JP7476762B2 - Active energy ray curable resin composition, coating film and article - Google Patents

Description

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

Conventionally, polymerizable monomers having perfluoroalkyl groups, and polymers containing fluorine-containing alkyl esters of acrylic acid and fluorine-containing alkyl esters of methacrylic acid have been widely known as fluorine compounds that can be cured by irradiation with light such as ultraviolet light. A representative example is a compound represented by the following structural formula, which has been widely used for the purpose of imparting low reflectivity, water and oil repellency, stain resistance, abrasion resistance, scratch resistance, etc. to the surface of a substrate.

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

On the other hand, photocurable fluorine compounds are known that incorporate a perfluoropolyether group consisting of a perfluoroalkylene group with three or less consecutive carbon atoms and an ether-bonded oxygen atom. For example, a fluorine-containing acrylic compound derived from a hexafluoropropylene oxide oligomer (Patent Document 1) and a urethane acrylate consisting of a reaction product of a fluorine-containing polyether diol and 2-isocyanatoethyl methacrylate have been proposed (Patent Document 2). However, due to the water- and oil-repellent properties of the fluorine-containing compound, it has low compatibility with photopolymerization initiators, non-fluorinated acrylates, and non-fluorinated organic solvents, and the components and applications that can be blended are limited.

In response to this, a fluorine-containing acrylate compound has been proposed that has a cyclic siloxane structure and a urethane structure and has excellent compatibility with non-fluorine-based solvents (Patent Document 3). However, the anti-soiling film formed from the above-mentioned fluorine-containing acrylate compound is inferior in terms of the ability to allow water and oil droplets to fall off and in terms of the smoothness of the film.

Japanese Patent Application Laid-Open No. 5-194322 Japanese Patent Application Laid-Open No. 11-349651 Japanese Patent No. 4873666

Polymer Essay Collection Vol. 64, No. 4, pp. 181-190 (Apr. 2007)

The present invention has been made in consideration of the above circumstances, and aims to provide an active energy ray-curable resin composition capable of forming a cured coating that has excellent smoothness and water and oil droplets falling off.

As a result of extensive research into achieving the above object, the inventors have discovered that a composition containing the following fluorine-containing siloxane acrylate can form a cured coating that is smooth and allows water and oil droplets to fall off, and have thus completed the present invention.

［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 provides:
1. (A) 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 each X ¹ is independently a group selected from a siloxane chain represented by the following formula (2) and a siloxane chain represented by the following formula (3),

In formula (2) and formula (3), each R ¹ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, each R ² is independently a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, each G is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, and each Q is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the * symbol represents a bonding site with a silicon atom.)
a is an integer from 1 to 5, b is an integer from 0 to 3, a+b is an integer from 3 to 6, c is an integer from 0 to 2, d is an integer from 1 to 3, e is an integer from 0 to 2, and c+d+e is 3. The dashed lines represent bonds. In addition, the order of arrangement of the siloxane units in formula (2) may be arbitrary.}
Each Z ¹ is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the ** mark represents a binding site with the PFPE ^1. )
(B) A fluorine-containing siloxane acrylate represented by the following formula (1′):

[In the formula, ^PFPE2 represents a divalent perfluoropolyether chain having a number average molecular weight of 500 or more and less than 3,500, each ^X2 is independently a group selected from the siloxane chain represented by the above formula (2) and the siloxane chain represented by the above formula (3), and each ^Z2 is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the ** mark represents a binding site with the PFPE ^2. )
(C) a polymerization initiator that generates radicals when exposed to active energy rays; (D) an active energy ray-curable resin composition containing an acrylate not containing a fluorine atom, a urethane acrylate not containing a fluorine atom, or both of these;
2. The active energy ray-curable resin composition according to 1, wherein PFPE ¹ in formula (1) and PFPE ² in formula (1') are perfluoropolyether chains represented by the following formula (5), PFPE ¹ has a number average molecular weight of 3,500 to 6,500, and PFPE ² has a number average molecular weight of 500 to 2,500:

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

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

(In the formula, the dashed line represents a bond, and the * symbol represents a bonding site with a silicon atom.)
5. The active energy ray-curable resin composition according to any one of 1 to 4, wherein in formula (1), X ¹ is each independently a group represented by the above formula (2), and in formula (1'), X ² is each independently a group represented by the above formula (3).
6. The active energy ray-curable resin composition according to any one of 1 to 5, wherein in 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 in formula (3), c=0.
7. The active energy ray-curable resin composition according to any one of 1 to 6, wherein in the formula (2), b = 0, and in the formula (3), e = 0.
8. The active energy ray-curable resin composition according to any one of 1 to 7, wherein the blending ratio of the component (A) to the component (B) is 1/9 to 9/1 in terms of mass ratio.
9. The active energy ray-curable resin composition according to any one of 1 to 8, wherein 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 relative to 100 parts by mass in total of the component (A) and the component (B).
10. The active energy ray-curable resin composition according to any one of 1 to 9, further comprising 10 to 100,000 parts by mass of a solvent (E) relative to a total of 100 parts by mass of the component (A) and the component (B).
11. A cured coating film formed from the active energy ray-curable resin composition according to any one of 1 to 10.
12. The cured coating according to 11, having an average surface roughness of 1 nm or less.
13. A coated article is provided, which has a substrate and a cured coating laminated to at least one surface of the substrate directly or via at least one other layer, the cured coating being the cured coating according to 11 or 12.

