JP7600894B2 - Fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition and article - Google Patents

Description

The present invention relates to a fluorine-containing acrylic composition that can impart excellent liquid repellency, stain resistance, and abrasion resistance by adding it to an active energy ray-curable composition such as ultraviolet light or electron beams, a fluorine-containing active energy ray-curable composition containing the fluorine-containing acrylic composition, and an article having a cured layer of this composition on the surface of a substrate.

Hard coat treatment has been widely used as a means of protecting the surface of resin molded products and the like. This involves forming a hard cured resin layer (hard coat layer) on the surface of the molded product to make it less susceptible to scratches. The materials that make up the hard coat layer are often thermosetting resins or compositions that are curable by active energy rays, such as ultraviolet or electron beam curable resins.

As the range of applications for resin molded products expands and the trend towards higher added value continues, there is an increasing demand for more functional cured resin layers (hard coat layers), one of which is the need to impart stain resistance to hard coat layers. This is achieved by imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, making it less susceptible to stains, or making it easier to remove stains if any do occur.

A widely used method for imparting antifouling properties to a hard coat layer is to apply and/or fix a fluorine-containing antifouling agent to the surface of a hard coat layer once it has been formed, but a method has also been considered in which a fluorine-containing curable component is added to a curable resin composition before curing, and this is applied and cured to simultaneously form a hard coat layer and impart antifouling properties. For example, JP-A-6-211945 (Patent Document 1) shows the production of a hard coat layer imparted with antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing it.

The inventors have also been developing various fluorine compounds that can impart antifouling properties to such curable resin compositions, and have proposed photocurable fluorine compounds, for example, as shown in JP-A-2010-53114 (Patent Document 2), JP-A-2010-138112 (Patent Document 3), and JP-A-2010-285501 (Patent Document 4).

These compounds can impart high antifouling properties to curable resin compositions by having a fluoropolyether structure and multiple acrylic groups in one molecule, but on the other hand, they are highly viscous liquids that are difficult to handle on their own, so to make them easier to handle and to improve their mixability with resin compositions, they need to be treated as solutions diluted with highly volatile organic solvents. This poses the problem that they cannot be directly incorporated into solvent-free hard coat agents or paints.

On the other hand, hard coat treatment is widely carried out using coating liquids diluted with organic solvents to improve the coatability and film performance. However, in recent years, there has been a growing movement to curb the use of volatile organic compounds (VOCs) such as volatile organic solvents due to concerns about their impact on the environment and human body, and there is a strong demand for hard coat coating liquids to be highly solid or solvent-free. Accordingly, there is a demand for additive compositions that do not contain volatile organic compounds that have no reactive groups, such as volatile organic solvents, to be added to hard coat coating liquids as described above to impart liquid repellency and stain resistance.

Furthermore, hard coat compositions containing volatile organic compounds without reactive groups, such as conventional volatile organic solvents, undergo particularly large dimensional changes between the time of application and the time of curing, making them particularly unsuitable for applications requiring high dimensional accuracy for the cured product, such as curable compositions for nanoimprints and curable compositions for 3D printers.

The present inventors have been developing various fluorine-containing acrylic compositions that do not contain volatile organic compounds without reactive groups such as volatile organic solvents and that can impart liquid repellency and stain resistance to curable resin compositions. For example, JP 2017-190429 A (Patent Document 5) proposes a fluorine-containing acrylic composition that can impart liquid repellency and stain resistance to curable resin compositions when added to a curable composition without increasing the amount of volatile organic compounds (non-reactive) that do not have groups that react with acrylic groups in the curable composition as a whole by suppressing the content of volatile organic compounds without reactive groups.

However, in recent years, there has been an increasing trend to use hard coats containing fluorine-containing compositions on items that are likely to be touched by people's fingers, such as touch panels. However, when conventional fluorine-containing compositions are used for such purposes, the hard coat surface is worn away by abrasion caused by people's fingers, and the stain-resistant properties decrease, so the abrasion resistance is not satisfactory for practical use.

Japanese Patent Application Publication No. 6-211945 JP 2010-53114 A JP 2010-138112 A JP 2010-285501 A JP 2017-190429 A

The present invention has been made in consideration of the above circumstances, and aims to provide a fluorine-containing acrylic composition that can impart excellent liquid repellency, stain resistance, and abrasion resistance by adding it to an active energy ray-curable composition such as ultraviolet light or electron beams, a fluorine-containing active energy ray-curable composition containing the fluorine-containing acrylic composition, and an article having a cured layer of this composition on the surface of a substrate.

As a result of further investigations to achieve the above object, the present inventors have found that
(A) A fluorine-containing acrylic compound represented by the following general formula (1): Y-Rf ¹ -Z ¹ -Q ¹ -[Z ² -X] _a (1)
[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms and silicon atoms, and may contain a cyclic structure in the middle, provided that the structure does not contain a urethane bond. ^{Q 1} is independently an (a+1)-valent linking group containing at least (a+1) silicon atoms, which may form a cyclic structure and may contain at least one atom selected from oxygen atoms, nitrogen atoms and fluorine atoms, provided that the structure does not contain a urethane bond. Z ² is independently a group represented by the following formula: -C _O H _{2 O} -(OC ₄ H ₈ ) _i (OC ₃ H ₆ ) _j (OC ₂ H ₄ ) _k (OCH ₂ ) _l -
(wherein each repeating unit may be linear or branched, and each repeating unit may be bonded randomly to another repeating unit; i, j, k, and l are each independently an integer of 0 to 10, and i+j+k+l=1 to 10, within the range in which the molecular weight of ^Z2 is 58 to 748; and o is an integer of 2 to 10). X is independently a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one type selected from an oxygen atom and a nitrogen atom, and contains on average at least one monovalent organic group containing the acrylic group or α-substituted acrylic group per molecule, with the proviso that the structure does not contain a urethane bond. a is independently an integer of 1 to 10. Y is a fluorine atom or a monovalent group represented by -Z ¹ -Q ¹ -[Z ² -X] _a . In formula (1), Z ¹ and a number of Z ^2s bracketed by [ ] are all bonded to a silicon atom in the Q ¹ structure. ], and (B) 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 as essential components, the mass ratio of component (A) to component (B) being within the range of 0.01<(A)/(B)<10, and not containing a volatile organic compound having no group reactive with an acrylic group, can be added to an active energy ray-curable composition without increasing the content of the volatile organic compound having no group reactive with an acrylic group, and can be a fluorine-containing active energy ray-curable composition that has good compatibility with the active energy ray-curable composition, has liquid repellency and antifouling properties, suppresses the content of volatile organic compounds, and exhibits high abrasion resistance, thereby completing the present invention.

［式中、Ｒｆ ² は－ＣＦ ₂ Ｏ－（ＣＦ ₂ Ｏ） _p （ＣＦ ₂ ＣＦ ₂ Ｏ） _q －ＣＦ ₂ －であり、ｐは１～１９９の整数、ｑは１～１７０の整数、ｐ＋ｑは６～２００であり、（ ）で括られた繰り返し単位の配列はランダムである。ｖは４～１２０の整数である。Ｒ ² は独立に水素原子又はメチル基であり、Ｒ ³ は独立に水素原子、メチル基又はフェニル基である。Ｚ ⁴ は下記式
－Ｃ _O Ｈ _2O －（ＯＣ ₃ Ｈ ₆ ） _j’ （ＯＣ ₂ Ｈ ₄ ） _k’ （ＯＣＨ ₂ ） _l’ －
（式中、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｊ’、ｋ’、ｌ’はそれぞれ独立に０～４の整数であり、ｊ’＋ｋ’＋ｌ’＝１～１０であり、ｏは２～１０の整数である。）で表される２価のアルキレンエーテル基であり、ｍは２～５の整数である。］、及び
（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
を必須成分として含有し、（Ａ）成分と（Ｂ）成分の質量比が０．０１＜（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ものである含フッ素アクリル組成物。
［２］
（Ｂ）成分の一部又は全部として、下記一般式（６）
ＣＨ₂＝ＣＲ⁵Ｃ（＝Ｏ）ＯＲ⁴ （６）
（式中、Ｒ⁴はウレタン結合、エーテル結合、イソシアネート基又は水酸基を含んでいてもよい炭素数１～２０の１価の炭化水素基である。Ｒ⁵は水素原子、メチル基、フッ素原子又は炭素数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を含むものである［１］に記載の含フッ素アクリル組成物。
［３］
（Ｂ）成分の一部又は全部として、下記一般式（７）
ＣＨ₂＝ＣＲ⁷Ｃ（＝Ｏ）Ｏ－Ｒ⁶－Ｏ（Ｏ＝）ＣＲ⁷Ｃ＝ＣＨ₂ （７）
（式中、Ｒ⁶はウレタン結合、エーテル結合、イソシアネート基又は水酸基を含んでいてもよい炭素数１～２０の２価の炭化水素基である。Ｒ⁷はそれぞれ独立に水素原子、メチル基、フッ素原子又は炭素数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を含むものである［１］又は［２］に記載の含フッ素アクリル組成物。
［４］
（Ｂ）成分のアクリル化合物が、フッ素原子で置換されたアルキル基を含まないものである［１］～［３］のいずれかに記載の含フッ素アクリル組成物。
［５］
活性エネルギー線硬化性組成物（Ｅ）１００質量部に対し、［１］～［４］のいずれかに記載の含フッ素アクリル組成物を０．００５～４０質量部含むものである含フッ素活性エネルギー線硬化性組成物。
［６］
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［５］に記載の含フッ素活性エネルギー線硬化性組成物。
［７］
２５℃、相対湿度４０％における水接触角が９０°以上である硬化物を与えるものである［５］又は［６］に記載の含フッ素活性エネルギー線硬化性組成物。
［８］
［５］～［７］のいずれか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, fluorine-containing active energy ray-curable composition, and article.
[1]
(A) One or more fluorine-containing acrylic compounds selected from the group consisting of fluorine-containing acrylic compounds represented by the following formulas:

