JP5049542B2 - Antireflection film, polarizing plate, and image display device using the same - Google Patents

Description

  The present invention relates to an antireflection film, a polarizing plate, and an image display device.

  In general, an antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD) to reduce contrast or reflect an image due to reflection of external light. In order to prevent engraving, it is placed on the outermost surface of the display to reduce reflectivity using the principle of optical interference.

  Such an antireflection film is prepared by forming a low refractive index layer having an appropriate 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 and the support. it can. 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, it is expected to function as a protective film for the display device. It is required that dirt and dust are difficult to adhere and that scratch resistance is strong. 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 and lowering the density (introducing voids), but both are in the direction that the film strength and adhesion are impaired and the scratch resistance is lowered, and low Reconciling refractive index and high scratch resistance has been a difficult task.

In particular, the binder containing fluorine atoms has a problem that the binder tends to be negatively charged, and when used on the display surface, dust in the environment tends to adhere. Furthermore, when a fluorine-based antifouling material is used, the fluorine-based antifouling agent is oriented on the film surface and exhibits antifouling properties, so that the surface is more likely to be negatively charged and dust is likely to adhere. There is a need for improved technology.
As a technique for imparting dust resistance, it is described that a cationic or anionic material is added. However, when this material is used, there are problems such as separation in the coating solution, unevenness during coating, and deterioration of the scratch resistance of the film.
Further, Patent Document 1 is known to provide a so-called antistatic layer containing conductive particles. This method has a problem that it is necessary to provide a new layer, and equipment and time load during production are large. In addition, the conductive particles for antistatic that are generally used in the past have many particles having a refractive index of about 1.6 to 2.2, and the refractive index of the antistatic layer containing these particles is increased. End up. Since the refractive index of the antistatic layer is high, the optical film is desired to be improved in terms of unintentional interference unevenness due to the difference in refractive index from the adjacent layer, and the reflected color becomes strong. It was.

  From the viewpoint of reducing the refractive index of the conductive particles, Patent Document 2 describes that particles having the surface of silica particles coated with antimony oxide are used for the low refractive index layer. However, this patent document does not describe a technique for improving the antifouling property, and further improvement is necessary in terms of the antifouling property.

  On the other hand, Patent Document 3 describes that the scratch resistance is greatly improved by adding a silane coupling agent to a low refractive index layer material using a fluorine-containing polymer. However, the silane coupling agent having a low boiling point has a problem that it volatilizes in the coating and drying process, and requires an excessive amount of addition considering the volatilized content, and there is a problem that it is difficult to obtain stable performance.

  On the other hand, Patent Document 4 describes that an antifouling layer is overcoated to impart antifouling properties. However, although these antifouling property-imparting compounds can be coated on a layer containing a hydrolyzed condensate of an organosilane compound as a main binder, they can be easily repelled on a widely used ionizing radiation curable binder. However, it has problems such as unevenness.

The prior art according to the present invention is as follows.
JP 2005-196122 A JP 2005-119909 A JP 2003-222704 A JP 2002-277604 A

  An object of the present invention is to provide an antireflection film which is excellent in adhesion, scratch resistance, dust resistance and antifouling properties and has sufficient antireflection performance. In particular, an object of the present invention is to provide an antireflection film having a sufficient antireflection performance excellent in antifouling property and dustproofness when a fluorine-containing polymer or a fluorine-containing antifouling agent is used. Furthermore, it is providing the polarizing plate and image display apparatus using such an antireflection film.

｛一般式（Ｉ）中、Ｒ ^１ 及びＲ ^２ は同一であっても異なっていてもよく、アルキル基又はアリール基を表す。ｐは１０〜５００の整数を表す。｝
［９］
前記１分子中に少なくとも２個以上のエチレン性不飽和基を含有する電離放射線硬化性化合物（Ａ）が、下記一般式（１）で表されることを特徴とする、［１］〜［８］のいずれか一項に記載の反射防止フイルム。
一般式（１）：

｛一般式（１）中、Ｌ ^１１ は炭素数１〜１０の連結基を表し、ｓ１は０又は１を表す。Ｒ ^１１ は水素原子又はメチル基を表す。Ａ ^１１ は側鎖に水酸基を持つ繰り返し単位を表す。Ｙ ^１１ はポリシロキサン構造を主鎖に含む構成成分を表わす。ｘ、ｙ、及びｚは、Ｙ ^１１ 以外の全繰返し単位を基準とした場合のそれぞれの繰返し単位のモル％を表し、３０≦ｘ≦６０、３０≦ｙ≦７０、０≦ｚ≦４０を満たす値を表す。ただし、ｘ＋ｙ＋ｚ＝１００（モル％）である。ｕは共重合体中の構成成分Ｙ ^１１ の質量％を表し、０．０１≦ｕ≦２０である。｝
［１０］
前記１分子中に少なくとも２個以上のエチレン性不飽和基を含有する電離放射線硬化性化合物（Ａ）が、下記一般式（２）で表されることを特徴とする、［１］〜［８］のいずれか一項に記載の反射防止フイルム。
一般式（２）：

｛一般式（２）中、Ｒｆ ^２１ は炭素数１〜５のペルフルオロアルキル基を表し、Ｒｆ ^２２ は炭素数１〜３０の直鎖、分岐又は脂環構造を有する含フッ素アルキル基を表し、エーテル結合を有していてもよく、Ａ ^２１ は架橋反応に関与し得る反応性基を有する構成単位を表し、Ｂ ^２１ は任意の構成成分を表す。Ｒ ^２１ 及びＲ ^２２ は、同一であっても異なっていてもよく、アルキル基又はアリール基を表す。ｐ１は１０〜５００の整数を表す。Ｒ ^２３ 〜Ｒ ^２５ は、互いに独立に、置換又は無置換の１価の有機基又は水素原子を表し、Ｒ ^２６ は水素原子又はメチル基を表わす。Ｌ ^２１ は炭素数１〜２０の任意の連結基又は単結合を表す。ａ〜ｄはそれぞれポリシロキサンを含有する重合単位を除く各構成成分のモル分率（％）を表し、それぞれ１０≦ａ＋ｂ≦５５、１０≦ａ≦５５、０≦ｂ≦４５、１０≦ｃ≦５０、０≦ｄ≦４０の関係を満たす値を表す。ｅはポリシロキサンを含有する重合単位の、他の成分全体の質量に対する質量分率（％）を表し、０．０１＜ｅ＜２０の関係を満たす。｝
［１１］
［１］〜［１０］のいずれか一項に記載の反射防止フイルムを、少なくとも一方の側に備えたことを特徴とする偏光板。
［１２］
［１］〜［１０］のいずれか一項に記載の反射防止フイルム及び［１１］に記載の偏光板のうちの少なくとも一つが配置されていることを特徴とする画像表示装置。
本発明は上記［１］〜［１２］に関するものであるが、以下、その他の事項についても参考のために記載した。 As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved, and the present invention has been completed.
That is, the present invention achieves the object by the following configuration.
[1]
Of the at least one layer having a refractive index of 1.28 to 1.48, the layer farthest from the transparent support is formed by coating a coating composition containing at least the following components: Characteristic anti-reflection film.
(A) Ionizing radiation curable compound containing at least two ethylenically unsaturated groups in one molecule
(B) Porous inorganic fine particles having a conductive metal oxide coating layer or fine particles having cavities inside
(D) At least one ionizing radiation curable fluorine-containing antifouling agent
(The fluorine-containing antifouling agent is at least one kind represented by the following general formula (F-3).)
Formula (F-3):
(Rf)-[(W)-(R _A ) _n ] _m
(In General Formula (F-3), Rf represents a (per) fluoropolyether group, W represents a linking group, and _RA represents a (meth) acrylic group. N represents an integer of 1 to 3, and m represents an integer of 1 to 3. And n and m are not 1 at the same time.)
[2]
The antireflective film according to [1], wherein the compound (A) is a fluoropolymer containing at least one perfluoroolefin polymer unit and (meth) acryloyl group-containing polymer unit.
[3]
The antireflection film according to [1] or [2], wherein the porous inorganic fine particles or fine particles (B) having cavities therein are silica-based fine particles having an antimony oxide coating layer.
[4]
Any one of [1] to [3], wherein the porous inorganic fine particles or the fine particles (B) having cavities therein are porous silica-based fine particles or silica-based fine particles having cavities therein. The antireflection film as described.
[5]
The porous inorganic fine particles or fine particles (B) having cavities therein are formed on a conductive metal oxide coating layer, a silica coating layer, or an organosilane hydrolyzate represented by the following general formula (3) and / or Alternatively, the antireflection film according to any one of [1] to [4], which has a silica coating layer surface-treated with a partial condensate thereof.
Formula (3): (R ³⁰ ) _m1 Si (X ³¹ ) _4-m1
(In general formula (3), R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ³¹ represents a hydroxyl group or a hydrolyzable group. Represents an integer.)
[6]
The porous inorganic fine particles or fine particles (B) having cavities therein have a refractive index in the range of 1.35 to 1.60 and a volume resistance value in the range of 10 to 5000 Ω / cm. [1] The antireflection film according to any one of [5].
[7]
The average particle diameter of the porous inorganic fine particles or fine particles (B) having cavities therein is in the range of 5 to 300 nm, and the thickness of the conductive metal oxide coating layer is in the range of 0.5 to 30 nm. The antireflection film according to any one of [1] to [6], which is characterized in that
[8]
The coating composition further
(C) The antireflection film as described in any one of [1] to [7], which has a compound containing a polysiloxane partial structure represented by the following general formula (I).
Formula (I)

{In General Formula (I), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. p represents an integer of 10 to 500. }
[9]
The ionizing radiation curable compound (A) containing at least two or more ethylenically unsaturated groups in one molecule is represented by the following general formula (1): [1] to [8] ] The antireflection film as described in any one of the above.
General formula (1):

{In General Formula (1), L ¹¹ represents a linking group having 1 to 10 carbon atoms, and s1 represents 0 or 1. R ¹¹ represents a hydrogen atom or a methyl group. A ¹¹ represents a repeating unit having a hydroxyl group in the side chain. Y ¹¹ represents a constituent component containing a polysiloxane structure in the main chain. x, y, and z ^represent mol% of respective repeating units in the case relative to the total repeating units other than ^{Y 11,} satisfy 30 ≦ x ≦ 60,30 ≦ y ≦ 70,0 ≦ z ≦ 40 Represents a value. However, it is x + y + z = 100 (mol%). u represents the mass% of the component ^{Y 11} in the copolymer is 0.01 ≦ u ≦ 20. }
[10]
The ionizing radiation curable compound (A) containing at least two or more ethylenically unsaturated groups in one molecule is represented by the following general formula (2): [1] to [8] ] The antireflection film as described in any one of the above.
General formula (2):

{In General Formula (2), Rf ²¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ²² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether A ²¹ may have a bond, A ²¹ represents a structural unit having a reactive group capable of participating in a crosslinking reaction, and B ²¹ represents an arbitrary structural component. R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group. p1 represents an integer of 10 to 500. R ^{23 to} R ²⁵ each independently represent a substituted or unsubstituted monovalent organic group or a hydrogen atom, and R ²⁶ represents a hydrogen atom or a methyl group. L ²¹ represents an arbitrary linking group having 1 to 20 carbon atoms or a single bond. a to d represent the mole fraction (%) of each constituent component excluding polymer units containing polysiloxane, and 10 ≦ a + b ≦ 55, 10 ≦ a ≦ 55, 0 ≦ b ≦ 45, 10 ≦ c ≦, respectively. It represents a value satisfying the relationship of 50, 0 ≦ d ≦ 40. e represents the mass fraction (%) of the polymer unit containing polysiloxane with respect to the mass of the other components, and satisfies the relationship of 0.01 <e <20. }
[11]
A polarizing plate comprising the antireflection film according to any one of [1] to [10] on at least one side.
[12]
At least one of the antireflection film according to any one of [1] to [10] and the polarizing plate according to [11] is disposed.
The present invention relates to the above [1] to [12], but other matters are also described below for reference.

(1)
Of the at least one layer having a refractive index of 1.28 to 1.48, the layer farthest from the transparent support is formed by coating a coating composition containing at least the following components: Characteristic anti-reflection film.
(A) Ionizing radiation curable compound (B) Fine particles having a conductive metal oxide coating layer (2)
The antireflection film according to (1), wherein the fine particles (B) having the conductive metal oxide coating layer are porous inorganic fine particles or fine particles having cavities therein.
(3)
The antireflection film according to (1) or (2), wherein the fine particles (B) having the conductive metal oxide coating layer are silica-based fine particles having an antimony oxide coating layer.
(4)
The reflection according to any one of (1) to (3), wherein the fine particles (B) having the conductive metal oxide coating layer are porous silica-based fine particles or silica-based fine particles having cavities therein. Prevention film.
(5)
The fine particles (B) having the conductive metal oxide coating layer are a silica coating layer on the conductive metal oxide coating layer, or a hydrolyzate of organosilane represented by the following general formula (3) and / or The antireflection film according to any one of (1) to (4), wherein the antireflection film has a silica coating layer surface-treated with the partial condensate.
Formula (3): (R ³⁰ ) _m1 Si (X ³¹ ) _4-m1
(In general formula (3), R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ³¹ represents a hydroxyl group or a hydrolyzable group. Represents an integer.)
(6)
The fine particles (B) having the conductive metal oxide coating layer have a refractive index in the range of 1.35 to 1.60 and a volume resistance value in the range of 10 to 5000 Ω / cm (1). ) To (5).
(7)
The fine particles (B) having the conductive metal oxide coating layer have an average particle diameter in the range of 5 to 300 nm, and the conductive metal oxide coating layer has a thickness in the range of 0.5 to 30 nm. The antireflection film according to any one of (1) to (6).
(8)
The antireflective film according to any one of (1) to (7), wherein the compound (A) contains at least two ethylenically unsaturated groups in one molecule.
(9)
Any of (1) to (8), wherein the compound (A) is a fluoropolymer containing at least one perfluoroolefin polymer unit and (meth) acryloyl group-containing polymer unit. The antireflection film as described.
(10)
The coating composition further comprises (C) a compound containing a polysiloxane partial structure represented by the following general formula (I): Antireflection according to any one of (1) to (9) Film.
Formula (I)

{In General Formula (I), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. p represents an integer of 10 to 500. }
(11)
The anti-reflection film according to any one of (1) to (10), wherein the ionizing radiation-curable compound (A) is represented by the following general formula (1).
General formula (1):

{In General Formula (1), L ¹¹ represents a linking group having 1 to 10 carbon atoms, and s1 represents 0 or 1. R ¹¹ represents a hydrogen atom or a methyl group. A ¹¹ represents a repeating unit having a hydroxyl group in the side chain. Y ¹¹ represents a constituent component containing a polysiloxane structure in the main chain. x, y, and z ^represent mol% of respective repeating units in the case relative to the total repeating units other than ^{Y 11,} satisfy 30 ≦ x ≦ 60,30 ≦ y ≦ 70,0 ≦ z ≦ 40 Represents a value. However, it is x + y + z = 100 (mol%). u represents the mass% of the component ^{Y 11} in the copolymer is 0.01 ≦ u ≦ 20. }
(12)
The anti-reflection film according to any one of (1) to (9), wherein the ionizing radiation curable compound (A) is represented by the following general formula (2).
General formula (2):

{In General Formula (2), Rf ²¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ²² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether A ²¹ may have a bond, A ²¹ represents a structural unit having a reactive group capable of participating in a crosslinking reaction, and B ²¹ represents an arbitrary structural component. R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group. p1 represents an integer of 10 to 500. R ^{23 to} R ²⁵ each independently represent a substituted or unsubstituted monovalent organic group or a hydrogen atom, and R ²⁶ represents a hydrogen atom or a methyl group. L ²¹ represents an arbitrary linking group having 1 to 20 carbon atoms or a single bond. a to d represent the mole fraction (%) of each constituent component excluding polymer units containing polysiloxane, and 10 ≦ a + b ≦ 55, 10 ≦ a ≦ 55, 0 ≦ b ≦ 45, 10 ≦ c ≦, respectively. It represents a value satisfying the relationship of 50, 0 ≦ d ≦ 40. e represents the mass fraction (%) of the polymer unit containing polysiloxane with respect to the mass of the other components, and satisfies the relationship of 0.01 <e <20. }
(13)
The antireflection film as described in any one of (1) to (12), wherein the coating composition further contains at least one ionizing radiation curable fluorine-containing antifouling agent (D).
(14)
A polarizing plate comprising the antireflection film according to any one of (1) to (13) on at least one side.
(15)
At least one of the antireflection film according to any one of (1) to (13) and the polarizing plate according to (14) is disposed.

  An object of the present invention is to provide an antireflection film which is excellent in scratch resistance, dust resistance and antifouling properties and has sufficient antireflection performance. Furthermore, by using such an antireflection film, a high-quality polarizing plate and an image display device can be provided.

  Hereinafter, the present invention will be described in more 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”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

<Anti-reflective film>
The antireflective film of the present invention is formed by coating a coating composition containing at least the following components on a low refractive index layer located farthest from the transparent support among at least one low refractive index layer. It is characterized by.
(A) Ionizing radiation curable compound (B) Fine particles having a conductive metal oxide coating layer

(Low refractive index layer)
First, the low refractive index layer of the antireflection film of the present invention will be described.
The refractive index of the low refractive index layer in the present invention is in the range of 1.28 to 1.48, preferably 1.34 to 1.44. Further, the low refractive index layer preferably satisfies the following formula (1) from the viewpoint of reducing the reflectance.
Formula (1): (m ₁ λ / 4) × 0.7 <n ₁ d ₁ <(m ₁ λ / 4) × 1.3
Where m ₁ is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
Note that satisfies the above equation (1), it means that m ₁ satisfying the formula (1) in the above range _{wavelengths (positive} odd number, usually 1) is present.

