JP2007011309A - Optical film containing fluorinated photopolymerization initiator, antireflective film, polarizing plate and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical film and an antireflective film which has a sufficient antireflection performance and an improved scratch resistance, and to provide a polarizing plate and an image display device. <P>SOLUTION: In the optical film, a layer applied on a support is made of a cured product of a composition which contains a fluorinated photopolymerization initiator and an ionizing radiation-curing compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an optical film and an antireflection film that have a low reflectance and improved scratch resistance, and more particularly to an optical film and an antireflection film used in an image display device such as a liquid crystal display device.

In display devices such as cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), and liquid crystal display (LCD), anti-reflection to prevent background reflection and improve visibility A film is used.
The antireflection film is disposed on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference in order to prevent the contrast from being reduced and the reflection of the image due to reflection.
Therefore, there is a high probability of scratching, and it was an important issue to provide excellent abrasion resistance.

  Such an antireflection film forms a low refractive index layer with an appropriate film thickness on the outermost surface, and optionally a high refractive index layer, a medium refractive index layer, a hard coat layer, etc. between the support (base material). It can produce by doing. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, high scratch resistance is required. In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the material, there are means of introducing fluorine atoms into the monomer binder polymer having an ethylenically unsaturated group and lowering the density (introducing voids). This is a direction in which the scratch resistance is deteriorated and the low refractive index and the high scratch resistance are both difficult problems.

  Patent Document 1 describes a means for improving the scratch resistance by reducing the friction coefficient of the coating surface by introducing a polysiloxane structure into the fluorine-containing polymer. Although this means is effective to some extent for improving scratch resistance, sufficient scratch resistance cannot be obtained only by this method for a film having an insufficient film strength and interfacial adhesion.

On the other hand, Patent Document 2 describes that the hardness is increased by curing a photocurable resin at a low oxygen concentration. However, in order to efficiently produce an antireflection film with a web, there is a limit to a low oxygen concentration by, for example, nitrogen substitution, and satisfactory hardness cannot be obtained.
Patent Document 3 describes a method of irradiating ionizing radiation by wrapping around the surface of a hot roll, but this is also not possible for curing a special thin film such as a low refractive index layer sufficiently. It was enough.

JP-A-11-189621 JP 2002-156508 A Japanese Patent Publication No. 7-51641

  An object of the present invention is to provide an optical film or an antireflection film having improved anti-scratch properties while having sufficient antireflection performance. Another object of the present invention is to provide the above optical film or antireflection film that can be produced under inexpensive production conditions, that is, under relatively high oxygen concentration conditions. It is a further object of the present invention to provide a polarizing plate and an image display device provided with such an optical film or antireflection film.

  As a result of intensive studies, the present inventors have found that the above object of the present invention can be achieved from an antireflection film composed of the following components and a method for producing the same.

一般式(１)において、Ｙはハロゲン原子を表す。Ｙ¹は−ＣＹ₃、−ＮＨ₂、−ＮＨＲ′、−ＮＲ′₂、−ＯＲ′を表す。Ｒ′はアルキル基、フルオロアルキル基、またはアリール基を表す。またＲは、Ｒ_a−Ｙ₁−、Ｒ_a−Ｙ₁−（ＣＨ₂）_r−、Ｒ_a−（ＣＨ₂）_r−Ｙ₁−、Ｒ_a−Ｙ₁−（ＣＨ₂）_s−Ｏ−、Ｒ_a−Ｙ₁−（ＣＨ₂）_s−Ｓ−及びＲ_a−Ｙ₁−（ＣＨ₂）_s−ＮＲ₁−からなる群より選択される置換基、−ＣＹ₃、アルキル基、置換アルキル基、フルオロアルキル基、置換フルオロアルキル基、アリール基、置換アリール基、または置換アルケニル基を表す。Ｒ₁は水素原子、メチル基またはエチル基を表し、rは1〜10の整数、ｓは2〜10の整数を表す。Ｙ₁は、互いに独立して、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−及び−Ｏ−Ｓｉ（Ｒ₂）₂−（ＣＨ₂）_r−からなる群より選択される二価の置換基を表す。Ｒ₂は炭素数１〜１２のアルキル又はフェニル基を表す。Ｒ_aは、直鎖状又は分岐鎖状の末端鎖：Ｚ¹ＣＦ₂（−Ｏ−Ｃ₂Ｆ₄）_p−（ＣＦ₂）_q−（ここで、Ｚ¹はＨ又はＦを表し；ｐ及びｑのうちの一方は、０〜２０の整数を表し、他方は１〜２０の整数を表す）を表す。

一般式(２)において、Ａ¹はフェニル基、ナフチル基、置換フェニル基、置換ナフチル基、または一般式(1)のＲと同じものを表し、ここで置換基とはハロゲン原子、アルキル基、フルオロアルキル基、アルコキシ基、ニトロ基、シアノ基もしくはメチレンジオキシ基である。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式（３）において、Ｗは無置換もしくは置換されたフェニル基、無置換のナフチル基、または一般式(1)のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。置換基の数は、置換基としてハロゲン原子を含むときは1つ又は２つであり、その他の場合は１つである。Ｘ¹は水素原子、フェニル基又は炭素数１〜３のアルキル基を表す。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式(４)において、Ｗ¹は無置換もしくは置換されたフェニル基、無置換のナフチル基、または一般式(1)のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。置換基の数は、置換基としてハロゲン原子を含むときは1つ又は２つであり、その他の場合は1つである。Ｘ²は水素原子、ハロゲン原子、シアノ基、アルキル基、またはアリル基を表す。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式(５)において、Ｚは無置換もしくは置換されたフェニル基、無置換のナフチル基、フルオロアルキル基、または一般式（１）のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。Ｘは同一でも異なっていても良く、水素原子、ハロゲン原子、アルキル基、または一般式（１）のＲと同じものを表す。ｎは1〜5の整数を表す。Ｚ、Ｘの内、少なくとも一つは一般式（１）のＲと同じものを表す。
（６）
前記フッ素化光重合開始剤が下記一般式（１）〜（５）のいずれか一つで表わされることを特徴とする（３）または（４）に記載の反射防止フィルム。

一般式(１)において、Ｙはハロゲン原子を表す。Ｙ¹は−ＣＹ₃、−ＮＨ₂、−ＮＨＲ′、−ＮＲ′₂、−ＯＲ′を表す。Ｒ′はアルキル基、フルオロアルキル基、またはアリール基を表す。またＲは、Ｒ_a−Ｙ₁−、Ｒ_a−Ｙ₁−（ＣＨ₂）_r−、Ｒ_a−（ＣＨ₂）_r−Ｙ₁−、Ｒ_a−Ｙ₁−（ＣＨ₂）_s−Ｏ−、Ｒ_a−Ｙ₁−（ＣＨ₂）_s−Ｓ−及びＲ_a−Ｙ₁−（ＣＨ₂）_s−ＮＲ₁−からなる群より選択される置換基、−ＣＹ₃、アルキル基、置換アルキル基、フルオロアルキル基、置換フルオロアルキル基、アリール基、置換アリール基、または置換アルケニル基を表す。Ｒ₁は水素原子、メチル基またはエチル基を表し、rは1〜10の整数、ｓは2〜10の整数を表す。Ｙ₁は、互いに独立して、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−及び−Ｏ−Ｓｉ（Ｒ₂）₂−（ＣＨ₂）_r−からなる群より選択される二価の置換基を表す。Ｒ₂は炭素数１〜１２のアルキル又はフェニル基を表す。Ｒ_aは、直鎖状又は分岐鎖状の末端鎖：Ｚ¹ＣＦ₂（−Ｏ−Ｃ₂Ｆ₄）_p−（ＣＦ₂）_q−（ここで、Ｚ¹はＨ又はＦを表し；ｐ及びｑのうちの一方は、０〜２０の整数を表し、他方は１〜２０の整数を表す）を表す。

一般式(２)において、Ａ¹はフェニル基、ナフチル基、置換フェニル基、置換ナフチル基、または一般式(1)のＲと同じものを表し、ここで置換基とはハロゲン原子、アルキル基、フルオロアルキル基、アルコキシ基、ニトロ基、シアノ基もしくはメチレンジオキシ基である。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式（３）において、Ｗは無置換もしくは置換されたフェニル基、無置換のナフチル基、または一般式(1)のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。置換基の数は、置換基としてハロゲン原子を含むときは1つ又は２つであり、その他の場合は１つである。Ｘ¹は水素原子、フェニル基又は炭素数１〜３のアルキル基を表す。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式(４)において、Ｗ¹は無置換もしくは置換されたフェニル基、無置換のナフチル基、または一般式(1)のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。置換基の数は、置換基としてハロゲン原子を含むときは1つ又は２つであり、その他の場合は1つである。Ｘ²は水素原子、ハロゲン原子、シアノ基、アルキル基、またはアリル基を表す。Ｙはハロゲン原子を表し、ｎは１〜３の整数を示す。

一般式(５)において、Ｚは無置換もしくは置換されたフェニル基、無置換のナフチル基、フルオロアルキル基、または一般式（１）のＲと同じものを表し、フェニル基の置換基はハロゲン原子、ニトロ基、シアノ基、炭素数１〜３のアルキル基又は炭素数１〜４のアルコキシ基である。Ｘは同一でも異なっていても良く、水素原子、ハロゲン原子、アルキル基、または一般式（１）のＲと同じものを表す。ｎは1〜5の整数を表す。Ｚ、Ｘの内、少なくとも一つは一般式（１）のＲと同じものを表す。
（７）
前記電離放射線硬化性化合物が二個以上のエチレン性不飽和基を有する化合物であることを特徴とする（１）、（２）、または（５）のいずれかに記載の光学フィルム。
（８）
前記電離放射線硬化性化合物が二個以上のエチレン性不飽和基を有する化合物であることを特徴とする（３）、（４）、または（６）のいずれかに記載の反射防止フィルム。
（９）
前記反射防止層が低屈折率層を有し、該低屈折率層が含フッ素ポリマーを含有する塗布液によって形成されたことを特徴とする（３）、（４）、（６）、または（８）のいずれかに記載の反射防止フィルム。
（１０）
前記含フッ素ポリマーが、下記一般式１で表わされる含フッ素ポリマーであることを特徴とする（９）に記載の反射防止フィルム。

〔一般式１中、Ｌは炭素数１〜１０の連結基を表し、ｍは０または１を表す。Ｘは水素原子またはメチル基を表す。Ａは任意のビニルモノマーの重合単位を表し、単一成分であっても複数の成分で構成されていてもよい。また、シリコーン部位を含んでいても良い。ｘ、ｙ、ｚはそれぞれの構成成分のモル％を表し、３０≦ｘ≦６０、５≦ｙ≦７０、０≦ｚ≦６５を満たす値を表す。〕
（１１）
前記含フッ素ポリマーが、下記一般式２で表わされる含フッ素ポリマーであることを特徴とする（９）に記載の反射防止フィルム。
一般式２

(1)
An optical film, wherein the layer coated on the support contains a cured product of a composition containing at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound.
(2)
The layer coated on the support contains a cured product of a composition containing at least one fluorinated photopolymerization initiator, an ionizing radiation curable compound, and at least one non-fluorinated photopolymerization initiator. (1) The optical film described in the above.
(3)
An antireflection film having at least an antireflection layer on a support, wherein at least one layer laminated on the support contains at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound. An antireflection film comprising a layer obtained by curing a composition to be cured by ionizing radiation irradiation.
(4)
(3) The composition containing the at least one fluorinated photopolymerization initiator and the ionizing radiation curable compound further contains at least one non-fluorinated photopolymerization initiator. Antireflection film.
(5)
The optical film according to (1) or (2), wherein the fluorinated photopolymerization initiator is represented by any one of the following general formulas (1) to (5).

In the general formula (1), Y represents a halogen atom. Y ¹ represents —CY ₃ , —NH ₂ , —NHR ′, —NR ′ ₂ , —OR ′. R ′ represents an alkyl group, a fluoroalkyl group, or an aryl group. R is R _a —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _r —, R _a — (CH ₂ ) _r —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _s —O. A substituent selected from the group consisting of-, R _a -Y _1- (CH ₂ ) _s -S- and R _a -Y _1- (CH ₂ ) _s -NR _1- , -CY ₃ , an alkyl group, An alkyl group, a fluoroalkyl group, a substituted fluoroalkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group is represented. R ₁ represents a hydrogen atom, a methyl group or an ethyl group, r represents an integer of 1 to 10, and s represents an integer of 2 to 10. Y ₁ is independently selected from the group consisting of —O—, —S—, —O—C (═O) — and —O—Si (R ₂ ) ₂ — (CH ₂ ) _r —. Represents a divalent substituent. R ₂ represents an alkyl or phenyl group having 1 to 12 carbon atoms. R _a is a linear or branched terminal chain: Z ¹ CF ₂ (—O—C ₂ F ₄ ) _p — (CF ₂ ) _q — (where Z ¹ represents H or F; p And one of q and q represents an integer of 0 to 20, and the other represents an integer of 1 to 20.

In the general formula (2), A ¹ represents a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group, or the same as R in the general formula (1), where the substituent is a halogen atom, an alkyl group, A fluoroalkyl group, an alkoxy group, a nitro group, a cyano group or a methylenedioxy group; Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a nitro group, A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ¹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), W ¹ represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1). The substituent of the phenyl group is a halogen atom or a nitro group. , A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (5), Z represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, a fluoroalkyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom. , A nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, or the same as R in the general formula (1). n represents an integer of 1 to 5. At least one of Z and X represents the same as R in the general formula (1).
(6)
The antireflection film as described in (3) or (4), wherein the fluorinated photopolymerization initiator is represented by any one of the following general formulas (1) to (5).

In the general formula (1), Y represents a halogen atom. Y ¹ represents —CY ₃ , —NH ₂ , —NHR ′, —NR ′ ₂ , —OR ′. R ′ represents an alkyl group, a fluoroalkyl group, or an aryl group. R is R _a —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _r —, R _a — (CH ₂ ) _r —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _s —O. A substituent selected from the group consisting of-, R _a -Y _1- (CH ₂ ) _s -S- and R _a -Y _1- (CH ₂ ) _s -NR _1- , -CY ₃ , an alkyl group, An alkyl group, a fluoroalkyl group, a substituted fluoroalkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group is represented. R ₁ represents a hydrogen atom, a methyl group or an ethyl group, r represents an integer of 1 to 10, and s represents an integer of 2 to 10. Y ₁ is independently selected from the group consisting of —O—, —S—, —O—C (═O) — and —O—Si (R ₂ ) ₂ — (CH ₂ ) _r —. Represents a divalent substituent. R ₂ represents an alkyl or phenyl group having 1 to 12 carbon atoms. R _a is a linear or branched terminal chain: Z ¹ CF ₂ (—O—C ₂ F ₄ ) _p — (CF ₂ ) _q — (where Z ¹ represents H or F; p And one of q and q represents an integer of 0 to 20, and the other represents an integer of 1 to 20.