The active energy ray-curable resin composition of the present invention can form a cured coating that is smooth and allows water and oil droplets to fall off. Furthermore, it is possible to provide an article having such a cured coating.

（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 The present invention will be specifically described below.
The active energy ray-curable resin composition of the present invention contains the following components (A) to (D).
(A) A fluorine-containing siloxane acrylate represented by the following formula (1):

(B) A fluorine-containing siloxane acrylate represented by the following formula (1′):

(C) a polymerization initiator that generates radicals when exposed to active energy rays; (D) an acrylate not containing fluorine atoms, a urethane acrylate not containing fluorine atoms, or both of these.

[Component (A)]
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, more preferably 3,500 to 6,500. In particular, one having a structure in which perfluoroalkylene groups and oxygen atoms are alternately linked, as represented by the following structural formula (4), is preferred. In the present invention, the number average molecular weight is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).

（式中、破線は、Ｚ¹との結合手を表す。）

(In the formula, the dashed line represents a bond to ^Z1 .)

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

Specific examples of perfluoroalkylene groups 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 dashed line represents a bond to ^Z1 .)

In the divalent perfluoropolyether chain represented by PFPE ¹ , A is more preferably a perfluoromethylene group represented by the above formula (i) or a perfluoroethylene group represented by the above formula (ii), because there are many oxygen atoms that become bending points that exhibit slipperiness and there is no branched structure that inhibits bending motion of the chain.

In particular, the divalent perfluoropolyether chain represented by ^PFPE1 is preferably one represented by the following formula (5), in which an oxydifluoromethylene group and an oxytetrafluoroethylene group coexist, in view of the ease of industrial production.

（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 formula, the dashed line represents a bond to Z, and the sequence of the repeating units in the parentheses with p and q may be any sequence.)

In formula (5), the number of perfluorooxymethylene groups (p) is a number that satisfies p≧1, and the number of perfluorooxyethylene groups (q) is a number that satisfies q≧1.
In 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 preferably 1/10 to 10/1, and more preferably 3/10 to 10/3.

In the above formula (1), ^X1 's are each independently a group selected from a siloxane chain represented by the following formula (2) and a siloxane chain represented by the following formula (3): In the component (A), ^X1 's are each preferably independently a group represented by formula (2), but in consideration of ease of production, it is preferable that the two ^X1 's are the same group.

（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 dashed lines represent bonds. Note that, in formula (2), the siloxane units may be arranged in any order.)

Each 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 specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl; aryl groups such as phenyl, etc. R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group, an ethyl group, or an n-propyl group.

Each R ² independently represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

Each G 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 examples thereof include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, and cyclohexyl. G is preferably an alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 3 carbon atoms, and a methyl group, an ethyl group, and an n-propyl group are particularly preferred.

Each Q is independently a divalent organic group having 1 to 20 carbon atoms that may contain an ether bond and may have a cyclic or branched structure, but in the present invention, the one represented by the following formula is particularly preferred.

（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 dashed line represents a bond, and the * symbol represents a bonding site with a 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。） Each Q is preferably independently a divalent organic group represented by the following structural formula:

(In the formula, the dashed line represents a bond, and the * symbol represents a bonding site with a 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, and 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, and more preferably 0.
c+d+e is 3.

Z ¹ is each independently a group selected from divalent organic groups represented by the following formulas. In consideration of the availability of raw materials and the ease of production, it is preferable that the two Z ¹ are the same 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 dashed line represents a bond, and the ** mark represents a binding site with the 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, ^Z1 is preferably a group represented by the following formula:

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

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

When X ¹ in formula (1) is a group represented by formula (3), the component (A) can be produced, for example, by the following method.
[1] Synthesis of hydrogensiloxane First, a perfluoropolyether having alkoxysilyl groups at both ends, represented by the following formula (8), is co-hydrolytically condensed with a compound having a Si-H bond, represented by the following formula (9a) and/or (9b), to produce a hydrogensiloxane having a perfluoropolyether group, represented by the following formula (10).

In the formula, R ³ and R ⁴ are each independently an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6, and more preferably 1 to 4 carbon atoms, and R ⁵ is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6, and more preferably 1 to 4 carbon atoms. Each w is independently an integer of 0 to 2, and PFPE ¹ and Z ¹ are as defined 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 preferred are methyl, ethyl, n-propyl and n-butyl groups.

