JP4686381B2 - Antireflection film, polarizing plate and image display device using the same - Google Patents

Description

  The present invention relates to an antireflection film having a low refractive index layer formed of a specific curable composition, and a polarizing plate and an image display device using such an antireflection film. In particular, an antireflective film having a low refractive index layer formed from a curable composition comprising a cationically polymerizable compound having a silyl group in the molecule, inorganic fine particles, and a photopolymerization initiator, a polarizing plate using the same, and The present invention relates to an image display device.

  Antireflection films are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT) to reflect external light and In order to prevent a decrease in contrast due to reflection, it is arranged on the surface of the display. Therefore, the antireflection film is required to have high transmittance and high physical strength (such as scratch resistance) in addition to high antireflection performance.

  Conventionally, an antireflection layer used for an antireflection film has been formed as a single-layer or multilayer thin film. In the case of a single layer, a layer having a lower refractive index than that of the substrate (low refractive index layer) may be formed with an optical thickness of 1/4 of the design wavelength. If further low reflection is required, a layer (high refractive index layer) having a refractive index higher than that of the substrate may be formed between the substrate and the layer having a low refractive index.

  As the multilayer antireflection film, a multilayer film obtained by laminating a transparent thin film of metal oxide has been widely used. The metal oxide transparent thin film has been usually formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method which is a kind of physical vapor deposition method.

  The multilayer antireflection film can also be formed by a wet coating method. Since it is suitable for mass production and cost reduction as compared with the vacuum deposition method, formation of an antireflection film by Roll To Roll by a wet coating method has been widely used in recent years. Along with the growing demand for antireflection films by this wet coating method, there is a strong demand for a method for producing antireflection films at a lower cost.

  When an antireflection film is produced by a wet coating method, a coating composition prepared by dissolving or dispersing a film-forming composition having a specific refractive index in a solvent is applied to a substrate, dried, and necessary. It is implemented by curing accordingly.

For forming a low refractive index layer, many methods for curing a curable resin composition containing a fluorine-containing compound or an inorganic material as a substance having a low refractive index have been disclosed. (For example, Patent Documents 1 and 2)
In particular, such low refractive index layer formation is generally performed by ultraviolet polymerization by thermal polymerization using a thermosetting composition and radical polymerization containing a (meth) acrylic resin having an unsaturated double bond. Various thermosetting compositions and radical photopolymerizable compositions for forming a low refractive index layer have been developed.

  However, when continuous heat curing is performed with Roll To Roll, a long heat curing zone is required, and therefore, a large equipment investment is required for the manufacturing apparatus. In addition, in order to increase the speed for the purpose of further cost reduction, it is necessary to expand the thermosetting zone in proportion to the original length, and a higher capital investment is also required to increase the speed. It becomes.

On the other hand, when ultraviolet curing by radical polymerization is used, since radical polymerization is affected by the inhibition of curing by oxygen, ultraviolet irradiation under a low oxygen concentration is required. Therefore, in the process of continuously forming an ultraviolet curing layer with Roll To Roll, ultraviolet curing must be performed under a low oxygen concentration, and there is a special ultraviolet irradiation zone in which portions other than the film transporting portion are shielded from the atmosphere. Equipment is necessary, and expensive capital investment is required.
In particular, since the low refractive index layer is a thin film with a film thickness of around 0.1 μm, it has a high surface area / volume ratio and is particularly susceptible to curing inhibition by oxygen. In addition, the layer located under the low refractive index layer (on the support side) is irradiated with ultraviolet rays every time the layer is laminated on it, so that even when it is first laminated, it may be somewhat affected by curing inhibition by oxygen. It can be cured when a new layer is laminated on top. On the other hand, this effect cannot be expected from the low refractive index layer located in the uppermost layer. For the above two reasons, oxygen must be removed more strictly than other layers when the low refractive index layer is cured.

In order to obtain a low oxygen concentration, a method (nitrogen purge) is generally used in which nitrogen gas is blown into an ultraviolet irradiation zone that is cut off from the atmosphere and oxygen is expelled from the zone. In order to form a low refractive index layer having sufficient scratch resistance without being affected by curing inhibition, it is necessary to introduce a large amount of nitrogen into the ultraviolet irradiation zone, and therefore a large amount of nitrogen gas must be consumed. Therefore, in addition to the problem of initial capital investment, there is also a problem of running cost.
In addition, if the production rate is increased for the purpose of cost reduction, the amount of oxygen in the atmosphere that flows into the UV irradiation zone increases as the film is transported. Come on. As a result, the consumption of nitrogen gas per unit area increases, and the effect of cost reduction due to an increase in production speed is greatly diminished.

In order to solve the problem of curing inhibition by radical polymerization due to oxygen, a method of forming a low refractive index layer with a cationic polymerizable curable composition that is not affected by curing inhibition by oxygen in the atmosphere can be considered.
A method of forming a low refractive index layer with a cationic polymerizable composition has been proposed. However, the method disclosed in Patent Document 4 is a method in which a low refractive index layer is directly laminated on a plastic plate by a dip method, and the method disclosed in Patent Document 5 is This is a method of laminating a low refractive index layer on a glass plate, and an application method to an antireflection film having a hard coat layer as a lower layer is not disclosed. In particular, in order to obtain an antireflection film having good surface physical properties such as scratch resistance, it is necessary that the adhesion with the lower layer determined in relation to the lower layer is good.
Patent Document 3 discloses a method for applying an antireflection film having a four-layer structure including a hard coat layer, but discloses an application method for a two-layer antireflection film that can be manufactured at a lower cost. There wasn't.

In recent years, with the spread of image display devices equipped with antireflection films such as liquid crystal televisions, liquid crystal display devices that are resistant to scratches in various environments at lower prices have been demanded in the market. Accordingly, it is desired to develop an antireflection film that has higher scratch resistance and can be produced at lower cost.
JP 2001-188104 A JP 2003-292831 A JP 2004-093947 A JP 2004-314468 A JP 2005-023258 A

An object of the present invention is to provide an antireflection film that has high antireflection properties, is suitable for mass production, and has excellent scratch resistance.
Another object of the present invention is to provide a polarizing plate with antireflection ability that has high antireflection properties, is suitable for mass productivity, and has excellent scratch resistance.
Furthermore, another object of the present invention is to provide an image display device that has a high antireflection property, is suitable for mass production, and has an antireflection treatment excellent in scratch resistance.

  As a result of intensive studies, the inventor has made photocuring containing inorganic fine particles on the outermost surface of the transparent plastic film substrate with a hard coat layer, a cationically polymerizable compound having a silyl group in the molecule, and a photocationic polymerization initiator. The present inventors have found that an antireflection film having excellent antireflection properties, suitable for mass production, and excellent scratch resistance can be produced by forming a low refractive index layer with an adhesive composition.

（式中、ｘ、ｙ、ｚはモル比を表す。Ｄはカチオン重合性基を有するビニルモノマーの重合単位を表し、Ｅは任意のビニルモノマー重合単位を表す。）
［６］
低屈折率層を形成する硬化性組成物が更に（ｆ）分子内にフッ素原子もケイ素原子も含まず、２個以上のカチオン重合性基を有する化合物含有することを特徴とする［１］〜［５］の何れか１項に記載の反射防止フィルム。
［７］
低屈折率層の屈折率が１．３５〜１．４５であることを特徴とする［１］〜［６］の何れか１項に記載の反射防止フィルム。
［８］
低屈折率層が下記一般式［Ｃ］で表されるオルガノシラン又はその加水分解物およびその部分縮合物の少なくともいずれかを含む硬化性組成物から形成されていることを特徴とするハードコート層上に直接、形成されていることを特徴とする［１］〜［７］の何れか１項に記載の反射防止フィルム。
一般式［Ｃ］：（Ｒ ^１０ ） _ｎ Ｓｉ（Ｘ ^１１ ） _４−ｎ
（式中、Ｒ ^１０ は、置換もしくは無置換のアルキル基または置換もしくは無置換のアリール基、Ｘ ^１１ は水酸基または加水分解可能な基を表す。ｎは０〜３の整数を表す。）
［９］
低屈折率層がカチオン重合性基を有する化合物を含有する硬化性組成物から形成されているハードコート層上に直接、形成されていることを特徴とする［１］〜［８］の何れか１項に記載の反射防止フィルム。
［１０］
低屈折率層が酸素濃度１体積％以上の条件で紫外線照射し、硬化されたことを特徴とする［１］〜［９］の何れか１項に記載の反射防止フィルム。
［１１］
表面が凹凸形状となっており、光防眩性を有することを特徴とする［１］〜［１０］の何れか１項に記載の反射防止フィルム。
［１２］
［１］〜［１１］の何れか１項に記載の反射防止フィルムを、偏光膜の保護フィルムの少なくとも一方に用いたことを特徴とする偏光板。
［１３］
［１］〜［１２］の何れか１項に記載の反射防止フィルムを、偏光膜の保護フィルムの一方に、光学異方性のある光学補償フィルムを偏光膜の保護フィルムのもう一方に用いたことを特徴とする偏光板。
［１４］
［１］〜［１１］の何れか１項に記載の反射防止フィルム、または［１２］または［１３］に記載の偏光板が画像表示面に配置されていることを特徴とする、画像表示装置。
［１５］
画像表示装置が、ＴＮ、ＳＴＮ、ＩＰＳ、ＶＡ及びＯＣＢの何れかのモードの透過型、反射型又は半透過型の液晶表示装置であることを特徴とする［１４］に記載の画像表示装置。
本発明は、上記［１］〜［１５］に関するものであるが、その他の事項についても参考のために記載した。
（１）透明プラスチックフィルム基材に直接または、他の層を介してハードコート層が積層されてなり、更にハードコート層上に直接または他の層を介して以下の（ａ）〜（ｃ）を含有する硬化性組成物から形成される低屈折率層が積層されていることを特徴とする反射防止フィルム。
（ａ）無機微粒子
（ｂ）分子内にシリル基を有するカチオン重合性化合物、その加水分解物および部分縮合物の少なくとも１つ
（ｃ）光カチオン重合開始剤
（２）前記分子内にシリル基を有するカチオン重合性化合物が下記一般式［Ａ］で表されるオルガノシランであることを特徴とする請求項１に記載の反射防止フィルム。
一般式［Ａ］：（Ｒ^１）_ｍＳｉ（Ｒ^２）（Ｘ^１０）_３−ｍ
（式中、Ｒ^１０は、置換もしくは無置換のアルキル基または置換もしくは無置換のアリール基を表す。Ｒ^１はカチオン重合性官能基を有する１価の置換基、Ｘ^１０は水酸基または加水分解可能な基を表す。ｍは０〜２の整数を表す。） That is, this invention achieves the said objective by each structure of the following [1]-[15] .
[1]
A hard coat layer is laminated directly on the transparent plastic film substrate or via another layer, and further contains the following (a) to (d) on the hard coat layer directly or via another layer: 1. An antireflection film comprising a low refractive index layer formed from a curable composition.
(A) Hollow silica fine particles whose surface is modified with an organosilane compound
(B) At least one of a cationically polymerizable compound having a silyl group in the molecule, a hydrolyzate and a partial condensate thereof
(C) An iodonium salt-type acid generator or an active halogen as a photocationic polymerization initiator
(D) Polysiloxane compound having a cationically polymerizable functional group
[2]
The antireflection film as described in [1], wherein at least one of the cationically polymerizable compounds having a silyl group in the molecule (b) is an organosilane represented by the following general formula [A].
Formula [A]: (R ¹ ) _m Si (R ² ) (X ¹⁰ ) _3-m
(In the formula, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ² is a monovalent substituent having a cationic polymerizable functional group, and X ¹⁰ is a hydroxyl group or hydrolyzable. M represents an integer of 0 to 2.)
[3]
The antireflection film as described in [1] or [2], wherein 50% by mass or more of all silica fine particles contained in the curable composition forming the low refractive index layer is hollow silica fine particles.
[4]
50% by mass or more of silica fine particles contained in the curable composition forming the low refractive index layer has an average particle size of 40 nm or more, according to any one of [1] to [3] Antireflection film.
[5]
The curable composition forming the low refractive index layer contains (e) a fluorine compound represented by the following general formula [B], according to any one of [1] to [4], Antireflection film.

(In the formula, x, y, and z represent molar ratios. D represents a polymerization unit of a vinyl monomer having a cationic polymerizable group, and E represents an arbitrary vinyl monomer polymerization unit.)
[6]
The curable composition for forming the low refractive index layer further comprises (f) a compound having no fluorine atom or silicon atom in the molecule and having two or more cationically polymerizable groups [1] to [5] The antireflection film according to any one of [5].
[7]
The antireflective film according to any one of [1] to [6], wherein the low refractive index layer has a refractive index of 1.35 to 1.45.
[8]
The hard coat layer, wherein the low refractive index layer is formed from a curable composition containing at least one of organosilane represented by the following general formula [C] or a hydrolyzate thereof and a partial condensate thereof The antireflection film according to any one of [1] to [7], which is directly formed on the top.
[C]: (R ¹⁰ ) _n Si (X ¹¹ ) _4-n
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, X ¹¹ represents a hydroxyl group or a hydrolyzable group, and n represents an integer of 0 to 3.)
[9]
Any one of [1] to [8], wherein the low refractive index layer is formed directly on the hard coat layer formed from a curable composition containing a compound having a cationic polymerizable group. 2. The antireflection film according to item 1.
[10]
The antireflective film according to any one of [1] to [9], wherein the low refractive index layer is cured by being irradiated with ultraviolet rays under a condition where the oxygen concentration is 1% by volume or more.
[11]
The antireflection film according to any one of [1] to [10], wherein the surface has an uneven shape and has an antiglare property.
[12]
A polarizing plate characterized by using the antireflection film according to any one of [1] to [11] as at least one of a protective film of a polarizing film.
[13]
The antireflection film according to any one of [1] to [12] is used for one of the protective films for the polarizing film, and an optical compensation film having optical anisotropy is used for the other protective film for the polarizing film. A polarizing plate characterized by that.
[14]
[1]-[11] The antireflection film according to any one of [1] to [11], or the polarizing plate according to [12] or [13] is disposed on an image display surface. .
[15]
[14] The image display device according to [14], wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any of TN, STN, IPS, VA, and OCB modes.
The present invention relates to the above [1] to [15], but other matters are also described for reference.
(1) A hard coat layer is laminated directly on the transparent plastic film substrate or via another layer, and the following (a) to (c): An antireflective film, wherein a low refractive index layer formed from a curable composition containing bismuth is laminated.
(A) inorganic fine particles (b) at least one of a cationically polymerizable compound having a silyl group in the molecule, a hydrolyzate and a partial condensate thereof (c) a photocationic polymerization initiator (2) a silyl group in the molecule The antireflective film according to claim 1, wherein the cationic polymerizable compound is an organosilane represented by the following general formula [A].
Formula [A]: (R ¹ ) _m Si (R ² ) (X ¹⁰ ) _3-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ¹ is a monovalent substituent having a cationically polymerizable functional group, and X ¹⁰ is a hydroxyl group or hydrolyzable. M represents an integer of 0 to 2.)