In the general formula (2), A ¹ represents a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group, or the same as R in the general formula (1), where the substituent is a halogen atom, an alkyl group, A fluoroalkyl group, an alkoxy group, a nitro group, a cyano group or a methylenedioxy group; Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a nitro group, A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ¹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), W ¹ represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1). The substituent of the phenyl group is a halogen atom or a nitro group. , A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (5), Z represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, a fluoroalkyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom. , A nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, or the same as R in the general formula (1). n represents an integer of 1 to 5. At least one of Z and X represents the same as R in the general formula (1).
(7)
The optical film according to any one of (1), (2), and (5), wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.
(8)
The antireflection film according to any one of (3), (4), and (6), wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.
(9)
(3), (4), (6), or (3), wherein the antireflection layer has a low refractive index layer, and the low refractive index layer is formed of a coating solution containing a fluorine-containing polymer. The antireflection film as described in any one of 8).
(10)
The antireflection film as described in (9), wherein the fluoropolymer is a fluoropolymer represented by the following general formula 1.

[In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. Moreover, the silicone site | part may be included. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. ]
(11)
The antireflection film as described in (9), wherein the fluoropolymer is a fluoropolymer represented by the following general formula 2.
General formula 2

In the general formula 2 R represents an alkyl group having 1 to 10 carbon atoms, or an ethylenically unsaturated group (-C (= O) C ( -X) = CH 2).
m represents an integer of 1 ≦ m ≦ 10.
n represents an integer of 2 ≦ n ≦ 10.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included.
x, y, z1, and z2 represent mol% of each repeating unit. However, x + y + z1 + z2 = 100.
(12)
The antireflective film according to any one of (9) to (11), wherein the low refractive index layer contains hollow silica fine particles.
(13)
A method for producing an antireflection film having an antireflection layer comprising at least one layer on a transparent substrate, wherein at least one layer laminated on the transparent substrate is subjected to the following steps (i) to (iii): In addition, a method for producing an antireflection film, which is formed by a layer forming method in which the following transport step (ii) and curing step (iii) are continuously performed.
(I) a step of coating an application layer on the transparent substrate;
(Ii) a step of conveying the film having the coating layer in an oxygen concentration atmosphere lower than the oxygen concentration in the atmosphere while heating the film surface temperature to be 25 ° C. or higher;
(Iii) A step of curing the coating layer by irradiating the film with ionizing radiation while heating the film so that the film surface temperature is 25 ° C. or higher in an atmosphere having an oxygen concentration of 15% by volume or less.
(14)
The manufacturing method of the antireflection film has a step of applying a coating liquid from the slot of the tip lip by bringing a land of the tip lip of the slot die close to the surface of the web that is continuously supported by a backup roll. When the coating liquid has a land length in the web traveling direction of the tip lip on the web traveling direction side of the slot die of 30 μm or more and 100 μm or less, and the slot die is set at the coating position, the progress of the web The gap between the tip lip and the web opposite to the direction is applied using a coating apparatus installed so that the gap between the tip lip and the web on the web traveling direction side is 30 μm or more and 120 μm or less. The method for producing an antireflection film according to any one of (3), (4), and (6) to (13).
(15)
The viscosity at the time of application | coating of the said coating liquid is 2.0 [mPa * sec] or less, and the quantity of the coating liquid apply | coated to the web surface is 2.0-5.0 [ml / m < ² >]. The manufacturing method of the antireflection film as described in (14).
(16)
The method for producing an antireflection film as described in (14) or (15), wherein the coating liquid is applied to a continuously running web surface at a speed of 25 [m / min] or more.
(17)
An antireflection film produced by the method according to any one of (13) to (16), wherein the antireflection film according to any one of (3), (4), or (6) to (13) is produced.
(18)
The antireflection film according to any one of (3), (4), and (6) to (13) is used for one of the two protective films in the polarizing plate. .
(19)
The optical film according to any one of (1), (2) or (5), the antireflection film according to any one of (3), (4), or (6) to (13), or (18) An image display device using the polarizing plate described in 1.

The image display device provided with the optical film, antireflection film or polarizing plate of the present invention has less reflection of external light and reflection of the background, and is not only highly visible, but more than the conventional one. Excellent scratch resistance.
Moreover, according to the manufacturing method of this invention, said antireflection film can be manufactured cheaply.

  Hereinafter, the present invention will be described in detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. .

[Layer structure of antireflection film]
The antireflection film of the present invention has a hard coat layer, which will be described later, on a support (hereinafter sometimes referred to as a substrate or a substrate film) as necessary, and has a reflectivity due to optical interference thereon. The antireflection layer is laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so as to decrease. The simplest structure of a general antireflection layer is obtained by coating only a low refractive index layer on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably composed of a combination of a high refractive index layer having a higher refractive index than the substrate and a low refractive index layer having a lower refractive index than the substrate. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer). , A layer having a lower refractive index than a high refractive index layer) / a high refractive index layer / a low refractive index layer, and the like. Among them, in view of durability, optical characteristics, cost, productivity, and the like, those laminated in the order of medium refractive index layer / high refractive index layer / low refractive index layer on a substrate having a hard coat layer are preferable. The antireflection film of the present invention may have a functional layer such as an antiglare layer or an antistatic layer in addition to the hard coat layer described above.

The example of the preferable structure of the antireflection film of this invention is shown below.
Base film / low refractive index layer,
Base film / antiglare layer / low refractive index layer,
Base film / hard coat layer / antiglare layer / low refractive index layer,
Base film / hard coat layer / high refractive index layer / low refractive index layer,
Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer.
The antireflection film of the present invention is not particularly limited to these layer configurations as long as the reflectance can be reduced by optical interference. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Light diffusion layer]
The light diffusion layer includes translucent particles and a translucent resin. The scattered light profile and the haze value are adjusted by the translucent particles and the translucent resin. In the present invention, it is preferable to use translucent fine particles having two or more types and / or materials in addition to using one type of particles.

The refractive index of the light-transmitting fine particles and the refractive index of the light-transmitting resin constituting the entire light diffusion layer (described later, when inorganic fine particles are added to the light-transmitting resin for adjusting the refractive index of the layer, The difference from the optical average refractive index is preferably 0.03 to 0.30. It is preferably 0.03 or more because there is a sufficient difference in refractive index between them and a light diffusion effect is easily obtained, and it is 0.30 or less because the light diffusibility is not too high and the entire film is difficult to whiten. Preferably there is.
The difference in refractive index is more preferably 0.06 to 0.25, and most preferably 0.09 to 0.20.

  In the present invention, the particle diameter of translucent fine particles (first translucent fine particles) for improving display quality (viewing angle characteristics improvement) is preferably 0.5 to 3.5 μm, and preferably 0.5 μm to 2.0 μm. It is more preferable that By adjusting the particle diameter, an angular distribution of light scattering can be obtained.

  The light diffusing layer suitable for the present invention is adjusted by appropriately combining the refractive index difference between the translucent particles and the translucent resin constituting the entire light diffusing layer and the particle size of the translucent fine particles. However, it is particularly preferable in terms of achieving both viewing angle characteristics and whitening (blur).

  The greater the diffusion effect, the better the viewing angle characteristics. However, in order to maintain the front brightness in terms of display quality, it is also necessary to increase the transmittance as much as possible. When the particle diameter is less than 0.5 μm, the effect of scattering is great and the viewing angle characteristics are improved, but the backscattering becomes large and the brightness is greatly reduced. On the other hand, when it is larger than 2.0 μm, the scattering effect is reduced, and the improvement in viewing angle characteristics is reduced. Accordingly, the particle diameter is preferably 0.6 μm to 1.8 μm, and most preferably 0.7 μm to 1.6 μm.

  Further, it is also preferable to further add translucent fine particles (second translucent fine particles) that are not intended to impart a diffusion effect. It is used for providing unevenness on the surface of the diffusion film and providing a reflection preventing function. The particle diameter of the second light transmissive fine particles is preferably larger than the particle diameter of the first light transmissive particles, and more preferably 2.5 μm to 10.0 μm. Thereby, suitable surface scattering can be provided. In order to achieve good display quality, it is also necessary to prevent reflection of external light. The lower the haze value of the surface, the less the whiteness caused by external light and the clear display display can be obtained. However, if the surface haze value is too low, the reflection increases, so the light diffusion layer is the outermost layer. Therefore, it is necessary to provide a low refractive index layer having a refractive index lower than that of the refractive index to lower the reflectance. In order to control the surface haze value, it is preferable to provide appropriate irregularities on the surface of the resin layer with the second light-transmitting fine particles, but this is not restrictive. When the particle diameter is 2.5 μm or more, it is not necessary to reduce the thickness of the layer when providing desired surface irregularities, and this is preferable in terms of film hardness. On the other hand, when the particle diameter is 10 μm or less, each particle is one by one. In view of the stability of particle sedimentation in the coating solution, it is preferable. Therefore, the particle diameter of the second light transmitting fine particles is preferably 2.7 to 9 μm, and most preferably 3 to 8 μm.

  The difference between the refractive index of the second light-transmitting particles and the refractive index of the light-transmitting resin constituting the entire light diffusion layer is preferably smaller than that of the first light-transmitting particles.

  The surface roughness is preferably 0.5 μm or less, more preferably 0.3 μm or less, and most preferably 0.2 μm or less. The surface roughness Ra (centerline average roughness) can be measured according to JIS-B0601.

  The haze value of the light diffusion layer, particularly the internal scattering haze (internal haze) that greatly contributes to the diffusion of transmitted light has a strong correlation with the effect of improving the viewing angle characteristics. The light emitted from the backlight is diffused by the light diffusion layer installed on the surface of the polarizing plate on the viewing side, whereby the viewing angle characteristics are improved. However, since the front luminance is reduced if it is excessively diffused, the internal haze of the light diffusion layer is preferably 45% or more and 80% or less, more preferably 45% or more and 70% or less, and particularly preferably 45% or more and 60% or less. As a method of increasing noise to internal scattering, increasing the particle concentration of translucent fine particles for the purpose of imparting diffusibility, increasing the coating film thickness, and further increasing the refractive index difference between the particles and the resin, etc. There is a way.

  In order to improve display quality (improve viewing angle characteristics) in the present invention, it is particularly preferable that the scattered light intensity of 30 ° with respect to the light intensity at the output angle of 0 ° of the scattered light profile of the goniophotometer is within a specific range. . The scattered light intensity of 30 ° with respect to the light intensity of the goniophotometer scattered light profile with an emission angle of 0 ° is preferably 0.05% or more from the viewpoint of visual characteristics, and 0.3% from the viewpoint of not greatly reducing the front luminance. The following is preferred. Therefore, the light diffusion layer of the present invention is preferably 0.05 to 0.3%, more preferably 0.05 to 0.2%, and 0.05 to 0.15%. Particularly preferred. It is more preferable to satisfy the above preferable range of the internal haze.

  The haze due to surface scattering of the polarizing plate of the present invention (surface haze) is preferably 0.1 to 30%, more preferably 10% or less, and more preferably 5% or less from the viewpoint of achieving both reduction in reflection and reduction in white-brown feeling. Is particularly preferred. If importance is attached to the reduction of white-brown feeling due to external light, it is preferably 4% or less, and more preferably 2% or less. Since reflection increases when surface haze is reduced, a low refractive index layer is provided, and it is preferable that the average value in the wavelength region from 450 nm to 650 nm of the integrated reflectance at 5 ° incidence be 3.0% or less, It is more preferably 2.0% or less, and most preferably 1.0% or less. In order to improve display quality (improve viewing angle characteristics) in the present invention, it is necessary to adjust the internal scattering property as described above. At the same time, by setting the surface haze and / or reflectivity within a suitable range, The contrast is improved and the most preferable effect can be exhibited.

  The translucent fine particles, monodispersed organic fine particles, or inorganic fine particles may be used. As the particle size is not more varied, the scattering characteristics are less varied, and the haze value can be easily designed. As the translucent fine particles, plastic beads are preferred, and those having particularly high transparency and a difference in refractive index from the translucent resin are preferred. As organic fine particles, polymethyl methacrylate beads (refractive index 1.49), acrylic-styrene copolymer beads (refractive index 1.54), melamine beads (refractive index 1.57), polycarbonate beads (refractive index 1.57). ), Styrene beads (refractive index 1.60), cross-linked polystyrene beads (refractive index 1.61), polyvinyl chloride beads (refractive index 1.60), benzoguanamine-melamine formaldehyde beads (refractive index 1.68), etc. It is done. As the inorganic fine particles, silica beads (refractive index 1.44 to 1.46), alumina beads (refractive index 1.63), and the like are used. The translucent fine particles may be contained in an amount of 5 to 30 parts by mass with respect to 100 parts by mass of the translucent resin.

  In the case of the above translucent fine particles, since the translucent fine particles are likely to settle in the resin composition (translucent resin), an inorganic filler such as silica may be added to prevent sedimentation. . As the amount of the inorganic filler added increases, it is more effective in preventing the sedimentation of the translucent fine particles, but it may adversely affect the transparency of the coating film. Therefore, it is preferable that an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than 0.1% by mass so as not to impair the transparency of the coating film with respect to the translucent resin.

  As the translucent resin, there are three types of resins that are mainly cured by ultraviolet rays and electron beams, that is, an ionizing radiation curable resin, a mixture of an ionizing radiation curable resin and a thermoplastic resin and a solvent, and a thermosetting resin. Is done. In order to impart hard coat properties, an ionizing radiation curable resin is preferably the main component. The thickness of the light diffusion layer is usually 1.5 μm to 30 μm, preferably 3 μm to 20 μm. In general, the light diffusion layer also serves as a hard coat layer. When the thickness of the light diffusion layer is 1.5 μm or more, the hard coat property is sufficient, and on the other hand, the thickness is 30 μm or less. From the viewpoint of curling and brittleness. When providing the low refractive index layer, the refractive index of the translucent resin is preferably 1.46 to 2.00, more preferably 1.48 to 1.90, and further preferably 1.50. 1.80. The refractive index of the translucent resin is an average value of the light diffusion layer measured without including the translucent fine particles. When the refractive index of the light diffusing layer is too small, the antireflection property is lowered. If it is too large, the color of the reflected light becomes strong, which is not preferable. From this point, the above range is preferable. The refractive index of the light diffusion layer is set to a desired value in terms of antireflection properties and reflected light color.

  The binder used for the translucent resin is preferably a polymer having a saturated hydrocarbon or polyether as the main chain, and more preferably a polymer having a saturated hydrocarbon as the main chain. The binder is preferably crosslinked. The polymer having a saturated hydrocarbon as the main chain is preferably obtained by a polymerization reaction of an ethylenically unsaturated monomer. In order to obtain a crosslinked binder, it is preferable to use a monomer having two or more ethylenically unsaturated groups.

  Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, penta Erythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene derivatives Examples include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. included. Among these, acrylate or methacrylate monomers having at least three functional groups, and further acrylate monomers having at least five functional groups are preferable from the viewpoint of film hardness, that is, scratch resistance. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is commercially available and is particularly preferably used.

  These monomers having an ethylenically unsaturated group can be cured by a polymerization reaction by ionizing radiation or heat after being dissolved in a solvent, coated and dried together with various polymerization initiators and other additives.

