JP2022019575A - Fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition and article - Google Patents

Abstract

To provide a fluorine-containing acrylic composition capable of imparting excellent liquid-repelling property, antifouling property and abrasion resistance without increasing a volatile organic compound which does not have a group reactive with an acrylic group (non reactive) as the whole curable composition when added to a curable composition and to provide a fluorine-containing active energy ray-curable composition comprising the composition and an article having a cured product layer of the composition on a substrate surface.SOLUTION: There is provided a fluorine-containing acrylic composition which comprises (A) a fluorine-containing acrylic compound having a specific structure which has a perfluoropolyether group, an acrylic group or an α-substituted acrylic group and has no urethane bond in the molecule 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 the essential components, wherein the mass ratio between the component (A) and the component (B) is 0.01<(A)/(B)<10 and a volatile organic compound which does not have a group reactive with an acrylic group is not blended.SELECTED DRAWING: None

Description

The present invention is a fluorine-containing acrylic composition capable of imparting excellent liquid repellency, stain resistance, and abrasion resistance by adding to an active energy ray-curable composition such as ultraviolet rays and electron beams, and a fluorine-containing acrylic composition thereof. The present invention relates to a fluorine-containing active energy ray-curable composition having a fluoroacrylic composition, and an article having a cured product layer of this composition on the surface of a substrate.

Conventionally, a hard coat treatment is widely and generally used as a means for protecting the surface of a resin molded product or the like. This forms a hard cured resin layer (hard coat layer) on the surface of the molded product to prevent it from being scratched. As a material constituting the hard coat layer, a curable composition using active energy rays such as a thermosetting resin, ultraviolet rays, or an electron beam curable resin is often used.

With the expansion of the fields of use of resin molded products and the trend toward higher added value, there is an increasing demand for higher functionality of the cured resin layer (hard coat layer), and one of them is the antifouling property of the hard coat layer. Is required to be granted. By imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, it is difficult to get dirty or even if it gets dirty, it can be easily removed.

As a method of imparting antifouling property to the hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent on the surface of the once formed hard coat layer is widely used, but a fluorine-containing curable component is widely used. Has been studied as a method of simultaneously forming a hard coat layer and imparting antifouling property by adding fluorinated resin composition to a cured resin composition before curing and applying and curing the fluorinated resin composition. For example, Japanese Patent Application Laid-Open No. 6-21945 (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.

Further, the present inventors are proceeding with various developments as a fluorine compound capable of imparting antifouling property to such a curable resin composition. For example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 2). We propose photocurable fluorine compounds shown in JP-A-2010-138112 (Patent Document 3), JP-A-2010-285501 (Patent Document 4) and the like.

By having a fluoropolyether structure and a structure having a plurality of acrylic groups in one molecule, these can give high antifouling property to the curable resin composition, but on the other hand, they are highly viscous liquids that are difficult to handle by themselves. Therefore, in order to facilitate handling and enhance the mixing property with the resin composition, it is necessary to handle the solution as a solution diluted with a highly volatile organic solvent. Therefore, there is a problem that it cannot be blended as it is in a solvent-free hard coat agent or paint.

On the other hand, the hard coat treatment is widely handled with a coating liquid diluted with an organic solvent in order 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 the impact on the environment and the human body, and hard coat coating liquids have become high-solid and solvent-free. There is a strong demand for conversion. Along with this, the additive composition added to impart liquid repellency and antifouling property to the hard coat coating liquid as described above is also a volatile organic compound having no reactive group such as a volatile organic solvent. There is a demand for a composition that does not contain the above.

Furthermore, the hard coat composition containing a volatile organic compound having no reactive group such as a conventional volatile organic solvent has a particularly large dimensional change between coating and curing, and therefore has high dimensional accuracy with respect to the cured product. Is particularly unsuitable for applications that require the above, for example, curable compositions for nanoimprints, curable compositions for 3D printers, and the like.

The present inventors do not contain such volatile organic compounds having no reactive group such as volatile organic solvents, and can impart liquid repellency and antifouling property to the curable resin composition. Various developments are underway as compositions. For example, Japanese Patent Application Laid-Open No. 2017-190429 (Patent Document 5) describes a curable composition by suppressing the content of a volatile organic compound having no reactive group. It is possible to impart liquid repellency and antifouling property without increasing the number of (non-reactive) volatile organic compounds that do not have a group that reacts with the acrylic group of the curable composition as a whole when added to the curable composition. We are proposing a fluoroacrylic composition.

However, in recent years, there has been an increasing tendency to use hard coats containing a fluorine-containing composition for articles such as touch panels that are easily touched by human fingers, but conventional fluorine-containing compositions have been used for this purpose. Since the surface of the hard coat is consumed by wear by human fingers and the antifouling property is lowered, the hard coat surface does not have practically satisfactory wear resistance.

Japanese Unexamined Patent Publication No. 6-21945 Japanese Unexamined Patent Publication No. 2010-53114 Japanese Unexamined Patent Publication No. 2010-138112 Japanese Unexamined Patent Publication No. 2010-285501 Japanese Unexamined Patent Publication No. 2017-190429

The present invention has been made in view of the above circumstances, and by adding it to an active energy ray-curable composition such as ultraviolet rays or electron beams, excellent liquid repellency, stain resistance, and abrasion resistance can be imparted. It is an object of the present invention to provide a fluorine-containing acrylic composition, a fluorine-containing active energy ray-curable composition having the fluorine-containing acrylic composition, and an article having a cured product layer of the composition on the surface of a substrate.

As a result of further studies to achieve the above object, the present inventors have conducted further studies.
(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 independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, it does not contain urethane bonds in the structure. Q ¹ is a (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure. Z ² is independently expressed by the following formula-C _O H _2O- (OC ₄ H ₈ ) _i (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 each other, and i, j, k, and l have a molecular weight of Z ² of 58. It is a divalent alkylene ether group represented by (i + j + k + l = 1 to 10. o is an integer of 2 to 10), which are independently integers of 0 to 10 in the range of up to 748. X is a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains a monovalent organic group containing at least one acrylic group or α-substituted acrylic group, but does not contain a urethane bond in the structure. a is an independently integer from 1 to 10. Y is a fluorine atom or a monovalent group represented by −Z ¹ −Q ¹ − [Z ² −X] _a . Z ¹ in formula (1) and a Z ² enclosed in [] are all bonded to silicon atoms in the Q ¹ 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 in one molecule is contained as an essential component, and the component (A) and (B) are contained. The mass ratio of the components is in the range of 0.01 <(A) / (B) <10, and the volatile organic compound having no group that reacts with the acrylic group is not blended. The acrylic composition can be added to the active energy ray-curable composition without increasing the content of volatile organic compounds having no group that reacts with the acrylic group, and is compatible with the active energy ray-curable composition. The present invention has been found that the composition can be a fluorine-containing active energy ray-curable composition having good, liquid-repellent and antifouling properties, suppressing the content of volatile organic compounds, and exhibiting high wear resistance. It came to make.