(3) The antireflection film as described in any one of (1) to (2) above, wherein (a) the inorganic fine particles are metal oxide fine particles.
(4) The antireflection film as described in (3) above, wherein the inorganic fine particles are silica fine particles.
(5) Of the total silica fine particles contained in the curable composition forming the low refractive index layer, 50% by mass or more is porous silica and / or hollow silica, and the reflection as described in (4) above Prevention film.
(6) Any of (3) to (5) above, wherein 50% by mass or more of the silica fine particles contained in the curable composition forming the low refractive index layer has an average particle size of 40 nm or more. The antireflection film as described.
(7) (a) At least a part of the inorganic fine particles is surface-treated with an organosilane compound represented by the above general formula [A]. The antireflection film as described.
(8) The antireflection film as described in any one of (1) to (7), wherein the content of the inorganic fine particles is from 5% by mass to 70% by mass with respect to the total solid content in the curable composition.
(9) The antireflection film as described in any one of (1) to (7), wherein the content of the inorganic fine particles is from 10% by mass to 50% by mass with respect to the total solid content in the curable composition.
(10) The antireflection film as described in any one of (1) to (7) above, wherein the content of the inorganic fine particles is from 20% by mass to 40% by mass with respect to the total solid content in the curable composition.

(11) The curable composition for forming the low refractive index layer contains (d) a polysiloxane compound having a cationically polymerizable functional group, as described in any one of (1) to (10) above Antireflection film.
(12) The antireflection film as described in (11) above, wherein the polysiloxane compound having a cationic polymerizable functional group (d) is a polydimethylsiloxane compound.
(13) The antireflection film as described in (12) above, wherein the polydimethylsiloxane compound is a polydimethylsiloxane compound having a cationic polymerizable group at both ends.
(14) The antireflective film as described in any one of (1) to (13) above, wherein the curable composition forming the low refractive index layer contains a fluorine compound.
(15) The antireflection according to any one of (1) to (13), wherein the curable composition forming the low refractive index layer contains a fluorine compound having a cationic polymerizable group in the molecule. the film.
(16) The antireflective film as described in any one of (1) to (13) above, wherein the curable composition forming the low refractive index layer contains a fluoropolymer.
(17) The antireflective film as described in any one of (1) to (13) above, wherein the curable composition forming the low refractive index layer contains a fluoropolymer in the molecule.
(18) The curable composition for forming the low refractive index layer contains (e) a fluorine compound represented by the following general formula [B]. The antireflection film as described.

(In the formula, x, y, and z represent molar ratios. D represents a polymerization unit of a vinyl monomer having a cationic polymerizable group, and E represents an arbitrary vinyl monomer polymerization unit.)
(19) The curable composition forming the low refractive index layer further comprises (f) a compound having no fluorine atom or silicon atom in the molecule and having two or more cationically polymerizable groups. The antireflection film according to any one of (1) to (18) above.

(20) The above (1), wherein the ratio of the compound having a cationic polymerizable group to the binder component (excluding inorganic fine particles) contained in the curable composition forming the low refractive index layer is 70% by mass or more. ) To (19).
(21) The above (1), wherein the ratio of the compound having a cationic polymerizable group to the binder component (excluding inorganic fine particles) contained in the curable composition forming the low refractive index layer is 80% by mass or more. ) To (19).
(22) The above (1), wherein the ratio of the compound having a cationic polymerizable group to the binder component (excluding inorganic fine particles) contained in the curable composition forming the low refractive index layer is 90% by mass or more. ) To (19).

(23) The antireflective film as described in any one of (1) to (22) above, wherein the refractive index of the low refractive index layer is from 1.35 to 1.45.
(24) The low refractive index layer is formed from a curable composition containing at least one of an organosilane represented by the following general formula [C] or a hydrolyzate thereof and a partial condensate thereof. The antireflection film as described in any one of (1) to (23) above, which is formed directly on the hard coat layer.
[C]: (R ¹⁰ ) _n Si (X ¹¹ ) _4-n
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, X ¹¹ represents a hydroxyl group or a hydrolyzable group, and n represents an integer of 0 to 3.)
(25) The above-mentioned (1) to (1), wherein the low refractive index layer is directly formed on the hard coat layer formed from a curable composition containing a compound having the following cationic polymerizable group. 24) The antireflection film as described in any one of 24).

(26) The antireflection film as described in any one of (1) to (25) above, wherein the low refractive index layer is cured by irradiating with ultraviolet rays under conditions of an oxygen concentration of 1% by volume or more.
(27) The antireflection film as described in (26) above, wherein the oxygen concentration is 3% by volume or more.
(28) The antireflection film as described in (26) above, wherein the oxygen concentration is 10% by volume or more.
(29) The antireflection film as described in (26) above, wherein the oxygen concentration is 18% by volume or more.
(30) The antireflection film as described in any one of (1) to (29) above, which has a low refractive index layer continuously laminated with Roll To Roll.
(31) The antireflection film as described in any one of (1) to (30) above, wherein the film transport speed when the low refractive index layer is laminated is 10 m / min or more.
(32) The antireflection film as described in any one of (1) to (30) above, wherein the film transport speed when the low refractive index layer is laminated is 20 m / min or more.
(33) The antireflection film as described in any one of (1) to (30) above, wherein the film transport speed when the low refractive index layer is laminated is 30 m / min or more.

(34) The antireflection film as described in any one of (1) to (33), wherein the low refractive index layer is directly laminated on the hard coat layer.
(35) The antireflection film as described in any one of (1) to (34) above, which has a configuration of “transparent support / hard coat layer / low refractive index layer”.
(36) The antireflection film as described in any one of (1) to (35) above, wherein the hard coat layer is formed from a curable composition containing a cationic polymerizable composition.
(37) The antireflection film as described in (36) above, wherein the cationically polymerizable compound in the curable composition for forming a hard coat is 5% by mass or more based on the total binder.
(38) The antireflection film as described in (36) above, wherein the cationically polymerizable compound in the curable composition for forming a hard coat is 10% by mass or more based on the total binder.
(39) The antireflection film as described in (36) above, wherein the cationically polymerizable compound in the curable composition for forming a hard coat is 20% by mass or more based on the total binder.
(40) The antireflection film as described in any one of (1) to (39) above, wherein the hard coat layer has a thickness of 1 to 10 μm.
(41) The antireflection film as described in any one of (1) to (39) above, wherein the hard coat layer has a thickness of 1.2 to 6 μm.
(42) The antireflection film as described in any one of (1) to (41) above, wherein the surface has an uneven shape and has an antiglare property.

(43) A polarizing plate, wherein the antireflection film according to any one of (1) to (42) is used for at least one of a protective film of a polarizing film.
(44) The antireflection film according to any one of (1) to (42) above is applied to one of the protective films for the polarizing film, and an optical compensation film having optical anisotropy is applied to the other protective film for the polarizing film. A polarizing plate characterized by being used.
(45) The antireflection film according to any one of (1) to (42) above or the polarizing plate according to any of (43) or (44) above is disposed on an image display surface. An image display device.
(46) The image display device according to (45), wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any of TN, STN, IPS, VA, and OCB modes. Image display device.

  The antireflection film of the present invention has excellent antireflection properties, is suitable for mass production, and has excellent scratch resistance.

  A polarizing plate using the antireflection film of the present invention as a surface protective film is a polarizing plate provided with an antireflection film excellent in optical performance and physical strength, and can be provided in a large amount at a low cost.

  Furthermore, the image display device of the present invention includes an antireflection film or a polarizing plate excellent in the above characteristics, is excellent in antireflection performance, and is excellent in scratch resistance and visibility.

  Hereinafter, a method for producing the antireflection film of the present invention will be described.

  In addition, in this specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” represents the meaning of “numerical value 1 or more and numerical value 2 or less”. In the present specification, the description “(meth) acryloyl” means “at least one of acryloyl and methacryloyl”. The same applies to “(meth) acrylate”, “(meth) acrylic acid” and the like.

<Layer structure>
For the antiglare antireflection film of the present invention, the following known layer structures can be used.
For example, representative examples are: a: transparent support / antiglare layer b: transparent support / antiglare layer / low refractive index layer c: transparent support / hard coat layer / low refractive index layer d: transparent support / Hard coat layer / Medium refractive index layer / High refractive index layer / Low refractive index layer E: Low / High Examples of alternating multilayers.
An object of the present invention is to provide an antireflection film having a high antireflection property and a low cost, and among the above-mentioned configurations, (2) or (3) is preferable, and (2) is particularly preferable in terms of antireflection properties.

In addition, as a layer that may be provided between the transparent support and the layer on the surface side of the transparent support, an antistatic layer (when there is a request to reduce the surface resistance value from the display side, dust on the surface etc. is a problem ), Hard coat layer (if the antiglare layer alone is insufficient in hardness), moisture proof layer, adhesion improving layer, interference spot prevention layer (difference in refractive index between transparent support and antiglare layer or hard coat layer) And the like). Further, when the antiglare layer is used on the transparent support and the hardness is insufficient only by the antiglare layer, a hard coat layer may be provided between the transparent support and the antiglare layer.
The antistatic layer can be disposed at a position other than between the transparent support and the layer thereon.
Here, FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the antireflection film of the present invention.
An antiglare antireflection film 1 of the present embodiment shown in FIG. 1 includes a transparent support 2, an antiglare layer 3 formed on the transparent support 2, and a low refraction formed on the antiglare layer 3. The rate layer 4.
The antiglare layer 3 includes a translucent resin and translucent fine particles 5 dispersed in the translucent resin.
The refractive index of each layer constituting the antiglare antireflection film having an antireflection layer in the invention preferably satisfies the following relationship.
Refractive index of the antiglare layer> Refractive index of the transparent support> Refractive index of the low refractive index layer The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties. Although one formed by one layer is illustrated, it may be composed of a plurality of layers, for example, two to four layers. Moreover, although you may provide directly on a transparent support body like this embodiment, you may provide via other layers, such as an antistatic layer and a moisture-proof layer.

Next, the low refractive index layer will be described below.
<Low refractive index layer>
The refractive index of the low refractive index layer in the antireflection film of the present invention is 1.30 to 1.55, preferably 1.35 to 1.45.
When the refractive index is less than 1.30, the antireflection performance is improved, but the mechanical strength of the film is lowered, and when it exceeds 1.55, the antireflection performance is remarkably deteriorated.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I)
(M ₁ /4)×0.7<n ₁ × d ₁ <(m ₁ /4)×1.3
In the formula, 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.
Incidentally, the A satisfies the formula (I), _(positive odd number, usually 1) m ₁ satisfying the formula (I) in the range of the wavelength means that is present.

Examples of the low refractive index layer include a low refractive index layer (embodiment 1) formed by crosslinking a fluorine-containing resin that is crosslinked by heat or ionizing radiation (hereinafter also referred to as “fluorinated resin before crosslinking”), and a low refractive index by a sol-gel method. A layer (embodiment 2), and a low refractive index layer (embodiment 3) having voids between or inside the particles using the particles and the binder polymer are used.
The low refractive index layer is a cured film formed, for example, by applying, drying and curing a curable composition containing a fluorine-containing polymer as a main component.

<Curable composition>
The curable composition used for the low refractive index layer of the present invention contains (a) inorganic fine particles, (b) a cationically polymerizable compound having a silyl group in the molecule, and (c) a photocationic polymerization initiator as essential components. It is characterized by that.

Next, (a) inorganic fine particles will be described.
[Inorganic fine particles for low refractive index]
The amount of the inorganic fine particles ^is preferably 1mg / ^{m 2} ~100mg / m 2 is ^1mg / ^{m 2 ~100mg} / m 2, more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the scratch resistance is improved and cured.If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may deteriorate. Is preferable.

  Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include magnesium fluoride and silica fine particles. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.

The average particle size of the inorganic fine particles is preferably 30% or more and 100% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, when the thickness of the low refractive index layer is 100 nm, the average particle size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm. If the particle size of the inorganic fine particles is not less than the lower limit, the effect of improving the scratch resistance is remarkably exhibited, and if the particle size is not less than the upper limit, fine irregularities are formed on the surface of the low refractive index and black tightening is achieved. Such an appearance and a problem such as an increase in integrated reflectance do not occur, which is preferable.

The inorganic fine particles may be either crystalline or amorphous, and may be monodisperse particles or aggregated particles that satisfy a predetermined particle size. The shape is most preferably spherical, but there is no problem even if it is indefinite.
The content of the inorganic fine particles with respect to the total solid content of the low refractive index layer is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and more preferably 20 to 40% by mass.
Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

  In the curable composition for forming a low refractive index layer of the present invention, “fine particles having voids” are preferably used in order to further reduce the increase in the refractive index of the low refractive index layer. “Fine particles with voids” have fine voids on the outside and inside, and are filled with air, so they have a low refractive index, and even when dispersed uniformly in the coating film Since the refractive index of a coating film can be reduced, it is preferable. Preferable examples of the fine particles having voids include porous silica fine particles and hollow silica fine particles.

[Hollow silica fine particles]
Hereafter, it describes about the hollow silica fine particle used suitably for the curable composition of this invention.
The hollow silica fine particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica fine 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 represented by the following equation (1) is preferably from 10 to 60%, more preferably 20 -60%, most preferably 30-60%.
Formula (1): x = (r _i / r _o ) ³ × 100
The average particle diameter of the hollow silica fine particles can be determined from an electron micrograph.

Reducing the hollow silica fine particles to a lower refractive index and increasing the porosity reduces the thickness of the outer shell and weakens the strength of the particles. From the viewpoint of scratch resistance, the refractive index of the hollow silica fine particles The rate is usually 1.17 or higher.
The refractive index of these hollow silica fine particles was measured with an Abbe refractometer {manufactured by Atago Co., Ltd.}.

  The method for producing hollow silica fine particles is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616.

Further, at least one kind of inorganic fine particles (hereinafter referred to as “small-size inorganic fine particles”) having an average particle size of less than 25% of the thickness of the low refractive index layer is referred to as “inorganic fine particles (hereinafter referred to as“ small size inorganic fine particles ”). It may be used in combination with “large-size inorganic fine particles”.
Since the small-sized inorganic fine particles can exist in the gaps between the large-sized inorganic fine particles, they can contribute as a retaining agent for the large-sized inorganic fine particles.
When the low refractive index layer is 100 nm, the average particle size of the small-sized inorganic fine particles 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 inorganic fine particles is preferable in terms of raw material costs and a retaining agent effect.
As described above, the inorganic fine particles have an average particle diameter of 30 to 100% of the thickness of the low refractive index layer as described above, have a hollow structure, and have a refractive index of 1.17 to 1. What is 40 is used especially preferably.

Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is preferable to make it contain in a layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Next, (b) the organosilane compound will be described.
<Organosilane compound for low refractive index layer>
The curable composition of the present invention is a hydrolyzate of an organosilane compound and / or a partial condensate thereof (hereinafter referred to as “sol component”) for the purpose of improving the scratch resistance of the antireflection film. Containing). Thereby, antireflection ability and abrasion resistance can be made compatible.
As the surface treatment agent for inorganic fine particles as the component (a) contained in the low refractive index layer, at least one of the organosilane compound, the hydrolyzate thereof, and the partial condensate thereof as the component (b) of the present invention It can also be used as a surface treatment agent before the preparation of the low refractive index layer coating solution. Moreover, it can also be added as an additive at the time of coating liquid preparation. Further, it can be added twice for the purpose of both a surface treatment agent and an additive.
This sol component functions as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, in this invention, when it has a postscript fluoropolymer, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
The organosilane compound is preferably represented by the following general formula [A].
Formula [A]: (R ¹ ) _n Si (R ² ) (X ¹⁰ ) _3-n

In the general formula [A], R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, hexyl, decyl, hexadecyl 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 phenyl and naphthyl, and a phenyl group is preferable.

In the general formula [A], R ² represents a monovalent substituent having a cationic polymerizable functional group. Examples of the cationic polymerizable group include an epoxy group, an oxetane group, and an oxazolyl group.

X ¹⁰ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I And R ¹² COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably an alkoxy group, particularly preferably Is a methoxy group or an ethoxy group.
a represents an integer of 0 to 2, preferably 0 and 1, particularly preferably 0.