[In the formula, Rf ² is --CF ₂ O--(CF ₂ O) _p (CF ₂ CF ₂ O) _q --CF ₂ --, p is an integer from 1 to 199, q is an integer from 1 to 170, p+q is 6 to 200, and the arrangement of the repeating units enclosed in parentheses is random. v is an integer from 4 to 120. R ² is independently a hydrogen atom or a methyl group, and R ³ is independently a hydrogen atom, a methyl group, or a phenyl group. Z ⁴ is a group represented by the following formula:
-C _O H _2O - (OC ₃ H ₆ ) _j' (OC ₂ H ₄ ) _k' (OCH ₂ ) _l' -
(in the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to another repeating unit, j', k', and l' are each independently an integer of 0 to 4, j'+k'+l'=1 to 10, and o is an integer of 2 to 10), and m is an integer of 2 to 5.], and (B) a fluorine-containing acrylic composition comprising, as an essential component, an acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acrylic groups per molecule, wherein the mass ratio of component (A) to component (B) is within the range of 0.01<(A)/(B)<10, and which does not contain a volatile organic compound having no group reactive with an acrylic group.
［ 2 ］
As a part or the whole of the component (B),
CH ₂ =CR ⁵ C(=O)OR ⁴ (6)
(In the formula, ^R4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. ^R5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to [1] , which contains an acrylic compound represented by the following formula:
［ ３ ］
As a part or the whole of the (B) component, the following general formula (7)
CH ₂ =CR ⁷ C(=O)OR ⁶ -O(O=)CR ⁷ C=CH ₂ (7)
(In the formula, ^R6 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. Each ^R7 is independently a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to [1] or [2] , which contains an acrylic compound represented by the following formula:
［ 4 ］
The fluorine-containing acrylic composition according to any one of [1] to [ 3 ], wherein the acrylic compound of the component (B) does not contain an alkyl group substituted with a fluorine atom.
［ 5 ］
A fluorine-containing active energy ray-curable composition comprising 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of [1] to [ 4 ], relative to 100 parts by mass of the active energy ray-curable composition (E).
［ ６ ］
The active energy ray-curable composition (E) is
(Ea) Acrylic compound: 100 parts by mass,
The fluorine-containing active energy ray-curable composition according to [ 5 ], further comprising: (Eb) a photopolymerization initiator: 0.1 to 15 parts by mass.
［ ７ ］
The fluorine-containing active energy ray-curable composition according to [ 5 ] or [ 6 ], which gives a cured product having a water contact angle of 90° or more at 25° C. and a relative humidity of 40%.
［ 8 ］
An article having, on a surface thereof, a layer of the cured product of the fluorine-containing active energy ray-curable composition according to any one of [ 5 ] to [ 7 ].

According to the fluorine-containing acrylic composition of the present invention, it is possible to provide a fluorine-containing active energy ray curable composition that can be added to an active energy ray curable composition to impart liquid repellency and stain resistance without increasing the content of 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). In addition, since the fluorine-containing acrylic compound contained in the fluorine-containing acrylic composition of the present invention does not contain a urethane bond in the molecule, the stain resistance is unlikely to decrease even with wear. Therefore, the fluorine-containing acrylic composition is useful as an antifouling additive for imparting liquid repellency, stain resistance, and wear resistance to ultraviolet-curable or heat-curable hard coating agents, paints, resins, anti-reflective coating compositions, etc.

The fluorine-containing acrylic composition of the present invention comprises
(A) A fluorine-containing acrylic compound represented by the following general formula (1): Y-Rf ¹ -Z ¹ -Q ¹ -[Z ² -X] _a (1)
[In the formula, Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms and silicon atoms, and may contain a cyclic structure in the middle, provided that the structure does not contain a urethane bond. ^{Q 1} is independently an (a+1)-valent linking group containing at least (a+1) silicon atoms, which may form a cyclic structure and may contain at least one atom selected from oxygen atoms, nitrogen atoms and fluorine atoms, provided that the structure does not contain a urethane bond. Z ² is independently a group represented by the following formula: -C _O H _{2 O} -(OC ₄ H ₈ ) _i (OC ₃ H ₆ ) _j (OC ₂ H ₄ ) _k (OCH ₂ ) _l -
(wherein each repeating unit may be linear or branched, and each repeating unit may be bonded randomly to another repeating unit; i, j, k, and l are each independently an integer of 0 to 10, and i+j+k+l=1 to 10, within the range in which the molecular weight of ^Z2 is 58 to 748; and o is an integer of 2 to 10). X is independently a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one type selected from an oxygen atom and a nitrogen atom, and contains on average at least one monovalent organic group containing the acrylic group or α-substituted acrylic group per molecule, with the proviso that the structure does not contain a urethane bond. a is independently an integer of 1 to 10. Y is a fluorine atom or a monovalent group represented by -Z ¹ -Q ¹ -[Z ² -X] _a . In formula (1), ^Z1 and a number of ^Z2s bracketed by [ ] are all bonded to silicon atoms in the ^Q1 structure. ], and (B) an acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups per molecule is contained as an essential component, the mass ratio of component (A) to component (B) is within the range of 0.01<(A)/(B)<10, and no volatile organic compound having no group reactive with the acrylic group is blended.

The fluorine-containing acrylic composition of the present invention is capable of imparting excellent liquid repellency, stain resistance, and abrasion resistance when added to an active energy ray-curable composition, since the fluorine-containing acrylic compound of component (A) has perfluoropolyether groups as water- and oil-repellent groups, and an acrylic group or an α-substituted acrylic group, and does not contain a urethane bond in the molecule.

The fluorine-containing acrylic compound of component (A), which 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 term "acrylic compound" is a general term for compounds having an acrylic group or an α-substituted acrylic group, and includes compounds in which two or more acrylic groups or α-substituted acrylic groups have been introduced into the side chain or end of various polymers by any method. In the present invention, the term "(meth)acrylate" refers to either or both of acrylate and methacrylate.
Y-Rf ¹ -Z ¹ -Q ¹ -[Z ² -X] _a (1)

In the above formula (1), Rf ¹ is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 constituted by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ¹ is preferably one having a perfluorooxyalkylene structure having 1 to 6 carbon atoms, particularly the following perfluorooxyalkylene structure having 1 to 3 carbon atoms, as a main repeating unit.
_{-CF2O-
-CF2CF2O- ​}
-CF( _CF3 ) _CF2O-
-CF ₂ CF ₂ CF ₂ O-
These structures may be a homopolymer of any one of these structures, or a random or block polymer consisting of a plurality of structures.

（式中、ｂは単位毎に独立に１～３の整数である。ｃ、ｄ、ｅ、ｆ、ｇ、ｈはそれぞれ０～２００の整数で、ｃ＋ｄ＋ｅ＋ｆ＋ｇ＋ｈ＝３～２００である。これら各単位は直鎖状であっても分岐状であってもよく、また、ｃ、ｄ、ｅ、ｆ、ｇ、ｈが付された括弧内に示され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 ^Rf1 having such a structure include the following structures.

