JP2008040262A - Curable composition for antireflection coating formation - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a low-refractive-index layer excellent in chemical resistance, antifouling property, abrasion resistance and surface lubricity, and to provide an antireflection coating having the layer and a practical antireflection film of a three-layer structure excellent in antifouling property as well as in visibility. <P>SOLUTION: A curable composition is provided comprising (A) a curable fluorine-containing polymer, (B) a fluorine-containing surface modifier and (C) hollow silica fine particles, wherein the component (A) comprises a structural unit having a fluoroalkyl group having an ethylenic carbon-carbon double bond at an end and the component (B) is a fluorine-containing compound having CH<SP>2</SP>=CX<SP>1</SP>COO- (X<SP>1</SP>is H, Cl, F, CF<SB>3</SB>or a 1-10C alkyl group) and optionally having a perfluoro-polyether unit. An antireflection coating formed using the curable composition and an antireflection film are obtained. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition for forming an antireflection film having a low refractive index and excellent antifouling property, and an antireflection film and an antireflection film produced from the composition.

  With the recent development of multimedia, it has become increasingly important for various display devices to improve their visibility (because they are less visible when viewed from an angle; hereinafter referred to as “visibility”). Also, large display devices such as televisions are required to be easier to see, and this improvement in visibility is a technical issue.

  As a method for improving the visibility, there is a method of attaching an antireflection film having an antireflection film. Such an antireflection film is usually produced by providing a hard coat layer on a transparent substrate film and providing a low refractive index layer thereon.

  As one of methods for lowering the refractive index of the low refractive index layer, there is a method of blending hollow silica fine particles and providing a fine space in the low refractive index layer. However, when hollow silica fine particles are blended, the chemical resistance is lowered and dirt is likely to adhere.

  By the way, the improvement in visibility of the antireflection film is the biggest problem. Therefore, if the surface becomes dirty, there is a problem in practical use even if the problem of antireflection (prevention of reflection) can be solved.

  In order to improve the antifouling property of the antireflection film, it has been proposed to provide an antifouling layer on the outermost layer (Patent Document 1).

  The antireflection film of Patent Document 1 includes a hard coating layer, a low refractive index layer composed of an organosilicon compound or a polymer thereof and hollow silica fine particles, and an antifouling layer composed of a fluorine-containing silane compound on at least one surface of a transparent plastic film substrate. The film has a four-layer structure in which are sequentially laminated.

  However, this four-layer antireflection film, in addition to the workability and productivity decline due to the addition of one layer, it is necessary to fully consider the adhesion between the low refractive index layer and the antifouling layer, The selection of materials is limited.

  An antireflection film having a three-layer structure in which an antifouling component is blended in a low refractive index layer has also been proposed (Patent Document 2).

  In the antireflection film of Patent Document 2, a hard coat layer provided on a transparent substrate has a composition comprising either an organosilicon compound or a polymer thereof and a perfluoropolyether group-containing silicon compound or a polymer thereof. An antifouling low refractive index layer is formed by applying a copolymer with any of the compositions and a low refractive index coating agent containing hollow silica fine particles.

  However, the antireflection film described in Patent Document 2 is inferior in resistance to chemicals such as sodium hydroxide and sodium hypochlorite contained in cleaning articles used in daily life, and the antireflection film peels off. The problem remains.

JP 2002-277604 A JP 2002-265866 A

  The present invention solves the problem of peeling off the antireflection film by chemicals in Patent Document 2, and further provides an antireflection film capable of imparting a characteristic that low reflectance can be achieved while maintaining antifouling properties, and such antireflection It aims at providing the curable composition which can form a film | membrane, and the antireflection film which has this antireflection film.

That is, the present invention
(A) A curable composition containing a curable fluorine-containing polymer, (B) a fluorine-containing surface modifier, and (C) hollow silica fine particles, wherein the component (A) is represented by the formula (1):
-(M)-(A)-(1)

（式中、Ｘ^aおよびＸ^bは同じかまたは異なり、ＨまたはＦ；Ｘ^cはＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ^dおよびＸ^eは同じかまたは異なり、Ｈ、ＦまたはＣＦ₃；Ｒｆは炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ（Ｙは末端にエチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基）が１〜３個結合している有機基；ｍ１は０〜３の整数；ｍ２およびｍ３は同じかまたは異なり、０または１）で示される含フッ素エチレン性単量体に由来する構造単位；
構造単位Ａは、構造単位Ｍを与える含フッ素エチレン性単量体と共重合可能な単量体に由来する構造単位である］で示され、構造単位Ｍを０．１〜１００モル％および構造単位Ａを０〜９９．９モル％含む数平均分子量５００〜１００００００の含フッ素ポリマーを１００モル％まで含む硬化性含フッ素ポリマーであり、 [Wherein, the structural unit M represents the formula (M):

Wherein X ^a and X ^b are the same or different and H or F; X ^c is H, F, CH ₃ or CF ₃ ; X ^d and X ^e are the same or different and H, F or CF ₃ ; Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms; Y (Y is a carbon atom having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal); An organic group in which 1 to 3 monovalent organic groups are bonded; m1 is an integer of 0 to 3; and m2 and m3 are the same or different, and the fluorine-containing ethylenic monomer represented by 0 or 1) Derived structural unit;
The structural unit A is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer that gives the structural unit M]. A curable fluorinated polymer containing up to 100 mol% of a fluorinated polymer having a number average molecular weight of 500 to 1,000,000 containing 0 to 99.9 mol% of unit A;

（式中、Ｘ¹はＨ、Ｃｌ、Ｆ、ＣＦ₃または炭素数１〜１０のアルキル基；Ｒ¹はケイ素原子を有しないが、環構造、ヘテロ原子および／または官能基は有していてもよい（ｎ１＋ｎ４）価の有機基；Ｒｆ¹はパーフルオロポリエーテル基；Ｒ²はアルキル基、フルオロアルキル基、またはＣＨ₂＝ＣＸ²ＣＯＯ−（Ｘ²はＨ、Ｃｌ、Ｆ、ＣＦ₃または炭素数１〜１０のアルキル基）；ｎ１は１〜３の整数；ｎ２は０または１；ｎ３は０〜５０；ｎ４は１〜３の整数）で示され、かつフッ素原子を含む数平均分子量が１００〜６０００の含フッ素化合物である反射防止膜形成用の硬化性組成物に関する。 The component (B) is represented by the formula (2):

(Wherein X ¹ is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms; R ¹ does not have a silicon atom, but has a ring structure, a hetero atom and / or a functional group. which may (n1 + n4) valent organic group; Rf ¹ is a perfluoropolyether group; R ² is an alkyl group, fluoroalkyl group or ^{_{CH 2 = CX 2 COO- (X}} 2, is H, Cl, F, CF ₃ or N1 is an integer of 1 to 3; n2 is 0 or 1; n3 is 0 to 50; n4 is an integer of 1 to 3) and contains a fluorine atom. Relates to a curable composition for forming an antireflection film, which is a fluorine-containing compound having a molecular weight of 100 to 6000.

  Such a curable composition is further active as a curing agent containing two or more α, β-unsaturated ester groups as the component (D) (but different from the component (B)) and / or as the component (E). An energy ray curing initiator may be included.

  The present invention is also a cured coating of these curable compositions, wherein the cured coating has a thickness of 0.03 to 0.5 μm, further a hard coat layer on the transparent substrate film, Next, the present invention also relates to an antireflection film in which a cured film of the curable composition is directly formed without any other layer.

  According to the curable composition of the present invention, a low refractive index layer excellent in chemical resistance, antifouling property, scratch resistance, surface lubricity and the like can be formed, and an antireflection film having this layer and The antireflection film having a three-layer structure can provide a practical antireflection film having excellent visibility and antifouling properties.

  The curable composition for forming an antireflection film of the present invention comprises (A) a curable fluorine-containing polymer, (B) a fluorine-containing surface modifier, and (C) hollow silica fine particles. Hereinafter, each component will be described.

(A) Curable fluorine-containing polymer:
The curable fluorine-containing polymer (A) is a curable fluorine-containing polymer represented by the formula (1) in WO 02/18457 pamphlet.

That is, Formula (1):
-(M)-(A)-(1)

（式中、Ｘ^aおよびＸ^bは同じかまたは異なり、ＨまたはＦ；Ｘ^cはＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ^dおよびＸ^eは同じかまたは異なり、Ｈ、ＦまたはＣＦ₃；Ｒｆは炭素数１〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基にＹ（Ｙは末端にエチレン性炭素−炭素二重結合を有する炭素数２〜１０の１価の有機基）が１〜３個結合している有機基；ｍ１は０〜３の整数；ｍ２およびｍ３は同じかまたは異なり、０または１）で示される含フッ素エチレン性単量体に由来する構造単位；
構造単位Ａは、構造単位Ｍを与える含フッ素エチレン性単量体と共重合可能な単量体に由来する構造単位である］で示され、構造単位Ｍを０．１〜１００モル％および構造単位Ａを０〜９９．９モル％含む数平均分子量５００〜１００００００の含フッ素ポリマーを１００モル％まで含む硬化性含フッ素ポリマーである。 [Wherein, the structural unit M represents the formula (M):

Wherein X ^a and X ^b are the same or different and H or F; X ^c is H, F, CH ₃ or CF ₃ ; X ^d and X ^e are the same or different and H, F or CF ₃ ; Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms; Y (Y is a carbon atom having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal); An organic group in which 1 to 3 monovalent organic groups are bonded; m1 is an integer of 0 to 3; and m2 and m3 are the same or different, and the fluorine-containing ethylenic monomer represented by 0 or 1) Derived structural unit;
The structural unit A is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer that gives the structural unit M]. It is a curable fluorinated polymer containing 0 to 99.9 mol% of unit A and up to 100 mol% of a fluorinated polymer having a number average molecular weight of 500 to 1,000,000.

Structural formula M is represented by formula (m):
^{CX a X b = CX c -} (CX d X e) m1 - (C = O) m2 - (O) m3 -Rf (m)
(Wherein, X ^a , X ^b , X ^c , X ^d , X ^e , Rf, m1, m2 and m3 are the same as those in formula (M)), and are structural units derived from the fluorine-containing ethylenic monomer is there.

  That is, a homopolymer of a fluorine-containing ethylenic monomer having an ethylenic carbon-carbon double bond curable by reaction in the above side chain, or a copolymer having the fluorine-containing ethylenic monomer as an essential component It is a coalescence.

  At least one of Y is preferably bonded to the end of Rf. Note that Y used in the following structural formulas is Y defined by formula (M) unless otherwise specified.

（式中、Ｘ^a、Ｘ^b、Ｘ^c、Ｘ^d、Ｘ^e、Ｒ^f、ｍ１およびｍ３は式（Ｍ）と同じ）で示される構造単位である。 In the curable fluorinated polymer of the formula (1) of the present invention, the structural unit M is preferably M1, and M1 is represented by the formula (M1):

(Wherein, X ^a , X ^b , X ^c , X ^d , X ^e , R ^f , m1 and m3 are the same as those in formula (M)).

The structural unit M1 is represented by the formula (m1):
^{CX a X b = CX c -} (CX d X e) m1 - (O) m3 -Rf (m1)
(Wherein, X ^a , X ^b , X ^c , X ^d , X ^e , Rf, m1 and m3 are the same as those in the formula (M)).

  The polymer containing the structural unit M1 has a particularly low refractive index, and is particularly preferable because the refractive index can be lowered even in a homopolymer of M1 or a polymer having an increased M1.

（式中、Ｒｆは式（Ｍ）と同じ）で示される構造単位である。 A more preferred specific example of M1 is the structural unit M2, and the structural unit M2 is represented by the formula (M2):

(Wherein Rf is the same as formula (M)).

The structural unit M2 has the formula (m2):
_{CH 2 = CF-CF 2 -O} -Rf (m2)
(Wherein Rf is the same as the formula (M)) and is a structural unit derived from a fluorine-containing ethylenic monomer.

  That is, the above M2 is a fluorine-containing allyl ether structural unit having an ethylenic carbon-carbon double bond at the end, and not only has a low refractive index, but also has good polymerizability, particularly homopolymerization, fluorine-containing. This is preferable because of good copolymerizability with an ethylene monomer.

（式中、Ｒｆは式（Ｍ）と同じ）で示される構造単位である。 Another preferred specific example of M1 is the structural unit M3, and the structural unit M3 is represented by the formula (M3):

(Wherein Rf is the same as formula (M)).

The structural unit M3 has the formula (m3):
_{CF 2 = CF-O-Rf} (m3)
(Wherein Rf is the same as the formula (M)) and is a structural unit derived from a fluorine-containing ethylenic monomer.

  M3 is a structural unit of a fluorinated vinyl ether having an ethylenic carbon-carbon double bond at its end, which is preferable in that the refractive index can be lowered and the copolymerization with a fluorinated ethylene monomer is good. .

  In the curable fluorine-containing polymer of the formula (1) of the present invention, Y contained in the structural units M, M1, M2 and M3 is an organic group having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal. .

  That is, the carbon-carbon double bond in Y has the ability to cause a polycondensation reaction, a cyclization reaction, an addition reaction, and the like, and a cured (crosslinked) product can be obtained. Specifically, for example, a polymerization reaction or a condensation reaction is performed between the curable fluorine-containing polymer molecules of the present invention by contact with radicals or cations, or between the curable fluorine-containing polymer and a curing (crosslinking) agent added as necessary. A cured (crosslinked) product can be obtained.

（式中、Ｙ¹は末端にエチレン性炭素−炭素二重結合を有する炭素数２〜５のアルケニル基、または含フッ素アルケニル基、ｍ４およびｍ５は同じかまたは異なり０または１）であり、Ｙ¹の好ましくは
−ＣＸ^f＝ＣＸ^gＸ^h
（式中、Ｘ^fはＨ、Ｆ、ＣＨ₃またはＣＦ₃；Ｘ^gおよびＸ^hはＨまたはＦ）であり、ラジカルやカチオンの接触による硬化反応性が高く好ましいものである。 In the curable fluorine-containing polymer of the formula (1) of the present invention, Y is preferably

Wherein Y ¹ is an alkenyl group having 2 to 5 carbon atoms having an ethylenic carbon-carbon double bond at the terminal, or a fluorine-containing alkenyl group, and m4 and m5 are the same or different, and are 0 or 1, ¹ is preferably -CX ^f = CX ^g X ^h
(Wherein the X ^f H, ^F, CH ₃ or CF _3; is X ^g and X ^h H or F) is, those preferred for high curing reactivity by contact with a radical or a cation.

などがあげられる。 As a preferred specific example of Y ¹ ,

Etc.