When R ¹ or ^{that X 10} there are a plurality, it may be different even in a plurality of ^{R 1} or ^{X 10} same.
The substituent contained in R ¹ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-). Propyl, propyl, t-butyl, etc.), aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryl Oxy (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups ( Methoxycarbonyl, ethoxycarbonyl, etc.) , Aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino) , Methacrylamino and the like), and these substituents may be further substituted. When there are a plurality of R ^{10 s} , at least one is preferably a substituted alkyl group or a substituted aryl group.
Examples of such a compound include (M-28) to (M-36) in [Chemical Formula 8] described later, and (M-37) to (M-38) in [Chemical Formula 9].

  Of these specific examples, (M-30) and (M-35) are particularly preferred.

  In the present invention, the amount of the organosilane compound represented by the general formula [A] is not particularly limited, but is preferably 1 to 300% by mass, more preferably 3 to 100% by mass, most preferably per inorganic fine particle. Is 5-50 mass%. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, most preferably 10 to 200 mol% per 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 great when forming a coating film.

[Improved dispersibility of inorganic fine particles]
In the present invention, it is preferable to improve the dispersibility of the inorganic fine particles by allowing the hydrolyzate and / or partial condensate thereof described above to act on the surface of the inorganic fine particles. Specifically, the component derived from the organosilane compound is bonded to the surface of the inorganic fine particles by the hydrolysis / condensation reaction of the organosilane compound. In the hydrolysis / condensation reaction of the organosilane compound, 0 to 2.0 mol of water is usually added to 1 mol of the hydrolyzable group (X ¹⁰ ), and the acid catalyst or metal chelate compound can be used in the present invention. It is preferable to carry out by stirring at 15-100 degreeC in presence of this.

[Acid catalyst, metal chelate compound]
(Acid catalyst)
The preparation of the sol component, that is, the hydrolyzate or condensation reaction product of the organosilane compound, or a mixture of both is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium. From the viewpoint of production stability and storage stability of the inorganic fine particle liquid, an acid catalyst (inorganic Acids, organic acids) and / or metal chelate compounds are used. Of inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant {pKa value (25 ° C.)} of 4.5 or less in water, and an acid dissociation constant of 3.0 or less in hydrochloric acid, sulfuric acid, or water. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

  When the hydrolyzable group of the organosilane is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added to 1 mol of the alkoxide group is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

  When the acid catalyst is an inorganic acid, the acid catalyst is used in an amount of 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. In this case, the optimum amount of use varies depending on the amount of water added, but when water is added, it is 0.01 to 10 mol%, preferably 0.1 to 5 mol% based on the hydrolyzable group. In the case where water is not substantially added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50%, based on the hydrolyzable group. It is -150 mol%, Most preferably, it is 50-120 mol%.

  Although a process is performed by stirring at 15-100 degreeC, it is preferable to adjust with the reactivity of organosilane.

(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 (2-1) and / or a compound represented by the following general formula (2-2). As long as it is a central metal, it can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination.
Formula (2-1): R ²¹ OH
Formula (2-2): R ²² COCH ₂ COR ²³
(In the formula, R ²¹ and R ²² may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, and R ²³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. Show.)

The metal chelate compound suitably used in the present invention has the following general formula:
Zr (OR ²¹ ) _c1 (R ²² COCHCOR ²³ ) _c2 ,
Ti (OR ²¹ ) _d1 (R ²² COCHCOR ²³ ) _d2 and Al (OR ²¹ ) _e1 (R ²² COCHCOR ²³ ) _e2
Are preferably selected from the group of compounds represented by the formula (I), which serve to promote the condensation reaction of the organosilane compound.

R ²¹ and R ²² in the metal chelate compound may be the same or different as described above, specifically an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, an n-propyl group, an i-propyl group, and n-butyl. Group, sec-butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ²³ is an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, and the like. Moreover, c1, c2, d1, d2, e1, and e2 in a metal chelate compound represent the integer determined so that it may become 4 or 6-dentate coordination.

Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxy-bis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. . These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass with respect to the organosilane compound from the viewpoint of the speed of the condensation reaction and the film strength when it is used as a coating film. More preferably, it is used in a proportion of 0.5 to 10% by mass.

[Solvent for dispersibility improvement treatment]
The dispersibility improvement treatment of at least one of the hydrolyzate of the organosilane compound or the partial condensate thereof can be performed in the absence of a solvent or in a solvent. When a solvent is used, the concentration of the hydrolyzate of the organosilane compound or its partial condensate can be determined as appropriate. As the solvent, an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable.

  The solvent is preferably a solvent in which the hydrolyzate of the organosilane compound or a partial condensate thereof and the catalyst are dissolved. In addition, the solvent is preferably used as a solvent for the layer-forming curable composition or as a part of the solvent for the curable composition as it is in the process, and when mixed with other materials such as a fluorine-containing polymer, Those which do not impair the solubility or dispersibility are preferred.

  Among these, as alcohols, a monohydric alcohol or a dihydric alcohol can be mentioned, for example, As a monohydric alcohol, a C1-C8 saturated aliphatic alcohol is preferable. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, s-butyl alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. Examples thereof include monobutyl ether and ethylene glycol monoethyl ether acetate.

Specific examples of aromatic hydrocarbons include benzene, toluene and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more.

Although the density | concentration of the organosilane compound with respect to the solvent in a dispersibility improvement process is not specifically limited, Usually, it is the range of 0.1-70 mass%, Preferably it is the range of 1-50 mass%.

  In the present invention, it is preferable to disperse the inorganic fine particles with an alcohol solvent and then perform a dispersibility improvement treatment, and subsequently replace the dispersion solvent with an aromatic hydrocarbon solvent or a ketone solvent. Substitution with a ketone solvent is preferable from the viewpoint of improving the affinity with the binder used at the time of coating and the stability of the dispersion itself.

[Catalyst for Dispersibility Improvement Treatment]
The dispersibility improving treatment using at least one component of the hydrolyzate of the organosilane compound and the partial condensation reaction product is preferably performed in the presence of a catalyst. As the catalyst, those described in the above section (acid catalyst, metal chelate compound) can be preferably used.

[Stabilizing additive for curable composition]
In addition to the organosilane compound and the acid catalyst or chelate compound, the layer-forming curable composition used in the present invention includes a β-diketone compound and / or a β-ketoester compound represented by the following general formula (3). It is preferable to contain these, and these act as stability improvers of the curable composition for layer formation used in the present invention.
Formula (3): R ³¹ COCH ₂ COR ³²

That is, the compound represented by the general formula (3) is coordinated to a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), whereby organosilane and metal by these metal chelate compounds. It is considered that the action of promoting the condensation reaction of the chelate component is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ³¹ and R ³² in the compound represented by the general formula (3) are the same as R ²² and R ²³ constituting the metal chelate compound.

Specific examples of the β-diketone compound and β-ketoester compound represented by the general formula (3) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate. Acetic acid-n-butyl, acetoacetic acid-s-butyl, acetoacetic acid-t-butyl, 2,4-hexadione, 2,4-heptadione, 3,5-heptadione, 2,4-octadione, 2,4-nonadione, 5-methylhexadione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred.
These β-diketone compounds and β-ketoester compounds may be used alone or in combination of two or more.

  In the present invention, the β-diketone compound and β-ketoester compound are preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is 2 mol or more, there is no possibility of being inferior in the storage stability of the composition obtained, and it is preferable.

  Next, (c) the photopolymerization initiator will be described.

<Photopolymerization initiator for low refractive index layer>
Ionic curable resins such as triarylsulfonium salts, diaryliodonium salts, monoaryldialkylsulfonium salts, triarylselenonium salts, tetraarylphosphonium salts, aryldiazonium salts as photoacid generators that generate cations by ultraviolet rays And non-ionic curable resins such as nitrobenzyl ester of sulfonic acid, and active halogens, etc., described in “Organic Materials for Imaging” published by Bunshin Publishing Co., Ltd. (1997) Various known photoacid generators such as curable resins can be used. Of these, triarylsulfonium salts are preferred, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , BF ₄ ⁻ , HSO ₄ ⁻ , ClO ₄ ⁻ are preferred as counter ions. Etc. are preferable. It is also a preferred embodiment to use a combination of triarylsulfonium salt and diaryliodonium salt. Furthermore, active halogens can also be preferably used.

Examples of the iodonium salt-type photoacid generator are described in, for example, “imaging organic material” (Bunshin Publishing Co., Ltd., Organic Electronics Materials Research Group, 1997), Japanese Patent Application Laid-Open No. 11-322900, and the like. As what is used for this invention, Preferably it is represented with the following general formula (1 ').
General formula (1 ')
_{^{(Ar 1) m -I + -}} (Ar 2) n X - where, Ar ^1, Ar ² each represent an aromatic hydrocarbon group or an aromatic heterocyclic group, by combining the Ar ¹ and Ar ² A ring may be formed. Aromatic hydrocarbon groups include phenyl, 1-naphthyl, 2-naphthyl and the like. Examples of the aromatic heterocyclic group include 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyrrolyl, 3-pyrrolyl, 2-thiazolyl and the like. Ar ¹ and Ar ² are preferably aromatic hydrocarbon groups, and more preferably phenyl groups. These may further have a substituent, and the substituent is not particularly limited, but those having a basicity such as an amino group are not preferable in order to neutralize the generated acid. Specific examples of the substituent include alkyl groups (methyl, ethyl, isopropyl, t-butyl, t-amyl, 2-ethylhexyl, dodecyl, etc.), cycloalkyl (cyclohexyl, cyclopentyl, etc.), aryl groups (phenyl, 2-naphthyl, etc.) ), Alkenyl group (vinyl etc.), alkoxy group (methoxy, ethoxy, isopropoxy, octyloxy, cyclohexyloxy etc.), aryloxy group (phenoxy etc.), halogen (fluorine, chlorine, bromine, iodine etc.), alkoxycarbonyl group (Ethoxycarbonyl, butoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.), acyloxy groups (acetoxy, benzoyloxy, etc.), carbamoyl groups, acylamino groups, cyano groups, hydroxyl groups, carboxyl groups, heterocyclic groups ( - thienyl, 3-thienyl, 2-furyl, 2-pyrrolyl, oxiranyl, oxetanyl, etc.) and the like can be mentioned, which may be further substituted.

m and n each represent 1 or 2, preferably 1. When a plurality of Ar ¹ or Ar ² are present, m and n may be the same or different. X ⁻ is a counter anion of the iodonium salt and is preferably a conjugate base of a strong acid. X ^- as the PF ₆ ^-, BF ₄ ^-
, HSO ₄ ⁻ , ClO ₄ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₃ ⁻ , CH ₃ —C ₆ H ₄ —SO ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , Cl ⁻ , Br ⁻ Of these, PF ₆ ⁻ , BF ₄ ⁻ and CF ₃ SO ₃ ^— are preferable, and PF ₆ ⁻ is particularly preferable.
As specific examples of the iodonium salt type photoacid generator, the compounds (1) to (28) described in JP-A-2003-268141 [0078] to [0081] and Rhodia Japan Co., Ltd. are available. However, the present invention is not limited to these examples.

The triarylsulfonium salt type photoacid generator is represented by the following general formula (1 ″).
(R) ₃ S ⁺ X ⁻ ,
Here, R represents an aryl group or an alkyl group having 1 to 20 carbon atoms, and when R appears multiple times in one molecule, they may be the same or different, and X ⁻ is a counter anion as described above. It is preferably a conjugate base of a strong acid.
Specific examples of the triarylsulfonium salt type photoacid generator include compounds described in JP-A No. 11-322900, “Syracure UVI-6990” and “Syracure UVI” sold by Dow Chemical Japan Co., Ltd. -6974 "," Adekaoptomer SP-150 "and" Adekaoptomer SP-170 "sold by Asahi Denka Kogyo Co., Ltd., but the present invention is not limited thereto. .

  Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M.M. P. Examples include the compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and particularly, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, 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, 2- {4 -(4-hydroxybenzoylamino) phenyl) -4,6-bis (trichloromethyl) -s-triazine is included. Specifically, Nos. Described in p14 to p30 of JP-A-58-15503, p6-p10 of JP-A-55-77742, and p287 of 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.

[Other materials contained in curable composition for low refractive index layer]
The material for forming the low refractive index layer will be described below.
The low refractive index layer may further contain a monomer or polymer that crosslinks by heat or ionizing radiation as a binder. Of the binder component (excluding inorganic fine particles) contained in the low refractive index layer, the ratio of the compound having a cationic polymerizable group is preferably 70% by mass or more, more preferably 80% by mass or more, and 90 It is particularly preferable that the content is at least mass%. When the ratio of the compound having a cationic polymerizable group is 70% by mass or more, a strong film can be obtained even when cured at a high oxygen concentration.

  There is no particular limitation on the monomer or polymer that is cross-linked by heat or ionizing radiation used in the low refractive index layer. The monomer is particularly preferably an ionizing radiation-curable polyfunctional monomer as in the high (medium) refractive index layer described below. The polymer is preferably a crosslinkable fluorine-containing compound typified by the above compound, but in addition to this, in addition to a perfluoroalkyl group-containing silane compound such as the compounds exemplified in the following [Chemical Formula 11] and [Chemical Formula 12]. Examples thereof include a fluorine-containing copolymer of a fluorine monomer and a monomer for imparting a crosslinkable group. Specific examples of the fluorine-containing monomer include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.) , Part of (meth) acrylic acid or fully fluorinated alkyl ester derivatives [for example, “Biscoat 6FM” {manufactured by Osaka Organic Chemical Industry Co., Ltd.}, “M-2020” {manufactured by Daikin Industries Ltd.}, etc.], complete Or partially fluorinated vinyl ethers. As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers {for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.}. It is described in JP-A-10-25388 and JP-A-10-147739 that the latter can introduce a crosslinked structure after copolymerization.

  Moreover, not only the copolymer of the said fluorine-containing monomer and the monomer for crosslinkable group provision but the copolymer by which the monomer other than these was copolymerized may be used. The monomer 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, 2-acrylic acid 2- Ethyl hexyl), 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) Etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), acrylamides (Nt-butylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides, acrylo It can be mentioned tolyl derivatives and the like. Examples of the binder that can be preferably used in the low refractive index layer include copolymers described in JP-A-2004-45462, [0030] to [0047].

<Fluoropolymer for low refractive index layer>
The fluoropolymer has a cured film having a coefficient of dynamic friction of 0.03 to 0.20, a contact angle with water of 90 to 120 °, and a sliding angle of pure water of 70 ° or less, and heat or ionization. A polymer that is cross-linked by radiation is preferable from the viewpoint of improving productivity in the case of applying and curing a roll film while conveying the web.
Also, when the antireflection film of the present invention is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a seal or memo, so the peel strength is preferably 500 gf or less, 300 gf or less is more preferable, and 100 gf or less is most preferable. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

  The fluorine-containing polymer used for the low refractive index layer is a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group, for example, containing a perfluoroalkyl group In addition to hydrolysates and dehydration condensates of silane compounds [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], fluorinated monomer units and crosslinking reactive units are used as constituent units. A fluorine-containing copolymer is mentioned. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer 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. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as 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.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluoropolymer.

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 crosslinking reaction alone (radical reactive group such as (meth) acryloyl group, ring-opening polymerizable group such as epoxy group and oxetanyl group).
These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  A preferred form of the fluorine-containing polymer for the low refractive index layer used in the present invention is a copolymer represented by the general formula 1.

  (In the formula, x, y, and z represent molar ratios. D represents a polymerization unit of a vinyl monomer having a cationic polymerizable group, and E represents an arbitrary vinyl monomer polymerization unit.)

