JP2022073585A - Active energy ray-curable resin composition, coated film, and article - Google Patents

Abstract

To provide an active energy ray-curable resin composition capable of forming a cured coated film excellent in falling property of water droplets and oil droplets, and smoothness.SOLUTION: An active energy ray-curable resin composition includes: (A) a fluorine-containing siloxane acrylate having a cyclic siloxane group and a perfluoropolyether chain; (B) a fluorine-containing siloxane acrylate represented by the following formula (1') where PFPE2 is a bivalent perfuluoropolyether chain, X2 is a cyclic siloxane group, and Z2 is a bivalent organic group; (C) a polymerization initiator; and (D) an acrylate containing no fluorine atom, urethane acrylate, or both of these.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable resin composition, and more specifically, it contains an active energy ray-curable siloxane acrylate having a photocurable perfluoropolyether group (hereinafter referred to as "fluorine-containing siloxane acrylate"). With respect to the resin composition, its cured coating and the article.

Conventionally, as a fluorocompound that can be cured by irradiation with light such as ultraviolet rays, a polymer containing a polymerizable monomer having a perfluoroalkyl group, an acrylic acid-containing fluoroalkyl ester, and a methacrylic acid-containing fluoroalkyl ester is widely known. .. As a typical example, a compound represented by the following structural formula has been widely used for the purpose of imparting low reflectivity, water repellency, oil repellency, stain resistance, abrasion resistance, scratch resistance, etc. to the surface of the base material. rice field.

However, in recent years, due to concerns about environmental load, there is a growing movement to limit the use of compounds containing long-chain perfluoroalkyl groups having 8 or more carbon atoms. However, it is known that acrylic compounds containing a perfluoroalkyl group having less than 8 carbon atoms have significantly worse surface properties than those having a long-chain perfluoroalkyl group having 8 or more carbon atoms. (Non-Patent Document 1).

On the other hand, a photocurable fluorine compound having a perfluoropolyether group composed of a perfluoroalkylene group having 3 or less consecutive carbon atoms and an ether-bonding oxygen atom is known. For example, a fluorine-containing acrylic compound derived from a hexafluoropropylene oxide oligomer (Patent Document 1) and a urethane acrylate composed of a reaction product of a fluorine-containing polyether diol and 2-isocyanate ethyl methacrylate have been proposed (Patent Document 1). 2). However, due to the water- and oil-repellent properties of the fluorine-containing compound, the compatibility with the photopolymerization initiator, the non-fluorinated acrylate, and the non-fluorinated organic solvent is low, and the components and applications that can be blended are limited.

On the other hand, a fluorine-containing acrylate compound having a cyclic siloxane structure and a urethane structure and having excellent compatibility with a non-fluorine-based solvent has been proposed (Patent Document 3). However, the antifouling film formed from the above-mentioned fluorine-containing acrylate compound is inferior in the falling property of water droplets and oil droplets and the smoothness of the film.

Japanese Unexamined Patent Publication No. 5-194322 Japanese Unexamined Patent Publication No. 11-349651 Japanese Patent No. 4873666

Polymer essay collection Vol. 64, No. 4, pp. 181-190 (A pr. 2007)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an active energy ray-curable resin composition capable of forming a cured film having excellent smoothness and falling property of water droplets and oil droplets. ..

As a result of diligent studies to achieve the above object, the present inventor has found that the composition containing the following fluorine-containing siloxane acrylate can form a cured film having both the falling property of water droplets and oil droplets and smoothness. The present invention has been completed.

［式中、ＰＦＰＥ¹は、数平均分子量３，５００～１０，０００の２価のパーフルオロポリエーテル鎖を表し、Ｘ¹は、それぞれ独立して、下記式（２）で表されるシロキサン鎖および下記式（３）で表されるシロキサン鎖から選ばれる基であり、

｛式（２）および式（３）中、Ｒ¹は、それぞれ独立して、炭素原子数１～１２の１価炭化水素基であり、Ｒ²は、それぞれ独立して、水素原子、メチル基、フッ素原子またはトリフルオロメチル基であり、Ｇは、それぞれ独立して、炭素原子数１～１２の１価炭化水素基であり、Ｑは、それぞれ独立して、下記式で表される２価の有機基であり、

（式中、破線は、結合手を表し、＊印は、ケイ素原子との結合部位を表す。）
ａは、１～５の整数であり、ｂは、０～３の整数であり、ａ＋ｂは、３～６の整数であり、ｃは、０～２の整数であり、ｄは、１～３の整数であり、ｅは、０～２の整数であり、ｃ＋ｄ＋ｅは、３である。破線は、結合手を表す。なお、式（２）において、シロキサン単位の配列順は任意であってよい。｝
Ｚ¹は、それぞれ独立して、下記式で表される２価の有機基である。

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ¹との結合部位を表す。）］
（Ｂ）下記式（１’）で表される含フッ素シロキサンアクリレート

［式中、ＰＦＰＥ²は、数平均分子量５００以上３，５００未満の２価のパーフルオロポリエーテル鎖を表し、Ｘ²は、それぞれ独立して、上記式（２）で表されるシロキサン鎖および上記式（３）で表されるシロキサン鎖から選ばれる基であり、Ｚ²は、それぞれ独立して、下記式で表される２価の有機基である。

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ²との結合部位を表す。）］
（Ｃ）活性エネルギー線によりラジカルを発生する重合開始剤
（Ｄ）フッ素原子を含まないアクリレート、フッ素原子を含まないウレタンアクリレートまたはこれらの両方
を含む活性エネルギー線硬化性樹脂組成物、
２． 式（１）におけるＰＦＰＥ¹および式（１’）におけるＰＦＰＥ²が、下記式（５）で表されるパーフルオロポリエーテル鎖であり、ＰＦＰＥ¹の数平均分子量が、３，５００～６，５００であり、ＰＦＰＥ²の数平均分子量が、５００～２，５００である１記載の活性エネルギー線硬化性樹脂組成物、

（式中、破線は、結合手を表し、ｐおよびｑが付された括弧内の繰り返し単位の配列は、任意であってよく、ｐは、ｐ≧１の数であり、ｑは、ｑ≧１の数であり、ｐ／ｑは、１／１０～１０／１の数である。）
３． 式（１）におけるＺ¹および式（１’）におけるＺ²が、それぞれ独立して、下記式で表される２価の有機基である１または２記載の活性エネルギー線硬化性樹脂組成物、

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ¹またはＰＦＰＥ²との結合部位を表す。）
４． 式（２）および式（３）において、Ｑが、それぞれ独立して、下記式で表される２価の有機基から選択される１種以上である１～３のいずれかに記載の活性エネルギー線硬化性樹脂組成物、