  In the present invention, the refractive index of the constituent layer of the optical film can be determined from the reflectance of the optical film by the optical simulation of the refractive index and film thickness of each layer. Moreover, what hardened the component of the structural layer with the Abbe refractometer can be measured as it is.

[Ionizing radiation curable compound] (low refractive index layer component (A) of the present invention)
In coating the low refractive index layer in the present invention, an ionizing radiation curable compound (a compound that is cured by irradiation with ionizing radiation) is used. As such an ionizing radiation curable compound, for example, a fluorine-containing polymer or a fluorine-containing sol / gel material having a low refractive index is preferably used. The fluorine-containing polymer or fluorine-containing sol / gel material is usually crosslinked by ionizing radiation and, if necessary, heat. The dynamic friction coefficient of the formed low refractive index layer surface is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 °. Moreover, the compound which has at least 2 or more ethylenically unsaturated group in 1 molecule which hardens | cures by ionizing radiation irradiation can also be used.
The ionizing radiation curable compound is preferably used in an amount of 10 to 100% by mass, more preferably 30 to 95% by mass, and particularly preferably 40 to 80% by mass with respect to the solid content of the low refractive index layer.

[Compound having at least two ethylenically unsaturated groups in one molecule]
Examples of the compound 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 diester). (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, -Cyclohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide modified form of the above ester, vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide), methacrylamide and the like. Two or more of these compounds may be used in combination. These compounds can increase the density of cross-linking groups in the binder and form a cured film having high hardness, but the refractive index is not low as compared with the fluorine-containing polymer binder. However, among the silica-based fine particles (hereinafter, sometimes referred to as antimony oxide-coated silica-based fine particles) having an antimony oxide-coated layer (to be described later) as the fine particles having the conductive metal oxide coating layer (B), for example, porous or By using together with a cavity having a cavity inside, a sufficiently effective refractive index can be obtained as the low refractive index layer of the present invention.

[Fluoropolymer]
Fluorine-containing polymers and fluorine-containing sol / gel materials used for the low refractive index layer are hydrolyzed perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). In addition to decomposition and dehydration condensates, there may be mentioned fluorine-containing copolymers having a fluorine-containing monomer unit and a constituent unit for imparting crosslinking reactivity as constituent components.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.), (meta ) A part of acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (manufactured by Osaka Organic Chemical) or M-2020 (manufactured by Daikin)), a complete or partially fluorinated vinyl ether, and the like. From the viewpoint of refractive index, solubility, transparency, availability, etc., hexafluoropropylene is particularly preferred.

Examples of the structural unit for imparting crosslinking reactivity mainly include units represented by the following (a), (b), and (c).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether, (b): a carboxyl group, a hydroxy group, an amino group, or a sulfo group A structural unit obtained by polymerization of monomers having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. , (C): a compound that reacts with the functional groups (a) and (b) in the molecule and a compound having a crosslinkable functional group separately from the above, reacts with the structural units (a) and (b). A structural unit obtained by (for example, acrylic with respect to hydroxyl group) Structural units can be synthesized by a method such as the action of chlorides), and the like.

  In the present invention, the structural unit (c) is preferably such that the crosslinkable functional group is a photopolymerizable group. Here, examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide. Group, carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclo A propene group, an azadioxabicyclo group, etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
(1) A method of esterifying a crosslinkable functional group-containing copolymer containing a hydroxyl group by reacting (meth) acrylic acid chloride,
(2) A method of urethanizing a crosslinkable functional group-containing copolymer containing a hydroxyl group with a (meth) acrylic acid ester containing an isocyanate group,
(3) A method of esterifying by reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
(4) A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is esterified by reacting a containing (meth) acrylic acid ester containing an epoxy group.
The amount of the photopolymerizable group introduced can be arbitrarily adjusted. From the viewpoint of surface stability of the coating film, reduction of surface failure when coexisting with inorganic fine particles, and improvement of film strength, carboxyl group, hydroxyl group, etc. It is also preferable to leave a certain amount.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tertbutylacrylamide, N-silane) B hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP-A-2004-45462.

  The fluorine-containing polymer useful in the present invention preferably has a polysiloxane structure introduced for the purpose of imparting antifouling properties. There is no limitation on the method for introducing the polysiloxane structure, but for example, as described in JP-A-11-189621, JP-A-11-228631, and JP-A-2000-313709, a polysiloxane block using a silicone macroazo initiator is used. A method of introducing a copolymer component and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806 are preferred. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the coating surface condition and scratch resistance.

As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluoropolymer. A combination with a compound having a fluorine-containing polyfunctional polymerizable unsaturated group is also preferred as described in JP-A Nos. 2000-17028 and 2002-145952. Examples of the compound having a polyfunctional polymerizable unsaturated group include the above-mentioned [compound having two or more ethylenically unsaturated groups]. 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.
These compounds are preferably used in an amount of 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and most preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polymer main body.

[Compound having a polysiloxane partial structure]
In the present invention, compounds having a polysiloxane partial structure that can be particularly preferably used will be described in detail below.
Such compounds can be broadly classified as those containing a polysiloxane partial structure represented by the general formula (1) in the polymer main chain and a polysiloxane partial structure represented by the general formula (2) on the polymer side. Those contained in the chain can be preferably used.

(Polymer having a polysiloxane partial structure in the polymer main chain)
As a polymer having a polysiloxane partial structure in the polymer main chain, a repeating unit having a (meth) acryloyl group in the side chain including a repeating unit from a fluorine-containing vinyl monomer, a polysiloxane partial structure in the main chain, and a hydroxyl group. It is preferable that it is a fluorine-containing polymer containing the repeating unit which has. Such a polymer can serve both as a compound that is cured by irradiation with ionizing radiation and a compound having a polysiloxane partial structure. This polymer is preferably represented by the following general formula (1).
General formula (1):

In the general formula (1), L ¹¹ represents a linking group having 1 to 10 carbon atoms, preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, and linear. 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.

s1 represents 0 or 1.
R ¹¹ represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.

A ¹¹ represents a repeating unit having a hydroxyl group in the side chain, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Adhesion to the substrate, Tg of the polymer (in terms of film hardness) Can be selected from various viewpoints such as solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc., and may be composed of a single or a plurality of vinyl monomers depending on the purpose. Good.

Preferred examples of the vinyl monomers constituting the A ¹¹ is methyl vinyl ether, ethyl vinyl ether, t- butyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether and allyl vinyl ether, Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyl (Meth) acrylates such as trimethoxysilane, styrene derivatives such as styrene and p-hydroxymethylstyrene, Examples thereof include unsaturated carboxylic acids such as rotonic acid, maleic acid, and itaconic acid, and derivatives thereof. Preferred are vinyl ether derivatives and vinyl ester derivatives, and particularly preferred are vinyl ether derivatives.

Y ¹¹ represents a constituent component containing a polysiloxane partial structure in the main chain.
There is no particular limitation on the method for introducing the polysiloxane partial structure into the main chain. For example, an azo group-containing polysiloxane amide described in JP-A-6-93100 (VPS-0501, 1001 (trade name; Wako Pure) is commercially available. A method using a polymer-type initiator such as Yaku Kogyo Co., Ltd.), a polymerization initiator, a reactive group derived from a chain transfer agent (for example, a mercapto group, a carboxyl group, a hydroxyl group, etc.) is introduced into the polymer terminal, Examples thereof include a method of reacting with a polysiloxane containing one or both terminal reactive groups (for example, epoxy group, isocyanate group, etc.), a method of copolymerizing a cyclic siloxane oligomer such as hexamethylcyclotrisiloxane by anionic ring-opening polymerization, and the like. However, among them, a method using an initiator having a polysiloxane partial structure is easy and preferable.

x, y, and z ^represent mol% of respective repeating units in the case relative to the total repeating units other than ^{Y 11,} satisfy 30 ≦ x ≦ 60,30 ≦ y ≦ 70,0 ≦ z ≦ 40 Value, preferably in the range of 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, 0 ≦ z ≦ 35. However, it is x + y + z = 100 (mol%). u represents the mass% of the component ^{Y 11} in the copolymer is 0.01 ≦ u ≦ 20.

Among them, particularly preferable polymers include those represented by the following general formula (1-2).
General formula (1-2):

In said general formula (1-2), R < ¹¹ >, Y < ¹¹ >, x, y, and u each represent the same meaning as General formula (1), and its preferable range is also the same.
B ¹¹ represents a repeating unit from any vinyl monomer, and may be a single component or a plurality of components. Examples include those described as examples of A ¹¹ in the general formula (1) applies.

z1 and z2 ^are the case relative to the total repeating units other than ^{Y 11} represents a mole% of the respective repeating units, it represents a value satisfying 0 ≦ z1 ≦ 40,0 ≦ z2 ≦ 40, respectively 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 are preferable, and 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5 are particularly preferable. However, it is x + y + z1 + z2 = 100 (mol%). T1 represents an integer satisfying 2 ≦ t1 ≦ 10, preferably 2 ≦ t1 ≦ 6, and particularly preferably 2 ≦ t1 ≦ 4. More preferably, the copolymer represented by the general formula (1-2) satisfies 40 ≦ x ≦ 60, 40 ≦ y ≦ 60, and z2 = 0.

The polysiloxane partial structure introduced into the copolymer of the present invention is particularly preferably a structure represented by the following general formula (1-3).
General formula (1-3):

In General Formula (1-3), R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms. Examples include a methyl group and an ethyl group. ), An aryl group (preferably having a carbon number of 6 to 10. Examples include a phenyl group and a naphthyl group), an alkoxycarbonyl group (preferably having a carbon number of 2 to 5. Examples include a methoxycarbonyl group and an ethoxycarbonyl group). Or a cyano group, preferably an alkyl group and a cyano group, and particularly preferably a methyl group and a cyano group.

R ^{115 to} R ¹²⁰ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 5. Examples include a methyl group and an ethyl group), and a haloalkyl group (a fluorinated alkyl having 1 to 5 carbon atoms). A trifluoromethyl group and a pentafluoroethyl group), or a phenyl group, preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

  t2 and t5 each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. t3 and t4 each independently represents an integer of 0 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. p2 represents an integer of 10 to 1000, preferably an integer of 20 to 500, and particularly preferably an integer of 50 to 200.

  The polysiloxane partial structure represented by the general formula (1-3) is preferably introduced in the range of 0.01 to 20% by mass in the polymer that can be used in the present invention, and more preferably is in the range of 0.0. It is a case where it introduce | transduces in the range of 05-10 mass%, Most preferably, it is a case where it introduce | transduces in the range of 0.5-5 mass%.

  By introducing the polysiloxane partial structure described above, the film is imparted with antifouling properties and dustproof properties, and at the same time, slipperiness is imparted to the surface of the film, which is advantageous for scratch resistance.

  In the polymer useful in the present invention, in addition to the repeating unit 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). ), Other vinyl monomers can be suitably copolymerized from various viewpoints such as solubility in a solvent, transparency, 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 40 mol% in the copolymer, and in the range of 0 to 30 mol%. More preferably, it is especially preferably in the range of 0 to 20 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-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, Nt-butylacrylamide, N -Cyclohexyl acrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  Although the preferable example of a polymer useful by this invention is shown below, this invention is not limited to these.

  In the above table, 50 / y / z represents a molar ratio, u represents mass%, and VPS-1001 is derived from Wako Pure Chemical Industries, Ltd. polysiloxane-containing macroazo initiator “VPS1001” (trade name). Represents components (the same applies hereinafter).

  In the said table | surface, x / y / z shows molar ratio and u shows the mass% in a copolymer. VPS-0501 represents a component derived from a polysiloxane-containing macroazo initiator “VPS0501” (trade name) manufactured by Wako Pure Chemical Industries, Ltd.

  In the said table | surface, x / y / z1 / z2 and 50 / y / z each show molar ratio, u shows the mass%. T1 represents the number of methylene units.

  In the above table, x / y / z indicates a molar ratio, and u indicates mass%. T1 represents the number of methylene units.

  In the said table | surface, ratio (50/50) of the component of a vinyl monomer shows molar ratio, u shows the mass%, p2 shows the number of dimethylsiloxane partial structures.

(Polymer having a polysiloxane partial structure in the polymer side chain)
Next, the polymer having a polysiloxane partial structure in the polymer side chain will be described in detail.

A particularly preferable form of the polymer in the present invention is a form represented by the general formula (2). Such a polymer can serve both as a compound that is cured by irradiation with ionizing radiation and a compound having a polysiloxane partial structure.
General formula (2):

In the general formula (2), R _f ²¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, and R _f ²² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms. , May have an ether bond, A ²¹ represents a structural unit having a reactive group capable of participating in a crosslinking reaction, and B ²¹ represents an optional structural component. R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group. p1 represents an integer of 10 to 500. R ^{23 to} R ²⁵ each independently represent a substituted or unsubstituted monovalent organic group or a hydrogen atom, and R ²⁶ represents a hydrogen atom or a methyl group. L ²¹ represents an arbitrary linking group having 1 to 20 carbon atoms or a single bond.

  a to d each represent a molar fraction (%) of each constituent component excluding a polymer unit containing a polysiloxane partial structure, and 10 ≦ a + b ≦ 55, 10 ≦ a ≦ 55 (more preferably 40 ≦ a), respectively. ≦ 55), 0 ≦ b ≦ 45 (more preferably 0 ≦ b ≦ 30), 10 ≦ c ≦ 50 (more preferably 20 ≦ c ≦ 50), 0 ≦ d ≦ 40 (more preferably 0 ≦ d <30). ) Represents a value satisfying the relationship. e represents a mass fraction (%) of the polymerization unit containing the polysiloxane partial structure with respect to the mass of the other four components, and 0.01 <e <20 (preferably 0.1 <e <10, more preferably Satisfies the relationship 0.5 <e <5).

  The perfluoroolefin is preferably one having 3 to 7 carbon atoms, preferably perfluoropropylene or perfluorobutylene from the viewpoint of polymerization reactivity, and particularly preferably perfluoropropylene from the viewpoint of availability.

  The content of perfluoroolefin in the polymer is 10 to 55 mol%. In order to lower the refractive index of the material, it is desired to increase the introduction rate of perfluoroolefin, but in terms of polymerization reactivity, introduction of about 50 to 70 mol% is the limit in a general solution-based radical polymerization reaction. There is more than that. In the present invention, the content is preferably 10% to 55 mol%, particularly preferably 40 to 55 mol%.

(Fluorine-containing vinyl ether)
In the present invention, the compound represented by the general formula (2) may be copolymerized with a fluorinated vinyl ether represented by the following general formula (M1) in order to reduce the refractive index. The copolymer component may be introduced into the polymer in a co-range of 0 to 45 mol%, preferably 0 to 30 mol%, particularly preferably 0 to 20 mol%. In particular, when the film hardness of the low refractive index layer should be set high (for example, a high amount of low refractive index filler is included in the low refractive index layer, and the film strength is increased rather than lowering the refractive index of the layer with a binder polymer) In this case, the introduction ratio of the copolymer component represented by the fluorine-containing vinyl ether represented by the following general formula (M1) is preferably 0 mol%. This is because by removing the copolymer component, it is possible to increase the rate of introduction of polymerized units having a reactive group that can participate in the crosslinking reaction in the side chain described later.

In Formula _(M1), ^{R f 22} represents a fluorinated alkyl group having 1 to 30 carbon atoms, preferably a fluorine-containing alkyl group having 1 to 15 carbon 1 to 20 carbon atoms, and particularly preferably carbon, straight-chain {For example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.} {E.g., CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.} And may have an alicyclic structure (preferably a 5- or 6-membered ring such as a perfluorocyclohexyl group, a perfluorocyclopentyl group or an alkyl group substituted with these), and an ether bond (e.g. _{CH 2 OCH} 2 CF 2 CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.) .

  Examples of the monomer represented by the general formula (M1) include “Macromolecules”, vol. 32 (21), p. 7122 (1999), as disclosed in JP-A-2-721, etc., a fluorinated alcohol in the presence of a base catalyst is used for leaving group-substituted alkyl vinyl ethers such as vinyloxyalkyl sulfonate and vinyloxyalkyl chloride. A method of acting; a method of exchanging a vinyl group by mixing a fluorine-containing alcohol and a vinyl ether such as butyl vinyl ether in the presence of a palladium catalyst as described in International Patent Application No. 92/05135; described in US Pat. No. 3,420,793 As described above, it can be synthesized by a method in which a fluorine-containing ketone and dibromoethane are reacted in the presence of a potassium fluoride catalyst, followed by a deHBr reaction with an alkali catalyst.

  The preferable example of the structural component represented by general formula (M1) below is shown.

(Structural unit having a reactive group capable of participating in the crosslinking reaction)
In the present invention, the fluorine-containing polymer constituting the low refractive index layer, for example, a reactive group (hereinafter also referred to as a crosslinking reactive group) that can participate in a crosslinking reaction, contained in the compound represented by the general formula (2). Although there is no restriction | limiting in particular in the structure of a structural unit, From a viewpoint of polymerization reactivity with a fluorine-containing olefin, it is preferable that it is a compound which has a vinyl group, and it is more preferable that they are vinyl ethers or vinyl esters.

  Examples of the crosslinking reactive group include a group having an active hydrogen atom (for example, a hydroxyl group, an amino group, a carbamoyl group, a mercapto group, a β-ketoester group, a hydrosilyl group, a silanol group, etc.), a group capable of cationic polymerization (for example, Epoxy groups, oxetanyl groups, oxazolyl groups, vinyloxy groups, etc.), acid anhydrides, groups having unsaturated double bonds that can be added or polymerized by radical species (eg, acryloyl groups, methacryloyl groups, allyl groups, etc.), Examples include hydrolyzable silyl groups (for example, alkoxysilyl groups, acyloxysilyl groups, etc.), groups that can be substituted by nucleophiles (for example, active halogen atoms, sulfonate esters, etc.), and the like.

