JP5172129B2 - Optical film, polarizing plate and image display apparatus using the optical film, and method for producing optical film - Google Patents

Description

  The present invention relates to a curable composition, an optical film using the curable composition, a polarizing plate using the optical film, and an image display device using the optical film or the polarizing plate on the outermost surface of a display.

  An optical film, particularly an antireflection film, is generally used in an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), and a liquid crystal display (LCD). In order to prevent contrast reduction and image reflection due to reflection, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate thickness on a support or a high refractive index layer formed thereon. As a material for the low refractive index layer, a material having a refractive index as low as possible is desired from the viewpoint of antireflection performance, and at the same time it is used for the outermost surface of the display, so it has high antifouling properties, scratch resistance, and adhesion to the lower layer. Sex is required.

  As a polymer for forming a low refractive index layer, it is well known that a fluorine-containing polymer having a low refractive index is cured, and various curing methods are known. For example, a polymer having a hydroxyl group or the like. Has been cured with a curing agent (Patent Documents 1 to 3). However, it was not sufficient in terms of film hardness, and an improvement was desired.

  As means for lowering the refractive index of the material, there are also means for lowering the density (introducing voids) in addition to (1) means for introducing fluorine atoms, as in the above-mentioned patent documents 1 to 3. In either case, the film strength may be impaired, and the scratch resistance may be reduced.

  As a means for greatly improving antifouling properties and scratch resistance while maintaining a low refractive index, imparting slipperiness to the surface is effective. Techniques such as introduction of fluorine and introduction of silicon are effective for imparting slipperiness. In particular, by adding a small amount of a silicone compound to a low refractive index material, the effect of developing slipperiness, the effect of improving antifouling properties, and the effect of improving scratch resistance are remarkably exhibited. However, on the other hand, compatibility with low refractive index layer materials, bleeding out over time or high temperature conditions, transfer of silicone components to contact media, performance degradation associated with these, production line contamination, etc. are expected .

  In particular, in an antireflection film, the occurrence of haze due to lack of compatibility may deteriorate the optical performance. Moreover, when the film after application of the low refractive index layer is wound, a silicone compound may adhere to the back surface of the film, which is inconvenient for the subsequent processing steps. That is, there is a demand for a technique in which only the siloxane sites are effectively segregated on the surface and the remaining sites bonded to silicon are effectively anchored in the low refractive index layer coating.

In response to this problem, a fluorine-containing olefin copolymer in which a polysiloxane block copolymer component is introduced using a silicone-based macroazo initiator, and a technique for applying the fluorine-containing olefin copolymer to an antireflection film (Patent Document) 4-7) have been proposed. These techniques are extremely effective in terms of suppressing bleeding out and transfer of the silicone component to the contact medium, and improving the uniformity of the coating, but are less antifouling than means for adding silicone compounds. There is a need for improvement in terms of heat resistance and scratch resistance.
Sho 57-34107 Sho 61-275311 JP-A-8-92323 JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-17028 A JP 2000-313709 A

  From the above background, bleed-out of materials is improved while suppressing bleed out over time or high temperature conditions, transfer of silicone components to contact media, performance degradation associated with these, and contamination of production lines. Therefore, development of a technique capable of improving antifouling property and scratch resistance has been demanded.

  The purpose of the present invention is: First, bleed out under aging or high temperature conditions, transfer of silicone component to contact medium, performance degradation associated with these, less contamination of production line, etc., improving material slipperiness And secondly, bleed out over time or at high temperature, transfer of silicone components to contact media, associated performance degradation, production line contamination, etc. The third object is to provide a coating-type optical film that has a small amount of antifouling property, scratch resistance and adhesion, and is suitable for mass production; third, such an optical film as a protective film for a polarizing film; There is to provide the used polarizing plate; and fourth, by using such an optical film or polarizing plate on the outermost surface, an image display device having excellent antifouling property and scratch resistance on the surface is provided. Especially That.