（式中、破線は、結合手を表し、＊印は、ケイ素原子との結合部位を表す。）
５． 式（１）において、Ｘ¹が、それぞれ独立して、上記式（２）で表される基であり、かつ、式（１’）において、Ｘ²が、それぞれ独立して、上記式（３）で表される基である１～４のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
６． 式（２）において、ａが、２～４の整数であり、ｂが、０～２の整数であり、ａ＋ｂが、３または４であり、かつ、式（３）において、ｃ＝０である、１～５のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
７． 前記式（２）において、ｂ＝０であり、かつ、式（３）においてｅ＝０である１～６のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
８． （Ａ）成分と（Ｂ）成分の配合比が、質量比で、１／９～９／１である１～７のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
９． （Ａ）成分と（Ｂ）成分の合計１００質量部に対し、（Ｃ）成分が、０．０１～１０質量部、（Ｄ）成分が、５～３００質量部含まれる１～８のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
１０． さらに、（Ｅ）溶剤が、（Ａ）成分と（Ｂ）成分の合計１００質量部に対し、１０～１００，０００質量部含まれる１～９のいずれかに記載の活性エネルギー線硬化性樹脂組成物、
１１． １～１０のいずれかに記載の活性エネルギー線硬化性樹脂組成物から形成される硬化被膜、
１２． 平均表面粗さが１ｎｍ以下である１１記載の硬化被膜、
１３． 基材と、該基材の少なくとも一方の面に直接または少なくとも１種のその他の層を介して積層された硬化被膜とを有し、該硬化被膜が、１１または１２記載の硬化被膜である被覆物品
を提供する。 That is, the present invention
1. 1. (A) Fluorine-containing siloxane acrylate represented by the following formula (1)

[In the formula, PFPE ¹ represents a divalent perfluoropolyether chain having a number average molecular weight of 3,500 to 10,000, and X ¹ is a siloxane chain represented by the following formula (2) independently. And a group selected from the siloxane chain represented by the following formula (3).

{In the formulas (2) and (3), R ¹ is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is an independent hydrogen atom and a methyl group, respectively. , Fluorine atom or trifluoromethyl group, G is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently, and Q is a divalent group represented by the following formula independently. Is an organic group of

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.)
a is an integer of 1 to 5, b is an integer of 0 to 3, a + b is an integer of 3 to 6, c is an integer of 0 to 2, and d is an integer of 1 to 3. Is an integer of, e is an integer of 0 to 2, and c + d + e is 3. The dashed line represents the bond. In the formula (2), the sequence order of the siloxane units may be arbitrary. }
Z ¹ is a divalent organic group represented by the following formula independently.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^1. )]
(B) Fluorine-containing siloxane acrylate represented by the following formula (1')

[In the formula, PFPE ² represents a divalent perfluoropolyether chain having a number average molecular weight of 500 or more and less than 3,500, and X ² independently represents a siloxane chain represented by the above formula (2) and a siloxane chain. It is a group selected from the siloxane chain represented by the above formula (3), and Z ² is a divalent organic group represented by the following formula independently.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^2. )]
(C) Polymerization initiator that generates radicals by active energy rays (D) Fluorine atom-free acrylate, fluorine atom-free urethane acrylate, or active energy ray-curable resin composition containing both of them.
2. 2. PFPE ¹ in the formula (1) and PFPE ² in the formula (1') are perfluoropolyether chains represented by the following formula (5), and the number average molecular weight of PFPE ¹ is 3,500 to 6,500. 1. The active energy ray-curable resin composition according to 1, wherein the number average molecular weight of PFPE ² is 500 to 2,500.

(In the equation, the dashed line represents the bond, the array of repeating units in parentheses with p and q may be arbitrary, p is the number p ≧ 1, and q is q ≧. It is a number of 1, and p / q is a number of 1/10 to 10/1.)
3. 3. The active energy ray-curable resin composition according to 1 or 2, wherein Z ¹ in the formula (1) and Z ² in the formula (1') are independently represented by a divalent organic group represented by the following formula.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ¹ or PFPE ^2. )
4. In the formula (2) and the formula (3), the active energy according to any one of 1 to 3 in which Q is one or more selected from divalent organic groups represented by the following formulas independently of each other. Linear curable resin composition,

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.)
5. In the formula (1), X ¹ is an independent group represented by the above formula (2), and in the formula (1'), X ² is an independent group, respectively, in the above formula (3). The active energy ray-curable resin composition according to any one of 1 to 4, which is a group represented by).
6. In the formula (2), a is an integer of 2 to 4, b is an integer of 0 to 2, a + b is 3 or 4, and c = 0 in the formula (3). The active energy ray-curable resin composition according to any one of 1 to 5.
7. The active energy ray-curable resin composition according to any one of 1 to 6, wherein b = 0 in the formula (2) and e = 0 in the formula (3).
8. The active energy ray-curable resin composition according to any one of 1 to 7, wherein the compounding ratio of the component (A) and the component (B) is 1/9 to 9/1 in terms of mass ratio.
9. One of 1 to 8 in which the component (C) is contained in an amount of 0.01 to 10 parts by mass and the component (D) is contained in an amount of 5 to 300 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). The active energy ray-curable resin composition according to.
10. Further, the active energy ray-curable resin composition according to any one of 1 to 9, wherein the solvent (E) is contained in an amount of 10 to 100,000 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). Stuff,
11. A cured film formed from the active energy ray-curable resin composition according to any one of 1 to 10.
12. 11. The cured coating having an average surface roughness of 1 nm or less.
13. A coating having a substrate and a cured coating laminated directly on at least one surface of the substrate or via at least one other layer, wherein the cured coating is the cured coating according to 11 or 12. Providing goods.

The active energy ray-curable resin composition of the present invention can form a cured film having both the falling property of water droplets and oil droplets and smoothness. Further, it is possible to provide an article having such a cured film.

（Ｂ）下記式（１’）で表される含フッ素シロキサンアクリレート

（Ｃ）活性エネルギー線によりラジカルを発生する重合開始剤
（Ｄ）フッ素原子を含まないアクリレート、フッ素原子を含まないウレタンアクリレートまたはこれらの両方 Hereinafter, the present invention will be specifically described.
The active energy ray-curable resin composition of the present invention contains the following components (A) to (D).
(A) Fluorine-containing siloxane acrylate represented by the following formula (1)

(B) Fluorine-containing siloxane acrylate represented by the following formula (1')

(C) Polymerization initiator that generates radicals by active energy rays (D) Fluorine atom-free acrylate, fluorine atom-free urethane acrylate, or both.

[(A) component]
The component (A) is a fluorine-containing siloxane acrylate represented by the following formula (1).

In formula (1), PFPE ¹ is a divalent perfluoropolyether chain having a number average molecular weight of 3,500 to 10,000, preferably 3,500 to 7,500, and more preferably 3,500 to 6,500. Is. In particular, those having a structure in which perfluoroalkylene groups represented by the following structural formula (4) and oxygen atoms are alternately linked are preferable. In the present invention, the number average molecular weight is a standard polystyrene-equivalent value obtained by gel permeation chromatography (GPC).

（式中、破線は、Ｚ¹との結合手を表す。）

(In the formula, the broken line represents the bond with Z ^1. )

In the formula (4), A represents a perfluoroalkylene group having 1 to 3 carbon atoms, which may be the same or different, and the sequence may be arbitrary. n is a number that satisfies the above number average molecular weight.

Specific examples of the perfluoroalkylene group having 1 to 3 carbon atoms represented by A include the structures shown below.

（式中、破線は、Ｚ¹との結合手を表す。）

(In the formula, the broken line represents the bond with Z ^1. )

In the divalent perfluoropolyether chain represented by PFPE ¹ , there are many oxygen atoms that serve as bending points that exhibit slipperiness, and there is no branching structure that inhibits the bending movement of the chain. Is more preferably a perfluoromethylene group represented by the above formula (i) and a perfluoroethylene group represented by the above formula (ii).