(Other cationic polymerizable compounds)
The composition for forming a low refractive index layer of the present invention may contain a curing agent containing a cationic polymerizable group that does not contain fluorine or silicon. Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, an oxazolyl group, and a vinyloxy group, preferably a ring-opening polymerizable group, more preferably an epoxy group or an oxetanyl group, and particularly preferably an epoxy group. It is. These groups may have a substituent at a possible position.

  A plurality of these cationic polymerizable groups are preferably introduced per molecule of the curing agent, more preferably 2 to 20 are introduced per molecule, and particularly preferably 3 to 10 are introduced. It has been done. Although there is no restriction | limiting in particular in the molecular weight of a hardening | curing agent, Preferably it is 200-10000, More preferably, it is 200-3000, Especially preferably, it is the range of 400-1500. If the molecular weight is too small, volatilization in the film forming process becomes a problem, and if it is too large, the compatibility with the fluorine-containing polymer is deteriorated.

  The addition amount of the curing agent having a cationic polymerizable group is preferably added in the range of 0.1 to 50% by mass, more preferably 1 to 30% by mass with respect to the solid content forming the film, The case of 3-20 mass% is especially preferable.

  Examples of the curing agent suitably used in the present invention include commercially available products such as Denacol EX 314, 411, 421, 521, 611, 612, etc. (Nagase Kasei Kogyo Co., Ltd.), Celoxide GT301. 401, etc. (manufactured by Daicel Industries, Ltd.).

  In addition, examples of the curing agent useful in the present invention include compounds A-1 to A-39 described in JP-A-2004-354740 [0067] to [0073].

(Other additives)
Furthermore, for the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties and the like to the low refractive index layer, a known polysiloxane compound or antifouling agent such as a fluorine-based compound, a slipping agent, etc. are appropriately used. It can also be added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

(Polysiloxane compound)
Preferable examples of the polysiloxane compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.

  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, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.

Although there is no restriction | limiting in particular in silicon atom content of a polysiloxane compound, It is preferable that it is 18.0 mass% or more, It is especially preferable that it is 25.0-37.8 mass%, 30.0-
Most preferably, it is 37.0 mass%.

  The polymerizable polysiloxane compound contained in the curable composition for forming the low refractive index layer of the present invention is a cationic polymerizable polysiloxane having a cationic polymerizable group because the low refractive index layer is formed by a cationic polymerizable binder. A siloxane compound is preferable from the viewpoint of antifouling durability.

  Examples of cationically polymerizable functional groups include epoxy groups contained in glycidyl groups and epoxycyclohexyl groups, oxetane rings, vinyl ether groups, aziridine rings, cyclic sulfides, cyclic carbonates, lactone rings, oxazoline rings, and the like. .

Examples of cationically polymerizable polysiloxane compounds include polydimethylsiloxane compounds with glycidyl groups introduced at one end, polydimethylsiloxane compounds with glycidyl groups introduced at both ends, and polydimethyls with glycidyl groups introduced into side chains. Examples thereof include a siloxane compound, a polydimethylsiloxane compound in which an epoxycyclohexyl group is introduced at both ends, and a polydimethylsiloxane compound in which an epoxycyclohexyl group is introduced into a side chain. Functional groups such as amino group, carboxyl group, carbinol group, (meth) acryloyl group, mercapto group, and polyether group may be further introduced into these cationically polymerizable polysiloxane compounds.
In the present invention, among these compounds, a polydimethylsiloxane compound having a cationic polymerizable group at both ends is particularly preferable.

The cationically polymerizable polysiloxane compound preferably has a kinematic viscosity (value at 25 ° C., hereinafter the same) of about 10 to 20,000 mm ² / s.

Some polymerizable polysiloxane compounds are commercially available as reactive silicone oils, which can be used. Among these, as examples of commercially available products of the cationic polymerizable polysiloxane compound, “KF-105” (both ends glycidyl-modified silicone oil; kinematic viscosity 15 mm ² / s) sold by Shin-Etsu Chemical Co., Ltd. “X-22-163A” (both ends glycidyl-modified silicone oil; kinematic viscosity 30 mm ² / s), “X-22-163B” (both ends glycidyl-modified silicone oil; kinematic viscosity 60 mm ² / s), “X-22 -163C "(both ends glycidyl modified silicone oil; kinematic viscosity 120 mm ² / s)," X-22-173DX "(single end glycidyl modified silicone oil; kinematic viscosity 65 mm ² / s)," KF-1001 "(side chain glycidyl-modified silicone oil; kinematic viscosity ^{17,000mm 2 / s), "KF} -101" ( side chain glycidyl Sex silicone oil; kinematic viscosity ^{1,500mm 2 / s), "X} -22-169AS" ( both ends epoxycyclohexyl-modified silicone oil; kinematic viscosity ^{30mm 2 / s), "X} -22-169B" ( both ends epoxycyclohexyl Modified silicone oil; kinematic viscosity 65 mm ² / s), “KF-102” (both ends epoxy cyclohexyl modified silicone oil; kinematic viscosity 4,000 mm ² / s), “X-22-3667” (side chain epoxy / side chain) Polyether modified silicone oil; kinematic viscosity 4,500 mm ² / s) and “X-22-4741” (side chain epoxy / side chain polyether modified silicone oil; kinematic viscosity 400 mm ² / s), Toray Dow Corning "BY16-855D" (both ends glyci sold by Silicone Co., Ltd.) Le-modified silicone oil; kinematic viscosity ^{10mm 2 / s), "SF8411} " ( side chain glycidyl-modified silicone oil; kinematic viscosity ^{8,000mm 2 / s), "SF8413} " ( side chain glycidyl-modified silicone oil; kinematic viscosity 18,000mm ² / s) and “BY16-839” (side-chain epoxycyclohexyl-modified silicone oil; kinematic viscosity 6,000 mm ² / s), “TSF4730” (both terminal glycidyl-modified silicone oils) sold by GE Toshiba Silicone Corp. A kinematic viscosity of 6,000 mm ² / s).

[Method of forming low refractive index layer]
In the present invention, the low refractive index layer of the antireflection film is a coating composition obtained by mixing the above curable composition, the above binder as a binder contained in the curable composition, and, if necessary, an additive and an organic solvent. It is preferable to form by coating, drying and curing. Since cationic polymerization proceeds even with heat, it is preferable that the coating composition is applied and dried, and then heated at 80 to 150 ° C., preferably for 1 to 30 minutes, to cure the unreacted cationic polymerizable resin. After winding up the roll, curing can also proceed by storing in a room at 25 ° C. or more for 24 hours or more.

[Hard coat layer]
The hard coat layer will be described below.
The hard coat layer is a curable composition, a binder for imparting hard coat properties as a binder contained in the curable composition, and mat particles for imparting antiglare property or internal scattering property as necessary. And inorganic fine particles for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.

In the present invention, when the low refractive index layer is directly laminated on the hard coat layer, the hard coat layer preferably contains a hydrolyzate of an organosilane compound or a partial condensate thereof.
The organosilane compound that can be preferably used in the hard coat layer will be described below.

The organosilane compound is represented by the following general formula [C].
[C]: (R ¹⁰ ) _m Si (X ¹¹ ) _4-m

In the general formula [C], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, hexyl, decyl, hexadecyl 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 phenyl and naphthyl, and a phenyl group is preferable.

X ¹¹ represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.). And R ¹² COO (R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably an alkoxy group, particularly preferably Is a methoxy group or an ethoxy group.
m represents an integer of 0 to 3, preferably 0, 1, 2, more preferably 2, and particularly preferably 1.

When R ¹⁰ or ^{the X 11} there are a plurality, it may be different even in a plurality of ^{R 10} or ^{X 11} same.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-). Propyl, propyl, t-butyl, etc.), aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryl Oxy (phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups ( Methoxycarbonyl, ethoxycarbonyl, etc. ), Aryloxycarbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylic) Amino, methacrylamino and the like), and these substituents may be further substituted. When there are a plurality of R ¹⁰ , at least one of them is preferably a substituted alkyl group or a substituted aryl group, and among them, an organosilane compound having a substituent represented by the following general formula (1-2) is preferable.
General formula (1-2):

In General Formula (1-2), R ¹¹ 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. Among them, a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom is preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom is more preferable, and a hydrogen atom or a methyl group Is particularly preferred. Y ¹¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Among these, a single bond or an ester group or an amide group is preferable, a single bond or an ester group is more preferable, and an ester group is particularly preferable.

L ¹¹ represents a divalent or unsubstituted arylene group, and a linking group (for example, an ether, ester, amide linking chain; specifically, a substituted or unsubstituted alkylene group or substituted). Examples include a substituted alkylene group, a substituted or unsubstituted arylene group having a linking group therein, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, An alkylene group having 3 to 10 carbon atoms having a linking group inside is preferred, an unsubstituted alkylene group, an unsubstituted arylene group, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, An alkylene group having an ether or ester linking group therein is particularly preferred. 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.

b represents 0 or 1, preferably 0. X ¹¹ has the same meaning as in formula (1), 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, 3 is more preferable, and a methoxy group is particularly preferable. When a plurality of X ¹¹ are present, they may be the same or different. R ¹⁰ has the same meaning as in formula (1), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.

  Two or more compounds of the general formula (1) and the general formula (1-2) may be used in combination. Although the specific example of a compound represented by General formula (1) and General formula (1-2) below is shown, this invention is not limited to these.

  Among these specific examples, (M-1), (M-2), (M-30), (M-35), (M-49) and the like are particularly preferable.

[Binder for forming hard coat layer]
The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure. As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.

  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-dichlorohexane diacrylate, pentaerythritol tetra (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol triacrylate, polyurethane polyacrylate, polyester polyacrylate, etc.}, vinylbenzene and Derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, etc.), vinyl sulfones (eg, divinyl sulfone), acrylamides (eg, methylene bisacrylamide) and methacrylamide Etc.

When the low refractive index layer is directly laminated on the hard coat layer, a curable composition containing a compound having a cationic polymerizable group in the hard coat layer for the purpose of improving the adhesion between the low refractive index layer and the hard coat layer Preferably it is formed from a product. An unreacted cationic polymerizable group can be present on the surface of the hard coat layer, and when the low refractive index layer is laminated, it polymerizes with the cationic polymerizable group in the curable composition for the low refractive index layer, and the hard layer becomes hard. The adhesion between the coat layers can be enhanced.
The proportion of the compound having a cationic polymerizable group in the curable composition for forming a hard coat layer in the total binder is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 20% by mass or more. preferable.

  In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.

  Polymerization of these monomers having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator. Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and inorganic fine particles is prepared. For example, after applying the coating liquid on a transparent support, ionizing radiation or A hard coat layer can be formed on the transparent support by curing by a polymerization reaction by heat.

  The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator. Accordingly, a coating solution containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles, and inorganic fine particles is prepared, and the coating solution is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. It can be cured to form a hard coat layer on the transparent support.

  Two or more kinds of these polyfunctional monomers, that is, a monomer having two or more ethylenically unsaturated groups and a ring-opening polymerizable polyfunctional monomer such as a polyfunctional epoxy compound may be used in combination.

  The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer for forming the binder is preferably a light, electron beam, or radiation polymerizable functional group, among which a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

  Examples of the photoradical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  As a commercially available photo radical polymerization initiator, “Kayacure (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC” manufactured by Nippon Kayaku Co., Ltd. , MCA, etc.), “Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.)” manufactured by Ciba Specialty Chemicals Co., Ltd., “Esacure (KIP100F, KB1) manufactured by Sartomer , EB3, BP, X33, KT046, KT37, KIP150, TZT) "and the like.

  In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991).

  Examples of commercially available photocleavable photoradical polymerization initiators include “Irgacure (651,184,907)” manufactured by Ciba Specialty Chemicals.

  As a photocationic polymerization initiator, the photocationic polymerization initiator which can be used for the said curable composition for low refractive index layer formation can be used. Of these, diaryliodonium salts are particularly preferred in the hard coat layer because they are less colored after curing.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, 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.
Examples of commercially available photosensitizers include “Kaya Cure (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

  The photopolymerization reaction is preferably performed by ultraviolet irradiation after the coating liquid for forming the hard coat layer is applied and dried.

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

[Matte particles]
In order to impart antiglare property or internal scattering property to the hard coat layer, mat particles having an average particle diameter of 1 to 10 μm, preferably 1.5 to 7.0 μm, for example, inorganic compound particles or Resin particles are contained. Specific examples of the mat particles include inorganic particles such as silica particles and TiO ₂ particles, and resin particles such as crosslinked acrylic particles, crosslinked acrylic-styrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles. Can be mentioned. Of these, crosslinked acrylic particles, crosslinked acrylic-styrene particles, and crosslinked styrene particles are preferred. As the shape of the matte particle, either a true sphere or an indefinite shape can be used. Further, two or more different kinds of mat particles may be used in combination. The mat particles are formed on the anti-glare hard coat layer so that the amount of the mat particles in the formed anti-glare hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 30 to 100 mg / m ^2. It should be contained.
In a particularly preferred embodiment, cross-linked styrene particles are used as mat particles, and the cross-linked styrene particles having a particle size larger than one half of the film thickness of the hard coat layer occupy 40 to 100% of the entire cross-linked styrene particles. It is an aspect. Here, 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.

[Inorganic fine particles]
The hard coat layer is made of an oxide of at least one metal 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. Therefore, it is preferable that inorganic fine particles having an average particle diameter of 0.001 to 0.2 μm or less, preferably 0.001 to 0.1 μm, more preferably 0.001 to 0.06 μm or less are contained. Specific examples of the inorganic fine particles used for the hard coat layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , tin-doped indium oxide (ITO), etc. Is mentioned. TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic fine particles 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 addition amount of these inorganic fine particles is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass with respect to the total mass of the hard coat layer.

  Such inorganic fine particles have a particle size sufficiently smaller than the wavelength of light and therefore do not scatter, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The refractive index of the mixture of binder and inorganic fine particles in the hard coat layer is preferably 1.57 to 2.00, more preferably 1.60 to 1.80. In order to make the refractive index within the above range, the type and amount ratio of the binder and the inorganic fine particles may be appropriately selected. How to select can be easily known experimentally in advance.

  The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

(Anti-glare layer)
The antiglare layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering and preferably hard coat properties for improving the scratch resistance of the film. Therefore, it preferably contains a translucent resin capable of imparting hard coat properties, translucent fine particles for imparting antiglare properties, and a solvent as essential components.

  The antiglare layer and / or the above-mentioned antiglare hard coat layer in the present invention preferably has a center line average roughness Ra of 0.08 to 0.30 μm as the surface uneven shape. If Ra is less than 0.08, sufficient antiglare property cannot be obtained, and if it exceeds 0.30, problems such as glare and surface whitening when external light is reflected occur.

[High (medium) refractive index layer]
The refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably 1.60 to 2.20, still more preferably 1.65 to 2.10, most preferably Is 1.80 to 2.00. When the middle refractive index layer is used for the antireflection film, the refractive index is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less.

[High refractive index inorganic fine particles]
For the high refractive index layer and the medium refractive index layer, a cured product of a composition in which inorganic fine particles having a high refractive index are dispersed in a monomer and an initiator described later and an organosilane compound is preferably used.
Such high refractive index inorganic fine particles are preferably metal (eg, aluminum, titanium, zirconium, antimony) oxides, and titanium dioxide fine particles are most preferred from the viewpoint of refractive index. When using a monomer and an initiator, a medium refractive index layer or a high refractive index layer excellent in scratch resistance and adhesion can be formed by curing the monomer by ionizing radiation or heat polymerization after coating. The average particle size of the inorganic fine particles is preferably 10 to 100 nm.