｛一般式（１）中、Ｒ^１１、Ｒ^１２は、水素原子、アルキル基、又はアリール基を表す。ｐは１０〜５００の整数を表す。｝
一般式（３）：

｛一般式（３）中、Ｘ^３１は上記一般式（１）で表されるポリシロキサン構造を含む単位を表す。Ｙ^３１は任意のビニルモノマーに基づく重合単位を表し、単一であっても複数種で構成されていてもよい。Ｌ^３１は単結合又は２価の連結基を表し、該２価の連結基は、＊−（ＣＨ _２ ） _２ −Ｏ−＊＊、＊−（ＣＨ _２ ） _２ −ＮＨ−＊＊、＊−（ＣＨ _２ ） _４ −Ｏ−＊＊、＊−（ＣＨ _２ ） _６ −Ｏ−＊＊、＊−（ＣＨ _２ ） _２ −Ｏ−（ＣＨ _２ ） _２ −Ｏ−＊＊、＊−ＣＯＮＨ−（ＣＨ _２ ） _３ −Ｏ−＊＊、＊−ＣＨ _２ ＣＨ（ＯＨ）ＣＨ _２ −Ｏ−＊＊、＊−ＣＨ _２ ＣＨ _２ ＯＣＯＮＨ（ＣＨ _２ ） _３ −Ｏ−＊＊、又は下記式のいずれかである。式中、＊は共重合体主鎖側の連結部位を表し、＊＊は（メタ）アクリロイル基側の連結部位を表す。Ｒ^３１及びＲ^３２は、それぞれ独立して、水素原子又はメチル基を表す。ｘ〜ｚはそれぞれ各構成単位のモル分率（％）を表し、５０≦ｘ＜１００、０≦ｙ≦４０、１０≦ｚ≦３５を満たす値を表す。
（Ｂ）１分子中に２個以上のエチレン性不飽和基を有するモノマー化合物、
（Ｄ）電離放射線硬化性の重合開始剤。

＜２＞
一般式（３）中のＹ^３１の重合単位を構成する単量体が、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレート、イソブチルアクリレート、シクロヘキシルアクリレート、メチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、ステアリルメタクリレート、メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、イソブチルビニルエーテル、スチレン、α−メチルスチレン、アクリロニトリル、及びメタクリロニトリルから選択される単量体である＜１＞に記載の光学フィルム。
＜３＞
前記硬化組成物中、前記成分（Ａ）が、前記成分（Ｂ）の１００質量部に対して０．００１〜１５質量部となるように配合されている＜１＞又は＜２＞に記載の光学フィルム。
＜４＞
前記ハードコート層が防眩機能を有する＜１＞〜＜３＞のいずれか一項に記載の光学フィルム。
＜５＞
＜１＞〜＜４＞のいずれか一項に記載の光学フィルムが、偏光板における偏光膜の２枚の保護フィルムのうちの一方に用いられている偏光板。
＜６＞
＜１＞〜＜４＞のいずれか一項に記載の光学フィルム、又は＜５＞に記載の偏光板がディスプレイの最表面に用いられている画像表示装置。
＜７＞
透明支持体上の最表層にハードコート層を含有する光学フィルムの製造方法であって、前記ハードコート層が＜１＞に記載の硬化性組成物を硬化して形成することを特徴とする光学フィルムの製造方法。
本発明は上記＜１＞〜＜７＞に関するものであるが、以下、その他の事項についても参考のために記載した。 According to the present invention, a curable composition, an optical film, a polarizing plate, and an image display device having the following constitution are provided, and the above object is achieved.
<1>
An optical film having a hard coat layer on a transparent support, the hard coat layer being the outermost layer, and curing a curable composition containing the following components (A), (B), and (D) In the cured composition, the optical film is blended so that the component (A) is 0.001 to 40 parts by mass with respect to 100 parts by mass of the component (B).
(A) A copolymer containing a structural unit having a polysiloxane structure represented by the following general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain, 3) a copolymer represented by the polymer initiator method,
General formula (1):

{In General Formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. p represents an integer of 10 to 500. }
General formula (3):

{In General Formula (3), X ³¹ represents a unit containing a polysiloxane structure represented by General Formula (1). Y ³¹ represents a polymerized unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. L ³¹ represents a single bond or a divalent linking group, and the divalent linking group includes * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * —. _{(CH 2) 4 -O - **} , * - (CH 2) 6 -O - **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- ( _{CH 2) 3 -O - **,} * - CH 2 CH (OH) CH 2 -O - **, * - CH 2 CH 2 OCONH (CH 2) 3 -O - **, or any one of the following formulas It is. In the formula, * represents a linking site on the copolymer main chain side, and ** represents a linking site on the (meth) acryloyl group side. R ³¹ and R ³² each independently represents a hydrogen atom or a methyl group. x to z each represents a mole fraction (%) of each structural unit, and represents values satisfying 50 ≦ x <100, 0 ≦ y ≦ 40, and 10 ≦ z ≦ 35.
(B) a monomer compound having two or more ethylenically unsaturated groups in one molecule;
(D) An ionizing radiation curable polymerization initiator.