  Among these, a group having an unsaturated double bond is obtained by synthesizing a polymer having a hydroxyl group, then an acid halide such as (meth) acrylic acid chloride, an acid anhydride such as (meth) acrylic anhydride, or (meta ) A method of allowing acrylic acid to act; It can be formed by a conventional method such as a method of dehydrochlorination after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety. Similarly, other functional groups may be introduced from the monomer stage, or a polymer having a reactive group such as a hydroxyl group may be introduced after synthesis.

  Among the crosslinking reactive groups, a hydroxyl group, an epoxy group, a (meth) acryloyl group or a hydrolyzable silyl group is preferable, an epoxy group or a (meth) acryloyl group is more preferable, and a (meth) acryloyl group is most preferable. The amount of the copolymerization component having a crosslinking reactive group introduced is in the range of 10 to 50 mol%, preferably in the range of 20 to 50 mol%, and preferably in the range of 25 to 50 mol%. Particularly preferred.

  Although the preferable example of the polymerization unit which can participate in a crosslinking reaction below is shown, this invention is not limited to these.

(Polysiloxane partial structure)
The polysiloxane partial structure in the polymer having a polysiloxane partial structure in the side chain used in the present invention will be described. The polysiloxane partial structure generally has a repeating siloxane moiety represented by the following general formula (2-1).
General formula (2-1):

In General Formula (2-1), R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p1 represents an integer of 10 to 500, preferably 10 to 350, and particularly preferably 10 to 250.

  Examples of the polymer having a polysiloxane structure represented by the general formula (2-1) in the side chain are “JA Appl. Polym. Sci.”, 2000, p. 78 (1955), as disclosed in JP-A-56-28219 and the like, a reactive group having reactivity with a polymer having a reactive group such as an epoxy group, a hydroxyl group, a carboxyl, or an acid anhydride group. Polysiloxane [for example, “Silaplane” series {manufactured by Chisso Corporation, etc.] having a polymer at one end (for example, an amino group, a mercapto group, a carboxyl group, a hydroxyl group, etc. with respect to an epoxy group or an acid anhydride group) is a polymer. It can be synthesized by a method of introducing by reaction; a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

  The polymer unit containing a siloxane moiety in the side chain preferably occupies 0.01 to 20% by mass in the copolymer, more preferably 0.1 to 10% by mass, and particularly preferably 0. .5 to 5%.

  Although the preferable example of the polymerization unit which is useful for this invention and contains a siloxane part repeatedly in a side chain is shown below, this invention is not limited to these.

Other than the above, as the polymerized unit containing a siloxane moiety repeatedly in the side chain, as described above, a polysiloxane having a reactive group at one end with respect to a reactive group possessed by another polymerized unit. What is formed by carrying out a polymer reaction can also be used, and the following can be illustrated as such commercially available polysiloxane.
S- (36): “Silaplane FM-0711” {manufactured by Chisso Corporation}
S- (37): “Silaplane FM-0721” (same as above)
S- (38): “Silaplane FM-0725” (same as above)

(Other copolymer components)
Copolymerization components other than the above can also be appropriately selected from various viewpoints such as hardness, adhesion to a substrate, solubility in a solvent, and transparency.

  Examples of such copolymerization components include methyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, and isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, and cyclohexane. Examples include vinyl esters such as vinyl carboxylate. The introduction amount of these copolymerization components is in the range of 0 to 40 mol%, preferably in the range of 0 to 30 mol%, and particularly preferably in the range of 1 to 20 mol%.

Specific examples of polymers useful in the present invention are shown in Table 8 and Table 9 below, but the present invention is not limited to these. In Tables 8 and 9, they are expressed as combinations of polymerization units. The molar fraction in the component except the polymerized unit containing silicone and the mass fraction of the polymerized unit containing silicone are shown.
Table 8

  The polymer having a polysiloxane structure in the main chain or side chain, which is a compound having a polysiloxane partial structure used in the present invention, has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography. The range is preferably, and more preferably in the range of 5,000 to 300,000.

  The synthesis of a polymer having a polysiloxane structure in the main chain or side chain is a precursor of a hydroxyl group-containing polymer or the like by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. After the body is synthesized, it can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be carried out by any operation such as batch, semi-continuous or continuous.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu and Masato Kinoshita, “Experimental Methods for Polymer Synthesis” ( Chemistry Dojin, published in 1972), pages 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 are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, It may be a single organic organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more thereof, or a mixed solvent with water.

  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 1-100 kg / cm ² , particularly about 1-30 kg / cm ² 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.

(Combination of polyfunctional monomers)
The ionizing radiation curable compound of the present invention is used in combination with a compound having two or more ethylenically unsaturated groups from the viewpoint of improving the film strength, improving the coating surface condition, and stabilizing the surface condition when adding fine particles. Is preferred. Further, the ionizing radiation curable compound of the present invention itself may be a compound having two or more ethylenically unsaturated groups. 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, 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-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester Polyacrylate, etc., vinylbenzene and derivatives thereof (for example, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, etc.), vinyl sulfones (for example, divinylsulfone, etc.) Acrylamide derivatives (for example, methylenebisacrylamide) and methacrylamide derivatives. Two or more of these monomers may be used in combination.

[Polysiloxane Partial Structure-Containing Compound] (Low Refractive Index Layer Component (C) of the Present Invention)
A compound containing a polysiloxane partial structure represented by the following general formula (I) can be added to the low refractive index layer in the present invention in order to impart antifouling properties.
Formula (I)

(In general formula (I), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. P represents an integer of 10 to 500.)
The polysiloxane partial structure-containing compound preferably contains at least one reactive group. Examples include KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-5002, X-22-173B, X-22-174D, X- 22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above trade name, manufactured by Toagosei Co., Ltd.), and the like. Among these, examples of preferable silicone compounds having a photopolymerizable functional group in the molecule include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, FM6621, FM-1221, Silaplane FM0275, Silaplane FM0721, Gelest DMS-U22, RMS-033, RMS -083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (the above-mentioned product names), and the like, but are not limited thereto. In addition, silicone compounds described in Tables 2 and 3 of JP-A No. 2003-112383 can also be preferably used.
At this time, these polysiloxanes are preferably added in the range of 0.5 to 10% by mass, and particularly preferably in the range of 1 to 5% by mass, based on the total solid content of the low refractive index layer.

[Ionizing radiation curable fluorine-containing antifouling agent] (low refractive index layer component (D) of the present invention)
For the purpose of imparting properties such as antifouling property, water resistance, chemical resistance and slipperiness to the low refractive index layer of the present invention, it is preferable to add a fluorine-based antifouling agent, a slipping agent and the like as appropriate. From the viewpoint of suppressing the back transfer of the fluorine compound during storage of the coated product in a roll state and improving the scratch resistance of the coating film, it is preferable to use a fluorine-containing antifouling agent containing an ionizing radiation curable functional group. . The fluorine-containing antifouling agent containing an ionizing radiation curable functional group is an antifouling agent containing a fluorine-based compound. The ionizing radiation curable functional group is not particularly limited, but a functional group having an unsaturated double bond is preferable, and a methacryloyloxy group or an acryloyloxy group is most preferable.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH _{2 CH 2 CH 2 C 8 F 17} , CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name) and the like, but are not limited thereto.

  In the present invention, the preferred embodiments (general formulas (F-1), (F-2), (F-3)) of the compound in which the ionizing radiation curable functional group is a (meth) acryloyloxy group are described in detail. State.

  As a preferred first embodiment, a compound represented by the following general formula (F-1) can be exemplified.

Formula (F-1):
_{Rf (CF 2 CF 2) n} CH 2 CH 2 R 2 OCOCR 1 = CH 2

(In the formula, Rf represents any of a fluoroalkyl group having 1 to 10 carbon atoms, R ¹ represents a hydrogen atom or a methyl group, R ² represents a single bond or an alkylene group, and n represents a polymerization degree. The degree of polymerization n is k or more (k is any integer of 3 or more).)
Examples of the telomer acrylate containing a fluorine atom in the general formula (1) include a (meth) acrylic acid moiety or a fully fluorinated alkyl ester derivative.

  Specific examples of the compound represented by formula (F-1) are shown below, but the present invention is not limited thereto.

When telomerization is used in the synthesis of the compound represented by the general formula (F-1), the group of the general formula (F-1) may be used depending on the conditions of telomerization and the separation conditions of the reaction mixture. Rf (CF ₂ CF ₂ ) nR ² CH ₂ CH ₂ O—, where n is k, k + 1, k + 2,. . . And a plurality of fluorine-containing (meth) acrylic acid esters.

  As a preferred second embodiment, a compound represented by the following general formula (F-2) can be exemplified.

Formula (F-2):
_{F (CF 2) n O (} CF 2 CF 2 O) m CF 2 CH 2 OCOCR = CH 2

In general formula (F-2), R is a hydrogen atom or a methyl group, m is an integer of 1 to 6, and n is an integer of 1 to 4.
The fluorine atom-containing monofunctional (meth) acrylate represented by the general formula (F-2) is represented by the following general formula (FG-2).

General formula (FG-2):
_{F (CF 2) n O (} CF 2 CF 2 O) m CF 2 CH 2 OH

(In General Formula (FG-2), m is an integer of 1 to 6, and n is an integer of 1 to 4). The fluorine atom-containing alcohol compound represented by (meth) acrylic acid halide is reacted. Can be obtained.

  Specific examples of the fluorine atom-containing alcohol compound represented by the general formula (FG-2) include, for example, 1H, 1H-perfluoro-3,6-dioxaheptan-1-ol, 1H, 1H-perfluoro-3. , 6-Dioxaoctane-1-ol, 1H, 1H-perfluoro-3,6-dioxadecan-1-ol, 1H, 1H-perfluoro-3,6,9-trioxadecan-1-ol, 1H, 1H -Perfluoro-3,6,9-trioxaundecan-1-ol, 1H, 1H-perfluoro-3,6,9-trioxatridecan-1-ol, 1H, 1H-perfluoro-3,6,9, 12-tetraoxatridecan-1-ol, 1H, 1H-perfluoro-3,6,9,12-tetraoxatetradecan-1-ol, 1H, 1H-pe Fluoro-3,6,9,12-tetraoxahexadecan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxahexadecan-1-ol, 1H, 1H-perfluoro-3, 6,9,12,15-pentaoxaheptadecan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15-pentaoxanonadecan-1-ol, 1H, 1H-perfluoro-3, 6,9,12,15,18-hexaoxaicosan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18-hexaoxadocosan-1-ol, 1H, 1H- Perfluoro-3,6,9,12,15,18,21-heptaoxatricosan-1-ol, 1H, 1H-perfluoro-3,6,9,12,15,18,2 - it can be mentioned hepta oxa pen octopus San-1-ol and the like. These are available on the market. Specific examples thereof include, for example, 1H, 1H-perfluoro-3,6-dioxaheptan-1-ol: trade name: C5GOL: manufactured by Exfloor, 1H, 1H-perfluoro-3, 6,9-trioxadecan-1-ol: trade name: C7GOL: manufactured by Exfloor 1H, 1H-perfluoro-3,6-dioxadecan-1-ol: trade name: C8GOL: manufactured by Exfloor 1H, 1H-perfluoro-3,6,9-trioxatridecan-1-ol: Trade name: C10GOL: manufactured by Exfloor 1H, 1H-perfluoro-3,6,9,12-tetraoxahexadecan-1-ol : Product name: C12GOL: Exfloor, etc. In the present invention, 1H, 1H-perfluoro-3,6,9-trioxadecan-1-ol is preferably used.

  The (meth) acrylic acid halide to be reacted with the fluorine atom-containing alcohol compound represented by the general formula (FG-2) includes (meth) acrylic acid fluoride, (meth) acrylic acid chloride, and (meth) acrylic acid. Although bromide and (meth) acrylic acid iodide can be mentioned, (meth) acrylic acid chloride is usually preferred from the viewpoint of availability.

Although the preferable specific example of a compound represented by general formula (F-2) below is shown, it is not limited to these.
_{(B-1): F 9} C 4 OC 2 F 4 OC 2 F 4 OCF 2 CHOCOCH = CH 2
_{(B-2): F 9} C 4 OC 2 F 4 OC 2 F 4 OCF 2 CHOCOC (CH 3) = CH 2

  As a preferred third embodiment, a compound represented by the following general formula (F-3) can be mentioned.

Formula (F-3):
(Rf)-[(W)-(R _A ) _n ] _m

In general formula (F-3), Rf represents a (per) fluoropolyether group, W represents a linking group, and _RA represents a (meth) acrylic group. n represents an integer of 1 to 3, m represents an integer of 1 to 3, and n and m are not 1 at the same time.

  In the compound represented by the general formula (F-3), W represents, for example, alkylene, arylene, heteroalkylene, or a linking group in combination thereof. Those linking groups may further contain a functional group such as carbonyl, carbonyloxy, carbonylimino, sulfonamide, or the like or a combination thereof.

Preferred structures of Rf include the following structures.
F (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) −
Here, the average value of p is 4-15.
400-5000 are preferable, as for the number average molecular weight of the compound represented by general formula (F-3), 800-4000 are more preferable, Most preferably, it is 1000-3000.
Preferred specific examples and synthesis methods of the compound represented by the general formula (F-3) are described in International Publication WO 2005/008570.
Hereinafter, F (CF (CF ₃ ) CF ₂ O) _p CF (CF ₃ ) — in which the average value of p is 6 to 7 is referred to as “HFPO-”, and is a specific compound of the general formula (F-3) However, it is not limited to these.

_{(C-1): HFPO-} CONH-C- (CH 2 OCOCH = CH 2) 2 CH 2 CH 3
_{(C-2): HFPO-} CONH-C- (CH 2 OCOCH = CH 2) 2 H
(C-3): of _{HFPO-CONH-C 3 H 6} NHCH 3 trimethylolpropane triacrylate 1: 1 Michael addition polymer

[Fine Particles Having Conductive Metal Oxide Coating Layer] (Low Refractive Index Layer Component B of the Present Invention)
In the present invention, the fine particles that can be used as the component (B) of the low refractive index layer will be described. The low refractive index layer of the present invention contains fine particles having a conductive metal oxide coating layer. In the present invention, the fine particles having a conductive metal oxide coating layer include core / shell type composite fine particles having fine particles as nuclei and a conductive metal oxide shell layer on the outside, and an acid, alkali or organic solvent. After forming soluble fine particles as nuclei and forming a conductive metal oxide shell layer on the outside to form composite fine particles, treatment with acid, alkali or organic solvent removes the nuclei particles to form internal vacancies And internal pore-type hollow fine particles.

In either form of fine particles, there is no particular limitation on the conductive metal oxide used. For example, tin oxide (SnO ₂ ), antimony tin oxide (ATO), indium tin oxide (ITO), antimony oxide Those selected from (Sb ₂ O ₅ ), aluminum zinc oxide (AZO), gallium zinc oxide, and mixtures thereof.

  The core particles used for the core / shell type composite fine particles include silica fine particles, for example, inorganic fine particles such as colloidal silica fine particles and silicon oxide fine particles; polymer fine particles such as fluororesin fine particles, acrylic resin particles, and silicone resin particles; organic inorganic composites Fine particles such as particles can be used, and the refractive index can be lowered if the fine particles are porous and hollow fine particles.

The core particles used for the internal pore-type hollow fine particles are not limited as long as they can be dissolved and washed away through the shell layer by treatment with acid, alkali or organic solvent, but 2A, 2B, 3A, 3B in the periodic table, Inorganic oxide fine particles of metals selected from 4A, 4B, 5B and 6A group elements are preferred, and Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , SnO ₂ , Ce ₂ O _3, P ₂ O ₅ , Sb ₂ O. ₃ , MoO ₃ , ZnO ₂ , WO _{3 and the} like. Among these, Al ₂ O ₃ , ZnO ₂ , Y ₂ O ₃ , and Sb ₂ O ₅ fine particles are more preferable. Further, when used for the inner void type hollow fine particles, the combination of the core particles and the shell material includes fine particles such as Al ₂ O ₃ , ZnO ₂ , Y ₂ O ₃ , Sb ₂ O ₅ , ATO, ITO, SnO _2. Etc. are preferred.
As a method for producing the internal enveloping hollow fine particles, the surface of fine particles such as Al ₂ O ₃ , ZnO, Y ₂ O ₃ , Sb ₂ O ₅ is coated with ultra fine particles such as ATO, ITO, SnO ₂ or thin films thereof. After that, a method of forming hollow conductive inorganic fine particles by eluting the internal fine particles with an acid or alkaline aqueous solution can be used.

The coated amount of the fine particles (B) having a conductive metal oxide coating layer used in the present invention is preferably from 1 to 100 mg / ^{m 2,} more preferably 5-80 mg / ^{m 2,} more preferably 10～60Mg / a m ^2. If the coating amount of the fine particles is not less than the lower limit value, the scratch resistance is remarkably improved. If the coating amount is not more than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening is achieved. This is preferable because it does not cause problems such as deterioration of integrated reflectance. Since the fine particles are contained in the low refractive index layer, it is desirable that the fine particles have a low refractive index.

In the present invention, from the viewpoint of production stability of fine particles, composite oxide fine particles having silica particles as the core and a conductive inorganic metal oxide coating layer on the outside thereof are preferable. Particularly preferable are composite oxide fine particles in which the conductive inorganic metal oxide is antimony oxide. Hereinafter, the silica-based fine particles having an antimony oxide coating layer will be described in detail.
[Silica-based fine particles having an antimony oxide coating layer]
The silica-based fine particles (also referred to as antimony oxide-coated silica-based fine particles) having an antimony oxide-coated layer, which is a particularly preferred embodiment of the present invention, are silica-based fine particles having an antimony oxide-coated layer, preferably porous silica-based fine particles. Or the silica type microparticles | fine-particles which have a cavity inside are represented. The silica-based fine particles refer to particles containing silica.
The porous silica-based fine particles include porous silica fine particles and composite oxide fine particles containing silica as a main component. For example, as described in JP-A-7-133105, porous inorganic oxide fine particles are used. It is possible to use nanometer-sized composite oxide fine particles having a low refractive index in which the surface of the product fine particles is coated with silica or the like.
Further, as silica-based fine particles having a cavity inside, for example, as described in JP-A-2001-233611, a low refractive index nano-particle made of silica and an inorganic oxide other than silica and having a cavity inside. Meter-sized silica-based fine particles can be used.