  As the fine particles of titanium dioxide, inorganic fine particles containing at least one element selected from cobalt, aluminum, and zirconium and containing titanium dioxide as a main component are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.

  The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. 80 is most preferred.

  The mass average diameter of primary particles of inorganic fine particles mainly composed of titanium dioxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  The crystal structure of the inorganic fine particles mainly composed of titanium dioxide is preferably a rutile, mixed crystal of rutile and anatase, anatase, or an amorphous structure, and particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

  By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, The weather resistance of the high refractive index layer and the medium refractive index layer can be improved. A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.

[Dispersant for inorganic fine particles]
A dispersant can be used for dispersing inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer and the medium refractive index layer. For dispersing inorganic fine particles mainly composed of titanium dioxide, it is particularly preferable to use a dispersant having an anionic group.

As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more. A plurality of anionic groups may be contained for the purpose of further improving the dispersibility of the inorganic fine particles. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

  A preferred dispersant used for dispersion of inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer has an anionic group and a crosslinkable or polymerizable functional group, and the crosslinkable or polymerizable functional group is a side chain. It is a dispersing agent to have.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The amount of the dispersant used relative to the inorganic fine particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.

[Dispersion method of inorganic fine particles]
The inorganic fine particles mainly composed of titanium dioxide used for the high refractive index layer and the medium refractive index layer are preferably used for forming the high refractive index layer and the medium refractive index layer in a dispersion state. The inorganic fine particles are usually dispersed in a dispersion medium in the presence of the dispersant.

(Dispersion medium)
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (eg, methyl acetate, acetic acid). Ethyl, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane, etc.), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride) Etc.), aromatic hydrocarbons (eg benzene, toluene, xylene etc.), amides (eg dimethylformamide, dimethylacetamide, n-methylpyrrolidone etc.), ethers (eg diethyl ether, dioxane, tetra Dorofuran etc.), ether alcohols (e.g., 1-methoxy-2-propanol, etc.). Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred. Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic fine particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The inorganic fine particles are preferably made as fine as possible in the dispersion medium, and the mass average diameter is preferably 1 to 200 nm. More preferably, it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. By refining the inorganic fine particles to 200 nm or less, a high refractive index layer and a medium refractive index layer that do not impair transparency can be formed.

[Method for forming high (medium) refractive index layer]
The high refractive index layer and medium refractive index layer used in the present invention are preferably a binder precursor (for example, described later) required for forming a matrix in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium as described above. Ionizing radiation curable polyfunctional monomers and polyfunctional oligomers), photopolymerization initiators and the like to form a coating composition for forming a high refractive index layer and a middle refractive index layer, and a high refractive index layer on a transparent support In addition, it is preferable to form by applying a coating composition for forming a medium refractive index layer and curing it by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

  Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer. As the binder of the high refractive index layer and the medium refractive index layer, it is preferable to use the binder described in the hard coat layer and a polymerization initiator corresponding to the binder type.

  The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic fine particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains the inorganic fine particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer for forming the binder is preferably a light, electron beam, or radiation polymerizable functional group, among which a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;

(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane, 2-2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Is mentioned.
Two or more polyfunctional monomers may be used in combination.

  It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

  As the radical photopolymerization initiator, the same ones as those used for the curable composition in the hard coat layer can be used, and as the commercially available radical photopolymerization initiator, the same ones can be mentioned. it can. The photoradical polymerization initiator is particularly preferably a photocleavable photoradical polymerization initiator, and the same can be mentioned as a commercially available photocleavable photoradical polymerization initiator.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, 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 can include those similar to those used for the curable composition in the hard coat layer, and commercially available photosensitizers can also include the same.

  The photopolymerization reaction is preferably performed by ultraviolet irradiation after coating and drying of the high refractive index layer.

  In order to construct a two-layer thin film interference type antireflection film by constructing a low refractive index layer on the high refractive index layer, the refractive index of the high refractive index layer is 1.55 to 2.40. Is preferable, more preferably 1.60 to 2.20, still more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  In the case of the three-layer thin film interference type in which the middle refractive index layer and the low refractive index layer are constructed on the high refractive index layer, the refractive index of the high refractive index layer is preferably 1.65 to 2.40. More preferably, it is .70 to 2.20, and more preferably 1.80 to 2.10. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.55 to 1.80, more preferably 1.58 to 2.00, and still more preferably 1.60 to 1.80. The haze of the high refractive index layer and the medium refractive index layer is preferably 3% or less.

In addition to the above-mentioned components (inorganic fine particles, polymerization initiators, photosensitizers, etc.), the high (medium) refractive index layer contains resins, surfactants, antistatic agents, coupling agents, thickeners, and coloring prevention. Agent, colorant (pigment, dye), antifoaming agent, leveling agent, flame retardant, ultraviolet absorber, infrared absorber, adhesion-imparting agent,
A polymerization inhibitor, an antioxidant, a surface modifier, conductive metal fine particles, and the like can also be added.

(Antistatic layer)
Next, the antistatic layer in the present invention will be described.
In the academic functional film such as the antireflection film of the present invention, by constructing the antistatic layer, it is possible to prevent dust (dust etc.) from adhering to the surface of the optical functional film, that is, to exhibit excellent dust resistance. it can. Dust resistance is expressed by lowering the surface resistance value of the surface of an optical functional film (such as an antireflection film), and a higher effect is obtained as the conductivity of the antistatic layer is higher.

In the antireflection film of the present invention, the surface resistance value of the surface having the low refractive index layer containing the fluorine-containing compound is preferably 1 × 10 ¹³ Ω / □ or less, and preferably 1 × 10 ¹² Ω / □. □ or less is more preferable, preferably 1 × 10 ¹¹ Ω / □ or less is further preferable, 1 × 10 ⁹ Ω / □ or less is still more preferable, and 1 × 10 ⁸ Ω / □ or less is preferable. It is particularly preferred.

  In the optical functional film such as the antireflection film of the present invention, the antistatic layer may be produced by either a vapor phase method (vacuum deposition method, sputtering method, ion plating method, plasma CVD method, etc.) or a coating method. However, the coating method is preferable because an antistatic layer can be produced at low cost.

  It is preferable that at least one antistatic layer is formed on the transparent support. The antistatic layer is produced either between the transparent support and the outermost low-refractive index layer having a fluorine-containing compound, or on the opposite side of the transparent support where the low-refractive index layer is formed. Preferably, the transparent support and the low refractive index layer are preferably disposed between the transparent support and the low refractive index layer, and closer to the low refractive index layer. .

  The production of the antistatic layer by the vapor phase method can be carried out, for example, by vacuum deposition or sputtering of a conductive material on the film. Specific examples of the conductive substance include aluminum, copper, gold, silver, nickel, chromium, iron, molybdenum, titanium, tungsten, tantalum, and other metals or alloys, or zinc oxide doped with ATO, ITO, and aluminum. A metal oxide such as can be used.

When the antistatic layer is produced by coating, an antistatic layer can be produced by incorporating a conductive material (electroconductive particles, electron conductive organic compounds, etc.) in a binder (binder, etc.). preferable. In particular, an electron conductive type conductive material is preferable in that it is less susceptible to environmental changes, has stable conductive performance, and exhibits good conductive performance even in a low humidity environment.
Hereinafter, preferable modes for producing the antistatic layer by a coating method will be described.

[Conductive material]
As a preferable conductive material used for the antistatic layer, an electron conductive conductive material such as a π-conjugated conductive organic compound or conductive fine particles is preferable.
Examples of π-conjugated conductive organic compounds include aliphatic conjugated polyacetylene, aromatic conjugated poly (paraphenylene), heterocyclic conjugated polypyrrole, polythiophene, heteroatom-containing polyaniline, and mixed conjugated systems. And poly (phenylene vinylene).

  Examples of the conductive fine particles include carbon-based, metal-based, metal oxide-based, and conductive coating-based fine particles.

  Examples of the carbon-based fine particles include carbon powders such as carbon black, ketjen black, and acetylene black, carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, and carbon flakes of pulverized expanded graphite.

  Examples of metal-based fine particles include metals such as aluminum, copper, gold, silver, nickel, chromium, iron, molybdenum, titanium, tungsten, and tantalum, and powders of alloys containing these metals, metal flakes, iron, and copper. And metal fibers such as stainless steel, silver-plated copper, and brass.

  Examples of the metal oxide fine particles include tin oxide, ATO, ITO, zinc oxide, and zinc oxide doped with aluminum.

  As the conductive coating fine particles, for example, the surface of various fine particles such as titanium oxide (spherical, needle-shaped), potassium titanate, aluminum borate, barium sulfate, mica, silica, etc. is made of a conductive material such as tin oxide, ATO, or ITO. Resin beads such as coated fine particles, polystyrene, acrylic resin, epoxy resin, polyamide resin, polyurethane resin and the like surface-treated with a metal such as gold and / or nickel are preferable.

  As the conductive material of the antistatic layer, π-conjugated conductive organic compound (especially polythiophene-based conductive polymer), and as conductive fine particles, metal-based fine particles (especially gold, silver, silver / palladium alloy, copper, nickel, Aluminum) and metal oxide fine particles (in particular, tin oxide, ATO, ITO, zinc oxide, aluminum-doped zinc oxide) are preferable. In particular, an electroconductive conductive material such as a metal or metal oxide is preferable, and metal oxide fine particles are particularly preferable.

  The primary particle of the conductive material preferably has a mass average particle diameter of 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm. The average particle diameter of the conductive material can be measured by a light scattering method or an electron micrograph.

The specific surface area of the conductive material is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  The shape of the conductive material is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a scale shape, a needle shape, or an indefinite shape, and particularly preferably an indefinite shape, a needle shape, or a scale shape.

[Method of forming antistatic layer]
When the antistatic layer is produced by a coating method, the conductive material is preferably used for forming the antistatic layer in a dispersion state. In dispersing the conductive material, it is preferable to disperse in the dispersion medium in the presence of a dispersant. By dispersing using a dispersant, the conductive material can be dispersed very finely, and a transparent antistatic layer can be produced. In particular, when an antistatic layer is used as an optical interference layer and the layer also has an antireflection function, the transparency of the layer can be increased and the antireflection performance can be improved by finely dispersing the conductive material. preferable.

  For dispersing the conductive material of the present invention, it is preferable to use a dispersant having an anionic group. As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo group), a phosphoric acid group (phosphono group), a sulfonamide group, or a salt thereof is effective. Group, phosphoric acid group or a salt thereof are preferred, and carboxyl group and phosphoric acid group are particularly preferred.

The number of anionic groups contained in the dispersant per molecule may be one or more. In order to further improve the dispersibility of the conductive material, the dispersant may contain a plurality of anionic groups per molecule. The average number per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

  Examples of the dispersant having an anionic polar group include “phosphanol (PE-510, PE-610, LB-400, EC-6103, RE-410)” and the like {above, manufactured by Toho Chemical Co., Ltd.}, “ Disperbyk (-110, -111, -116, -140, -161, -162, -163, -164, -170, -171, etc. {above, manufactured by Big Chemie Japan Co., Ltd.}) and the like.

The dispersant preferably further contains a crosslinkable or polymerizable functional group.
Examples of the crosslinkable or polymerizable functional group include an ethylenically unsaturated group {for example, a (meth) acryloyl group, an allyl group, a styryl group, a vinyloxy group, etc.} that can undergo a crosslinking reaction / polymerization reaction with a radical species, a cationic polymerizable group (Epoxy group, oxatanyl group, vinyloxy group, etc.), polycondensation reactive group (hydrolyzable silyl group, etc., N-methylol group) and the like can be mentioned, and a functional group having an ethylenically unsaturated group is preferred. The crosslinkable or polymerizable functional group of the dispersant is particularly preferably present in the side chain.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is 1000 or more. Preferably there is. The dispersant preferably has a mass average molecular weight (Mw) of 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

  The amount of the dispersant used for the conductive material is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 30% by mass, and most preferably 5 to 20% by mass. Two or more dispersants may be used in combination.

(Dispersion medium)
The conductive material is preferably dispersed in a dispersion medium in the presence of a dispersant.
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (eg, methyl acetate, acetic acid). Ethyl, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane, etc.), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride) Etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg, diethyl ether, dioxane, tetrahydride) Furan, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, etc.). Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred. Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The conductive material is preferably dispersed using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with a pin), a dyno mill, a high-speed impeller mill, a pebble mill, a roller mill, an attritor and a colloid mill. A media disperser such as a sand grinder mill or a dyno mill is particularly preferable. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The conductive material is preferably made as fine as possible in the dispersion medium, and the mass average particle diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. By miniaturizing the conductive material to 200 nm or less, an antistatic layer that does not impair the transparency can be produced.

[binder]
The antistatic layer of the present invention preferably contains an organic compound binder in addition to the conductive material, and it is preferable to form a layer matrix with the binder and disperse the conductive material. For this reason, the antistatic layer is preferably prepared by adding a binder or a binder precursor to a dispersion obtained by dispersing a conductive material in a dispersion medium. As the binder or binder precursor, a non-curable thermoplastic resin, or a curable resin such as a thermosetting resin or an ionizing radiation curable resin can be used.

  The softening temperature or glass transition point of the binder or binder precursor is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and particularly preferably 100 ° C. or higher.

  As the compound having a crosslinkable or polymerizable functional group as a binder precursor of the antistatic layer in the present invention, an ionizing radiation curable compound is preferable. For example, an ionizing radiation curable polyfunctional monomer or a polyfunctional monomer described later is used. Oligomers are preferred.

  In the method for forming the antistatic layer, the binder of the antistatic layer is formed as a cured product of a compound having a crosslinkable or polymerizable functional group. Further, it is preferable to form the binder of the antistatic layer by curing it by carrying out a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the application of the antistatic layer.

  The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.

  Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Specific examples of the photopolymerizable polyfunctional monomer can be the same as those used for the curable composition in the high (medium) refractive index layer, and preferable monomers are the same. be able to.

  Also, the radical photopolymerization initiator can be the same as that used for the curable composition in the hard coat layer, and the same can be cited as a commercially available radical photopolymerization initiator. it can. The photoradical polymerization initiator is particularly preferably a photocleavable photoradical polymerization initiator, and the same can be mentioned as a commercially available photocleavable photoradical polymerization initiator.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, 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 can include those similar to those used for the curable composition in the hard coat layer, and commercially available photosensitizers can also include the same.

The photopolymerization reaction is preferably performed by ultraviolet irradiation after the antistatic layer is applied and dried.
For ultraviolet irradiation, ultraviolet rays emitted from light rays such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used.

  In the binder that is crosslinked or polymerized in the antistatic layer, the main chain of the polymer preferably has a crosslinked structure or a polymerized structure. Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

The anionic group is preferably bonded to the main chain as a side chain of the binder via a linking group.
The linking group that bonds the anionic group and the main chain of the binder is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof. A crosslinked or polymerized structure chemically bonds (preferably covalently bonds) two or more main chains. The cross-linked structure or polymerized structure is preferably covalently bonded to three or more main chains. The crosslinked structure or polymerized structure may be composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof. preferable.

The binder is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked or polymerized structure.
The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96 mol%, more preferably 4 to 94 mol%, and most preferably 6 to 92 mol%. The repeating unit may have two or more anionic groups.
The proportion of the repeating unit having a crosslinked structure or a polymerized structure in the copolymer is preferably 4 to 98 mol%, more preferably 6 to 96 mol%, and most preferably 8 to 94 mol%. .