  In place of or in addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder by reaction of a crosslinkable group. Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition. The binder having these crosslinkable functional groups can form a crosslinked structure by heating after coating.

The translucent resin is preferably formed from a monomer having a high refractive index and / or metal oxide ultrafine particles having a high refractive index in addition to the binder polymer. Examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether and the like. Examples of the metal oxide ultrafine particles having a high refractive index include a particle diameter of 100 nm or less, more preferably 50 nm or less, including at least one oxide selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony. It is preferable to contain the fine particles. The metal oxide ultrafine particles having a high refractive index are preferably oxide ultrafine particles of at least one metal selected from Al, Zr, Zn, Ti, In and Sn. Specific examples include ZrO ₂ , TiO ₂ , _{al 2 O 3, In 2 O} 3, ZnO, SnO 2, Sb 2 O 3, ITO , and the like. Among these, ZrO ₂ is particularly preferably used. The addition amount of the high refractive index monomer and the metal oxide ultrafine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the translucent resin.

  The light diffusion layer is preferably formed by coating on a cellulose acetate film. The solvent of the coating solution for forming the light diffusion layer is transparent to prevent excessive penetration of the diffusion layer component into the transparent base film and to ensure adhesion between the diffusion layer and the transparent base film. It comprises at least one solvent that dissolves the substrate film (for example, triacetyl cellulose support) and at least one solvent that does not dissolve the transparent substrate film. More preferably, at least one of the solvents that dissolve the transparent substrate film has a higher boiling point than at least one of the solvents that do not dissolve the transparent substrate film. More preferably, the boiling point temperature difference between the solvent having the highest boiling point among the solvents that dissolve the transparent substrate film and the solvent having the highest boiling point among the solvents that do not dissolve the transparent substrate film is 30 ° C. or more. Yes, most preferably 40 ° C or higher.

  As a solvent for dissolving a transparent base film (preferably triacetyl cellulose), ethers having 3 to 12 carbon atoms: specifically, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1 Ketones having 3 to 12 carbon atoms such as 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole: specifically, acetone, methyl ethyl ketone, diethyl ketone, dipropyl Esters having 3 to 12 carbon atoms such as ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone and methylcyclohexanone: specifically, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate , Propionate Organic solvents having two or more kinds of functional groups, such as thiol, propion brewed ethyl, n-pentyl acetate, and γ-ptyrolactone: specifically, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate , Ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate. These can be used alone or in combination of two or more. The solvent for dissolving the transparent substrate is preferably a ketone solvent.

  As a solvent that does not dissolve the transparent base film (preferably triacetyl cellulose), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-methyl- Examples include 2-butanol, cyclohexanol, isobutyl acetate, methyl isobutyl ketone, 2-octanone, 2-pentanone, 2-hexanone, 2-heptanone, 3-pentanone, 3-heptanone, 4-heptanone, and toluene. These can be used alone or in combination of two or more.

  The mass ratio (A / B) of the total amount (A) of the solvent that dissolves the transparent substrate film and the total amount (B) of the solvent that does not dissolve the transparent substrate film is preferably 5/95 to 50/50, more preferably It is 10 / 90-40 / 60, More preferably, it is 15 / 85-30 / 70.

  As a curing method of the ionizing radiation curable resin composition as described above, the ionizing radiation curable resin composition can be cured by a normal curing method, that is, irradiation with an electron beam or ultraviolet rays.

  For example, in the case of electron beam curing, 50 to 1000 keV emitted from various electron beam accelerators such as a Cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type. Preferably, an electron beam having an energy of 100 to 300 keV is used, and in the case of ultraviolet curing, ultraviolet rays emitted from rays such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used. it can.

[Fluorinated photopolymerization initiator]
The optical film and antireflection film of the present invention have a layer formed on a support by curing a composition containing at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound by irradiation with ionizing radiation. This layer may be, for example, any one or more of the layers listed above as a preferred configuration of the antireflection film.
Fluorinated photopolymerization initiators generally tend to increase in concentration near the surface layer after coating and drying, and radicals generated by ionizing radiation quench the oxygen near the surface layer, thereby reducing the influence of oxygen from the surface layer. Effective polymerization of the entire film can proceed.
In the present invention, it is particularly preferable to use at least one compound selected from the compounds represented by the following general formulas (1) to (5).
Hereinafter, the compounds represented by the general formulas (1) to (5) will be described.

In the general formula (1), Y represents a halogen atom. Y ¹ represents —CY ₃ , —NH ₂ , —NHR ′, —NR ′ ₂ , —OR ′. R ′ represents an alkyl group, a fluoroalkyl group, or an aryl group. R is R _a —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _r —, R _a — (CH ₂ ) _r —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _s —O. A substituent selected from the group consisting of-, R _a -Y _1- (CH ₂ ) _s -S- and R _a -Y _1- (CH ₂ ) _s -NR _1- , -CY ³ , an alkyl group, An alkyl group, a fluoroalkyl group, a substituted fluoroalkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group is represented. Y ₁ is independently selected from the group consisting of —O—, —S—, —O—C (═O) — and —O—Si (R ₂ ) ₂ — (CH ₂ ) _r —. Represents a divalent substituent. R ₂ represents an alkyl or phenyl group having 1 to 12 carbon atoms.
R _a is a linear or branched terminal chain: Z ¹ CF ₂ (—O—C ₂ F ₄ ) _p — (CF ₂ ) _q — (where Z ¹ represents H or F; p And one of q and q represents an integer of 0 to 20, and the other represents an integer of 1 to 20.

If Y ¹ of the general formula (1) is used a compound that is -CY ₃ is particularly preferred. Y is preferably a Cl, Br, or F atom.
Specific examples of the compound represented by the general formula (1) are as follows.

A ¹ is a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group (the substituted phenyl group, the substituent in the substituted naphthyl group is a halogen atom, an alkyl group, a fluoroalkyl group, an alkoxy group, a nitro group, a cyano group, or It is a methylenedioxy group) or the same as R in the general formula (1), Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (2) are as follows.

W represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a nitro group, a cyano group, 3 alkyl groups or alkoxy groups having 1 to 4 carbon atoms. The number of substituents of the phenyl group is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ¹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (3) are as follows.

W ¹ represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a fluoroalkyl group, a nitro group, a cyano group , An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. The number of substituents of the phenyl group is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a fluoroalkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.
Specific examples of the compound represented by the general formula (4) are as follows.

In the general formula (5), Z represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, a fluoroalkyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom. , A nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, or the same as R in the general formula (1). n represents an integer of 1 to 5. At least one of Z and X represents the same as R in the general formula (1).
Specific examples of the compound represented by the general formula (5) are as follows.

  The compounds represented by the general formulas (1) to (5) are described in, for example, MP Hutt, EF Elslager and LMWerbel, Journal of Heterocyclic Chemistry, Vol. 7 (No. 3), pages 511 and after (1970). It can be easily synthesized by those skilled in the art according to the synthesis method currently used. The S-triazine compound is synthesized by the following method. That is, the method described in R. Adams et al. `` Organic Syntheses '' (J. Wiley & Sons) Collective Volume 2, page 623, or V. Coviello et al., Helvetica Chimica Acta, 59, 819-834 (1976). By cyclization according to the method described in K. Wakabayashi et al., Bulletin of the Chemical Society of Japan, 42, 2924-2930 (1969), using an aromatic nitrile compound and haloacetonitrile. Can be synthesized.

  Although there is no restriction | limiting in particular in the usage-amount of a fluorinated photoinitiator, It is preferable to use in the range of 0.1-30 mass parts with respect to 100 mass parts of ionizing radiation-curable compounds, More preferably, it is 1-20. Part by mass. Also, a plurality of fluorinated photopolymerization initiators may be used, or used in combination with other polymerization initiators (non-fluorinated polymerization initiators) such as radical polymerization initiators and photosensitizers. Also good.

[Other polymerization initiators]
Examples of other radical polymerization initiators and photosensitizers include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (Japanese Patent Laid-Open No. 2001-139663) Gazette), 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins Etc.

Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone.
Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.

Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler's ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like.
Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Specifically, Examples 1 to 21 described in JP-A 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Examples of the borate salt include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech'98.
eding April 19-22, 1998 “Chicago” and the like. Examples thereof include compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, Specific examples include organoboron transition metal coordination complexes such as 7-292014, and specific examples include ion complexes with cationic dyes.

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds. 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.

Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in combination. “Latest UV Curing Technology”, Technical Information Association, 1991, p. 159 and “UV curing system” written by Kayo Kiyomi, 1989, published by the General Technology Center, p. 65-148, are useful for the present invention.
Commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 819, 907, 1870 (CGI-403 / Irg184 = 7/3 mixed initiator, 500) manufactured by Ciba Specialty Chemicals Co., Ltd. , 369, 1173, 2959, 4265, 4263), OXE01), etc., and Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, manufactured by Nippon Kayaku Co., Ltd. , ITX, QTX, BTC, MCA, etc.), Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) manufactured by Sartomer, and combinations thereof are preferable examples.

When using said other photoinitiator (non-fluorinated photoinitiator), it is used in 0.1-15 mass parts with respect to 100 mass parts of ionizing radiation-curable compounds. More preferably, it is the range of 1-10 mass parts.
Fluorinated photopolymerization initiators are expected to function effectively to accelerate the hardening of the surface layer by mitigating the influence of oxygen in the surface layer, while non-fluorinated photopolymerization initiators reliably promote the hardening of the interior of the layer. Therefore, the combined use is considered preferable.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Furthermore, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as ammonium sulfate, potassium persulfate and the like, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. And diazoaminobenzene, p-nitrobenzenediazonium and the like.

[Coating method]
The method for producing an antireflection film of the present invention preferably includes a step of forming at least one layer laminated on the support by the following steps (1) and (2).
(1) A step of coating and drying a coating liquid containing at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound on a web that includes a support, which runs continuously, and forms a coating layer;
(2) A step of curing the coating layer by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 15% by volume or less (hereinafter, the coating layer of (2) The step of curing is sometimes referred to as “curing step”).

The irradiation with ionizing radiation is preferably performed in an atmosphere having an oxygen concentration of 15% by volume or less. More preferably, it is 10 volume% or less, More preferably, it is 5.0 volume% or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas is required, which is not preferable from the viewpoint of production cost. As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, and particularly preferably with nitrogen (nitrogen purge). It is.
In the present invention, the coating layer is preferably cured by irradiating the coating layer on the web with ionizing radiation for 0.5 seconds or more in an atmosphere having an oxygen concentration of 5% by volume or less. The irradiation time is preferably from 0.7 seconds to 60 seconds, more preferably from 0.7 seconds to 10 seconds from the start of irradiation. If it is less than 0.5 seconds, the curing reaction cannot be completed and sufficient curing cannot be performed.
In the present specification, the “web” may be the support itself or a layer formed on the support.

In the present invention, the curing step is preferably performed in an ionizing radiation reaction chamber (hereinafter sometimes simply referred to as “reaction chamber”) controlled to a desired oxygen concentration. When supplying the inert gas to the ionizing radiation reaction chamber, the reaction chamber is designed to eliminate the transport air accompanying the web transport by slightly blowing it out to the web entrance side of the reaction chamber (which is the entrance for loading the web). Can be effectively reduced, and the substantial oxygen concentration at the extreme surface where the inhibition of curing by oxygen is large can be efficiently reduced. The direction of the inert gas flow on the web entrance side of the reaction chamber can be controlled by adjusting the balance between supply and exhaust of the reaction chamber. In addition, it is also preferable as a method for removing the carry air that the inert gas is blown directly onto the surface of the coating layer on the web immediately before the coating layer on the web is irradiated with ionizing radiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and is thin is cured by this method.

It is also preferable to provide a front chamber before the reaction chamber. The anterior chamber is preferably replaced with an inert gas and has a low oxygen concentration, preferably an oxygen concentration of 5% by volume or less and an oxygen concentration of 0.01% by volume or more. It is possible to simply pass (carry) the web before irradiation with ionizing radiation through the front chamber, and by directly blowing the inert gas onto the surface of the coating layer on the web, which is a method of removing the above-described carried air. Also good.
By providing the front chamber and excluding oxygen on the surface of the coating layer of the web in advance, it becomes possible to maintain a low oxygen concentration in the reaction chamber, and the curing can proceed more efficiently.

Further, at least one of the side surfaces constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber has a gap of 0.2 to 15 mm with the surface of the coating layer on the web in order to use the inert gas efficiently. It is preferable that the thickness is 0.2 to 10 mm, and most preferably 0.2 to 5 mm. Here, the gap refers to the length between the surface of the coating layer on the web and the upper end of the web entrance on the side surface constituting the web entrance side.
However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance of the ionizing radiation reaction chamber or the front chamber and the surface of the coating layer on the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable and to widen the gap by the junction thickness when the junction enters. In order to realize this, (A) an ionization radiation reaction chamber or an entrance surface of an anterior chamber is made movable forward and backward, and when the joint passes, it moves forward and backward to widen the gap, or (B) The entrance surface of the ionizing radiation reaction chamber or the front chamber can be moved vertically with respect to the web surface, and the gap can be widened by moving up and down as the joint passes.

In the following, the operation of the web entrance surface of the front chamber is taken as an example, and an example of the operation of the web entrance surface of the reaction chamber or the front chamber applicable in the present invention will be described with reference to FIGS. Then, a web having a coating layer (not shown) is simply referred to as “web”).
FIG. 1 is a schematic view of a production apparatus equipped with an ionizing radiation reaction chamber and an anterior chamber of the present invention.
FIG. 2 is a side view showing an example of the apparatus operation on the web entrance surface of the manufacturing apparatus equipped with the ionizing radiation reaction chamber and the front chamber of the present invention, and shows the mode (A). The apparatus having the configuration of FIG. 2 detects a joining member with a sensor before the joining member that joins and joins the web enters the front chamber entrance at the time of web conveyance, and the sensor and the sensor through a control unit (not shown). An air cylinder attached to at least a part of the web entrance surface of the front chamber that operates in conjunction with it allows the entrance surface to be moved back and forth in the direction of web travel, thereby escaping the thickness of the joining member It is something that can be done.

  3 and 4 are views showing the above-described embodiment (B), FIG. 3 is a view schematically showing the web entrance surface of the front chamber, and FIG. 4 is an operation of the web entrance surface of the front chamber. FIG. A gap between the web and the entrance surface is determined by making a part of the web entrance surface of the front chamber movable and contacting both ends of the web with the bearing touch roll. When the joining member passes, the bearing touch roll gets over the joining member, and the gap at the web entrance surface is kept constant. The moving means at the entrance is not limited as long as it can escape the joint.