Y is more preferably
^{-O (C = O) CX f} = CX g X h
(Wherein, X ^f, X ^g and X ^h is as defined above) Y ² represented by and the like, particularly preferably at a higher point curing reactivity by contact with radical, easily cured product such as a light-curing It is preferable in that it can be obtained.

などがあげられる。 As a more preferable specific example of Y ² ,

Etc.

があげられる。 As other Y,

Is given.

Among these, those having a structure of —O (C═O) CF═CH ₂ are preferable in that the refractive index can be lowered, and the curing (crosslinking) reactivity is particularly high, and a cured product can be obtained efficiently.

  In the curable fluorine-containing polymer of the formula (1) of the present invention, Rf contained in the structural units M, M1, M2 and M3 is preferably one containing 1 to 40 carbon atoms, particularly when the functional group Y is one. It is a fluorine alkylene group and a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms. These organic groups only need to have a fluorine atom bonded to the carbon atom contained, and are generally a fluorine-containing alkylene group in which a fluorine atom and a hydrogen atom or a chlorine atom are bonded to a carbon atom, or a fluorine-containing alkylene group having an ether bond. However, those containing more fluorine atoms (high fluorine content) are preferred, and the fluorine content is 50% or more, preferably 70% or more, relative to the molecular weight excluding oxygen atoms of the organic group excluding the functional group, More preferred is a perfluoroalkylene group or a perfluoroalkylene group having an ether bond. These make it possible to lower the refractive index of the curable fluorinated polymer. In particular, the refractive index can be kept low even if the degree of curing (crosslinking density) is increased for the purpose of increasing the hardness of the cured product.

  If the number of carbon atoms is too large, in the case of a fluorine-containing alkylene group, the solubility in a solvent may be lowered or the transparency may be lowered. In the case of a fluorine-containing alkylene group having an ether bond, the polymer itself or its curing may be caused. This is not preferable because the hardness and mechanical properties of the article may be lowered. Carbon number of a fluorine-containing alkylene group becomes like this. Preferably it is 1-20, More preferably, it is 1-10. The carbon number of the fluorine-containing alkylene group having an ether bond is preferably 2 to 30, more preferably 2 to 20.

（ＸⁱおよびＸ^jは同じかまたは異なりＦまたはＣＦ₃；Ｘ^k、Ｘ^lは同じかまたは異なりＨまたはＦ；ｏ＋ｐ＋ｑは１〜３０；ｒは０または１；ｓ、ｔは０または１）
である。 Preferred examples are

(X ⁱ and X ^j are the same or different F or CF ₃ ; X ^k , X ^l are the same or different H or F; o + p + q is 1 to 30; r is 0 or 1; s, t is 0 or 1)
It is.

があげられ、より詳しくは、 As a preferable specific example of the monomer that gives the structural unit M2,

For more details,

などがあげられる。

Etc.

などがあげられる。 Preferable specific examples of the monomer (m3) that gives the structural unit M3 include

Etc.

などがあげられる。 For more details,

Etc.

などがあげられる。 As preferable specific examples of the monomer constituting the structural unit M of the curable fluorinated polymer of the present invention other than the structural units M2 and M3, for example,

Etc.

などがあげられる。 More specifically,

Etc.

  In the curable fluorinated polymer (A) of the present invention, the structural unit A is an optional component, and the monomers (m), (m1), (m2) and (m3) which give the structural units M, M1, M2 or M3 The monomer is not particularly limited as long as it is a monomer that can be copolymerized with the polymer, and may be appropriately selected according to the intended use of the curable fluorine-containing polymer or its cured product, required characteristics, and the like.

（式中、Ｘ^m、Ｘⁿ、Ｘ^oはＨまたはＦ；Ｘ^pはＨ、ＦまたはＣＦ₃；ｈは０〜２；ｉは０または１；Ｒｆ^3aは炭素数１〜４０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を有する含フッ素アルキレン基；Ｄ¹は−ＯＨ、−ＣＨ₂ＯＨ、−ＣＯＯＨ、カルボン酸誘導体、−ＳＯ₃Ｈ、スルホン酸誘導体、エポキシ基またはシアノ基から選ばれるもの）で示される構造単位であり、なかでも式（Ａ１−１）： For example, the following structural units can be exemplified.
(1) Structural unit derived from a fluorine-containing ethylenic monomer having a functional group (A1)
These are preferable in that they can provide adhesion to a substrate and solubility in a solvent, particularly a general-purpose solvent while maintaining the refractive index of the curable fluorine-containing polymer and its cured product low, and other than that Y is involved. It is preferable at the point which can provide functions, such as crosslinking | crosslinked property. The structural unit of a preferred fluorine-containing ethylenic monomer having a functional group is represented by the general formula (A1):

(In the formula, X ^m , X ⁿ and X ^o are H or F; X ^p is H, F or CF ₃ ; h is 0 to 2; i is 0 or 1; Rf ^3a is fluorine containing 1 to 40 carbon atoms. An alkylene group or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; D ¹ is —OH, —CH ₂ OH, —COOH, a carboxylic acid derivative, —SO ₃ H, a sulfonic acid derivative, an epoxy group or a cyano group; A structural unit represented by formula (A1-1):

（式中、Ｒｆ^3aおよびＤ¹は式（Ａ１）と同じ）
で示される構造単位が好ましい。

(Wherein Rf ^3a and D ¹ are the same as in formula (A1))
Is preferred.

などの含フッ素エチレン性単量体から誘導される構造単位が好ましくあげられる。 More specifically,

A structural unit derived from a fluorine-containing ethylenic monomer such as is preferred.

（式中、Ｒｆ^3aおよびＤ¹は式（Ａ１）と同じ）
で示される構造単位も好ましく例示でき、より具体的には、 Formula (A1-2):

(Wherein Rf ^3a and D ¹ are the same as in formula (A1))
The structural unit represented by can also be preferably exemplified, and more specifically,

などの単量体から誘導される構造単位があげられる。

And structural units derived from monomers such as

などがあげられる。 In addition, as the functional group-containing fluorine-containing ethylenic monomer,
_{CF 2 = CFCF 2 -O-Rfa} -D 1, CF 2 = CF-Rfa-D 1,
_{CH 2 = CH-Rfa-D} 1, CH 2 = CHO-Rfa-D 1
(In these formulas, Rfa is a group obtained by removing Y from Rf in formula (M)).
And more specifically,

Etc.

(2) Structural unit derived from a fluorine-containing ethylenic monomer not containing a functional group (A2)
These are preferable in that the refractive index of the curable fluorinated polymer or the cured product thereof can be kept low, and further in that the refractive index can be further reduced. Further, by selecting a monomer, the mechanical properties of the polymer, the glass transition point, etc. can be adjusted. Particularly, the copolymerization with the structural unit M can increase the glass transition point, which is preferable.

  As a structural unit of the fluorine-containing ethylenic monomer, the general formula (A2):

（式中、Ｘ^q、Ｘ^r、Ｘ^sはＨまたはＦ；Ｘ^tはＨ、ＦまたはＣＦ₃；ｈ１、ｉ１、ｊは０または１；Ｄ²はＨ、ＦまたはＣｌ；Ｒｆ^4aは炭素数１〜２０の含フッ素アルキレン基または炭素数２〜１００のエーテル結合を含む含フッ素アルキレン基）で示されるものが好ましい。

( ^Wherein X ^q , X ^r and X ^s are H or F; X ^t is H, F or CF ₃ ; h1, i1, j is 0 or 1; D ² is H, F or Cl; Rf ^4a is carbon A fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms is preferable.

などの単量体から誘導される構造単位が好ましくあげられる。 As a specific example,

Preferred are structural units derived from monomers such as

(3) Aliphatic cyclic structural unit having a fluorine atom (A3)
When these structural units are introduced, the transparency can be increased, the refractive index can be further lowered, and a curable fluorine-containing polymer having a high glass transition point can be obtained, and the cured product can be expected to have higher hardness. This is preferable.

（式中、Ｘ^a1、Ｘ^a2、Ｘ^a4、Ｘ^a5、Ｘ^a7、Ｘ^a8は同じかまたは異なりＨまたはＦ；Ｘ^a3、Ｘ^a6は同じかまたは異なりＨ、Ｆ、ＣｌまたはＣＦ₃；Ｒｆ^5aは炭素数１〜１０の含フッ素アルキレン基または炭素数２〜１０のエーテル結合を有する含フッ素アルキレン基；ｐ２は０〜３の整数；ｐ１、ｐ３、ｐ４、ｐ５は同じかまたは異なり０または１の整数）で示されるものが好ましい。 As the fluorine-containing aliphatic cyclic structural unit, the formula (A3):

^Wherein X ^a1 , X ^a2 , X ^a4 , X ^a5 , X ^a7 , X ^a8 are the same or different H or F; X ^a3 , X ^a6 are the same or different H, F, Cl or CF ₃ ; Rf ^5a is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 10 carbon atoms; p2 is an integer of 0 to 3; p1, p3, p4 and p5 are the same or different and 0 or An integer of 1 is preferable.

（式中、Ｒｆ^5a、Ｘ^a3、Ｘ^a6は前記と同じ）で示される構造単位があげられる。 For example,

(Wherein, Rf ^5a , X ^a3 , and X ^a6 are the same as those described above).

In particular,

（式中、Ｘ^a4、Ｘ^a5は前記と同じ）などがあげられる。

(Wherein, X ^a4 and X ^a5 are the same as described above).

(4) Structural units derived from ethylenic monomers that do not contain fluorine atoms Introduced structural units derived from ethylenic monomers that do not contain fluorine atoms as long as the refractive index is not deteriorated (higher refractive index). May be.

  Thereby, the solubility in a general-purpose solvent is improved, and the compatibility with an additive such as a photocatalyst or a curing agent added as necessary is preferable.

Specific examples of non-fluorinated ethylenic monomers include
α-olefins:
Vinyl ether or vinyl ester monomers such as ethylene, propylene, butene, vinyl chloride, vinylidene chloride:
CH ₂ = CHOR, CH ₂ = CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms), etc.

Allyl monomers:
CH ₂ = CHCH ₂ Cl, CH ₂ = CHCH ₂ OH, CH ₂ = CHCH ₂ COOH, CH ₂ = CHCH ₂ Br, etc.

など Allyl ether monomers:
CH ₂ = CHCH ₂ OR (R: a hydrocarbon group having 1 to 20 carbon atoms),
CH ₂ = CHCH ₂ OCH ₂ CH ₂ COOH,

Such

Acrylic or methacrylic monomers:
In addition to acrylic acid, methacrylic acid, acrylic esters and methacrylic esters, maleic anhydride, maleic acid, maleic esters and the like can be mentioned.

(5) Structural unit derived from alicyclic monomer As a copolymerization component of structural unit M, structural unit M and the above-mentioned fluorine-containing ethylenic monomer or non-fluorine ethylenic monomer (described above) In addition to the structural units of (3) and (4)), an alicyclic monomer structural unit may be introduced as the third component, thereby increasing the glass transition point and increasing the hardness. preferable.

（ｍ：０〜３、Ａ、Ｂ、Ｃ、Ｄは、Ｈ、Ｆ、Ｃｌ、ＣＯＯＨ、ＣＨ２ＯＨ、炭素数１〜５のパーフルオロアルキルなど）で示されるノルボルネン誘導体、 Specific examples of alicyclic monomers include

A norbornene derivative represented by (m: 0 to 3, A, B, C, D is H, F, Cl, COOH, CH2OH, perfluoroalkyl having 1 to 5 carbon atoms, etc.),

などの脂環式単量体や、これらに置換基を導入した誘導体などがあげられる。

And alicyclic monomers such as these, and derivatives obtained by introducing substituents into these.

  In the curable fluorine-containing polymer of the present invention, the combination and composition ratio of the structural unit M (M1, M2, M3) and A are the intended use, physical properties (especially, glass transition point, hardness, etc.), function, and function. Various selections can be made depending on (transparency, refractive index) and the like.

  In the curable fluorine-containing polymer of the present invention, the structural unit M (M1, M2, M3) is contained as an essential component, and the structural unit M itself maintains a low refractive index and imparts transparency and curing. Therefore, the cured product has a feature that can provide hardness, abrasion resistance, scratch resistance and solvent resistance. Accordingly, the curable fluorinated polymer of the present invention can maintain a low refractive index even if it is a polymer containing a large amount of structural units M, extremely a polymer consisting of only structural units M (100 mol%). At the same time, a cured product having a high cured (crosslinked) density is obtained, which is preferable in that a film having high hardness, abrasion resistance, and scratch resistance is obtained.

  Furthermore, in the case of a copolymer comprising the structural unit M of the present invention and a structural unit A of a monomer that can be copolymerized, by selecting the structural unit A from the above-mentioned examples, it is possible to further increase the hardness (high glass transition). Point) or a polymer that gives a cured product having a low refractive index.

  In the copolymer of the structural unit M and the structural unit A, the content ratio of the structural unit M may be 0.1 mol% or more with respect to all monomers constituting the curable fluorinated polymer. In order to obtain a cured product having high hardness, excellent wear resistance and scratch resistance, and excellent chemical resistance and solvent resistance by crosslinking, it is 2.0 mol% or more, preferably 5 mol% or more, more preferably It is preferable to set it as 10 mol% or more.

  In particular, in the use of an antireflection coating that requires the formation of a cured coating having excellent scratch resistance and scratch resistance, it is preferably contained in an amount of 10 mol% or more, preferably 20 mol% or more, and more preferably 50 mol% or more.

  The curable fluorinated polymer of the present invention is particularly preferable for use in an antireflection film because the antireflection effect does not decrease even if the proportion of the structural unit M is increased (even if the curing site is increased).

  Further, when transparency is required such as for use in an antireflection film, it is preferable that the combination of the structural unit M and the structural unit A is a curable fluorine-containing polymer having a combination and composition that can be amorphous.

Especially, as a preferable form of the fluorine-containing polymer for coating compositions aiming at a low refractive index and high hardness, Formula (1-1):
-(M)-(A1)-(A2)-(1-1)
Is a curable fluorine-containing polymer.

  The structural unit M in the formula (1-1) is the structural unit M having the ethylenic carbon-carbon double bond of the formula (1) in the side chain, and in the formulas (M1), (M2), and (M3) The same preferred specific examples as shown can be applied.

  The structural unit A1 is a structural unit derived from a fluorine-containing ethylenic monomer having a functional group in the side chain, and more specifically is a structural unit represented by the formula (A1), and has the above-described functional group. Specific examples of the structural unit A1 derived from an ethylenic monomer can also be preferably applied.