In particular, the divalent perfluoropolyether chain represented by PFPE ¹ has the following formula (5) in which an oxydifluoromethylene group and an oxytetrafluoroethylene group coexist, considering that it is easily obtained industrially. What is represented is particularly preferred.

（式中、破線は、Ｚとの結合手を表し、ｐおよびｑが付された括弧内の繰り返し単位の配列は、任意であってよい。）

(In the equation, the broken line represents the bond with Z, and the array of repeating units in parentheses with p and q may be arbitrary.)

In the formula (5), the number of perfluorooxymethylene groups (p) is the number of p ≧ 1, and the number of perfluorooxyethylene groups (q) is the number of q ≧ 1.
In the formula (5), the ratio (p / q) of the number of perfluorooxymethylene groups (p) to the number of perfluorooxyethylene groups (q) is not particularly limited, but is 1/10 to 1/10. 10/1 is preferable, and 3/10 to 10/3 is more preferable.

In the above formula (1), X ¹ is a group independently selected from the siloxane chain represented by the following formula (2) and the siloxane chain represented by the following formula (3). As the component (A), X ¹ is preferably a group represented by the formula (2) independently of each other, but considering the ease of production and the like, the two X ^1s may be the same group. preferable.

（式中、破線は、結合手を表す。なお、式（２）において、シロキサン単位の配列順は任意であってよい。）

(In the formula, the broken line represents the bond. In the formula (2), the arrangement order of the siloxane units may be arbitrary.)

Each of R ¹ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms, and specifically, for example, for example. Alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclohexyl; aryl groups such as phenyl and the like can be mentioned. As R ¹ , an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable.

R ² is independently a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, and a hydrogen atom and a methyl group are preferable, and a hydrogen atom is particularly preferable.

G is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms, and is, for example, methyl, ethyl, n-. Alkyl groups such as propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl and cyclohexyl can be mentioned. G is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 1 to 3 carbon atoms, and a methyl group, an ethyl group or an n-propyl group is particularly preferable. ..

Q is a divalent organic group having 1 to 20 carbon atoms which may independently contain an ether bond and may have a cyclic structure or a branched structure. In the present invention, Q is particularly the following formula. The one represented by is preferable.

（式中、破線は、結合手を表し、＊印は、ケイ素原子との結合部位を表す。）

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.)

（式中、破線は、結合手を表し、＊印は、ケイ素原子との結合部位を表す。） Q is a divalent organic group independently and preferably represented by the following structural formula.

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.)

a is an integer of 1 to 5, preferably 2 to 4, and more preferably 3.
b is an integer of 0 to 3, preferably 0 to 2, and more preferably 0.
a + b is an integer of 3 to 6, preferably 3 or 4, and more preferably 3.
c is an integer of 0 to 2, preferably 0 or 1, more preferably 0.
d is an integer of 1 to 3, preferably 3.
e is an integer of 0 to 2, preferably 0 or 1, more preferably 0.
c + d + e is 3.

Z ¹ is a group independently selected from divalent organic groups represented by the following formulas, but considering the availability of raw materials and the ease of production, the two Z ^1s are the same. It is preferably a group.

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ¹との結合部位を表す。）

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^1. )

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ¹との結合部位を表す。） Among these, as Z ¹ , a group represented by the following formula is preferable.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^1. )

When X ¹ in the formula (1) is a group represented by the formula (2), the component (A) can be produced, for example, by the method described in JP-A-2010-285501.

Further, when X ¹ in the formula (1) is a group represented by the formula (3), the component (A) can be produced, for example, by the following method.
[1] Synthesis of Hydrogensiloxane First, a perfluoropolyether having an alkoxysilyl group at both ends represented by the following formula (8) is represented by Si represented by the following formulas (9a) and / or (9b). A hydrogen siloxane having a perfluoropolyether group represented by the following formula (10) is produced by co-hydrolysis-condensing with a compound having a −H bond.

In the formula, R ³ and R ⁴ are independently alkyl groups having 1 to 12, preferably 1 to 6, and more preferably 1 to 4, respectively, and R ⁵ has 1 to 12 carbon atoms. It is preferably an alkyl group of 1 to 6, more preferably 1 to 4. w is an integer of 0 to 2 independently of each other, and PFPE ¹ and Z ¹ are as described above.

Examples of R ³ , R ⁴ , and R ⁵ include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl. , And preferably a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.

In the co-hydrolysis, the compounding amount of the compound (9a) and / or (9b) with respect to the compound (8) is the compound with respect to 1 equivalent of the alkoxy group of the compound (8) in order to prevent cross-linking between the compounds (8). After co-hydrolysis using (9a) and / or (9b) in an amount of 2 equivalents or more in terms of silicon atoms, it is preferable to remove the unreacted compounds (9a) and / or (9b) by distillation under reduced pressure. , It is preferable to react the compound (9a) and / or (9b) in the presence of 2 to 10 equivalents, particularly 2 to 6 equivalents, in terms of silicon atoms with respect to 1 equivalent of the alkoxy group of the compound (8). When the compound (9a) and the compound (9b) are used in combination, the addition amount (mass ratio) of the compound (9a) and the compound (9b) is (9a) / (9b) = 50/1 to 1/50. The ratio of is preferable.

When carrying out co-hydrolysis, it is preferable to use a hydrolysis catalyst.
As the hydrolysis catalyst, a conventionally known catalyst can be used, for example, an acid such as hydrochloric acid, nitric acid, sulfuric acid, hydrogen halide, carboxylic acid, sulfonic acid; an acidic or weakly acidic inorganic salt; an ion exchange resin or the like. Solid acids; inorganic bases such as ammonia and sodium hydroxide; tributylamine, 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene. Organic bases such as -7 (DBU); organic metal compounds such as organic tin compounds, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds can be mentioned, and these may be used alone or in combination of two or more. Multiple types may be used together.

Among these hydrolysis catalysts, acids such as hydrochloric acid, nitric acid, sulfuric acid, and methanesulfonic acid; organometallic compounds selected from organotin compounds, organotitanium compounds, and organoaluminum compounds are particularly preferable.
Suitable organic metal compounds include, for example, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate, tetra. Butyl titanate, tetranonyl titanate, tetraxethylene glycol methyl ether titanate, tetraxethylene glycol ethyl ether titanate, bis (acetylacetonyl) dipropyl titanate, acetylacetone aluminum, aluminum bis (ethylacetate acetate) mononormal butyrate, aluminum ethylacetate acetate Examples include dinormal butyrate, aluminum tris (ethylacetoacetate), and their hydrolyzates.
In particular, from the viewpoint of reactivity, acids such as hydrochloric acid, nitric acid and methanesulfonic acid; tetrabutyl titanate, aluminum ethylacetate acetate dinormal butyrate, aluminum bis (ethylacetate acetate) mononormal butyrate and their hydrolyzates. Preferred, methanesulfonic acid is particularly preferred.

The amount of the hydrolysis catalyst used is not particularly limited, but is preferably 0.001 to 15 mol%, preferably 0.001 to 10 mol%, based on 1 mol of the alkoxy group on the silicon atom of the compound of the formula (8). Mol% is particularly preferred.