In the cohydrolysis, the amount of compound (9a) and/or (9b) to be used relative to compound (8) is preferably such that, in order to prevent crosslinking between compounds (8), 2 equivalents of compound (9a) and/or (9b) in terms of silicon atoms or more are used relative to 1 equivalent of the alkoxy group of compound (8) to perform the cohydrolysis, and then the unreacted compound (9a) and/or (9b) is removed by distillation under reduced pressure. It is preferable to react compound (9a) and/or (9b) in the presence of 2 to 10 equivalents, particularly 2 to 6 equivalents, in terms of silicon atoms, relative to 1 equivalent of the alkoxy group of compound (8). When compound (9a) and compound (9b) are used in combination, the amount (mass ratio) of compound (9a) and compound (9b) added is preferably in the ratio of (9a)/(9b) = 50/1 to 1/50.

In carrying out the cohydrolysis, it is preferred to use a hydrolysis catalyst.
As the hydrolysis catalyst, a conventionally known catalyst can be used, and examples thereof include acids such as hydrochloric acid, nitric acid, sulfuric acid, hydrogen halide, carboxylic acid, and sulfonic acid; acidic or weakly acidic inorganic salts; solid acids such as ion exchange resins; inorganic bases such as ammonia and sodium hydroxide; organic bases such as tributylamine, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU); and organometallic compounds such as organotin compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. These may be used alone or in combination of two or more kinds.

Among these hydrolysis catalysts, particularly preferred are acids such as hydrochloric acid, nitric acid, sulfuric acid and methanesulfonic acid; and organometallic compounds selected from organotin compounds, organotitanium compounds and organoaluminum compounds.
Suitable organometallic compounds include, for example, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate, tetrabutyl titanate, tetranonyl titanate, tetrakisethylene glycol methyl ether titanate, tetrakisethylene glycol ethyl ether titanate, bis(acetylacetonyl)dipropyl titanate, acetylacetonium, aluminum bis(ethylacetoacetate)monon-normal butyrate, aluminum ethylacetoacetate di-normal butyrate, aluminum tris(ethylacetoacetate), and hydrolysates thereof.
In particular, from the viewpoint of reactivity, acids such as hydrochloric acid, nitric acid, and methanesulfonic acid; tetrabutyl titanate, aluminum ethylacetoacetate di-n-butyrate, aluminum bis(ethylacetoacetate) mono-n-butyrate, and hydrolysates thereof are preferred, with methanesulfonic acid being particularly preferred.

The amount of hydrolysis catalyst used is not particularly limited, but is preferably 0.001 to 15 mol %, and particularly preferably 0.001 to 10 mol %, per mole of alkoxy groups on silicon atoms of the compound of formula (8).

The cohydrolysis and 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 the above-mentioned raw material compounds. 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; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, and t-butanol; fluorine-based solvents, and the like. These may be used alone or in combination of two or more.

Examples of fluorine-based solvents include fluorine-containing aromatic hydrocarbons such as 1,3-bis(trifluoromethyl)benzene and trifluorotoluene; perfluorocarbons having 3 to 12 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane _; hydrofluorocarbons such as 1,1,2,2,3,3,4 _- heptafluorocyclopentane _and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane; hydrofluoroethers such as _C3F7OCH3 , C4F9OCH3 _{, C4F9OC2H5 , and C2F5CF(OCH3)C3F7 ; and perfluoroalkylene ethers} such as Fomblin _, Galden ₍ manufactured by Solvay), Demnum (manufactured by Daikin Industries, Ltd.), and Krytox (manufactured _by Chemours).

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

Specific examples of polyfunctional hydrogen siloxanes obtained by the above reaction include those represented by the following formulas, but are not limited to these.

（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, the hydrogensiloxane (10) is subjected to an addition reaction by hydrosilylation with an olefin compound represented by the following formula (11a) and, if necessary, an olefin compound represented by the following formula (11b).

^R6 is an olefin group capable of addition reacting with a Si-H group, and is preferably an alkenyl group having 2 to 8 carbon atoms, such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, isobutenyl, etc. Of these, vinyl and allyl groups are preferred.
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 which contain O at the bond terminal with the oxygen atom to form an -O-O- bond), and may have a cyclic structure or a branched structure.
The divalent organic group for Y may be an alkylene group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, and specific examples 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 dashed line represents a bond, and the dot represents a bonding site with the olefin group ^R6 .)