In the present invention, when the coating layer on the web is cured, it is also preferable to perform the ionizing radiation irradiation performed in an atmosphere of 5% by volume or less in the curing step in a plurality of times.
In this case, it is preferable that the ionizing radiation irradiation is performed at least twice in a reaction chamber having a continuous oxygen concentration of 5% by volume or less. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured. In particular, when the production rate is increased for high productivity, multiple ionizing radiation irradiations are necessary to ensure the energy of ionizing radiation necessary for the curing reaction, and this is combined with ensuring the reaction time necessary for the curing reaction. The above aspect is effective.
“Consecutive reaction chamber” refers to an embodiment in which ionizing radiation is irradiated at least twice in a reaction chamber having an oxygen concentration of 5% by volume or less, or at least two reaction chambers having an oxygen concentration of 5% by volume or less are provided. There is an embodiment in which the gap is a low oxygen zone having an oxygen concentration of 5 vol% or less. In the latter case, each reaction chamber may have a different oxygen concentration as long as the oxygen concentration is 5% by volume or less.

  In this invention, it is also preferable to perform the said hardening process, heating a web so that the coating layer surface temperature may be 25 degreeC or more. It is also preferable to heat in an atmosphere having an oxygen concentration of 5% by volume or less simultaneously and / or continuously with ionizing radiation irradiation. By performing the curing step while heating, the curing reaction is accelerated by heat, and a film excellent in physical strength and chemical resistance can be formed.

  The heating is preferably performed at a coating layer surface temperature of 25 ° C. or more and 170 ° C. or less. A temperature of 25 ° C. or higher is preferable from the viewpoint of sufficient curing by heating, while a temperature of 170 ° C. or lower is preferable from the viewpoint that problems such as deformation of the substrate hardly occur. A more preferable temperature is 25 ° C to 100 ° C. Further, the time during which the surface temperature of the coating layer is maintained at the above temperature is preferably 0.1 seconds or more and 300 seconds or less from the start of ionizing radiation irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the coating layer surface temperature in the above temperature range is too short, the reaction of the curable composition for forming the film cannot be promoted. There are also problems in manufacturing such as an increase in size.

  The heating method is not particularly limited, but a method of heating a roll to contact the web, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

The ionizing radiation species in the present invention is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays and the like according to the type of curable composition forming the film. You can choose. In the present invention, irradiation with ultraviolet rays is preferred. Ultraviolet curing is preferred because the polymerization rate is fast and the equipment can be made compact, and there are abundant and low-priced compound types that can be selected.
In the case of ultraviolet rays, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used. In the case of electron beam irradiation, energy of 50 to 1000 keV emitted from various electron beam accelerators such as Cockloft Walton type, bandegraph type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type. An electron beam having the following is used.

[Film-forming binder]
In the present invention, it is possible to contain an ionizing radiation curable compound, preferably a compound having an ethylenically unsaturated group, as a film-forming binder component in the curable composition for forming a film. From the viewpoints of productivity and productivity of the coating film. The content of the ionizing radiation curable compound is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, and still more preferably 30% by mass or more, among the film forming components excluding inorganic particles. 95% or less.
In the present specification, the “ionizing radiation curable compound” may be any compound that is cured by irradiation with ionizing radiation.
The film-forming binder and the ionizing radiation curable compound are preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. Furthermore, these polymers preferably have a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
Further, in the case of forming a film having a high refractive index, the monomer structure contains at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. It is preferable.

Monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester poly Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide.
Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate”, “(meth) acryloyl”, and “(meth) acrylic acid” are “acrylate or methacrylate”, “acryloyl or methacryloyl”, “acrylic acid or methacrylic acid”, respectively. ".

  Furthermore, specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of these monomers having an ethylenically unsaturated group is carried out by ionizing radiation in the presence of the fluorinated photopolymerization initiator described above and optionally other polymerization initiators such as a photoradical initiator or a thermal radical initiator. It can be carried out by irradiation or heating.

  In the present invention, a polymer having a polyether as a main chain can also be used. A ring-opening polymer of a polyfunctional epoxy compound is preferred. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Known photoacid generators and thermal acid generators can be used.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

[Material for low refractive index layer]
The antireflection layer of the antireflection film of the present invention may have a low refractive index layer formed by a coating solution containing a fluorine-containing polymer.
The low refractive index layer of the present invention is formed by applying and curing a curable composition containing a fluorine-containing compound as a main component or a monomer having a plurality of bonding groups in the molecule and low refractive index particles. And it is preferable that the refractive index is adjusted in the range of 1.20 to 1.50. 1.25 to 1.45 is more preferable. More preferably 1.30 to 1.40.
Preferred embodiments of the cured product composition include (1) a composition containing a fluorine-containing polymer having a crosslinkable or polymerizable functional group, and (2) a hydrolysis condensate of a fluorine-containing organosilane material as a main component. Composition, (3) a composition containing a monomer having two or more ethylenically unsaturated groups and inorganic fine particles having a hollow structure, thereby comparing with a low refractive index layer using magnesium fluoride or calcium fluoride Even when used as the outermost layer, an optical film and an antireflection film excellent in scratch resistance can be obtained. The dynamic friction coefficient of the cured low refractive index layer surface is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 degrees.

(1) Fluorine-containing compound having a crosslinkable or polymerizable functional group As the fluorine-containing compound having a crosslinkable or polymerizable functional group, co-polymerization of a fluorine-containing monomer and a monomer having a crosslinkable or polymerizable functional group Coalescence can be mentioned. Examples of the fluorine-containing monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) (meta ) Acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like.

  As an example of the monomer for imparting a crosslinkable group, a (meth) acrylate monomer having a crosslinkable functional group in the molecule in advance such as glycidyl methacrylate can be exemplified. In another embodiment, after synthesizing a fluorinated copolymer using a monomer having a functional group such as a hydroxyl group, the monomer is further modified to introduce a crosslinkable or polymerizable functional group by modifying the substituent. It is. These monomers include (meth) acrylate monomers having a carboxyl group, hydroxyl group, amino group, sulfonic acid group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.) Is mentioned. The latter embodiment is disclosed in Japanese Patent Laid-Open Nos. 10-25388 and 10-147739.

The fluorine-containing copolymer may contain a copolymerizable component as appropriate from the viewpoints of solubility, dispersibility, coating property, antifouling property, antistatic property and the like. In particular, for imparting antifouling properties and slipperiness, it is preferable to introduce silicone, and it can be introduced into both the main chain and the side chain.
The polysiloxane partial structure introduction method to the main chain is, for example, an azo group-containing polysiloxane amide described in JP-A-6-93100 (VPS-0501, 1001 (trade name; Wako Pure Chemical Industries, Ltd. And a method using a polymer-type initiator such as a company)). Further, the method of introducing into the side chain is, for example, as described in J. Appl. Polym. Sci. 2000, 78, 1955, JP-A-56-28219, etc. For example, a silaplane series (manufactured by Chisso Corporation) can be synthesized by a method of introducing a polymer reaction or a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used.

As described in JP 2000-17028 A, a curing agent having a polymerizable unsaturated group may be used in combination with the above polymer. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the above-described monomers having two or more ethylenically unsaturated groups. Moreover, the hydrolysis-condensation product of the organosilane described in Unexamined-Japanese-Patent No. 2004-170901 is also preferable, and the hydrolysis-condensation product of the organosilane containing a (meth) acryloyl group is especially preferable.
These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

  When the polymer itself does not have sufficient curability, necessary curability can be imparted by blending a crosslinkable compound. For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like. For curing these compounds, an organic acid or a salt thereof is preferably used.

  Specific examples of these fluoropolymers are described in JP2003-222702A, JP2003-183322A, and the like.

(2) Hydrolyzed condensate of fluorine-containing organosilane material A composition containing a hydrolyzed condensate of a fluorine-containing organosilane compound as a main component is also preferable because of its low refractive index and high hardness on the coating film surface. A condensate of a tetraalkoxysilane with a hydrolyzable silanol-containing compound at one or both ends with respect to the fluorinated alkyl group is preferred. The specific composition is described in Unexamined-Japanese-Patent No. 2002-265866, 317152.

(3) A composition containing a monomer having two or more ethylenically unsaturated groups and inorganic fine particles having a hollow structure As yet another preferred embodiment, a low refractive index layer comprising low refractive index particles and a binder can be mentioned. . The low refractive index particles may be organic or inorganic, but particles having pores inside are preferable. Specific examples of the hollow particles are described in the silica-based particles described in JP-A-2002-79616. The particle refractive index is preferably 1.15 to 1.40, more preferably 1.20 to 1.30. Examples of the binder include monomers having two or more ethylenically unsaturated groups described in the page of the light diffusion layer.

  In the low refractive index layer of the present invention, it is preferable to add the polymerization initiator described on the light diffusion layer page. When a radically polymerizable compound is contained, 1 to 10 parts by mass, preferably 1 to 5 parts by mass of a polymerization initiator can be used with respect to the compound.

  In the low refractive index layer of the present invention, inorganic particles can be used in combination. In order to impart scratch resistance, fine particles having a particle size of 15% to 150%, preferably 30% to 100%, more preferably 45% to 60% of the thickness of the low refractive index layer can be used. .

  In the low refractive index layer of the present invention, for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipping property, a known polysiloxane-based or fluorine-based antifouling agent, slipping agent, etc. are appropriately used. Can be added.

The copolymer preferably used for the low refractive index layer of the present invention will be described below.
Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (trade name) , Osaka Organic Chemical Industry Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)), and fully or partially fluorinated vinyl ethers, and the like, preferably perfluoroolefins, From the viewpoints of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferred. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, the fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50%. This is a case of mass%.

  The copolymer preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential component. If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. Generally, the (meth) acryloyl group-containing repeating unit preferably accounts for 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight.

  In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

  The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) -2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethyl) Styrene, p-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (acetic acid) Nyl, vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide) N-cyclohexylacrylamide), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  In the present invention, a fluorine-containing polymer represented by the following general formula 1 is preferably used.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, or may have a heteroatom selected from O, N, and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, - (CH} 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connecting site on the (meth) acryloyl group side) And the like. m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

A particularly preferred form of the copolymer used in the present invention is General Formula 2.
General formula 2

In General Formula 2, R may be an alkyl group having 1 to 10 carbon atoms or an ethylenically unsaturated group (—C (═O) C (—X) ═CH ₂ ).
m represents an integer of 1 ≦ n ≦ 10, preferably 1 ≦ n ≦ 6, and particularly preferably 1 ≦ n ≦ 4.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included.
x, y, z1 and z2 represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 0 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦ 55. 0 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55 and 0 ≦ y ≦ 55. z1 and z2 preferably satisfy 1 ≦ z1 ≦ 65 and 1 ≦ z2 ≦ 65, more preferably 1 ≦ z1 ≦ 40, and 1 ≦ z2 ≦ 10, preferably 1 ≦ z1 ≦ 30, It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

  The copolymer represented by the general formula 1 or 2 can be synthesized, for example, by introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component.

  The copolymers useful in the present invention are preferably those shown in paragraph numbers [0043] to [0047] of JP-A No. 2004-45462.

  The copolymer used for this invention is compoundable by the method as described in Unexamined-Japanese-Patent No. 2004-45462. The copolymer used in the present invention can be synthesized by various polymerization methods other than those described above, for example, precursors such as a hydroxyl group-containing polymer by solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. Can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating ionizing radiation, and the like. These polymerization methods and polymerization initiation methods are described in, for example, Tsuruta Junji, “Polymer Synthesis Method” revised edition, Nikkan Kogyo Shimbun, 1971 and Takatsu Otsu, Masaaki Kinoshita, “Experimental Methods for Polymer Synthesis”, Chemistry Doujin, 1972, pp. 124-154.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, Benzene, toluene, acetonitrile, methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more kinds of organic solvents may be used. A mixed solvent may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

  The reaction pressure can be selected as appropriate, but usually 1 to 100 kPa, particularly about 1 to 30 kPa is desirable. The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

The inorganic fine particles that can be preferably used for the low refractive index layer in the antireflection film of the present invention will be described.
The coating amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of silica or hollow silica. The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, if the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x expressed by the following formula (VIII) is (Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10-60%, More preferably, it is 20-60%, Most preferably, it is 30-60%. Since the thickness of the outer shell is sufficiently thick and the strength of the particles is increased, particles having a refractive index of 1.15 or more are preferable from the viewpoint of scratch resistance.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of lowering the refractive index and the effect of improving the scratch resistance will be reduced.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.
Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It can also be used in combination with "silica fine particles having a diameter".
Since the fine silica particles having a small particle size can exist in the gaps between the fine silica particles having a large particle size, they can contribute as a retaining agent for the fine silica particles having a large particle size.
The average particle size of the silica fine particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

Silica fine particles are treated by physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding to the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, treatment with a silane coupling agent having an acryloyl group or a methacryloyl group is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment. Specific examples of the surface treatment agent and the catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 2004/017105.

  In the present invention, it is preferable to add a hydrolyzate of organosilane and / or a partial condensate (sol) thereof from the viewpoint of improving the film strength. The preferable amount of sol added is preferably 2 to 200% by mass of inorganic fine particles, more preferably 5 to 100% by mass, and most preferably 10 to 50% by mass.

  In the present invention, it is preferable to reduce the surface free energy on the surface of the antireflection film from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a silicone compound having a polysiloxane structure for the low refractive index layer. Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), manufactured by Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto. In addition, silicone compounds described in Tables 2 and 3 of JP-A No. 2003-112383 can also be preferably used. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

The fluoropolymer can be polymerized by irradiation with ionizing radiation or heating in the presence of the above-described polymerization initiator, for example, a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing the above fluoropolymer, a polymerization initiator such as a photo radical initiator or a thermal radical initiator, and inorganic fine particles is prepared, and after coating the coating liquid on a support, polymerization by ionizing radiation or heat is performed. It can be cured by reaction to form a low refractive index layer.

[Hard coat layer]
The hard coat layer has a hard coat property for improving the scratch resistance of the film. Further, it is also preferably used for the purpose of contributing to the film the light diffusibility due to scattering of at least one of surface scattering and internal scattering. Accordingly, it is preferable to contain a translucent resin for imparting hard coat properties and translucent particles for imparting light diffusibility. Further, if necessary, the refractive index is increased, crosslinking shrinkage is prevented, Contains an inorganic filler for strengthening.

  The thickness of the hard coat layer is preferably 1 to 10 μm and more preferably 1.2 to 6 μm for the purpose of imparting hard coat properties. When the film thickness is in the above range, the hard coat property is sufficiently imparted, and further, the curability and brittleness are not deteriorated and the workability is not lowered.

The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to make the binder polymer have a higher refractive index, the monomer structure contains an aromatic ring, a high atom containing at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms. A refractive index monomer can also be selected.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], modified ethylene oxide of the above ester, vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone], vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of the polymerization initiator contained in the low refractive index layer.
Therefore, the hard coat layer contains a monomer for forming a light-transmitting resin such as the above-mentioned ethylenically unsaturated monomer, an initiator that generates radicals by ionizing radiation or heat, light-transmitting particles, and an inorganic filler as necessary. It can be formed by preparing a coating liquid to be contained and curing the coating liquid on a support by ionizing radiation or a polymerization reaction with heat.