The co-hydrolysis / condensation reaction may be carried out in the presence of an organic solvent.
The organic solvent is not particularly limited as long as it is compatible with each of the above-mentioned raw material compounds, and specific examples thereof include aromatic hydrocarbons such as toluene and xylene; hydrocarbons such as hexane and octane; and methyl ethyl ketone. , Methylisobutylketone and other ketones; Ethyl acetate, isobutylacetate and other esters; Methanol, ethanol, isopropanol, butanol, isobutanol, t-butanol and other alcohols; It may be used alone or in combination of two or more.

Examples of the fluorine-based solvent include fluorine-containing aromatic hydrocarbons such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; and perfluorohexane, perfluoromethylcyclohexane and the like having 3 to 12 carbon atoms. Perfluorocarbons; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,5,5,6-tri Hydrofluorocarbons such as decafluorooctane; Hydrofluorocarbons such as C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ F ₇ Kind: Perfluoroalkylene ethers such as Fomblin, Galden (manufactured by Solvay), Demnum (manufactured by Daikin Industries, Ltd.), Kleitox (manufactured by Chemers) and the like.

In the above reaction, it is preferable to add water. The amount of water added at the time of hydrolysis is preferably 1 to 5 times, and particularly preferably 1.5 to 3 times the amount required for hydrolyzing all of the alkoxy groups of the raw material.
The reaction conditions are usually preferably −5 to 20 ° C. for 15 to 300 minutes, and more preferably 0 to 10 ° C. for 30 to 180 minutes.

Specific examples of the polyfunctional hydrogensiloxane obtained by the above reaction include those represented by the following formulas, but are not limited thereto.

（式中、ＰＦＰＥ¹は、上記と同じ意味を表す。）

(In the formula, PFPE ¹ has the same meaning as above.)

[2] Hydrosilylation reaction Next, an olefin compound represented by the following formula (11a) and, if necessary, an olefin compound represented by the formula (11b) are added to the hydrogen siloxane (10) by hydrosilylation. React.

R ⁶ is an olefin group capable of addition reaction with a Si—H group, and an alkenyl group having 2 to 8 carbon atoms is preferable, and examples thereof include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, and isobutenyl. Be done. Of these, vinyl groups and allyl groups are preferable.
A'is a hydrogen atom or -SiR ⁷ (R ⁷ is the same as R ¹ ).
R ¹ is the same as above.
Y is a divalent organic group which may contain a single bond or an ether bond (excluding those containing O at the end of the bond with an oxygen atom to form an —O— bond), and having a cyclic structure or branching. It may have a structure.
Examples of the divalent organic group of Y include an alkylene group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, and specific examples thereof include those represented by the following structural formula.

（式中、破線は、結合手を表し、・印は、オレフィン基Ｒ⁶との結合部位を表す。）

(In the formula, the broken line represents the bond, and the · mark represents the binding site with the olefin group R ^6. )

Y is preferably a single bond or a divalent organic group represented by the following structural formula.

Specific examples of the compound represented by the formula (11a) include, but are not limited to, those represented by the following formulas.

Specific examples of the compound represented by the formula (11b) include, but are not limited to, those represented by the following formula.

In the hydrosilylation reaction, the amount of the compound (11a) added is preferably 0.2 to 5 equivalents, more preferably 0.5 to 3 equivalents, relative to 1 equivalent of the hydrosilyl group of the hydrogensiloxane (10).
When the compound (11b) is used, the addition amount thereof is preferably 0.1 to 0.8 equivalents, more preferably 0.1 to 0.5 equivalents, relative to 1 equivalent of the hydrosilyl group of the hydrogensiloxane (10). be.
When the compound (11a) and the compound (11b) are used in combination, the addition amount (mass ratio) of the compound (11a) and the compound (11b) is (11a) / (11b) = 50/1 to 0.5 / 1. The ratio of is preferable.

The hydrosilylation reaction proceeds without the use of a solvent, but a solvent may be used if necessary.
As the solvent, it is preferable that the following compound (12a) produced after the reaction is soluble without inhibiting the hydrosilylation reaction, and the compound (10), the compound (11a) and the compound used as necessary at the desired reaction temperature are used. Those that dissolve (11b) are preferable.
Specifically, for example, aromatic hydrocarbons such as benzene, toluene and xylene; fluorine-modified aromatic hydrocarbons such as m-xylene hexafluoride and benzotrifluoride; methyl perfluorobutyl ether and perfluoro (2-). Fluoro-modified ethers such as butyltetrahydrocarbon are preferable, and among these, toluene, xylene, and m-xylene hexafluoride are preferable.

It is preferable to use a catalyst for the hydrosilylation reaction. As the catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium, and palladium can be used. Among these, compounds containing platinum are preferable, for example, hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde. / Octanol complexes, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, etc., platinum carried on activated carbon, and the like can be used.
The blending amount of the catalyst is preferably in the range of 0.1 to 5,000 ppm, more preferably 1 to 1,000 ppm, based on the mass of the entire reaction system.

In the hydrosilylation reaction, the order in which each component is mixed is not particularly limited, but for example, a mixture containing compound (10), compound (11a), and if necessary, compound (11b) and a catalyst is gradually mixed from room temperature. A method of heating to the addition reaction temperature, compound (10), compound (11a), and if necessary, compound (11b) and a mixture containing a solvent are heated to the desired reaction temperature and then the catalyst is added. Method, a method of dropping compound (10) into a mixture containing a compound (11a) heated to a target reaction temperature, a compound (11b) if necessary, and a catalyst, a compound heated to a target reaction temperature (10). ), A method of dropping a mixture containing the compound (11a), the compound (11b) if necessary, and a catalyst can be adopted.
Among these, a method or a method of adding a catalyst after heating a mixture containing compound (10), compound (11a), and if necessary, compound (11b) and a solvent to a target reaction temperature. A method of dropping a mixture containing the compound (11a) and, if necessary, the compound (11b) and a catalyst onto the compound (10) heated to the reaction temperature to be considered is particularly preferable. These methods can be used by diluting each component or mixture with a solvent, if necessary.

In the case of addition reaction of compound (11a) and (11b) to compound (10), addition reaction of compound (10) and compound (11b) is carried out, and then addition is carried out using an excess amount of compound (11a). It is desirable to react and remove and purify the unreacted compound (11a). At this time, in the compound (11a) and the compound (11b), compounds having different R6, Y, ^R7 , and ^A'may be mixed and used.
The addition reaction is usually preferably carried out at 20 to 120 ° C. for 30 to 300 minutes, more preferably 50 to 100 ° C. for 30 to 120 minutes.

By the above method, a compound represented by the following formula (12a) can be obtained.

（Ａ’、Ｑ、Ｒ⁴、Ｒ⁷、ｗは上記のとおりであり、ｈは１～３の整数であり、ｉは０～２の整数であり、ｈ＋ｉ＋ｗ＝３である。） In formula (12a), X ⁰ is independently based on the following.

(A', Q, R ⁴ , R ⁷ , w are as described above, h is an integer of 1 to 3, i is an integer of 0 to 2, and h + i + w = 3.)

[3] Deprotection reaction Next, by deprotecting all of the silyl groups, they are converted into hydrogen atoms, and then a reaction point with an acid chloride compound containing a (meth) acrylic group to be reacted is constructed. In the present invention, the (meth) acrylic group represents an acrylic group or a methacrylic group.