(In the formula, b is an integer of 1 to 3, independently for each unit. c, d, e, f, g, and h are each an integer of 0 to 200, and c+d+e+f+g+h=3 to 200. Each of these units may be linear or branched, and each repeating unit shown in parentheses with c, d, e, f, g, and h may be randomly bonded.)

In the above formula, b is an integer of 1 to 3, independently for each unit.
Further, c, d, e, f, g, and h are each an integer of 0 to 200, preferably c is an integer of 5 to 100, d is an integer of 5 to 100, e is an integer of 0 to 100, f is an integer of 0 to 100, g is an integer of 0 to 100, and h is an integer of 0 to 100, and c+d+e+f+g+h=3 to 200, preferably 10 to 105, more preferably c+d is an integer of 10 to 105, particularly 15 to 60, and e=f=g=h=0. If c+d+e+f+g+h is smaller than the upper limit, adhesion and curability are good, and if it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable.
In the above formula, each unit may be linear or branched, and each repeat unit shown in parentheses with c, d, e, f, g, and h may be randomly bonded.

（式中、（ ）で括られた繰り返し単位の配列はランダムであり、ｓは０～６の整数、ｔは１～１００の整数、ｕは１～１００の整数、ｔ＋ｕは２～１２０、好ましくは４～１００の整数、ｓ＋ｔ＋ｕは３～１２６、好ましくは４～１００の整数である。ｖは４～１２０、好ましくは４～８０の整数である。） Suitable examples of Rf ¹ having such a structure include the following structures.
-CF ₂ O- (CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF ₂ -
(In the formula, the arrangement of the repeating units enclosed in ( ) is random, p is an integer of 1 to 199, preferably 1 to 99, q is an integer of 1 to 170, preferably 1 to 99, and p+q is an integer of 6 to 200, preferably 10 to 100.)

(In the formula, the arrangement of the repeating units enclosed in ( ) is random, s is an integer of 0 to 6, t is an integer of 1 to 100, u is an integer of 1 to 100, t+u is an integer of 2 to 120, preferably an integer of 4 to 100, and s+t+u is an integer of 3 to 126, preferably an integer of 4 to 100. v is an integer of 4 to 120, preferably an integer of 4 to 80.)

The molecular weight of Rf ¹ may be such that the number average molecular weight of the corresponding structural portion is within the range of 400 to 20,000, preferably 800 to 10,000, and the molecular weight distribution (or polymerization degree distribution) is not particularly limited. In the present invention, the molecular weight (or polymerization degree or number of repeating units) can be determined as the polystyrene-equivalent number average molecular weight (or number average polymerization degree) by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the developing solvent, but is preferably ^the number average molecular weight (or number average polymerization degree) calculated from the characteristic peak intensity ratio of the terminal structure and main chain structure of the fluorine-containing acrylic compound based on 1 H-NMR analysis and ¹⁹ F-NMR analysis (hereinafter the same).

In the above formula (1), ^Z1 is independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms and silicon atoms, and may contain a cyclic structure in the middle, but does not contain a urethane bond in the structure. Particularly preferred structures of ^Z1 include the following. In the following structures, it is preferable that the bond on the left side is bonded to ^Rf1 , and the bond on the right side is bonded to ^Q1 .
_{-CH2CH2- ​}
-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 -

As ^Z1 , the following is more preferable.
-CH ₂ CH ₂ CH ₂ CH ₂ -
-CH ₂ OCH ₂ CH ₂ CH ₂ -

In the above formula (1), a is independently an integer from 1 to 10, and preferably an integer from 2 to 8.

In the above formula (1), ^Q1 is an (a+1)-valent linking group that independently contains at least (a+1) silicon atoms, may form a cyclic structure, may contain at least one selected from oxygen atom, nitrogen atom and fluorine atom, but does not contain urethane bond in the structure.Preferable examples of such ^Q1 include a siloxane structure having (a+1) silicon atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or an (a+1)-valent linking group consisting of a combination of two or more of these.Specifically, the following structure is shown as a particularly preferred structure.

In the following formula, a is the same as a in formula (1) above and is independently an integer of 1 to 10, preferably an integer of 2 to 8. a' is an integer of 2 to 10, preferably an integer of 2 to 7. r is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, and the bonds (silicon atoms) of each of the (a+1) and (a'+1) units are bonded to any one of the groups ^Z2 and ^Z1 in the a number of units enclosed in [ ] in formula (1) above.

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

（式中、ａ’は前述の通りである。）
で表される（ａ’＋１）価の連結基が好ましい。 Among these, Q ¹ in the above formula (1) is

(In the formula, a' is as defined above.)
A linking group having a valence of (a'+1) represented by the following formula is preferred.

In the above formula ( ₁ ), ^Z2 independently represents the _following formula: _{-C0H2O- (OC4H8 ) i} ( _{OC3H6 ) j} ( _OC2H4 ) _k ( _OCH2 ) _l-
(wherein each repeating unit may be linear or branched, and each repeating unit may be bonded randomly, and i, j, k, and l are each independently an integer of 0 to 10 (i.e., the sum of i, j, k, and l is 1 to 10) within the range in which the molecular weight of ^Z2 is 58 to 748, preferably 72 to 300, and preferably i is an integer of 0 to 5, j is an integer of 0 to 5, k is an integer of 0 to 5, and l is an integer of 0 to 5, and i+j+k+l=1 to 10. o is an integer of 2 to 10, preferably an integer of 2 to 8.) It is a divalent alkylene ether group represented by the following formula. In the above structure, it is preferable that the bond on the left side is bonded to ^Q1 , and the bond on the right side is bonded to X.

As ^Z2 , preferred structures include the following.
-CH ₂ CH ₂ OCH ₂ -
-CH ₂ CH ₂ OCH 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 (OC ₂ H ₄ ) _k1 (OC ₃ H ₆ ) _j1 (OC ₄ H ₈ ) _i1 -

Here, k1 is an integer from 0 to 10, j1 is an integer from 0 to 10, i1 is an integer from 0 to 10, and the molecular weight of ^Z2 is 86 to 330. The arrangement of the repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers rather than a single unit. If the molecular weight of ^Z2 is less than 58, it becomes difficult to mix with the acrylic compound of component (B), and if it exceeds 748, the ability of the fluorine-containing acrylic compound to provide antifouling properties becomes insufficient.

Particularly preferred structures for ^Z2 include the following, and among these, those in which k1 is 1 to 4 and j1 is 1 to 4 are preferred.
-CH ₂ CH ₂ CH ₂ (OC ₂ H ₄ ) _k1 -
-CH ₂ CH ₂ CH ₂ (OC ₃ H ₆ ) _j1 -

In the above formula (1), X is independently a hydrogen atom or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one atom selected from oxygen and nitrogen atoms, and contains at least one monovalent organic group containing the acrylic group or α-substituted acrylic group on average per molecule, but does not contain a urethane bond in the structure.

（式中、Ｒ¹はそれぞれ独立に、水素原子、フッ素原子、メチル基、又はトリフルオロメチル基であり、Ｚ³は単結合、又は炭素数１～１８の、エーテル結合及び／又はエステル結合を含んでいてもよい２価又は３価の炭化水素基であり、ｎは１又は２である。） X is preferably a structure represented by the following formula:

(In the formula, R ¹ 's are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, Z ³ 's are a single bond, or a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms which may contain an ether bond and/or an ester bond, and n's are 1 or 2.)

Here, R ¹ is each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and a hydrogen atom or a methyl group is preferred.
In addition, n here is 1 or 2, and preferably 1.

In addition, ^Z3 here is a single bond or a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms which may contain an ether bond and/or an ester bond. Preferably, Z3 is a single bond or the following structure:
_{-CH2-
-CH2CH2- ​}
-CH ₂ CH ₂ CH ₂ -

X is preferably a group represented by the following formula:
-Z'-OC(=O)-CR ⁸ =CH ₂
(In the formula, R ⁸ is a hydrogen atom or a methyl group, and Z′ is a single bond, a methylene group, an ethylene group, or a propylene group.)

（式中、Ｒｆ¹、Ｚ¹、Ｚ²、Ｑ¹、Ｒ¹、ａは前述の通りである。） The fluorine-containing acrylic compound represented by the above formula (1) is preferably one represented by the following general formula (2) or (3).

(In the formula, Rf ¹ , Z ¹ , Z ² , Q ¹ , R ¹ and a are as defined above.)