<2>
The monomer constituting the Y ³¹ polymerization unit in the general formula (3) is methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate. <1>, which is a monomer selected from styrene, stearyl methacrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, and methacrylonitrile.
<3>
<1> or <2> according to <1> or <2>, wherein the component (A) is blended to be 0.001 to 15 parts by mass with respect to 100 parts by mass of the component (B) in the cured composition. Optical film.
<4>
The optical film according to any one of <1> to <3>, wherein the hard coat layer has an antiglare function.
<5>
The optical film as described in any one of <1>-<4> is a polarizing plate used for one of the two protective films of the polarizing film in a polarizing plate.
<6>
The optical display as described in any one of <1>-<4>, or the polarizing plate as described in <5> is used for the outermost surface of a display.
<7>
An optical film production method comprising a hard coat layer as an outermost layer on a transparent support, wherein the hard coat layer is formed by curing the curable composition according to <1>. A method for producing a film.
Although the present invention relates to the above <1> to <7>, other matters are also described below for reference.

[1] contains the following components (A) and (B), and the following components (C), a curable composition containing at least one component in the (D) and (E):
(A) a copolymer containing a structural unit having a polysiloxane structure represented by the following general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain;

General formula (1):

｛一般式（３）中、Ｘ ³¹ は上記一般式（１）で表されるポリシロキサン構造を含む単位を表す。Ｙ ³¹ は任意のビニルモノマーに基づく重合単位を表し、単一であっても複数種で構成されていてもよい。Ｌ ³¹ は単結合又は２価の連結基を表し、Ｒ ³¹ 及びＲ ³² は、それぞれ独立して、水素原子又はメチル基を表す。ｘ〜ｚはそれぞれ各構成単位のモル分率（％）を表し、１０≦ｘ＜１００、０≦ｙ≦９０、１≦ｚ≦５０を満たす値を表す。｝
［２］ 成分（Ｃ）におけるオルガノシラン化合物が、下記一般式（２）で表される［１］に記載の硬化性組成物。 {In General Formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. p represents an integer of 10 to 500. }
(B) a compound having at least one ethylenically unsaturated group in one molecule;
(C) an organosilane compound or a hydrolyzate of the organosilane compound and / or a partial condensate thereof,
(D) a polymerization initiator,
(E) inorganic fine particles ,
And,
The copolymer of the component (A) is a copolymer represented by the following general formula (3), and the copolymer is produced by a polymer initiator method. .
General formula (3):

{In General Formula (3), X ³¹ represents a unit containing a polysiloxane structure represented by General Formula (1). Y ³¹ represents a polymerization unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. L ³¹ represents a single bond or a divalent linking group, and R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group. x to z each represents a mole fraction (%) of each structural unit, and represents values satisfying 10 ≦ x <100, 0 ≦ y ≦ 90, and 1 ≦ z ≦ 50. }
[2] The curable composition according to [1], wherein the organosilane compound in the component (C) is represented by the following general formula (2).

General formula (2):

{In General Formula (2), R ²² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. U ²¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. L ²¹ represents a divalent linking chain. m1 represents 0 or 1. R ²⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X ²¹ represents a hydroxyl group or a hydrolyzable group. When X ²¹ there are a plurality, the plurality of X ²¹ may be different even in respectively the same. }
[3] The curable composition according to [1] or [2], wherein the inorganic fine particles of component (E) are silica fine particles.
[4] The curable composition according to [3], wherein the silica fine particles are hollow silica fine particles having an average particle diameter of 30 nm to 150 nm .

[5] In the general formula (3), the molar fraction of the structural unit X ³¹ containing a polysiloxane structure represented by the above general formula (1) (%) x satisfies the 50 ≦ x <100 [1] ~ [4] The curable composition according to any one of [4] .
[ 6 ] The curable composition according to any one of [1] to [ 5 ], wherein the compound (B) having at least one ethylenically unsaturated group in one molecule is a polyfunctional (meth) acrylate monomer. .
[7] The curable composition according to any one of [1] to [6], wherein the polymer unit Y ³¹ of the copolymer represented by the general formula (3) is a polymer unit based on a fluorine-containing vinyl monomer.
[8] The compound of [1] to [7], wherein the compound (B) having at least one ethylenically unsaturated group in one molecule is a fluorine-containing copolymer represented by the following general formula (4): The curable composition in any one.