The conditions for deprotection can be a conventionally known method and are not particularly limited, and are limited to a method using a fluoride ion, a method using an acid (Bronsted acid, Lewis acid), and a method using a base (Bronsted base, Lewis base). , A method in which an excess of alcohol is allowed to act under neutral conditions, a method using N-bromosuccinimide, diisobutylaluminum hydride, a palladium complex, or the like can be mentioned.
Among these, a method using an acid (Bronsted acid, Lewis acid) and a method in which excess alcohol is allowed to act under neutral conditions are preferable, and a method in which excess alcohol is allowed to act under neutral conditions is particularly preferable. At this time, as the alcohol to act on, methanol, ethanol, propanol, butanol, pentanol and the like are preferable, and methanol and ethanol are particularly preferable.
The amount of alcohol added is preferably 1 to 50 equivalents with respect to 1 equivalent of the silyl group of A'. The reaction conditions are usually 50 to 100 ° C., preferably 60 to 1,440 minutes.

[4] Esteration reaction When all of the hydroxy groups contained in the silyl group deprotected compound (12b) in the above formula (12a) or A'of the compound (12a) is a hydrogen atom (compound (12c)). By reacting all of the hydrosilyl groups of the above with the (meth) acrylic acid chloride represented by the following formula (13) to form an ester bond, a fluorine-containing siloxane acrylate represented by the formula (3) can be obtained. can.

（式中、Ｒ²は上記のとおりである。）

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

The reaction of compound (12b) or (12c) with compound (13) is 30 in the presence of a base, preferably at 0-100 ° C, preferably 0-80 ° C, in order to neutralize by-product hydrochloric acid. It proceeds by mixing both for ~ 180 minutes.
The type of base is not particularly limited, but for example, ammonia, trimethylamine, triethylamine, diisopropylamine, tripropylamine, N, N-diisopropylethylamine, tributylamine, pyridine, N, N-dimethylaminopyridine, 1,5-diazabicyclo [ 4.3.0] Amine compounds such as Nonen-5 (DBN), 1,8-diazabicyclo [5.4.0] Undecene-7 (DBU); Sodium hydrogen carbonate, Potassium hydrogen carbonate, Lithium hydrogen carbonate, Sodium carbonate , Inorganic bases such as potassium carbonate, lithium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide; examples thereof include aqueous solutions thereof. These are not limited to one of them, and may be used as a mixture of two or more.
Among these, triethylamine, pyridine, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide, potassium hydroxide are preferable, and triethylamine is particularly preferable.

The compounding amount of the compound (13) with respect to the compound (12c) or (12b) is preferably 1 to 10 equivalents with respect to the hydroxyl group of the compound (12c) or (12b), more preferably 1 to 5 equivalents, and 1 to 3 equivalents. Equivalents are particularly preferred.
The blending amount of the base with respect to the compound (13) is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, and particularly preferably 1 to 3 equivalents with respect to the hydrochloric acid generated from the compound (13).

In the above esterification reaction, the mixing order of each component is not particularly limited, and for example, a mixture containing compound (12b) or (12c), compound (13), and a base is gradually heated from room temperature to the esterification reaction temperature. A method of adding a base after heating a mixture containing the compound (12b) or (12c) and the compound (13) to a desired reaction temperature, a method of adding a base to the mixture containing the compound (12b) or (12c) and a base. Method of adding compound (13) after heating to the reaction temperature of, compound (13) and a method of adding compound (12b) or (12c) after heating a mixture containing a base to a desired reaction temperature, compound (13). After heating to a desired temperature, a method of dropping a mixture containing the compound (12b) or (12c) and a base can be taken. Among these, a method in which the compound (12b) or a mixture containing (12c) and a base is heated to a desired reaction temperature and then the compound (13) is added dropwise is particularly preferable.

In these methods, a solvent can be used if necessary.
The solvent can be used without particular limitation as long as it does not react with hydroxyl groups and acid chlorides, but specifically, aromatic hydrocarbons (benzene, toluene, xylene); fluorine-modified aromatic hydrocarbons (). m-xylene hexafluoride, benzotrifluoride, etc.); Fluorine-modified ethers (methyl perfluorobutyl ether, perfluoro (2-butyltetratetra), etc.); Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.) Etc.); Ethers (hydrocarbons, diethyl ethers, diisopropyl ethers, dibutyl ethers, etc.) are preferable.
Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, and m-xylene hexafluoride are preferable.

[(B) component]
The component (B) is a fluorine-containing siloxane acrylate represented by the following formula (1').

In formula (1'), PFPE ² is a divalent perfluoropolyether chain having a number average molecular weight of 500 or more and less than 3,500. It is preferably 700 to 2,500, more preferably 1,000 to 2,000, and has a structure in which a perfluoroalkylene group represented by the above structural formula (4) and an oxygen atom are alternately linked. Those are preferable. Specific examples and preferable examples of A in the formula (4) are the same as those described for the component (A).
Further, as PFPE ² , those represented by the above formula (5) are particularly preferable, and p and q of the formula (5) are the same as those described for the component (A).

In the formula (1'), X ² is a group independently selected from the siloxane chain represented by the above formula (2) and the siloxane chain represented by the above formula (3). The R ¹ , R ² , Q, G, a to e in the siloxane chain represented by the above formula (2) and the above formula (3) are the same as those exemplified as X ¹ in the above component (A). Can be mentioned.
In the component (B), X ² is preferably a group represented by the formula (3) independently of each other, but in consideration of ease of production and the like, it is preferable that the two X ² are the same group. ..

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ²との結合部位を表す。） Z ² is a divalent organic group represented by the following formula independently.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^2. )

（式中、破線は、結合手を表し、＊＊印は、前記ＰＦＰＥ²との結合部位を表す。） Of these, the group represented by the following formula is preferable.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^2. )

The component (B) can be produced in the same manner as the component (A).

The component (A) and the component (B) are blended so that the total amount thereof is 100 parts by mass.
The mixing ratio of the component (A) and the component (B) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2 in terms of mass ratio.

[(C) component]
The component (C) is a polymerization initiator that generates radicals by active energy rays, and may be appropriately selected from known photopolymerization initiators such as benzophenone type and thioxanthone type. Specific examples thereof include benzophenone, benzyl, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyldimethylketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone, and acylphosphine oxide derivative. , 2-Methyl-1- {4- (methylthio) phenyl} -2-morpholinopropane-1-one, 4-benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine, etc. Can be mentioned. These may be used alone or in combination of two or more.

Further, as the polymerization initiator, a commercially available product can also be used.市販品としては、例えば、Ｏｍｎｉｒａｄ １１７３、Ｏｍｎｉｒａｄ ＭＢＦ、Ｏｍｎｉｒａｄ １２７、Ｏｍｎｉｒａｄ １８４、Ｏｍｎｉｒａｄ ３６９、Ｏｍｎｉｒａｄ ３７９、Ｏｍｎｉｒａｄ ３７９ＥＧ、Ｏｍｎｉｒａｄ ６５１、Ｏｍｎｉｒａｄ ７５４、Ｏｍｎｉｒａｄ ７８４、Ｏｍｎｉｒａｄ ８１９、Ｏｍｎｉｒａｄ ８１９ＤＷ、Ｏｍｎｉｒａｄ ９０７、Ｏｍｎｉｒａｄ １８００、Ｏｍｎｉｒａｄ 2959, Omnirad TPO H (both manufactured by IGM Resins B.V.) and the like can be mentioned.

The blending amount of the component (C) is preferably 0.01 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). be.