（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。）
で表される２価のパーフルオロポリエーテル基である［１］に記載の含フッ素アクリル組成物。
［３］
一般式（１）において、Ｒｆ¹が下記構造式
－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１～１９９の整数、ｑは１～１７０の整数、ｐ＋ｑは６～２００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、ｓ＋ｔ＋ｕは３～１２６の整数である。ｖは４～１２０の整数である。）
で表される２価のパーフルオロポリエーテル基のいずれかである［１］又は［２］に記載の含フッ素アクリル組成物。
［４］
一般式（１）において、Ｚ¹が下記式
－ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂－
－ＣＨ₂ＯＣＨ₂ＣＨ₂ＣＨ₂－

で表されるいずれかの構造である［１］～［３］のいずれかに記載の含フッ素アクリル組成物。
［５］
一般式（１）において、Ｑ¹が下記式

（式中、ａ’は２～１０の整数である。）
で表される（ａ’＋１）価の連結基である［１］～［４］のいずれかに記載の含フッ素アクリル組成物。
［６］
一般式（１）において、Ｘが下記式

（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。）
で表される構造である［１］～［５］のいずれかに記載の含フッ素アクリル組成物。
［７］
（Ａ）成分が、下記一般式（２）又は（３）で表される含フッ素アクリル化合物である［１］～［６］のいずれかに記載の含フッ素アクリル組成物。

（式中、Ｒｆ¹、Ｚ¹、Ｚ²、Ｑ¹、ａは前述の通りである。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る。）
［８］
（Ａ）成分が、下記一般式（４）又は（５）で表される含フッ素アクリル化合物である［１］～［７］のいずれかに記載の含フッ素アクリル組成物。

［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。］
［９］
（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１種又は２種以上である［１］～［８］のいずれかに記載の含フッ素アクリル組成物。

［式中、Ｒｆ²は－ＣＦ₂Ｏ－（ＣＦ₂Ｏ）_p（ＣＦ₂ＣＦ₂Ｏ）_q－ＣＦ₂－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。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。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り、ｍは２～５の整数である。］
［１０］
（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］～［９］のいずれかに記載の含フッ素アクリル組成物。
［１１］
（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］～［１０］のいずれかに記載の含フッ素アクリル組成物。
［１２］
（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］～［１１］のいずれかに記載の含フッ素アクリル組成物。
［１３］
活性エネルギー線硬化性組成物（Ｅ）１００質量部に対し、［１］～［１２］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。
［１４］
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［１３］に記載の含フッ素活性エネルギー線硬化性組成物。
［１５］
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［１３］又は［１４］に記載の含フッ素活性エネルギー線硬化性組成物。
［１６］
［１３］～［１５］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。 Therefore, the present invention provides the following fluorine-containing acrylic compositions, fluorine-containing active energy ray-curable compositions, and articles.
[1]
(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 independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, it does not contain urethane bonds in the structure. Q ¹ is a (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure. Z ² is independently expressed by the following formula-C _O H _2O- (OC ₄ H ₈ ) _i (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 each other, and i, j, k, and l have a molecular weight of Z ² of 58. It is a divalent alkylene ether group represented by (i + j + k + l = 1 to 10. o is an integer of 2 to 10), which are independently integers of 0 to 10 in the range of up to 748. X is a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains a monovalent organic group containing at least one acrylic group or α-substituted acrylic group, but does not contain a urethane bond in the structure. a is an independently integer from 1 to 10. Y is a fluorine atom or a monovalent group represented by −Z ¹ −Q ¹ − [Z ² −X] _a . Z ¹ in formula (1) and a Z ² enclosed in [] are all bonded to silicon atoms 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 is contained as an essential component, and the component (A) and (B) are contained. The mass ratio of the components is in the range of 0.01 <(A) / (B) <10, and the volatile organic compound having no group that reacts with the acrylic group is not blended. Acrylic composition.
[2]
In the general formula (1), Rf ¹ is the following formula.

(In the formula, b is an integer of 1 to 3 independently for each unit. C, d, e, f, g, and h are integers of 0 to 200, respectively, 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, h may be randomly combined. )
The fluorine-containing acrylic composition according to [1], which is a divalent perfluoropolyether group represented by.
[3]
In the general formula (1), Rf ¹ is the following structural formula-CF ₂ O- (CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the array of repeating units enclosed in () is random, p is an integer of 1 to 199, q is an integer of 1 to 170, p + q is an integer of 6 to 200, and s is an integer of 0 to 6. t and u are integers of 1 to 100, t + u is an integer of 2 to 120, s + t + u is an integer of 3 to 126, and v is an integer of 4 to 120.)
The fluorine-containing acrylic composition according to [1] or [2], which is any of the divalent perfluoropolyether groups represented by.
[4]
In the general formula (1), Z ¹ is 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 [3], which has any structure represented by.
[5]
In the general formula (1), Q ¹ is the following formula

(In the formula, a'is an integer from 2 to 10.)
The fluorine-containing acrylic composition according to any one of [1] to [4], which is a linking group having a (a'+1) valence represented by.
[6]
In the general formula (1), X is the following formula

(In the formula, R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Z ³ contains a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent hydrocarbon group which may be used, and n is 1 or 2).
The fluorine-containing acrylic composition according to any one of [1] to [5], which has a structure represented by.
[7]
The fluorine-containing acrylic composition according to any one of [1] to [6], wherein the component (A) is a fluorine-containing acrylic compound represented by the following general formula (2) or (3).

(In the formula, Rf ¹ , Z ¹ , Z ² , Q ¹ , and a are as described above. R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)
[8]
The fluorine-containing acrylic composition according to any one of [1] to [7], wherein the component (A) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5).

[In the formula, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ has the following formula- _CO 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 connected to each other, and j', k', and l'are independently 0 to 0 to l'. It is an integer of 4, j'+ k'+ l'= 1 to 10, and o is an integer of 2 to 10), which is a divalent alkylene ether group. ]
[9]
The fluorine-containing acrylic composition according to any one of [1] to [8], wherein the component (A) is one or more selected from the fluorine-containing acrylic compounds represented by the following formulas.

[In the equation, 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 sequence of repeating units enclosed in () is random. v is an integer from 4 to 120. R ² is a hydrogen atom or a methyl group independently, and R ³ is a hydrogen atom, a methyl group or a phenyl group independently. Z ⁴ has the following formula- _CO 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 connected to each other, and j', k', and l'are independently 0 to 0 to l'. It is an integer of 4, j'+ k'+ l'= 1 to 10, and o is an integer of 2 to 10.)
It is a divalent alkylene ether group represented by, and m is an integer of 2 to 5. ]
[10]
(B) As a part or all of the components, the following general formula (6)
CH ₂ = CR ⁵ C (= O) OR ⁴ (6)
(In the formula, R ⁴ is a urethane bond, an ether bond, an isocyanate group or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an isocyanate group or a hydroxyl group. R ⁵ is a hydrogen atom, a methyl group, a fluorine atom or It is a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to any one of [1] to [9], which contains an acrylic compound represented by.
[11]
(B) As a part or all of the components, the following general formula (7)
CH ₂ = CR ⁷ C (= O) O-R ⁶ -O (O =) CR ⁷ C = CH ₂ (7)
(In the formula, R ⁶ is a urethane bond, an ether bond, an isocyanate group or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydroxyl group. R ⁷ is an independently hydrogen atom and a methyl group, respectively. It is a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to any one of [1] to [10], which contains an acrylic compound represented by.
[12]
The fluorine-containing acrylic composition according to any one of [1] to [11], wherein the acrylic compound of the component (B) does not contain an alkyl group substituted with a fluorine atom.
[13]
The fluorine-containing active energy ray-curing composition containing 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of [1] to [12] with respect to 100 parts by mass of the active energy ray-curable composition (E). Sex composition.
[14]
The active energy ray-curable composition (E)
(Ea) Acrylic compound: 100 parts by mass,
(Eb) The fluorine-containing active energy ray-curable composition according to [13], which contains 0.1 to 15 parts by mass of a photopolymerization initiator.
[15]
The fluorine-containing active energy ray-curable composition according to [13] or [14], which gives a cured product having a water contact angle of 90 ° or more at 25 ° C. and a relative humidity of 40%.
[16]
An article having a cured product layer of the fluorine-containing active energy ray-curable composition according to any one of [13] to [15] on its surface.