  Such porous silica-based fine particles or silica-based fine particles having cavities therein preferably have an average particle size in the range of 4 to 270 nm, more preferably 8 to 170 nm.

  The refractive index of the porous silica-based fine particles or the silica-based fine particles having cavities therein is preferably 1.45 or less, more preferably 1.40 or less, which is the refractive index of silica.

  The silica-based fine particles are coated with antimony oxide having an average coating layer thickness of preferably 0.5 to 30 nm, more preferably 1 to 10 nm. The average thickness of the coating layer is preferably 0.5 nm or more from the viewpoint that the silica-based fine particles can be sufficiently coated and the resulting antimony oxide-coated silica-based fine particles have sufficient conductivity. The average thickness of the coating layer is preferably 30 nm or less in that the effect of improving conductivity is sufficient and the refractive index is sufficient even when the average particle size of the antimony oxide-coated silica-based fine particles is small.

  For the average thickness of the coating layer, the average particle size of the particles before and after coating was determined by observation with an electron microscope, the difference between the two was calculated, and this was taken as the average thickness of the coating layer. As the average particle size, an average value of 100 particles was adopted.

The antimony oxide may be any of Sb ₂ O ₃ , Sb ₂ O ₅ , SbO _2, etc., and the antimony oxide coating layer may contain tin oxide or the like. The total content of these antimony oxides in the antimony oxide coating layer is preferably 10% or more.
The antimony oxide-coated silica-based fine particles may be further coated with silica or the like.

  The average particle diameter of the antimony oxide-coated silica-based fine particles according to the present invention is preferably 5 to 300 nm, and more preferably 10 to 200 nm. By setting it as this range, electroconductivity and a refractive index can be made compatible and the whiteness of a coating film can be suppressed.

  The refractive index of the antimony oxide-coated silica-based fine particles is preferably 1.35 to 1.60, and more preferably 1.35 to 1.50.

The volume resistance value of the antimony oxide-coated silica-based fine particles is preferably 10 to 5000 Ω / cm, and more preferably 10 to 2000 Ω / cm. The antimony oxide-coated silica-based fine particles of the present invention can be used after surface treatment with a silane coupling agent according to a conventional method, if necessary.
By setting the volume resistance value in the above range, the surface resistance of the low refractive index coating film can be lowered while keeping the refractive index of the particles low. The volume resistance value can be controlled by adjusting the particle size of the core particles, the film thickness of the surface-coated metal oxide layer, and the composition.
The volume resistance value was measured by the following method.

[Measurement of volume resistivity]
A ceramic cell having a cylindrical hollow (cross-sectional area: 0.5 cm ² ) inside is used. First, the cell is placed on a gantry electrode, and 0.6 g of sample powder is filled inside, and a cylindrical protrusion is provided. Insert the protrusion of the upper electrode, pressurize the upper and lower electrodes with a hydraulic machine, measure the resistance value (Ω) and the height of the sample (cm) when 100 kg / cm ^{2 is} applied, and multiply the resistance value by the height Sought by.

The coating amount of the low refractive index layer of the antimony oxide-coated silica-based fine particles is preferably 1 to 100 mg / ^{m 2,} more preferably 5-80 mg / ^{m 2,} more preferably from 10~60mg / ^{m 2.}
Moreover, it is preferable to use as an organic solvent dispersion, and the organic solvent used for the following other fine particles can be used suitably.

[Production method of antimony oxide-coated silica-based fine particles]
In the method for producing antimony oxide-coated silica-based fine particles according to the present invention, an antimonic acid dispersion (aqueous solution) is added to a dispersion of porous silica-based fine particles or silica-based fine particles having cavities therein, and the surface of the silica-based fine particles is added. It is characterized by coating with antimonic acid.

  The porous silica-based fine particles include porous silica fine particles and composite oxide fine particles mainly composed of porous silica. Here, the porous fine particles refer to fine particles having a surface area measured by a titration method or a BET method, etc., larger than the external surface area of the fine particles calculated from the average particle diameter of the fine particles. Examples of such porous silica-based fine particles include: As described in JP-A-7-133105, nanometer-sized composite oxide fine particles having a low refractive index in which the surface of porous inorganic oxide fine particles is coated with silica or the like can be used.

  Further, as silica-based fine particles having a cavity inside, for example, as described in JP-A-2001-233611, a low refractive index nano-particle made of silica and an inorganic oxide other than silica and having a cavity inside. Meter-sized silica-based fine particles can be used. In addition, about a cavity, it can confirm by observing the transmission electron micrograph (TEM) of fine particle cross section.

  First, a dispersion of porous silica-based fine particles or silica-based fine particles having cavities inside is prepared. The concentration of the dispersion is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass as the solid content. When the solid content concentration is less than 0.1% by mass, the production efficiency is low. On the other hand, when the solid content concentration exceeds 40% by mass, the obtained antimony oxide-coated silica-based fine particles may agglomerate. In use, the dispersibility in the film may be lowered, the transparency of the film may be lowered, and the haze may be deteriorated.

Separately, a dispersion (aqueous solution) of antimonic acid is prepared. The antimonic acid preparation method is not particularly limited as long as a coating layer of antimony oxide can be formed on the surface of the fine particles without filling the pores or cavities of the porous fine particles of silica or fine particles having voids inside. However, the method exemplified below is preferable because a uniform and thin coating layer of antimony oxide can be formed.
Specifically, an alkali antimonate aqueous solution is treated with a cation exchange resin to prepare an antimonic acid (gel) dispersion, and then treated with an anion exchange resin. As the alkali antimonate aqueous solution, for example, an alkali antimonate aqueous solution used in a method for producing an antimony oxide sol described in JP-A-2-180717 is suitable.

The alkali antimonate aqueous solution is preferably obtained by reacting antimony trioxide (Sb ₂ O ₃ ), an alkali substance and hydrogen peroxide, and the molar ratio of antimony oxide, alkali substance and hydrogen peroxide is 1: 2.0 to 2.5: 0.8 to 1.5, preferably 1: 2.1 to 2.3: 0.9 to 1.2, and the system containing antimony trioxide and an alkaline substance is peroxidized. It is obtained by adding hydrogen at a rate of 0.2 mole / hr or less per mole of antimony trioxide.

The antimony trioxide used at this time is preferably a powder, particularly a fine powder having an average particle size of 10 μm or less, and examples of the alkaline substance include LiOH, KOH, NaOH, Mg (OH) ₂ , and Ca (OH) _2. Among them, alkali metal hydroxides such as KOH and NaOH are preferable. These alkaline substances have the effect of stabilizing the resulting antimonic acid solution.

First, a predetermined amount of an alkaline substance and antimony trioxide are added to water to prepare an antimony trioxide suspension. The antimony trioxide concentration of the antimony trioxide suspension is preferably in the range of ₃ to 15% by mass as Sb ₂ O ₃ . Next, this suspension was heated to 50 ° C. or higher, preferably 80 ° C. or higher, and hydrogen peroxide solution having a concentration of 5 to 35% by mass was added with hydrogen peroxide of 0.2 mole / hr or less per mole of antimony trioxide. Add at a rate of When the addition rate of hydrogen peroxide is faster than 0.2 mole / hr, the resulting antimony oxide fine particles have a large particle size and a wide particle size distribution, which is not preferable.

  Further, when the addition rate of hydrogen peroxide is very slow, the production amount does not increase, so the addition rate of hydrogen peroxide is in the range of 0.04 mole / hr to 0.2 mole / hr, particularly 0.1 mole / hr to 0. A range of .15 mole / hr is preferred. Further, the particle size of the obtained antimony oxide fine particles tends to decrease as the molar ratio of hydrogen peroxide to antimony trioxide decreases, but it is desirable that the amount of undissolved antimony trioxide increases when it is less than 0.8. Absent. On the other hand, when the molar ratio is larger than 1.5, the resulting antimony oxide fine particles have a large particle size, which is not preferable.

The alkali antimonate aqueous solution (when MHSbO ₃ : M is an alkali metal) obtained by the above reaction is separated from the undissolved residue as necessary, and further diluted as necessary, and treated with a cation exchange resin. Then, an antimonic acid gel ((HSbO ₃ −) _n ) dispersion is prepared by removing alkali ions.
The alkali antimonate aqueous solution may contain an aqueous solution containing a doping agent such as an alkali stannate aqueous solution or a sodium phosphate aqueous solution. When such a doping agent is contained, antimony oxide-coated silica-based fine particles having higher conductivity can be obtained.

Here, the antimonic acid can be represented by (HSbO ₃ −) _n (n = 2 or more polymer), and is composed of a polymer of antimonic acid (HSbO ₃ −) having a particle diameter of about 1 to 5 nm. Are aggregated to form a gel state.
The concentration of the aqueous alkali antimonate solution when treating with the cation exchange resin is preferably in the range of 0.01 to 5% by mass, more preferably 0.1 to 3% by mass as the solid content (Sb ₂ O ₅ ). . When the solid content is less than 0.01% by mass, the production efficiency is low. On the other hand, when the solid content exceeds 5% by mass, large aggregates of antimonic acid may be formed, and silica-based fine particles can be coated with antimonic acid. Difficult, and even if it can, it may be non-uniform.

The amount of the cation exchange resin used is preferably such that the pH of the obtained antimonic acid dispersion is in the range of 1 to 4, more preferably 1.5 to 3.5. When the pH is less than 1, aggregated particles tend to be formed instead of chain particles. On the other hand, when the pH exceeds 4, monodispersed particles tend to be generated.
Further, when the pH of the antimonic acid dispersion is less than 1, it is difficult to coat a predetermined amount of antimony oxide due to the high solubility of antimony oxide, and the antimony oxide coating obtained when the pH of the antimonic acid dispersion exceeds 4 Silica-based fine particles may form aggregates, which may reduce the dispersibility in the coating or may have an insufficient antistatic effect on the coated substrate.

Subsequently, the antimonic acid dispersion and the porous silica-based fine particles or the dispersion of silica-based fine particles having cavities inside are mixed and aged at 50 to 250 ° C., preferably 70 to 120 ° C., usually for 1 to 24 hours. Thus, an antimony oxide-coated silica-based fine particle dispersion can be obtained.
The mixing ratio of the antimonic acid dispersion and the silica-based fine particle dispersion is 1 to 200 parts by mass, preferably ₅ to 100 parts by mass, with silica-based fine particles as solids and 100 parts by mass, and antimonic acid as Sb ₂ O _5. Add to be. When the mixing ratio of antimonic acid is less than 1 part by mass, the coating is uneven or the thickness of the coating layer becomes insufficient, and the effect of coating with antimony oxide, that is, the effect of imparting and improving conductivity is obtained. It may not be obtained sufficiently. Even when the mixing ratio of antimonic acid exceeds 200 parts by mass, the antimony oxide that does not contribute to the coating does not increase, and the conductivity of the obtained antimony oxide-coated silica-based fine particles is not further improved, and the refractive index is 1.60. It may be higher than

It is preferable that the density | concentration of the mixed dispersion exists in the range of 1-40 mass% as solid content, and also 2-30 mass%. When the concentration of the mixed dispersion is less than 1% by mass, the coating efficiency of antimony oxide is insufficient or the production efficiency is lowered. On the other hand, when the amount exceeds 40% by mass, the obtained antimony oxide-coated silica-based fine particles may aggregate when the amount of antimonic acid used is large.
When the aging temperature is less than 50 ° C., the antimony oxide coating layer may not be dense, or the conductivity improving effect may not be sufficiently obtained. When the aging temperature exceeds 200 ° C., the porosity may decrease when porous silica-based fine particles are used, and the refractive index of the resulting antimony oxide-coated silica-based fine particles may not be sufficiently lowered.

As for the mixing of the antimonic acid dispersion and the silica-based fine particle dispersion, the antimonic acid dispersion and the silica-based fine particle dispersion can be added at one time as described above, but the antimony is added to the dispersion of porous silica-based fine particles or silica-based fine particles having cavities inside. The acid gel dispersion may be added and mixed continuously or intermittently over time.
The antimony oxide-coated silica-based fine particle dispersion thus obtained has a pH in the range of about 1 to 4.

  In addition, the antimony oxide-coated silica-based fine particles at this time preferably have a refractive index in the range of 1.35 to 1.60, a volume resistance value in the range of 10 to 5000 Ω / cm, and an average particle diameter of 5 The thickness of the antimony oxide coating layer is preferably in the range of 0.5 to 30 nm.

The silica-based fine particle dispersion having cavities therein used in the present invention is preferably obtained by the following steps (a) and (b).
(A) An aqueous solution of silicate and / or an acidic silicic acid solution and an aqueous solution of an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution or an alkaline aqueous solution in which seed particles are dispersed, if necessary. When preparing a composite oxide fine particle dispersion in which the molar ratio MO _X / SiO ₂ is in the range of 0.3 to 1.0 when SiO ₂ is represented by SiO ₂ and inorganic oxides other than silica are represented by MO _X When the average particle size of the composite oxide fine particles becomes approximately 5 to 50 nm, the electrolyte salt is converted into the ratio of the number of moles of electrolyte salt (M _E ) to the number of moles of SiO ₂ (M _S ) / (M _E ) / ( M _S ) is added in the range of 0.1 to 10 to prepare a composite oxide fine particle dispersion,
(B) If necessary, an electrolyte salt is further added to the composite oxide fine particle dispersion, and then an acid is added to remove at least a part of the elements other than silicon constituting the composite oxide fine particles to obtain silica-based fine particles. A step of preparing a dispersion liquid.

Step (a)
As the silicate, one or more silicates selected from alkali metal silicates, ammonium silicates and organic base silicates are preferably used. Examples of the alkali metal silicate include sodium silicate (water glass) and potassium silicate, and examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or organic base silicate includes an alkaline solution in which ammonia, quaternary ammonium hydroxide, an amine compound, or the like is added to the silicic acid solution.

As the acidic silicic acid solution, a silicic acid solution obtained by removing alkali by treating an alkali silicate aqueous solution with a cation exchange resin can be used. In particular, pH _{2 to} pH 4 and SiO ₂ concentration is about 7% by mass. The following acidic silicic acid solutions are preferred.
Examples of the inorganic oxide include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , Ce ₂ O _3, P ₂ O ₅ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO ₃ . 1 type or 2 or more types can be mentioned. Examples of the two or more inorganic oxides include TiO ₂ —Al ₂ O ₃ and TiO ₂ —ZrO ₂ .

As a raw material for such an inorganic oxide, an alkali-soluble inorganic compound is preferably used, and an alkali metal salt, an alkaline earth metal salt, or an ammonium salt of a metal or a non-metal oxo acid constituting the inorganic oxide described above. Quaternary ammonium salts, and more specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, Sodium phosphate or the like is suitable.
In order to prepare the composite oxide fine particle dispersion, either an alkali aqueous solution of the inorganic compound is separately prepared in advance, or a mixed aqueous solution is prepared, and the target silica and inorganic other than silica are prepared. Depending on the composite ratio of the oxide, it is gradually added with stirring to an aqueous alkali solution, preferably an aqueous alkali solution having a pH of 10 or higher.

The addition ratio of the silica raw material and the inorganic compound added to the alkaline aqueous solution is such that the molar ratio MO _X / SiO ₂ is 0.3 to 1 when the silica component is represented by SiO ₂ and the inorganic compound other than silica is represented by MO _X. 0.0, particularly preferably in the range of 0.35 to 0.85. When MO _X / SiO ₂ is less than 0.3, the finally obtained silica-based fine particles do not have a sufficiently large cavity volume. On the other hand, when MO _X / SiO ₂ exceeds 1.0, spherical composite oxide fine particles As a result, the ratio of the cavity volume in the obtained hollow microparticles decreases.

If the molar ratio MO _X / SiO ₂ is in the range of 0.3 to 1.0, the structure of the composite oxide fine particle is mainly a structure in which silicon and elements other than silicon are alternately bonded through oxygen. That is, oxygen atoms are bonded to the four bonds of silicon atoms, and many structures in which elements M other than silica are bonded to the oxygen atoms are generated, and the elements M other than silica are removed in the step (b) described later. At this time, the silicon atom can be removed as a silicic acid monomer or oligomer in association with the element M.

In the production method of the present invention, it is also possible to use a seed particle dispersion as a starting material when preparing a composite oxide fine particle dispersion. In this case, inorganic particles such as SiO ₂ , Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO _2, and CeO ₂ or complex oxides thereof such as SiO ₂ —Al ₂ O ₃ , Fine particles such as TiO ₂ —Al ₂ O ₃ , TiO ₂ —ZrO ₂ , SiO ₂ —TiO ₂ , SiO ₂ —TiO ₂ —Al ₂ O ₃ are used, and usually these sols can be used. Such a dispersion of seed particles can be prepared by a conventionally known method. For example, it can be obtained by adding an acid or alkali to a metal salt, a mixture of metal salts, a metal alkoxide, or the like corresponding to the inorganic oxide, hydrolyzing, and aging as necessary.

  In the seed particle-dispersed alkaline aqueous solution, the aqueous solution of the compound is preferably added to the seed particle-dispersed alkaline aqueous solution adjusted to a pH of 10 or more with stirring in the same manner as in the method of adding the above-mentioned alkaline aqueous solution. As described above, when the composite oxide fine particles are grown using the seed particles as seeds, it is easy to control the particle size of the grown particles, and particles having uniform particle sizes can be obtained. The addition ratio of the silica raw material and the inorganic oxide to be added to the seed particle dispersion is set to the same range as the case of adding to the aqueous alkali solution.