  In addition to the polymerization initiator that generates radicals by ionizing radiation or heat, a photosensitizer that may be contained in the low refractive index layer may be used.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent particles and an inorganic filler is prepared, and the coating liquid is applied onto a support and then subjected to a polymerization reaction by ionizing radiation or heat. The hard coat layer can be formed by curing.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

The translucent particles used in the hard coat layer are used for the purpose of imparting antiglare properties or light diffusibility, and the average particle size is preferably 0.5 to 5 μm, more preferably 1.0 to 4. 0.0 μm. The average particle size is preferably 0.5 μm or more from the viewpoint that the light scattering angle distribution does not spread to a wide angle, hardly reduces the character resolution of the display, and is easy to form surface irregularities so that the antiglare property is sufficient. . On the other hand, the thickness of the hard coat layer is preferably 5 μm or less because it is not necessary to increase the film thickness, curl is not increased, and the material cost is not increased.
Specific examples of the translucent particles include particles of inorganic compounds such as silica particles and TiO ₂ particles; acrylic particles, crosslinked acrylic particles, methacrylic particles, crosslinked methacrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, Preferred examples include resin particles such as benzoguanamine resin particles and crosslinked acrylic styrene particles. Of these, crosslinked styrene particles, crosslinked acrylic particles, crosslinked acrylic styrene particles, and silica particles are preferable.
The translucent particles can be either spherical or indefinite.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. It is possible to impart an antiglare property with a light-transmitting particle having a larger particle size and to impart another optical characteristic with a light-transmitting particle having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare is derived from the fact that the unevenness of the film surface (which contributes to antiglare properties) causes the pixels to be enlarged or reduced and loses brightness uniformity, but is smaller than the light-transmitting particles that impart antiglare properties. The diameter can be greatly improved by using translucent particles different from the refractive index of the binder.

  Further, the particle size distribution of the translucent particles is most preferably monodispersed, and the particle size of each particle is preferably as close as possible. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less, more preferably 0.1% of the total number of particles. Or less, more preferably 0.01% or less. The translucent particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree thereof.

The light-transmitting particles are preferably 3 to 30% by mass in the total solid content of the hard coat layer in consideration of light scattering effect, image resolution, surface turbidity, glare and the like in the formed hard coat layer. Formulated to contain. More preferably, it is 5-20 mass%.
Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the translucent particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

In order to increase the refractive index of the hard coat layer, in addition to the above light-transmitting particles, at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony is used. It is preferable to contain an inorganic filler made of an oxide and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
Conversely, in order to increase the difference in refractive index from the light-transmitting particles, the hard coat layer using the high-refractive index light-transmitting particles uses silicon oxide to keep the refractive index of the layer low. It is also preferable. The preferred particle size is the same as that of the inorganic filler.
Specific examples of the inorganic filler used in the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
When using these inorganic fillers, the addition amount is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such an inorganic filler does not scatter because its particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

Also, at least one of an organosilane compound, a hydrolyzate of organosilane and / or a partial condensate (sol) thereof can be used for the hard coat layer.
The amount of the sol component added to a layer other than the low refractive index layer, for example, the hard coat layer, is preferably 0.001 to 50% by mass, and 0.01 to 20% by mass of the total solid content of the containing layer (added layer). More preferably, 0.05-10 mass% is still more preferable, and 0.1-5 mass% is especially preferable. In the case of the hard coat layer, the organosilane compound is preferably used because the restriction on the amount of the organosilane compound or its sol component added is less stringent than the low refractive index layer.

The bulk refractive index of the mixture of translucent resin and translucent particles is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to set the refractive index within the above range, the kind and amount ratio of the light-transmitting resin and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
The difference in refractive index between the translucent resin and the translucent particles (the refractive index of the translucent particles−the refractive index of the translucent resin) is preferably 0.02 to 0.2, more preferably 0.05. ~ 0.15. When this difference is within the above range, the effect of internal scattering is sufficient, no glare occurs, and the film surface does not become cloudy.
The refractive index of the translucent resin is preferably 1.45 to 2.00, more preferably 1.48 to 1.70.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry.

In order to ensure surface uniformity such as uneven coating, uneven drying, point defects, etc., the hard coat layer should be coated with either a fluorine-based or silicone-based surfactant, or both for forming a hard coat layer. Contained in the composition. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the antireflection film of the present invention appears in a smaller addition amount.
The purpose is to improve productivity by giving high-speed coating suitability while improving surface uniformity.

[High (medium) refractive index layer]
In order to impart better antireflection performance to the antireflection film of the present invention, it is preferable to provide a high refractive index layer and / or a medium refractive index layer. The refractive index of the high refractive index layer in the antireflection film of the present invention is preferably 1.60 to 2.40, and more preferably 1.70 to 2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55 to 1.80. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less. The refractive index can be appropriately adjusted by adjusting the amount of inorganic fine particles to be added and the amount of binder used.

The high (medium) refractive index layer is made of an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in order to increase the refractive index of the layer. Is preferably 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
In order to increase the difference in refractive index from the mat particles contained in the high (medium) refractive index layer, the high (medium) refractive index layer using the high refractive index mat particles has a low refractive index. It is also preferred to use silicon oxide to maintain. The mat particles preferably have a refractive index of 1.80 to 2.80 and an average primary particle size of 3 to 150 nm. Particles having a refractive index of less than 1.80 are not preferred because the effect of increasing the refractive index of the film is small, and particles having a refractive index of more than 2.80 are colored. Further, particles having an average primary particle diameter exceeding 150 nm are not preferable because the haze value when a film is formed is high and the transparency of the film is impaired, and if it is less than 3 nm, it is difficult to maintain a high refractive index. The preferred particle size is the same as that of the inorganic filler in the hard coat layer described above.
Specific examples of the inorganic filler used in the high (medium) refractive index layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO _2. Can be mentioned. TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The addition amount of these inorganic fillers is adjusted according to the required refractive index, but in the case of a high refractive index layer, it is preferably 10 to 90% of the total mass, more preferably 20 to 80%, Especially preferably, it is 30 to 70%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The high (medium) refractive index layer used in the present invention is preferably used in the dispersion liquid in which the inorganic fine particles are dispersed in the dispersion medium as described above, preferably a binder precursor necessary for matrix formation (in the above-mentioned hard coat layer). A monomer having two or more ethylenically unsaturated groups as described above), a photopolymerization initiator and the like to obtain a coating composition for forming a high refractive index layer, and a coating composition for forming a high refractive index layer on a support. It is preferable to form the product by applying a product and curing it by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

  It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable. As the radical photopolymerization initiator, the same one as the above-mentioned low refractive index layer is used.

In addition to the above-mentioned components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high (medium) refractive index layer contains resins, surfactants, antistatic agents, coupling agents, thickeners, and coloring prevention. Agent, coloring agent (pigment, dye), anti-glare imparting particles, antifoaming agent, leveling agent, flame retardant, ultraviolet absorber, infrared absorber, adhesion promoter, polymerization inhibitor, antioxidant, surface modifier In addition, conductive metal fine particles can be added.
The film thickness of the high (medium) refractive index layer can be appropriately designed depending on the application. When a high (medium) refractive index layer is used as the optical interference layer, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

[Support]
The support for the optical film and antireflection film of the present invention is preferably transparent, and a plastic film is preferably used. As a polymer for forming a plastic film, cellulose acylate (eg, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UF manufactured by Fuji Photo Film Co., Ltd., etc.) ), Polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON CORPORATION) ), Etc. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. In addition, a cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are described in JIII Journal of Technical Disclosure No. 2001-1745 (issued on March 15, 2001). The cellulose acylate described here can also be preferably used in the present invention.

[Saponification]
When the optical film and antireflection film of the present invention are used in a liquid crystal display device, it is preferable to dispose on the outermost surface of the display by providing an adhesive layer on one side. Further, the antireflection film of the present invention and a polarizing plate may be used in combination. When the transparent substrate is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

The optical film and the antireflection film of the present invention are disposed on the outermost surface of the display by providing an adhesive layer on one side, or when used as it is as a protective film for a polarizing plate, It is preferable to carry out a saponification treatment after forming an outermost layer mainly composed of a fluoropolymer on a transparent substrate. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent substrate opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the polarizing film and the antireflection film when adhered to the polarizing film, and this prevents point defects caused by dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent substrate opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2), for example. (1) is superior in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the saponification treatment is performed up to the antireflection layer surface, the antireflection layer deteriorates due to alkali hydrolysis of the surface. The problem that the treatment liquid becomes dirty can be a problem. In that case, although it becomes a special process, (2) is excellent.
(1) After the antireflection layer is formed on the transparent substrate, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the antireflection layer on the transparent substrate, the alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed with water and / or inside By summing, only the back surface of the film is saponified.

[Coating method]
The antireflection film of the present invention can be formed by the following method, but is not limited to this method.

[Formation of antireflection film]
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294) Can be formed by coating, but it is preferably coated by a die coating method, and more preferably by using a new die coater described later. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, “Coating Engineering”, Asakura Shoten (1973), page 253.

In order to continuously produce the antireflection film of the present invention, for example, a process of continuously feeding a roll-shaped base film, a process of applying and drying a coating liquid, a process of curing a coating film, a cured layer The process of winding up the base film which has this is performed.
Specifically, it can be performed as follows.
The base film is continuously fed from the roll-shaped base film to the clean room. In the clean room, the static electricity charged in the base film is removed by the electrostatic static neutralizer, and then it adheres to the base film. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the base film in the coating section installed in the clean room, and the coated base film is sent to the drying room and dried.
The base film having the dried coating layer is sent from the drying chamber to the radiation curing chamber, irradiated with radiation, and the monomer contained in the coating layer is polymerized and cured. Furthermore, the base film having a layer cured by radiation is sent to the thermosetting section and heated to complete the curing, and the base film having the layer that has been completely cured is wound up into a roll shape.

The above process may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to form each layer continuously. In view of the above, it is preferable to continuously form each layer. An example of the configuration of an apparatus for continuously applying each layer is shown in FIG. The apparatus has an appropriate number of film forming units 100, 200, 300, and 400 installed between Step 1 for continuously feeding a roll-shaped base film and Step 2 for winding the roll-shaped base film. Is. The apparatus shown in FIG. 5 is an example of a configuration in which four layers are continuously applied without winding up, but it is of course possible to change the number of film forming units in accordance with the layer configuration. The film forming unit 100 includes a process 101 for applying a coating liquid, a process 102 for drying a coating film, and a process 103 for curing the coating film.
Using an apparatus in which three film forming units are installed, a roll-shaped base film coated with the hard coat layer is continuously fed, and a medium refractive index layer, a high refractive index layer, and a low refractive index layer are provided for each. From the viewpoint of productivity, it is more preferable to wind up after sequentially coating with a film forming unit. Using the apparatus shown in FIG. 5 in which four film forming units are installed, a roll-shaped base film is continuously formed. It is more preferable from the viewpoint of significantly reducing the coating cost that the coating, the hard coat layer, the medium refractive index layer, the high refractive index layer, and the low refractive index layer are sequentially coated by each film forming unit. If necessary, the number of coating stations is reduced to two, and only two layers, the middle refractive index layer and the high refractive index layer, are formed in one step, and the results of checking the surface shape, film thickness, etc. are fed back. Thus, improving the yield is another preferable embodiment.

In the present invention, a die coating method is preferably used as a coating method from the viewpoint of a higher production rate. The die coating method is preferably used because it can achieve a high level of productivity and a surface shape without coating unevenness.
As a manufacturing method of the antireflection film of the present invention, the following coating method using such a die coating method is preferable.
That is, the manufacturing method includes a coating step of applying a coating liquid from the slot of the tip lip by bringing the land of the tip lip of the slot die close to the surface of the web that is continuously supported by the backup roll. A slot die having a land length of 30 μm or more and 100 μm or less in the web traveling direction of the tip lip on the web traveling direction side of the slot die is opposite to the web traveling direction when the slot die is set at the coating position. The gap between the tip lip and the web on the side is larger by 30 μm or more and 120 μm or less than the gap between the tip lip on the web traveling direction side and the web (hereinafter, this numerical limitation is referred to as “over bit length”). It is preferable to apply | coat using the coating device installed so that it might become.
In particular, a die coater that can be preferably used in the production method of the present invention will be described below with reference to the drawings. The die coater can be used when the wet coating amount is small (20 ml / m ² or less), and is preferable.

<Die coater configuration>
FIG. 6 is a cross-sectional view of an example of a coater (coating apparatus) using a slot die that can suitably implement the present invention.
The coater 10 includes a backup roll 11 and a slot die 13, and a coating liquid 14 is discharged from the slot die 13 in a bead shape 14 a and applied to a web W that is supported by the backup roll 11 and continuously runs. Thus, the coating film 14b is formed on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular or semicircular. The pocket 15 extends with its cross-sectional shape in the width direction of the slot die 13 (here, the width direction of the slot die 13 refers to the front side or the back side toward the drawing shown in FIG. 6). In the liquid storage space for the applied coating solution, the effective extension length is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper (not shown) that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W. The slot 16 has a cross-sectional shape in the width direction of the slot die 13 like the pocket 15, and the opening 16a located on the web side is generally Using a thing such as a width regulating plate (not shown), the length is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent to the web W running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. The upstream side of the land 18 in the traveling direction of the web W with respect to the slot 16 (the traveling direction, that is, opposite to the arrow direction in the drawing) is the upstream lip land 18a, and the downstream side (the traveling direction side) is downstream. This is called side lip land 18b.
The shape of the tip lip 17 is extended on the downstream side compared to the upstream side (over bite shape), and the gap between the upstream lip land 18a and the web W is correspondingly larger than the gap between the downstream lip land 18b and the web W. Large in the above range. Further, the length of the downstream side lip land 18b is in the above-described range.
Referring to FIG. 7A, the part relating to the numerical limitation described above will be described. The land length on the traveling direction side (downstream side) of the web is a portion indicated by I _LO in FIG. The length of the overbyte is a portion indicated by LO in FIG.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is preferably 30 μm to 100 μm, more preferably 30 μm to 80 μm, and most preferably 30 μm to 60 μm. If the land length I _LO of the downstream lip is 30 μm or more, the edge or land of the tip lip is hardly chipped, and it is preferable because the generation of streaks on the coating film can be suppressed. Moreover, it is easy to set the wet line position on the downstream side. Furthermore, the spread of the coating liquid on the downstream side can be suppressed, which is preferable. Spreading of the coating liquid on the downstream side due to wetting means non-uniformity of the wetting line and leads to a problem of causing a defective shape such as a streak on the coating surface. On the other hand, if the land length I _LO of the downstream lip is 100 μm or less, the bead 14a can be formed. When the coating solution forms the beads 14a, thin layer coating can be performed.