  The structural unit A2 is a structural unit derived from a fluorine-containing ethylenic monomer having no functional group. Specifically, the structural unit is a structural unit represented by the above formula (A2), and does not have the functional group described above. Specific examples of the structural unit A2 derived from a fluorine ethylenic monomer are also preferably applicable. Among these, a structural unit derived from at least one monomer selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, and hexafluoropropylene is preferable.

  The respective abundance ratios of the structural units M, A1 and A2 are M = 0 to 90 mol%, A1 = 0 to 99.9 mol% and A2 = 0 to 99.9 mol%, and A1 + A2 = 10 to 99 It is preferably 9 mol%. Especially, it is preferable that they are M = 10-80 mol%, A1 = 1-60 mol% and A2 = 20-85 mol%, and A1 + A2 = 20-90 mol%. When the structural unit M is too small, the hardness of the film after curing tends to be low or the strength tends to be insufficient. When the amount of A1 is too small, adhesion to a substrate, coating property, solvent solubility, etc. tend to be insufficient. If the amount of A2 is too small, the coating property to the substrate, the leveling property, and the solvent solubility tend to be insufficient.

  The fluorine-containing polymer composed of these structural units M, A1, and A2 can impart hardness, mechanical strength, and dissolution resistance to the coating film and the like by the curable site of the structural unit M. The functional group of the structural unit A1 can provide adhesion to the substrate, solvent solubility, and good coatability (wetability and leveling property) to the substrate. Furthermore, the structural unit A2 can impart mechanical strength, solvent solubility, and good coatability to the base material to the fluoropolymer.

  Further, since the structural units M, A1, and A2 all contain a large number of fluorine atoms, the above functions can be imparted while maintaining a low refractive index. It is a fluoropolymer.

  The molecular weight of the curable fluorinated polymer (A) of the present invention can be selected, for example, from the range of 500 to 1,000,000 in terms of number average molecular weight, preferably from 1,000 to 500,000, particularly preferably from 2,000 to 200,000.

  If the molecular weight is too low, mechanical properties are likely to be insufficient even after curing, and in particular, the cured product and the cured film tend to be brittle and insufficient in strength. When the molecular weight is too high, the solvent solubility is deteriorated, the film formability and leveling property are liable to be deteriorated particularly during the formation of a thin film, and the storage stability of the curable fluorine-containing polymer is liable to be unstable. As a coating application, the number average molecular weight is most preferably selected from the range of 5000 to 100,000.

  The curable fluorinated polymer (A) of the present invention can be variously determined depending on the type and content of the structural unit M, and the type of the copolymer structural unit A used as necessary. ) Is preferably 1.45 or less, more preferably 1.40 or less, and particularly preferably 1.38 or less. Although it changes depending on the type of the base material or the base, it can be preferable as a base polymer for an antireflection film by maintaining these low refractive indexes and allowing curing (crosslinking).

  Further, the curable fluorine-containing polymer is preferably soluble in a general-purpose solvent. For example, it is soluble in at least one of a ketone-based solvent, an acetate-based solvent, an alcohol-based solvent, and an aromatic solvent, or the above-mentioned general-purpose solvent. It is preferably soluble in a mixed solvent containing at least one kind.

  It is preferable to be soluble in a general-purpose solvent because it is excellent in film formability and homogeneity when it is formed on various transparent films and display substrates for antireflection films that require coating use, particularly about 0.1 μm, This is also advantageous in terms of productivity in forming the antireflection film.

  In order to obtain the curable fluorine-containing polymer of the present invention, generally, a method in which a monomer having Y is synthesized in advance and polymerized; a polymer having another functional group is once synthesized, and the polymer A method described in International Publication No. 02/18457 pamphlet, such as a method in which a functional group is converted by a polymer reaction and a functional group Y is introduced, can be employed.

（式中、Ｘ¹はＨ、Ｃｌ、Ｆ、ＣＦ₃または炭素数１〜１０のアルキル基；Ｒ¹はケイ素原子を有しないが、環構造、ヘテロ原子および／または官能基は有していてもよい（ｎ１＋ｎ４）価の有機基；Ｒｆ¹はパーフルオロポリエーテル基；Ｒ²はアルキル基、フルオロアルキル基、またはＣＨ₂＝ＣＸ²ＣＯＯ−（Ｘ²はＨ、Ｃｌ、Ｆ、ＣＦ₃または炭素数１〜１０のアルキル基）；ｎ１は１〜３の整数；ｎ２は０または１；ｎ３は０〜５０；ｎ４は１〜３の整数）で示され、かつフッ素原子を含む数平均分子量が１００〜６０００の含フッ素化合物である。 (B) Fluorine-containing surface modifier The fluorine-containing surface modifier (B) is a component mainly having a role of imparting antifouling properties to the surface of the low refractive index layer, and the formula (2):

(Wherein X ¹ is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms; R ¹ does not have a silicon atom, but has a ring structure, a hetero atom and / or a functional group. which may (n1 + n4) valent organic group; Rf ¹ is a perfluoropolyether group; R ² is an alkyl group, fluoroalkyl group or ^{_{CH 2 = CX 2 COO- (X}} 2, is H, Cl, F, CF ₃ or N1 is an integer of 1 to 3; n2 is 0 or 1; n3 is 0 to 50; n4 is an integer of 1 to 3) and contains a fluorine atom. Is a fluorine-containing compound of 100 to 6000.

  Unlike the perfluoropolyether group-containing organosilicon compound described in Patent Document 2, this fluorine-containing surface modifier (B) is advantageous in that it does not contain a siloxane bond and is excellent in chemical resistance.

The fluorine-containing surface modifier (B) used in the present invention has the property of being easily segregated on the free surface of the low refractive index layer, and imparts excellent antifouling properties to the surface of the low refractive index layer even in a small amount. can do. In addition, it has CH ₂ ═CX ¹ COO— and it reacts with the carbon-carbon double bond of the curable fluorine-containing polymer and is chemically fixed to the polymer, so it is difficult to bleed out and is antifouling for a long time. Sex can be maintained.

In Formula (2), X ¹ is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms, and particularly H, CH from the viewpoint of easy synthesis and good low refractive index. ₃ , F and CF ₃ are preferred.

Rf ¹ is a perfluoropolyether group, preferably a group in which one or more perfluoroether units having 1 to 10 carbon atoms are combined. Specific examples of the perfluoro ether units, e.g., _{-OCF 2 -, - CF 2 O} -, - OCF 2 CF 2 -, - CF 2 CF 2 O -, - OCF 2 CF 2 CF 2 -, - CF 2 CF ₂ CF ₂ O—, —OCF (CF ₃ ) —, —CF (CF ₃ ) O—, —OCF ₂ CF (CF ₃ ) —, —CF (CF ₃ ) CF ₂ O—, —OCF (CF ₃ ) CF ₂ —, —CF ₂ CF (CF ₃ ) O— and the like can be exemplified.

The repeating number n3 of the perfluoroether unit is 0 to 50, preferably 1 to 40, more preferably 5 to 30. When n3 is 0, R ² is preferably a fluoroalkyl group, particularly a perfluoroalkyl group.

R ² is an alkyl group, a fluoroalkyl group, or CH ₂ ═CX ² COO— (X ² is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms).

  Examples of the alkyl group include linear or molecular chain alkyl groups having 1 to 20 carbon atoms, and further 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

Examples of the fluoroalkyl group include linear or molecular chain fluoroalkyl groups having 1 to 20 carbon atoms, and further 1 to 8 carbon atoms. In particular, a perfluoroalkyl group is preferable from the viewpoint of good low refractive index. Specific examples include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₆ F ₁₃ , and C ₈ F ₁₇ .

R ² may be CH ₂ ═CX ² COO—. X ² in R ² is H, Cl, F, a CF ₃ or an alkyl group having 1 to 10 carbon atoms, H in particular synthesis easy is point and a low refractive index is good point, CH _3, F, CF ₃ is preferred.

  n1 is 1 to 3, preferably 1 or 2.

  More specific examples of the fluorine-containing surface modifier (B) represented by the formula (2) include the following.

(B1) International Publication be reactive surface modifier are described in WO03 / 002,628 pamphlet and JP 2006-37024 JP, CH ₂ = CX ¹ COO- compound having a reactive group:
That is, a reactive group-containing composition comprising a combination of triisocyanate (B1a) obtained by trimerizing diisocyanate and at least two active hydrogen-containing compounds (B1b), and component (B1b) contains at least one active hydrogen. It is a composition comprising perfluoropolyether (B1b-1) having an active hydrogen and a monomer (B1b-2) having a self-reactive group as an essential combination.

  Examples of the self-reactive group include radical polymerizable self-reactive groups.

  For example, by reacting triisocyanate (B1a) with component (B1b), ie by reacting NCO groups present in triisocyanate (B1a) with active hydrogen present in component (B1b), at least one self-reaction It can be obtained in the form of a perfluoropolyether-containing compound (B1A) having a functional group. The equivalent ratio of the NCO group present in the triisocyanate (B1a) to the active hydrogen present in the component (B1b) is preferably at least 1 equivalent, particularly 1: 1, of active hydrogen per 1 equivalent of NCO group.

  The NCO group present in the triisocyanate (B1a) and the components (B1b-1) and (B1b-2) may be reacted simultaneously, or the components (B1b-1) and (B1b-2) may be reacted sequentially. Also good.

  With respect to 1 mol of triisocyanate (B1a), the sum of active hydrogen of component (B1b-1) and active hydrogen of component (B1b-2) is 2.5 to 3.5 mol, more preferably at least 3 mol. Preferably there is.

  An appropriate amount of component (B1b-1) is 0.0001 mol, more preferably 0.01 mol, especially 0.1 mol, and an upper limit of 2 mol, based on 1 mol of triisocyanate (B1a). Is 1.5 mol, in particular 1.0 mol.

  An appropriate amount of the component (B1b-2) is 1 mol, more preferably 1.2 mol, especially 1.5 mol, and an upper limit is 2.5 mol, based on 1 mol of triisocyanate (B1a). Is 2 mol, in particular 1.8 mol.

  Component (B1b) may further contain a compound (B1b-3) having active hydrogen other than (B1b-1) and (B1b-2). When the component (B1b-3) is contained, the compound (B1A) is obtained by reacting the component (B1a) with the components (B1b-1), (B1b-2) and (B1b-3). The components (B1b-1), (B1b-2) and (B1b-3) may be reacted simultaneously with the triisocyanate (B1a), or the components (B1b-1), (B1b-2) and (B1b- 3) may be added sequentially (addition is not limited to the order described) and reacted.

  It is preferable to react 1 mol or more of the component (B1b-2) with the NCO group present in the triisocyanate (B1a) and react the remaining NCO group with the components (B1b-1) and (B1b-3). The total amount of active hydrogens of the components (B1b-1), (B1b-2) and (B1b-3) is 2.5 to 3.5 mol, at least 3 mol, especially 1 mol of triisocyanate (B1a) It is preferably 3 moles.

  Examples of the diisocyanate used to obtain the triisocyanate (B1a) include diisocyanates in which isocyanate groups such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate are aliphatically bonded; Examples include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, and diisocyanate in which naphthalene diisocyanate groups are bonded aromatically.

などが例示できるが、これらに限定されるものではない。 As an example of triisocyanate (B1a), for example,

However, it is not limited to these.

  As described above, (B1b), which is a combination of at least two active hydrogen-containing compounds, includes a perfluoropolyether (B1b-1) having at least one active hydrogen and a monomer having a self-reactive functional group with active hydrogen (B1b-1). Although the combination of B1b-2) is included, as needed, you may further combine the compound (B1b-3) which has active hydrogen other than the said (B1b-1) and (B1b-2). Examples of the group having active hydrogen include an active hydrogen-containing group such as an active hydroxyl group.

  As the perfluoropolyether (B1b-1), in addition to the perfluoropolyether group, a compound having one hydroxyl group at one molecular terminal or one hydroxyl group at each of both terminals is preferable.

（式中、Ｘ⁴はＦまたは−ＣＨ₂ＯＨ基；Ｙ⁴およびＺ⁴は同じかまたは異なりＦまたは−ＣＦ３；ａは１〜１６の整数、ｃは０〜５の整数、ｂ、ｄ、ｅおよびｇは同じかまたは異なり、０〜１００の整数、ｈは０〜１６の整数）で示される化合物であることが特に好ましい。 Perfluoropolyether (B1b-1) has the general formula:

Wherein X ⁴ is F or —CH ₂ OH group; Y ⁴ and Z ⁴ are the same or different F or —CF 3; a is an integer of 1 to 16, c is an integer of 0 to 5, b, d, e and g are the same or different and are particularly preferably a compound represented by an integer of 0 to 100 and h is an integer of 0 to 16.

  Specific examples include those described in WO03 / 002628 pamphlet. Among them, the number average molecular weight of the perfluoropolyether (PEPE) portion is 1000 or more, particularly 1500 or more and 10,000. In particular, those of 5000 or less, more preferably 3000 or less are preferred. When the molecular weight is small, the antifouling property and lubricity tend to be lowered. When the molecular weight is too large, it is difficult to dissolve in the solvent. Moreover, the one-end alcohol modified body is preferable from the point from which an appropriate crosslinking density is obtained also for a terminal part.

  The monomer (B1b-2) having an active hydrogen and a self-reactive functional group is preferably an active hydrogen, particularly a (meth) acrylic acid ester having a hydroxyl group and a vinyl monomer.

Examples of the monomer (B1b-2) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, aminoethyl (meth) acrylate, HO (CH ₂ CH ₂ O) _i COC (R _{^{3) C = CH 2 (R}} 3: H, CH 3, i = 2~10), CH 3 CH (OH) CH 2 OCOC (R 3) C = CH 2 (R 3: H, CH 3; 2- hydroxy dibutyl (meth) _{acrylate), CH 3 CH 2 CH (} OH) CH 2 OCOC (R 3) C = CH 2 (R 3: H, CH 3; 2- hydroxy dibutyl (meth) acrylate), C ₆ H _{5 OCH 2 CH (OH) CH 2} OCOC (R 3) C = CH 2 (R 3: H, CH 3; 2- hydroxy-3-phenoxypropyl (meth) acrylate), allyl alcohol _{Le, HO (CH 2) k CH} = CH 2 (k = 2~20) , and the like. In particular, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxybutyl (meth) from the viewpoint of excellent solvent solubility of the reaction product. Acrylate is preferred.

  The compound (B1b-3) having active hydrogen which is an optional component is preferably a compound which does not have both a perfluoropolyether group and a self-reactive functional group and has at least one active hydrogen. Preferred examples of (B1b-3) are given below.