  The silica raw material and inorganic oxide raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into colloidal particles, or seed particles. Particle deposition occurs on the top.

In preparation of the composite oxide fine particle dispersion, an organosilicon compound represented by the following chemical formula (1) and / or a hydrolyzate thereof may be added as a silica raw material to an alkaline aqueous solution.
R _n SiX _(4-n) (1)
[However, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen or hydrogen, n: integer of 0 to 3]

  Specific examples of the organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, and dimethyldiethoxy. Silane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl- 3,3,3-trifluoropropyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxytripropyltrimethoxysilane, -Glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ- Methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane Examples include orchid, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, and diethylsilane.

  Since the above-mentioned organosilicon compound having n of 1 to 3 is poor in hydrophilicity, it is preferable that the compound be uniformly mixed in the reaction system by hydrolysis in advance. For the hydrolysis, a well-known method can be adopted as a hydrolysis method of these organosilicon compounds. When a basic catalyst such as an alkali metal hydroxide, aqueous ammonia, or an amine is used as the hydrolysis catalyst, these basic catalysts can be removed after hydrolysis and used as an acidic solution. Moreover, when preparing a hydrolyzate using acidic catalysts, such as an organic acid and an inorganic acid, it is preferable to remove an acidic catalyst by ion exchange etc. after a hydrolysis. The obtained hydrolyzate of the organosilicon compound is desirably used in the form of an aqueous solution. Here, the aqueous solution means a state in which the hydrolyzate has transparency without being clouded as a gel.

In the present invention, in this step (a), when the average particle diameter of the composite oxide fine particles becomes approximately 5 to 50 nm (the composite oxide fine particles at this time may be referred to as primary particles), the electrolyte salt is converted into the electrolyte salt. moles _{(M E)} and SiO ₂ of moles _{(M S)} and the ratio of _{(M E) / (M S} ) is 0.1 to 10, preferably added in the range of 0.2 to 8 of.
Examples of the electrolyte salt include water-soluble electrolyte salts such as sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, ammonium nitrate, ammonium sulfate, magnesium chloride, and magnesium nitrate.
The electrolyte salt may be added in its entirety at this point, or continuously or intermittently while adding inorganic compounds other than alkali metal silicate and silica and growing the composite oxide fine particles. Also good.

The amount of electrolyte salt added depends on the concentration of the composite oxide fine particle dispersion, but when the molar ratio (M _E ) / (M _S ) is less than 0.1, the effect of adding the electrolyte salt is insufficient. In the step (b), when adding at least a part of elements other than silicon constituting the composite oxide fine particles by adding an acid, the composite oxide fine particles cannot be maintained in a spherical shape and are destroyed, and silica having a cavity inside It may be difficult to obtain fine particles. The reason for the effect of adding such an electrolyte salt is not clear, but the amount of silica on the surface of the grown complex oxide fine particles increases, and the acid-insoluble silica acts as a protective film for the composite oxide fine particles. It is thought that.
Even if the molar ratio (M _E ) / (M _S ) exceeds 10, the effect of adding the electrolyte is not improved, new fine particles are generated, and the economical efficiency is lowered.

In addition, when the average particle size of the primary particles when the electrolyte salt is added is less than 5 nm, new fine particles are generated and selective particle growth of the primary particles does not occur, and the particle size distribution of the composite oxide fine particles is May be non-uniform.
If the average particle size of the primary particles when adding the electrolyte salt exceeds 50 nm, it may take time or be difficult to remove elements other than silicon in step (b).
The composite oxide fine particles thus obtained have an average particle diameter in the range of 4 to 270 nm, which is the same as that of silica-based fine particles obtained later.

Step (b)
Subsequently, hollow spherical silica-based fine particles having cavities therein can be produced by removing some or all of the elements other than silicon constituting the composite oxide fine particles from the composite oxide fine particles.
In this step, an electrolyte salt is added again to the composite oxide fine particle dispersion as necessary. The addition amount of the electrolyte salt of this time, the number of moles of the electrolyte salt _{(M E)} and SiO ₂ of moles _{(M S)} and the ratio of _{(M E) / (M S} ) is 0.1 to 10, preferably Add in the range of 0.2-8.

Next, some or all of the elements constituting the composite oxide fine particles are removed. As a method for removing, for example, a mineral acid or an organic acid is added for dissolution or removal, or a cation exchange resin is used. Examples thereof include a method of removing ions by contact and a method of removing them in combination.
The concentration of the composite oxide fine particles in the composite oxide fine particle dispersion at this time varies depending on the treatment temperature, but is in the range of 0.1 to 50% by mass, particularly 0.5 to 25% by mass in terms of oxide. Preferably there is. If the concentration is less than 0.1% by mass, the amount of silica dissolved increases, and the shape of the composite oxide fine particles may not be maintained. Even if it is possible, the processing efficiency decreases due to the low concentration. If the concentration of the composite oxide fine particles exceeds 50% by mass, the dispersibility of the particles becomes insufficient, and the composite oxide fine particles containing a large amount of elements other than silicon are uniformly or efficiently removed in a small number of times. There are things that cannot be done.

The removal of the element is preferably performed until the MO _X / SiO ₂ of the obtained silica-based fine particles becomes 0.0001 to 0.2, particularly 0.0001 to 0.1.
The dispersion from which the elements have been removed can be washed by a known washing method such as ultrafiltration. In this case, a sol in which silica-based fine particles with high dispersion stability are dispersed can be obtained by previously removing a part of alkali metal ions, alkaline earth metal ions, ammonium ions and the like in the dispersion liquid and then performing ultrafiltration. An organic solvent-dispersed sol can be obtained by substituting with an organic solvent as necessary.

  In the method for producing silica-based fine particles of the present invention, it is then washed, dried, and fired as necessary. The silica-based fine particles thus obtained have cavities inside and have a low refractive index, and the coating formed using the silica-based fine particles has a low refractive index, and a coating excellent in antireflection performance is obtained. It is done.

In the method for producing silica-based fine particles of the present invention, the silica-based fine particle dispersion obtained in the step (b) is added to an alkaline aqueous solution, an organosilicon compound represented by the chemical formula (1) and / or a partial hydrolyzate thereof. Alternatively, an acidic silicic acid solution obtained by dealkalizing an alkali metal silicate can be added to form a silica coating layer on the fine particles.
R _n SiX _(4-n) (1)
[However, R: unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, X: alkoxy group having 1 to 4 carbon atoms, silanol group, halogen or hydrogen, n: integer of 0 to 3]
As the organosilicon compound represented by the chemical formula (1), the same organosilicon compound as described above can be used. In the chemical formula (1), when an organosilicon compound with n = 0 is used, it can be used as it is, but when an organosilicon compound with n = 1 to 3 is used, a partial hydrolyzate of the same organosilicon compound as described above. Is preferably used.

Since such a silica coating layer is dense, the inside is kept in a gas phase or a liquid layer having a low refractive index, and when used for forming a film, a substance having a high refractive index, such as a coating resin, is contained inside. A film having a low refractive index and a high effect can be formed without entering.
In the above, when an organosilicon compound of n = 1 to 3 is used for forming the silica coating layer, a silica-based fine particle dispersion having good dispersibility in an organic solvent and high affinity with a resin can be obtained. . Furthermore, it can be used after being surface-treated with a silane coupling agent or the like, but since it is excellent in dispersibility in an organic solvent, affinity with a resin, etc., such treatment is not particularly required. .

  When a fluorine-containing organosilicon compound is used for forming the silica coating layer, since the coating layer containing F atoms is formed, the resulting particles have a lower refractive index and good dispersibility in organic solvents. A silica-based fine particle dispersion having high affinity with the resin can be obtained. Such fluorine-containing organic silicon compounds include 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, heptadecafluorodecylmethyldimethoxysilane, heptadecafluorodecyl. Examples include trichlorosisilane, heptadecafluorodecyltrimethoxysilane, trifluoropropyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane.

  The silica-based fine particles on which the silica coating layer is formed can be aged at room temperature to 300 ° C., preferably 50 to 250 ° C., for about 1 to 24 hours, if necessary. When aging is performed, the silica coating layer becomes uniform and denser, and as described above, a substance having a high refractive index cannot enter the inside of the particle, so that a film having a high low refractive index effect can be formed.

The silica-based fine particles thus obtained preferably have an average particle size in the range of 4 to 270 nm, more preferably 8 to 170 nm. If the average particle diameter is less than 4 nm, sufficient cavities cannot be obtained, and the effect of low refractive index may not be sufficiently obtained. When the average particle diameter of the silica-based fine particles exceeds 270 nm, the average particle diameter of the obtained antimony oxide-coated silica-based fine particles may exceed 300 nm, and the transparent coating using such antimony oxide-coated silica-based fine particles is formed on the surface. Unevenness may occur, transparency may decrease, and haze may increase. The average particle size of the silica-based fine particles and antimony oxide-coated silica-based fine particles of the present invention can be determined by a dynamic light scattering method.
Silica-based fine particles have cavities inside. For this reason, the refractive index of silica fine particles was 1.20 to 1.38, whereas the refractive index of silica was usually 1.45. In addition, about a cavity, it can confirm by observing the transmission electron micrograph (TEM) of a particle | grain cross section.

The refractive index of the low refractive index layer used in the present invention is preferably 1.25 to 1.46, more preferably 1.30 to 1.43, and most preferably 1.30 to 1.40. The surface resistance (Ω / □) of the optical film of the present invention is preferably 1.0 × 10 ⁵ or more and 1.0 × 10 ¹³ or less, more preferably 1.0 × 10 ⁷ or more and 1.0 × 10 ^12. Or less, and most preferably 1.0 × 10 ⁸ or more and 1.0 × 10 ¹⁰ or less. According to the present invention, by setting the refractive index and the surface resistance within the above ranges, the scratch resistance can be kept good while keeping the low reflectance and dust resistance good.

  Antimony oxide-coated silica-based fine particles can be used alone or in combination with at least one kind of fine particles described below.

[Other fine particles]
In addition to the fine particles having the conductive metal oxide coating layer as the component (B) of the present invention, the following fine particles can be suitably used. The fine particles are preferably inorganic oxide particles, and are selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium from the viewpoint of the colorlessness of the resulting low refractive index layer. The oxide particles of at least one element are preferable.

  Examples of these inorganic fine particles include silica, magnesium fluoride, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, antimony-doped tin oxide (ATO), and tin-doped indium oxide. Examples thereof include oxide particles such as (ITO), antimony oxide, and cerium oxide. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used alone or in combination of two or more.

  Further, the inorganic fine particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility.

  Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone. , Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the inorganic fine particles is preferably 1 to 200 nm, more preferably 3 to 150 nm, and particularly preferably 5 to 100 nm. If the number average particle diameter is 200 nm or less, there is no inconvenience such as a decrease in transparency when it is used as a cured product or a deterioration of the surface state when it is used as a film. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Examples of products that are commercially available as silicon oxide particle dispersions (for example, silica particles) include colloidal silica such as silica sol “MA-ST-MS”, “IPA-ST”, “Nissan Chemical Industry Co., Ltd.”, “ “IPA-ST-MS”, “IPA-ST-L”, “IPA-ST-ZL”, “IPA-ST-UP”, “EG-ST”, “NPC-ST-30”, “MEK-ST” , “MEK-ST-L”, “MIBK-ST”, “NBA-ST”, “XBA-ST”, “DMAC-ST”, “ST-UP”, “ST-OUP”, “ST-20” , “ST-40”, “ST-C”, “ST-N”, “ST-O”, “ST-50”, “ST-OL”, etc .; hollow silica “CS60-” manufactured by Catalyst Chemical Industry Co., Ltd. IPA "and the like. As the powder silica, “Aerosil 130”, “Aerosil 300”, “Aerosil 380”, “Aerosil TT600”, “Aerosil OX50” manufactured by Nippon Aerosil Co., Ltd .; “Sildex H31, H32” manufactured by Asahi Glass Co., Ltd. H51, H52, H121, H122 ”;“ E220A ”,“ E220 ”,“ SS-50 ”,“ SS50A ”,“ SS-50F ”manufactured by Nippon Silica Industry Co., Ltd .;“ SYLYSIA470 ”manufactured by Fuji Silysia Co., Ltd .; Examples thereof include “SG Flakes” manufactured by Nippon Sheet Glass Co., Ltd.

  Moreover, as an aqueous dispersion of alumina, “Alumina sol-100, -200, -520” manufactured by Nissan Chemical Industries, Ltd .; as an isopropanol dispersion of alumina, “AS-150I” manufactured by Sumitomo Osaka Cement Co., Ltd .; As the toluene dispersion of alumina, “AS-150T” manufactured by Sumitomo Osaka Cement Co., Ltd. As the toluene dispersion of zirconia, “HXU-110JC” manufactured by Sumitomo Osaka Cement Co., Ltd .; water dispersion of zinc antimonate powder For example, “CELNAX” manufactured by NISSAN CHEMICAL INDUSTRY CO., LTD .; powders and solvent dispersions such as alumina, titanium oxide, tin oxide, indium oxide, and zinc oxide include “NANOTECH” manufactured by CI Kasei Co., Ltd .; As an aqueous dispersion sol, “SN-100D” manufactured by Ishihara Sangyo Co., Ltd .; as an ITO powder, a product manufactured by Mitsubishi Materials Corporation; The cerium aqueous dispersion, mention may be made of Taki Chemical Co., Ltd. Nidoraru like.

The shape of the inorganic fine particles is spherical, hollow, porous, rod-like, plate-like, fiber-like, chain-like, pearl necklace-like, or indefinite shape, and preferably spherical or hollow. The hollow silica particles will be described later. The specific surface area of the inorganic fine particles (by BET method using nitrogen) is preferably, 10 to 1000 m ² / g, more preferably from 20 to 500 m ² / g, and most preferably 50~300m ² / g. These inorganic fine particles can be obtained by dispersing powder in a dry state in an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide is directly used. Can do.

(Hollow silica particles)
In the low refractive index layer of the antireflection film of the present invention, it is particularly preferable to use hollow inorganic fine particles having a low refractive index in addition to the fine particles having the conductive metal oxide coating layer as the component (B) of the present invention. preferable. The hollow silica particles are described below.

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.15 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. In this case, the radius r _i of the cavity inside the _particle, and the radius of the outer shell of the particle is r _o, the porosity x is expressed by the following equation (2). The porosity x of the hollow silica particles is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.
Formula (2): x = (r _i / r _o ) ³ × 100
The average particle diameter of the hollow silica fine particles can be determined from an electron micrograph.

  If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the refractive index of hollow silica particles The rate is usually 1.17 or higher.

  A method for producing hollow silica particles is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. The hollow silica particles used in the present invention are particularly preferably particles having cavities inside the outer shell and in which the pores of the outer shell are closed. The refractive index of these hollow silica particles can be calculated by the method described in JP-A No. 2002-79616.

  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 fine particles is equal to or greater than the lower limit value, the ratio of the cavities is sufficient and a decrease in the refractive index can be expected. This is preferable because it does not cause adverse effects such as the appearance of black tightening and the deterioration of the integrated reflectance. 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 determined 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.

(Silica fine particles with small size)
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 “silica fine particles having a small size particle size”) is used as silica particles having the above particle size (“large size”). It can also be used in combination with “silica particles having a particle size”.
Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.

  The average particle diameter 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.

(Surface treatment of inorganic fine particles)
The inorganic fine particles that can be used in the low refractive index layer of the present invention are plasma discharges in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding properties with the binder component. A physical surface treatment such as a treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed.
These surface treatments may be performed on the silica-based fine particles having the antimony oxide coating layer.

The inorganic fine particles are surface-treated with a hydrolyzate of organosilane represented by the following general formula (3) and / or a partial condensate thereof, and at the time of treatment, either an acid catalyst or a metal chelate compound, Or it is preferable that both are used.
Formula (3): (R ³⁰ ) _m1 Si (X ³¹ ) _4-m1
In the formula, R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ³¹ represents a hydroxyl group or a hydrolyzable group. m1 represents an integer of 1 to 3.

  The treatment for improving the dispersibility of inorganic fine particles involves bringing organosilane, inorganic fine particles, and, if necessary, water into contact with each other in the presence of at least one of a catalyst having a hydrolysis function and a metal chelate compound having a condensation function. Is done. The organosilane may be partially hydrolyzed or partially condensed. The organosilane undergoes partial condensation subsequent to hydrolysis, which modifies the surface of the inorganic fine particles to improve the dispersibility and obtain a stable dispersion of inorganic fine particles.

(Metal chelate compound)
The metal chelate compound is a metal selected from Zr, Ti, or Al having a ligand represented by an alcohol represented by the following general formula (4-1) and a compound represented by the following general formula (4-2). Any metal chelate compound having at least one metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination.
Formula (4-1): R ⁴¹ OH
Formula (4-2): R ⁴² COCH ₂ COR ⁴³
In the formula, R ⁴¹ and R ⁴² may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, and R ⁴³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. .

[Organosilane compound]
The antireflection film of the present invention is produced in the presence of at least one of an acid catalyst and a metal chelate compound in any one of the low refractive index layer and the layer below the low refractive index layer. It is preferable to use either a hydrolyzate or a partial condensate thereof of an organosilane represented by the following general formula (3). Next, this organosilane compound will be described in detail.
Formula _{^{(3) :( R 30) m1}} -Si (X 31) 4-m1

In the general formula (3), R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X ³¹ represents a hydroxyl group or a hydrolyzable group. As the hydrolyzable group, for example, an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, etc.), a halogen atom (eg, Cl, Br, I, etc.), and an R ³² COO group ( R ³² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, CH ₃ COO group, C ₂ H ₅ COO group, etc.), preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. It is.

m1 represents an integer of 1 to 3. When R ³⁰ or ^{X 31} there are a plurality, a plurality of ^{R 30} or ^{X 31} may be different even in the same, respectively. m1 is preferably 1 or 2, particularly preferably 1.