Furthermore, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be reduced, and the bead formation 14a suitable for thin film coating can be achieved. The difference in the distance between the downstream lip land 18b and the web W of the upstream lip land 18a (hereinafter referred to as the overbite length LO) is preferably 30 μm to 120 μm, more preferably 30 μm to 100 μm, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap _GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

Next, the overall coating process will be described with reference to FIG.
FIG. 8 is an example of a perspective view showing the slot die 13 and its periphery in the coating process in which the present invention can be suitably implemented. A decompression chamber 40 is installed at a position where it does not come into contact with the slot die 13 on the side opposite to the moving direction side of the web W (that is, on the upstream side of the bead 14a) so that sufficient decompression adjustment can be performed on the bead 14a. Vacuum chamber 40, the gap between its operating efficiency has a back plate 40a and side plates 40b for holding a gap between the back plate 40a and the web W G _B, the side plate 40b and the web W G _S exists.
The relationship between the decompression chamber 40 and the web W will be described with reference to FIGS. 9 and 10 are sectional views showing the decompression chamber 40 and the web W which are close to each other.
Side plate 40b and the back plate 40a is may be of the chamber 40 body and integrally as shown in FIG. 9, for example, the back plate 40a to be appropriately changed gap G _B as shown in FIG. 10 into the chamber 40 A structure that is fastened with a screw 40c or the like may be used. In any structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W in the vacuum chamber 40, when the vacuum chamber 40 is placed under the web W and the slot die 13 as shown in FIG. 8, the uppermost end of the back plate 40a to the web W The gap is shown.

Is preferably installed to be larger than the gap G _L (see FIG. 7 (A)) of the end lip 17 and the web W of the slot die 13 the gap G _B between the back plate 40a and the web W, thereby backup roll Thus, the change in the degree of decompression near the bead due to the eccentricity of 11 can be suppressed. For example, when the gap G _L between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap G _B between the back plate 40a and the web W is preferably 100μm or 500μm or less.

<Material and accuracy>
Length in the web running direction of the traveling direction side of the end lip of the web (downstream lip land length shown in FIG. 7 (A) I _LO) is preferably in the range described above, also, the I _LO It is preferable that the fluctuation width in the slot die width direction is within 20 μm. Within this range, it is preferable that the bead does not become unstable due to slight disturbance.
As for the material of the tip lip of the slot die, it is not preferable to use a material such as stainless steel because it will sag at the stage of die processing. In the case of stainless steel or the like, it is difficult to satisfy the accuracy of the tip lip even if the downstream lip land length I _LO is in the range of 30 to 100 μm. In order to maintain high processing accuracy, it is preferable to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.
The downstream lip land length I _LO is important for realizing high-precision coating, and it is desirable to control the fluctuation width of the gap _{GL in} the slot die width direction. It is desirable that the backup roll 11 and the tip lip 17 achieve straightness within a range in which the fluctuation range of the gap _{GL in} the slot die width direction can be controlled. Preferably, the straightness of the tip lip 17 and the backup roll 11 is set so that the fluctuation width of the gap _{GL in} the slot die width direction is 5 μm or less.

When the antireflection film has a laminated structure, bright spot defects are easily noticeable when foreign matters such as dust and dust are present. The bright spot defect in the present invention is a defect that can be seen by reflection on the coating film as described above, and can be detected by an operation such as black coating on the back surface of the antireflection film after coating. The bright spot defects that can be visually observed are generally 50 μm or more. When there are many bright spot defects, the yield at the time of manufacture will fall and a large-area antireflection film cannot be manufactured.
In the antireflection film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

  In order to produce an antireflection film with few bright spot defects, it is possible to precisely control the degree of dispersion of the high refractive index ultrafine particles in the coating material for the high refractive index layer and to perform a fine filtration operation of the coating solution. At the same time, each layer forming the antireflection layer is subjected to a dusting process on the film before the coating process in the coating unit and the drying process performed in the drying chamber are performed in a clean air atmosphere and before the coating is performed. It is preferable that dust is sufficiently removed. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

As a dust removal method used in the dust removal step as a pre-process for coating, a method of pressing a nonwoven fabric, a blade or the like against the film surface described in JP-A-59-150571, or JP-A-10-309553 Highly clean air is blown at a high speed to peel off the deposit from the film surface, and suction is performed by a suction port close to the surface. Ultrasonic-vibrated compressed air described in JP-A-7-333613 is sprayed to deposit. And a dry dust removal method such as a method of peeling and suctioning (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off the adhered material by an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in Japanese Patent Application Laid-Open No. 2001-38306, a wet dust removing method such as a method in which a web is continuously rubbed with a roll wetted with a liquid and then a liquid is sprayed onto the rubbed surface for cleaning. be able to. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the base film before performing such a dust removal step in terms of increasing dust removal efficiency and suppressing dust adhesion. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the base film before and after dust removal and application is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

<Dispersion medium for coating>
The dispersion medium for coating is not particularly limited. You may use individually or in mixture of 2 or more types. Preferred dispersion media include aromatic hydrocarbons such as toluene, xylene and styrene, chlorinated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene, methane derivatives such as monochloromethane, ethane derivatives such as monochloroethane, and the like. Chlorinated aliphatic hydrocarbons, alcohols such as methanol, isopropyl alcohol and isobutyl alcohol, esters such as methyl acetate and ethyl acetate, ethers such as ethyl ether and 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketones such as cyclohexanone, glycol ethers such as ethylene glycol monomethyl ether, alicyclic hydrocarbons such as cyclohexane, aliphatic hydrocarbons such as normal hexane, and mixtures of aliphatic or aromatic hydrocarbons. Among these solvents, a dispersion medium for coating prepared by alone or mixing two or more ketones is particularly preferable.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For the filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is preferably used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

<Physical properties of coating solution>
The above-mentioned coating method suitable for the present invention is greatly affected by the upper limit speed at which coating is possible due to the liquid physical properties, so it is necessary to control the liquid physical properties, particularly the viscosity and surface tension at the moment of coating.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a web also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the web is preferably 2.0 to 5.0 [ml / m ² ]. Increasing the amount of application liquid applied to the web is preferable because the upper limit of the application rate can be increased. However, excessively increasing the amount of application liquid applied to the web increases the load on drying, so the liquid formulation / process It is preferable to determine the optimum amount of coating solution to be applied to the web depending on the conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed decreases, so the range of 17 [mN / m] to 32 [mN / m] is more preferred, and 19 [mN / m] to 26 [ mN / m] is more preferable.

<Application speed>
By the manufacturing method using the die coating method as described above, the above-described coating method has high film thickness stability during high-speed coating. Furthermore, since the above-described coating method is a pre-measuring method, it is easy to ensure a stable film thickness even during high-speed coating. As described above, when the wet coating amount is small (20 ml / m ² or less), the above-described coating method can be applied at high speed with good film thickness stability to a low coating amount coating solution. As a manufacturing method of the antireflection film of the present invention, the above-described manufacturing method using such a die coating method is preferable. There is no problem of vibration of the coating liquid in the liquid receiving tank, and stepped unevenness is unlikely to occur. Also, because there is no eccentricity or deflection of the roll related to application, stepwise unevenness is unlikely to occur. Furthermore, since the pre-weighing method has high film thickness stability, it is preferable to use the above-described manufacturing method. From the viewpoint of productivity, it is preferable to apply at 25 m / min or more by using the above-described production method.

[Polarizer]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate excellent in scratch resistance, antifouling property and the like can be obtained.

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs [0020] to [0030] of JP-A-2002-86554.

[Image display device]
The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for an image display device such as a transmissive, reflective, or transflective liquid crystal display device in a mode such as a curry compensate bend cell (OCB).

The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).
For a VA mode liquid crystal cell, a polarizing plate prepared by combining a triacetyl cellulose film stretched biaxially with the antireflection film of the present invention is preferably used. As for the method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. These are disclosed in the specifications of Japanese Patent Nos. 4583825 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In a TN mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Of these, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate by using it on the surface opposite to the antireflection film of the present invention.

[Example 1]
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto.
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by weight of trimethylolpropane triacrylate (Biscoat # 295 (manufactured by Osaka Organic Chemical Co., Ltd.)), 270.0 parts by mass of polyglycidyl methacrylate having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 cyclohexanone Mass parts and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) were added and stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm for the hard coat layer. A polyglycidyl methacrylate was prepared by dissolving glycidyl methacrylate (Tokyo Kasei Kogyo Co., Ltd.) in methyl ethyl ketone (MEK) and adding a thermal polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) dropwise. The reaction solution was allowed to react at 80 ° C. for 2 hours. It was added dropwise to Sun, the precipitate obtained was dried under reduced pressure.

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5 weight ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a weight average diameter of 70 nm.

(Preparation of coating solution for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.6 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.2 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 279.6 parts by mass of methyl ethyl ketone, and 1049.0 of cyclohexanone. A part by mass was added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer)
To 469.8 parts by mass of the above titanium dioxide dispersion, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Specialty Chemicals Co., Ltd., 1.1 parts by mass of photosensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and cyclohexanone 459. 6 parts by mass was added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of coating solution for low refractive index layer)
A fluorine-containing copolymer P-3 (weight average molecular weight of about 50000) described in JP-A-2004-45462 according to the present invention is dissolved in methyl isobutyl ketone so as to have a concentration of 7% by mass, and contains a terminal methacrylate group. Silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) was 3% based on the solid content, and the photo radical generator Irgacure 907 (trade name) was 5% by mass based on the solid content (Sample No. 107). ˜110 is Irgacure 9 in addition to Exemplified Compound 1
07 or 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine compound was added in an amount of 5% by mass) to prepare a coating solution for a low refractive index layer.

(Preparation of antireflection film 101)
A hard coat layer coating solution was applied onto a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ² , the coating layer was cured by irradiating with an irradiation amount of 300 mJ / cm ² to form a hard coat layer having a thickness of 8 μm.
A medium refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution on a hard coat layer at a speed of 5 to 100 m / min using a gravure coater having three coating stations. It was applied continuously.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was a 180 W / cm air-cooled metal halide lamp (eye graphics The irradiance was 200 mW / cm ² and the irradiation amount was 200 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

Drying conditions of the low refractive index layer 90 ° C., and 30 seconds, 1.40 m in the reaction chamber of the nitrogen purge (0.2 m ³ as the ultraviolet curing conditions the oxygen concentration falls below the ambient 0.1% by volume ³ / Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the irradiation amount was 200 mW / cm ² and the irradiation amount was 200 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.440 and a film thickness of 85 nm. Thus, the antireflection film 101 was produced.
Samples 102 to 115 were prepared by changing the initiator type and curing conditions of the low refractive index layer to the conditions shown in Table 1. The amount of initiator was replaced by this mass. Sample 116 further used 50.0 parts by mass of Exemplified Compound 1 as an initiator for the hard coat layer, and Sample 117 further showed Exemplified Compound 1 and 2- (p-methoxyphenyl) as an initiator for the hard coat layer. -4,6-bis (trichloromethyl) -s-triazine compound is used in an amount of 50.0 parts by mass, Exemplified Compound 1 is on Sample 116, Exemplified Compound 1 and 2- (p It was produced under the conditions shown in Table 1 except that a low refractive index layer prepared by using 5% by mass of each of -methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine compound was applied. Nitrogen gas was blown by providing a front chamber immediately before the UV irradiation chamber (reaction chamber), and setting the position of the nozzle so that the inert gas directly hit the film surface. In addition, the irradiation chamber and the front chamber were adjusted so that an inert gas was blown out from the web entrance of the front chamber. The gap between the web entrance and the coating layer surface of the web was 4 mm.
The UV irradiation amount when the coating speed was changed was set so that the irradiation amount became constant by changing the illuminance.

  In Table 1, “low oxygen maintenance time from the start of UV irradiation” means the time during which UV irradiation is actually performed in an environment maintained at a predetermined oxygen concentration.

  In addition, the said exemplary compound 1 grade | etc., Has already been described in this specification. In particular, Example Compound 1 is described below again.

The following items were evaluated for the obtained film. The results are shown in Table 2.
[Specular reflectance]
A spectroscopic hardness meter V-550 (manufactured by JASCO Corporation) is equipped with an adapter ARV-474, and the specular reflectance at an incident angle of -5 degrees is measured at an incident angle of 5 degrees in a wavelength range of 380 to 780 nm. The average reflectance at 650 nm was calculated and the antireflection property was evaluated.
[Pencil hardness]
The pencil hardness evaluation described in JIS K 5400 was performed. After conditioning the antireflection film at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, it was evaluated using the H-5H test pencil specified in JIS S 6006 at a load of 500 g as follows. The highest hardness that results in OK was taken as the evaluation value.
In evaluation of n = 5, no scratch to one scratch: OK
In evaluation of n = 5, 3 or more scratches: NG

[Steel wool scuff resistance]
The condition of scratches was observed when a load of 1.96 N / cm ² was applied to steel steel of # 0000 and reciprocated 30 times, and the following five stages were evaluated.
◎: Scratch not found ○: Slightly invisible scratch △: Clearly visible scratch ×: Clearly visible scratch XX: Delamination of film occurred thing

By using a fluorinated photopolymerization initiator compound and curing under the curing conditions according to the present invention, the antireflection film has sufficient antireflection performance and excellent scratch resistance, and the oxygen concentration in the reaction chamber It can be seen that even if the value is high, the scratch resistance is excellent.
It can also be seen that the scratch resistance is high by using a fluorinated photopolymerization initiator compound in combination with another initiator.

[Example 2]
In the method for producing Samples 101, 103, 109, and 116 of Example 1, samples 118 to 129 that differ only in that the web temperature during ultraviolet irradiation was raised were produced, and the same evaluation was performed.
The temperature of the coated surface of the web was adjusted by changing the temperature of the metal plate in contact with the web back surface.

  In the present invention, further excellent scratch resistance was obtained by raising the temperature during UV irradiation to 40 ° C. or higher. Further, in addition to the exemplified compound 1, the sample 109 to which the combined compound A was further added, and the sample 116 to which the combined compound A was added to the hard coat layer and the low refractive index layer, respectively, even when the heating temperature during UV irradiation was as low as 40 ° C. Excellent pencil hardness and scratch resistance were obtained.

[Example 3]
In the sample 103 produced in Example 1, samples 130 to 133 in Table 4 were produced by changing the number of divisions of ultraviolet irradiation and the degree of nitrogen substitution during ultraviolet irradiation. Evaluation similar to Example 1 was performed with respect to these samples.
In the ultraviolet irradiation division, the illuminance was adjusted so that the total irradiation amount was constant. The results are shown in Table 5.
Even when the ultraviolet irradiation was divided and the illuminance was reduced once, the performance of the comparative examples 101 and 102 (oxygen concentration of 0.1% or less) or higher was achieved even during the ultraviolet irradiation even at a high oxygen concentration. It was also found that there was suitability for high-speed production.

[Example 4]
The same evaluation was performed by replacing the fluorine-containing polymers used in the low refractive index layers in Examples 1 to 3 with fluorine-containing copolymers P-1 and P-2 described in JP-A No. 2004-45462, respectively (substitution of equal mass). As a result, the same effects as in Examples 1 to 3 were obtained.

[Example 5]
The low-refractive index layers of Examples 1 to 4 were changed to the following low-refractive index layers A and B, respectively, and evaluation was performed, and similar effects of the present invention were confirmed.
By using the hollow silica particles, it was possible to produce a low-reflectance antireflection film with further excellent scratch resistance.

(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, After 3 parts of Hope Pharmaceutical Co., Ltd. were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. A sol solution a was prepared with methyl ethyl ketone so that the solid content concentration was 29%.