［式中、Ｒｆ¹、Ｚ¹、Ｑ¹、ａは前述の通りである。Ｚ⁴は、下記式
－Ｃ_OＨ_2O－（ＯＣ₃Ｈ₆）_j’（ＯＣ₂Ｈ₄）_k’（ＯＣＨ₂）_l’－
（式中、各繰り返し単位は直鎖状であっても分岐状であってもよく、各繰り返し単位同士はランダムに結合されていてよく、ｊ’、ｋ’、ｌ’はそれぞれ独立に０～４の整数であり、ｊ’＋ｋ’＋ｌ’＝１～１０であり、ｏは２～１０の整数である。）で表される２価のアルキレンエーテル基である。］ The fluorine-containing acrylic compound represented by the above formula (1) is more preferably one represented by the following general formula (4) or (5).

[wherein Rf ¹ , Z ¹ , Q ¹ and a are as defined above. Z ⁴ is a group represented by the following formula: -C _O H ₂ O-(OC ₃ H ₆ ) _j' (OC ₂ H ₄ ) _k' (OCH ₂ ) _l' -
(In the formula, each repeating unit may be linear or branched, each repeating unit may be randomly bonded to another repeating unit, j', k', and l' are each independently an integer of 0 to 4, j'+k'+l'=1 to 10, and o is an integer of 2 to 10.)

（式中、Ｒｆ²は－ＣＦ₂Ｏ－（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_q－ＣＦ₂－であり、（ ）で括られた繰り返し単位の配列はランダムであり、Ｒ²は独立に水素原子又はメチル基であり、Ｒ³は独立に水素原子、メチル基又はフェニル基である。ｍは２～５の整数である。ｐ、ｑ、ｐ＋ｑ、Ｚ⁴、ｖは前述の通りである。） More specific examples of the fluorine-containing acrylic compound represented by the above formula (1) include those shown below.

(In the formula, Rf ² is --CF ₂ O--(CF ₂ O) _p (CF ₂ CF ₂ O) _q --CF ₂ --, the arrangement of the repeating units enclosed in ( ) is random, R ² is independently a hydrogen atom or a methyl group, R ³ is independently a hydrogen atom, a methyl group or a phenyl group, m is an integer of 2 to 5, and p, q, p+q, Z ⁴ and v are as defined above.)

（式中、Ｒｆ²、ｍ、Ｒ²、Ｒ³、Ｚ⁴、ｖは前述の通りである。） Among these, the following are particularly preferred.

(In the formula, ^Rf2 , m, ^R2 , ^R3 , ^Z4 , and v are as defined above.)

（式中、Ｒ¹、ｉ、ｊ、ｋ、ｌは前述の通りである。ｗは０～８の整数である。）
で表されるアルキレンエーテル基を有する（隣接する）末端脂肪族不飽和基（例えば、アルケニル基等の脂肪族不飽和二重結合を末端に含有するアルキル基、又は末端アルケニル基）、及びアクリル基もしくはα置換アクリル基を含有する化合物をヒドロシリル化付加反応させることにより得ることができる。 The synthesis method of the fluorine-containing acrylic compound represented by the general formula (1) is not particularly limited. For example, as an embodiment of the fluorine-containing acrylic compound represented by the general formula (2) or (3), first, a compound represented by the following general formula (8) or (9) is
F-Rf ¹ -Z ¹ -Q ¹ -[H] _a (8)
[H] _a -Q ¹ -Z ¹ -Rf ¹ -Z ¹ -Q ¹ -[H] _a (9)
(In the formulae, Rf ¹ , Z ¹ , Q ¹ and a are as defined above, and all of the a hydrogen atoms (H) enclosed in [ ] in formulae (8) and (9) are bonded to silicon atoms in the Q ¹ structure.)
and a fluoropolyether compound having a polyfunctional Si—H group represented by the following general formula (10):

(In the formula, R ¹ , i, j, k, and l are as defined above. w is an integer of 0 to 8.)
The above-mentioned alkylene ether groups can be obtained by subjecting a compound containing a terminal aliphatic unsaturated group (for example, an alkyl group having an aliphatic unsaturated double bond at its terminal, such as an alkenyl group, or a terminal alkenyl group) having (adjacent to) an alkylene ether group represented by the following formula:

（式中、Ｒｆ²、ｖは上記と同じである。） Examples of the fluoropolyether compounds having polyfunctional Si--H groups represented by the above formulas (8) and (9) include those shown below.

(In the formula, Rf ² and v are the same as above.)

Furthermore, examples of compounds containing a terminal aliphatic unsaturated group (adjacent to) the alkylene ether group represented by the above formula (10) (for example, an alkyl group containing an aliphatic unsaturated double bond at its terminal, such as an alkenyl group, i.e., an alkyl group whose terminal is blocked with an external olefin (vinyl group) represented by _CH2 =CH-, or the external olefin (vinyl group)) and an acrylic group or an α-substituted acrylic group include the following.
CH ₂ =CHCH ₂ (OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -O-C(=O)-CH=CH ₂
CH ₂ =CHCH ₂ (OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -O-C(=O)-C(CH ₃ )=CH ₂
CH ₂ =CH(OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -OC(=O)-CH=CH ₂
CH ₂ =CH(OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -OC(=O)-C(CH ₃ )=CH ₂
(In the formula, k2 is an integer from 0 to 10, j2 is an integer from 0 to 10, i2 is an integer from 0 to 10, i2+j2+k2=1 to 16 _, and the molecular weight of the portion corresponding to _CH2 =CH- _{CwH2w- (OC4H8 ) i} ( _OC3H6 ) _j ( _OC2H4 ) _k ( _OCH2 ) _l- in formula ( ₁₀ ) should be 57 to 747. The arrangement of the repeating units is random regardless of the type. Furthermore, each repeating unit may not be _a single unit but may be a mixture of structural isomers.)

Among these, the following are particularly preferred:
CH ₂ =CHCH ₂ -(OC ₂ H ₄ ) _k3 -OC(=O)-C(CH ₃ )=CH ₂
CH ₂ =CHCH ₂ -(OC ₃ H ₆ ) _j3 -OC(=O)-C(CH ₃ )=CH ₂
(In the formula, k3 is an integer from 1 to 4, and j3 is an integer from 1 to 4.)

Conventionally, allyl methacrylate has been mainly used when introducing acrylic groups or α-substituted acrylic groups into fluorine-containing compounds by hydrosilylation addition reactions, but the allyl group (terminal aliphatic unsaturated group) in allyl methacrylate has low reactivity in hydrosilylation addition reactions, and therefore is unsuitable because the hydrosilylation addition reaction proceeds not only at the target allyl group (terminal aliphatic unsaturated group) as a reaction site, but also at the methacrylic group as a side reaction. In the present invention, the reactivity of the terminal aliphatic unsaturated group (adjacent to the terminal aliphatic unsaturated group) having an alkylene ether group is sufficiently guaranteed by using a compound containing an acrylic group or α-substituted acrylic group, and the hydrosilylation addition of the acrylic group or α-substituted acrylic group as a side reaction is effectively suppressed.

The fluoropolyether compound having polyfunctional Si-H groups represented by the above formulas (8) and (9) and the compound containing a terminal aliphatic unsaturated group and an acrylic group or an α-substituted acrylic group represented by formula (10) are mixed and stirred, and reacted in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 72 hours, and particularly 5 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if it is too high, the reaction may become uncontrollable due to the temperature rise caused by the heat of reaction of hydrosilylation, and bumping or decomposition of the raw materials may occur.

In this case, the ratio of the charge of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9) and the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group is preferably 0.8 to 5 times, particularly 1 to 2 times, the molar amount of the unsaturated group of the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group relative to the total moles of H enclosed in [ ] of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9). If the amount of the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group is too small, there is a possibility that a large amount of Si-H groups will remain in the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9), and the desired effect will not be obtained. If the amount is too large, the uniformity of the reaction solution decreases, the reaction rate becomes unstable, and when removing the terminal aliphatic unsaturated group represented by formula (10) and the compound containing an acrylic group or an α-substituted acrylic group after the reaction, the conditions for heating, decompression, extraction, etc. must be made stricter in proportion to the increase in the amount of excess unreacted components.

The addition reaction catalyst may be, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium. Of these, a compound containing platinum is preferred, and examples of the compound that may be used include hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like, and platinum supported on activated carbon.
The amount of the addition reaction catalyst to be added is preferably such that the metal content is 0.1 to 5,000 ppm by mass, more preferably 0.1 to 1,000 ppm by mass, relative to the fluoropolyether compound having a polyfunctional Si—H group represented by formula (8) or (9).