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

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

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

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

The hydrosilylation reaction proceeds without the use of a solvent, but a solvent may be used if necessary.
The solvent is preferably one that does not inhibit the hydrosilylation reaction, is capable of dissolving the following compound (12a) produced after the reaction, and is capable of dissolving compound (10), compound (11a), and optionally compound (11b) at the intended reaction temperature.
Specifically, for example, aromatic hydrocarbons such as benzene, toluene, and xylene; fluorine-modified aromatic hydrocarbons such as m-xylene hexafluoride and benzotrifluoride; and fluorine-modified ethers such as methyl perfluorobutyl ether and perfluoro(2-butyltetrahydrofuran are preferred, and among these, toluene, xylene, and m-xylene hexafluoride are preferred.

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

In the hydrosilylation reaction, the order of mixing the components is not particularly limited, and examples of the method that can be used include a method of gradually heating a mixture containing compound (10), compound (11a), and optionally compound (11b), and a catalyst from room temperature to the addition reaction temperature; a method of heating a mixture containing compound (10), compound (11a), and optionally compound (11b), and a solvent to the desired reaction temperature and then adding a catalyst; a method of adding compound (10) dropwise to a mixture containing compound (11a), optionally compound (11b), and a catalyst that has been heated to the desired reaction temperature; and a method of adding a mixture containing compound (11a), optionally compound (11b), and a catalyst that has been heated to the desired reaction temperature.
Among these, a method of heating a mixture containing compound (10), compound (11a), and optionally compound (11b) and a solvent to a desired reaction temperature, followed by adding a catalyst, or a method of dropping a mixture containing compound (11a), and optionally compound (11b), and a catalyst to compound (10) that has been heated to a desired reaction temperature, is particularly preferred. These methods can be used by diluting each component or the mixture with a solvent as necessary.

When compounds (11a) and (11b) are added to compound (10), it is preferable to carry out the addition reaction of compound (10) with compound (11b), and then carry out the addition reaction using an excess amount of compound (11a), and remove and purify the unreacted compound (11a). In this case, compounds (11a) and (11b) in which R ⁶ , Y, R ⁷ and A' are different from each other may be mixed and used.
The addition reaction is usually carried out at 20 to 120° C. for 30 to 300 minutes, preferably at 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), each X ⁰ is independently the following group.

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

[3] Deprotection Reaction Next, all of the silyl groups are deprotected to convert them to hydrogen atoms, and a reaction site is formed with an acid chloride compound containing a (meth)acrylic group to be reacted next. In the present invention, the (meth)acrylic group refers to an acrylic group or a methacrylic group.

The deprotection conditions may be those that are publicly known in the art and are not particularly limited. Examples of the deprotection conditions include a method using fluoride ions, a method using an acid (Bronsted acid, Lewis acid), a method using a base (Bronsted base, Lewis base), a method using an excess of alcohol under neutral conditions, and a method using N-bromosuccinimide, diisobutylaluminum hydride, a palladium complex, or the like.
Among these, the method using an acid (Bronsted acid, Lewis acid) and the method using an excess alcohol under neutral conditions are preferred, and the method using an excess alcohol under neutral conditions is particularly preferred. In this case, the alcohol to be used is preferably methanol, ethanol, propanol, butanol, pentanol, or the like, and more preferably methanol or ethanol.
The amount of alcohol added is preferably 1 to 50 equivalents per equivalent of the silyl group of A'. The reaction conditions are usually preferably 50 to 100° C. and 60 to 1,440 minutes.

[4] Esterification Reaction All of the hydroxy groups contained in compound (12b) obtained by deprotecting the silyl groups in the above formula (12a), or all of the hydrosilyl groups in the compound (12a) where A' is a hydrogen atom (compound (12c)), are reacted with (meth)acrylic acid chloride represented by the following formula (13) to form ester bonds, thereby obtaining a fluorine-containing siloxane acrylate represented by formula (3).

（式中、Ｒ²は上記のとおりである。）

(In the formula, ^R2 is as defined above.)

The reaction of compound (12b) or (12c) with compound (13) proceeds by mixing the two in the presence of a base at 0 to 100° C., preferably 0 to 80° C., for 30 to 180 minutes in order to neutralize the by-produced hydrochloric acid.
The type of base is not particularly limited, and examples thereof include amine compounds such as ammonia, trimethylamine, triethylamine, diisopropylamine, tripropylamine, N,N-diisopropylethylamine, tributylamine, pyridine, N,N-dimethylaminopyridine, 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU); inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, lithium hydroxide, and potassium hydroxide; aqueous solutions of these bases, etc. These bases are not limited to one type, and may be used as a mixture of two or more types.
Among these, triethylamine, pyridine, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, and potassium hydroxide are preferred, and triethylamine is particularly preferred.

The amount of compound (13) to be added to compound (12c) or (12b) is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, and particularly preferably 1 to 3 equivalents, relative to the hydroxyl groups of compound (12c) or (12b).
The amount of base to be added to compound (13) is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, and particularly preferably 1 to 3 equivalents, relative to the hydrochloric acid generated from compound (13).