（Ｂ１ｂ−３−３）炭素数１〜１６の直鎖状あるいは分岐鎖状炭化水素からなる２級アミン、
（Ｂ１ｂ−３−４）芳香族基を有する２級アミン、
（Ｂ１ｂ−３−５）フルオロアルキルアルコール：
Ｑ（ＣＦ₂）_l（ＣＨ＝ＣＨ）_m（ＣＨ₂）_oＯＨ
（式中、Ｑは水素原子、フッ素原子、（ＣＦ₃）２ＣＦ−基；ｌは１〜１０の整数；ｍは同じかまたは異なり０または１；ｏは１〜１０の整数）、
（Ｂ１ｂ−３−６）ポリアルキレングリコールモノエステル、たとえば式：
Ｒ⁴（ＯＣＨ₂ＣＨ₂）_pＯＨ、Ｒ⁴（ＯＣＨ₂ＣＨ₂ＣＨ₂）_qＯＨ
（式中、Ｒ⁴は炭素数１〜１６の直鎖状もしくは分岐鎖状炭化水素、アセチル基またはアルキルフェノキシ基；ｐおよびｑは１〜２０の整数）、
（Ｂ１ｂ−３−７）芳香族アルコール
などがあげられる。 (B1b-3-1) a monovalent alcohol comprising a linear or branched hydrocarbon having 1 to 16 carbon atoms,
(B1b-3-2)

(B1b-3-3) a secondary amine comprising a linear or branched hydrocarbon having 1 to 16 carbon atoms,
(B1b-3-4) a secondary amine having an aromatic group,
(B1b-3-5) Fluoroalkyl alcohol:
Q (CF ₂ ) _l (CH═CH) _m (CH ₂ ) _o OH
(Wherein Q is a hydrogen atom, fluorine atom, (CF ₃ ) 2CF— group; l is an integer of 1 to 10; m is the same or different 0 or 1; o is an integer of 1 to 10),
(B1b-3-6) polyalkylene glycol monoesters, for example the formula:
R ⁴ (OCH ₂ CH ₂ ) _p OH, R ⁴ (OCH ₂ CH ₂ CH ₂ ) _q OH
(Wherein R ⁴ is a linear or branched hydrocarbon having 1 to 16 carbon atoms, acetyl group or alkylphenoxy group; p and q are integers of 1 to 20),
(B1b-3-7) aromatic alcohol and the like.

を含み、反応副生成物として Of these, particularly preferred are, for example,

As a reaction by-product

などを含んでもよい。

Etc. may be included.

(B2) Patent fluorinated graft polymer is described in JP 2005-29743 or among the fluorine-containing block polymer, CH ² = CX ₁ COO- a compound having:
That is, it has a branch polymer and a trunk polymer, at least one of the branch polymer and the trunk polymer has a block composed of a repeating unit having a fluoroalkyl group having 1 to 8 carbon atoms, and the other has a repeating unit having an oxyalkylene group Is a fluorine-containing graft polymer.

  Examples of the monomer having a fluoroalkyl group include a fluoroalkyl group-containing vinyl monomer.

The fluoroalkyl group-containing vinyl monomer may be a (meth) acrylate having a fluoroalkyl group or an acrylate in which the α-position having a fluoroacryl group is substituted with a halogen atom, CF ₃ , CF ₂ H or CFH ₂ .

  Examples of fluoroacrylate group-containing acrylates include the following.

（式中、Ｒｆは炭素数１〜２１のフルオロアルキル基；Ｒ⁵は水素原子または炭素数１〜１０のアルキル基；Ｒ⁶は炭素数１〜１０のアルキレン基；Ｒ⁷は水素原子、フッ素原子、塩素原子、ＣＦ₃、ＣＦＨ₂またはメチル基；Ａｒは置換基を有していてもよいアリーレン基；ｎは１〜１０の整数）

(Wherein Rf is a fluoroalkyl group having 1 to 21 carbon atoms; R ⁵ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ⁶ is an alkylene group having 1 to 10 carbon atoms; R ⁷ is a hydrogen atom, fluorine. An atom, a chlorine atom, CF ₃ , CFH ₂ or a methyl group; Ar is an arylene group which may have a substituent; n is an integer of 1 to 10)

Specific examples of the fluoroalkyl group-containing (meth) acrylate include the following.
CF ₃ (CF ₂ ) _p (CH ₂ ) _q OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) _p CH═CH (CH ₂ ) _q OCOCH═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p (CH ₂ ) _q OCOCH═CH ₂ ,
H (CF ₂ ) _p (CH ₂ ) _q OCOCH═CH ₂ ,
CF ₃ CHFCF ₂ (CH ₂ ) _q OCOCH═CH ₂ ,
CF ₃ (CF ₂ ) _p (CH ₂ ) _q OCOC (CH ₃ ) = CH ₂ ,
CF ₃ (CF ₂ ) _p CH═CH (CH ₂ ) _q OCOC (CH ₃ ) ═CH ₂ ,
(CF ₃ ) ₂ CF (CF ₂ ) _p (CH ₂ ) _q OCOC (CH ₃ ) = CH ₂ ,
_{H (CF 2) p (CH} 2) q OCOC (CH 3) = CH 2,
_{CF 3 CHFCF 2 (CH 2)} p OCOC (CH 3) = CH 2,

CF ₃ (CF ₂ ) _p SO ₂ N (C _s H _{2s + 1} ) (CH ₂ ) _q OCOCH═CH ₂ ,
_{CF 3 (CF 2) p SO} 2 N (C s H 2s + 1) (CH 2) q OCOC (CH 3) = CH 2,
CF ₃ C ₆ F ₁₀ (CF ₂ ) _p SO ₂ N (CH ₃ ) (CH ₂ ) _q OCOCH═CH ₂ ,
CF ₃ C ₆ F ₁₀ (CF ₂ ) _p SO ₂ N (CH ₃ ) (CH ₂ ) _q OCOC (CH ₃ ) = CH ₂ ,
_{(CF 3) 2 CF (CF} 2) p CH 2 CH (OCOCH 3) CH 2 OCOCH = CH 2,
_{(CF 3) 2 CF (CF} 2) p CH 2 CH (OCOCH 3) CH 2 OCOC (CH 3) = CH 2,
(CF ₃ ) ₂ CF (CF ₂ ) _p CH ₂ CH (OH) CH ₂ OCOCH═CH ₂ ,
_{(CF 3) 2 CF (CF} 2) p CH 2 CH (OH) CH 2 OCOC (CH 3) = CH 2,
[P = 0-20, q = 1-10, s = 1 or 2]

  Of course, a mixture of two or more of the above-mentioned fluoroalkyl group-containing (meth) acrylates can be used.

  The repeating unit having an oxyalkylene group can be derived from a vinyl monomer having an oxyalkylene group. A vinyl monomer having an oxyalkylene group constitutes a branched polymer or a trunk polymer, for example, a trunk polymer.

  A vinyl monomer having an oxyalkylene group is a monomer having an oxyalkylene group and a carbon-carbon double bond. The oxyalkylene group may have 2 to 6 carbon atoms, and the oxyalkylene group is preferably an oxyethylene group or an oxypropylene group.

The following are mentioned as an example of the vinyl monomer which has a polyoxyalkylene group.
HO (C ₂ H ₄ O) _n COC (R ⁸ ) C═CH ₂
[R ^8: H or CH _3, n = 1~100],
HO (C ₃ H ₆ O) _n COC (R ⁸ ) C═CH ₂
[R ^8: H or CH _3, n = 1~100],
_{HO (C 2 H 4 O)} m - (C 3 H 6 O) n COC (R 8) C = CH 2
[R ^8: H or _{CH 3, m = 1~20, n} = 1~20],
_{H (CH 2) p O (} C 2 H 4 O) n COC (R 8) C = CH 2
[R ^8: H or _{CH 3, p = 1~20, n} = 1~100],
_{H (CH 2) p O (} C 3 H 6 O) n COC (R 8) C = CH 2
[R ^8: H or _{CH 3, p = 1~20, n} = 1~100],
_{H (CH 2) p O (} C 2 H 4 O) m - (C 3 H 6 O) n COC (R 8) C = CH 2
[R ^8: H or _{CH 3, p = 1~20, m} = 1~20, n = 1~20],
_{H (CH 2) p O (} C 2 H 4 O) m - (C 3 H 6 O) n COC (R 8) C = CH 2
[R ^8: H or _{CH 3, p = 1~20, m} = 1~20, n = 1~20],

［Ｒ⁸：ＨまたはＣＨ₃、ｍ＝１〜２０、ｎ＝１〜２０］

[R ^8: H or _{CH 3, m = 1~20, n} = 1~20]

  The branch polymer and the backbone polymer may contain other copolymerizable monomers in addition to the fluoroalkyl group-containing vinyl monomer and the oxyalkylene group-containing vinyl monomer. The other copolymerizable monomer may be any addition-polymerizable monomer (that is, a compound having a carbon-carbon double bond). The other copolymerizable monomer may be a non-fluorinated monomer or a fluorine-based monomer. Either may be sufficient.

  As a non-fluorine-type monomer, (meth) acrylate ester is mentioned, for example. The (meth) acrylate ester may be an ester of (meth) acrylic acid and an aliphatic alcohol, for example, a monohydric alcohol or a polyhydric alcohol (for example, a dihydric alcohol).

Examples of non-fluorinated monomers include the following.
2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyalkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, polyoxyalkylene (meth) acrylate, alkoxy Polyoxyalkylene (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Benzyl (meth) acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl Acrylate, glycerol monomethacrylate, β-acryloyloxyethyl hydrogen succinate, β-methacryloyloxyethyl hydrogen phthalate, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxy Ethyl-2-hydroxyethylphthalic acid, hydroxypropyltrimethylammonium chloride methacrylate, 2-acryloyloxyethyl acid phosphate, glucosylethyl methacrylate, methacrylamide, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-methacryloyloxy (Meth) acrylates such as ethyl acid phosphate and hydroxypivalate neopentyl glycol diacrylate; styrene, -Styrenes such as isopropyl styrene; (meth) acrylamide, N, N-dimethylacrylamide, acryloylmorpholine, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethylacrylamide, 2-acrylamide-2- (Meth) acrylamides such as methylpropanesulfonic acid; vinyl ethers such as vinyl alkyl ether.

  Furthermore, vinyl halides such as ethylene, butadiene, vinyl acetate, chloroprene and vinyl chloride, vinylidene halides, acrylonitrile, vinyl alkyl ketone, maleic anhydride, N-vinyl carbazole, vinyl pyrrolidone, (meth) acrylic acid and the like can be mentioned. .

（Ｒ⁹は、Ｈ、Ｃｌ、Ｆ、ＣＦ₃または炭素数１〜１０のアルキル基）
などが挙げられる。 As fluorine-based monomers,
Fluorinated olefins (carbon number, eg 2-20), eg CF ₃ (CF ₂ ) ₇ CH═CH ₂ ,

(R ⁹ is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms)
Etc.

  In the present invention, the graft polymer may be a graft polymer in which a branch polymer is grafted to the isocyanate group portion of the trunk polymer.

  In one embodiment, the backbone polymer is a repeating unit derived from an isocyanate group-containing vinyl monomer and other copolymerizable monomers (eg, vinyl monomers having fluoroalkyl groups and / or vinyl monomers having oxyalkylene groups, in particular A vinyl monomer having an oxyalkylene group). Isocyanate groups present in repeating units derived from isocyanate group-containing vinyl monomers can react with the active hydrogen groups of the branch polymer to bond with the branch polymer.

  In this specification, the isocyanate group-containing vinyl monomer means a polymerizable compound having a carbon-carbon double bond and an isocyanate group. Generally, in the isocyanate group-containing vinyl monomer, the number of each of the carbon-carbon double bond and the isocyanate group is 1. Usually, a molecule of an isocyanate group-containing vinyl monomer has a carbon-carbon double bond at one end of the molecule and an isocyanate group at the other end.

Examples of isocyanate group-containing vinyl monomers are:
(I) isocyanate group-containing (meth) acrylate ester,
(Ii) _{formula: H 2 C = C (R} 10) -A 1 -NCO
[R ¹⁰ : H or a linear, branched or cyclic hydrocarbon group (for example, alkyl group) having 1 to 20 carbon atoms (for example, 1 to 10), A ¹ : direct bond or carbonization having 1 to 20 carbon atoms Or a compound (iii-1) having two isocyanate groups and a compound having a carbon-carbon double bond and active hydrogen (generally one carbon-carbon double bond). And a compound having one active hydrogen-containing group) (iii-2).

As the isocyanate group-containing (meth) acrylate ester (i),
^{_{H 2 C = C (R 11}} ) COO (CH 2 CH 2 O) n (CH 2) m -NCO
[R ^11: H or _{CH 3, n: 0~20, m} : 1~20]
(For example, 2-isocyanatoethyl (meth) acrylate)
Is mentioned.

As vinyl isocyanate (ii),
^{_{H 2 C = C (R 12}} ) -NCO
[R ^12: having 1 to 20 carbon atoms (e.g., 1 to 10) linear, branched or cyclic hydrocarbon group (e.g., an alkyl group or a cyclohexyl group)],
^{_{H 2 C = C (R 13}} ) - (CH 2) n -NCO
[R ^13: H or a carbon number from 1 to 20 (e.g., 1 to 10) linear, branched or cyclic hydrocarbon group (e.g., an alkyl group or a cyclohexyl group,), n: 2 to 20],
^{_{H 2 C = C (R 14}} ) -Ph-C (R 15) 2 -NCO
[R ^14: H or CH _3, R ^15: H or CH _3, Ph: a phenylene group]
Is mentioned.

  Examples of the compound (iii-1) having two isocyanate groups include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and isophorone diisocyanate. .

As the compound (iii-2) having a carbon-carbon double bond and active hydrogen (hereinafter also referred to as “monomer having active hydrogen”),
Hydroxyethyl (meth) acrylate,
_{HO (CH 2 CH 2 O)} n COC (R 16) C = CH 2
[R ¹⁶ : H or CH ₃ , n = 2 to 20],
Aminoethyl (meth) acrylate is mentioned.

  The reaction of the compound (iii-1) having two isocyanate groups and the monomer (iii-2) having active hydrogen is carried out in a solvent (particularly an aprotic solvent such as an ester solvent), if necessary dibutyltin dilaurate. Or a catalyst such as In the reaction, the amount of the active hydrogen-containing monomer (iii-2) is 1.0 to 2.0 equivalents, preferably 1.0 to 1.7, relative to the compound (iii-1) having two isocyanate groups. It may be equivalent.