According to the fluorine-containing acrylic composition of the present invention, a volatile organic compound having no 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). It is possible to provide 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. Further, 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 antifouling property is unlikely to be lowered by wear. Therefore, the fluorine-containing acrylic composition is used to impart liquid repellency, stain resistance, and abrasion resistance to ultraviolet curable and thermosetting hard coat agents, paints, resins, antireflection coat compositions, and the like. It is useful as an antifouling additive.

The fluorine-containing acrylic composition of the present invention is
(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 independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, it does not contain urethane bonds in the structure. Q ¹ is a (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure. Z ² is independently expressed by the following formula-C _O H _2O- (OC ₄ H ₈ ) _i (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 each other, and i, j, k, and l have a molecular weight of Z ² of 58. It is a divalent alkylene ether group represented by (i + j + k + l = 1 to 10. o is an integer of 2 to 10), which are independently integers of 0 to 10 in the range of up to 748. X is a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains a monovalent organic group containing at least one acrylic group or α-substituted acrylic group, but does not contain a urethane bond in the structure. a is an independently integer from 1 to 10. Y is a fluorine atom or a monovalent group represented by −Z ¹ −Q ¹ − [Z ² −X] _a . Z ¹ in formula (1) and a Z ² enclosed in [] are all bonded to silicon atoms 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 is contained as an essential component, and the component (A) and (B) are contained. The mass ratio of the components is in the range of 0.01 <(A) / (B) <10, and the volatile organic compound having no group that reacts with the acrylic group is not blended. It is a feature.

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

The fluorine-containing acrylic compound of the 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 "acrylic compound" is a general term for compounds having an acrylic group and an α-substituted acrylic group, and two or more acrylic groups and α-substituted acrylics are attached to the side chains and ends of various polymers by any method. It also includes compounds into which groups have been introduced. Further, in the present invention, "(meth) acrylate" means one 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 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf ¹ is carbon. Those having a perfluorooxyalkylene structure having the number 1 to 6, particularly the following perfluorooxyalkylene structures having 1 to 3 carbon atoms as the main repeating unit are suitable.
-CF ₂ O-
-CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
These structures may be any one homopolymer, or a random or block polymer composed 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 Rf ¹ 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 integers of 0 to 200, respectively, 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, h may be randomly combined. )

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

（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。） Preferable 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 array of repeating units enclosed in () is random, p is 1 to 199, preferably an integer of 1 to 99, q is 1 to 170, preferably an integer of 1 to 99, and p + q is 6. It is an integer of ~ 200, preferably 10-100.)

(In the formula, the array of 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, and t + u is 2 to 120, preferably. Is an integer of 4 to 100, s + t + u is an integer of 3 to 126, preferably 4 to 100. V is an integer of 4 to 120, preferably 4 to 80.)

The molecular weight of Rf ¹ may be such that the number average molecular weight of the corresponding structural portion is contained in the range of 400 to 20,000, preferably 800 to 10,000, respectively, and the molecular weight distribution (or degree of polymerization distribution) thereof. Is not particularly limited. In the present invention, the molecular weight (or the degree of polymerization or the number of repeating units) is defined as the number average molecular weight (or the number average degree of polymerization) in terms of polystyrene by gel permeation chromatography (GPC) analysis using a fluorosolvent as a developing solvent. Although it can be obtained, preferably, the number average molecular weight (or number) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluoroacrylic compound based on ¹ H-NMR analysis and ¹⁹ F-NMR analysis. Average degree of polymerization) (hereinafter the same).

In the above formula (1), Z ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may independently contain one or more selected from an oxygen atom, a nitrogen atom and a silicon atom. Yes, it may contain an annular structure in the middle, but does not contain a urethane bond in the structure. Particularly preferable structures of Z ¹ include the following. In the following structure, it is preferable that the bond on the left side binds to Rf ¹ and the bond on the right side binds to Q ¹ .
-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 －

As Z ¹ , those shown below are more preferable.
－CH ₂ CH ₂ CH ₂ CH ₂ －
－CH ₂ OCH ₂ CH ₂ CH ₂ －

In the above equation (1), a is independently an integer of 1 to 10, preferably an integer of 2 to 8.

In the above formula (1), Q ¹ is a (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms and may have a cyclic structure, and is composed of oxygen atom, nitrogen atom and fluorine atom. It may contain at least one selected, provided that it does not contain a urethane bond in its structure. Preferred Q ¹ is a (a + 1) valence consisting of 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. The linking group of. Specifically, the following structure is shown as a particularly preferable structure.

However, in the following equation, a is the same as a in the above equation (1), 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 bond (silicon atom) of each of (a + 1) and (a'+ 1) units is a Z ² enclosed by [] in the above formula (1). And Z ¹ binds to any of the groups.

Here, T is a linking group having a (a + 1) valence, and for example, the following are exemplified.

（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 equation (1) is

(In the formula, a'is as described above.)
A (a'+1) valent linking group represented by (a'+1) is preferred.

In the above equation (1), Z ² independently has the following equation- _CO H _2O- (OC ₄ H ₈ ) _i (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 each other, and i, j, k, and l have a molecular weight of Z ² of 58. In the range of 748, preferably 72 to 300, they are independently integers of 0 to 10 (that is, the total of i, j, k, and l is 1 to 10), and i is preferably 0 to 10. 5 is an integer, j is an integer of 0 to 5, k is an integer of 0 to 5, 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 2 to 10. It is a divalent alkylene ether group represented by an integer of 8). 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 Z ² , preferable 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 of 0 to 10, j1 is an integer of 0 to 10, i1 is an integer of 0 to 10, and the molecular weight of Z ² may be 86 to 330. The repeating unit array is random regardless of type. Further, each repeating unit may be a mixture of structural isomers instead of a simple substance. If the molecular weight of Z ² is less than 58, it becomes difficult to mix with the acrylic compound of the component (B), and if it exceeds 748, the ability of the fluorine-containing acrylic compound to impart antifouling property becomes insufficient.

As Z ² , particularly preferable structures include the following, and among them, those in which k1 is 1 to 4 and j1 is 1 to 4 are preferable.
-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 a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom. Moreover, one molecule contains a monovalent organic group containing at least one acrylic group or α-substituted acrylic group on average, 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。） As X, a structure represented by the following formula is preferable.

(In the formula, R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and Z ³ is a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent hydrocarbon group that may be contained, and n is 1 or 2).

Here, R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and a hydrogen atom and a methyl group are preferable.
Further, here, n is 1 or 2, preferably 1.

Further, here, Z ³ is a divalent or trivalent hydrocarbon group which may contain a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms. A single bond or the following structure is preferable.
-CH _2-
-CH ₂ CH _2-
－CH ₂ CH ₂ CH ₂ －

As X, a group represented by the following formula is preferable.
-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。） As the fluorine-containing acrylic compound represented by the above formula (1), those represented by the following general formula (2) or (3) are preferable.

(In the equation, Rf ¹ , Z ¹ , Z ² , Q ¹ , R ¹ , and a are as described 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。］ As the fluorine-containing acrylic compound represented by the above formula (1), those represented by the following general formula (4) or (5) are more preferable.

[In the formula, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ has the following formula- _CO 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 connected to each other, and j', k', and l'are independently 0 to 0 to l'. It is an integer of 4, j'+ k'+ l'= 1 to 10, and o is an integer of 2 to 10), which is a divalent alkylene ether group. ]

（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 specifically, the following can be exemplified as the fluorine-containing acrylic compound represented by the above formula (1).

(In the formula, Rf ² is -CF ₂ O- (CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2- , and the sequence of repeating units enclosed in () is random, and R ² Is a hydrogen atom or a methyl group independently, R ³ is a hydrogen atom, a methyl group or a phenyl group independently. M is an integer of 2 to 5. p, q, p + q, Z ⁴ and v are described above. It's a street.)