  The repeating unit of the binder may have both an anionic group and a crosslinked structure or a polymerized structure. The binder may contain other repeating units (repeating units having neither an anionic group nor a crosslinked or polymerized structure).

  The binder that has been crosslinked or polymerized is preferably prepared by coating a coating solution for forming an antistatic layer on a transparent support and performing crosslinking or polymerization reaction simultaneously with or after coating.

  In the antistatic layer, the conductive material is preferably dispersed as finely as possible, and the mass average particle size is generally in the range of 1 to 200 nm. The mass average particle diameter of the conductive material in the antistatic layer is preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm. By miniaturizing the conductive material to 200 nm or less, an antistatic layer that does not impair the transparency can be produced.

  The content of the conductive material in the antistatic layer is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and particularly preferably 50 to 75% by mass with respect to the mass of the antistatic layer. Two or more kinds of conductive materials may be used in combination in the antistatic layer.

Preferred coating solvents for the antistatic layer include ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, 1,4-dioxane, etc.) ), Alcohols (eg, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.), water and the like. Particularly preferred coating solvents include ketones. , Aromatic hydrocarbons or esters, and most preferred solvents are ketones. Of the ketones, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are particularly preferable.

  The coating solvent may contain other solvents. For example, aliphatic hydrocarbons (eg hexane, cyclohexane etc.), halogenated hydrocarbons (eg methylene chloride, chloroform, carbon tetrachloride etc.), amides (eg dimethylformamide, dimethylacetamide, n-methylpyrrolidone etc.), Ether (for example, diethyl ether, dioxane, tetrahydrofuran, etc.) and ether alcohol (for example, 1-methoxy-2-propanol, etc.) are included.

  As for a coating solvent, it is preferable that content of a ketone solvent is 10 mass% or more of all the solvents contained in a coating liquid. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

  The antistatic layer is preferably formed in an atmosphere having an oxygen concentration of 4% by volume or less, particularly when the antistatic layer is formed by crosslinking or polymerization reaction of an ionizing radiation curable compound. By producing the antistatic layer in an atmosphere having an oxygen concentration of 4% by volume or less, the physical strength (scratch resistance, etc.), chemical resistance and weather resistance of the antistatic layer, as well as the antistatic layer and the antistatic layer, Adhesion between adjacent layers can be improved. Preferably, it is prepared by crosslinking or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 3% by volume or less, more preferably 2% by volume or less, particularly preferably 1% by volume of oxygen. Hereinafter, it is most preferably 0.5% by volume or less.

  As a method of reducing the oxygen concentration to 4% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  The film thickness of the antistatic layer can be appropriately designed depending on the application. When producing an antistatic layer having excellent transparency, the film thickness is preferably 1 μm or less, more preferably 500 nm or less, still more preferably 200 nm or less, and particularly preferably 150 nm or less. Moreover, when an antistatic layer is hard-coated and serves also as a hard-coat layer, 1-10 micrometers is preferable, More preferably, it is 2-7 micrometers, Most preferably, it is 3-5 micrometers.

  The haze of the antistatic layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

  The hardness of the antistatic layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K-5400.

  Moreover, in the Taber test according to JIS K-5400, the smaller the amount of wear of the test piece before and after the test, the better. For this reason, it is also preferable that the antistatic layer is hard-coated.

  In the antistatic layer, in addition to the above components (conductive material, polymerization initiator, photosensitizer, binder, etc.), resin, surfactant, coupling agent, thickener, anti-coloring agent, coloring agent (pigment) Dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, infrared absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like.

(Interference spot prevention layer)
When there is a refractive index difference of 0.03 or more between the transparent support and the antiglare layer (or hard coat layer), interference spots (also called interference fringes, rainbow unevenness, etc.) are observed under a three-wavelength fluorescent lamp. There is a case. Such interference spots are formed by forming an interference spot prevention layer having an intermediate refractive index and an optical film thickness of about 546 nm × 1/4 between the transparent support and the antiglare layer (or hard coat layer). The interface reflection between the transparent support and the antiglare layer (or hard coat layer) can be reduced by the principle of thin film interference. Such an interference spot preventing layer is described in detail in JP-A-2004-34533, and such an interference spot preventing layer can also be used in the present invention.

<Antireflection film>
(Transparent support)
The antireflection film of the present invention is produced by forming each layer including an optical functional layer on a transparent support. The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7.

  The transparent support is preferably a plastic film rather than a glass plate. Examples of plastic film materials include cellulose esters, polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4, 4′-dicarboxylate, polybutylene terephthalate, etc.), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, polypropylene, polyethylene, polymethylpentene, etc.), polysulfone, polyethersulfone, polyarylate, polyetherimide, poly Methyl methacrylate and polyether ketone are included. Cellulose ester, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

[Cellulose acylate film]
In particular, when the antireflection film of the present invention is used in a liquid crystal display device, a cellulose acylate film is preferable. Cellulose acylate is produced by esterifying cellulose. As the cellulose before esterification, linter, kenaf and pulp are used after purification.

(Cellulose acylate)
In the present invention, cellulose acylate means a fatty acid ester of cellulose, and a lower fatty acid ester is particularly preferable. Furthermore, a fatty acid ester film of cellulose is preferable.

  Lower fatty acid means a fatty acid having 6 or less carbon atoms. A cellulose acylate having 2 to 4 carbon atoms is preferred. Cellulose acetate is particularly preferred. It is also preferable to use mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate.

  The viscosity average degree of polymerization (Dp) of cellulose acylate is preferably 250 or more, and more preferably 290 or more. Cellulose acylate preferably has a narrow molecular weight distribution based on Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. A specific value of Mw / Mn is preferably 1.0 to 5.0. More preferably, it is 1.0-3.0, Most preferably, it is 1.0-2.0.

As the transparent support, it is preferable to use cellulose acylate having an acetylation degree of 55.0 to 62.5%. The acetylation degree is more preferably 57.0 to 62.0%, and particularly preferably 59.0 to 61.5%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation is determined by measurement and calculation of the degree of acylation in ASTM: D-817-91 (testing method for cellulose acylate, etc.).

  In cellulose acylate, the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are not evenly substituted, but the substitution degree at the 6-position tends to be small. In the cellulose acylate used in the present invention, it is preferable that the degree of substitution at the 6-position of cellulose is the same or greater than that at the 2- and 3-positions. The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-position, the 3-position, and the 6-position is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to 40%. Most preferably it is.

Various additives are added to the transparent support to adjust the mechanical properties (film strength, curl, dimensional stability, slipperiness, etc.) and durability (wet heat resistance, weather resistance, etc.) of the film. Can be used. For example, plasticizers (phosphate esters, phthalate esters, esters of polyols and fatty acids, etc.), UV inhibitors (eg, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds) Etc.), deterioration inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines, etc.), fine particles (eg, SiO ₂ , Al ₂ O ₃ , TiO _2). , BaSO ₄ , CaCO ₃ , MgCO ₃ , talc, kaolin, etc.), release agents, antistatic agents, infrared absorbers, and the like.

  These details are disclosed in the Invention Association Public Technique No. 2001-1745 (issued March 15, 2001, Invention Association), p. Materials described in detail in 17-22 are preferably used.

  The amount of these additives used is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.

[Surface treatment]
Surface treatment may be performed on the transparent support.
Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Specifically, for example, Invention Association Public Technique No. 2001-1745 (issued March 15, 2001) p. The content described in 30-31, the content described in JP 2001-9973 A, and the like can be given. Preferably, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment, and more preferably glow discharge treatment and ultraviolet treatment.

[Method of forming antireflection film]
The method for forming the antireflection film of the present invention will be described.
Each layer of the antireflection film can be formed by coating using a coating method such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, or a gravure coating method. it can. Of these coating methods, a gravure coating method is preferable because a coating solution with a small coating amount such as each layer of the antireflection film can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method has a high film thickness uniformity and is more preferable. In addition, a coating solution with a small coating amount can be applied with high film thickness uniformity even by using a die coating method. Further, since the die coating method is a pre-weighing method, the film thickness can be controlled relatively easily, and the solvent in the coating part can be controlled. Is preferred because of less transpiration. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,789, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

  The order of forming each layer is usually as follows. First, a coating solution for forming a hard coat layer is coated on a transparent support, and then heated and dried. Thereafter, the monomer for forming the hard coat layer is polymerized and cured by light irradiation or heating. Thereby, a hard coat layer is formed. Next, a coating solution for forming a medium refractive index layer and a high refractive index layer or a low refractive index layer is applied on the hard coat layer in the same manner, and the medium refractive index layer and the high refractive index layer are irradiated with light or heated. Alternatively, a low refractive index layer is formed. In the formation of the antireflection film of the present invention, it is preferable that curing by light irradiation (so-called ionizing radiation irradiation) and curing by heating are used in combination when forming the same layer (especially a low refractive index layer).

  About thermosetting and curing by light irradiation, as described in International Publication No. 03 / 27189A pamphlet etc., heat curing may be carried out after curing by light irradiation, but the order may be any , Each may be divided into a plurality of times. It is particularly preferable to cure by light irradiation after heat curing.

  In the formation of each layer other than the low refractive index layer of the antireflection film of the present invention, the ionizing radiation curable compound is preferably subjected to a crosslinking reaction or a polymerization reaction in an atmosphere having an oxygen concentration of 10% by volume or less. By forming each layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, weather resistance of each layer, and adhesion between the high refractive index layer and the layer adjacent to the high refractive index layer can be obtained. It can be improved. Preferably, it is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration. 2% by volume or less, most preferably 1% by volume or less.

  In the antireflection film of the present invention, the crosslinking reaction or polymerization reaction of the ionizing radiation curable compound of the low refractive index layer is preferably carried out in an atmosphere having an oxygen concentration of 1% by volume or more. The oxygen concentration is more preferably 3% by volume or more, further preferably 10% by volume or more, and particularly preferably an oxygen concentration equivalent to atmospheric pressure without control for lowering the oxygen concentration. Generally, in order to lower the oxygen concentration in the process of continuously curing the low refractive index layer with Roll To Roll, the inert gas such as nitrogen must be blown into the ionizing radiation irradiation zone to continue to consume the inert gas. I must. This is because the amount of inert gas consumed can be reduced as the concentration of oxygen to be controlled is closer to that of atmospheric pressure.

  The film transport speed during continuous production with Roll To Roll is preferably 10 m / min or more, more preferably 20 m / min or more, and particularly preferably 30 m / min or more. This is because as the film conveyance speed increases, heat treatment requires a longer heat treatment zone, and in photo radical polymerization, the consumption per unit area increases, and in any case, the production cost increases.

<Polarizing plate>
The preferable polarizing plate of this invention has the antireflection film of this invention as at least one protective film (protective film for polarizing plates) of a polarizing film. As described above, the polarizing plate protective film has a contact angle with water of 10 ° on the surface of the transparent support opposite to the side having the antiglare layer or antireflection layer, that is, the surface to be bonded to the polarizing film. It is preferably in the range of ˜50 °.

By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having physical strength and an antireflection function can be produced, and the cost can be greatly reduced and the display device can be thinned. In addition, by using an antireflection film having a light scattering function as a protective film for a polarizing plate, or by laminating a light scattering film on an antireflection film, light with excellent light resistance as well as physical strength and an antireflection function is used. A polarizing plate having a scattering function can also be manufactured.

  Further, by preparing a polarizing plate using the antireflection film of the present invention as one of the protective films for polarizing plates and an optical compensation film having optical anisotropy described later as the other protective film of the polarizing film, In addition, it is possible to improve the visibility and contrast in a bright room of a liquid crystal display device and to produce a polarizing plate that can greatly widen the vertical and horizontal viewing angles.

[Optical compensation layer]
By providing the polarizing plate with an optical compensation layer (retardation layer), the viewing angle characteristics of the liquid crystal display screen can be improved.

  As the optical compensation layer, a known layer can be used. However, in terms of widening the viewing angle, the optical compensation layer has a layer having optical anisotropy made of a compound having a discotic structural unit, and is transparent to the discotic compound. An optical compensation layer characterized in that the angle formed with the support varies with the distance from the transparent support. The angle preferably increases as the distance from the transparent support surface side of the optically anisotropic layer made of the discotic compound increases.

  When the optical compensation layer is used as a protective film for a polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

[Polarizing film]
A known polarizing film may be used as the polarizing film, but a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.

  That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

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

<Image display device>
The image display device of the present invention is characterized in that at least one of the above-described antireflection film and polarizing plate (polarizing plate with antireflection ability) is disposed on the image display surface. The antireflection film and polarizing plate of the present invention can be applied to image display devices such as liquid crystal display devices (LCD) and organic EL displays. The image display device of the present invention is preferably applied to a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, and OCB modes. This will be further described below.

[Liquid Crystal Display]
Any conventionally known liquid crystal display device can be used. For example, supervised by Tatsuo Uchida, “Reflective color LCD integrated technology” {CMC, published in 1999}, “New development of flat panel display” {Research Division, Toray Research Center, published in 1996}, “Liquid crystal related market” And the future prospects (first volume), (second volume) "{Fuji Chimera Research Institute, Inc., published in 2003}, and the like.

  Specifically, for example, a transmissive type or a reflective type such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), etc. It can be preferably used for a liquid crystal display device of a type or a transflective type.

  In addition, the polarizing plate of the present invention realizes a good contrast and a wide viewing angle even when the size of the attached liquid crystal display device display image is 17 inches or more, and prevents hue change and transfer of external light. This is preferable because it has good durability.

[TN mode liquid crystal display]
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and many literatures are cited. The alignment state in the liquid crystal cell in the T mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

[OCB mode liquid crystal display]
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystal molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. Since the liquid crystal display device using the bend alignment mode liquid crystal cell is aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the devices disclosed in the specifications of US Pat. Nos. 4,583,825 and 5,410,422 are provided. 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.

  Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal molecules rise in the center of the cell and the rod-like liquid crystal molecules lie in the vicinity of the cell substrate. .

[VA mode liquid crystal display]
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

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) VA mode liquid crystal cell (SID97, “Digest of Tech. Papers” (preliminary report) 28 (1997) 845 described)]
(3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied. ) Description] and
(4) SURVAVAL mode liquid crystal cell (announced at LCD International 98).

[IPS mode liquid crystal display]
In the IPS mode liquid crystal cell, liquid crystal molecules are always rotated in a horizontal plane with respect to the substrate, and are aligned so as to have a slight angle with respect to the longitudinal direction of the electrode when no electric field is applied. When an electric field is applied, the liquid crystal molecules change direction in the direction of the electric field. The light transmittance can be changed by arranging the polarizing plates sandwiching the liquid crystal cell at a predetermined angle.

  As the liquid crystal molecules, nematic liquid crystal having a positive dielectric anisotropy Δε is used. The thickness (gap) of the liquid crystal layer is more than 2.8 μm and less than 4.5 μm. This is because when the retardation Δn · d is more than 0.25 μm and less than 0.32 μm, a transmittance characteristic having almost no wavelength dependency within the visible light range can be obtained. By combining the polarizing plates, the maximum transmittance can be obtained when the liquid crystal molecules are rotated 45 ° from the rubbing direction to the electric field direction. The thickness (gap) of the liquid crystal layer is controlled by polymer beads. Of course, the same gap can be obtained with glass beads, fibers, and resin columnar spacers. The liquid crystal molecules are not particularly limited as long as they are nematic liquid crystals. When the value of the dielectric anisotropy Δε is large, the driving voltage can be reduced, and when the refractive index anisotropy Δn is small, the thickness (gap) of the liquid crystal layer can be increased, the liquid crystal sealing time is shortened, and the gap Variation can be reduced.