In the above esterification reaction, the order of mixing each component is not particularly limited, but for example, a method of gradually heating a mixture containing compound (12b) or (12c), compound (13), and a base from room temperature to the esterification reaction temperature, a method of heating a mixture containing compound (12b) or (12c) and compound (13) to the desired reaction temperature and then adding a base, a method of heating a mixture containing compound (12b) or (12c) and a base to the desired reaction temperature and then adding compound (13), a method of heating a mixture containing compound (13) and a base to the desired reaction temperature and then adding compound (12b) or (12c), a method of heating compound (13) to the desired temperature and then dropping a mixture containing compound (12b) or (12c) and a base, etc. can be taken. Among these, a method of heating a mixture containing compound (12b) or (12c) and a base to the desired reaction temperature and then dropping compound (13) can be taken. Among these, a method of heating a mixture containing compound (12b) or (12c) and a base to the desired reaction temperature and then dropping compound (13) can be taken.

In these methods, a solvent can be used as necessary.
The solvent can be any solvent that does not react with hydroxyl groups and acid chlorides, and specific examples of the solvent that can be used include aromatic hydrocarbons (benzene, toluene, xylene); fluorine-modified aromatic hydrocarbons (m-xylene hexafluoride, benzotrifluoride, etc.); fluorine-modified ethers (methyl perfluorobutyl ether, perfluoro(2-butyltetrahydrofuran), etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.); ethers (tetrahydrofuran, diethyl ether, diisopropyl ether, dibutyl ether, etc.), and the like.
Of these, acetone, methyl ethyl ketone, methyl isobutyl ketone, and m-xylene hexafluoride are preferred.

[Component (B)]
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 perfluoroalkylene groups and oxygen atoms are alternately linked as represented by the above structural formula (4). Specific examples and preferred examples of A in formula (4) are the same as those explained for component (A).
As ^PFPE2 , the one represented by the above formula (5) is particularly preferable, and p and q in formula (5) are the same as those explained for the component (A).

In formula (1'), ^X2 's are each independently a group selected from the siloxane chain represented by formula (2) above and the siloxane chain represented by formula (3) above. ^R1 , ^R2 , Q, G, and a to e in the siloxane chain represented by formula (2) above and formula (3) above include the same groups as those exemplified as ^X1 in component (A) above.
In the component (B), X ² is preferably each independently a group represented by formula (3). Taking into consideration ease of production, it is preferable that the two X ^{2 '} s 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。） ^Each Z2 is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the ** mark represents a bonding site with the ^PFPE2 .)

（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。） Among these, groups represented by the following formula are preferred.

(In the formula, the dashed line represents a bond, and the ** mark represents a bonding site with the ^PFPE2 .)

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

The components (A) and (B) are mixed so that their total amount is 100 parts by mass.
The mixing ratio of the components (A) and (B) is preferably from 1/9 to 9/1, and more preferably from 2/8 to 8/2, by mass ratio.

[Component (C)]
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 benzophenones and thioxanthones. Specific examples thereof include benzophenone, benzil, Michler's ketone, thioxanthone derivatives, benzoin ethyl ether, diethoxyacetophenone, benzil dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, acylphosphine oxide derivatives, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzoyldiphenylphosphine. These may be used alone or in combination of two or more.

The polymerization initiator may be a commercially available product. Examples of commercially available products include 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, and Omnirad TPO H (all manufactured by IGM Resins B.V.).

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

[Component (D)]
Component (D) is at least one selected from the group consisting of fluorine-free acrylates and fluorine-free urethane acrylates. Component (D) is an important component for adjusting the crosslink density during curing and the hardness of the resulting cured coating.

Examples of acrylates that do not contain fluorine atoms 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, 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)acryl These include di- to hexafunctional (meth)acrylate compounds such as acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol hexa(meth)acrylate; ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, and urethane modified versions of these (meth)acrylate compounds; epoxy acrylates obtained by adding acrylic acid to epoxy resins; and copolymers in which a (meth)acryloyl group has been introduced into the side chain of an acrylic acid ester copolymer.

Examples of urethane acrylates that do not contain fluorine atoms include those obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyester of polyisocyanate and a terminal diol with a (meth)acrylate having a hydroxyl group, and those obtained by reacting a polyisocyanate obtained by reacting a polyol with an excess of diisocyanate with a (meth)acrylate having a hydroxyl group. Among these, those containing urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate are preferred.

As component (D), a coating composition containing such an acrylate or urethane acrylate may be used. Such compositions may be commercially available products, such as "Beam Set" (manufactured by Arakawa Chemical Industries Co., Ltd.), "Ubic" (manufactured by Ohashi Chemical Industries Co., Ltd.), "UV Coat" (manufactured by Origin Electric Co., Ltd.), "Cashew UV" (manufactured by Cashew Co., Ltd.), "Desolite" (manufactured by JSR Corporation), "Seika Beam" (manufactured by Dainichi Seika Chemical Industry Co., Ltd.), "Shikou" (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), "Fujihard" (manufactured by Fujikura Chemical Industries Co., Ltd.), "Dia Beam" (manufactured by Mitsubishi Rayon Co., Ltd.), and "Ultravine" (manufactured by Musashi Paint Co., Ltd.).