(Preparation of hollow silica fine particle dispersion (dispersion A-1))
Hollow silica fine particle sol (particle size about 40-50 nm, shell thickness 6-8 nm, refractive index 1.31, solid content concentration 20%, main solvent isopropyl alcohol, particle size according to Preparation Example 4 of JP-A-2002-79616 500 parts, acryloyloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-5103) 30 parts, and diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) ) After 1.5 parts were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 parts of acetylacetone, and obtained the hollow silica dispersion liquid. The resulting hollow silica dispersion had a solid content concentration of 18% by mass and a refractive index after solvent drying of 1.31.

(Preparation of coating solution A for low refractive index layer)
44.0 parts by mass of fluorine-containing copolymer P-3 (weight average molecular weight of about 50000) described in JP-A No. 2004-45462, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by mass of methyl ethyl ketone A mixture (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 6.0 parts by mass, terminal methacrylate group-containing silicone RMS-033 (manufactured by Gelest) 3.0 parts by mass, 3.0 parts by mass of exemplified compound 1 are added and dissolved. did. Thereafter, 195 parts by mass (39.0 parts by mass as silica + surface treatment agent solid content) and 17.2 parts by mass of sol liquid a (5.0 parts by mass as solid content) were added to dispersion (A-1). A coating solution (coating solution A) was prepared by diluting with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating solution was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 10:90.

(Preparation of coating solution B for low refractive index layer)
93.0 parts by mass of fluorine-containing copolymer P-3 (weight average molecular weight of about 50000) described in JP-A No. 2004-45462, terminal methacrylate group-containing silicone RMS-033 (Gelest Co., Ltd.) with respect to 200 parts by mass of methyl ethyl ketone (Product) 3.0 parts by mass and 4.0 parts by mass of Exemplified Compound 1 were added and dissolved. A coating solution (coating solution B) was prepared by diluting with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating solution was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 10:90.

[Example 6]
The low refractive index layers of Examples 1 to 5 were changed to the following low refractive index layers C, respectively, and evaluation was performed, and similar effects of the present invention could be confirmed. The same effect was also obtained with a low refractive index layer in which OPSTA JN7228A was replaced with JTA113 (manufactured by JSR Co., Ltd.) having a higher degree of cross-linking with equal weight.
(Preparation of sol liquid a ′)
A reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM5103 (trade name); manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, After 3 parts of Hope Pharmaceutical Co., Ltd. were added and mixed, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The weight average molecular weight is 1800,
Among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution C for low refractive index layer)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution C for a low refractive index layer. Dispersion A-1 with respect to 783.3 parts by mass (47.0 parts by mass as the solid content) of OPSTAR JN7228A (thermally crosslinkable fluorine-containing silicone polymer composition liquid (solid content: 6%): manufactured by JSR Corporation) 195 parts by mass (silica + 39.0 parts by mass as surface treatment agent solids), colloidal silica dispersion (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, Nissan Chemical ( 30.0 parts by mass (9.0 parts by mass as the solid content) and 17.2 parts by mass of the sol liquid a ′ (5.0 parts by mass as the solids) were added. A coating solution (coating solution C) was prepared by diluting with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating solution was 6% by mass and the ratio of cyclohexane and methyl ethyl ketone was 10:90.
The compounds used are shown below.
KBM-5103: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
RMS-033: Reactive silicone (manufactured by Gelest Co., Ltd.)

The low-refractive index layer coating liquid C was applied at a conveyance speed of 10 m / min using a microgravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern of 200 lines / inch and a depth of 30 μm, and 120 ° C. After drying for 150 seconds at 140 ° C. for 12 minutes, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, an illuminance of 200 mW / cm ² and an irradiation amount of 450 mJ / Cm ² of ultraviolet light was irradiated to form a low refractive index layer and wound up. After curing, the rotation speed of the gravure roll was adjusted so that the thickness of the low refractive index layer was 100 nm.

[Example 7]
(Preparation of protective film for polarizing plate)
A saponification solution in which a 1.5 mol / L sodium hydroxide aqueous solution was kept at 50 ° C. was prepared.
Further, a 0.005 mol / L dilute sulfuric acid aqueous solution was prepared.
In the antireflection film according to the present invention produced in Examples 1 to 6, the surface of the transparent substrate opposite to the side having the low refractive index layer of the present invention was saponified using the saponification solution.
The aqueous sodium hydroxide solution on the surface of the saponified transparent substrate is thoroughly washed with water, then washed with the above diluted sulfuric acid aqueous solution, and further, the diluted sulfuric acid aqueous solution is thoroughly washed with water and sufficiently dried at 100 ° C. It was.
When the contact angle of the surface of the saponified transparent substrate on the side opposite to the side having the low refractive index layer of the antireflection film was evaluated, it was 40 degrees or less. Thus, the protective film for polarizing plates was produced.

(Preparation of polarizing plate)
A polyvinyl alcohol film having a thickness of 75 μm (manufactured by Kuraray Co., Ltd.) was immersed in an aqueous solution consisting of 1000 parts by mass of water, 7 parts by mass of iodine, and 105 parts by mass of potassium iodide to adsorb iodine.
Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.
A saponified triacetyl cellulose surface of the antireflection film of the present invention (protective film for polarizing plate) was bonded to one surface of the polarizing film using a polyvinyl alcohol-based adhesive as an adhesive. Further, a triacetyl cellulose film saponified in the same manner as described above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device was excellent in antireflection performance and extremely excellent in visibility. In particular, the effect is remarkable in the VA mode.

[Example 8]
(Preparation of polarizing plate)
In the optical compensation film having an optical compensation layer (Wide View Film SA 12B, manufactured by Fuji Photo Film Co., Ltd.), the surface opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 7.
Using the polyvinyl alcohol adhesive as the adhesive for the polarizing film produced in Example 7, the antireflection film according to the present invention produced in Examples 1 to 7 (protecting for polarizing plate) on one surface of the polarizing film The saponified triacetyl cellulose surfaces of the film) were bonded together. Further, the triacetyl cellulose surface of the saponified optical compensation film was bonded to the other surface of the polarizing film using the same polyvinyl alcohol adhesive.

(Evaluation of image display device)
The TN, STN, IPS, VA, OCB mode transmission type, reflection type, or transflective type in which the polarizing plate of the present invention thus prepared is mounted so that the antireflection film is the outermost surface of the display. The liquid crystal display device has better contrast in the bright room than the liquid crystal display device equipped with a polarizing plate that does not use an optical compensation film, has a very wide viewing angle in the vertical and horizontal directions, and has excellent antireflection performance and extremely high visibility. The display and display quality were excellent.
In particular, the effect is remarkable in the VA mode.

[Example 9]
In the method for producing the antireflection film of Example 1, the coating solution formulation for the low refractive index layer was changed to DY-91 below, and coating was performed at a coating speed of 25 m / min using the following die coater. Then, after drying at 90 ° C. for 30 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less, An ultraviolet ray having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² was irradiated to form a low refractive index layer (refractive index 1.45, film thickness 83 nm). In this way, an antireflection film (9-1) was produced.
Furthermore, the antireflective films (9-2) to (9-3) were produced by changing the low refractive index layer coating solution to the following DY-92 to 93.

(Die coater configuration)
The slot die 13 has an upstream lip land length I _UP of 0.5 mm, a downstream lip land length I _LO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and a length of the slot 16 of 50 mm. I used one. The gap between the upstream lip land 18a and the web 12 is made 50 μm longer than the gap between the downstream lip land 18b and the web 12 (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web 12 _GL was set to 50 μm. Further, the gap G _B between the gap G _S, and the back plate 40a and the web 12 between the side plate 40b and the web 12 of the decompression chamber 40 were both 200 [mu] m.

(Preparation of coating solution for low refractive index layer (DY-91))
152.4 parts by mass of a solution obtained by dissolving the following fluorine-containing copolymer in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 0.1 parts by mass, 1.8 parts by mass of a fluorinated photopolymerization initiator (Exemplary Compound 1), 815.9 parts by mass of methyl ethyl ketone, and 28.8 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (DY-91). The viscosity of the coating solution was 0.48 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 2.8 [ml / m ² ]. .

(Preparation of coating solution for low refractive index layer (DY-92))
426.6 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 0.0 parts by mass, 5.1 parts by mass of a fluorinated photopolymerization initiator (Exemplary Compound 1), 538.6 parts by mass of methyl ethyl ketone, and 26.7 parts by mass of cyclohexanone were added and stirred. The solution was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (DY-92). The viscosity of the coating solution was 0.79 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 2.2 [ml / m ² ]. .

(Preparation of coating solution for low refractive index layer (DY-93))
213.3 parts by mass of a solution obtained by dissolving the above fluorinated copolymer in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 0.5 parts by mass, 2.5 parts by mass of the fluorinated photopolymerization initiator (Exemplary Compound 1) and 2.5 parts by mass of the combined compound B in Table 1 above, 754.3 parts by mass of methyl ethyl ketone, and 28.4 cyclohexanone A part by mass was added and stirred. The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (DY-93). The viscosity of the coating solution was 0.82 [mPa · sec], the surface tension was 24 [mN / m], and the amount of the coating solution applied to the transparent support was 2.0 [ml / m ² ]. .

  The surface condition when the coating solution for the low refractive index layer was changed to DY-91 to DY-93 was evaluated. The results are shown in Table 6. All showed good performance.

[Evaluation of antireflection film]
The surface state of the obtained antireflection film was evaluated. Further, the average reflectance was measured in the same manner as in Example 1.
(Surface shape)
The back surface of the film 1 m ² after coating all the layers was black-coated with magic ink, and the uniformity of the density of the coated surface was visually evaluated.
○: Contrast difference is inconspicuous ×: Contrast difference is conspicuous The obtained antireflection films (9-1), (9-2), and (9-3) are displayed in the same procedure as in Examples 7 and 8. As a result, the color unevenness was less than that of the display devices of Examples 7 and 8 produced by a gravure coater, and the quality was high.

[Example 10]
[Preparation of coating solution for forming each layer]
[Preparation of Sol Solution (a-1)]
In a 1000 mL reaction vessel equipped with a thermometer, a nitrogen inlet tube, and a dropping funnel, 187 g (0.80 mol) of 3-acryloxyoxypropyltrimethoxysilane, 27.2 g (0.20 mol) of methyltrimethoxysilane, methanol 320 g (10 mol) and 0.06 g (0.001 mol) of potassium fluoride (KF) were charged, and 15.1 g (0.86 mol) of water was slowly added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then heated and stirred for 2 hours under methanol reflux. Then, 120 g of sol liquid (a-1) was obtained by depressurizingly distilling a low boiling-point component and further filtering.

  As a result of measuring the substance thus obtained by GPC, the mass average molecular weight was 1500, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 30% by mass. Moreover, from the measurement result of 1H-NMR, the structure of the obtained substance was a structure represented by the following general formula.

Furthermore, the condensation rate α as determined by ²⁹ Si-NMR was 0.56. From this analysis result, it was found that the silane coupling agent sol was mostly composed of a linear structure. From the gas chromatography analysis, the raw material acryloxypropyltrimethoxysilane had a residual ratio of 5% by mass or less.

[Preparation of Sol Solution (b-1)]
In a reactor equipped with a stirrer and a reflux condenser, 119 parts by mass of methyl ethyl ketone, 3-acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} 101 parts by mass, diisopropoxyaluminum ethylacetate After adding 3 parts by mass of acetate and mixing, 30 parts by mass of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution (b-1).

  The mass average molecular weight of the sol liquid (b-1) was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100% by mass. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

[Adjustment of hard coat layer coating solution]

The hard coat layer coating solutions HC-1 to HC-7 were adjusted according to the above table. The numbers in the table are in mass g.
Incidentally, PETA: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.
DPHA: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [manufactured by Nippon Kayaku Co., Ltd.]
“Desolite Z7526”: a commercially available silica-containing UV curable hard coat solution, solid content concentration 72% by mass, silica content 38% by mass, average particle diameter 20 nm, manufactured by JSR Corporation.
“MEK-ST”: Silica sol, average particle size 15 nm, solid content concentration 30% by mass, manufactured by Nissan Chemical Co., Ltd.
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm (refractive index of 1.60), 30% by mass toluene dispersion, manufactured by Soken Chemical Co., Ltd. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55), 30% by weight toluene dispersion, manufactured by Soken Chemical Co., Ltd.
Irgacure 184: Polymerization initiator, [Ciba Specialty Chemicals Co., Ltd.]
Irgacure 907: polymerization initiator, [manufactured by Ciba Specialty Chemicals Co., Ltd.].
“FP-132”: a fluorine-based surface modifier having the following structural formula.

Fluorine leveling agent R-30 Dainippon Ink and Chemicals (commercially available)
“KBM-5103”: silane coupling agent, 3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.
Each liquid in which the above was sufficiently mixed was filtered through a polypropylene filter having a pore diameter of 30 μm to complete hard coat layer coating liquids HC-1 to HC-7.

(Coating of hard coat layer)
Using the slot die coater described in FIG. 1 of Japanese Patent Application Laid-Open No. 2003-211052, an 80 μm thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, Hard coat layer coating liquids HC-1 to HC-10 were each applied to a coating amount of 16 cm ³ / m ² , dried at 30 ° C. for 15 seconds, 90 ° C. for 20 seconds, and further under a nitrogen purge. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm, the coating layer was cured by irradiating ultraviolet rays with an irradiation amount of 50 mJ / cm ² , and each of the hard layers having a thickness of 2.5 to 6.0 μm. An optical film having a coating layer was produced and wound up.

[Preparation of coating solution for low refractive index layer]
The low refractive index layer coating liquids LN-1 to LN-8 were adjusted according to the following table. The numbers in the table are parts of mass.

  Each of the above coating solutions was filtered through a polypropylene filter having a pore size of 1 μm to complete low refractive index layer coating solutions (LN-1 to 8).