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

(In the equation, Rf ² , m, R ² , R ³ , Z ⁴ , and v are as described 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 fluorine-containing acrylic compound represented by the general formula (1) is not particularly limited in its synthesis method, but is, for example, the embodiment of the fluorine-containing acrylic compound represented by the general formula (2) or (3). As one, first, the following general formula (8) or (9)
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 equation, Rf ¹ , Z ¹ , Q ¹ , and a are as described above, and all of the a hydrogen atoms (H) enclosed in [] in the equations (8) and (9) are Q ¹ respectively. It is bonded to a silicon atom in the structure.)
A fluoropolyether compound having a polyfunctional Si—H group represented by the following and the following general formula (10).

(In the equation, R ¹ , i, j, k, l are as described above. W is an integer of 0 to 8.)
(Adjacent) terminal aliphatic unsaturated group having an alkylene ether group represented by (for example, an alkyl group containing an aliphatic unsaturated double bond such as an alkenyl group at the end, or a terminal alkenyl group), and an acrylic group. Alternatively, it can be obtained by subjecting a compound containing an α-substituted acrylic group to a hydrosilylation addition reaction.

（式中、Ｒｆ²、ｖは上記と同じである。） Here, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (8) and (9) include those shown below.

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

Further, an alkyl group having an (adjacent) terminal aliphatic unsaturated group having an alkylene ether group represented by the above formula (10) (for example, an alkyl group containing an aliphatic unsaturated double bond such as an alkenyl group at the end, that is, Examples of the compound containing an alkyl group whose end is blocked with an external olefin (vinyl group) represented by CH ₂ = CH-, or the external olefin (vinyl group)), and an acrylic group or an α-substituted acrylic group are as follows. Can be exemplified.
CH ₂ = CHCH ₂ (OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -OC (= O) -CH = CH ₂
CH ₂ = CHCH ₂ (OC ₂ H ₄ ) _k2 (OC ₃ H ₆ ) _j2 (OC ₄ H ₈ ) _i2 -OC (= 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 equation, k2 is an integer of 0 to 10, j2 is an integer of 0 to 10, i2 is an integer of 0 to 10, i2 + j2 + k2 = 1 to 16, and CH ₂ = CH-C _w H _2w in the equation (10). -(OC ₄ H ₈ ) _i (OC ₃ H ₆ ) _j (OC ₂ H ₄ ) _k (OCH ₂ ) _l -The molecular weight of the portion corresponding to-should be 57 to 747. Regardless, it is random. Also, each repeating unit may be a mixture of structural isomers instead of a single unit.)

Among them, the following are particularly suitable.
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 of 1 to 4, and j3 is an integer of 1 to 4.)

Conventionally, when an acrylic group or an α-substituted acrylic group is introduced into a fluorine-containing compound by a hydrosilylation addition reaction, allyl methacrylate is mainly used, but the allyl group (terminal aliphatic unsaturated group) in allyl methacrylate is used. Since the reactivity is low in the hydrosilylation addition reaction, the hydrosilylation addition reaction proceeds not only in the target allylic group (terminal aliphatic unsaturated group) as the reaction site but also in the methacrylic group as a side reaction. Not suitable. In the present invention, the reactivity of the terminal aliphatic unsaturated group is sufficiently ensured by using a compound containing a (adjacent) terminal aliphatic unsaturated group having an alkylene ether group and an acrylic group or an α-substituted acrylic group. Therefore, the progress of hydrosilyl addition of the acrylic group or α-substituted acrylic group of the side reaction is effectively suppressed.

A fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (8) and (9), a terminal aliphatic unsaturated group represented by the formula (10), and an acrylic group or an α-substituted acrylic group. The compounds containing the above are mixed and stirred at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. in the presence of a platinum group metal-based addition reaction catalyst for 1 minute to 72 hours, particularly 5 minutes to 12 hours. It is desirable to carry out the reaction. If the reaction temperature is too low, the reaction may stop without progressing sufficiently, and if it is too high, the reaction may become uncontrollable due to the temperature rise due to the reaction heat of hydrosilylation, and bumping or decomposition of the raw material may occur. ..

In this case, the fluoropolyether compound having a polyfunctional Si—H group represented by the formulas (8) and (9), the terminal aliphatic unsaturated group represented by the formula (10), and the acrylic group or α substitution. The charging ratio of the compound containing an acrylic group is the total number of moles of H enclosed in [] of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (8) or (9). , The terminal aliphatic unsaturated group represented by the formula (10), and the unsaturated group of the compound containing an acrylic group or an α-substituted acrylic group are used in an amount of 0.8 to 5 times mol, particularly 1 to 2 times mol. It is desirable to react. If the amount of the compound containing the terminal aliphatic unsaturated group represented by the formula (10) and the acrylic group or the α-substituted acrylic group is too small, the polyfunctional Si-represented by the formulas (8) and (9) In a fluoropolyether compound having an H group, a large amount of Si—H groups may remain and the desired effect may not be obtained. If the amount is more than this, the uniformity of the reaction solution is lowered and the reaction rate becomes unstable, and after the reaction, the terminal aliphatic unsaturated group represented by the formula (10) and the acrylic group or the α-substituted acrylic group are contained. When removing compounds, it is necessary to tighten the conditions such as heating, depressurization, and extraction as the excess unreacted components increase.

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, compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, etc. A complex of chloroplatinic acid and an olefin, aldehyde, vinylsiloxane, acetylene alcohol, or the like, or platinum supported on activated carbon can be used.
The blending amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (8) or (9). It is preferably 0.1 to 1,000 mass ppm.

The above addition reaction can be carried out in the absence of a solvent, but may be diluted with a solvent if necessary. At this time, as the diluting solvent, a widely used organic solvent such as toluene, xylene, and isooctane can be used. As such an organic solvent, a fluorine-containing acrylic compound represented by the formula (2) or (3), which has a boiling point above the target reaction temperature and does not inhibit the reaction and is produced after the reaction, is used at the above reaction temperature. Soluble ones are preferred. For example, a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluorolide and benzotrifloride, and a partially fluorine-modified solvent such as a fluorine-modified ether solvent such as methyl perfluorobutyl ether are desirable, and particularly m-xylene. Hexafluorolides are preferred.
When a solvent is used, the amount used is preferably 5 to 2,000 mass by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (8) or (9). Parts, more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with a solvent is weak, and if it is more than this, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.

After completion of the reaction, known methods such as distillation, extraction, and adsorption of compounds and diluting solvents containing unreacted terminal aliphatic unsaturated groups represented by the formula (10) and acrylic groups or α-substituted acrylic groups under reduced pressure. By removing with, a fluorine-containing acrylic compound represented by the formula (2) or (3) can be obtained.

The fluorine-containing acrylic compound represented by the general formula (1) obtained by the above reaction is used by performing purification and isolation operations 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 fluoroacrylic compound (A) may be used alone or in combination of two or more.

The second essential component in the fluorine-containing acrylic composition of the present invention is (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. .. The acrylic compound of the component (B) may contain an oxygen atom or a nitrogen atom other than the acrylic structure, and specifically, may contain an ether bond, a urethane bond, an isocyanate group, or a hydroxyl group.

The component (B) has a viscosity at 25 ° C. of 100 mPa · s or less, preferably 0.4 to 20 mPa · s, due to its solubility in the component (A). When the viscosity at 25 ° C. exceeds 100 mPa · s, it becomes difficult to mix with the component (A) and the handleability is inferior. In the present invention, the viscosity can be measured by a rotational viscometer (for example, BL type, GH type, BS type, cone plate type, rheometer, etc.) (hereinafter, the same).