[(D) component]
The component (D) is one or more selected from an acrylate containing no fluorine atom and a urethane acrylate containing no fluorine atom. The component (D) is an important component for adjusting the crosslink density during curing and adjusting the hardness of the obtained cured film.

Examples of the acrylate containing no fluorine atom include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified di (meth) acrylate, and isocyanuric acid. Ethylene oxide modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, hydrogen phthalate- (2,2) , 2-Tri- (meth) acryloyloxymethyl) ethyl, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol 2- to 6-functional (meth) acrylate compounds such as hexa (meth) acrylate and sorbitol hexa (meth) acrylate, ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, urethane modified product, epoxy resin of these (meth) acrylate compounds. Examples thereof include epoxy acrylates obtained by adding acrylic acid to the acrylic acid ester copolymer, and copolymers in which a (meth) acryloyl group is introduced into the side chain of the acrylic acid ester copolymer.

As the urethane acrylate containing no fluorine atom, one obtained by reacting polyisocyanate with a (meth) acrylate having a hydroxyl group, and one obtained by reacting polyisocyanate with polyester having a hydroxyl group and having a hydroxyl group (meth) acrylate. Examples thereof include those obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate obtained by reacting a polyol with an excess of diisocyanate. Among these, (meth) acrylates having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, isophorone diisocyanate, and triacrylate. Those containing urethane acrylates obtained by reacting with range isocyanate and polyisocyanate selected from diphenylmethane diisocyanate are preferable.

As the component (D), a coating composition containing such an acrylate or urethane acrylate may be used. As such a composition, a commercially available product may be used, for example, "Beam Set" (manufactured by Arakawa Chemical Industry Co., Ltd.), "Ubic" (manufactured by Ohashi Chemical Industry Co., Ltd.), "UV Coat" ( Origin Electric Co., Ltd.), "Cashew UV" (Cashew Co., Ltd.), "Desolite" (JSR Co., Ltd.), "Seika Beam" (Dainichi Seika Kogyo Co., Ltd.), "Shikou" (Japan) Synthetic Chemical Co., Ltd.), "Fujihard" (Fujikura Kasei Co., Ltd.), "Diabeam" (Mitsubishi Rayon Co., Ltd.), "Ultravine" (Musashi Paint Co., Ltd.), etc.

The blending amount of the component (D) is preferably 5 to 300 parts by mass, more preferably 5 to 200 parts by mass, still more preferably, with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is 5 to 100 parts by mass. Within such a range, the hardness can be improved without impairing the falling property of water droplets and oil droplets of the film and the smoothness of the film. When the composition is used, it is the blending amount as acrylate or urethane acrylate.

[(E) component]
The active energy ray-curable resin composition of the present invention may further contain a solvent as the component (E). This component is a component that appropriately lowers the viscosity of the composition and contributes to the improvement of coating workability. The solvent is not particularly limited as long as it dissolves or disperses the component (A), the component (B), and the component (C) constituting the active energy ray-curable resin composition of the present invention.
Specific examples thereof include aromatic hydrocarbons such as toluene and xylene; hydrocarbons such as hexane and octane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isobutyl acetate; methanol, ethanol, and the like. Alcohols such as isopropanol, butanol, isobutanol, t-butanol; fluoroaromatic hydrocarbons such as 1,3-bis (trifluoromethyl) benzene and trifluorotoluene; perfluorohexane, perfluoromethylcyclohexane and the like Perfluorocarbons with 3 to 12 carbon atoms; 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4,5 Hydrofluorocarbons such as 5,6,6-tridecafluorooctane; C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₂ F ₅ CF (OCH ₃ ) C ₃ Hydrofluoroethers such as F7 _; Fluorine-based solvents such as poly (perfluoroalkylene ethers) such as von Bryn, Galden (manufactured by Solvay), Demnum (manufactured by Daikin Industries, Ltd.), and Crytox (manufactured by Chemers) Can be mentioned.
When a solvent is used, the blending amount thereof is preferably 10 to 100,000 parts by mass, more preferably 10 to 10,000 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is 50 to 1,000 parts by mass.

Any additive can be added to the active energy ray-curable resin composition of the present invention as long as the effect of the present invention is not impaired. Specific examples of the additive include non-reactive silicone oil, reactive silicone oil, reactive silica fine particles, non-reactive silica fine particles, reactive hollow silica fine particles, non-reactive hollow silica fine particles, silane coupling agent, and the like. Excipients, anti-aging agents, rust preventives, colorants, surfactants, rheology adjusters, UV absorbers, infrared absorbers, fluorescent agents, abrasives, fragrances, fillers, fillers, dyes, leveling agents, reactions Examples thereof include sex diluents, non-reactive polymer resins, antioxidants, ultraviolet absorbers, light stabilizers, defoaming agents, dispersants, antistatic agents, and thixotropy-imparting agents. In particular, when the present invention is used as an antireflection film, there is no problem even if reactive hollow silica fine particles, non-reactive hollow fine particles, or both of them are added in order to lower the refractive index.

The active energy ray-curable resin composition of the present invention can be obtained by uniformly mixing each of the above components according to a conventional method.

The cured film obtained from the active energy ray-curable resin composition of the present invention can achieve both excellent water droplets, oil droplet falling property and smoothness, and has antifouling property, water repellency and oil repellency on the surface of the substrate. It is useful for imparting fingerprint resistance and smoothness. Further, since the film formed from the present composition contains a fluorine-containing siloxane acrylate, it is expected to be excellent in low reflectivity. Due to these characteristics, it becomes difficult to be soiled by fingerprints, sebum, human oil such as sweat, cosmetics, etc., and even when stains are attached, the film is excellent in wiping property and the reflection of light is suppressed. Therefore, the active energy ray-curable resin composition of the present invention is for forming a coating film or a protective film applied to the surface of an article that may be contaminated by human fat, cosmetics, etc. when touched by the human body. It is useful as a coating agent.

Examples of the article to be coated in this way include optical recording media such as optical magnetic disks, optical disks such as CDs, LDs, DVDs, and Blu-ray disks, and optical recording media such as hologram recording; glasses lenses, prisms, lens sheets, and pellicle films. Optical components / optical devices such as polarizing plates, optical filters, wrenchular lenses, frennel lenses, antireflection films, optical fibers and optical couplers; CRTs, liquid crystal displays, plasma displays, electroluminescence displays, rear projection displays, fluorescent display tubes ( Various screen display devices such as VFD), field optics projection display, toner display; especially PC, mobile phone, mobile information terminal, game machine, digital camera, digital video camera, automatic cash withdrawal deposit device, cash automatic payment machine, Vending machines, navigation devices for automobiles, image display devices such as security system terminals, and touch panel (touch sensor, touch screen) type image display input devices that also operate them; mobile phones, mobile information terminals, portable music players, etc. Input devices such as panel switches for in-vehicle devices such as portable game machines, remote controllers, controllers, keyboards, etc .; housing surfaces of mobile phones, mobile information terminals, cameras, portable music players, portable game machines, etc .; automobile exteriors, pianos, etc. Surfaces of luxury furniture, marble, etc .; protective glass for art exhibitions, show windows, showcases, advertising covers, photostand covers, watches, automobile front glass, train, aircraft window glass, automobile headlights, tail lamps Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members; various mirror members, etc. may be mentioned.