The above-mentioned addition reaction can be carried out even in the absence of a solvent, but may be diluted with a solvent as necessary. In this case, the dilution solvent may be a widely used organic solvent such as toluene, xylene, isooctane, etc. As such an organic solvent, it is preferable that the boiling point is equal to or higher than the target reaction temperature, does not inhibit the reaction, and the fluorine-containing acrylic compound represented by formula (2) or (3) produced after the reaction is soluble at the above-mentioned reaction temperature. For example, 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 are desirable, and m-xylene hexafluoride is particularly preferable.
When a solvent is used, the amount of the solvent used is preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9). If the amount is less than this, the effect of dilution by the solvent is weak, and if the amount is more, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.

After the reaction is completed, the unreacted terminal aliphatic unsaturated group represented by formula (10), and the compound containing an acrylic group or an α-substituted acrylic group, and the diluting solvent can be removed by a known method such as vacuum distillation, extraction, or adsorption to obtain the fluorine-containing acrylic compound represented by formula (2) or (3).

The fluorine-containing acrylic compound represented by general formula (1) obtained by the above reaction is used after purification and isolation procedures such as concentration, column purification, distillation, and extraction.

The fluorine-containing acrylic compound thus obtained does not contain a volatile organic compound (volatile organic solvent). The fluorine-containing acrylic compound (A) may be used alone or in combination of two or more kinds.

The second essential component in the fluorine-containing acrylic composition of the present invention is (B) an acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups per molecule. The acrylic compound of component (B) may contain oxygen atoms and nitrogen atoms other than the acrylic structure, and specifically may contain an ether bond, a urethane bond, an isocyanate group, or a hydroxyl group.

The viscosity of component (B) at 25°C is 100 mPa·s or less, preferably 0.4 to 20 mPa·s, due to its solubility with component (A). If the viscosity at 25°C exceeds 100 mPa·s, it becomes difficult to mix with component (A) and handling becomes poor. In the present invention, the viscosity can be measured using a rotational viscometer (e.g., BL type, GH type, BS type, cone-plate type, rheometer, etc.) (hereinafter the same).

Of such components (B), preferred examples of compounds having one (meth)acryl group in the molecule include those represented by the following general formula (6).
CH ₂ =CR ⁵ C(=O)OR ⁴ (6)
(In the formula, ^R4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. ^R5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)

In the above formula (6), ^R4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group, and is preferably an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, which may be branched or cyclic and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. Specific examples of R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethyl-hexyl group, an isodecyl group, a tridecyl group, an isostearyl group, a phenyl group, a benzyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a furfuryl group, a tetrahydrofuryl group, a tetrahydropyranyl group, a 2-(2-ethoxyethoxy)ethyl group, -CH ₂ CH ₂ -OH, -CH ₂ CH(CH ₃ )-OH, -CH 2 CH ₂ CH ₂ -OH, -CH ₂ CH 2 CH 2 CH 2 -OH, -CH ₂ CH _{2 CH 2} CH ₂ CH ₂ -OH, -CH ₂ CH ₂ CH 2 CH 2 CH 2 -OH, -CH 2 CH 2 CH ₂ CH ₂ CH ₂ -OH, -CH ₂ CH ₂ CH ₂ CH ₂ CH _{2 -OH} , Examples include --OH, a 4-hydroxycyclohexyl group, and --CH ₂ CH ₂ --NCO.
R ⁵ is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group, a trifluoropropyl group or a nonafluorobutyl group, and particularly preferably a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.

More specifically, such compounds include 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, benzyl (meth)acrylate, 2-hydroxyethyl ... Examples of such acrylates include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, and neopentyl glycol-(meth)acrylic acid-benzoic acid ester.

In addition, compounds not falling under formula (6), such as acrylate compounds having a repeating unit structure of ethylene oxide, propylene oxide, tetramethylene oxide, lactone, etc. and having various alkoxy terminals, such as commercially available (meth)acrylic compounds under the names of methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, nonylphenol EO adduct acrylate, etc., can also be used as long as they have a viscosity of 100 mPa·s or less at 25°C.

Furthermore, among the components (B), preferred examples of compounds having two (meth)acryl groups in the molecule include those represented by the following general formula (7).
CH ₂ =CR ⁷ C(=O)OR ⁶ -O(O=)CR ⁷ C=CH ₂ (7)
(In the formula, ^R6 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. Each ^R7 is independently a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)

In the above formula (7), R ⁶ is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group, and is preferably an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, which may be branched or cyclic and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. Specific examples of ^R6 include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexylene group (hexamethylene group), a cyclohexylene group, an octamethylene group, a nonamethylene group, a decamethylene group, _{-CH2CH2- O-} CH2CH2-, _{-C3H6 - O - C3H6-} , a phenylene group, a dicyclopentanylene group, a dicyclopentenylene group, a furfurylene _group , a tetrahydrofulrylene group, and a tetrahydropyranylene group.
Each R ⁷ is independently a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a trifluoropropyl group, a nonafluorobutyl group or other fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.

Specific examples of such compounds include 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, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, etc.

The acrylic compound of component (B) may contain an alkyl group substituted with a fluorine atom. However, acrylic compounds containing an alkyl group substituted with a fluorine atom are of greater concern for the environmental impact than acrylic compounds that do not contain fluorine atoms. From the standpoint of VOC emission regulations, it is desirable for the acrylic compound of component (B) to contain a small amount of acrylic compounds containing an alkyl group substituted with a fluorine atom, and it is particularly desirable for the acrylic compound of component (B) to contain no acrylic compounds containing an alkyl group substituted with a fluorine atom.

Component (B) may be a single compound or a mixture of multiple compounds that meet the above definition. In the case of a mixture, the total content of the compounds that fall under component (B) can be calculated as the content of component (B). Compounds that fall under component (B) can be synthesized by known methods as necessary, but various compounds are commercially available from reagent manufacturers, etc., and these can also be used as they are.

The fluorinated acrylic composition of the first embodiment of the present invention contains the above-mentioned components (A) and (B) as essential components, and the mass ratio of component (A) to component (B) is within the range of 0.01<(A)/(B)<10, preferably 0.015≦(A)/(B)≦8, and more preferably 0.02≦(A)/(B)≦5.
In another embodiment of the present invention, the fluorine-containing acrylic composition is mixed with the active energy ray curable composition (E) described later to form a fluorine-containing active energy ray curable composition, which is then applied and cured to provide a liquid-repellent and stain-resistant cured layer on a substrate. The liquid-repellent and stain-resistant properties are expressed by the presence of the component (A) dispersed in the component of the active energy ray curable composition (E) on the surface of the cured layer. Therefore, when the mass ratio (A)/(B) is 0.01 or less, the content of the component (A) in the fluorine-containing acrylic composition becomes too small, making it difficult to finally express the liquid-repellent and stain-resistant properties. On the other hand, when the mass ratio (A)/(B) is 10 or more, the workability decreases due to the high viscosity of the component (A), and the compatibility and mixability with the component (E) decrease.

When (A)/(B) is within the above range, the viscosity of the fluorinated acrylic composition at 25°C is preferably 0.1 to 10,000 mPa·s, more preferably 0.5 to 5,000 mPa·s, and even more preferably 1 to 1,000 mPa·s. When the composition has such a viscosity, a curable composition with good handleability is obtained.

The fluorine-containing acrylic composition of the present invention is one that does not contain a volatile organic compound that does not have a group that reacts with an acrylic group (particularly a non-reactive volatile organic compound (or volatile organic solvent) that does not contain a (meth)acrylic group in the molecule) (i.e., a solvent-free fluorine-containing acrylic composition).

The fluorine-containing acrylic composition of the present invention can be added to an active energy ray-curable composition (E) described below to form a fluorine-containing active energy ray-curable composition.
The amount of the fluorine-containing acrylic composition added is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the active energy ray-curable composition (E) described below. If the amount of the compound is less than this, the compound cannot be sufficiently arranged on the surface when a cured product is formed, and the expected liquid repellency and antifouling properties cannot be exhibited, whereas if the amount is greater than this, the effect of the fluorine-containing acrylic compound on the strength and hardness of the cured product layer becomes too large, resulting in the loss of the original cured product properties of the active energy ray-curable composition.