General formula (4):

{In General Formula (4), Rf ⁴¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ⁴² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and ether You may have a bond. L ⁴¹ represents a single bond or a divalent linking group, and R ⁴¹ represents a hydrogen atom or a methyl group. A ⁴¹ represents a polymerized unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. B ⁴¹ represents a structural unit containing a polysiloxane structure in the main chain or side chain. a to d each represent a mole fraction (%) of each structural unit, and satisfy values of 30 ≦ a + b ≦ 95, 5 ≦ a ≦ 90, 0 ≦ b ≦ 70, 5 ≦ c ≦ 50, and 0 ≦ d ≦ 90. Represents. e represents a mass fraction (%) of the polymerization unit B ⁴¹ with respect to the mass of the other constituent units, and satisfies the relationship of 0 ≦ e <20. }
[9] An optical film having at least one functional layer obtained by curing the curable composition according to any one of [1] to [8].
[10] The optical film according to [9], wherein the functional layer is a low refractive index layer, and the optical film has an antireflection function or an antiglare function due to optical interference.
[11] A polarizing plate in which the optical film according to [9] or [10] is used for one of the two protective films of the polarizing film in the polarizing plate.
[12] An image display device in which the optical film according to [9] or [10] or the polarizing plate according to [11] is used on the outermost surface of the display.

  (A) a copolymer containing a structural unit having a polysiloxane structure in the main chain, a copolymer having a structural unit having an ethylenically unsaturated group in the side chain, and (B) one molecule of an ethylenically unsaturated group used in the present invention And (C) an organosilane compound or a hydrolyzate and / or partial condensate thereof, (D) a polymerization initiator, and (E) an inorganic fine particle. Among them, the curable composition containing at least one component forms a film having excellent strength, bleed-out under time or high temperature conditions, little transfer of the silicone component to the contact medium, and slipperiness. Further, the amount of silicone component introduced can be easily controlled without impairing the uniformity of the coating.

  The optical film having a functional layer obtained by curing the composition of the present invention has excellent bleeding resistance and scratch resistance, as well as bleed out over time or at high temperature, little transfer of the silicone component to the contact medium. Excellent adhesion to the lower layer.

  The polarizing plate and the liquid crystal display device using the optical film of the present invention have an excellent effect of having high antifouling properties, scratch resistance, and adhesion. Further, the optical film provided with the antireflection function using the composition of the present invention as a composition for low refractive index has a lower reflectance in addition to these properties, and a polarizing plate device and a liquid crystal display device using the optical film Has an excellent feature that reflection of external light is sufficiently prevented.

< Curable composition>
The curable composition of the present invention contains the following components (A) and (B), and contains at least one of the following components (C), (D) and (E) (in the specification) It may be referred to as a curable composition of the present invention).

  (A) a copolymer comprising a structural unit having a polysiloxane structure represented by the following general formula (1) in the main chain, and a structural unit having an ethylenically unsaturated group in the side chain;

General formula (1):

{In General Formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. p represents an integer of 10 to 500. }

(B) a compound having at least one ethylenically unsaturated group in one molecule;
(C) an organosiloxane compound or a hydrolyzate and / or partial condensate of the organosilane compound,
(D) a polymerization initiator,
(E) Inorganic fine particles.

[Component (A): a copolymer containing a structural unit having a polysiloxane structure represented by the general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain]
The curable composition of the present invention comprises a copolymer (A having a structural unit having a polysiloxane structure represented by the following general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain. ) {Hereinafter simply referred to as a polysiloxane structure-containing copolymer (A)}, and a compound (B) having at least one ethylenically unsaturated group in one molecule, and an organosilane compound or the organo It is a curable composition containing at least one component of a hydrolyzate of a silane compound and / or a partial condensate thereof (C), a polymerization initiator (D), and inorganic fine particles (E).

General formula (1):

In general formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p represents an integer of 10 to 500, preferably 50 to 300, and particularly preferably 100 to 250.

  The amount of the siloxane component introduced can be controlled by appropriately adjusting the addition amount of the copolymer (A). Furthermore, due to the surface uneven distribution of siloxane and the presence of ethylenically unsaturated groups, only the siloxane sites can be effectively segregated on the surface and effectively anchored in the low refractive index layer coating.

  The copolymer (A) is preferably a copolymer represented by the following general formula (3).