The active energy ray-curable resin composition of the present invention is applied to at least one surface of these substrates directly or via at least one other layer, and the coating is formed by curing the coating. Goods can be obtained.

The base material to which the active energy ray-curable resin composition of the present invention is applied has a base material whose surface is treated with chemical conversion treatment, corona discharge treatment, plasma treatment, acid or alkaline solution, or a base material body and a surface layer. A decorative plywood or the like coated with a different type of paint can also be used.

Further, the surface of the base material on which other functional layers are formed may be coated with the coating agent of the present invention, and the other functional layers include a primer layer, a rust preventive layer, a gas barrier layer, a waterproof layer, and a heat ray. Shielding layers and the like may be mentioned, and any one or a plurality of these layers may be pre-formed on the substrate.

The coated article is a surface on which a film made of the composition of the present invention is formed, and further, a vapor deposition layer, a hard coat layer, a rust preventive layer, a gas barrier layer, a waterproof layer, and a heat ray shielding layer by a CVD (chemical vapor deposition) method. , An antifouling layer, a photocatalyst layer, an antistatic layer, or the like, or a plurality of layers may be used.

Further, in the coated article, the surface opposite to the surface on which the coating film made of the composition of the present invention is formed is a hard coat layer, a rust preventive layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, and a photocatalyst. It may be covered with one layer or a plurality of layers such as a layer and an antistatic layer.

Further, the active energy ray-curable resin composition of the present invention can be used as an antireflection coating composition. In this case, the blending amount of the fluorine-containing siloxane acrylate is preferably 5 to 100 parts by mass, more preferably 5 to 100 parts by mass, as the total amount of the components (A) and (B) with respect to 100 parts by mass of the active ingredient of the coating composition. Is 5 to 50 parts by mass. Within such a range, it is possible to obtain an antireflection film having good falling properties of water droplets and oil droplets and smoothness of the film while maintaining the strength of the film.

Further, the active energy ray-curable resin composition of the present invention is added to an ultraviolet curable resist liquid and exposed to a large difference in the liquid repellency between the cured resist surface and the portion from which the resist has been removed. It can be attached, and it is possible to prevent the developer and the liquid crystal solution from remaining and contaminating the surface of the resist resin.

The method for applying the active energy ray-curable resin composition of the present invention may be appropriately selected from known methods, for example, bar coater, brush coating, spraying, dipping, flow coating, roll coating, curtain coating, spin coating. , Various coating methods such as knife coating can be used.

As a light source for curing the active energy ray-curable resin composition, a light source containing light having a wavelength in the range of 200 to 450 nm, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, etc. Can be mentioned. The irradiation amount is not particularly limited, but is preferably 10 to 5,000 mJ / cm ² , and more preferably 20 to 2,000 mJ / cm ² . The curing time is usually 0.5 seconds to 2 minutes, preferably 1 second to 1 minute.

The film thickness of the cured film using the active energy ray-curable resin composition is preferably 0.01 to 50 μm, more preferably 1 to 20 μm, and even more preferably 5 to 15 μm in consideration of transparency.
The surface roughness of the cured film obtained from the composition of the present invention is preferably 1 nm or less, more preferably 0.98 nm or less. The lower limit is not particularly limited, but is about 0.1 nm or more. The method for measuring the surface roughness is as described later.

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.
In the example below, ^{1 1} H-NMR measurement was performed using ULTRA SHIELD 400 Plus (manufactured by Bruker). In the following example, Me represents a methyl group.

（式中、ｐ１≧１、ｑ１≧１、ｐ１／ｑ１＝１．１であり、ｐ１およびｑ１が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は４，０００である。） [1] Synthesis of raw material compound [Synthesis Example 1-1]
According to Example 1 of JP-A-2010-285501, a fluorine-containing siloxane acrylate represented by the following formula (6) was obtained.

(In the formula, p1 ≧ 1, q1 ≧ 1, p1 / q1 = 1.1, the sequence of repeating units in parentheses with p1 and q1 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 4,000.)

[Synthesis Example 1-2]
Under a dry nitrogen atmosphere, in a 5,000 mL three-necked flask equipped with a reflux device and a stirrer, 1,255 g of the compound represented by the following formula (14), 665 g of tetramethyldisiloxane, 1,255 g of methyl ethyl ketone, and 20 g of methanesulfonic acid. Was added, and the mixture was cooled to 5 ° C. with stirring. 71 g of ion-exchanged water was added dropwise thereto, and stirring was continued for 3 hours while maintaining the internal temperature at 0 to 10 ° C. After that, 100 g of hydrotalcite (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 2 hours while maintaining the internal temperature at 0 to 10 ° C. to distill the solvent and excess tetramethyldisiloxane under reduced pressure. After leaving, hydrotalcite was filtered off to obtain 1,130 g of a colorless and transparent liquid represented by the following formula (15).

（式中、ｐ２≧１、ｑ２≧１、ｐ２／ｑ２＝０．７６であり、ｐ２およびｑ２が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は１，５００である。）

(In the formula, p2 ≧ 1, q2 ≧ 1, p2 / q2 = 0.76, the sequence of repeating units in parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 1,500.)

Under a dry nitrogen atmosphere, for 190 g of compound (15), 117 g of allyloxytrimethylsilane, 229 g of toluene, and 4.3 g of a toluene solution of platinum chloride acid / vinylsiloxane complex (8.3 × 10 ^-5 mol as Pt alone). Was mixed and stirred at 80 ° C. for 2 hours. ¹ After confirming the disappearance of the signal derived from the Si—H group by 1 H-NMR measurement and FT-IR measurement, the solvent and excess allyloxytrimethylsilane were distilled off under reduced pressure, activated carbon treatment was performed, and then filtration was performed. 230 g of a pale yellow transparent liquid represented by the following formula (16) was obtained.

（式中、ｐ２≧１、ｑ２≧１、ｐ２／ｑ２＝０．７６であり、ｐ２およびｑ２が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は１，５００である。）

(In the formula, p2 ≧ 1, q2 ≧ 1, p2 / q2 = 0.76, the sequence of repeating units in parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 1,500.)

Under a dry nitrogen atmosphere, 2,300 g of methanol was added to 230 g of compound (16), and the mixture was heated and stirred at 67 ° C. for 12 hours to distill off by-produced trimethylmethoxysilane under normal pressure, and then excess methanol was used. And trimethylsilane were distilled off under reduced pressure to obtain 197 g of a pale yellow transparent liquid represented by the following formula (17).

（式中、ｐ２≧１、ｑ２≧１、ｐ２／ｑ２＝０．７６であり、ｐ２およびｑ２が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は１，５００である。）

(In the formula, p2 ≧ 1, q2 ≧ 1, p2 / q2 = 0.76, the sequence of repeating units in parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 1,500.)

Under a dry nitrogen atmosphere, 41 g of triethylamine and 505 g of hexafluoro-m-xylene were added to 101 g of compound (17), and the temperature was raised to 60 ° C. with stirring. A mixture of 25 g of chloride chloride diluted with 50 g of toluene was added dropwise thereto while maintaining the internal temperature at 55 to 60 ° C., and stirring was continued for 30 minutes. Next, 5.8 g of ethanol was added dropwise while maintaining the internal temperature at 55 to 60 ° C., and stirring was continued for 1 hour. Hydrotalsite (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) 5.6 g and aluminum silicate (Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.) 5.6 g in the filtrate obtained by filtering the precipitated salt. After stirring for 2 hours, the mixture was distilled off under reduced pressure, and hydrotalcite and aluminum silicate were filtered off to obtain 56 g of a pale yellow transparent liquid.
It was confirmed by ¹ H-NMR measurement that the obtained product was a fluorine-containing siloxane acrylate represented by the following formula (7). ¹ Table 1 shows the chemical shifts of the 1 H-NMR spectrum.