The substituent contained in R ³⁰ is not particularly limited, but a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group, etc.), alkoxy group (methoxy group, ethoxy group) Group, i-propoxy group, hexyloxy group etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl) Groups), acyloxy groups (acetoxy groups, acryloyloxy groups, methacryloyloxy groups, etc.), alkoxycarbons Group (methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-) Octylcarbamoyl group, etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like. These substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.

When there are a plurality of R ³⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group. In this case, the compound represented by the general formula (3) is a vinyl polymer represented by the following general formula (3-1). It can be expressed as an organosilane compound having a functional substituent.
General formula (3-1):

In General Formula (3-1), R ³² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ³² is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And a methyl group are particularly preferred.

U ³¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

L ³¹ is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (eg, ether group, ester group, amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number An arylene group having 6 to 20 carbon atoms and an alkylene group having 3 to 10 carbon atoms having a linking group therein are preferred, and an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group therein. More preferably, an unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

m2 represents 0 or 1. When X ³¹ there are a plurality, the plurality of X ³¹ may be different even in respectively the same. m2 is preferably 0.
R ³⁰ has the same meaning as R ^{30 in} formula (3), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X ³¹ has the same meaning as X ^{31 in} formula (3), preferably a halogen, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, An alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group is particularly preferable.

As the organosilane compound used in the present invention, those represented by the following general formula (3-2) are also preferred.
Formula ^{_{(3-2) :( R f 31 -L}} 32) m3 -Si (R 33) m3-4

In the general formula (3-2), R _f ³¹ represents a linear, branched, or cyclic fluorinated alkyl group having 1 to 20 carbon atoms, or a fluorinated aromatic group having 6 to 14 carbon atoms. R _f ³¹ is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ³² represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ³³ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. m3 represents an integer of 1 to 3.

Next, among the fluorine-containing organosilane compounds represented by the general formula (3-2), the fluorine-containing organosilane compounds represented by the following general formula (3-3) are preferable.
Formula _{(3-3): C n F 2n} + 1 - (CH 2) t6 -Si (R 34) 3

In the general formula (3-3), n represents an integer of 1 to 10, and t6 represents an integer of 1 to 5. R ³⁴ represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 10, t6 is preferably 1 to 3, and R ³⁴ is preferably a methoxy group, an ethoxy group, or a chlorine atom.

  Two or more kinds of the compound of the general formula (3) may be used in combination. Specific examples of the compound represented by the general formula (3) are shown below, but the present invention is not limited thereto.

  Among these specific examples, (OS-1), (OS-2), (OS-56), (OS-57) and the like are particularly preferable. Further, the compounds of A, B and C described in Reference Examples of Japanese Patent No. 3474330 are also preferable because of excellent dispersion stability.

  In the present invention, the amount of the organosilane compound represented by the general formula (3) is not particularly limited, but is preferably 1% by mass to 300% by mass, more preferably 3% by mass to 100% by mass, per inorganic fine particle. %, Most preferably 5% by mass to 50% by mass. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per normal density based on the hydroxyl group on the surface of the inorganic fine particles. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also increased during coating film formation.

  It is also preferable to use a plurality of types of organosilane compounds in combination, and a plurality of types of compounds can be added simultaneously, or the addition time can be shifted for reaction. Also, it is preferable to add a plurality of types of compounds after making them into partial condensates in advance because the reaction control is easy.

(Use layer of organosilane compound)
In the present invention, at least one of the above-mentioned organosilane compound, its hydrolyzate, and its hydrolysis condensate is used in at least one of the low refractive index layer and the layer below the low refractive index layer. It is preferable to do. For the hydrolysis and condensation of the organosilane compound, it is preferable to use the acid catalyst and / or metal chelate compound described in the description regarding the inorganic fine particles.

  The preferred amount used in the low refractive index layer is preferably from 1 to 95% by mass, more preferably from 2 to 70% by mass, and most preferably from 2 to 45% per solid content forming the low refractive index layer. . When used in a layer adjacent to the low refractive index layer, the content is preferably 0.1 to 70% by weight, more preferably 0.2 to 50% by weight, most preferably the solid content forming the low refractive index layer adjacent layer. Preferably it is 1 to 30%.

[Curing method of low refractive index layer]
In the present invention, a compound that is cured by irradiation with ionizing radiation, a fine particle having a conductive metal oxide coating layer (preferably a silica-based fine particle having an antimony oxide coating layer), and, if necessary, a compound having a polysiloxane partial structure or a fluorine-containing compound Curing is performed by applying a coating composition for forming a low refractive index layer containing an antifouling agent on a support and combining irradiation with ionizing radiation with heat treatment before, simultaneously with, or after irradiation. It is preferable. Although the pattern of some manufacturing processes is shown below, it is not limited to these.
Before irradiation → At the same time as irradiation → After irradiation (-indicates that heat treatment is not performed)
(1) Heat treatment → ionizing radiation curing → −
(2) Heat treatment → ionizing radiation curing → heat treatment (3) − → ionizing radiation curing → heat treatment In addition, a step of performing heat treatment simultaneously with ionizing radiation curing is also preferable.

(Heat treatment)
In the present invention, as described above, heat treatment is preferably performed in combination with irradiation with ionizing radiation. The heat treatment is not particularly limited as long as it changes the existence state of various components from the interface between the low refractive index layer and its lower layer to the surface of the low refractive index layer, preferably 60 to 200 ° C., more preferably 80-130 ° C, most preferably 80-110 ° C.

  When a polysiloxane component or a fluorine-containing component that lowers the surface free energy is contained by raising the temperature, orientation near the surface of the low refractive index layer can be promoted. Each component is not fixed before curing by ionizing radiation irradiation, and the above orientation occurs relatively quickly, but after curing by ionizing radiation irradiation, each component is fixed and orientation occurs only partially. . The time required for the heat treatment varies depending on the molecular weight of the components used, the interaction with other components, the viscosity, etc., but is preferably 30 seconds to 24 hours, more preferably 60 seconds to 5 hours, and most preferably 3 minutes to 30 minutes. is there.

  Although there is no particular limitation on the method of bringing the film surface temperature of the film to a desired temperature, a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method described in Japanese Patent No. 2523574 may also be used, in which hot water or steam is passed through a rotating metal roll and heated. On the other hand, at the time of irradiation of ionizing radiation described below, when the film surface temperature of the film rises, a method of cooling the roll and bringing it into contact with the film can be used.

(Ionizing radiation irradiation conditions)
The film surface temperature during irradiation with ionizing radiation is not particularly limited, but is generally 20 to 200 ° C., preferably 30 to 150 ° C., and most preferably 40 to 120 ° C. in view of handling properties and in-plane performance uniformity. It is. If the film surface temperature is not more than the above upper limit value, the fluidity of the low molecular component in the binder is excessively increased and the surface state is not deteriorated, and the problem that the support is damaged by heat does not occur. Moreover, if it is more than this lower limit, the curing reaction proceeds sufficiently and the film has good scratch resistance, which is preferable.

There is no restriction | limiting in particular about the kind of ionizing radiation, Although an x-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used widely. For example, if the coating film is UV curable, it is to cure each layer by irradiating an irradiation amount of ultraviolet rays of 10mJ ^/ cm ² ~1000mJ ^/ cm 2 by an ultraviolet lamp preferred. When irradiating, the energy may be applied at once, or divided and irradiated. In particular, from the viewpoint of reducing the performance variation in the surface of the coating film, it is also preferable to irradiate by dividing into about 2 to 8 times.

  The time during which the film is kept at the above-mentioned temperature after irradiation with ionizing radiation is preferably from 0.1 second to 300 seconds, more preferably from 0.1 second to 10 seconds from the end of irradiation with ionizing radiation. If the time for keeping the film surface temperature in the above-mentioned temperature range is too short, the reaction of the coating composition for forming a low refractive index layer that forms a film cannot be promoted. The above problem will occur.

(Oxygen concentration)
The oxygen concentration at the time of ionizing radiation irradiation is preferably 3% by volume or less, more preferably 1% by volume or less, and still more preferably 0.1% or less. In contrast to the step of irradiating with ionizing radiation at an oxygen concentration of 3% by volume or less, by providing a step of maintaining in an atmosphere at an oxygen concentration of 3% by volume immediately before or immediately after that, the curing of the film is sufficiently promoted, A film excellent in strength and chemical resistance can be formed.

  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. By carrying it in an atmosphere having a low oxygen concentration before the step of irradiating with ionizing radiation, the oxygen concentration inside the coating film surface and inside can be effectively reduced, and curing can be promoted. The oxygen concentration in the transport step before ionizing radiation irradiation is preferably 3% by volume or less, more preferably 1% volume or less, and still more preferably 0.1% or less.

(Polymerization initiator)
Polymerization of the ionizing radiation curable compound of the present invention and other polymerizable compounds can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

(Photo radical initiator)
As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  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 and the like are included.

  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. included.

  Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of phosphine oxides include 2,4,6-trimethylbenzoyl diphenylphosphine 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, compounds described in Examples in JP-A No. 2000-80068 are particularly preferable.

  Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts. Examples of borate salts include ion complexes with cationic dyes.

  Examples of active halogens include S-triazine and oxathiazole compounds, such as 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 It is. Specifically, Nos. In p14 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, U.S. Pat. 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.

In the present invention, an oligomer type polymerization initiator is preferred as the compound having a high molecular weight and hardly volatilizing from the coating film. The oligomer type radiation polymerization initiator is not particularly limited as long as it has a site that generates a photo radical upon irradiation. In order to prevent volatilization due to heat treatment, the molecular weight of the polymerization initiator is preferably 250 or more and 10,000 or less, more preferably 300 or more and 10,000 or less. More preferably, the mass average molecular weight is 400 to 10,000. A mass average molecular weight of 400 or more is preferable because of low volatility, and 10,000 or less is preferable because hardness of the resulting cured coating film is sufficient. Specific examples of the oligomer type radiation polymerization initiator include oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the following general formula (5). .
General formula (5):

In the general formula (5), R ⁵¹ represents a monovalent group, preferably a monovalent organic group, and q represents an integer of 2 to 45.

  As a commercially available product of the oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the general formula (5), trade name “Ezacure KIP150” manufactured by Fratelli Lamberti (CAS-No. 163702-01-0, q = 4-6), “Ezacure KIP65LT” (a mixture of “Ezacure KIP150” and tripropylene glycol diacrylate), “Ezacure KIP100F” (“Ezacure KIP150” and 2- Hydroxy-2-methyl-1-phenylpropan-1-one), “Ezacure KT37”, “Ezacure KT55” (above, “Ezacure KIP150” and a mixture of methylbenzophenone derivatives), “Ezacure KTO46” (“Ezacure KIP150”) ”Methylbenzofu Non-derivative and a mixture of 2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Ezacure KIP75 / B” (a mixture of “Ezacure KIP150” and 2,2-dimethoxy-1,2-diphenylethane-1-one), etc. Can be mentioned.

  “Latest UV Curing Technology” {Technical Information Association, Inc.} (1991), p. 159, and “UV Curing System” written by Kiyomi Kato (published by the General Technology Center in 1989), p. Various examples are also described in 65-148 and are useful in the present invention.

  Commercially available photocleavable photoradical polymerization initiators include “Irgacure 651”, “Irgacure 184”, “Irgacure 819”, “Irgacure 907”, “Irgacure 1870” (CGI) manufactured by Ciba Specialty Chemicals Co., Ltd. -403 / Irg184 = 7/3 mixed initiator), “Irgacure 500”, “Irgacure 369”, “Irgacure 1173”, “Irgacure 2959”, “Irgacure 4265”, “Irgacure 4263”, “OXE01”, etc .; “Kaya Cure DETX-S”, “Kaya Cure BP-100”, “Kaya Cure BDK”, “Kaya Cure CTX”, “Kaya Cure BMS”, “Kaya Cure 2-EAQ”, “Kaya Cure ABQ”, “Kaya Cure CPTX” manufactured by Yakuhin Co., Ltd. ”,“ Kaya "Sure EPD", "Kayacure ITX", "Kayacure QTX", "Kayacure BTC", "Kayacure MCA", etc .; Etc., and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 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.

  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. Further, 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 “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

(Thermal radical initiator)
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 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

[Layer structure of antireflection film]
The antireflection film of the present invention has a hard coat layer, which will be described later, on a transparent substrate (also referred to as a support), if necessary, and is refracted so that the reflectance decreases due to optical interference. The layers are laminated in consideration of the rate, film thickness, number of layers, layer order, and the like. In the simplest configuration, the antireflection film has a configuration in which only a low refractive index layer is coated on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably constituted by combining a high refractive index layer having a higher refractive index than that of the base material and a low refractive index layer having a lower refractive index than that of the base material. 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 refractive index lower than that of a high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index, and the like. Especially, it is preferable to apply | coat in order of a middle refractive index layer / high refractive index layer / low refractive index layer on the base material which has a hard-coat layer from durability, an optical characteristic, cost, productivity, etc.

An example of a preferred layer structure of the antireflection film of the present invention is shown below. In the following configuration, the base film refers to a support composed of a film.
・ Base film / low refractive index layer,
・ Base film / Antistatic layer / Low refractive index layer,
・ Base film / Anti-glare layer / Low refractive index layer,
・ Base film / Anti-glare layer / Antistatic layer / Low refractive index layer ・ Base film / Hard coat layer / Anti-glare layer / Low refractive index layer,
・ Base film / hard coat layer / antiglare layer / antistatic layer / low refractive index layer ・ Base film / hard coat layer / antistatic 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 / antistatic 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 / Anti-glare 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, ATO, ITO), and can be provided by coating or atmospheric pressure plasma treatment. When providing an antifouling layer, it can be provided in the uppermost layer of the above-mentioned configuration.

(High refractive index layer)
In the present invention, it is preferable to provide a high refractive index layer. The high refractive index layer can be formed from, for example, a binder, mat particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.

[Matte particles]
For the purpose of imparting antiglare properties, the high refractive index layer is larger than the inorganic filler particles, and preferably has an average particle size of 0.1 to 5.0 μm, more preferably 1.5 to 3.5 μm, for example, Inorganic compound particles or resin particles may be contained. The refractive index difference between the matte particles and the binder is preferably 0.02 to 0.20, and preferably 0.04 to 0.10, from the viewpoint of preventing the film from becoming cloudy and having good light diffusion effect. Particularly preferred. The addition amount of the mat particles to the binder is preferably 3 to 30% by mass, particularly preferably 5 to 20% by mass, from the same viewpoint as the refractive index.

As specific examples of the mat particles, particles of inorganic compounds such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
As the shape of the mat particle, either a true sphere or an indefinite shape can be used.

Two or more different kinds of mat particles may be used in combination.
When two or more kinds of mat particles are used, the refractive index difference is preferably 0.02 or more and 0.10 or less in order to effectively exert the refractive index control by mixing the two. As mentioned above, it is especially preferable that it is 0.07 or less.

  Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or more, it is required that there is no optical performance defect called glare. Glitter is derived from the fact that the unevenness (contributing to anti-glare properties) present on the film surface causes the pixels to be enlarged or reduced, resulting in loss of brightness uniformity, but with a particle size smaller than the matte particles that impart anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder.

  Further, the particle size distribution of the mat particles is most preferably monodispersed, and the particle sizes of the particles are preferably closer to each other. For example, when a particle having a particle size 20% or more larger than the average particle size is defined as “coarse particle”, the ratio of the coarse particle is preferably 1% or less of the total number of particles, more preferably It is 0.1% or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The mat particles are contained in the high refractive index layer so that the amount of mat particles in the formed high refractive index layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

  The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

[High refractive index particles]
The high refractive index layer is selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer and to reduce cure shrinkage. It is preferable to contain an inorganic filler composed of an oxide of at least one metal and having an average particle size of preferably 0.2 μm or less, more preferably 0.1 μm or less, and still more preferably 0.06 μm or less.

  In order to increase the difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the layer low in the high refractive index layer using the high refractive index mat particles. The preferred particle size is the same as that of the inorganic fine particles used in the low refractive index layer.

[Inorganic filler]
Specific examples of the inorganic filler used for the high 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 . TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to silane coupling treatment or 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 amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the high refractive index layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.

  In addition, since such a filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of the binder and the inorganic filler of the high refractive index layer of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

[Hard coat layer]
The hard coat layer is provided on the surface of the support as necessary in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the support and the high refractive index layer (or medium refractive index layer). The hard coat layer can also serve as a high refractive index layer by containing the above high refractive index particles in the layer.

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable resin. For example, it can be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a support and causing the polyfunctional monomer or polyfunctional oligomer to undergo a crosslinking reaction or a polymerization reaction.

  Further, the hard coat layer can use mat particles and inorganic fillers in the same amount range as in the high refractive index layer.

  The antireflection film of the present invention thus formed has a haze value of preferably 3 to 70%, more preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm, preferably 3. It is 0% or less, more preferably 2.5% or less. When the optical antireflection of the present invention has a haze value and an average reflectance in these ranges, good antiglare and antireflection properties can be obtained without deteriorating the transmitted image.

[Surface improver]
The coating liquid used to produce any layer on the support has at least one of fluorine and silicone surfaces to improve surface defects (coating irregularities, drying irregularities, point defects, etc.) It is preferable to add a state improver.

  The surface improver preferably changes the surface tension of the coating solution by 1 mN / m or more. Here, when the surface tension of the coating liquid changes by 1 mN / m or more, the surface tension of the coating liquid after the addition of the surface conditioner is added, including the concentration process during coating / drying. It means that it changes by 1 mN / m or more as compared with the surface tension of the coating liquid that has not been applied. Preferably, it is a surface conditioner that has the effect of lowering the surface tension of the coating solution by 1 mN / m or more, more preferably a surface conditioner that lowers by 2 mN / m or more, and particularly preferably a surface conditioner that lowers by 3 mN / m or more. .