The active energy ray curable composition (E) is not particularly limited as long as it gives a cured product when irradiated with active energy rays such as ultraviolet rays or electron beams, but it is particularly preferable that the composition contains an acrylic compound (Ea) and a photopolymerization initiator (Eb).

The acrylic compound (Ea) can be either monofunctional or polyfunctional. For example, the monofunctional and bifunctional acrylic compounds of component (B) described above can be used, but it is particularly preferable for component (Ea) to contain a non-fluorinated acrylic compound having two or more acrylic groups in one molecule.

Such non-fluorinated acrylic compounds may be any compounds having two or more acrylic groups or α-substituted acrylic groups in one molecule, such as 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl) phthalate, and the like. Preferred examples of the (meth)acrylic compound include difunctional to hexafunctional (meth)acrylic compounds such as ethyl acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol hexa(meth)acrylate; epoxy acrylates obtained by adding acrylic acid to these (meth)acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, or alkyl-modified products; and copolymers in which a (meth)acryloyl group has been introduced into the side chain of an acrylic acid ester copolymer.

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

It may also be a mixture of at least two types of acrylic compounds, including a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond, or a polyfunctional urethane acrylate having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group.

In this case, examples of polyfunctional acrylic compounds having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and compounds modified with ethylene oxide or propylene oxide.

In addition, examples of 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, isophorone diisocyanate, and trimers thereof, as well as difunctional or higher polyisocyanates obtained by reacting these difunctional or trifunctional isocyanates with aliphatic diols, aliphatic polyols, and polyacrylates having hydroxyl groups in the side chains, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, etc. , bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and their ethylene oxide and propylene oxide modified forms, as well as aliphatic polyols and polyacrylates having hydroxyl groups on the side chains reacted with acrylic compounds having isocyanate groups such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

Furthermore, the (Ea) component may include not only liquid components, but also fine particle-like high molecular weight substances or inorganic filler fine particles whose surfaces are modified with acrylic groups.

The above (Ea) components can be used alone, but multiple corresponding compounds can also be used in combination to improve coatability and the properties of the cured coating.

In addition, by including a photopolymerization initiator as the (Eb) component, it is possible to obtain a curable composition that has improved curability when ultraviolet light is used as the active energy ray.

The photopolymerization initiator of the (Eb) component is not particularly limited as long as it can cure the acrylic compound by irradiation with ultraviolet light, but preferable examples include acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone, 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-morpholinophenyl)butanone-1-one, 2- (Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, etc. may be used alone or in combination of two or more.

The content of component (Eb) can be appropriately determined depending on the curing conditions and the desired physical properties of the cured product of active energy ray-curable composition (E), but for example, it is desirable for the content to be 0.1 to 15 parts by mass, and particularly 1 to 10 parts by mass, per 100 parts by mass of component (Ea). If the amount added is less than this, the curability may decrease, and if the amount added is more than this, there is a risk of a significant effect on the physical properties after curing.

The active energy ray curable composition (E) may also contain other active energy ray reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers. There are no particular restrictions on the structure of these, and known compounds may be used as long as they do not impair the purpose of the present invention.

As the active energy ray curable composition (E), existing compositions that are commercially available from various companies as paints, inks, hard coat agents, etc., as active energy ray curable compositions containing the components (Ea) and (Eb) and various additives may be used as a part or the whole of the component (E). Even when using a commercially available hard coat agent in this way, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, fillers, etc. can be added and blended according to the purpose, within a range that does not inhibit the effects of the present invention.

The fluorine-containing active energy ray-curable composition of the present invention obtained in the above manner can suppress the inclusion of volatile organic compounds that are not incorporated into the structure of the cured product, and since it contains a fluorine-containing acrylic compound having a perfluoropolyether group as the water- and oil-repellent group and an acrylic group or an α-substituted acrylic group as the active energy ray-curable group, it gives a cured product with excellent water repellency, oil repellency, slipperiness, anti-fouling properties, fingerprint wiping properties, low refractive index properties, solvent resistance, chemical resistance, etc., and since this fluorine-containing acrylic compound does not contain a urethane bond in the molecule, it gives a cured product with excellent abrasion resistance.

Furthermore, the present invention provides an article (an article having a cured product layer (also called a cured coating or cured resin layer) on its surface) obtained by applying the above-mentioned fluorine-containing active energy ray curable composition of the present invention to the surface of a substrate and curing it. As described above, by using the fluorine-containing active energy ray curable composition of the present invention, it is possible to form a cured coating (cured resin layer) having excellent surface properties on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of an acrylic hard coat. This makes it difficult for stains due to fingerprints, sebum, sweat, and other human oils, cosmetics, etc. to adhere to the surface, and also provides the substrate (article) with a hard coat surface that is easy to wipe off. Therefore, the fluorine-containing active energy ray curable composition of the present invention can provide a coating film or protective film for the surface of a substrate (article) that may be stained by human oils, cosmetics, etc. when touched by the human body.

The cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention can be applied directly to the surface of an article to which properties are to be imparted and cured, or the fluorine-containing active energy ray-curable composition of the present invention can be applied to various substrate films (e.g., films of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyvinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, aramid, polyimide, etc.) to produce a cured coating, which can then be attached to the surface of the desired article, thereby imparting properties to various articles.

Here, the method of coating the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, and for example, known coating methods such as roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating, and screen printing can be used. After coating, the coating film is irradiated with active energy rays to cure it. Here, any active energy rays such as electron beams and ultraviolet rays can be used, but ultraviolet rays are particularly preferred. As the ultraviolet ray source, mercury lamps, metal halide lamps, and LED lamps are suitable. The amount of ultraviolet ray irradiation is preferably in the range of 10 to 10,000 mJ/cm ² , particularly 20 to 4,000 mJ/cm ² , since too little will leave uncured components, and too much may cause deterioration of the coating film and substrate. In order to prevent inhibition of curing by oxygen, the irradiation atmosphere during ultraviolet irradiation may be replaced with an inert gas not containing oxygen molecules, such as nitrogen, carbon dioxide, or argon, or the coating surface may be covered with a protective layer having releasability and ultraviolet light transmission and then irradiated with ultraviolet light, or if the substrate has ultraviolet light transmission, the coating surface may be covered with a protective layer having releasability and then ultraviolet light may be irradiated from the opposite side of the substrate to the coated surface. In order to effectively level the coating film or polymerize the acrylic groups in the coating film, the coating film and substrate may be heated by any method, such as a hot air drying oven, before and during ultraviolet light irradiation.

The thickness of the cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but if the resulting film thickness is too thin, sufficient surface hardness will not be obtained, and if it is too thick, the mechanical strength of the hard coat film will decrease and it will be prone to cracking. Therefore, it is usually preferable that the thickness is 5 nm to 100 μm, and particularly 1 μm to 20 μm.

In addition, it is desirable that the cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention has a water contact angle of 90° or more, preferably 95° or more, at 25°C and a relative humidity of 40%. In the present invention, the water contact angle is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a droplet: 2 μl. In order to achieve the above water contact angle, it is preferable that the fluorine-containing active energy ray-curable composition is mixed uniformly.

Such articles include, for example, the housings of various handheld devices such as tablet computers, mobile phones, and smartphones, notebook PCs, digital media players, watch-type and eyeglasses-type wearable computers, digital cameras, digital video cameras, and electronic book readers; the surfaces of display and operation devices such as liquid crystal displays, plasma displays, organic electroluminescence displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, and toner-based displays, as well as TV screens; the exteriors of automobiles, the glossy surfaces of pianos and furniture, the surfaces of architectural stone materials such as marble, decorative building materials for water-related areas such as toilets, baths, and washrooms; protective glass for displaying artworks, show windows, showcases, covers for photo frames, wristwatches, automobile window glass, window glass for trains and aircraft, transparent glass or transparent plastic (acrylic resin, polycarbonate, etc.) components such as automobile headlights and taillights, and various mirror components, and are useful as coating films and surface protective films.

In particular, it is useful as a surface protective film for various devices having a display input device such as a touch panel display that allows operations to be performed on the screen with a person's fingers or palm, for example, tablet computers, notebook PCs, watch-type wearable computers, activity monitors, mobile (communication) information terminals such as mobile phones and smartphones, digital media players, e-book readers, digital photo frames, game machines and game machine controllers, digital cameras, digital video cameras, navigation devices for automobiles, etc., automatic cash withdrawal and deposit machines, automated cash dispensers, vending machines, digital signage (electronic billboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

Furthermore, the cured coating formed by the fluorine-containing active energy ray-curable composition of the present invention is useful as a surface protective coating for optical recording media such as magneto-optical disks and optical disks; eyeglass lenses, camera lenses, projector lens prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers, optical couplers, and other optical components and optical devices, or as a surface protective coating for various protective parts of these devices.