[Other LCD mode]
For the ECB mode and STN mode liquid crystal display devices, the polarizing plate of the present invention can be provided in the same manner as described above.

[Formation of liquid crystal display device]
The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device generally includes a liquid crystal cell, an optical film such as an antireflection film or an optical compensation film, a polarizing plate, and a drive circuit by appropriately combining components such as an illumination system as necessary. It is formed. In this invention, there is no limitation in particular except the point which uses the antireflection film or polarizing plate by this invention, and it can apply according to the former.

  In forming the liquid crystal display device, for example, appropriate components such as a prism array, a lens array sheet, a light scattering plate, a light guide plate, and a backlight can be arranged in one or more layers at appropriate positions. Further, by combining with a λ / 4 plate, it can be used to reduce the reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass. Moreover, the following Examples 1-7 to 1-10 and 1-17 shall be read as reference examples.

Example 1
<Curable composition>
Synthesis Example 1 {Synthesis of Perfluoroolefin Copolymer (1)}
Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of a 1: 1 copolymer of hexafluoropropylene and hydroxyethyl vinyl ether was obtained. The obtained polymer had a refractive index of 1.406. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 4.6 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 15 g of a fluorinated copolymer (P-1). The number average molecular weight of the obtained polymer was 29,000, and the refractive index was 1.415.

Synthesis Example 2 {Synthesis of Perfluoroolefin Copolymer (2)}
A 100 ml stainless steel autoclave with a stirrer (made by pressure-resistant glass industry) was charged with 25 ml of ethyl acetate, 2.07 g of ethyl vinyl ether, 5.61 g of 2-glycidyloxyethyl vinyl ether, and 0.23 g of dilauroyl peroxide. The inside was deaerated and replaced with nitrogen gas. Further, 10.77 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.1 kg / cm ² . The temperature was maintained and stirring was continued for 8 hours. When the pressure reached 2.8 kg / cm ² , heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. After concentration, the polymer was dissolved in a small amount of ethyl acetate and reprecipitated with n-hexane. The obtained polymer was further reprecipitated twice with n-hexane to completely remove the residual monomer. The polymer was dried under reduced pressure to obtain 13 g of a fluorinated copolymer P-28. The number average molecular weight of the obtained polymer was 31,000, and the refractive index was 1.407.

[Preparation of Sol Solution a]
Stirrer, reactor equipped with reflux condenser, methyl ethyl ketone 120 parts, acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} 100 parts, diisopropoxyaluminum ethyl acetoacetate “Kelope EP-12 After adding 3 parts of {Hope Pharmaceutical Co., Ltd.} and mixing, 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 concentration was 29%.

[Preparation of Sol Solution b]
Sol solution a except that acryloyloxypropyltrimethoxysilane “KBM-5103” {manufactured by Shin-Etsu Chemical Co., Ltd.} is changed to glycidoxypropyltrimethoxysilane “KBM-403” {manufactured by Shin-Etsu Chemical Co., Ltd.} Sol solution b was obtained in the same manner as in the preparation.

[Preparation of coating liquids for hard coat layer (HCL-1) to (HCL-5)]
{Composition of coating liquid for hard coat layer (HCL-1)}
102 parts of zirconia fine particle-containing hard coat composition “Desolite Z7404” {particle size 20 nm: manufactured by JSR Corporation}
29 parts of UV curable resin “DPHA” {Nippon Kayaku Co., Ltd.}
Silane coupling agent 10 parts "KBM-5103" {Shin-Etsu Chemical Co., Ltd.}
Silica particles 8.9 parts “KE-P150” {1.5 μm: manufactured by Nippon Shokubai Co., Ltd.}
Crosslinked PMMA particles 3.4 parts “MXS-300” {3 μm: manufactured by Soken Chemical Co., Ltd.}
Methyl ethyl ketone (MEK) 29 parts Methyl isobutyl ketone (MIBK) 13 parts

{Composition of coating liquid for hard coat layer (HCL-2)}
740.0 parts of trimethylolpropane triacrylate “TMPTA” {manufactured by Nippon Kayaku Co., Ltd.}
280.0 parts of poly (glycidyl methacrylate) (mass average molecular weight 15000)
MEK 730.0 parts Cyclohexanone 500.0 parts Photopolymerization initiator “Irgacure 184” 50.0 parts {Ciba Specialty Chemicals Co., Ltd.}
Photocationic polymerization initiator “Lordsil 2074” 25.0 parts {manufactured by Rhodia}

{Composition of coating liquid for hard coat layer (HCL-3)}
UV curable resin 500.0 parts "PETA" {Nippon Kayaku Co., Ltd.}
“Irgacure 184” 20.0 parts Cross-linked polystyrene particle toluene dispersion (30%) 17.0 parts Cross-linked acrylic-styrene particle toluene dispersion (30%) 133.0 parts FP-1 0.3 part KBM-5103 100. 0 parts Toluene 385.0 parts

{Composition of coating liquid for hard coat layer (HCL-4)}
Silica fine particle-containing hard coat composition 272.0 parts "Desolite 7526" solvent composition modified product {manufactured by JSR Corporation}
3.5μ crosslinked polystyrene particle MIBK dispersion (25%) 44.0 parts 5.0μ crosslinked polystyrene particle MIBK dispersion (25%) 57.8 parts Methyl isobutyl ketone 26.2 parts Methyl ethyl ketone 48.0 parts

{Composition of coating liquid for hard coat layer (HCL-5)}
Silica fine particle-containing hard coat composition solution 245.0 parts "Desolite 7526" solvent composition modified product {manufactured by JSR Corporation}
Sol liquid b 67.6 parts 3.5μ crosslinked polystyrene particle MIBK dispersion (25%) 44.0 parts 5.0μ crosslinked polystyrene particle MIBK dispersion (25%) 57.8 parts Methyl isobutyl ketone 26.2 parts

  The coating liquids (HCL-1) and (HCL-3) to (HCL-3) are filtered through a polypropylene filter having a pore diameter of 30 μm, and (HCL-2) is a 0.4 μm pore diameter. Prepared.

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

[Preparation of Medium Refractive Index Layer Coating Solution (MLL-1)]
The following composition was sufficiently stirred and then filtered through a polypropylene filter having a pore size of 0.4 μm.

{Composition of Medium Refractive Index Layer Coating Solution (MLL-1)}
Titanium dioxide dispersion 99.1 parts UV curable resin “DPHA” 68.0 parts {Nippon Kayaku Co., Ltd.}
Photopolymerization initiator “Irgacure 907” 3.6 parts {manufactured by Ciba Specialty Chemicals Co., Ltd.}
Photosensitizer “Kayacure DETX” 1.2 parts {Nippon Kayaku Co., Ltd.}
MEK 279.6 parts Cyclohexanone 1049.0 parts

[Preparation of coating liquids for high refractive index layer (HLL-1) to (HLL-2)]
The following composition was sufficiently stirred and then filtered through a polypropylene filter having a pore size of 0.4 μm.

{Composition of coating solution for high refractive index layer (HLL-1)}
Titanium dioxide dispersion 469.8 parts UV curable resin “DPHA” 40.0 parts {manufactured by Nippon Kayaku Co., Ltd.}
Photopolymerization initiator “Irgacure 907” 3.3 parts {Ciba Specialty Chemicals Co., Ltd.}
Photosensitizer “Kayacure DETX” 1.1 parts {Nippon Kayaku Co., Ltd.}
MEK 526.2 parts Cyclohexanone 459.6 parts

{Composition of coating solution for high refractive index layer (HLL-2)}
Titanium dioxide dispersion 469.8 parts UV curable resin “DPHA” 36.0 parts {manufactured by Nippon Kayaku Co., Ltd.}
Sol liquid a 13.8 parts Photopolymerization initiator “Irgacure 907” 3.3 parts {Ciba Specialty Chemicals Co., Ltd.}
Photosensitizer “Kayacure DETX” 1.1 parts {Nippon Kayaku Co., Ltd.}
MEK 520.6 parts Cyclohexanone 459.6 parts

[Preparation of Coating Solutions for Low Refractive Index Layers (LLL-1) to (LLL-8)]
Each of the following compositions was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for each low refractive index layer.

{Composition of coating solution for low refractive index layer (LLL-1)}
Perfluoroolefin copolymer (2) 47.0 parts “MEK-ST” 160.0 parts Reactive silicone “X22-169AS” 1.4 parts {manufactured by Shin-Etsu Chemical Co., Ltd.}
Sol liquid b 53.0 parts Photocationic polymerization initiator “Lordsil 2074” 2.4 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1240.0 parts

{Composition of coating solution for low refractive index layer (LLL-2)}
Perfluoroolefin copolymer (2) 62.4 parts “MEK-ST-L” 160.0 parts Photocationic polymerization initiator “Lordsil 2074” 3.1 parts {manufactured by Rhodia)
Cyclohexanone 156.0 parts MEK 1277.5 parts

{Composition of coating liquid for low refractive index layer (LLL-3)}
Perfluoroolefin copolymer (2) 62.4 parts “MEK-ST-L” 160.0 parts Reactive silicone “X22-169AS” 1.4 parts {manufactured by Shin-Etsu Chemical Co., Ltd.}
Photocationic polymerization initiator “Lordsil 2074” 3.1 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1277.5 parts

{Composition of coating solution for low refractive index layer (LLL-4)}
Perfluoroolefin copolymer (2) 47.0 parts “MEK-ST-L” 160.0 parts Reactive silicone “X22-169AS” 1.4 parts {manufactured by Shin-Etsu Chemical Co., Ltd.}
Sol liquid b 53.0 parts Photocationic polymerization initiator “Lordsil 2074” 2.4 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1240.0 parts

{Composition of coating solution for low refractive index layer (LLL-5)}
Perfluoroolefin copolymer (1) 47.0 parts "Hollow silica A" (20.0%) 195.0 parts "MEK-ST-L" 30.0 parts Reactive silicone "X22-164C" 1.4 Department {manufactured by Shin-Etsu Chemical Co., Ltd.}
Sol liquid a 12.65 parts “Irgacure 907” 2.4 parts Cyclohexanone 156.0 parts MEK 1223.0 parts

{Composition of coating solution for low refractive index layer (LLL-6)}
Perfluoroolefin copolymer (2) 47.0 parts "Hollow silica B" (20.0%) 195.0 parts "MEK-ST-L" 30.0 parts Reactive silicone "X22-169AS 1.4 parts {Shin-Etsu Chemical Co., Ltd.}
Sol liquid b 12.65 parts Photocationic polymerization initiator "Lordsil 2074" 2.4 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1223.0 parts

{Composition of coating solution for low refractive index layer (LLL-7)}
Perfluoroolefin copolymer (2) 37.6 parts Curing agent A-14 9.4 parts (3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate)
"Hollow silica B" (20.0%) 195.0 parts "MEK-ST-L" 30.0 parts Reactive silicone "X22-169AS 1.4 parts {manufactured by Shin-Etsu Chemical Co., Ltd.}
Sol liquid b 12.65 parts Photocationic polymerization initiator "Lordsil 2074" 2.4 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1223.0 parts

{Composition of coating solution for low refractive index layer (LLL-8)}
Perfluoroolefin copolymer (2) 47.0 parts “Porous silica dispersion” (30%) 160.0 parts Reactive silicone “X22-169AS” 1.4 parts {manufactured by Shin-Etsu Chemical Co., Ltd.}
Sol liquid b 53.0 parts Photocationic polymerization initiator “Lordsil 2074” 2.4 parts {manufactured by Rhodia}
Cyclohexanone 156.0 parts MEK 1240.0 parts

[Preparation of Coating Solutions for Low Refractive Index Layer (LLL-9) to (LLL-12)]
Except for changing the photocationic polymerization initiator “Lordsil 2074” of the coating solutions LLL-1, LLL-3, LLL-6 and LLL-7 for the low refractive index layer to “UVI-6990” (manufactured by Union Carbide). Similarly, LLL-9 to LLL-12 were prepared.

[Preparation of coating solutions for low refractive index layer (LLL-13) to (LLL-16)]
Low-refractive index layer coating liquids LLL-1, LLL-3, LLL-6, and LLL-7 photocationic polymerization initiator “Lordyl 2074” were converted to 2- {4- (4-hydroxybenzoylamino) phenyl} -4, LLL-13 to LLL-16 were prepared in exactly the same manner except that 6-bis (trichloromethyl) -s-triazine was used.

The compounds used for the compositions of the coating solutions for the low refractive index layers are shown below.
・ "Irgacure 184": radical photopolymerization initiator {Ciba Specialty Chemicals Co., Ltd.}
・ "Irgacure 907": Photoradical polymerization initiator {Ciba Specialty Chemicals Co., Ltd.}
・ "Lordsil 2074": Photocationic polymerization initiator {manufactured by Rhodia)
"UVI-6990": Photocationic polymerization initiator {manufactured by Union Carbide Corporation}
-“Crosslinked polystyrene particle toluene dispersion (30%)”: 30% by mass toluene of SX-350H (trade name: average particle size 3.5 μm crosslinked polystyrene particles {refractive index 1.60, manufactured by Soken Chemicals Co., Ltd.}) Dispersion. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
-“Crosslinked acrylic-styrene particle toluene dispersion (30%)”: SX-350HL (trade name: average particle size 3.5 μm {refractive index 1.55, manufactured by Soken Chemical Co., Ltd.}) 30% by mass toluene dispersion . Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
-"3.5 micron crosslinked polystyrene particles MIBK dispersion (25%)": SX-350H (trade name: average particle size 3.5 micron crosslinked polystyrene particles {refractive index 1.60, manufactured by Soken Chemicals Co., Ltd.}) 25 Mass% methyl isobutyl ketone dispersion. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
-“5.0 μ cross-linked polystyrene particles MIBK dispersion (25%)”: 25 of SX-500H (trade name: cross-linked polystyrene particles having an average particle diameter of 5.0 μm {refractive index 1.60, manufactured by Soken Chemical Co., Ltd.}) Mass% methyl isobutyl ketone dispersion. Used after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser.
・ "FP-1": Fluorine surface modifier

  "KBM-5103": Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.).

"" Desolite 7526 "solvent composition modified product": silica-containing hard coat liquid UV curable hard coat liquid "Desolite 7526 (trade name, manufactured by JSR Corporation) solvent composition modified product, solid content concentration of about 72%, Silica fine particle content 38% in solid content, polymerization monomer, polymerization initiator included.
"JTA113": "OPSTAR JTA113 (trade name)", heat-crosslinkable fluorine-containing polymer {refractive index 1.44, solid content concentration 6%, manufactured by JSR Corporation}
"DPHA": a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate {Nippon Kayaku Co., Ltd.}
"PETA": mixture of pentaerythritol triacrylate and dipentaerythritol tetraacrylate {manufactured by Nippon Kayaku Co., Ltd.}
Curing agent A-14: JP-A-2004-354740 [0069] “Compound described in publication A-14 (3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate)
"MEK-ST": silica sol {silica, average particle size 15 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.}
"MEK-ST-L": silica sol {silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.}
"Hollow silica A": hollow silica sol surface-modified with "KBM-5103" {surface modification ratio versus hollow silica ( after preparing hollow silica particles according to Preparation Example 4 of JP-A-2002-79616 , KBM- 5103 ; average particle diameter of about 40 nm, shell thickness of about 7 nm, refractive index of silica particles 1.31), solid content concentration of 26% by mass, of which the solid content concentration attributable to silica particles is 20 The solid content concentration resulting from mass% and the surface modifier is 6 mass%. The solvent is MEK. }
"Hollow silica B": Hollow silica B was obtained in the same manner as in the production of "hollow silica A" except that "KBM-5103" was changed to "KBM-403" with respect to "hollow silica A".
"Porous silica dispersion" (30%): Porous silica fine particles (Nipsil SS50F: trade name, manufactured by Nippon Silica Kogyo Co., Ltd., primary particle diameter 20 nm, refractive index 1.38, specific surface area 82 m ² / g) The average particle size was dispersed in MEK so that the solid content concentration was 30% by mass.
"X22-164C": methacryl-modified polydimethylsiloxane at both ends (manufactured by Shin-Etsu Chemical Co., Ltd.)
"X22-169AS": both ends epoxy cyclohexyl modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Preparation of antireflection film>
Example 1-1
[Coating of hard coat layer (HC-1)]
As a support, a triacetyl cellulose film “TD80U” {manufactured by Fuji Photo Film Co., Ltd.} is unrolled in a roll form, and the hard coat layer coating solution (HCL-1) is directly applied to the number of lines of 135 / inch. Using a gravure pattern with a depth of 60 μm and a micro gravure roll with a diameter of 50 mm and a doctor blade, it was applied at a conveyance speed of 10 m / min, dried at 60 ° C. for 150 seconds, and then an oxygen concentration of 1.0 vol% or less Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, an ultraviolet ray having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² was irradiated to form a coating layer. It hardened | cured, the hard-coat layer (HC-1) was formed, and it wound up. After curing, the gravure roll rotation speed was adjusted so that the thickness of the hard coat layer was 3.6 μm.