The amount of component (D) blended is preferably 5 to 300 parts by mass, more preferably 5 to 200 parts by mass, and even more preferably 5 to 100 parts by mass, per 100 parts by mass of the total amount of components (A) and (B). Within this range, the hardness can be improved without impairing the rolling off properties of water droplets and oil droplets of the coating or the smoothness of the film. When a composition is used, the blending amount is that of an acrylate or urethane acrylate.

[Component (E)]
The active energy ray curable resin composition of the present invention may further contain a solvent as component (E). This component appropriately lowers the viscosity of the composition and contributes to improving the workability of coating. The solvent is not particularly limited as long as it dissolves or disperses the components (A), (B), and (C) that constitute the active energy ray curable resin composition of the present invention.
Specific examples of such compounds 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; alcohols such as methanol, ethanol, isopropanol, butanol, isobutanol, and t-butanol; fluorine-containing aromatic hydrocarbons such as 1,3-bis(trifluoromethyl)benzene and trifluorotoluene; perfluorocarbons having 3 to 12 carbon atoms such as perfluorohexane and perfluoromethylcyclohexane; hydrofluorocarbons such as 1,1,2,2,3,3,4-heptafluorocyclopentane and 1,1,1,2,2,3,3,4,4,5,5,6,6-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 F Fluorine-based solvents such as hydrofluoroethers such as _Fomblin , Galden (manufactured by Solvay), Demnum (manufactured by Daikin Industries, Ltd.), and Krytox (manufactured by Chemours) are examples of the fluorine-based solvents.
When a solvent is used, the amount thereof is preferably 10 to 100,000 parts by mass, more preferably 10 to 10,000 parts by mass, and even more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the combined amount of components (A) and (B).

In addition, any additives can be added to the active energy ray curable resin composition of the present invention as long as they do not inhibit the effects of the present invention. Specific examples of additives 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, adhesion imparting agents such as silane coupling agents, anti-aging agents, rust inhibitors, colorants, surfactants, rheology adjusters, ultraviolet absorbers, infrared absorbers, fluorescent agents, abrasives, fragrances, fillers, fillers, dyes and pigments, leveling agents, reactive diluents, non-reactive polymer resins, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, dispersants, antistatic agents, thixotropy imparting agents, etc. In particular, when using the present invention as an anti-reflective film, there is no problem in adding reactive hollow silica fine particles, non-reactive hollow fine particles, or both of these to lower the refractive index.

The active energy ray-curable resin composition of the present invention can be obtained by uniformly mixing the above components in a conventional manner.

The cured coating obtained from the active energy ray curable resin composition of the present invention can achieve both excellent water and oil drop falling properties and smoothness, and is useful for imparting antifouling properties, water repellency, oil repellency, fingerprint resistance, and smoothness to the surface of a substrate. Furthermore, since the coating formed from this composition contains a fluorine-containing siloxane acrylate, it is expected to have excellent low reflectivity. Due to these characteristics, it is difficult to get dirty with fingerprints, sebum, sweat, and other human oils, cosmetics, etc., and even if dirt does adhere, it provides a coating that is easy to wipe off and suppresses light reflection. For this reason, the active energy ray curable resin composition of the present invention is useful as a coating agent for forming a paint film or protective film applied to the surface of an article that may be touched by the human body and be soiled by human oils, cosmetics, etc.

Examples of articles that can be subjected to such coating treatment include optical recording media such as magneto-optical disks, optical disks such as CDs, LDs, DVDs, and Blu-ray disks, and holographic recording media; optical components and devices such as eyeglass lenses, prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers, and optical couplers; various screen display devices such as CRTs, liquid crystal displays, plasma displays, electroluminescent displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, and toner-based displays; in particular, navigation devices for PCs, mobile phones, personal digital assistants, game machines, digital cameras, digital video cameras, automatic cash withdrawal and deposit machines, automatic cash dispensers, vending machines, and automobiles. Examples of such materials include image display devices such as security system terminals and touch panel (touch sensor, touch screen) type image display input devices that also operate these devices; input devices such as panel switches for in-vehicle devices, such as mobile phones, mobile information terminals, portable music players, portable game consoles, remote controllers, controllers, keyboards, etc.; housing surfaces of mobile phones, mobile information terminals, cameras, portable music players, portable game consoles, etc.; surfaces of automobile exteriors, pianos, luxury furniture, marble, etc.; transparent glass or transparent plastic (acrylic, polycarbonate, etc.) parts such as protective glass for displaying art, show windows, showcases, advertising covers, photo stand covers, wristwatches, automobile windshields, window glass for trains and aircraft, automobile headlights, taillights, etc.; and various mirror parts.