Furthermore, the cured coating formed by the fluorine-containing active energy ray-curable composition of the present invention has a smaller change in dimension between application and curing than a cured coating formed by a conventional hard coat composition containing a volatile organic compound, and is therefore useful as a surface protective film for applications requiring high dimensional accuracy for the cured product, such as curable compositions for nanoimprints and curable compositions for 3D printers.

The present invention will be specifically explained below with the following synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５、¹⁹Ｆ－ＮＭＲより算出した数平均分子量≒４，８００） Synthesis Example 1 Synthesis of Fluorine-Containing Acrylic Compound (A-1) In a 2,000 mL three-neck flask equipped with a reflux device and a stirrer, a compound represented by 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, number average molecular weight calculated from ¹⁹ F-NMR≈4,300)
500g (0.12 mol) of perfluoropolyether represented by the formula (I), 700g of m-xylenehexafluoride, and 361g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90°C while stirring. 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ⁻⁶ mol of Pt alone) was added thereto, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 498g of a colorless, transparent liquid compound (a) 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, number average molecular weight calculated from ^19F -NMR≈4,800)

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Under a dry air atmosphere, 10.0 g (Si-H group amount 1.3 x ^10-2 moles) of the compound (a) obtained above was mixed with 3.2 g (1.88 x ^10-2 moles) of allyloxyethyl methacrylate, 10.0 g of m-xylene hexafluoride, and 1.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3 x ^10-7 moles of Pt alone) and stirred for 4 hours at 80°C. After confirming the disappearance of the Si-H groups by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 10.4 g of a colorless and transparent fluorine-containing acrylic compound (A-1) 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）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂－
（ｑ２／ｐ２＝１．３、ｐ２＋ｑ２≒１６、¹⁹Ｆ－ＮＭＲより算出した数平均分子量≒２，３００） Synthesis Example 2 Synthesis of fluorine-containing acrylic compound (A-2) In a 1,000 mL three-neck flask equipped with a reflux device and a stirrer, a compound represented by the following formula CH ₂ ═CH-CH ₂ -O-CH ₂ -Rf″-CH ₂ -O-CH ₂ -CH═CH ₂ was added under a dry nitrogen atmosphere.
Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≈16, number average molecular weight calculated from ^19F -NMR≈1,800)
188g (0.10 mol) of perfluoropolyether represented by the formula (I), 188g of m-xylenehexafluoride, and 361g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90°C while stirring. 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ⁻⁶ mol of Pt alone) was added thereto, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 192g of a colorless, transparent liquid compound (b) represented by the following formula.

Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≈16, number average molecular weight calculated from ^19F -NMR≈2,300)

Ｒｆ”：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂－
（ｑ２／ｐ２＝１．３、ｐ２＋ｑ２≒１６） Under a dry air atmosphere, 10.0 g (Si-H group amount 2.6 x ^10-2 moles) of the compound (b) obtained above was mixed with 5.1 g (2.60 x ^10-2 moles) of allyloxyethyl methacrylate, 10.0 g of m-xylene hexafluoride, and 2.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.6 x ^10-7 moles of Pt alone) and stirred for 4 hours at 80°C. After confirming the disappearance of the Si-H groups by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 11.6 g of a colorless and transparent fluorine-containing acrylic compound (A-2) represented by the following formula.

Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≒16)

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５、¹⁹Ｆ－ＮＭＲより算出した数平均分子量≒４，９００） Synthesis Example 3 Synthesis of Fluorine-Containing Acrylic Compound (A-3) In a 2,000 mL three-neck flask equipped with a reflux device and a stirrer, a compound represented by 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, number average molecular weight calculated from ¹⁹ F-NMR≈4,300)
500g (0.12 mol) of perfluoropolyether represented by the formula (I), 700g of m-xylene hexafluoride, and 451g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90°C while stirring. 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ⁻⁶ mol of Pt alone) was added thereto, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 511g of a colorless and transparent liquid compound (c) 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, number average molecular weight calculated from ^19F -NMR≈4,900)

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Under a dry air atmosphere, 10.0 g (Si-H group amount 1.6 x ^10-2 moles) of the compound (c) obtained above was mixed with 4.2 g (2.44 x ^10-2 moles) of allyloxyethyl methacrylate, 10.0 g of m-xylene hexafluoride, and 1.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.3 x ^10-7 moles of Pt alone) and stirred for 4 hours at 80°C. After confirming the disappearance of the Si-H groups by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 10.1 g of a colorless and transparent fluorine-containing acrylic compound (A-3) 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）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂－
（ｑ２／ｐ２＝１．３、ｐ２＋ｑ２≒１６、¹⁹Ｆ－ＮＭＲより算出した数平均分子量≒２，４００） Synthesis Example 4 Synthesis of fluorine-containing acrylic compound (A-4) In a 1,000 mL three-neck flask equipped with a reflux device and a stirrer, a compound represented by the following formula CH ₂ ═CH-CH ₂ -O-CH ₂ -Rf″-CH ₂ -O-CH ₂ -CH═CH ₂ was added under a dry nitrogen atmosphere.
Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≈16, number average molecular weight calculated from ^19F -NMR≈1,800)
188g (0.10 mol) of perfluoropolyether represented by the formula (I), 188g of m-xylene hexafluoride, and 451g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90°C while stirring. 0.442g of a toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ⁻⁶ mol of Pt alone) was added thereto, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 199g of a colorless, transparent liquid compound (d) represented by the following formula.

Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≈16, number average molecular weight calculated from ^19F -NMR≈2,400)

Ｒｆ”：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p2（ＣＦ₂ＣＦ₂Ｏ）_q2ＣＦ₂－
（ｑ２／ｐ２＝１．３、ｐ２＋ｑ２≒１６） Under a dry air atmosphere, 10.0 g (Si-H group amount 3.3 x ^10-2 moles) of the compound (d) obtained above was mixed with 8.7 g (5.11 x ^10-2 moles) of allyloxyethyl methacrylate, 10.0 g of m-xylene hexafluoride, and 2.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.6 x ^10-7 moles of Pt alone) and stirred for 4 hours at 80°C. After confirming the disappearance of the Si-H groups by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 11.6 g of a colorless and transparent fluorine-containing acrylic compound (A-4) represented by the following formula.

Rf”: -CF ₂ O (CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF ₂ -
(q2/p2=1.3, p2+q2≒16)

で表される化合物（ｅ）１０．０ｇ（Ｓｉ－Ｈ基量８．６５×１０^-3モル）、アリルオキシエチルメタクリレート２．２ｇ（１．３０×１０^-2モル）、ｍ－キシレンヘキサフロライド１０．０ｇを仕込み、窒素雰囲気下で９０℃まで加熱攪拌した。ここに、塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．０×１０^-2ｇ（Ｐｔ単体として０．６×１０^-7モルを含有）を投入し、８０℃で４時間攪拌した。¹Ｈ－ＮＭＲ及びＩＲでＳｉ－Ｈ基が消失したのを確認した後、溶剤と過剰のアリルオキシエチルメタクリレートを減圧溜去し、活性炭処理を行い、下記式で示される半透明白色高粘稠液体の含フッ素アクリル化合物（Ａ－５）８．９ｇを得た。

Synthesis Example 5 Synthesis of Fluorine-Containing Acrylic Compound (A-5) In a 100 mL four-neck flask equipped with a reflux device and a stirrer,

10.0 g of compound (e) represented by the formula (I) (Si-H group amount 8.65 x ^10-3 moles), 2.2 g (1.30 x ^10-2 moles) of allyloxyethyl methacrylate, and 10.0 g of m-xylene hexafluoride were charged and heated to 90°C under a nitrogen atmosphere with stirring. 2.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.6 x ^10-7 moles of Pt alone) was added thereto and stirred at 80°C for 4 hours. After confirming the disappearance of the Si-H group by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 8.9 g of a translucent white highly viscous liquid fluorine-containing acrylic compound (A-5) represented by the formula below.