[Coating of low refractive index layer (LL-6)]
The triacetyl cellulose film coated with the hard coat layer (HC-1) was rewound again, and the low refractive index layer coating solution (LLL-6) was gravure with a line number of 180 lines / inch and a depth of 40 μm. Using a micro gravure roll having a diameter of 50 mm and a doctor blade having a pattern, coating was performed under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, pre-drying at 120 ° C. for 150 seconds, and then irradiation of 400 mW / cm ² . An ultraviolet ray having an amount of 900 mJ / cm ² was irradiated to form a low refractive index layer (LL-6) having a thickness of 100 nm and wound up to prepare an antireflection film sample (101). The oxygen concentration in the ultraviolet irradiation atmosphere was 20% by volume.

Examples 1-2 to 1-21 and Comparative Examples 1-1 to 1-5
With respect to Example 1-1, the hard coat layer coating solution and the low refractive index layer coating solution were changed to produce antireflection film samples (102) to (126) having the configurations shown in Table 1. Here, in order to form the hard coat layers (HC-2) to (HC-4), the hard coat layer coating liquid (HCL-1) of Example 1-1 was used as (HCL-2) to (HCL). -4) and the low refractive index layers (LL-1) to (LL-5) or (LL-6) to (LL-16) can be formed by the low refractive index of Example 1-1. The rate layer coating solution (LLL-6) may be changed to (LLL-1) to (LLL-5) or (LLL-7) to (LLL-16).

[Coating of medium refractive index layer (ML-1)]
The triacetyl cellulose film coated with the hard coat layer (HC-2) produced by the same method as in Example 1-2 was unwound again, and the medium refractive index layer coating solution (MLL-1) was Using a gravure pattern having a gravure pattern of several 180 pieces / inch and a depth of 40 μm and a micro gravure roll having a diameter of 50 mm and a doctor blade, the coating was carried out under conditions of a conveyance speed of 15 m / min. Drying conditions were 90 ° C. and 30 seconds, and UV curing conditions were as follows: a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration was 1.0 vol% or less. The irradiance was 400 mW / cm ² and the irradiation amount was 400 mJ / cm ² . A medium refractive index layer (ML-1) was formed and wound up while adjusting the rotation speed of the gravure roll so that the thickness after application was 67 nm. The refractive index of the medium refractive index layer after curing was 1.630.

[Coating of high refractive index layer (HL-1)]
The triacetyl cellulose film coated up to the middle refractive index layer (ML-1) is unwound again, and the high refractive index layer coating liquid (HLL-1) is a gravure with 180 lines / inch and a depth of 40 μm. Using a microgravure roll having a diameter of 50 mm and a doctor blade having a pattern, the coating was performed under the condition of a conveyance speed of 15 m / min. Drying conditions were 90 ° C. and 30 seconds, and ultraviolet curing conditions were 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0 volume% or less. The irradiance was 600 mW / cm ² and the irradiation amount was 400 mJ / cm ² . The high refractive index layer (HL-1) or (HL-2) was formed and wound up while adjusting the rotation speed of the gravure roll so that the thickness after coating was 107 nm. The refractive index of the high refractive index layer after curing was 1.905.

[Coating of low refractive index layer (LL-6)]
The triacetyl cellulose film coated up to the high refractive index layer (HL-1) is rewound again, and the low refractive index layer coating liquid (LLL-6) is 180 lines / inch and the depth is 40 μm. Using a micro gravure roll having a gravure pattern with a diameter of 50 mm and a doctor blade, coating was performed at a conveyance speed of 15 m / min, pre-drying at 120 ° C. for 150 seconds, 400 mW / cm ² , and irradiation amount 900 mJ / cm ^2. Was applied to form a low refractive index layer (LL-6) having a thickness of 85 nm and wound up to prepare an antireflection film sample (120).

Examples 1-22 to 1-25 and Comparative Examples 1-6 to 1-7
Antireflective film samples (127) to (132) were prepared by changing the high refractive index coating liquid and the low refractive index layer coating liquid according to Table 1 with respect to Example 1-16. Here, in order to form the high refractive index layer (HL-2), the coating liquid for high refractive index layer (HLL-1) in Example 1-22 may be changed to (HLL-2). In order to form the refractive index layers (LL-2), (LL-5), (LL-11), and (LL-15), the coating solution for low refractive index layer (LLL-6) of Example 1-22 May be changed to (LLL-2), (LLL-5), (LLL-11), and (LLL-15), respectively.

[Saponification treatment of antireflection film]
After the production of the antireflection film samples, the following treatments were performed on these antireflection film samples.
A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in this aqueous sodium hydroxide solution for 2 minutes and then immersed in water to thoroughly wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

[Evaluation of antireflection film]
The following items were evaluated for the film samples obtained after the above saponification treatment. In addition, the evaluation of the surface condition showed the level of failure as a result of the surface inspection carried out by visually observing the application area of 10 m ² from the application part.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance of each antireflection film sample at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The average reflectance of 450-650 nm was used for the result.

(2) Steel Wool (SW) Scratch Resistance Evaluation A rubbing test was performed on the antireflection film sample using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH.
Rubbing material: Steel wool {manufactured by Nippon Steel Wool Co., Ltd., “Grade No. 0000”} was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Movement distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² . Tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.

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.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

(3) Eraser rubbing resistance An antireflection film sample is fixed on a glass surface with an adhesive, and an eraser hollowed to a diameter of 8 mm and a thickness of 4 mm, “MONO” (trade name) {manufactured by Dragonfly Pencil Co., Ltd.} is rubbed. As a machine head, after pressing vertically onto the surface of the antireflection film sample with a load of 500 g / cm ² , the stroke length was 3.5 cm and the rubbing speed was 1.8 cm / sec under the conditions of 25 ° C. and 60 RH%. After rubbed 200 times, after removing the attached eraser, the rubbing part of the sample was visually confirmed, this test was repeated three times, and the average degree of surface damage was evaluated in the following four stages.
○: Scratches are hardly recognized.
Δ: Slight scratches are observed.
X: Scratches are clearly recognized.
XX: Scratches are recognized on the entire surface after rubbing.

(4) Magic wiping property An anti-reflective film sample was fixed on the glass surface with an adhesive, and a black magic “Mackey Extra Fine (trade name: manufactured by Zebra Corporation)” nib (fine) under the condition of 25 ° C. and 60 RH%. ), 3 rounds of a 5 mm diameter circle are written, and after 5 seconds, 20 cycles of wiping are performed with a load that dents the bundle of Bencot (Brand name, manufactured by Asahi Kasei Co., Ltd.). The above writing and wiping were repeated under the above conditions until the magic mark did not disappear by wiping, and the number of times of wiping was determined. The above test was repeated 4 times, and the following 4 grades were evaluated on average.
○: Can be wiped 10 times or more.
Δ: Can be wiped off several times to less than 10 times.
×: Can be wiped off only once.
XX: Can not be wiped once.

  * The evaluation of curing in the table is x when the surface of the antireflective film after curing is touched with a hand wearing rubber gloves and X when it is not sticky.

From the results shown in Table 2, the following is clear.
The present invention in which the low refractive index layer was formed of a cationic polymerizable composition was sufficiently cured even when ultraviolet irradiation was performed under atmospheric pressure without performing a nitrogen purge. (All other samples for samples 122 and 132, especially 111 for sample 122 and 127 for sample 132).
By introducing the organosilane compound of the present invention into a layer adjacent to the low refractive index layer, the scratch resistance of the antireflection film caused by rubbing with steel wool can be improved. (124 for sample 123, 128 for sample 127)

<Preparation of polarizing plate>
Examples 11-1 and 11-2
Next, the antireflective film samples 111 and 128 of Example 1 of the present invention were each immersed in an aqueous solution of NaOH at 1.5 mol / L and 55 ° C. for 2 minutes, neutralized and washed with water, and triacetyl having a thickness of 80 μm. Cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is adsorbed with iodine on polyvinyl alcohol, and stretched and bonded to both sides of a polarizer. Each polarizing plate was produced. Using this polarizing plate, a liquid crystal display device having an antireflection layer disposed on the outermost layer was produced. As a result, the reflectance was low, the reflection of external light was small, the reflected image was not noticeable, and excellent visibility was obtained. It was. Moreover, it was excellent also in the antifouling property which becomes a problem in an actual use form.

Examples 21-1 and 21-2
A triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a thickness of 1.5 μm / L, immersed in an aqueous NaOH solution at 55 ° C. for 2 minutes, neutralized and washed with water. A polarizing plate was prepared by adhering and protecting the antireflection film sample 112 or 130 of Example 1 on both surfaces of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol and stretching it. The thus-prepared polarizing plate is a liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device so that the antireflection film side is the outermost surface {Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer] When "D-BEF" made by the company is replaced with the polarizing plate on the viewing side of "D-BEF" between the backlight and the liquid crystal cell, both have low reflectivity, very little background reflection, and very high display quality. A display device which is high and excellent in antifouling property was obtained.

<Liquid crystal display device>
Examples 31-1 and 31-2
The antireflection film sample 111 or 128 of the present invention of Example 1 was used as a viewing-side protective film for two protective films sandwiching the polarizer of the viewing-side polarizing plate of a transmissive TN liquid crystal display device. Further, instead of the protective film facing the liquid crystal cell of the polarizing plate on the viewing side and the polarizing plate on the backlight side of the liquid crystal display device, the viewing angle widening film “wide view film SA12B” having an optical compensation layer on the TAC support { Fuji Photo Film Co., Ltd.} was used. SA12B was used by attaching the support surface to a polarizer. By adopting this configuration, all have low reflectivity, very little background reflection, excellent contrast in a bright room, very wide viewing angles in the vertical and horizontal directions, extremely excellent visibility, and display quality. A liquid crystal display device having high antifouling properties was obtained.

Example 41-1
When the antireflection film sample 111 of the present invention of Example 1 was bonded to a glass plate on the surface of an organic EL display device via an adhesive, reflection on the glass surface was suppressed, visibility was high, and magic wipeability was achieved. As a result, a display device that can sufficiently withstand contamination with respect to the above was obtained.

Example 51-1
Using the antireflection film sample 128 of the present invention of Example 1, a polarizing plate with a single-side antireflection film was prepared, and a λ / 4 plate was bonded to the opposite surface of the polarizing plate having the antireflection film, When attached to the glass plate on the surface of the organic EL display device so that the antireflection film side is the outermost surface, it has excellent antifouling properties, low reflectance, and surface reflection and reflection from the inside of the surface glass are cut. As a result, a display with extremely high visibility was obtained.

It is a schematic sectional drawing which shows typically preferable embodiment of the antireflection film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Anti-glare antireflection film 2 Transparent support 3 Anti-glare layer 4 Low refractive index layer 5 Translucent fine particle

Claims (15)

A hard coat layer is laminated directly on the transparent plastic film substrate or via another layer, and further contains the following (a) to ( d ) on the hard coat layer directly or via another layer: 1. An antireflection film comprising a low refractive index layer formed from a curable composition.
(A) a cationically polymerizable compound having a silyl group in the surface-modified hollow silica fine particles (b) in the molecule with an organosilane compound, as at least one (c) a cationic photopolymerization initiator of the hydrolyzate and partial condensate , Iodonium salt acid generators or active halogens
(D) Polysiloxane compound having a cationically polymerizable functional group 2. The antireflection film according to claim 1, wherein at least one of the cationically polymerizable compounds having a silyl group in the molecule (b) is an organosilane represented by the following general formula [A].
Formula [A]: (R ¹ ) _m Si (R ² ) (X ¹⁰ ) _3-m
(In the formula, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. R ² is a monovalent substituent having a cationic polymerizable functional group, and X ¹⁰ is a hydroxyl group or hydrolyzable. M represents an integer of 0 to 2.) The antireflection film according to claim 1 or 2, characterized in that more than 50% by weight of the total silica particles contained in the curable composition for forming the low refractive index layer is a hollow silica fine particle. Antireflection according to any one of claims 1 to 3, wherein the more than 50 mass% of silica fine particles contained in the curable composition for forming the low refractive index layer is an average particle diameter of 40nm or more the film. Antireflection according to any one of claims 1-4, characterized by containing a fluorine compound represented by the curable composition for forming the low refractive index layer (e) the following formula [B] the film.

(In the formula, x, y, and z represent molar ratios. D represents a polymerization unit of a vinyl monomer having a cationic polymerizable group, and E represents an arbitrary vinyl monomer polymerization unit.) The curable composition forming the low refractive index layer further comprises (f) a compound having no fluorine atom or silicon atom in the molecule and having two or more cationically polymerizable groups. the antireflection film according to any one of 5. The antireflection film according to any one of claim 1 to 6, the refractive index of the low refractive index layer is characterized by a 1.35 to 1.45. The hard coat layer, wherein the low refractive index layer is formed from a curable composition containing at least one of organosilane represented by the following general formula [C] or a hydrolyzate thereof and a partial condensate thereof the antireflection film according to any one of claim 1 to 7, characterized in that it is directly formed thereon.
[C]: (R ¹⁰ ) _n Si (X ¹¹ ) _4-n
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, X ¹¹ represents a hydroxyl group or a hydrolyzable group, and n represents an integer of 0 to 3.) Any one of claims 1-8 having a low refractive index layer, characterized in that it is directly formed on the hard coat layer formed from the curable composition containing a compound having a cationically polymerizable group The antireflection film as described in 1. The antireflection film according to any one of claim 1 to 9, the low refractive index layer is irradiated with ultraviolet rays at an oxygen concentration of 1 vol% or more conditions, characterized in that it is cured. Surface has an uneven shape, anti-reflection film according to any one of claim 1 to 10, characterized in that it has a light antiglare. A polarizing plate with antireflection film according to any one of claim 1 to 11 characterized by using at least one protective film of the polarizing film. The antireflection film according to any one of claim 1 to 11 and one protective film of the polarizing film, for using the optical compensation film having optical anisotropy on the other side protective film of the polarizing film A characteristic polarizing plate. Wherein the polarizing plate according to the antireflection film or claim 12 or 13, according are arranged on the image display surface to any one of claim 1 to 12, an image display device. 15. The image display device according to claim 14 , wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any one mode of TN, STN, IPS, VA, and OCB.

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