（式中、ｐ２≧１、ｑ２≧１、ｐ２／ｑ２＝０．７６であり、ｐ２およびｑ２が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は１，５００である。）

(In the formula, p2 ≧ 1, q2 ≧ 1, p2 / q2 = 0.76, the sequence of repeating units in parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 1,500.)

[2] Preparation of composition [Examples 1 to 9 and Comparative Examples 1 and 2]
Each of the following components was mixed at the mass ratios shown in Tables 2 and 3 to prepare an active energy ray-curable resin composition.
Each of the obtained compositions was spin-coated on a polycarbonate plate, and a cured film was irradiated with ultraviolet rays of 1,200 mJ / cm ² in a nitrogen atmosphere using a conveyor-type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.). Formed.
The water fall angle and hexadecane fall angle were measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The surface roughness was measured using a scanning probe microscope (device name: SI-DF3, manufactured by Hitachi High-Tech Science Co., Ltd.).

（式中、ｐ２≧１、ｑ２≧１、ｐ１／ｑ１＝１．１であり、ｐ１およびｑ１が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は４，０００である。） [(A) component]
Fluorine-containing siloxane acrylate represented by the following formula (6) obtained in Synthesis Example 1-1

(In the formula, p2 ≧ 1, q2 ≧ 1, p1 / q1 = 1.1, the sequence of repeating units in parentheses with p1 and q1 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 4,000.)

（式中、ｐ２≧１、ｑ２≧１、ｐ２／ｑ２＝０．７６であり、ｐ２およびｑ２が付された括弧内の繰り返し単位の配列は不定であり、パーフルオロポリエーテル鎖の数平均分子量は１，５００である。） [(B) component]
Fluorine-containing siloxane acrylate represented by the following formula (7) obtained in Synthesis Example 1-2

(In the formula, p2 ≧ 1, q2 ≧ 1, p2 / q2 = 0.76, the sequence of repeating units in parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain. Is 1,500.)

[(C) component]
(C-1): 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H, manufactured by IGM Resins B.V.)
(C-2): 1-Hydroxycyclohexyl-phenylketone (Omnirad 184, manufactured by IGM Resins B.V.)
[(D) component]
4-functional acrylate (A-TMMT, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
[(E) component]
Methyl isobutyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.)

As shown in Examples 1 to 9, the cured coating obtained from the active energy ray-curable resin composition of the present invention can achieve both excellent water droplets, oil droplet falling property and smoothness, and can be used as a substrate. On the other hand, it is useful as an antifouling film that imparts antifouling properties, a coating agent that forms an antireflection film, and the like.
On the other hand, the cured film (Comparative Example 1) obtained from the composition containing no component (B) has excellent rolling angles of water and hexadecane, but has a large surface roughness. Further, the cured film obtained from the composition containing no component (A) has a smooth surface, but is inferior in the falling property of water and hexadecane (Comparative Example 2).

Claims (13)

(A) Fluorine-containing siloxane acrylate represented by the following formula (1)

[In the formula, PFPE ¹ represents a divalent perfluoropolyether chain having a number average molecular weight of 3,500 to 10,000, and X ¹ is a siloxane chain represented by the following formula (2) independently. And a group selected from the siloxane chain represented by the following formula (3).

{In the formulas (2) and (3), R ¹ is an independently monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is an independent hydrogen atom and a methyl group, respectively. , Fluorine atom or trifluoromethyl group, G is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently, and Q is a divalent group represented by the following formula independently. Is an organic group of

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.)
a is an integer of 1 to 5, b is an integer of 0 to 3, a + b is an integer of 3 to 6, c is an integer of 0 to 2, and d is an integer of 1 to 3. Is an integer of, e is an integer of 0 to 2, and c + d + e is 3. The dashed line represents the bond. In the formula (2), the sequence order of the siloxane units may be arbitrary. }
Z ¹ is a divalent organic group represented by the following formula independently.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^1. )]
(B) Fluorine-containing siloxane acrylate represented by the following formula (1')

[In the formula, PFPE ² represents a divalent perfluoropolyether chain having a number average molecular weight of 500 or more and less than 3,500, and X ² independently represents a siloxane chain represented by the above formula (2) and a siloxane chain. It is a group selected from the siloxane chain represented by the above formula (3), and Z ² is a divalent organic group represented by the following formula independently.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ^2. )]
(C) Polymerization initiator that generates radicals by active energy rays (D) An active energy ray-curable resin composition containing fluorine atom-free acrylate, fluorine atom-free urethane acrylate, or both. PFPE ¹ in the formula (1) and PFPE ² in the formula (1') are perfluoropolyether chains represented by the following formula (5), and the number average molecular weight of PFPE ¹ is 3,500 to 6,500. The active energy ray-curable resin composition according to claim 1, wherein the number average molecular weight of PFPE ² is 500 to 2,500.

(In the equation, the dashed line represents the bond, the array of repeating units in parentheses with p and q may be arbitrary, p is the number p ≧ 1, and q is q ≧. It is a number of 1, and p / q is a number of 1/10 to 10/1.) The active energy ray-curable resin composition according to claim 1 or 2, wherein Z ¹ in the formula (1) and Z ² in the formula (1') are independently represented by a divalent organic group represented by the following formula. thing.

(In the formula, the broken line represents the bond, and the ** mark represents the binding site with PFPE ¹ or PFPE ^2. ) 6. Active energy ray-curable resin composition.

(In the formula, the broken line represents the bond, and the * mark represents the binding site with the silicon atom.) In the formula (1), X ¹ is an independent group represented by the above formula (2), and in the formula (1'), X ² is an independent group, respectively, in the above formula (3). ) Is the active energy ray-curable resin composition according to any one of claims 1 to 4. In the formula (2), a is an integer of 2 to 4, b is an integer of 0 to 2, a + b is 3 or 4, and c = 0 in the formula (3). , The active energy ray-curable resin composition according to any one of claims 1 to 5. The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein b = 0 in the formula (2) and e = 0 in the formula (3). The active energy ray-curable resin composition according to any one of claims 1 to 7, wherein the compounding ratio of the component (A) and the component (B) is 1/9 to 9/1 in mass ratio. For a total of 100 parts by mass of the component (A) and the component (B)
(C) component is 0.01 to 10 parts by mass,
The active energy ray-curable resin composition according to any one of claims 1 to 8, wherein the component (D) is contained in an amount of 5 to 300 parts by mass. The active energy ray curing according to any one of claims 1 to 9, wherein the solvent (E) is contained in an amount of 10 to 100,000 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). Sex resin composition. A cured film formed from the active energy ray-curable resin composition according to any one of claims 1 to 10. The cured coating according to claim 11, which has an average surface roughness of 1 nm or less. It has a substrate and a cured coating laminated directly on at least one surface of the substrate or via at least one other layer, wherein the cured coating is the cured coating according to claim 11 or 12. A covering article.