Specific examples of such a compound having one (meth) acrylic group in the molecule among the components (B) are those represented by the following general formula (6).
CH ₂ = CR ⁵ C (= O) OR ⁴ (6)
(In the formula, R ⁴ is a urethane bond, an ether bond, an isocyanate group or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an isocyanate group or a hydroxyl group. R ⁵ is a hydrogen atom, a methyl group, a fluorine atom or It is a fluoroalkyl group having 1 to 6 carbon atoms.)

In the above formula (6), R ⁴ 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 has 1 to 20 carbon atoms, preferably 1. It is preferably an alkyl group of to 10 and an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, and these are cyclic even if branched. It may be absent, and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group, and a hydroxyl group. Specific examples of R ⁴ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, octyl group, 2-ethyl-hexyl group, isodecyl group, tridecyl group and isostearyl. Group, phenyl group, benzyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, flufuryl group, tetrahydrofurryl group, tetrahydropyranyl group, 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 CH ₂ -OH, 4-hydroxycyclohexyl group, -CH ₂ CH ₂ -NCO and the like can be mentioned.
Further, 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, and a nonafluorobutyl group, and in particular, a hydrogen atom, a methyl group, and the like. A fluorine atom and a trifluoromethyl group are preferable.

More specifically, such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 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 (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, neopentyl glycol- (meth) acrylic acid -A benzoic acid ester and the like can be mentioned.

Further, methoxypolyethylene glycol (meth) acrylates such as acrylate compounds having a repeating unit structure such as ethylene oxide, propylene oxide, tetramethylene oxide, and lactone and having various alkoxy terminals, which do not correspond to the formula (6). Even if it is a (meth) acrylic compound commercially available under the names of phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, nonylphenol EO adduct acrylate, etc., if the viscosity at 25 ° C. is 100 mPa · s or less. Can be used.

Further, as a preferable example of the compound having two (meth) acrylic groups in the molecule among the components (B), specifically, the compound represented by the following general formula (7) is shown.
CH ₂ = CR ⁷ C (= O) O-R ⁶ -O (O =) CR ⁷ C = CH ₂ (7)
(In the formula, R ⁶ is a urethane bond, an ether bond, an isocyanate group or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydroxyl group. R ⁷ is an independently hydrogen atom and a methyl group, respectively. It is 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 has 1 to 20 carbon atoms, preferably 1 carbon atom. It is preferably an alkylene group of about 10 and an arylene group having 6 to 20 carbon atoms, preferably 6 to 10 or an aralkylene group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, and these are cyclic even if branched. It may be absent, and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group, and a hydroxyl group. Specific examples of R ⁶ include a methylene group, an ethylene group, a propylene group (trimethylene group, a methylethylene group), a butylene group (tetramethylene group, a methylpropylene group), a hexylene group (hexamethylene group), and a cyclohexylene. Group, octamethylene group, nonamethylene group, decamethylene group, -CH ₂ CH ₂ -O-CH ₂ CH _2- , -C ₃ H ₆ -OC ₃ H _6- , phenylene group, dicyclopentanylene group, di Examples thereof include a cyclopentenylene group, a flufurylene group, a tetrahydrofurylene group, a tetrahydropyranylene group and the like.
Further, R ⁷ is independently a fluoroalkyl group having 1 to 6 carbon atoms such as a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a trifluoropropyl group, or a nonafluorobutyl group, and in particular, a hydrogen atom. , Methyl group, fluorine atom, trifluoromethyl group are preferable.

More specifically, such compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and tripropylene glycol di (). Meta) 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 -Decandiol di (meth) acrylate and the like can be mentioned.

As the acrylic compound of the component (B), a compound containing an alkyl group substituted with a fluorine atom may be used. However, the acrylic compound containing an alkyl group substituted with a fluorine atom has a stronger concern about environmental load than the acrylic compound containing no fluorine atom. From the viewpoint of VOC emission regulation, it is desirable that the acrylic compound of the component (B) contains a small amount of the acrylic compound containing an alkyl group substituted with a fluorine atom, and the acrylic compound containing an alkyl group substituted with a fluorine atom. Is particularly desirable not to contain.

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 the compounds corresponding to the component (B) can be calculated as the content of the component (B). good. The compound corresponding to the component (B) can be synthesized by a known method as needed, 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 contains the above components (A) and (B) as essential components, and the mass ratio of the components (A) and (B) is 0.01 <(A). ) / (B) <10, preferably 0.015 ≦ (A) / (B) ≦ 8, and more preferably 0.02 ≦ (A) / (B) ≦ 5.
As another embodiment of the present invention, the fluorine-containing acrylic composition is mixed with the active energy ray-curable composition (E) described later to obtain a fluorine-containing active energy ray-curable composition, which is applied and cured. A liquid-repellent and antifouling cured product layer can be provided on the substrate, and the liquid-repellent and antifouling properties are dispersed in the components of the active energy ray-curable composition (E). (A) It is expressed when the component is present on the surface of the cured product 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, and the final liquid repellency and antifouling property. Is difficult to express. On the other hand, when the mass ratio (A) / (B) is 10 or more, the workability is lowered due to the high viscosity of the component (A), and the compatibility and mixing with the component (E) are reduced. The sex is reduced.

When (A) / (B) is in the above range, the viscosity of the fluorine-containing acrylic composition at 25 ° C. is preferably 0.1 to 10,000 mPa · s, and more preferably 0.5 to 5, It is 000 mPa · s, more preferably 1 to 1,000 mPa · s. When it has such a viscosity, a curable composition having good handleability can be obtained.

The fluorine-containing acrylic composition of the present invention is a volatile organic compound having no group that reacts with an acrylic group (particularly, a non-reactive volatile organic compound (or volatile) that does not contain a (meth) acrylic group in the molecule. Organic solvent)) is not blended (that is, a solvent-free fluorine-containing acrylic composition).

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 amount of the fluorine-containing acrylic composition added is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition (E) described later. If the blending amount of the compound is smaller than this, the expected liquid repellency and antifouling property cannot be exhibited because the compound cannot be sufficiently arranged on the surface when the cured product is formed, and the compound is larger than this. In that case, the influence of the fluoroacrylic compound on the strength and hardness of the cured product layer becomes too large, and the cured product characteristics of the original active energy ray-curable composition are lost.

The active energy ray-curable composition (E) 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, but is particularly limited to an acrylic compound (Ea) and a photopolymerization initiator. (Eb) is preferably contained.

As the acrylic compound (Ea), it can be used regardless of whether it is monofunctional or polyfunctional. For example, the monofunctional and bifunctional acrylic compounds described above as the component (B) can be used, but the component (Ea) particularly contains a non-fluorinated acrylic compound having two or more acrylic groups in one molecule. Is preferable.

The 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 and 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, trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate , Gglycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2,2-tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra 2 to 6 functional (meth) acrylic compounds such as (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and sorbitol hexa (meth) acrylate. , These (meth) acrylic compounds are added to ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products, epoxy acrylates obtained by adding acrylic acid to epoxy resin, and side chains of acrylic acid ester copolymers (meth). ) Preferable examples include those containing an acryloyl group-introduced copolymer or the like.

Further, urethane acrylates, those obtained by reacting polyisocyanate with a (meth) acrylate having a hydroxyl group, those obtained by reacting polyisocyanate with a (meth) acrylate having a hydroxyl group with polyester of a terminal diol, and those obtained by reacting polyisocyanate with a (meth) acrylate having a hydroxyl group, and excess in a polyol. It is also possible to use a polyisocyanate obtained by reacting the diisocyanate of the above with 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, and tolylene diisocyanate. , Lysine diisocyanate, norbornan diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylenebis (4-cyclohexylisocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisosia Urethane acrylates obtained by reacting polyisocyanate selected from natocyclohexane and diphenylmethane diisocyanate can be preferably mentioned.