General formula (3):

In the general formula (3), X ³¹ represents a unit containing a polysiloxane structure represented by the general formula (1). Y ³¹ represents a polymerization unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. L ³¹ represents a single bond or a divalent linking group, and R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group. x to z each represents a mole fraction (%) of each structural unit, and represents values satisfying 10 ≦ x <100, 0 ≦ y ≦ 90, and 1 ≦ z ≦ 50.

[Constitutional unit having polysiloxane structure]
Copolymer containing component (A) in the present invention and a structural unit having a polysiloxane structure represented by the general formula (1) in the main chain (X ³¹ : hereinafter also simply referred to as “unit (X)”) As methods for synthesizing coalescence, several methods have been conventionally proposed.

  For example, J. et al. C. Saam et al., “Macromolecules”, Vol. 3, page 1 (1970), reported that a styrene-dimethylsiloxane block copolymer was obtained by an anionic polymerization method (hereinafter this method is called an anionic polymerization method). ).

  In addition, Takashi Tezuka et al., “Makromol. Chem., Rapid Commun.”, Vol. (Hereinafter, this method is referred to as a prepolymer method).

  Furthermore, Hiroshi Inoue et al. In “Science of Polymer Science Proceedings”, 34, 293 (1984), methyl methacrylate-dimethylsiloxane block copolymer by radical polymerization with azo group-containing polysiloxane amide having radical polymerization initiation ability. It has been reported that a coalescence was obtained (hereinafter, this method is referred to as a polymer initiator method).

However, in the anionic polymerization method and the prepolymer method, vinyl group monomers that can be applied to the reaction are limited, and the reaction process becomes multi-stage and the reaction conditions become difficult to use industrially. Yes. In order to produce a block copolymer industrially, it can be synthesized using radical polymerization, can be applied to many vinyl monomers, and preferably has few reaction steps.

  From the above viewpoints, the polysiloxane structure-containing copolymer (A) used in the present invention is preferably produced by a polymer initiator method. Such a polymer initiator is, for example, a polysiloxane compound having a radical-generating group such as an azo group or a peroxy group. Such an initiator can be synthesized as described in, for example, Japanese Patent Publication No. 6-104711 and Japanese Patent Laid-Open No. 6-93100.

(Preferred examples of polymer initiator)
Examples of preferred polymer initiators are shown below, but the present invention is not limited thereto.

  The polysiloxane structure-containing copolymer (A) used in the present invention contains a structural unit containing an ethylenically unsaturated group in the side chain (hereinafter also referred to as “unit (Z)”). By having the organic functional group, crosslinking is possible, and an effect of preventing transfer can be obtained.

[Structural unit having an ethylenically unsaturated group in the side chain]
Next, the structural unit (Z) having an ethylenically unsaturated group in the side chain in the copolymer (A) used in the present invention, that is, a polymerization unit represented by the following general formula (5) will be described.

General formula (5):

In the general formula (5), L ³¹ represents a single bond or a divalent linking group, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms. Alternatively, it may have a branched structure, may have a ring structure, and may have a heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom. R ³¹ and R ³² represent a hydrogen atom or a methyl group.

Preferable examples of the linking group L ³¹ include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * _{- (CH 2) 6 -O -} **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, * -CONH- (CH 2) 3 -O - **, * - _{CH 2 CH (OH) CH 2} -O- * *, * - CH 2 CH 2 OCONH (CH 2) 3 -O - ** (* represents a linking site of the copolymer main chain side and ** ( Represents a connecting site on the side of (meth) acryloyl group).

The method for introducing the (meth) acryloyl group into the copolymer (A) is not particularly limited, but for example:
(1) After synthesizing a copolymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) acrylic anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride A method of making things act,
(2) A method of allowing (meth) acrylic acid to act on the copolymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid,
(3) A method of allowing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the copolymer having the nucleophilic group,
(4) A method of allowing (meth) acrylic acid to act after synthesizing a copolymer having an epoxy group,
(5) A method of causing a compound having both an epoxy group such as glycidyl methacrylate and a (meth) acryloyl group to act on a copolymer having a carboxyl group,
(6) A method of dehydrochlorination after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety,
Etc.

  Among these, in the present invention, it is preferable to introduce a (meth) acryloyl group by the method (1) or (2), particularly for a copolymer containing a hydroxyl group. In the introduction of the (meth) acryloyl group into the copolymer, it is possible to completely replace the hydroxyl group of the copolymer with the (meth) acryloyl group by adjusting the amount of introduction, leaving a part of the hydroxyl group (meth) It can also be substituted with an acryloyl group. The same introduction is possible for a copolymer having a functional group other than a hydroxyl group.