  Preferable examples of the fluorine-based surface improving agent include compounds containing a fluoroaliphatic group (abbreviated as “fluorine surface improving agent”). In particular, an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable with the repeating unit corresponding to the monomer of the following general formula (6) and the repeating unit corresponding to the monomer of the following general formula (7) And a copolymer are preferred.

  Such monomers include “Polymer Handbook”, 2nd edition, J. MoI. Brandrup, Wiley lnterscience (1975), Chapter 2, P.I. It is preferable to use those described in 1-483.

  Specifically, for example, an addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Examples thereof include compounds having one compound.

  General formula (6):

In the general formula (6), R ⁶¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. U ⁶¹ represents an oxygen atom, a sulfur atom or —N (R ⁶² ) —, preferably an oxygen atom or —N (R ⁶² ) —, and more preferably an oxygen atom. R ⁶² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. a represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1. b represents an integer of 1 to 18, preferably 4 to 12, and more preferably 6 to 8.

  Two or more types of fluoroaliphatic group-containing monomers represented by the general formula (6) may be contained in the fluorine-based surface improver as a constituent component.

  General formula (7):

In the general formula (7), R ⁷¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. U ⁷¹ represents an oxygen atom, a sulfur atom or —N (R ⁷³ ) —, preferably an oxygen atom or —N (R ⁷³ ) —, and more preferably an oxygen atom. R ⁷³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ⁷² represents a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group, or a substituted or unsubstituted aromatic group (for example, A phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms in total is preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable.

The poly (alkyleneoxy) group will be described below.
A poly (alkyleneoxy) group is also called a poly (oxyalkylene) group.
Poly (alkyleneoxy) group, - (OR) - a group in which a repeating unit, R represents an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH _{2 -, - CH (CH 3} ) CH 2 -, - CH (CH 3) CH (CH 3) - and the like.

  The oxyalkylene units in the poly (oxyalkylene) group (-OR-) may be the same as in poly (oxypropylene), and two or more different oxyalkylenes are randomly distributed. It may be what was done. The oxyalkylene unit may be a linear or branched oxypropylene or oxyethylene unit, and is present as a linear or branched oxypropylene unit block or an oxyethylene unit block. May be.

  The poly (oxyalkylene) chain may also include those linked by one or more chain bonds (for example, —CONH—Ph—NHCO—, —S—, etc .: Ph represents a phenylene group). If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.

  Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials such as “Pluronic” (manufactured by Asahi Denka Kogyo Co., Ltd.), “Adeka Polyether” {manufactured by Asahi Denka Kogyo Co., Ltd.} , "Carvowax" (manufactured by Glico Products), "Torton" (manufactured by Rohm and Haas) and "PEG" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by a known method by reacting with acrylic acid, methacrylic acid, acrylic chloride, methacrylic chloride or acrylic acid anhydride. Separately, poly (oxyalkylene) diacrylate produced by a known method can also be used.

  In the fluorine-based surface improver used in the present invention, the amount of the fluoroaliphatic group-containing monomer represented by the general formula (6) is 50 mol% or more with respect to the total amount of monomers used for forming the fluorine-based surface improver. More preferably, it is 70-100 mol%, Most preferably, it is the range of 80-100 mol%.

  The preferred weight average molecular weight of the fluorine-based surface improver used in the present invention is preferably 3000 to 100,000, more preferably 6,000 to 80,000, and still more preferably 8,000 to 60,000. Here, the mass average molecular weight was determined using a GPC analyzer using a column of “TSKgel GMHxL”, “TSKgel G4000HxL”, “TSKgel G2000HxL” (both trade names manufactured by Tosoh Corporation), a solvent THF, a differential refractometer The molecular weight is expressed in terms of polystyrene by detection, and the content is the area% of the peak in the molecular weight range when the peak area of a component having a molecular weight of 300 or more is defined as 100%.

  Furthermore, the preferable addition amount of the fluorine-type surface conditioner used by this invention is the range of 0.001-5 mass% with respect to the coating liquid of the layer to add, Preferably it is 0.005-3 mass%. It is a range, More preferably, it is the range of 0.01-1 mass%.

  Hereinafter, although the example of the concrete structure of a fluorine-type surface improvement agent useful for this invention is shown, this invention is not limited to these. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  Surface improvers useful in the present invention include ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.) ) And a coating solution containing an aromatic hydrocarbon solvent (toluene, xylene, etc.). In particular, a ketone solvent is preferable. Among the ketone solvents, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferable.

  A planarity improving agent may worsen the adhesiveness of the interface of a layer. Therefore, it is preferable to elute the surface improver present on the surface of the layer into the coating solution for forming the adjacent layer of the layer so that the surface improver does not remain in the vicinity of the interface between the layers. . Therefore, it is preferable to include a solvent that dissolves the planarity improving agent in the coating solution of the adjacent layer. As such a solvent, the above ketone solvents are preferable.

  In the coating solution for the layer formed on the support, it is particularly preferable to add a surface conditioner to a hard coat layer, an antiglare hard coat layer, an antistatic layer, a high refractive index layer, or a low refractive index layer. A coating solution for forming a hard coat layer and an antiglare hard coat layer is particularly preferred.

[Support]
A plastic film is preferably used as the support of the antireflection film of the present invention. As a polymer for forming a plastic film, cellulose ester {for example, triacetylcellulose, diacetylcellulose, typically “TAC-TD80U”, “TAC-TD80UF”, etc., manufactured by Fuji Photo Film Co., Ltd.}, polyamide, polycarbonate, Polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, norbornene resin {“Arton” (trade name), manufactured by JSR Corporation}, amorphous polyolefin {“ZEONEX” (trade name), Japan ZEON Co., Ltd.}. 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 from halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in the JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, the following publication of technical publications). The cellulose acylate described here can also be preferably used in the present invention.

[Saponification]
When the antireflection film of the present invention is used in a liquid crystal display device, it is usually disposed on the outermost surface of the display by providing an adhesive layer on one side. When the support is, for example, triacetyl cellulose, triacetyl cellulose can be used as a protective film for protecting the polarizing film of the polarizing plate. Therefore, it is costly to use the antireflection film of the present invention as it is for the protective film. To preferred.

  As described above, when the antireflection film of the present invention is disposed on the outermost surface of the display or used as it is as a protective film for a polarizing plate, a low refractive index layer is provided on the support in order to improve adhesion. It is preferable to carry out a saponification treatment after the formation.

  The saponification treatment is carried out by a known method, for example, by immersing the antireflection film of the present invention in an alkaline solution for an appropriate time. After being immersed in the alkali solution, it is preferable to wash the substrate sufficiently with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film. By performing the saponification treatment, the surface of the support 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 it is bonded to the polarizing film, thereby preventing point defects due to dust. It is valid.

  The saponification treatment is preferably carried out so that the contact angle of water on the surface of the support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

  The specific means for the alkali saponification treatment can usually be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but the film is deteriorated due to alkaline hydrolysis of the surface because the antireflection layer of the antireflection film is saponified. However, the remaining saponification solution may become a problem. In that case, although it becomes a special process, (2) is excellent.

(1) After forming the antireflection layer on the support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after forming the antireflection layer on the support, an alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection layer is formed, and heated, washed and / or subjected to 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.

First, a coating solution containing components for forming each layer is prepared.
Using the obtained coating solution, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, extrusion coating method (see US Pat. No. 2,681,294), etc. Apply on the support by heating and drying. Of these coating methods, the gravure coating method is preferable because a coating solution with a small coating amount can be applied with high film thickness uniformity as in the case of forming each layer of the antireflection layer. Among the gravure coating methods, the micro gravure method is more preferable because of high film thickness uniformity.

  Even with the die coating method, a coating solution with a small coating amount can be applied with high film thickness uniformity. Furthermore, since the die coating method is a pre-measuring method, the film thickness control is relatively easy, This is preferable because of less evaporation of the solvent.

  Two or more layers may be applied simultaneously. For the simultaneous coating method, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528 and Yuji Harasaki, “Coating Engineering”, page 253, {Asakura Shoten (1973) )}.

<Polarizing plate>
The polarizing plate is mainly composed of two protective films sandwiching a 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 having excellent scratch resistance, antifouling property and the like can be obtained.

[Polarizing film]
As the polarizing film, a known polarizing film can be used, and a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction can be used. A long polarizing film in which the absorption axis of the polarizing film is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

  That is, both ends of a continuously supplied polymer film are stretched by applying a tension while being held by a holding means and stretched at least 1.1 to 20.0 times in the film width direction. The holding device has a longitudinal travel speed difference of 3% or less, and the angle formed by the film traveling 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 °. It can be manufactured by a stretching method in which the film traveling direction is bent while holding both ends of the film. In particular, those inclined at 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.

[Combination with liquid crystal display]
When the antireflection film of the present invention is used as one side of the surface protective film of the polarizing film, it is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or semi-transmissive liquid crystal display device in a mode such as a curly compensatory bend cell (OCB) or an ECB (electrically controlled birefringence).

In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) Liquid crystal cell ("SID97, Digest of tech. Papers" (Preliminary Collection), Vol. 28 (1997), p. 845},
(3) A liquid crystal cell of 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 Collection of “Japan Liquid Crystal Society”, p. 58-59 (1998) description}, and
(4) Includes 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. This is disclosed in US Pat. Nos. 4,583,825 and 5,410,422. 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 an ECB mode liquid crystal cell, rod-like liquid crystal 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” (issued by Toray Research Center) (2001).

  In particular, for a TN mode or IPS mode liquid crystal display device, as described in Japanese Patent Application Laid-Open No. 2001-100043, an optical compensation film having an effect of widening the viewing angle is protected on the two front and back surfaces of the polarizing film. By using the film on the side opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Unless otherwise specified, “part” and “%” are based on mass.
Also, the following Examples 1 to 58 and 401 to 405 are to be read as “reference examples”.

<Anti-reflective film>
Example 1

[Preparation of antimony oxide-coated silica-based fine particles (P1)]
1. Preparation of silica-based fine particles (A-1) A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.17% by mass sodium silicate aqueous solution as SiO ₂ and 9000 g of a 0.83% by mass sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion with a solid content concentration of 20% by mass.

1,700 g of pure water was added to 500 g of this primary particle dispersion and heated to 98 ° C. While maintaining this temperature, 53,200 g of ammonium sulfate having a concentration of 0.5% by mass was added, and then the concentration was 1 as SiO _2. A dispersion of composite oxide fine particles (1) was obtained by adding 3,000 g of a 17 mass% sodium silicate aqueous solution and 9,000 g of a 0.5 mass% sodium aluminate aqueous solution as Al ₂ O ₃ .
Next, 1,125 g of pure water was added to 500 g of the dispersion of composite oxide fine particles (1) washed with an ultrafiltration membrane to a solid content concentration of 13% by mass, and concentrated hydrochloric acid (concentration 35.5% by mass). Was dropped to pH 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water to obtain a silica-based fine particle (A-1) dispersion having a solid content concentration of 20% by mass.
The silica-based fine particles (A-1) had an average particle size of 58 nm, MO _x / SiO ₂ (molar ratio) of 0.0097, and a refractive index of 1.30.

2. Preparation of antimonic acid 111 g of antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd .: KN purity 98.5% by mass) was dissolved in a solution of 57 g of caustic potash (Asahi Glass Co., Ltd .: 85% by mass) in 1800 g of pure water. Suspended. This suspension was heated to 95 ° C., and then an aqueous solution obtained by diluting 32.8 g of hydrogen peroxide (produced by Hayashi Pure Chemical Co., Ltd .: special grade, purity 35% by mass) with 110.7 g of pure water was added in 9 hours. It was added (0.1 mole / hr) to dissolve antimony trioxide, and then aged for 11 hours. After cooling, 1000 g was taken from the resulting solution, and this solution was diluted with 6000 g of pure water, and then passed through a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: pk-216) for deionization treatment. At this time, the pH was 2.1 and the conductivity was 2.4 mS / cm.

3. Preparation of antimony oxide-coated silica-based fine particles (P1) 40 g of antimonic acid having a solid content concentration of 1% by mass was added to 400 g of a dispersion obtained by diluting the silica-based fine particle (A-1) dispersion prepared above to a solid content concentration of 1% by mass. In addition, the mixture was stirred at 70 ° C. for 10 hours and concentrated with an ultrafiltration membrane to prepare a dispersion of antimony oxide-coated silica-based fine particles (B-1) having a solid concentration of 20% by mass.
To 100 g of this antimony oxide-coated silica-based fine particle (B-1) dispersion, 300 g of pure water and 400 g of methanol are added, and 3.57 g of normal ethyl silicate (SiO ₂ concentration 28% by mass) is mixed therewith, and at 50 ° C. for 15 hours. An antimony oxide-coated silica-based fine particle (C-1) dispersion in which a silica coating layer was formed by heating and stirring was prepared.
This dispersion was subjected to solvent replacement with methanol using an ultrafiltration membrane and concentrated to a solid content concentration of 20% by mass. Subsequently, the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an isopropyl alcohol dispersion of silica-based fine particles (C-1) having a concentration of 20% by mass.

  Next, 0.73 g of a methacrylic silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503) was added to 100 g of the isopropyl alcohol dispersion of the antimony oxide-coated silica-based fine particles (C-1) on which the silica coating layer was formed. An antimony oxide-coated silica-based fine particle (P1) dispersion in which a silica coating layer surface-treated with a silane coupling agent was formed by heating and stirring at 50 ° C. for 15 hours was prepared. The refractive index of this particle was 1.41, the volume resistance value was 1500 Ω / cm, the average particle size was 61 nm, and the thickness of the antimony oxide coating layer was 1 nm.

[Preparation of antimony oxide-coated silica-based fine particles (P2)]
In the preparation of the antimony oxide-coated silica-based fine particles (P1), a surface-treated antimony oxide-coated silica-based fine particles (P2) dispersion was prepared in the same manner except that the antimonic acid having a solid concentration of 1% by mass was changed to 100 g. did. The refractive index of this particle was 1.46, the volume resistance value was 1100 Ω / cm, the average particle size was 61.5 nm, and the thickness of the antimony oxide coating layer was 1.5 nm.

[Preparation of coating liquid for hard coat layer (HCL-1)]
50.0 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate “Peta” {manufactured by Nippon Kayaku Co., Ltd.}, 2.0 parts of polymerization initiator “Irgacure 184” {manufactured by Ciba Geigy Japan Ltd.} 0.06 parts of the shape improver {text exemplified compound (F-63)}, 10.0 parts of the organosilane compound “KBM5103” {manufactured by Shin-Etsu Chemical Co., Ltd.}, and 38.5 parts of toluene were added and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.

  Furthermore, in this solution, a 30% toluene dispersion 1 of crosslinked polystyrene particles “SX-350” {refractive index 1.60, manufactured by Soken Chemical Co., Ltd.} having an average particle size of 3.5 μm dispersed at 10,000 rpm with a Polytron disperser 1 1 part, and 13.3 parts of a 30% toluene dispersion of a crosslinked acrylic-styrene particle {refractive index 1.55, manufactured by Soken Chemical Co., Ltd.} having an average particle size of 3.5 μm dispersed at 10,000 rpm in a polytron disperser Was added and stirred. Subsequently, it filtered with the polypropylene filter with a hole diameter of 30 micrometers, and prepared the coating liquid (HCL-1) for glare-proof hard-coat layers. The refractive index of the coating film by this coating solution was 1.51. The surface tension of the obtained antiglare hard coat layer coating solution (HCL-1) was 32 mN / m.

[Preparation of coating solution for low refractive index layer (LL-1)]
For 200 parts of methyl ethyl ketone, 124 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate “DPHA” {manufactured by Nippon Kayaku Co., Ltd.}} (solid content 29%), antimony oxide-coated silica-based fine particles ( P1) 120 parts of a dispersion (solid content concentration 20%) and 2 parts of a photo radical generator “Irgacure 970” {manufactured by Ciba Specialty Chemicals Co., Ltd.} were dissolved. The coating liquid for low refractive index layer (LL-1) was prepared by diluting with cyclohexanone and methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 6% and the ratio of cyclohexanone and methyl ethyl ketone was 20:80.

[Preparation of antireflection film (1)]
[Preparation of hard coat layer (HC-1)]
On the triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a film thickness of 80 μm and a width of 1340 mm, a hard coat layer coating solution (HCL-1) is transported by a microgravure coating method. After applying at 30 m / min, drying at 60 ° C. for 150 seconds, while purging with nitrogen (oxygen concentration 0.5% or less), 160 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.} Was used to cure the coating layer by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 150 mJ / cm ² to prepare a hard coat layer having an antiglare property having a film thickness of 5.5 μm. In this way, a hard coat layer (HC-1) was obtained.

[Formation of Low Refractive Index Layer (LL1-1)]
On the hard coat layer (HC-1) thus obtained, the low refractive index layer coating solution (LL-1) is used and the low refractive index layer thickness is adjusted to 95 nm. Then, a low refractive index layer (LL1-1) was formed by a microgravure coating method to prepare an antireflection film sample.

The curing conditions are shown below.
(1) Drying: 80 ° C. for 120 seconds (2) Pre-irradiation heat treatment: 95 ° C. for 5 minutes (3) UV curing: 90 ° C. for 1 minute; While purging, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiation amount of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² . (4) Post-irradiation heat treatment: 30 ° C. for 5 minutes

[Saponification treatment of antireflection film]
The antireflection film sample obtained as described above was subjected to the following saponification treatment.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C.
The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Next, after immersing in the dilute sulfuric acid aqueous solution for 1 minute, the dilute sulfuric acid aqueous solution was sufficiently washed away by immersing in water. Finally, the sample was thoroughly dried at 120 ° C. In this way, a saponified antireflection film (1) was produced.