Further, a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having a urethane bond, or this polyfunctional acrylic compound, and an acrylic compound having an aliphatic polyisocyanate and a hydroxyl group. It may be a mixture of at least two kinds of acrylic compounds including those composed of polyfunctional urethane acrylates having 3 or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting with.

In this case, examples of the polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and not having a urethane bond include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth). Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane 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.

Further, 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 and norbornan. Diisocyanates, isophorone diisocyanates and trimerates thereof, and bifunctional or higher bifunctionals obtained by reacting these bifunctional and trifunctional isocyanates with aliphatic diols, aliphatic polyols and polyacrylates having a hydroxyl group on the side chain. Trimethylol propanedi (meth) acrylate, glycerin di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylol propanetri (meth) in polyisocyanate. ) Acrylate, dipentaerythritol penta (meth) acrylate and these ethylene oxide and propylene oxide modified products reacted, aliphatic polyols and polyacrylates having a hydroxyl group on the side chain and 2-isocyanatoethyl (meth) acrylate And 1,1- (bisacryloyloxymethyl) ethyl isocyanate and the like, which are reacted with an acrylic compound having an isocyanate group can be shown.

Further, the component (Ea) may include not only a liquid component but also a fine particle-like high molecular weight body surface and an inorganic filler fine particle surface modified with an acrylic group.

The above (Ea) component can be used alone, but it can also be used by blending a plurality of applicable compounds in order to improve the coatability and the characteristics of the film after curing.

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

The photopolymerization initiator of the component (Eb) is not particularly limited as long as it can cure the acrylic compound by irradiation with ultraviolet rays, but is preferably, for example, acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone. , 2,2-Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2- (2-) Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-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-phosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, 1,2-octanedione-1- [4-( Phenylthio) -2- (o-benzoyloxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 2 -Hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, etc. may be mentioned, and one type alone or two or more types may be used in combination. May be good.

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 content of the component (Ea) is 100 parts by mass. It is desirable that the amount is 0.1 to 15 parts by mass, particularly 1 to 10 parts by mass. If the amount added is less than this, the curability may decrease, and if it is more than this, the effect on the physical properties after curing may increase.

The active energy ray-curable composition (E) also includes active energy ray-reactive compounds other than acrylic groups such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, defoaming agents, and viscosity. It is also possible to blend a modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, a filler of a polymer or an inorganic substance, and the like. The structure of these is not particularly limited, and known ones can be used as long as the object of the present invention is not impaired.

The active energy ray-curable composition (E) includes paints, inks, hard coat agents, etc. from various companies as an active energy ray-curable composition containing the components (Ea) and (Eb) and various additives. Existing compositions commercially available under the classification of (E) may be used as part or as a whole of the component (E). Even when a commercially available hard coat agent is used as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, and a viscosity adjustment are used according to the purpose, as long as the action and effect of the present invention are not impaired. Agents, light-resistant stabilizers, heat-resistant stabilizers, antioxidants, surfactants, colorants, fillers and the like can be added and blended.

The fluorine-containing active energy ray-curable composition of the present invention obtained as described above can suppress the inclusion of volatile organic compounds that are not incorporated into the structure of the cured product, and can be used as a water- and oil-repellent group. Since it contains a fluorine-containing acrylic compound having a perfluoropolyether group and an acrylic group or an α-substituted acrylic group as an active energy ray-curable group, it has water repellency, oil repellency, slipperiness, stain resistance, and fingerprint wiping property. It gives a cured product with excellent low refractive index characteristics, solvent resistance, chemical resistance, etc., and since this fluorine-containing acrylic compound does not contain urethane bonds in the molecule, a cured product with excellent wear resistance can be obtained. can get.

Further, in the present invention, the above-mentioned fluorine-containing active energy ray-curable composition of the present invention is applied to the surface of a substrate and cured to have an article (a cured product layer (also referred to as a cured film or a cured resin layer) on the surface. Goods). As described above, by using the fluorine-containing active energy ray-curable composition of the present invention, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of an acrylic hard coat. As a result, it is possible to give the base material (article) a hard coat surface that is less likely to be stained by fingerprints, sebum, human oil such as sweat, cosmetics, etc., and has excellent wiping properties. Therefore, the fluorine-containing active energy ray-curable composition of the present invention provides a coating film or a protective film for the surface of a base material (article) that may be contaminated by human fat, cosmetics, etc. when touched by the human body. Can be done.

The cured film (cured resin layer) formed by using the fluorine-containing active energy ray-curable composition of the present invention is directly applied to the surface of an article to be imparted with properties and cured, or various base films (for example, various base films). The fluorine-containing activity of the present invention on a film of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, aramid, polyimide, etc.) By applying an energy ray-curable composition to form a cured film and attaching the film to the surface of a target article, properties can be imparted to various articles.

Here, the method for applying the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but for example, roll coat, gravure coat, flow coat, dip coat, spray coat, spin coat, bar coat. , 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 beam such as an electron beam and ultraviolet rays can be used, but ultraviolet rays are particularly preferable. As the ultraviolet source, a mercury lamp, a metal halide lamp, and an LED lamp are suitable. If the amount of ultraviolet irradiation is too small, uncured components will remain, and if it is too large, the coating film and the base material may deteriorate. Therefore, 10 to 10,000 mJ / cm ² , especially 20 to 4,000 mJ / cm. It is desirable to be in the range of ² . In addition, in order to prevent curing inhibition due to oxygen, the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon during UV irradiation, and the surface of the coating film is UV-transmitted with releasability. Cover with a protective layer and irradiate UV light from above, or if the base material has UV transmission, cover the surface of the coating with a removable protective layer and oppose the coated surface of the base material. Ultraviolet rays may be irradiated from the side. Further, in order to effectively perform leveling of the coating film or polymerization of acrylic groups in the coating film, the coating film and the base material may be heated by any method such as a hot air drying oven before and during irradiation with ultraviolet rays.

Further, the thickness of the cured film (cured resin layer) formed by 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, the thickness is not particularly limited. 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. Therefore, it is usually preferably 5 nm to 100 μm, particularly preferably 1 μm to 20 μm.

Further, the cured film (cured resin layer) formed by 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%. Is desirable. In the present invention, the water contact angle is a value measured under the condition of droplets: 2 μl using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). Further, in order to obtain the water contact angle, it is preferable that the fluorine-containing active energy ray-curable composition is uniformly mixed.

Examples of such articles include tablet computers, mobile (communication) information terminals such as mobile phones and smartphones, notebook PCs, digital media players, watch-type and eyeglass-type wearable computers, digital cameras, digital video cameras, and electronic books. Housing for various devices that can be carried by hand 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. Display operation equipment surfaces such as displays and TV screens, automobile exteriors, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, decorative building materials around water such as toilets, baths, and washrooms, protection for art exhibitions Glass, show windows, showcases, photo frame covers, watches, automobile window glass, trains, aircraft window glass, automobile headlights, tail lamps, etc. made of transparent glass or transparent plastic (acrylic resin, polycarbonate, etc.) ) It is useful as a coating film and surface protection film for members, various mirror members, etc.

In particular, various devices having display input devices such as touch panel displays that operate on the screen with human fingers or palms, such as tablet computers, notebook PCs, watch-type wearable computers, activity meters, mobile phones, smartphones, etc. Communication) Information terminals, digital media players, electronic book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, navigation devices for automobiles, automatic cash withdrawal deposit devices, automatic cash payment machines, It is useful as a surface protective film for various controllers such as vending machines, digital signage (electronic signboards), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices.

