Z 1 -Q 1 - [Z 2} OR 1] a (1)
(In the formula, Rf ¹ , Z ¹ , Q ¹ , Z ² and a are the same as above. R ¹ may independently contain at least one selected from a hydrogen atom, an oxygen atom and a nitrogen atom. A monovalent organic group containing an acrylic group or an α-substituted acrylic group, wherein R ¹ is an average of at least one monovalent organic group containing the acrylic group or α-substituted acrylic group in one molecule; .X having a fluorine atom or a -Z ¹ -Q ¹ - is a monovalent group represented by _{^{[Z 2 oR 1] a)}} .
A group in which the mass ratio of the component (A) to the component (B) is in the range of 0.03 <(A) / (B) <10, and which reacts with an acrylic group. A method for producing a fluorine-containing acrylic composition, which comprises obtaining a fluorine-containing acrylic composition not containing a volatile organic compound having no odor. As part or all of the component (B), the following general formula (2)
CH ₂ = CR ⁶ COOR ⁵ (2)
(In the formula, R ⁵ is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, which may be branched or cyclic, an aliphatic unsaturated bond, a urethane bond, an ether bond, an isocyanate. R ⁶ may be a hydrogen atom, a methyl group, a fluorine atom, or a C 1-6 fluoroalkyl group.
And / or the following general formula (3)
CH ₂ = CR ² COOZ ³ Rf ² (3)
(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group is substituted with F, Cl, or Br. Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, may be branched, and may contain an oxygen atom or a hydroxyl group, and Rf ² is fluorine. (It is a fluoroalkyl group having 2 to 20 atoms, may contain a hydrogen atom or an oxygen atom, and may be branched.)
Including a fluorine-containing acrylic compound represented by
In the general formula (4) of the component (C) and the general formula (1) of the component (A), Rf ¹ is the following three structural formulas: —CF ₂ O— (CF ₂ O) _p (CF ₂ CF ₂ O) _q −CF ₂ −

(However, the arrangement of the repeating units enclosed in () is random, p is an integer of 1 to 200, q is an integer of 1 to 170, and p + q is 6 to 201. s is an integer of 0 to 6, (t and u are each an integer of 1 to 100, t + u is an integer of 2 to 120, and v is an integer of 1 to 120.)
In which Z ¹ is represented by the following formula —CH ₂ CH ₂ CH ₂ CH ₂ —
_{-CH 2 OCH 2 CH 2 CH 2} -

In which Q ¹ is represented by the following formula:

(In the formula, a is an integer of 1 to 10 independently.)
The manufacturing method of the fluorine-containing acrylic composition of Claim 9 which is a structure represented by these.   The fluorine-containing acryl composition containing 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 8 with respect to 100 parts by mass of the active energy ray-curable composition (E). An active energy ray-curable composition. The active energy ray-curable composition (E)
(Ea) Acrylic compound: 100 parts by mass,
(Eb) Photopolymerization initiator: The fluorine-containing active energy ray-curable composition according to claim 11, comprising 0.1 to 15 parts by mass.   An article having a cured product layer of the fluorine-containing active energy ray-curable composition according to claim 11 on the surface.