  The amount of the isocyanate group-containing vinyl monomer may be 1% by weight, more preferably 2% by weight, especially 6% by weight, and the upper limit is 30% by weight, further 20% by weight, especially 10%, based on the backbone polymer. It may be weight percent.

  In addition to the isocyanate group-containing vinyl monomer, the backbone polymer includes at least one of a fluoroalkyl group-containing vinyl monomer or an oxyalkylene group-containing vinyl monomer (particularly, an oxyalkylene group-containing vinyl monomer) and, if necessary, other monomers (non-fluorine). Monomer and / or fluorine monomer).

  The branched polymer is composed of a chain transfer agent, at least one of a fluoroalkyl group-containing vinyl monomer or an oxyalkylene group-containing vinyl monomer (particularly, a fluoroalkyl group-containing vinyl monomer), and, if necessary, other monomers (non-fluorine monomer and / or fluorine monomer). Monomer).

The chain transfer agent may be a chain transfer agent having an active hydrogen group at both ends, for example, an alkylene thiol chain transfer agent having an active hydrogen group or an aryl chain transfer agent having an active hydrogen group. Examples of the active hydrogen group include OH, NH ₂ , SO ₃ H, NHOH, COOH, and SH. Carbon number of the alkylene group of alkylene thiol may be 1-20.

Examples of alkylene thiol chain transfer agents are as follows.
HS (CH ₂ ) _n OH [n is 1 to 20, especially 2, 4, 6, 11],
HSCH ₂ COOH,
HSCH ₂ CH (CH ₃ ) COOH,
HSCH ₂ CH ₂ SO ₃ Na,
HSCH ₂ CH ₂ SO ₃ H,

  Examples of aryl chain transfer agents are:

The active hydrogen group of the chain transfer agent reacts with the isocyanate group of the trunk polymer to form a —NH—C (═O) — bond (amide bond). When the active hydrogen group is an OH group, a urethane bond (—NH—C (═O) —O—) is formed. When the active hydrogen group is an NH ₂ group, a urea bond (—NH—C (═O) —NH—) is formed. The amount of the isocyanate group of the trunk polymer is preferably 1.0 to 2.5 equivalents, more preferably 1.0 to 2.0 equivalents, relative to 1.0 equivalent of the chain transfer agent.

  The amount of chain transfer agent may be 0.05 to 0.7, preferably 0.1 to 0.6, in molar ratio to the amount of branch monomer. A chain transfer agent is bonded to one end of the branch polymer obtained by polymerizing the branch monomer. Chain transfer agents can adjust the chain length of the branched polymer. The number of molecules of the branch polymer may be 3 to 25 molecules, preferably 4 to 20 monomers, per molecule of the chain transfer agent.

Among these, as particularly preferred, for example as fluoro acryl group-containing _{acrylate, C 4 F 9 CH 2 CH} 2 OCOCH = CH 2, consisting of a polyoxyalkylene group of polypropylene glycol methacrylate and methoxypolyethylene glycol methacrylate as a vinyl monomer having a fluorine-containing Examples thereof include graft polymers.

  Of these fluorine-containing surface modifiers (B), (B1) is particularly preferable from the viewpoint of antifouling properties.

  In addition to this fluorine-containing surface modifier (B), other antifouling agents that impart antifouling properties may be blended. Examples of other antifouling agents include fluorine-containing polyether compounds not included in the fluorine-containing surface modifier (B). In that case, it is necessary to determine the addition amount in consideration of deterioration of mechanical properties and white turbidity due to phase separation from the fluorine-containing polymer. Specifically, if the terminal of the fluorine-containing polyether compound is a carboxyl group, a blocked carboxyl group, a hydroxyl group, an epoxy group, or an alkoxysilane group, the fluorine-containing polyether compound is easily fixed in the film. The same effect can be obtained by applying the same polyether compound to the surface of an antireflection film (a film before or after curing) formed in advance.

(C) Hollow silica fine particles Hollow silica fine particles (C) are components blended to lower the refractive index, and are known materials used in Patent Documents 1 and 2 and the like.

  Specifically, hollow silica fine particles described in JP 2004-203683 A, JP 2006-021938 A, and the like can be used. As a preferable example, ELCOM manufactured by Catalyst Chemical Industry Co., Ltd. can be exemplified.

  The preferable average particle diameter of the hollow silica fine particles is 1 to 100 nm, more preferably 10 to 80 nm, from the viewpoint of particularly good optical properties of the antireflection film.

  The blending ratio in the curable composition of the present invention is preferably 1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the (A) component. When blended in this range, properties such as antifouling property and scratch resistance become particularly excellent. It is preferable that (C) component is 1-150 mass parts with respect to 100 mass parts of (A) component, Furthermore, 1-100 mass parts. When blended in this range, properties such as antifouling property and chemical resistance become particularly excellent.

  The curable composition of the present invention may further contain (D) a curing agent containing two or more α, β-unsaturated ester groups.

  The component (D) has a role as a curing agent, and is a compound containing two or more α, β-unsaturated ester groups and is included in the formula (2). Is not included.

  As the curing agent (D), a known curing agent containing two or more α, β-unsaturated ester groups can be used.

  As a known curing agent (D1) containing two or more α, β-unsaturated ester groups, for example, hydroxyl groups of polyhydric alcohols such as diols, triols, tetraols, acrylate groups, methacrylate groups, α- Polyfunctional acrylic monomers substituted with fluoroacrylate groups are generally known.

  Specifically, each of 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include compounds in which two or more hydroxyl groups of polyhydric alcohols are replaced with any one of an acrylate group, a methacrylate group, and an α-fluoroacrylate group.

  Further, two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group, a fluorine-containing alkyl group containing an ether bond, a fluorine-containing alkylene group or a fluorine-containing alkylene group containing an ether bond are converted into an acrylate group, a methacrylate group, α A polyfunctional acrylic monomer substituted with a fluoroacrylate group can also be used, and is particularly preferable in that the refractive index of the cured product can be kept low.

（Ｒｆｄは炭素数１〜４０の含フッ素アルキル基またはエーテル結合を含む含フッ素アルキル基；Ｒ^hはＨまたは炭素数１〜３のアルキル基）、 As a specific example

(Rfd is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group containing an ether bond; R ^h is H or an alkyl group having 1 to 3 carbon atoms),

（Ｒｆｅは炭素数１〜４０の含フッ素アルキレン基またはエーテル結合を含む含フッ素アルキレン基；ＲⁱはＨまたは炭素数１〜３のアルキル基）
などの一般式で示される含フッ素多価アルコール類の２個以上のヒドロキシル基をアクリレート基、メタアクリレート基またはα−フルオロアクリレート基に置き換えた構造のものが好ましくあげられる。

(Rfe is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group containing an ether bond; R ⁱ is H or an alkyl group having 1 to 3 carbon atoms)
Preferred are those having a structure in which two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by the general formulas such as are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups.

  Among these, two or more hydroxyl groups of each polyhydric alcohol such as pentaerythritol and dipentaerythritol are replaced with any of acrylate group, methacrylate group and α-fluoroacrylate group because of good scratch resistance. Compound,

（ＲｆｅおよびＲⁱは前記と同じ）
などで示される含フッ素多価アルコール類の２個以上のヒドロキシル基をアクリレート基、メタアクリレート基またはα−フルオロアクリレート基に置き換えた構造のものが好ましい。

(RFE and R ⁱ are as defined above)
The thing of the structure which substituted two or more hydroxyl groups of fluorine-containing polyhydric alcohol shown by these by the acrylate group, the methacrylate group, or the alpha-fluoro acrylate group is preferable.

  When mix | blending a hardening | curing agent (D), it is 40 mass parts or less with respect to 100 mass parts of curable fluorine-containing polymers (A), Preferably it is 1-40 mass parts, Especially 1-30 mass parts. If the amount is too large, the refractive index tends to increase.

  As a curing method of the curable composition of the present invention, a method of curing by irradiating active energy rays, a method of curing by heat, or the like can be employed. Among these, active energy ray curing using an active energy ray curing initiator (E) is applicable because it can be applied to substrates that have low heat resistance and are susceptible to deformation, decomposition, and coloration due to heat, such as transparent resin substrates. The method is preferred.

  As the active energy ray curing initiator (E), for example, radicals and cations are generated and cured only when irradiated with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X rays, γ rays, etc. It functions as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the functional fluorine-containing polymer, and those that generate radicals and cations with ultraviolet light, particularly those that generate radicals are used.

  The active energy ray curing initiator (E) in the composition of the present invention is the type of the carbon-carbon double bond of the side chain in the curable fluorine-containing polymer (A) (whether it is radical reactive or cationic reactive), Fluorine-containing surface modifier (B), when blended, type of α, β-unsaturated bond (radical reactive or cationic reactive) in curing agent (D), type of active energy ray used ( Initiator for curing the curable fluorine-containing polymer (A) having a radical-reactive carbon-carbon double bond using an active energy ray in the ultraviolet region, although it is appropriately selected depending on the wavelength range and the irradiation intensity. For example, the following can be exemplified.

Acetophenone acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.

Benzoin benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, etc.

Benzophenone benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone, etc.

Thioxanthones Thioxanthone, Chlorothioxanthone, Methylthioxanthone, Diethylthioxanthone, Dimethylthioxanthone, etc.

Other benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

  Depending on the type of the fluorine-containing polymer and the type of the active energy ray curing initiator described above, the compatibility may be lost, and the coating composition itself or the coated film may become cloudy, resulting in transparency and curing reaction. May decrease.

  The present inventors have found that compatibility with a fluorine-containing polymer can be improved by introducing a fluorine atom or a fluorine-containing organic group into the active energy ray curing initiator (E) itself.

  Specifically, it is preferable that the initiator contains a fluorine-containing alkyl group, a fluorine-containing alkylene group, a fluorine-containing alkyl group having an ether bond, or a fluorine-containing alkylene group having an ether bond, for example, an initiator having an OH group. Fluorine-containing carboxylic acid (polyvalent carboxylic acid) having the above-mentioned fluorine-containing organic group, etc. introduced by an ester bond, fluorine-containing carboxylic acid (polyvalent carboxylic acid) introduced to an initiator having an amino group by an amide bond And the like.

  Introducing a fluorine-containing organic group into the curing initiator (E) is preferable in that the fluorine-containing polymer having a high fluorination rate has good compatibility and can improve the curing reactivity and transparency of the film.

  Moreover, you may add photoinitiator adjuvants, such as amines, sulfones, and sulfines, as needed.

  Moreover, when it has a cation reactive carbon-carbon double bond, the following can be illustrated as a hardening initiator.

Onium salt iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt, etc.

Sulfone compounds β-ketoesters, β-sulfonylsulfones and their α-diazo compounds, etc.

Sulfonic acid esters Alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, etc.

Other sulfonimide compounds, diazomethane compounds, etc. In these cationic reactive active energy ray curing initiators, compatibility with fluorine-containing polymers is improved in the same manner as above by introducing fluorine atoms or fluorine-containing organic groups. it can.

  In the curable composition of the present invention, a solvent (F) may be used, and various substrates can be coated by dissolving or dispersing in the solvent to form a coating film. This is preferable in that it can be efficiently cured by irradiation with an active energy ray and a cured film can be obtained.

  The solvent (F) is composed of a curable fluorinated polymer (A), a fluorinated surface modifier (B), a curing agent (D), an active energy ray curing initiator (E), and other curing added as necessary. The additive is not particularly limited as long as additives such as an agent, a leveling agent, and a light stabilizer can be uniformly dissolved or dispersed, but in particular, the curable fluorine-containing polymer (A), the fluorine-containing surface modifier (B) and the curing What dissolves agent (D) uniformly is preferable. The mode of using this solvent is particularly preferable in the field where a thin layer coating (around 0.1 μm) is required, such as an antireflection coating, and is highly transparent so that a uniform coating can be obtained with high productivity.

  Examples of the solvent (F) include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate. , Ester solvents such as amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol solvents such as rubacetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; methanol, ethanol, propanol, isopropanol, butanol, etc. Examples of the alcohol solvent include aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

  Furthermore, in order to improve the solubility of the curable fluorine-containing polymer (A), the fluorine-containing surface modifier (B), and if necessary, the curing agent (D), a fluorine-based solvent is used as necessary. Also good.

などのフッ素系アルコール類、
ベンゾトリフルオライド、パーフルオロベンゼン、パーフルオロ（トリブチルアミン）、ＣｌＣＦ₂ＣＦＣｌＣＦ₂ＣＦＣｌ₂などがあげられる。 Examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). , Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene,

Fluorine alcohols such as
Examples thereof include benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF ₂ CFClCF ₂ CFCl _{2 and the} like.

  These fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents.

  Of these, ketone solvents, acetate solvents, alcohol solvents, aromatic solvents, and the like are preferable in terms of paintability and coating productivity.

  Further, when the curable fluorinated polymer is dissolved, the leveling property of the polymer film on the substrate after coating and drying is improved by mixing the fluorinated alcohol solvent together with these general-purpose solvents.

  This leveling improvement effect is high for resin base materials, particularly acrylic resins, cellulosic resins, polyethylene terephthalate, polycarbonate, and polyolefin, and particularly remarkable for polyethylene terephthalate base materials.

  The fluorine-containing alcohol to be added may be one having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher and capable of dissolving the curable fluorine-containing polymer.

などが好ましい具体例である。 For example,

Etc. are preferable specific examples.

  The fluorinated alcohol may be used as a solvent by itself, but it is also effective when used in addition to general-purpose solvents such as the above-mentioned ketone solvents, acetate ester solvents, non-fluorine alcohol solvents, and aromatic solvents. It is.

  In the case of mixing and using, the addition amount is 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 10 to 30% by mass with respect to the whole solvent.

  Curing of curable fluorine-containing polymer (A), fluorine-containing surface modifier (B), hollow silica fine particles (C) of the present invention, and if necessary, curing agent (D) and active energy ray curing initiator (E) If necessary, another curing agent (G) may be added to the curable composition including the fluorinated resin composition and the solvent (F).

  The other curing agent (G) that can be used in combination is preferably one having at least one carbon-carbon unsaturated bond and capable of being polymerized with a radical or acid. Specifically, the fluorine-containing surface modifier (B). And radically polymerizable monomers such as acrylic monomers other than the curing agent (D), and cationically polymerizable monomers such as vinyl ether monomers. These monomers may be monofunctional having one carbon-carbon double bond.