The active energy ray-curable resin composition of the present invention can be applied to at least one surface of these substrates directly or via at least one other layer, and then cured to obtain a coated article having a coating.

The substrate to which the active energy ray-curable resin composition of the present invention is applied may be a substrate whose surface has been treated with a chemical conversion treatment, a corona discharge treatment, a plasma treatment, or an acid or alkaline solution, or a decorative plywood in which the substrate body and the surface layer are coated with different types of paint.

Furthermore, the coating agent of the present invention may be applied to the surface of a substrate on which other functional layers have already been formed. Examples of other functional layers include a primer layer, an anti-rust layer, a gas barrier layer, a waterproof layer, a heat shielding layer, etc., and one or more of these layers may be formed on the substrate in advance.

The coated article may be further coated on the surface on which the coating film made of the composition of the present invention is formed with one or more layers such as a deposition layer formed by a CVD (chemical vapor deposition) method, a hard coat layer, an anti-rust layer, a gas barrier layer, a waterproof layer, a heat shielding layer, an anti-fouling layer, a photocatalyst layer, an antistatic layer, etc.

Furthermore, the surface of the coated article opposite to the surface on which the coating film made of the composition of the present invention is formed may be coated with one or more layers such as a hard coat layer, an anti-rust layer, a gas barrier layer, a waterproof layer, a heat ray shielding layer, an antifouling layer, a photocatalyst layer, an antistatic layer, etc.

The active energy ray-curable resin composition of the present invention can also be used as an anti-reflective coating composition. In this case, the amount of the fluorine-containing siloxane acrylate is preferably 5 to 100 parts by mass, and more preferably 5 to 50 parts by mass, as the total amount of components (A) and (B) per 100 parts by mass of the active components of the coating composition. Within this range, it is possible to obtain an anti-reflective film that has good water and oil drop falling properties and film smoothness while maintaining the strength of the film.

Furthermore, by adding the active energy ray-curable resin composition of the present invention to an ultraviolet-curable resist liquid and exposing it to light, it is possible to create a large difference in the liquid repellency of the cured resist surface and the area where the resist has been removed, and it is possible to prevent developer or liquid crystal solution from remaining on the resist resin surface and causing contamination.

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

The light source for curing the active energy ray-curable resin composition is usually a light source containing light having a wavelength in the range of 200 to 450 nm, such as a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, etc. The irradiation amount is not particularly limited, but is preferably 10 to 5,000 mJ/ ^cm2 , more preferably 20 to 2,000 mJ/ ^cm2 . The curing time is usually 0.5 seconds to 2 minutes, and preferably 1 second to 1 minute.

Taking transparency into consideration, the thickness of the cured coating 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.
The surface roughness of the cured coating 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 below.

The present invention will be specifically described below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.
In the following examples, ¹ H-NMR measurements were carried out using an ULTRA SHIELD 400 Plus (manufactured by Bruker Corporation), where 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 compounds [Synthesis Example 1-1]
According to Example 1 of JP2010-285501A, 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 the repeating units in the parentheses with p1 and q1 is indefinite, and the number average molecular weight of the perfluoropolyether chain is 4,000.)

[Synthesis Example 1-2]
In a dry nitrogen atmosphere, 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 were added to a 5,000 mL three-neck flask equipped with a reflux device and a stirrer, and the mixture was cooled to 5° C. while 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. Thereafter, 100 g of hydrotalcite (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and stirring was continued for 2 hours while maintaining the internal temperature at 0 to 10° C., and the solvent and excess tetramethyldisiloxane were distilled off under reduced pressure, and the hydrotalcite was filtered to obtain 1,130 g of a colorless, 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 arrangement of the repeating units in the 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, 190 g of compound (15) was mixed with 117 g of allyloxytrimethylsilane, 229 g of toluene, and 4.3 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 8.3×10 ⁻⁵ mol of Pt alone), and the mixture was stirred for 2 hours at 80° C. After confirming the disappearance of signals derived from Si—H groups by ¹ H-NMR and FT-IR measurements, the solvent and excess allyloxytrimethylsilane were distilled off under reduced pressure, the mixture was treated with activated carbon, and then filtered, yielding 230 g of a pale yellow, transparent liquid represented by the following formula (16).

（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 arrangement of the repeating units in the parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain is 1,500.)

In 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. The by-product trimethylmethoxysilane was then distilled off under normal pressure, and the excess methanol and trimethylsilane were then 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 arrangement of the repeating units in the parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain is 1,500.)