Further, the cured film formed by the fluorine-containing active energy ray-curable composition of the present invention is an optical recording medium such as a photomagnetic disk or an optical disk; a glasses lens, a camera lens, a projector lens prism, a lens sheet, a pellicle film, and a polarizing plate. It is also useful as a surface protective film for optical components and optical devices such as optical filters, lenticular lenses, frennel lenses, antireflection films, optical fibers and optical couplers, or as a surface protective film for various protective components of these devices.

Furthermore, the cured film formed by the fluorine-containing active energy ray-curable composition of the present invention is cured at the time of coating as compared with the cured film formed by the conventional hard coat composition containing a volatile organic compound. Since the dimensional change over time is small, it is also useful as a surface protective film for applications that require high dimensional accuracy for cured products, for example, curable compositions for nanoimprints and curable compositions for 3D printers.

Hereinafter, the present invention will be specifically described with reference to 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) Under a dry nitrogen atmosphere, in a 2,000 mL three-necked flask equipped with a reflux device and a stirrer, the following formula CH ₂ = CH-CH ₂ -O -CH ₂ -Rf'-CH ₂ -O-CH ₂ -CH = CH ₂
Rf': -CF ₂ 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)
500 g (0.12 mol) of perfluoropolyether represented by (1), 700 g of m-xylenehexafluororide, and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. .. 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 thereto, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 498 g of a colorless and transparent liquid compound (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 ¹⁹ F-NMR ≈ 4,800)

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Under a dry air atmosphere, 3.2 g (1.88 × 10) of allyloxyethyl methacrylate is obtained with respect to 10.0 g (Si—H group amount 1.3 × 10 ⁻² mol) of the compound (a) obtained above. ^-2 mol), 10.0 g of m-xylene hexafloride, and 1.0 x 10 ^-2 g of toluene solution of platinum chloride acid / vinyl siloxane complex (containing 0.3 x 10 ^-7 mol of Pt alone). The mixture was mixed and stirred at 80 ° C. for 4 hours. ¹ After confirming that the Si—H group disappeared by 1 H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, treated with activated carbon, and the colorless and transparent fluorine-containing acrylic represented by the following formula was performed. 10.4 g of compound (A-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＝１．３、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) Under a dry nitrogen atmosphere, a 1,000 mL three-necked flask equipped with a reflux device and a stirrer was placed in 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) _q2 CF ₂ －
(Q2 / p2 = 1.3, p2 + q2 ≈ 16, ¹⁹ Number average molecular weight calculated from F-NMR ≈ 1,800)
188 g (0.10 mol) of perfluoropolyether represented by (1), 188 g of m-xylene hexafloride, and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90 ° C. with stirring. .. 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 thereto, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 192 g of a colorless and 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, ¹⁹ Number average molecular weight calculated from F-NMR ≈ 2,300)

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

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) Under a dry nitrogen atmosphere, in a 2,000 mL three-necked flask equipped with a reflux device and a stirrer, the following formula CH ₂ = CH-CH ₂ -O -CH ₂ -Rf'-CH ₂ -O-CH ₂ -CH = CH ₂
Rf': -CF ₂ 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)
500 g (0.12 mol) of perfluoropolyether represented by (1), 700 g of m-xylene hexafloride, and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90 ° C. with stirring. .. 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 thereto, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 511 g 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 ¹⁹ F-NMR ≈ 4,900)

Ｒｆ’：－ＣＦ₂Ｏ（ＣＦ₂Ｏ）_p1（ＣＦ₂ＣＦ₂Ｏ）_q1ＣＦ₂－
（ｑ１／ｐ１＝０．９、ｐ１＋ｑ１≒４５） Under a dry air atmosphere, 4.2 g (2.44 × 10) of allyloxyethyl methacrylate is obtained with respect to 10.0 g (Si—H group amount 1.6 × 10 ⁻² mol) of the compound (c) obtained above. ^-2 mol), 10.0 g of m-xylene hexafloride, and 1.0 x 10 ^-2 g of toluene solution of platinum chloride acid / vinyl siloxane complex (containing 0.3 x 10 ^-7 mol of Pt alone). The mixture was mixed and stirred at 80 ° C. for 4 hours. ¹ After confirming that the Si—H group disappeared by 1 H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, treated with activated carbon, and the colorless and transparent fluorine-containing acrylic represented by the following formula was performed. 10.1 g of compound (A-3) 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＝１．３、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) Under a dry nitrogen atmosphere, a 1,000 mL three-necked flask equipped with a reflux device and a stirrer was placed in 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) _q2 CF ₂ －
(Q2 / p2 = 1.3, p2 + q2 ≈ 16, ¹⁹ Number average molecular weight calculated from F-NMR ≈ 1,800)
188 g (0.10 mol) of perfluoropolyether represented by (1), 188 g of m-xylene hexafloride, and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90 ° C. with stirring. .. 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 thereto, and the internal temperature was maintained at 90 ° C. or higher. Stirring was continued for 4 hours. ¹ After confirming that the allyl group of the raw material had disappeared by 1 H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. After that, it was treated with activated carbon to obtain 199 g of a colorless and 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, ¹⁹ Number average molecular weight calculated from F-NMR ≈ 2,400)

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

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) The following formula is placed in a 100 mL four-necked flask equipped with a reflux device and a stirrer.

Compound (e) represented by (e) 10.0 g (Si—H group amount 8.65 × 10 ^-3 mol), allyloxyethyl methacrylate 2.2 g (1.30 × 10 ⁻² mol), m-xylene hexaflo 10.0 g of the ride was charged, and the mixture was heated and stirred to 90 ° C. under a nitrogen atmosphere. A toluene solution of platinum chloride / vinylsiloxane complex 2.0 × 10 ⁻² g (containing 0.6 × 10 ^-7 mol as a simple substance of Pt) was added thereto, and the mixture was stirred at 80 ° C. for 4 hours. ¹ After confirming that the Si—H group disappeared by 1 H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, treated with activated carbon, and the translucent white high viscosity represented by the following formula was performed. 8.9 g of a liquid fluorine-containing acrylic compound (A-5) was obtained.

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) The following formula is placed in a 100 mL four-necked flask equipped with a reflux device and a stirrer.

Compound (f) represented by (f) 10.0 g (Si—H group amount 8.88 × 10 ^-3 mol), allyloxyethyl methacrylate 2.3 g (1.33 × 10 ⁻² mol), m-xylene hexaflo 10.0 g of the ride was charged, and the mixture was heated and stirred to 90 ° C. under a nitrogen atmosphere. A toluene solution of platinum chloride / vinylsiloxane complex 2.0 × 10 ⁻² g (containing 0.6 × 10 ^-7 mol as a simple substance of Pt) was added thereto, and the mixture was stirred at 80 ° C. for 4 hours. ¹ After confirming that the Si—H group disappeared by 1 H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, treated with activated carbon, and the translucent white high viscosity represented by the following formula was performed. 8.9 g of a liquid fluorine-containing acrylic compound (A-6) was obtained.

The fluorinated acrylic compounds (A-1) to (A-6) obtained in Synthetic Examples 1 to 6 do not contain volatile organic compounds.

Using the fluorine-containing acrylic compounds (A-1) to (A-6) obtained in Synthesis Examples 1 to 6 and the following acrylic compounds (B-1) to (B-3), the following fluorine-containing acrylic composition Compounds (F-1) to (F-6) were prepared.
(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
The prepared fluorine-containing acrylic compositions (F-1) to (F-6) or the fluorine-containing acrylic compounds (A-1) and (A-2) were used and blended in the proportions shown in Table 1 below. A fluorine-containing active energy ray-curable composition was prepared.