The compounds used for the preparation of each of the above coating solutions are shown below.
“P-3”: fluorine-containing copolymer (P-3) described in JP-A No. 2004-45462, mass average molecular weight of about 50000, solid content concentration of 23.8% by mass, solvent methyl ethyl ketone,
“JTA-113”: Thermally crosslinkable silicone-containing fluorine-containing polymer solution, refractive index 1.44, solid content concentration 6% by mass, solvent methyl ethyl ketone, solid-containing fluorine-containing silicone-containing fluorine-containing solution 78% by mass of polymer, 20% by mass of melamine-based crosslinking agent, 2% by mass of paratoluene sulfonate, manufactured by JSR Corporation,
Fluorine-containing compound “F3035” (trade name; manufactured by NOF Corporation, solid content concentration 30%)
“MEK-ST” silica particle dispersion, average particle size 15 nm, solid content concentration 30% by mass, dispersion solvent methyl ethyl ketone, manufactured by Nissan Chemical Co., Ltd.
“MEK-ST-L”: Silica particle dispersion, average particle size 45 nm, solid content concentration 30% by mass, dispersion solvent methyl ethyl ketone, manufactured by Nissan Chemical Co., Ltd.
“Exemplary Compound 1 Solution”: solid content concentration 2% by mass, solvent methyl ethyl ketone,
“MP-triazine”: photopolymerization initiator, manufactured by Sanwa Chemical Co., Ltd.
“RMS-033”: reactive silicone resin, manufactured by Gelest,

(Coating of low refractive index layer-1)
After the various hard coat layers of the present invention are applied, the low refractive index layer coating liquids LN-1 to LN-5 are further dried with a die coater to a thickness of 95 nm. After applying the wet coating as described above, followed by drying at 120 ° C. for 70 seconds, and further using a nitrogen purge, an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm in an atmosphere with an oxygen concentration of 100 ppm, An ultraviolet ray with an irradiation amount of 400 mJ / cm ² was irradiated to form a low refractive index layer and wound up. (Coating of low refractive index layer-2)
After coating the various hard coat layers of the present invention, the low refractive index layer coating liquids LN-6 to LN-8 are further dried with a bar coater at a thickness of 95 nm. Then, after drying at 120 ° C. for 150 seconds, further drying at 100 ° C. for 8 minutes, and then nitrogen purge, an air-cooled metal halide lamp (240 ° / cm) in an atmosphere with an oxygen concentration of 100 ppm Was used to irradiate ultraviolet rays with an irradiation amount of 110 mJ / cm ² , and a low refractive index layer was formed and wound up.

  Evaluation similar to the above was performed with respect to the obtained film. The results are shown in Table 9.

  It can be seen that the antireflection film using the fluorinated photopolymerization initiator compound of the present invention has excellent antireflection performance while having sufficient antireflection performance.

[Example 11] ... Example of optical film preparation Hard coat layer coating solutions (HCL-1) to (HCL-4) and overcoat layer coating solutions (OCL-1) shown in Tables 10 and 11 ~ (OCL-4) was prepared.

The constituents in the table are expressed as mass percentages of solids. Details of the compounds used are shown below.
MANDA:
(Bifunctional acrylate, KAYARAD MANDA, Nippon Kayaku Co., Ltd., molecular weight 312)
PETA:
(A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, Nippon Kayaku Co., Ltd., average molecular weight of about 300)
DPHA:
(Dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate, Nippon Kayaku Co., Ltd., average molecular weight 540)
M-215:
(Isocyanuric acid EO-modified diacrylate, manufactured by Toa Gosei Co., Ltd., molecular weight 369)
IRG184:
(Photopolymerization initiator, Irgacure 184, manufactured by Ciba Geigy Japan Ltd.)
IRG369:
(Photopolymerization initiator, Irgacure 369, manufactured by Nippon Ciba Geigy Co., Ltd.)
“FZ-2191”: polyether-modified silicone. (Toray Dow Corning Co., Ltd.)

  Then, the following optical films were produced using the coating liquid for hard coat layers and overcoat layers obtained as described above.

(Preparation of optical film (11-1))
On a triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm and a width of 1340 mm, a hard coat layer coating (HCL-1) is applied by a microgravure coating method at a conveyance speed of 30 m / After applying for 150 minutes and drying at 60 ° C. for 150 seconds, using a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen (oxygen concentration 0.05% or less), The coating layer was cured by irradiating ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 20 mJ / cm ² to prepare a hard coat layer having a thickness of 5.0 μm.

On the hard coat layer obtained in this manner, the overcoat layer paint (OCL-1) was adjusted by a die coater coating method so that the film thickness after curing was 3.0 μm. After applying at a transfer speed of 30 m / min, drying at 60 ° C. for 150 seconds, and then purging with nitrogen (oxygen concentration 0.1%), a 160 W / cm air-cooled metal halide lamp {manufactured by Eye Graphics Co., Ltd.} Then, the coating layer was cured by irradiating ultraviolet rays having an irradiance of 400 mW / cm ² and an irradiation energy amount of 240 mJ / cm ² to obtain a sample 11-1.

  Table 12 below shows samples 11-2 to 11-12 processed in the same manner as the conditions described in Table 1 above.

  Table 13 shows the results of evaluation similar to Table 2 described above for Samples 11-1 to 11-12 thus obtained.

  It can be seen that an optical film of a level using a fluorinated photopolymerization initiator compound is sufficiently cured and excellent in scratch resistance even when the oxygen concentration is high.

It is the schematic diagram which showed an example of the manufacturing apparatus which comprised the ionizing radiation irradiation reaction chamber and the front chamber used in this invention. It is the side view which showed an example of operation | movement of the web entrance surface of the manufacturing apparatus which comprised the ionizing radiation irradiation reaction chamber and the front chamber of this invention. It is the figure which showed typically an example of the web entrance surface of the front chamber of the manufacturing apparatus which comprised the ionizing radiation irradiation reaction chamber and the front chamber used in this invention. It is the side view which showed typically the operation | movement of the web entrance surface of the front chamber of FIG. It is a figure which shows an example of the apparatus which performs coating and hardening of the antireflection layer of the antireflection film of this invention. It is a schematic sectional drawing which shows one Embodiment of the die-coater preferably used in this invention. (A) It is an enlarged view of the die coater of FIG. (B) It is a schematic sectional drawing which shows the conventional slot die. It is a perspective view which shows the slot die of the application | coating process preferably used in this invention, and its periphery. It is sectional drawing which shows typically the relationship between the pressure reduction chamber of FIG. 8, and a web. It is sectional drawing which shows typically the relationship between the pressure reduction chamber of FIG. 8, and a web.

Explanation of symbols

A Feeding roll B Winding roll 100, 200, 300, 400 Film forming unit 101, 201, 301, 401 Coating liquid coating process 102, 202, 302, 402 Coating film drying process 103, 203, 303, 403 Coating film curing process DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Light diffusion layer 4 Low refractive index layer 5 Translucent particle W Web 10 Coater 11 Backup roll 13 Slot die 14 Coating liquid 14a Bead shape 14b Coating film 15 Pocket 16 Slot 16a Slot opening 17 Tip lip 18 Land (flat part)
18a upstream lip land 18b downstream lip land I _UP land length I _UP upstream lip land 18a land length _LO downstream lip land 18b land length LO over bit length _GL gap between the tip lip 17 and web W 30 slot die 31a Upstream lip land 31b Downstream lip land 32 Pocket 33 Slot 40 Decompression chamber 40a Back plate 40b Side plate 40c Screw GB _B Gap between the back plate 40a and the web W G _S Gap between the side plate 40b and the web W

Claims (19)

  An optical film, wherein the layer coated on the support contains a cured product of a composition containing at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound.   The layer coated on the support contains a cured product of a composition containing at least one fluorinated photopolymerization initiator, an ionizing radiation curable compound, and at least one non-fluorinated photopolymerization initiator. The optical film according to claim 1.   An antireflection film having at least an antireflection layer on a support, wherein at least one layer laminated on the support contains at least one fluorinated photopolymerization initiator and an ionizing radiation curable compound. An antireflection film comprising a layer obtained by curing a composition to be cured by ionizing radiation irradiation.   The composition containing the at least one fluorinated photopolymerization initiator and the ionizing radiation curable compound further contains at least one non-fluorinated photopolymerization initiator. Antireflection film. The optical film according to claim 1 or 2, wherein the fluorinated photopolymerization initiator is represented by any one of the following general formulas (1) to (5).

In the general formula (1), Y represents a halogen atom. Y ¹ represents —CY ₃ , —NH ₂ , —NHR ′, —NR ′ ₂ , —OR ′. R ′ represents an alkyl group, a fluoroalkyl group, or an aryl group. R is R _a —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _r —, R _a — (CH ₂ ) _r —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _s —O. A substituent selected from the group consisting of-, R _a -Y _1- (CH ₂ ) _s -S- and R _a -Y _1- (CH ₂ ) _s -NR _1- , -CY ₃ , an alkyl group, An alkyl group, a fluoroalkyl group, a substituted fluoroalkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group is represented. R ₁ represents a hydrogen atom, a methyl group or an ethyl group, r represents an integer of 1 to 10, and s represents an integer of 2 to 10. Y ₁ is independently selected from the group consisting of —O—, —S—, —O—C (═O) — and —O—Si (R ₂ ) ₂ — (CH ₂ ) _r —. Represents a divalent substituent. R ₂ represents an alkyl or phenyl group having 1 to 12 carbon atoms. R _a is a linear or branched terminal chain: Z ¹ CF ₂ (—O—C ₂ F ₄ ) _p — (CF ₂ ) _q — (where Z ¹ represents H or F; p And one of q and q represents an integer of 0 to 20, and the other represents an integer of 1 to 20.

In the general formula (2), A ¹ represents a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group, or the same as R in the general formula (1), where the substituent is a halogen atom, an alkyl group, A fluoroalkyl group, an alkoxy group, a nitro group, a cyano group or a methylenedioxy group; Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a nitro group, A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ¹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), W ¹ represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1). The substituent of the phenyl group is a halogen atom or a nitro group. , A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (5), Z represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, a fluoroalkyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom. , A nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, or the same as R in the general formula (1). n represents an integer of 1 to 5. At least one of Z and X represents the same as R in the general formula (1). The anti-reflection film according to claim 3 or 4, wherein the fluorinated photopolymerization initiator is represented by any one of the following general formulas (1) to (5).

In the general formula (1), Y represents a halogen atom. Y ¹ represents —CY ₃ , —NH ₂ , —NHR ′, —NR ′ ₂ , —OR ′. R ′ represents an alkyl group, a fluoroalkyl group, or an aryl group. R is R _a —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _r —, R _a — (CH ₂ ) _r —Y ₁ —, R _a —Y ₁ — (CH ₂ ) _s —O. A substituent selected from the group consisting of-, R _a -Y _1- (CH ₂ ) _s -S- and R _a -Y _1- (CH ₂ ) _s -NR _1- , -CY ₃ , an alkyl group, An alkyl group, a fluoroalkyl group, a substituted fluoroalkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group is represented. R ₁ represents a hydrogen atom, a methyl group or an ethyl group, r represents an integer of 1 to 10, and s represents an integer of 2 to 10. Y ₁ is independently selected from the group consisting of —O—, —S—, —O—C (═O) — and —O—Si (R ₂ ) ₂ — (CH ₂ ) _r —. Represents a divalent substituent. R ₂ represents an alkyl or phenyl group having 1 to 12 carbon atoms. R _a is a linear or branched terminal chain: Z ¹ CF ₂ (—O—C ₂ F ₄ ) _p — (CF ₂ ) _q — (where Z ¹ represents H or F; p And one of q and q represents an integer of 0 to 20, and the other represents an integer of 1 to 20.

In the general formula (2), A ¹ represents a phenyl group, a naphthyl group, a substituted phenyl group, a substituted naphthyl group, or the same as R in the general formula (1), where the substituent is a halogen atom, an alkyl group, A fluoroalkyl group, an alkoxy group, a nitro group, a cyano group or a methylenedioxy group; Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (3), W represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom, a nitro group, A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ¹ represents a hydrogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (4), W ¹ represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, or the same as R in the general formula (1). The substituent of the phenyl group is a halogen atom or a nitro group. , A cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The number of substituents is 1 or 2 when a halogen atom is included as a substituent, and is 1 in other cases. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an allyl group. Y represents a halogen atom, and n represents an integer of 1 to 3.

In the general formula (5), Z represents an unsubstituted or substituted phenyl group, an unsubstituted naphthyl group, a fluoroalkyl group, or the same as R in the general formula (1), and the substituent of the phenyl group is a halogen atom. , A nitro group, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. X may be the same or different and represents a hydrogen atom, a halogen atom, an alkyl group, or the same as R in the general formula (1). n represents an integer of 1 to 5. At least one of Z and X represents the same as R in the general formula (1).   6. The optical film according to claim 1, wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.   The antireflection film according to claim 3, wherein the ionizing radiation curable compound is a compound having two or more ethylenically unsaturated groups.   The antireflection layer has a low refractive index layer, and the low refractive index layer is formed of a coating liquid containing a fluorine-containing polymer. The antireflection film as described. The antireflection film according to claim 9, wherein the fluoropolymer is a fluoropolymer represented by the following general formula 1.

[In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a polymerization unit of any vinyl monomer, and may be a single component or a plurality of components. Moreover, the silicone site | part may be included. x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. ] The antireflection film according to claim 9, wherein the fluoropolymer is a fluoropolymer represented by the following general formula 2.

In General Formula 2, R represents an alkyl group having 1 to 10 carbon atoms or an ethylenically unsaturated group (—C (═O) C (—X) ═CH 2).
m represents an integer of 1 ≦ m ≦ 10.
n represents an integer of 2 ≦ n ≦ 10.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. Moreover, the silicone site | part may be included.
x, y, z1, and z2 represent mol% of each repeating unit. However, x + y + z1 + z2 = 100.   The antireflective film according to claim 9, wherein the low refractive index layer contains hollow silica fine particles. A method for producing an antireflection film having an antireflection layer comprising at least one layer on a transparent substrate, wherein at least one layer laminated on the transparent substrate is subjected to the following steps (i) to (iii): In addition, a method for producing an antireflection film, which is formed by a layer forming method in which the following transport step (ii) and curing step (iii) are continuously performed.
(I) a step of coating an application layer on the transparent substrate;
(Ii) a step of conveying the film having the coating layer in an oxygen concentration atmosphere lower than the oxygen concentration in the atmosphere while heating the film surface temperature to be 25 ° C. or higher;
(Iii) A step of curing the coating layer by irradiating the film with ionizing radiation while heating the film so that the film surface temperature is 25 ° C. or higher in an atmosphere having an oxygen concentration of 15% by volume or less.   The manufacturing method of the antireflection film has a step of applying a coating liquid from the slot of the tip lip by bringing a land of the tip lip of the slot die close to the surface of the web that is continuously supported by a backup roll. When the coating liquid has a land length in the web traveling direction of the tip lip on the web traveling direction side of the slot die of 30 μm or more and 100 μm or less, and the slot die is set at the coating position, the progress of the web The gap between the tip lip and the web opposite to the direction is applied using a coating apparatus installed so that the gap between the tip lip and the web on the web traveling direction side is 30 μm or more and 120 μm or less. The method for producing an antireflection film according to any one of claims 3, 4, and 6 to 13. The viscosity at the time of application | coating of the said coating liquid is 2.0 [mPa * sec] or less, and the quantity of the coating liquid apply | coated to the web surface is 2.0-5.0 [ml / m < ² >]. The method for producing an antireflection film according to claim 14.   The method for producing an antireflection film according to claim 14 or 15, wherein the coating liquid is applied to a continuously running web surface at a speed of 25 [m / min] or more.   The antireflective film produced by the method in any one of Claims 13-16 in which the antireflective film in any one of Claim 3, 4, or 6-13 is produced.   14. A polarizing plate, wherein the antireflection film according to claim 3, 4 or 6 to 13 is used for one of two protective films in the polarizing plate.   The optical film according to any one of claims 1, 2, or 5, the antireflection film according to any one of claims 3, 4, or 6 to 13, or the polarizing plate according to claim 18 is used. An image display device characterized by that.

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