In 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. while stirring. A mixture of 25 g of acrylic acid chloride diluted with 50 g of toluene was added dropwise 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. 5.6 g of hydrotalcite (Kyoward 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) and 5.6 g of aluminum silicate (Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.) were added to the filtrate obtained by filtering off the precipitated salt, and the mixture was stirred for 2 hours, and then distilled off under reduced pressure, and the hydrotalcite and aluminum silicate were filtered off to obtain 56 g of a pale yellow transparent liquid.
The resulting product was confirmed by ¹ H-NMR measurement to be a fluorine-containing siloxane acrylate represented by the following formula (7). The chemical shifts of the ¹ H-NMR spectrum are shown in Table 1.

（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 arrangement of the repeating units in the 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]
The components listed below were mixed in the mass ratios shown in Tables 2 and 3 to prepare active energy ray-curable resin compositions.
Each of the obtained compositions was spin-coated onto a polycarbonate plate, and then irradiated with ultraviolet light at 1,200 mJ/cm ² in a nitrogen atmosphere using a conveyor-type ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd.) to form a cured coating.
The water sliding angle and the hexadecane sliding angle were measured using a contact angle meter (Kyowa Interface Science Co., Ltd.) The surface roughness was measured using a scanning probe microscope (instrument name: SI-DF3, 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。） [Component (A)]
The 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 the repeating units in the 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。） [Component (B)]
The 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 arrangement of the repeating units in the parentheses with p2 and q2 is indefinite, and the number average molecular weight of the perfluoropolyether chain is 1,500.)

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

As shown in Examples 1 to 9, the cured coating film obtained from the active energy ray-curable resin composition of the present invention can achieve both excellent water droplet and oil droplet rolling off properties and smoothness, and is useful as an antifouling film that imparts antifouling properties to a substrate, a coating agent that forms an antireflection film, and the like.
On the other hand, the cured coating obtained from the composition not containing component (B) (Comparative Example 1) has excellent water and hexadecane sliding angles but large surface roughness, while the cured coating obtained from the composition not containing component (A) has a smooth surface but is poor in water and hexadecane sliding properties (Comparative Example 2).

Claims (7)

(A) 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 6,500 and represented by the following formula (5) , and X ¹ represents a siloxane chain represented by the following formula (2),

In formula (2) , each R ¹ is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, each R ² is independently a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group , and each Q is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the * symbol represents a bonding site with a silicon atom.)
a is an integer of 1 to 5, b is 0 , and the dashed line represents a bond. In formula (2), the siloxane units may be arranged in any order.
In formula (5), the dashed line represents a bond, the arrangement of the repeating units in the parentheses with p and q may be arbitrary, p is a number of p≧1, q is a number of q≧1, and p/q is a number of 1/10 to 10/1.
Each Z ¹ is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the ** mark represents a binding site with the PFPE ^1. )
(B) A fluorine-containing siloxane acrylate represented by the following formula (1′):

[In the formula, ^PFPE2 represents a divalent perfluoropolyether chain having a number average molecular weight of 500 to 2,500 and represented by the following formula (5) , and ^X2 represents a siloxane chain represented by the following formula (3),

(In formula (3), R ¹ , R ² and Q are as defined above, each G is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms, c is an integer from 0 to 2, d is an integer from 1 to 3, e is 0, and c+d+e is 3. The dashed lines represent bonds.
In formula (5), the dashed line represents a bond, p and q have the same meanings as above, and the arrangement of the repeating units in the parentheses to which p and q are attached may be arbitrary.
^Each Z2 is independently a divalent organic group represented by the following formula:

(In the formula, the dashed line represents a bond, and the ** mark represents a binding site with the PFPE ^2. )
(C) A polymerization initiator that generates radicals when exposed to active energy rays (D) A di- to hexa-functional (meth) acrylate that does not contain fluorine atoms
(E) Solvent
The active energy ray-curable resin composition comprises the active energy ray-curable resin composition comprising: a compounding ratio of the (A) component to the (B) component of 1/9 to 9/1 in terms of mass ratio; and an amount of each of the components, relative to 100 parts by mass of the total of the (A) component and the (B) component, of 0.01 to 10 parts by mass of the (C) component, 5 to 300 parts by mass of the (D) component, and 50 to 1,000 parts by mass of the (E) component . The active energy ray-curable resin composition according to claim 1 , wherein in formula (2), a is an integer of 2 to 4 , and in formula (3), c=0. The active energy ray-curable resin composition according to claim 1 or 2, wherein the component (D) is selected from the group consisting of 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate and sorbitol hexa(meth)acrylate. 4. The active energy ray-curable resin composition according to claim 1, wherein the component (E) is selected from the group consisting of hydrocarbons, ketones, esters and alcohols. A cured coating formed from the active energy ray-curable resin composition according to any one of claims 1 to 4 . The cured coating according to claim 5 , having an average surface roughness of 1 nm or less. A coated article comprising a substrate and a cured coating laminated to at least one surface of the substrate directly or via at least one other layer, the cured coating being the cured coating according to claim 5 or 6 .