  The other curing agent (G) having these carbon-carbon unsaturated bonds is a radical or cation generated by the reaction of the active energy ray curing initiator (E) in the composition of the present invention with an active energy ray such as light. The side chain carbon-carbon double bond of the curable fluorinated polymer (A) in the composition of the present invention, and the α, β of the fluorinated surface modifier (B) and the curing agent (D) It can be crosslinked by unsaturated bonds and copolymerization.

  Monofunctional acrylic monomers include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, α-fluoroacrylic acid, α-fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid In addition to esters, (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.

（Ｘ^b1はＨ、ＣＨ₃またはＦ；Ｒｆｂは炭素数２〜４０の含フッ素アルキル基または炭素数２〜１００のエーテル結合を有する含フッ素アルキル基）で表わされる化合物が好ましい。 Among them, in order to keep the refractive index of the cured product low, an acrylate monomer having a fluoroalkyl group is preferable.

(X ^b1 is H, CH ₃ or F; Rfb is a fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms having 2 to 40 carbon atoms) compounds represented by are preferred.

（Ｘ^b1は前記と同じ）
などがあげられる。 In particular,

(X ^b1 is the same as above)
Etc.

  In addition, when these exemplified monofunctional acrylic monomers are used in the composition of the present invention as a curing agent, an α-fluoroacrylate compound is particularly preferable in terms of good curing reactivity.

  In the composition of the present invention, the amount of the active energy ray curing initiator (E) added is the content of the carbon-carbon double bond in the curable fluorinated polymer (A), the fluorinated surface modifier (B). Depending on the content of the curing agent (D), the presence / absence of the other curing agent (G) and the usage amount of the curing agent, the initiator (E) to be used, the type of active energy rays, and the irradiation energy amount ( Strength, time, etc.), but when no other curing agent (G) is used, the curable fluorine-containing polymer (A), fluorine-containing surface modifier (B), and curing agent (D) It is 0.01-30 mass parts with respect to 100 mass parts of total amounts, Furthermore, 0.05-20 mass parts, Most preferably, it is 0.1-10 mass parts.

  Specifically, the total amount of α, β-unsaturated bonds in the carbon-carbon double bond, the fluorine-containing surface modifier (B) and the curing agent (D) contained in the curable fluorine-containing polymer (A). It is 0.05-50 mol% with respect to content (number of moles), Preferably it is 0.1-20 mol%, Most preferably, it is 0.5-10 mol%.

  The content of the solvent (F) is appropriately selected depending on the type of solid content to be dissolved, the presence or absence of use of other curing agent (G), the type of substrate to be applied, the target film thickness, and the like. However, it is preferable that the total solid content concentration in the composition is 0.5 to 70% by mass, preferably 1 to 50% by mass.

  The composition of the present invention may contain various additives as necessary in addition to the above-mentioned compounds.

  Examples of such additives include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, antifouling agents (silicone-based and fluorine-based), reinforcing agents, and the like.

  The composition of the present invention can also contain inorganic compound fine particles for the purpose of increasing the hardness of the cured product.

  The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable. Specifically, magnesium fluoride (refractive index 1.38), organosilica sol (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. . The particle diameter of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 50 nm or less.

  When using inorganic compound fine particles, it should be used in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the composition and the adhesion in the low refractive index material. Is desirable. Furthermore, in order to improve the dispersion stability of the inorganic compound fine particles and the adhesion in the low refractive index material in the composition, the surface of the inorganic fine particle compound may be modified in advance using various coupling agents. it can. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

  In the curable composition of the present invention, the curable fluorine-containing polymer (A) or additive may be in a dispersion form or a solution form with respect to the solvent (F), but in order to form a uniform thin film. In addition, it is preferably a uniform solution from the viewpoint that a film can be formed at a relatively low temperature.

  As the coating method, a known coating method can be adopted as long as the film thickness can be controlled.

  For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted. Can be selected considering the controllability and controllability of the film thickness.

  The coating obtained by applying the curable resin composition of the present invention to a substrate and drying it can be photocured by irradiating active energy rays such as ultraviolet rays, electron beams or radiation.

  When photocured, if the carbon-carbon double bond in the curable fluorinated polymer (A) of the present invention contains intermolecular and fluorinated surface modifier (B) and curing agents (D), (G) Polymerization occurs through these curing agents, and the carbon-carbon double bonds in the polymer are reduced or eliminated. As a result, the resin hardness is increased, the mechanical strength is improved, the wear resistance, the scratch resistance is improved, and further, the resin becomes insoluble in the solvent dissolved before curing, It becomes insoluble in many other types of solvents.

As a more preferable combination of each component of the curable composition of this invention, the following can be illustrated, for example, However, This invention is not limited only to these.
(Example I)
Component (A): homopolymer of M1 and / or-(M1)-(A1)-(A2)-
(B) component: B1
Component (C): average particle diameter of 10 to 80 nm, refractive index of 1.25 to 1.35
(D) component: polyfunctional acrylate compound, α-fluoro acrylate compound (E) component: acetophenone and / or fluorine introduced (F) component: ketone solvent, acetate solvent, alcohol solvent, fluorine-containing alcohol -Based solvent, aromatic solvent composition ratio (amount based on 100 parts by mass (solid content) of component (A))
(B) Component: 1-10 parts by mass (C) Component: 1-100 parts by mass (D) Component: 0-30 parts by mass (E) Component: 0-10 parts by mass (F) Component: Appropriate effect: Low reflection It is possible to improve the rate, scratch resistance and antifouling property, and the chemical resistance is particularly good.
Application: Particularly suitable for antireflection film, antireflection film and the like.

  The present invention also relates to a cured coating of the curable composition of the present invention, and an antireflection film having a thickness of 0.03 to 0.5 μm.

  In the present invention, the curable fluorine-containing polymer (A) itself has a carbon-carbon unsaturated bond that can be cured (cross-linked), itself has a low refractive index, and further contains hollow silica fine particles (C). The refractive index can be further reduced by blending, and the fluorine-containing surface modifier (B) is segregated on the surface, so that it is applied to the transparent substrate with a predetermined film thickness, and if necessary, a curing agent is added. When used and cured, an antireflection effect and an antifouling property for a long period of time can be achieved, and an antireflection film with further improved hardness, abrasion resistance, and scratch resistance can be obtained. When such a fluorine-containing polymer (A) is used, the paintability (smoothness, film thickness uniformity) is also good, and the monomer component having a low molecular weight does not easily remain in the cured film. There is no tackiness and the coating performance is excellent.

  Curing can take measures such as heat and light (in a system containing an initiator), but when an antireflection film is applied to a transparent resin substrate, applying a high temperature may cause thermal degradation or thermal deformation of the substrate. It is not preferable because it is easy to cause. Therefore, curing by photocuring is preferable.

  As a method of photocuring the curable composition of the present invention to obtain an antireflection film, the curable composition is applied to a substrate, and a film (uncured) is formed by drying or the like, and then ultraviolet rays, electron beams A method of obtaining a cured film by irradiating active energy rays such as radiation is adopted, and light irradiation may be performed under any conditions of air or an inert gas stream such as nitrogen. Especially, the method of irradiating light in inert gas stream is preferable at the point with favorable curing reactivity, and the film of higher hardness is obtained.

  In addition, the curable fluorine-containing polymer (A) having an acid-polymerizable carbon-carbon double bond can be used in combination with an initiator that generates an acid upon irradiation with active energy rays. This is preferable in that it is not easily affected by (oxygen) and the like and can achieve a curing reaction.

  The curable fluorine-containing polymer used in the antireflection film of the present invention is, among the specific examples described above, the curable fluorine-containing polymer itself, which has high transparency, is amorphous, and has a refractive index of 1.40 or less. Preferably, a value of 1.38 or less is selected. Furthermore, among them, it is preferable to select and use as appropriate according to the target hardness, type of substrate, coating method, conditions, film thickness, uniformity, adhesion to the substrate, and the like.

  As the active energy ray curing initiator (E) used in the antireflection film of the present invention, the same ones as exemplified in the above curable fluorinated resin composition can be used. Considering the type of saturated bond (reactivity, content), fluorine-containing surface modifier (B), type of curing agent (D) (reactivity, content), curing conditions, pot life of paint, etc. The amount of use can be appropriately selected from the above ranges.

  The solvent (F) is appropriately selected from the above examples such as the type and amount used according to the target paintability, film formability, film thickness uniformity, and paint productivity. Solvents that dissolve or swell are not preferred. Particularly preferred are those selected from ketones, acetates, alcohols and aromatic hydrocarbon solvents.

  In the antireflection film of the present invention, if necessary, the curing agent (D) and another curing agent (G) similar to those described above may be used in combination. By using another curing agent (G) in combination, the hardness of the cured coating can be further increased.

  After applying these coating compositions, the cured product (film) after curing the fluoropolymer has a refractive index of 1.49 or less, preferably 1.45 or less, and further 1.40 or less. Is preferred. Most preferably, it is 1.38 or less, and the lower one is more advantageous as an antireflection effect.

  The preferable film thickness of the antireflection film applied to various substrates varies depending on the refractive index of the film and the refractive index of the base, but is selected from the range of 0.03 to 0.5 μm, preferably 0.07 to 0.2 μm. More preferably, it is 0.08 to 0.12 μm. If the film thickness is too low, the reduction in reflectance due to light interference in visible light will be insufficient, and if it is too high, the reflectance will depend only on the reflection at the interface between the air and the film. There is a tendency that the reduction of the reflectance due to is insufficient. In particular, it is preferable to set the film thickness so that the wavelength that indicates the minimum value of the reflectance of the article after applying the antireflection film is usually 420 to 720 nm, preferably 520 to 620 nm.

  The article to which the antireflection film of the present invention is applied, that is, the type of the substrate is not particularly limited. For example, inorganic materials such as glass, stone, concrete, tile; cellulose resins such as vinyl chloride resin, polyethylene terephthalate, triacetyl cellulose, polycarbonate resin, polyolefin resin, acrylic resin, phenol resin, xylene resin, urea resin, melamine Synthetic resins such as resin, diallyl phthalate resin, furan resin, amino resin, alkyd resin, urethane resin, vinyl ester resin, polyimide resin; metal such as iron, aluminum, copper; wood, paper, printed matter, photographic paper, painting, etc. I can give you. In addition, the decorativeness of the article can be improved by applying an antireflection film to a part other than the specific part of the article and causing the shape of the specific part to be raised by reflected light.

  Among the base materials, it is preferably applied to transparent resin base materials such as acrylic resins, polycarbonates, cellulose resins, polyethylene terephthalate, and polyolefin resins, particularly film-type base materials, and can effectively exhibit an antireflection effect.

The present invention is effective when applied to an article having the following form.
Optical components such as prisms, lens sheets, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, rear projection display screens, optical fibers and optical couplers;
Transparent protective plates such as show window glass, showcase glass, advertising covers, photo stand covers, etc .;
Protection plates such as CRT, liquid crystal display, plasma display, rear projection display;
Optical recording media represented by magneto-optical disks, read-only optical disks such as CD / LD / DVD, phase transition optical disks such as PD, hologram recording, etc .;
Photolithography-related members during semiconductor manufacturing, such as photoresists, photomasks, pellicles, and reticles;
Protective covers for illuminants such as halogen lamps, fluorescent lamps and incandescent lamps;
A sheet or film for attaching to the article.

  The antireflection film of the present invention may be formed by directly applying the solution of the curable composition of the present invention to a substrate and irradiating with light to form a cured film having a thickness of about 0.1 μm. A coating layer may be formed, and an antireflection film may be formed thereon as a top coat.

  The effect of the undercoat is roughly divided into three, and is to enhance the antireflection effect by increasing the scratch resistance of the topcoat, protecting the base material, and adding a layer having a higher refractive index than the base material. . In order to improve the scratch resistance of the top coat, a self-repairing undercoat as exemplified in JP-A-7-168005 may be used. Further, a paint generally called a hard coat may be used for protecting the substrate. Examples of the hard coat include curable acrylic resins and epoxy resins, cured products of silicon alkoxide compounds, and cured products of metal alkoxide compounds. The thermosetting method can be applied to all of these. For acrylic resins and epoxy resins, the light (ultraviolet) curing method is preferred in terms of productivity.

In a CRT or plasma display, static electricity tends to accumulate on the surface as a characteristic of the device. Therefore, it is preferable to mix an additive for imparting conductivity to the undercoat layer and / or the topcoat layer as described above. Examples of the additive include —COO—, —NH ₂ , —NH ₃ ⁺ , —NR ^11a R ^12a R ^13a (where R ^11a , R ^12a and R ^13a are, for example, methyl group, ethyl group, n-propyl group) , N-butyl group, etc.), polymers containing ionic groups such as —SO ₃ —, silicone compounds, inorganic electrolytes (eg NaF, CaF ₂ etc.) and the like.

  Further, for the purpose of preventing the adhesion of dust, it is preferable to add an antistatic agent to the undercoat layer and / or the topcoat layer of the antireflection film. As additives, in addition to the above-mentioned additives that impart conductivity, metal oxide fine particles, fluoroalkoxysilanes, surfactants (anionic, cationic, amphoteric, nonionic, etc.), organic polymers (pi-conjugated) System, solid electrolyte type, quaternary ammonium type, sulfonic acid type, etc.).

  As an antistatic agent added to the undercoat layer, the effect is permanent, the effect is not easily affected by humidity, the antistatic effect is high, the transparency and the refractive index are high, and the refractive index of the substrate is Because it can be adjusted, the anti-reflection effect can be enhanced. For example, solid electrolyte type organic polymer, quaternary ammonium type organic polymer, fine particles of metal oxide (specifically, tin oxide doped with antimony (ATO)) Indium-containing tin oxide (ITO) and the like are preferable. ATO is preferable in terms of transparency, and ITO is preferable in terms of antistatic effect or conductivity. Further, even when the antistatic effect is not required, the refractive index can be easily adjusted, so that the antireflection effect can be enhanced by using these additives.

  In addition, since ATO and ITO easily scatter and absorb light, the thickness of the undercoat layer is preferably about submicron so as not to prevent light transmission. In order to reduce the wavelength dependency of the antireflection effect and enhance the antireflection effect over all wavelengths, the film thickness is preferably 0.05 to 0.3 μm, although it depends on the refractive index of the fluoropolymer cured product. The optimum refractive index also depends on the refractive index of the fluorine-containing polymer, but is preferably 1.55 to 1.95.

  If the fluorine-containing polymer cured film is imparted with antistatic properties, an alkoxysilane-based antistatic agent is preferred from the viewpoint that the refractive index is difficult to increase and the antireflection effect is less adverse. Fluoroalkoxysilane is more preferable because the action of increasing the refractive index is further reduced and the effect of improving the surface characteristics can be expected.