Examples 2-56, Comparative Examples 1-28
[Preparation of coating solutions for low refractive index layer (LL-2) to (LL-84)]
The low refractive index layer was prepared in the same manner as in (LL-1) except that the composition was changed as shown in Tables 14-1 to 14-4 below in the preparation of the coating liquid for low refractive index layer (LL-1). Coating solutions (LL-2) to (LL-84) were prepared.

The contents of the compounds used in Tables 14-1 to 14-4 are shown below. Moreover, all the parts in a table | surface represent the mass part of solid content.
(A) ionizing radiation curable compound fluorine-containing siloxane polymer: (may be used as (C))
P-3: Exemplary compound P-3 of the present invention
PP-5: Exemplified compound PP-5 of the present invention
P-3A: A structure containing no silicone moiety with respect to the exemplified compound P-3 of the present invention.
DPHA: Photopolymerizable compound “DPHA”, pentaerythritol triacrylate, a mixture of pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.
(C) Compound containing polysiloxane partial structure represented by general formula (I) Photopolymerizable silicone:
RMS-33: “RMS-33”, manufactured by Gelest Co., Ltd., photopolymerization initiator:
Irgacure 907: “Irgacure 907”, manufactured by Ciba Specialty Chemicals, Inc., molecular weight 279.
(B) Fine particles having a conductive metal oxide coating layer P1, P2: Silica-based fine particles having the antimony oxide coating layer and other fine particles MEK-ST-L: “MEK-ST-L”, fine particle silica dispersion , Solvent MEK, average particle size 45 nm, manufactured by Nissan Chemical Co., Ltd.

[Preparation of Sol Solution a]
In a reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane “KBM5103” (manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 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. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

[Preparation of antireflection films (2) to (84)]
On the hard coat layer (HC-1) obtained in the same manner as in Example 1, the coating solutions (LL-2) to (LL-84) for the low refractive index layer obtained above were used. 1 was coated and cured under the same conditions as in the antireflection film sample (1) to form low refractive index layers (LL1-2) to (LL1-84), and then saponified in the same manner as in Example 1. Thus, antireflection film samples (2) to (84) were prepared.

[Evaluation of antireflection film]
The obtained film was evaluated for the following items.

(Evaluation 1) Specular reflectance Specular reflectance is measured by attaching an adapter "ARV-474" to a spectrophotometer "V-550" [manufactured by JASCO Corporation], and in a wavelength region of 380 to 780 nm. The antireflection property can be evaluated by measuring the specular reflectance at an exit angle of -5 ° at an incident angle of 5 °, and calculating an average reflectance of 450 to 650 nm.

(Evaluation 2) Magic wiping property A film is fixed on a glass surface with an adhesive, and the diameter is 5 mm with a pen tip (thin) of black magic "Mackey Extra Fine (product name: made by ZEBRA)" at 25 ° C and 60RH%. The circle is written 3 times, and after 5 seconds, it is wiped back and forth 20 times with a load that dents the bundle of Bencot (Brand name, Asahi Kasei Co., Ltd.). The writing and wiping are repeated under the above-mentioned conditions until the magic mark does not disappear by wiping, and the antifouling property can be evaluated by the number of times of wiping. The number of times of wiping up to 50 times was evaluated.
The number of times until disappearance is preferably 5 times or more, more preferably 10 times or more, and most preferably 50 times or more.

(Evaluation 3) Evaluation of scratch resistance A rubbing test was performed under the following conditions using a rubbing tester.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: Steel wool {No. 1 made by Nippon Steel Wool Co., Ltd. at the tip (1 cm × 1 cm) of the rubbing of the tester that comes into contact with the sample. A band was fixed so that it would not move. Then, the reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 500 g / cm ² , tip contact area: 1 cm × 1 cm,
Number of rubs: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(Evaluation 4) Evaluation of adhesion The antireflection film sample was conditioned for 2 hours under the conditions of a temperature of 25 ° C. and a relative humidity of 60%. On the surface of each sample having the low refractive index layer, 11 vertical and 11 horizontal cuts were made with a cutter knife in a grid pattern, and a total of 100 square squares were carved, and Nitto Denko ( A polyester pressure-sensitive adhesive tape (No. 31B) manufactured by Co., Ltd. was attached. After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Evaluation 5) Surface resistance value The surface resistance of the surface having the low refractive index layer (outermost layer) of the antireflection film was measured at 25 ° C. using a super insulation resistance / microammeter TR8601 (manufactured by Advantest). , And measured under conditions of relative humidity 60%.

Tables 15-1 to 15-2 show the layer configurations of the antireflection film samples (1) to (84) and the obtained evaluation results.
(Numerical values of surface resistance in Tables 15-1 and 15-2, for example, 3.10E + 09 represents 3.1 × 10 ⁹ )

  As a result of performing the above evaluation on the obtained antireflection film samples (1) to (84), the antireflection film having a low refractive index layer containing antimony-coated silica-based fine particles contains an equal amount of silica. It can be seen that the surface resistance value is lower and the reflectance is lower than that of the antireflection film having a low refractive index layer. Moreover, it turns out that it is excellent in antifouling resistance, adhesiveness, and abrasion resistance.

Example 57
[Preparation of coating liquid for hard coat layer (HCL-2)]
Desolite Z7404 (zirconia fine particle-containing hard coat composition, manufactured by JSR Corporation) 100 parts by mass, DPHA (UV curable resin, manufactured by Nippon Kayaku Co., Ltd.) 31 parts by mass, KBM-5103 (silane coupling agent, Shin-Etsu) Chemical Industry Co., Ltd.) 10 parts by mass, KE-P150 (1.5 μm silica particles, Nippon Shokubai Co., Ltd.) 8.9 parts by mass, MXS-300 (3 μm cross-linked PMMA particles, manufactured by Soken Chemical Co., Ltd.) 3.4 parts by mass, 29 parts by mass of MEK, and 13 parts by mass of MIBK were put into a mixing tank and stirred to obtain a hard coat layer coating solution (HCL-2).

[Preparation of antireflection film (201)]
As a support, a triacetyl cellulose film “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the above-mentioned coating liquid for hard coat layer (HCL-2) has a number of lines of 135 / inch, Using a microgravure roll having a diameter of 60 μm and a doctor blade having a gravure pattern of 60 μm in depth, the coating was performed at a conveyance speed of 10 m / min, drying at 60 ° C. for 150 seconds, and further 160 W / cm under a nitrogen purge. Using an “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.}, the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² , and the hard coat layer (HC-2) Formed and wound up. The rotation speed of the gravure roll was adjusted so that the thickness of the hard coat layer after curing was 4.0 μm. The surface roughness of the hard coat layer (HC-2) thus obtained was as follows: center line average roughness (Ra) = 0.02 μm, root mean square roughness (RMS) = 0.03 μm, n-point average roughness ( Rz) = 0.25 μm. Ra, RMS, and Rz were measured with a scanning probe microscope system “SPI3800” (manufactured by Seiko Instruments Inc.).

  On the hard coat layer (HC-2) formed above, the low refractive index layer (LL-67) is used under the same conditions as the low refractive index layer (LL1-67). LL2-67) was applied to prepare an antireflection film sample (267).

[Saponification treatment of antireflection film]
The antireflection film sample (267) obtained as described above was subjected to the following saponification treatment.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.005 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C.
The prepared antireflection film sample (267) was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Next, after immersing in the dilute sulfuric acid aqueous solution for 1 minute, the dilute sulfuric acid aqueous solution was sufficiently washed away by immersing in water. Finally, the sample was thoroughly dried at 120 ° C. In this way, a saponified antireflection film was produced.

[Preparation of polarizing plate with antireflection film]
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponified antireflection film (267) was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive so that the support side (triacetylcellulose) of the antireflection film was the polarizing film side. Further, the disc surface of the discotic structural unit is inclined with respect to the support surface, and the angle formed by the disc surface of the discotic structural unit and the support surface changes in the depth direction of the optically anisotropic layer. Wide-view film SA “Fuji Photo Film Co., Ltd.” having an optically anisotropic layer is saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive. I attached. In this way, a polarizing plate (267P) with an antireflection film was produced.

  The obtained polarizing plate with antireflection film (267P) was evaluated according to the above, and as a result, it was found that a polarizing plate with antireflection film having low reflection and excellent magic wiping and scratch resistance was obtained. .

Example 58
[Preparation of coating liquid for hard coat layer (HCL-3)]
90 parts MEK, 10 parts cyclohexanone, partially caprolactone-modified polyfunctional acrylate "DPCA-20" {manufactured by Nippon Kayaku Co., Ltd.} 85 parts, "KBM-5103" {Silane coupling agent: Shin-Etsu Chemical Co., Ltd. ) Made} 10 parts, photopolymerization initiator "Irgacure 184" {Ciba Specialty Chemicals Co., Ltd.} 5 parts, surface improver {text exemplified compound (F-63)} 0.04 parts Stir. Subsequently, it filtered with the polypropylene filter with the hole diameter of 0.4 micrometer, and prepared the coating liquid (HCL-3) for hard-coat layers.

[Preparation and evaluation of antireflection film]
On a triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.) as a support, a hard coat layer coating solution (HCL-3) was applied and cured according to Example 2-67. . At that time, the rotation speed of the gravure roll was adjusted so that the thickness of the hard coat layer (HC-3) after curing was 4.5 μm.

On the hard coat layer (HC-3) formed above, the low refractive index layer (LL-67) is used under the same conditions as the low refractive index layer (LL1-67). LL3-67) was applied to prepare an antireflection film sample (367), and then the antireflection film sample (367) was saponified.
The obtained antireflection film sample (367) was evaluated according to the above, and as a result, it was found that an antireflection film having low reflection and excellent magic wiping property and scratch resistance was obtained.

Examples 401-406, Comparative Examples 401-404
[Preparation of Coating Solutions for Low Refractive Index Layer (LL-85) to (LL-94)]
A coating solution for a low refractive index layer having the composition shown in Table 16 below was prepared. It was prepared by dissolving in a 95: 5 (mass ratio) mixture of MEK and cyclohexanone so that the solid content of the coating solution was 8% by mass.

Of the compounds used in Table 16, those not used in Tables 14-1 to 14-4 are shown below. Moreover, all the parts in a table | surface represent the mass part of solid content (nonvolatile content).
(B) Fine particles having a conductive metal oxide coating layer:
ATO-coated silica P3: silica particles coated with ATO instead of antimony oxide in silica particles P1 having an antimony oxide coating layer. The refractive index of the particles is 1.41, the volume resistivity is 1600 Ω / cm, the average particle diameter is 61 nm, and the thickness of the ATO coating layer is 1 nm.
ITO-coated silica P4: Silica particles coated with ITO instead of antimony oxide in silica particles P1 having an antimony oxide coating layer. The refractive index of the particles is 1.42, the volume resistivity is 1300 Ω / cm, the average particle diameter is 61 nm, and the thickness of the ITO coating layer is 1 nm.
Other fine particles IPA-ST-L: “IPA-ST-L” trade name, manufactured by Nissan Chemical Industries, silica fine particle dispersion, solvent IPA, average particle diameter of about 45 nm
・ Photopolymerization initiator:
Irgacure 369: “Irgacure 369” trade name, Ciba Specialty Chemicals

On the hard coat layer (HC-3) produced in Example 58, the coating liquids for low refractive index layers (LL-85) to (LL-94) are used so that the film thickness after curing is 95 nm. Anti-reflection film samples (401) to (410) were prepared by applying with a die coater and applying a low refractive index layer. Curing conditions were 80 ° C.-120 seconds of drying, purged with nitrogen so that the oxygen concentration was 0.01% or less, kept at 60 ° C., and 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). used to obtain a dose of illuminance ^{120mW / cm 2, 500mJ / cm} 2.
The evaluations (1) to (3) and (5) were performed using the samples thus obtained. In addition, the following evaluation (6) was performed.

(Evaluation 6) Dustproofness The transparent support side of each antireflective film sample was pasted on the CRT surface, and it was 24 hours in a room having 1 to ² million dust and tissue paper waste of 0.5 μm or more per 1 ft ³ (cubic foot). used. The number of adhering dust and tissue paper waste is measured per 100 cm ^{2 of the} antireflection film, and the average value of each result is less than 20, A is 20 to 49, B is 50 to 199 Was evaluated as C, and the case of 200 or more was evaluated as D.
The results are shown in Table 17.

  According to Table 17, it can be seen that the sample containing fine particles having the conductive oxide coating layer of the present invention has low reflection, low surface resistance, and excellent dust resistance and scratch resistance. Furthermore, by using together with the ionizing radiation curable fluorine-containing antifouling agent which is the component (D) of the present invention, the magic wiping property can be dramatically improved, and deterioration of the dustproof property is also recognized. There wasn't.

Claims (12)

Of the at least one layer having a refractive index of 1.28 to 1.48, the layer farthest from the transparent support is formed by coating a coating composition containing at least the following components: Characteristic anti-reflection film.
(A) An ionizing radiation curable compound containing at least two or more ethylenically unsaturated groups in one molecule (B) A porous inorganic fine particle having a conductive metal oxide coating layer or a fine particle having a cavity inside ( D) At least one ionizing radiation curable fluorine-containing antifouling agent (the fluorine-containing antifouling agent is at least one represented by the following general formula ( F-3))
One general formula (F-3):
(Rf)-[(W)-(R _A ) _n ] _m
(In General Formula (F-3), Rf represents a (per) fluoropolyether group, W represents a linking group, and _RA represents a (meth) acrylic group. N represents an integer of 1 to 3, and m represents an integer of 1 to 3. And n and m are not 1 at the same time.)   2. The antireflection film according to claim 1, wherein the compound (A) is a fluoropolymer containing at least one perfluoroolefin polymer unit and a (meth) acryloyl group-containing polymer unit. The porous inorganic particles or internally fine particles having a cavity (B) is an antireflection film according to claim 1 or 2, characterized in that the silica-based fine particles having an antimony oxide coating layer. The porous inorganic particles or internally fine particles having a cavity (B) is according to any one of claims 1 to 3, characterized in that the silica-based fine particles having voids inside or porous silica-based particles Anti-reflection film. The porous inorganic fine particles or fine particles (B) having cavities therein are formed on a conductive metal oxide coating layer, a silica coating layer, or an organosilane hydrolyzate represented by the following general formula (3) and / or Or it has a silica coating layer surface-treated with the partial condensate, The antireflection film as described in any one of Claims 1-4 characterized by the above-mentioned.
Formula (3): (R ³⁰ ) _m1 Si (X ³¹ ) _4-m1
(In general formula (3), R ³⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ³¹ represents a hydroxyl group or a hydrolyzable group. Represents an integer.) The porous inorganic fine particles or the fine particles (B) having cavities therein have a refractive index in the range of 1.35 to 1.60 and a volume resistance value in the range of 10 to 5000 Ω / cm. Item 6. The antireflection film according to any one of Items 1 to 5 . The average particle diameter of the porous inorganic fine particles or fine particles (B) having cavities therein is in the range of 5 to 300 nm, and the thickness of the conductive metal oxide coating layer is in the range of 0.5 to 30 nm. antireflection film according to any one of claims 1 to 6, wherein. The antireflection composition according to any one of claims 1 to 7 , wherein the coating composition further comprises (C) a compound containing a polysiloxane partial structure represented by the following general formula (I). Film.
Formula (I)

{In General Formula (I), R ¹ and R ² may be the same or different and each represents an alkyl group or an aryl group. p represents an integer of 10 to 500. } Wherein 1 ionizing radiation-curable compound containing at least two or more ethylenically unsaturated groups in the molecule (A) is characterized by being represented by the following general formula (1), of claim 1-8 The antireflection film according to any one of the above.
General formula (1):

{In General Formula (1), L ¹¹ represents a linking group having 1 to 10 carbon atoms, and s1 represents 0 or 1. R ¹¹ represents a hydrogen atom or a methyl group. A ¹¹ represents a repeating unit having a hydroxyl group in the side chain. Y ¹¹ represents a constituent component containing a polysiloxane structure in the main chain. x, y, and z ^represent mol% of respective repeating units in the case relative to the total repeating units other than ^{Y 11,} satisfy 30 ≦ x ≦ 60,30 ≦ y ≦ 70,0 ≦ z ≦ 40 Represents a value. However, it is x + y + z = 100 (mol%). u represents the mass% of the component ^{Y 11} in the copolymer is 0.01 ≦ u ≦ 20. } Wherein 1 ionizing radiation-curable compound containing at least two or more ethylenically unsaturated groups in the molecule (A) is characterized by being represented by the following general formula (2), according to claim 1-8 The antireflection film according to any one of the above.
General formula (2):

{In General Formula (2), Rf ²¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ²² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether A ²¹ may have a bond, A ²¹ represents a structural unit having a reactive group capable of participating in a crosslinking reaction, and B ²¹ represents an arbitrary structural component. R ²¹ and R ²² may be the same or different and each represents an alkyl group or an aryl group. p1 represents an integer of 10 to 500. R ^{23 to} R ²⁵ each independently represent a substituted or unsubstituted monovalent organic group or a hydrogen atom, and R ²⁶ represents a hydrogen atom or a methyl group. L ²¹ represents an arbitrary linking group having 1 to 20 carbon atoms or a single bond. a to d represent the mole fraction (%) of each constituent component excluding polymer units containing polysiloxane, and 10 ≦ a + b ≦ 55, 10 ≦ a ≦ 55, 0 ≦ b ≦ 45, 10 ≦ c ≦, respectively. It represents a value satisfying the relationship of 50, 0 ≦ d ≦ 40. e represents the mass fraction (%) of the polymer unit containing polysiloxane with respect to the mass of the other components, and satisfies the relationship of 0.01 <e <20. } A polarizing plate comprising the antireflection film according to any one of claims 1 to 10 on at least one side. An image display device, wherein at least one of the antireflection film according to any one of claims 1 to 10 and the polarizing plate according to claim 11 is disposed.