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 Hardened Film The fluorine-containing active energy ray-curable compositions of Examples and Comparative Examples were coated on a polycarbonate substrate by spin coating. After coating, leveling at room temperature (25 ° C) for 10 minutes, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.), in a nitrogen atmosphere, ultraviolet rays with an integrated irradiation dose of 1,600 mJ / cm ² . Was applied to the coated surface to cure the composition, and a cured film having a thickness of about 9 μm was obtained.

The appearance (transparency) of the cured film obtained above is visually measured, and water contact angle measurement, magic ink resistance evaluation, and wear resistance evaluation are performed as antifouling evaluation by the method shown below. After the wear test, the water contact angle was measured. These results are shown in Table 2.

Evaluation of antifouling property [Water contact angle measurement]
With respect to the cured film prepared above, the contact angle of the cured film with water was measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) (droplets: 2 μl, temperature: 25 ° C., humidity (). RH): 40%).

[Evaluation of magic ink resistance (magic repellent)]
For the cured film prepared above, a straight line was drawn with a magic pen (Magic Ink large size manufactured by Teranishi Chemical Industry Co., Ltd.), and those that repel ink were marked with ○ and those that did not repel were marked with ×.

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

Fluorine-containing acrylic compounds (A-1) to (A-6) that do not contain a urethane bond in the molecular structure as a water / oil repellency and antifouling agent, and 1 to 1 (meth) acrylic group in one molecule. Examples 1 to 6 using the fluorine-containing acrylic compositions (F-1) to (F-6) prepared by blending two acrylic compounds (B) in a specific ratio have excellent antifouling properties. It was shown and high wear resistance was confirmed. On the other hand, a fluorine-containing acrylic compound (A-1) or (A-2) that does not contain a urethane bond in its molecular structure is mixed with an acrylic compound (B) that contains one or two (meth) acrylic groups in one molecule. In Comparative Examples 1 and 2 to which the cured film was directly added, the appearance of the cured film became cloudy and low antifouling property was shown.

Claims (16)

(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 independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, it does not contain urethane bonds in the structure. Q ¹ is a (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure. Z ² is independently expressed by the following formula-C _O H _2O- (OC ₄ H ₈ ) _i (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 each other, and i, j, k, and l have a molecular weight of Z ² of 58. It is a divalent alkylene ether group represented by (i + j + k + l = 1 to 10. o is an integer of 2 to 10), which are independently integers of 0 to 10 in the range of up to 748. X is a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains a monovalent organic group containing at least one acrylic group or α-substituted acrylic group, but does not contain a urethane bond in the structure. a is an independently integer from 1 to 10. Y is a fluorine atom or a monovalent group represented by −Z ¹ −Q ¹ − [Z ² −X] _a . Z ¹ in formula (1) and a Z ² enclosed in [] are all bonded to silicon atoms 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 is contained as an essential component, and the component (A) and (B) are contained. The mass ratio of the components is in the range of 0.01 <(A) / (B) <10, and the volatile organic compound having no group that reacts with the acrylic group is not blended. Acrylic composition. In the general formula (1), Rf ¹ is the following formula.

(In the formula, b is an integer of 1 to 3 independently for each unit. C, d, e, f, g, and h are integers of 0 to 200, respectively, 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, h may be randomly combined. )
The fluorine-containing acrylic composition according to claim 1, which is a divalent perfluoropolyether group represented by. In the general formula (1), Rf ¹ is the following structural formula-CF ₂ O- (CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the array of repeating units enclosed in () is random, p is an integer of 1 to 199, q is an integer of 1 to 170, p + q is an integer of 6 to 200, and s is an integer of 0 to 6. t and u are integers of 1 to 100, t + u is an integer of 2 to 120, s + t + u is an integer of 3 to 126, and v is an integer of 4 to 120.)
The fluorine-containing acrylic composition according to claim 1 or 2, which is any of the divalent perfluoropolyether groups represented by. In the general formula (1), Z ¹ is 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 3, which has any structure represented by. In the general formula (1), Q ¹ is the following formula

(In the formula, a'is an integer from 2 to 10.)
The fluorine-containing acrylic composition according to any one of claims 1 to 4, which is a linking group having a (a'+1) valence represented by. In the general formula (1), X is the following formula

(In the formula, R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and Z ³ contains a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent hydrocarbon group which may be used, and n is 1 or 2).
The fluorine-containing acrylic composition according to any one of claims 1 to 5, which has a structure represented by. The fluorine-containing acrylic composition according to any one of claims 1 to 6, wherein the component (A) is a fluorine-containing acrylic compound represented by the following general formula (2) or (3).

(In the formula, Rf ¹ , Z ¹ , Z ² , Q ¹ , and a are as described above. R ¹ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.) The fluorine-containing acrylic composition according to any one of claims 1 to 7, wherein the component (A) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5).

[In the formula, Rf ¹ , Z ¹ , Q ¹ , and a are as described above. Z ⁴ has the following formula- _CO 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 connected to each other, and j', k', and l'are independently 0 to 0 to l'. It is an integer of 4, j'+ k'+ l'= 1 to 10, and o is an integer of 2 to 10), which is a divalent alkylene ether group. ] The fluorine-containing acrylic composition according to any one of claims 1 to 8, wherein the component (A) is one or more selected from the fluorine-containing acrylic compounds represented by the following formulas.

[In the equation, Rf ² is -CF ₂ O- (CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2- , p is an integer of 1 to 199, q is an integer of 1 to 170, p + q. Is 6 to 200, and the sequence of repeating units enclosed in () is random. v is an integer from 4 to 120. R ² is a hydrogen atom or a methyl group independently, and R ³ is a hydrogen atom, a methyl group or a phenyl group independently. Z ⁴ has the following formula- _CO 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 connected to each other, and j', k', and l'are independently 0 to 0 to l'. It is an integer of 4, j'+ k'+ l'= 1 to 10, o is an integer of 2 to 10), and is a divalent alkylene ether group, and m is an integer of 2 to 5. Is. ] (B) As a part or all of the components, the following general formula (6)
CH ₂ = CR ⁵ C (= O) OR ⁴ (6)
(In the formula, R ⁴ is a urethane bond, an ether bond, an isocyanate group or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an isocyanate group or a hydroxyl group. R ⁵ is a hydrogen atom, a methyl group, a fluorine atom or It is a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to any one of claims 1 to 9, which comprises an acrylic compound represented by. (B) As a part or all of the components, the following general formula (7)
CH ₂ = CR ⁷ C (= O) O-R ⁶ -O (O =) CR ⁷ C = CH ₂ (7)
(In the formula, R ⁶ is a urethane bond, an ether bond, an isocyanate group or a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a hydroxyl group. R ⁷ is an independently hydrogen atom and a methyl group, respectively. It is a fluorine atom or a fluoroalkyl group having 1 to 6 carbon atoms.)
The fluorine-containing acrylic composition according to any one of claims 1 to 10, which comprises an acrylic compound represented by. The fluorine-containing acrylic composition according to any one of claims 1 to 11, wherein the acrylic compound of the component (B) does not contain an alkyl group substituted with a fluorine atom. Fluorine-containing active energy ray-curable composition containing 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 12 with respect to 100 parts by mass of the active energy ray-curable composition (E). Sex composition. The active energy ray-curable composition (E)
(Ea) Acrylic compound: 100 parts by mass,
(Eb) The fluorine-containing active energy ray-curable composition according to claim 13, which contains 0.1 to 15 parts by mass of a photopolymerization initiator. The fluorine-containing active energy ray-curable composition according to claim 13 or 14, which provides 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 cured product layer of the fluorine-containing active energy ray-curable composition according to any one of claims 13 to 15 on the surface.