  Further, as a method completely different from the method of modifying a part of the film as described above, a surfactant having a film thickness that does not adversely affect the antireflection performance as disclosed in JP-A-8-142280. There is a method of forming the layer. When applied to the present invention, there is an effect of improving antifouling properties such as prevention of dust adhesion. The same effect can be obtained when a hard coat layer is formed.

  The hard coat layer can be formed by a method of heating and curing after applying a solution of alkoxysilane or polysilazane, which is a commonly used hard coat forming composition. Further, an ultraviolet curable acrylic paint or a cured film of melamine crosslinking can be used.

  Furthermore, the antireflection film of the present invention may be applied on a base film (for example, a TAC film) treated with a coating agent mixed with fine particles as a matting agent, that is, an antiglare (AG) treatment. . Thereby, an antireflection film with low gloss and low reflection can be obtained, and it is preferable to use it for an LCD or the like because a clearer image can be obtained.

  The antireflection film of the present invention has a high fluorine content and a low surface contact angle, and itself has water repellency, non-adhesiveness, and antifouling properties, and can have both antireflection and antifouling layers. .

  As a method of forming a thin film of a curable fluorinated polymer, a dispersion of a curable fluorinated polymer is applied, dried, and then fired as necessary to form a film, and a solution (uniform solution) is applied. There is a way to dry. Solution coating is preferred because it is easy to form a thin film. At that time, a known coating method can be employed if the film thickness can be sufficiently controlled. For example, a roll coating method, a micro gravure coating method, a gravure coating method, a flow coating method, a bar coating method, a spray coating method, a die coating method, a spin coating method, or a dip coating method can be employed. Among these methods, an optimum coating method is determined in consideration of the balance of productivity, film thickness controllability, yield, and the like. After an antireflection film is formed on a film, sheet, etc., it may be attached to a substrate.

  Also in the present invention, a silane compound may be added to improve the adhesion of the antireflection film to the substrate. The amount of the silane compound added to the film may be about several mass%. In addition, treating the substrate surface with a silane compound is also effective for improving adhesion. In any case in the present invention, since the silane compound hardly increases the refractive index of the cured film, the adverse effect on the antireflection effect is very small.

  The present invention also provides a reflection having a three-layer structure in which a hard coat layer and then a cured coating of the curable composition (an antireflection film of the present invention) is directly formed on the transparent substrate film without any other layer. It also relates to prevention films.

  Examples of the transparent substrate film include transparent resin substrate films such as the above-mentioned acrylic resins, polycarbonates, cellulose resins, polyethylene terephthalate, and polyolefin resins. The film thickness of the transparent substrate film is about 50 to 200 μm.

  As described above, the hard coat layer can be formed by a method of heating and curing after applying a solution of alkoxysilane or polysilazane, which is a commonly used hard coat forming composition. Further, an ultraviolet curable acrylic paint or a cured film of melamine crosslinking can be used. The film thickness of the hard coat layer is about 1 to 10 μm.

  The antireflection film of the present invention is obtained by forming the antireflection film of the present invention having the antifouling property as a top coat directly on the hard coat layer.

  In the antireflection film as the top coat, the fluorine-containing surface modifier (B) is segregated in the vicinity of the surface as described above, and excellent antifouling performance can be exhibited for a long period of time.

  Next, the present invention will be described based on synthesis examples, production examples, and examples, but the present invention is not limited to these examples.

  In addition, the apparatus and measurement conditions used for physical property evaluation are as follows.

(1) NMR: manufactured by BRUKER
¹ H-NMR measurement conditions: 300 MHz (tetramethylsilane = 0 ppm)
¹⁹ F-NMR measurement conditions: 282 MHz (trichlorofluoromethane = 0 ppm)

(2) IR analysis: FT-IR SPECTROMETER 1760X manufactured by PERKIN ELMER

(3) Weight average molecular weight Mw and number average molecular weight Mn:
By gel permeation chromatography (GPC). Using Shodex GPC-104 manufactured by Showa Denko KK, using a column manufactured by Shodex (1 GPC KF-604, 1 GPC KF-603, 2 GPC KF-602 connected in series) Calculated from data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 0.5 ml / min.

Synthesis Example 1 (Synthesis of fluorinated allyl ether homopolymer having OH group)
In a 100 mL glass four-necked flask equipped with a stirrer and a thermometer, perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) was added.

を２０ｇ、
［Ｈ−（ＣＦ₂ＣＦ₂）₃−ＣＯＯ−］₂
の８．０質量％パーフルオロヘキサン溶液を２１．２ｇ入れ、十分に窒素置換を行った後、窒素気流下２０℃で２４時間攪拌を行ったところ、高粘度の固体が生成した。

20g,
[H- (CF ₂ CF ₂ ) ₃ —COO—] ₂
After adding 21.2 g of the 8.0 mass% perfluorohexane solution and sufficiently purging with nitrogen, the mixture was stirred at 20 ° C. for 24 hours under a nitrogen stream to produce a highly viscous solid.

  A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, separated and vacuum dried to obtain 17.6 g of a polymer.

When this polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, it was a fluorine-containing polymer comprising only the structural unit of the fluorine-containing allyl ether and having a hydroxyl group at the end of the side chain. Further, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 9000, and the weight average molecular weight was 22,000.

Production Example 1 (Synthesis of fluorinated curable polymer having α-fluoroacryloyl group)
In a 200 mL four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 80 mL of diethyl ether, 5.0 g of the hydroxyl group-containing fluorine-containing allyl ether homopolymer obtained in Synthesis Example 1, and pyridine 1.0 g was charged and ice-cooled to 5 ° C. or lower. While stirring under a nitrogen stream, a solution of 1.2 g of α-fluoroacrylic acid fluoride: CH ₂ ═CFCOF in 20 mL of diethyl ether was added dropwise over about 30 minutes. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 4.0 hours. After the reaction, the ether solution was put into a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, dried over anhydrous magnesium sulfate, and then the ether solution was separated by filtration.

When this ether solution was examined by ¹⁹ F-NMR analysis,
-OOCCF = CH ₂ group-containing fluorine-containing allyl ether / OH group-containing fluorine-containing allyl ether = 50/50 mol%
Of the copolymer.

Further, by coating the NaCl plate, it was IR analysis what was cast film at room temperature, carbon - absorption of a carbon-carbon double bonds in 1661Cm ^-1, absorption of C = O group was observed at 1770 cm ^-1 .

  After methyl isobutyl ketone (MIBK) was added to the obtained fluorine-containing curable polymer (ether solution) having an α-fluoroacryloyl group, the ether was distilled off with an evaporator to adjust the solid content concentration to 15.0% by mass. (This fluoropolymer solution is abbreviated as “AR1”).

  To 10 g of the obtained polymer solution, 1.7 g of a solution prepared by dissolving 2-hydroxy-2-methylpropiophenone in MIBK at a concentration of 1% by mass as an active energy ray curing initiator was added to obtain a curable fluoropolymer composition. Prepared.

Synthesis Example 2 (Synthesis of OH-containing fluorine-containing allyl ether and vinylidene fluoride copolymer)
A perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanol) was added to a 300 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer. .2 g, 200 g of CH ₃ CCl ₂ F (HCFC-141b) and 0.16 g of a 50 wt% methanol solution of dinormalpropyl peroxycarbonate (NPP) were added, and the system was cooled with dry ice / methanol solution while nitrogen was added to the system. Replaced with gas. Next, 5.8 g of vinylidene fluoride (VdF) was charged from the valve, and the reaction was performed while shaking at 40 ° C. With the progress of the reaction was reduced to 12 hours after the gauge pressure in the system from the previous reaction 4.4MPaG (4.5kgf / cm ² G) to ^{0.98MPaG (1.0kgf / cm 2 G)} .

  At this point, the unreacted monomer was released, the precipitated solid was taken out, dissolved in acetone, and then reprecipitated with a mixed solvent of hexane and toluene (50/50) to separate the copolymer. This copolymer was vacuum-dried to obtain 31.2 g of a copolymer.

When the composition ratio of this copolymer was analyzed by ¹ H-NMR analysis and ¹⁹ F-NMR analysis, the fluorine-containing allyl ether containing VdF / OH group was 38/62 (mol%). Further, the number average molecular weight measured by GPC analysis using THF as a solvent was 12000, and the weight average molecular weight was 18000.

Production Example 2 (Synthesis of fluorinated curable polymer having α-fluoroacryloyl group)
The same procedure as in Production Example 1 was conducted, except that 5.0 g of the OH group-containing fluorine-containing allyl ether and VdF copolymer obtained in Synthesis Example 2 were used, 1.1 g of pyridine and 1.0 g of α-fluoroacrylic acid fluoride were used. Thus, a fluorine-containing curable polymer (ether solution) was synthesized.

When this ether solution was examined by ¹⁹ F-NMR analysis,
-OOCCF = CH ₂ group-containing fluorine-containing allyl ether / OH group-containing fluorine-containing allyl ether / VdF = 48/14/38 mol%
Of the copolymer.

  After methyl isobutyl ketone (MIBK) was added to the obtained fluorine-containing curable polymer (ether solution) having an α-fluoroacryloyl group, the ether was distilled off with an evaporator to adjust the solid content concentration to 15.0% by mass. (This fluoropolymer solution is abbreviated as “AR2”).

  To 10 g of the obtained polymer solution, 1.7 g of a solution prepared by dissolving 2-hydroxy-2-methylpropiophenone in MIBK at a concentration of 1% by mass as an active energy ray curing initiator was added to obtain a curable fluoropolymer composition. Prepared.

Synthesis Example 3 (Synthesis of a copolymer of a fluorine-containing allyl ether having an OH group and a fluorine-containing allyl ether having a methyl ester structure at the terminal)
Perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol) was added to a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. 9.6 g and CH ₂ = CFCF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCH ₃ were put in 9.6 g and stirred well,
_{[H- (CF 2 CF 2)} 3 -COO] 2 -
After adding 2.0 g of an 8.0 wt% perfluorohexane solution and thoroughly purging with nitrogen, the mixture was stirred at 20 ° C. for 20 hours under a nitrogen stream to produce a highly viscous solid.

  A solution obtained by dissolving the obtained solid in acetone was poured into an HCFC225 / hexane = 1/1 solution, separated and vacuum dried to obtain 15.5 g of a colorless and transparent polymer.

When this polymer was analyzed by ¹ H-NMR analysis and ¹⁹ F-NMR analysis, the ratio of OH group-containing fluorine-containing allyl ether / methyl ester-containing fluorine-containing allyl ether was 42/58 (mol%). Moreover, the number average molecular weight measured by GPC analysis using THF as a solvent was 72000, and the weight average molecular weight was 117000.

Production Example 3 (Synthesis of fluorinated curable polymer having α-fluoroacryloyl group)
Fluorine-containing curing in the same manner as in Production Example 1 except that 5.0 g of the hydroxyl group-containing fluorine-containing allyl ether copolymer obtained in Synthesis Example 3, 1.0 g of pyridine, and 1.7 g of α-fluoroacrylic acid fluoride were used. A functional polymer (ether solution) was synthesized.

When this ether solution was examined by ¹⁹ F-NMR analysis,
-OOOCCF = CH ₂ group-containing fluorine-containing allyl ether / OH group-containing fluorine-containing allyl ether / fluorine-containing allyl ether having a methyl ester terminal = 38/4/58 mol%
Of the copolymer.

  After methyl isobutyl ketone (MIBK) was added to the obtained fluorine-containing curable polymer (ether solution) having an α-fluoroacryloyl group, the ether was distilled off with an evaporator to adjust the solid content concentration to 15.0% by mass. (This fluoropolymer solution is abbreviated as “AR3”).

  To 10 g of the obtained polymer solution, 1.7 g of a solution prepared by dissolving 2-hydroxy-2-methylpropiophenone in MIBK at a concentration of 1% by mass as an active energy ray curing initiator was added to obtain a curable fluoropolymer composition. Prepared.

Production Example 4 (Synthesis of perfluoropolyether urethane acrylate composition)
Into a 2 L three-necked flask equipped with a dropping funnel, condenser, thermometer, and stirrer, 144 g of SUMIDUR N3300 (trade name. Cyclic trimer of hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane, NCO group content 21.9%) It is dissolved in 200 g of HCFC-225, 0.2 g of dibutyltin dilaurate (first grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) is added, and DEMNUM [trade name. Made by Daikin Industries. CF ₃ CF ₂ O— (CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ CH ₂ OH, n = 10.9] A solution of 202 g in 300 g of HCF-225 was added dropwise, and at room temperature for 6 hours. Stir. The mixture was heated to 30 ° C. to 40 ° C., 96 g of hydroxyethyl acrylate was added dropwise over 30 minutes, and the mixture was stirred for 6 hours. After confirming that the absorption of NCO completely disappeared by IR (the disappearance of —CF ₂ CH ₂ OH was confirmed also from ¹⁹ F-NMR analysis of the product), HCFC-225 was distilled off by distillation under reduced pressure at 50 ° C. or lower. And the following two perfluoropolyether urethane acrylates:

を含む組成物４４２ｇを得た（この組成物を「ＰＦＰＥ１」と略す）。

442 g of a composition containing the composition was obtained (this composition is abbreviated as “PFPE1”).

Production Example 5 (Synthesis of perfluoropolyether α-fluoroacrylate)
In a 500 ml four-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, DENNUM [trade name. Made by Daikin Industries. CF ₃ CF ₂ CF ₂ O— (CF ₂ CF ₂ CF ₂ O) _n —CF ₂ CF ₂ CH ₂ OH, n about 20] 18 g, 1.0 g of pyridine, 1,1,1,3,3,3- 125 g of hexafluorometaxylene was charged and cooled to 5 ° C. or lower with ice. A solution prepared by dissolving 0.84 g of α-fluoroacrylic acid fluoride in 5 ml of 1,1,1,3,3,3-hexafluorometaxylene was added dropwise over about 10 minutes while stirring in a nitrogen stream. After completion of the dropwise addition, the temperature was raised to room temperature and further stirred for 4 hours. The ether solution after the reaction was put in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water, and then dried over anhydrous magnesium sulfate, and then the solution was separated by filtration. After evaporating the solvent from the filtrate with an evaporator, vacuum drying while heating to 70 ° C,
_{CH 2 = CFCOOCH 2 CF 2 CF} 2 (OCF 2 CF 2 CF 2) OCF 2 CF 2 CF 3
18.8 g of a colorless transparent liquid having a high viscosity containing the above was obtained (this composition is abbreviated as “PFPE2”).