で表される化合物（ｆ）１０．０ｇ（Ｓｉ－Ｈ基量８．８８×１０^-3モル）、アリルオキシエチルメタクリレート２．３ｇ（１．３３×１０^-2モル）、ｍ－キシレンヘキサフロライド１０．０ｇを仕込み、窒素雰囲気下で９０℃まで加熱攪拌した。ここに、塩化白金酸／ビニルシロキサン錯体のトルエン溶液２．０×１０^-2ｇ（Ｐｔ単体として０．６×１０^-7モルを含有）を投入し、８０℃で４時間攪拌した。¹Ｈ－ＮＭＲ及びＩＲでＳｉ－Ｈ基が消失したのを確認した後、溶剤と過剰のアリルオキシエチルメタクリレートを減圧溜去し、活性炭処理を行い、下記式で示される半透明白色高粘稠液体の含フッ素アクリル化合物（Ａ－６）８．９ｇを得た。

Synthesis Example 6 Synthesis of Fluorine-Containing Acrylic Compound (A-6) In a 100 mL four-neck flask equipped with a reflux device and a stirrer,

10.0 g of compound (f) represented by the formula (1) (Si-H group amount 8.88 x ^10-3 moles), 2.3 g (1.33 x ^10-2 moles) of allyloxyethyl methacrylate, and 10.0 g of m-xylene hexafluoride were charged and heated to 90°C under a nitrogen atmosphere with stirring. 2.0 x ^10-2 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 0.6 x ^10-7 moles of Pt alone) was added thereto and stirred at 80°C for 4 hours. After confirming the disappearance of the Si-H groups by ^1H -NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the mixture was treated with activated carbon to obtain 8.9 g of a translucent white highly viscous liquid fluorine-containing acrylic compound (A-6) represented by the formula below.

The fluorine-containing acrylic compounds (A-1) to (A-6) obtained in Synthesis Examples 1 to 6 above do not contain volatile organic compounds.

The following fluorine-containing acrylic compositions (F-1) to (F-6) were prepared using the fluorine-containing acrylic compounds (A-1) to (A-6) obtained in the above Synthesis Examples 1 to 6 and the following acrylic compounds (B-1) to (B-3).
(B-1) Isobutyl acrylate (B-2) Tetrahydrofurfuryl acrylate (B-3) 1,6-hexanediol diacrylate

Fluorine-containing acrylic composition (F-1):
(A-1) 20 parts by mass (B-1) 80 parts by mass

Fluorine-containing acrylic composition (F-2):
(A-2) 20 parts by mass (B-3) 80 parts by mass

Fluorine-containing acrylic composition (F-3):
(A-3) 20 parts by mass (B-1) 80 parts by mass

Fluorine-containing acrylic composition (F-4):
(A-4) 20 parts by mass (B-3) 80 parts by mass

Fluorine-containing acrylic composition (F-5):
(A-5) 20 parts by mass (B-2) 80 parts by mass

Fluorine-containing acrylic composition (F-6):
(A-6) 20 parts by mass (B-2) 80 parts by mass

[Examples 1 to 6, Comparative Examples 1 and 2]
Preparation of fluorine-containing active energy ray-curable composition
Using the prepared fluorine-containing acrylic compositions (F-1) to (F-6), or the fluorine-containing acrylic compounds (A-1) and (A-2), fluorine-containing active energy ray-curable compositions were prepared in the proportions shown in Table 1 below.

A-9550: Dipentaerythritol penta/hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
A-TMM-3: Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
IBA: isobutyl acrylate THF-A: tetrahydrofurfuryl acrylate HDDA: 1,6-hexanediol diacrylate O-1173: 2-hydroxy-2-methylpropiophenone (Omnirad-1173, manufactured by BASF Japan Ltd.)

Coating and preparation of cured film Each of the fluorine-containing active energy ray curable compositions of the Examples and Comparative Examples was applied to a polycarbonate substrate by spin coating. After coating, the composition was cured by irradiating the coated surface with ultraviolet light at an accumulated irradiation dose of 1,600 mJ/ ^cm2 in a nitrogen atmosphere using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.) to obtain a cured film having a thickness of about 9 μm.

The appearance (transparency) of the cured film obtained above was visually measured, and the water contact angle was measured to evaluate the stain resistance, the resistance to marker ink, and the water contact angle after the abrasion test to evaluate the abrasion resistance, using the methods described below. The results are shown in Table 2.

Evaluation of antifouling properties [water contact angle measurement]
The contact angle of the cured film produced above with water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., humidity (RH): 40%).

[Evaluation of resistance to marker ink (marker repellency)]
A straight line was drawn on each of the cured films prepared above with a magic marker (large magic marker ink, manufactured by Teranishi Chemical Industry Co., Ltd.). Those that repelled ink were marked with an ◯, and those that did not repel ink were marked with an X.

Evaluation of abrasion resistance [Measurement of water contact angle after abrasion test]
The surface of the cured film was subjected to an abrasion test using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.), and the water contact angle after the test was measured. The average value of the measured values (N=8) was calculated.
The test conditions are shown below.
Eraser: RUBBER STICK (Minoan)
Travel distance (one way): 40 mm
Traveling speed: 3,200mm/min Load: 500g/6mm ^2φ
Number of wear cycles: 1,000

In Examples 1 to 6, which used fluorine-containing acrylic compositions (F-1) to (F-6) prepared by blending fluorine-containing acrylic compounds (A-1) to (A-6) that do not contain urethane bonds in the molecular structure and acrylic compound (B) that contains 1 to 2 (meth)acrylic groups in one molecule in a specific ratio as agents for imparting water/oil repellency and stain resistance, excellent stain resistance was observed and high abrasion resistance was confirmed. On the other hand, in Comparative Examples 1 and 2, in which fluorine-containing acrylic compounds (A-1) or (A-2) that do not contain urethane bonds in the molecular structure were added directly to acrylic compound (B) that contains 1 to 2 (meth)acrylic groups in one molecule without mixing, the cured film had a cloudy appearance and showed low stain resistance.

Claims (8)

(A) One or more fluorine-containing acrylic compounds selected from the group consisting of fluorine-containing acrylic compounds represented by the following formula:

[In the formula, Rf ² is --CF ₂ O--(CF ₂ O) _p (CF ₂ CF ₂ O) _q --CF ₂ --, p is an integer from 1 to 199, q is an integer from 1 to 170, p+q is 6 to 200, and the arrangement of the repeating units enclosed in parentheses is random. v is an integer from 4 to 120. R ² is independently a hydrogen atom or a methyl group, and R ³ is independently a hydrogen atom, a methyl group, or a phenyl group. Z ⁴ is a group represented by the following formula:
-C _O H _2O - (OC ₃ H ₆ ) _j' (OC ₂ H ₄ ) _k' (OCH ₂ ) _l' -
(in the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to another repeating unit, j', k', and l' are each independently an integer of 0 to 4, j'+k'+l'=1 to 10, and o is an integer of 2 to 10), and m is an integer of 2 to 5.], and (B) a fluorine-containing acrylic composition comprising, as an essential component, an acrylic compound having a viscosity at 25°C of 100 mPa·s or less and containing one or two (meth)acrylic groups per molecule, wherein the mass ratio of component (A) to component (B) is within the range of 0.01<(A)/(B)<10, and which does not contain a volatile organic compound having no group reactive with an acrylic group. As a part or the whole of the component (B),
CH ₂ =CR ⁵ C(=O)OR ⁴ (6)
(In the formula, ^R4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. ^R5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to claim 1 , which contains an acrylic compound represented by the formula: As a part or the whole of the (B) component, the following general formula (7)
CH ₂ =CR ⁷ C(=O)OR ⁶ -O(O=)CR ⁷ C=CH ₂ (7)
(In the formula, ^R6 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. Each ^R7 is independently a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to claim 1 or 2 , which contains an acrylic compound represented by the formula: 4. The fluorine-containing acrylic composition according to claim 1, wherein the acrylic compound of the component (B) does not contain an alkyl group substituted with a fluorine atom. A fluorine-containing active energy ray-curable composition comprising 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 4 relative to 100 parts by mass of the active energy ray-curable composition (E). The active energy ray-curable composition (E) is
(Ea) Acrylic compound: 100 parts by mass,
6. The fluorine-containing active energy ray-curable composition according to claim 5 , comprising: (Eb) a photopolymerization initiator: 0.1 to 15 parts by mass. 7. The fluorine-containing active energy ray-curable composition according to claim 5 or 6 , which gives a cured product having a water contact angle of 90° or more at 25° C. and a relative humidity of 40%. An article having a layer of the cured product of the fluorine-containing active energy ray-curable composition according to any one of claims 5 to 7 on its surface.