Examples 1-9
As shown in Table 1, AR1 obtained in Production Example 1, PFPE1 obtained in Production Example 4, PFPE2 obtained in Production Example 5, and hollow silica sol MIBK dispersion solution having a concentration of 20% by mass (manufactured by Catalyst Kasei Kogyo Co., Ltd.) ELECOM DK-1006SIV, trade name: average particle size 55 nm; refractive index 1.30) was added and stirred well to obtain a curable composition.

Comparative Examples 1-3
As a comparison, a curable composition in which PFPE1 and PFPE2 were not blended in Table 2 was also prepared.

  About the curable composition prepared in Examples 1-9 and Comparative Examples 1-3, the refractive index before hardening and after hardening was measured. The results are shown in Tables 1 and 2.

(Measurement of refractive index before curing)
A 5 mass% MIBK solution of a curable composition prepared in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 3 except that no curing initiator (2-hydroxy-2-methylpropiophenone) was added. Using an applicator, the coated film was coated on a PET film so that the film thickness after drying was about 100 μm, dried at 50 ° C. for 10 minutes, and then the obtained cast film was peeled off from the PET film. The refractive index was measured with a light having a wavelength of 550 nm at 25 ° C. The results are shown in Table 1.

(Measurement of refractive index after curing)
The curable compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were applied on an aluminum foil using an applicator so that the film thickness after drying was about 100 μm, and dried at 50 ° C. for 10 minutes. . A high-pressure mercury lamp was used for the dried film, and the film was cured by irradiation with ultraviolet rays at an intensity of 3000 mJ / cm ² U at room temperature, and then the aluminum foil was dissolved with dilute hydrochloric acid to prepare a cured film. About the obtained cured film, the refractive index was measured with the light of a wavelength of 550 nm at 25 degreeC with the Abbe refractometer. The results are shown in Table 1.

  Next, an antireflection film was formed using the curable compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3, respectively.

(Formation of antireflection film)
Each curable composition was coated on an untreated acrylic plate with a spin coater at 1000 to 2000 revolutions at room temperature and dried at 50 ° C. for 5 minutes. At this time, the rotation speed of the spin coater was adjusted so that the film thickness after drying was 90 to 110 nm. A high-pressure mercury lamp was used for the dried film, and it was cured by irradiation with ultraviolet rays at an intensity of 3000 mJ / cm ² U at room temperature to form an antireflection film.

  The obtained antireflection film was examined for the following characteristics. The results are shown in Tables 1 and 2.

(Coefficient of friction)
Measurement is performed at a moving speed of 10 mm / min and a moving distance of 10 mm using a friction resistance tester (HEIDON-14 manufactured by Shinto Chemical Co., Ltd., trade name).

(Contact angle)
Using a contact angle meter (CA-DT manufactured by Kyowa Interface Chemical Co., Ltd., trade name), the contact angle of pure water and n-hexadecane at a volume of 3 μL is measured.

(Repellent properties of oil-based inks)
Draw a line on the surface of the anti-reflective coating with an oil-based pen (Mckey made by Zebra Co., Ltd., trade name), repel the oil-based ink, and remove the oil-based ink adhering after standing for 1 minute. The state of the surface of the antireflection film when it is wiped three times is visually determined.

Evaluation is based on the following criteria.
○: The oil-based ink can be repelled and completely wiped off.
Δ: The ink is not repelled and a wiping trace remains.
X: Oil-based ink is not repelled and cannot be wiped off.

(Fingerprint wiping property)
A finger is pressed against the surface of the antireflection film, and the state of the surface of the antireflection film is visually determined when the fingerprint is easily attached and the attached fingerprint is wiped three times with Kimwipe (trade name, manufactured by Jujo Kimberley Co., Ltd.).

Evaluation is based on the following criteria.
○: Fingerprints are hard to stick and can be completely wiped off.
Δ: There is little adhesion of fingerprints, but a wiping trace remains.
X: Fingerprints are attached and cannot be wiped off.

In Tables 1 and 2, each abbreviation indicates the following.
AR1: Curable fluorinated polymer PFPE obtained in Production Example 1 1: Perfluoropolyether urethane acrylate PFPE2 obtained in Production Example 4: Perfluoropolyether α-fluoroacrylate PS1 obtained in Production Example 5: Concentration 20 Mass% hollow silica sol MIBK dispersion (ELECOM DK-1006SIV, manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name, average particle size 55 nm; refractive index 1.30)
Initiator 1: 2-hydroxy-2-methylpropiophenone MIBK: methyl isobutyl ketone

Examples 10 to 27 and Comparative Examples 4 to 9
A curable composition was prepared in the same manner as in Examples 1 to 9 and Comparative Examples 1 to 3 except that AR2 and AR3 obtained in Production Example 2 and Production Example 3 were used instead of AR1, and reflection was conducted in the same manner. A prevention film was produced.

  About the obtained anti-reflective film, it carried out similarly to Example 1, and evaluated the refractive index, the friction coefficient, the contact angle, the repellency wiping property of oil-based ink, and the fingerprint adhesion wiping property. The results are shown in Tables 3-5.

In Tables 3 to 5, each abbreviation indicates the following.
AR2: curable fluorine-containing polymer obtained in Production Example 2 AR3: curable fluorine-containing polymer PFPE obtained in Production Example 3 1: perfluoropolyether urethane acrylate PFPE2 obtained in Production Example 4: obtained in Production Example 5 Perfluoropolyether α-fluoroacrylate PS1: hollow silica sol MIBK dispersion solution having a concentration of 20% by mass (ELECOM DK-1006SIV manufactured by Catalytic Chemical Industry Co., Ltd., trade name, average particle size 55 nm; refractive index 1.30)
Initiator 1: 2-hydroxy-2-methylpropiophenone MIBK: methyl isobutyl ketone

の２．５ｇを１時間かけて滴下した。滴下終了後、さらに４時間攪拌した。反応後のエーテル溶液を分液漏斗に入れ、２％塩酸水洗浄、５％ＮａＣｌ水洗浄を行って有機層を分取し、無水硫酸マグネシウムで乾燥した後蒸留により生成物２．６ｇを単離した（収率６２％）。 Production Example 6 (Synthesis of fluorine-containing active energy ray curing initiator)
In a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer, and dropping funnel, 2.0 g of 2-hydroxy-2-methylpropiophenone, 1.0 g of pyridine, CF ₃ CF ₂ CHCl / CClF ₂ 20 g of CF ₂ CHClF mixture (HCFC-225) was charged and cooled to 5 ° C. While stirring under a nitrogen stream,

Was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred for 4 hours. The ether solution after the reaction is put into a separatory funnel, washed with 2% hydrochloric acid and 5% NaCl, and the organic layer is separated, dried over anhydrous magnesium sulfate, and then 2.6 g of product is isolated by distillation. (62% yield).

であった。 The obtained product was examined by ¹ H-NMR analysis, ¹⁹ F-NMR analysis and IR analysis.

Met.

Example 28
In the MIBK solution (AR1) having a solid content concentration of 15.0% by mass of the fluoropolymer having an α-fluoroacryloyl group obtained in Production Example 1, as shown in Table 2, PFPE1 obtained in Production Example 4 and its concentration 20% by mass of hollow silica sol MIBK dispersion (ELECOM DK-1006SIV manufactured by Catalytic Chemical Industry Co., Ltd., trade name, average particle size 55 nm; refractive index 1.30), dipentaerythritol hexaacrylate (curing agent (D)) Irgacure 907 (trade name, active energy ray curing initiator manufactured by Ciba Specialty Chemicals) was added to prepare a curable composition.

Examples 29-36 and Comparative Examples 10-15
A curable composition was prepared in the same manner as in Example 28 with the blending ratio as shown in Table 6 and Table 7.

In Tables 6 and 7, each abbreviation indicates the following.
AR1: Curable fluorine-containing polymer obtained in Production Example 1 AR2: Curable fluorine-containing polymer obtained in Production Example 2 AR3: Curable fluorine-containing polymer obtained in Production Example 3 PFPE1: Obtained in Production Example 4 Perfluoropolyether urethane acrylate PFPE2: Perfluoropolyether α-fluoroacrylate PS obtained in Production Example 5: hollow silica sol MIBK dispersion solution having a concentration of 20% by mass (ELECOM DK-1006SIV manufactured by Catalyst Chemical Industry Co., Ltd.). Trade name: Average particle size 55 nm; Refractive index 1.30)
Initiator 2: Irgacure 907 (trade name, manufactured by Ciba Specialty Chemicals)
Initiator 3:

MIBK: methyl isobutyl ketone d1: dipentaerythritol hexaacrylate d2:

  Next, an antireflection film was produced using the curable compositions prepared in Examples 28 to 36 and Comparative Examples 10 to 15, respectively.

(Preparation of antireflection film)
Hard coat treatment on one side of PET film (Lumirror U46 manufactured by Toray Industries, Inc.) (hard coat agent full shade UV-S4 (trade name) manufactured by Toyo Ink Manufacturing Co., Ltd., refractive index 1.55, film thickness 5 μm) The curable compositions prepared in Examples 28 to 36 and Comparative Examples 10 to 15 were applied using a bar coater # 7, dried at 70 ° C. for 1 minute, and then purged with nitrogen. An antireflection film was prepared by irradiating with 1 J / cm ² of ultraviolet rays.

  About each obtained antireflection film, it carries out similarly to Example 1, and evaluates a friction coefficient, a contact angle, oil-based ink repellency wiping off property, and fingerprint adhesion wiping off. In addition, the following reflectance, pencil hardness, abrasion resistance And chemical resistance tests were evaluated. The results are shown in Tables 8 and 9.

(Reflectance)
An acrylic plate with an antireflection film attached is set in a visible ultraviolet spectrometer equipped with a 5 ° specular reflection unit, and the average reflectance (%) and minimum reflectance (%) are measured. U-4000 / SPECTROMETER manufactured by Hitachi High-Technology Corporation is used for the measurement.

(Pencil hardness)
Measured according to JIS K5400.

(Abrasion resistance)
Steel wool (# 0000) was attached to a rubbing tester (rubbing tester model IMC-1506 manufactured by Imoto Seisakusho Co., Ltd., trade name), and the antireflection film surface of the antireflection film was rubbed 20 times with a load of 200 gf / cm ² . The surface state of the subsequent antireflection film is visually observed.

Evaluation is based on the following criteria.
○: No scratch △: 2-3 scratches ×: Dozens of scratches XX: Many scratches

(chemical resistance)
(I) Change in HAZE after immersion in alkaline aqueous solution The antireflection film was immersed in a 3% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, washed with pure water, dried, measured for HAZE value, and the difference in HAZE value before and after the test. Look at (ΔHAZE).

(Measurement method of HAZE value)
Conforms to ASTM D1003.

(Ii) Change of HAZE after soaking in bleach At 25 ° C, bleach (Hyter made by Lion Co., Ltd., trade name. Sodium hypochlorite, alkylamine oxide, sodium hydroxide contained) is immersed in pure water for 30 minutes. After washing and drying, the HAZE value is measured, and the difference between the HAZE values before and after the test (ΔHAZE) is observed.

Comparative Example 6
5 g of tetraethoxysilane, 0.15 g of 1N nitric acid, 2.5 g of pure water and 5 g of ethanol were mixed. 20% hollow silica sol MIBK dispersion solution (ELECOM DK-1006SIV manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name. Average particle size 55 nm; refractive index 1.30) 6.25 g and ethanol 105 g were added to obtain a curable composition. It was.

(Preparation of antireflection film)
Hard coat treatment (hard coat agent full shade UV-S4 (trade name) manufactured by Toyo Ink Manufacturing Co., Ltd., trade name) on one side of a PET film (U46 manufactured by Toray Industries, Inc.). Refractive index 1.55, film thickness The curable composition prepared above was applied onto the substrate having been subjected to 5 μm) using a bar coater # 7 and dried at 70 ° C. for 1 minute to produce a comparative antireflection film.

  The obtained antireflection film was evaluated in the same manner as in Example 28 on the friction coefficient, contact angle, oil-based ink repellency wiping property, fingerprint adhesion wiping property, reflectance, pencil hardness, scratch resistance and chemical resistance test. It was. The results are shown in Table 9.

Claims (7)

(A) A curable composition containing a curable fluorine-containing polymer, (B) a fluorine-containing surface modifier, and (C) hollow silica fine particles, wherein the component (A) is represented by the formula (1):
-(M)-(A)-(1)
[Wherein, the structural unit M represents the formula (M):

Wherein X ^a and X ^b are the same or different and H or F; X ^c is H, F, CH ₃ or CF ₃ ; X ^d and X ^e are the same or different and H, F or CF ₃ ; Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms; Y (Y is a carbon atom having 2 to 10 carbon atoms having an ethylenic carbon-carbon double bond at the terminal); An organic group in which 1 to 3 monovalent organic groups are bonded; m1 is an integer of 0 to 3; and m2 and m3 are the same or different, and the fluorine-containing ethylenic monomer represented by 0 or 1) Derived structural unit;
The structural unit A is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer that gives the structural unit M]. A curable fluorinated polymer containing up to 100 mol% of a fluorinated polymer having a number average molecular weight of 500 to 1,000,000 containing 0 to 99.9 mol% of unit A;
The component (B) is represented by the formula (2):

(Wherein X ¹ is H, Cl, F, CF ₃ or an alkyl group having 1 to 10 carbon atoms; R ¹ does not have a silicon atom, but has a ring structure, a hetero atom and / or a functional group. which may (n1 + n4) valent organic group; Rf ¹ is a perfluoropolyether group; R ² is an alkyl group, fluoroalkyl group or ^{_{CH 2 = CX 2 COO- (X}} 2, is H, Cl, F, CF ₃ or N1 is an integer of 1 to 3; n2 is 0 or 1; n3 is 0 to 50; n4 is an integer of 1 to 3) and contains a fluorine atom. Is a curable composition for forming an antireflection film, which is a fluorine-containing compound having a molecular weight of 100 to 6000. The composition according to claim 1, wherein the component (B) is 1 to 10 parts by mass and the component (C) is 1 to 150 parts by mass with respect to 100 parts by mass of the component (A). (D) The composition of Claim 1 or 2 containing the hardening | curing agent (however, different from (B) component) containing 2 or more (alpha), (beta)-unsaturated ester group. The composition according to claim 3, wherein the curing agent (D) is 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). The composition in any one of Claims 1-4 containing an active energy ray hardening initiator (E). It is a cured film of the curable composition in any one of Claims 1-5, Comprising: The antireflective film whose film thickness of this cured film is 0.03-0.5 micrometer. An antireflective film in which a hard coat layer and then a cured coating of the curable composition according to any one of claims 1 to 5 are directly formed on a transparent substrate film without any other layer.