  If the composition ratio of these (meth) acryloyl group-containing polymerization units is increased, the film strength is improved, but the refractive index is also increased. The composition ratio of the (meth) acryloyl group-containing polymer unit can vary depending on the type of the fluorine-containing vinyl monomer polymer unit, and it occupies 1 to 50 mol%, more preferably 1 to 40 mol%, and more preferably 1 to 30 mol%. It is particularly preferred to occupy a mol%.

  Hereinafter, although the preferable example of the polymerization unit represented by the said General formula (5) is shown, this invention is not limited to this.

[Polymerized units based on any vinyl monomer]
The polysiloxane structure-containing copolymer (A) used in the present invention represented by the general formula (3) has adhesion to a substrate, solubility in a solvent, and compatibility with other coating liquid compositions. From various viewpoints such as transparency, in addition to the structural units described above, other arbitrary vinyl monomer-based polymer units (Y ³¹ : hereinafter, also simply referred to as “unit (Y)”) may be included.

  Examples of the monomer constituting the polymer unit (Y) based on such an arbitrary vinyl monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n- Examples thereof include butyl methacrylate, isobutyl methacrylate, stearyl methacrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile and the like.

Other examples of monomers that constitute polymerized units based on arbitrary vinyl monomers include fluorine-containing vinyl monomers. In particular, when the compound having at least one ethylenically unsaturated group in one molecule, which is the component (B) of the curable composition of the present invention, is a fluorinated polymer, it is optional from the viewpoint of compatibility. The polymer unit (Y) based on the vinyl monomer is preferably a polymer unit derived from a fluorine-containing vinyl monomer.

(Fluorine-containing vinyl monomer)
As preferred examples of the fluorine-containing vinyl monomer, a polymer unit represented by the following general formula (6) and a polymer unit represented by the following general formula (7) will be described.

General formula (6):

General formula (7):

In the general formula (6) and (7), Rf ³¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms. Rf ³² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, preferably 1 to 15 carbon atoms, and may have an ether bond. Rf ³² is preferably a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 15 carbon atoms, and may have an ether bond.

  The polymer units represented by the general formula (6) and the general formula (7) are both polymer units based on a fluorinated vinyl monomer, and specific examples of the fluorinated vinyl monomer include fluoroolefins (for example, fluorocarbons). Ethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), perfluoro (alkyl vinyl ether) s {eg perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether)}, perfluoro (alkoxy) Alkyl vinyl ethers) {for example perfluoro (propoxypropyl vinyl ether)}. These may be used alone or in combination of two or more.

  From the viewpoint of solubility, transparency, availability, etc., hexafluoropropylene alone or a combination of hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) is particularly preferable.

  Hereinafter, preferred examples of the polymer unit represented by the general formula (6) in the polysiloxane structure-containing copolymer (A) represented by the general formula (3) of the present invention will be shown. It is not limited to these.

  Preferred examples of the polymer unit represented by the general formula (7) in the polysiloxane structure-containing copolymer (A) represented by the general formula (3) of the present invention are shown below. It is not limited to.

  From the above viewpoints, the polysiloxane structure-containing copolymer (A) in the present invention is a polymer unit (Y) based on an arbitrary vinyl monomer in addition to the structural unit (X) having a polysiloxane structure, and a side chain. The form which consists of a polymer unit (Z) which has a (meth) acryloyl group which is a structural unit containing an ethylenically unsaturated group in is preferable.

  The mole fraction (%) of each structural unit is selected so as to satisfy 10 ≦ x <100, 0 ≦ y ≦ 90, and 1 ≦ z ≦ 50.

  In the polysiloxane structure-containing copolymer (A) in the present invention, the structural unit (X) having a polysiloxane structure imparts sufficient scratch resistance to the material, and imparts transparency and antifouling durability. X which is a structural unit and represents the molar fraction (%) of the unit (X) is preferably 30 ≦ x <100, and more preferably 50 ≦ x <100.

  In the copolymer (A), the introduction amount of the polymer unit (Z) having a (meth) acryloyl group which is a structural unit containing an ethylenically unsaturated group in the side chain is too low in the ratio of the unit (X). Therefore, it is preferable to select appropriately within a range in which sufficient scratch resistance, antifouling durability and transparency are not easily obtained. Therefore, the range of the preferable molar fraction of the unit (Z) is 1 ≦ z ≦ 40, and more preferably 1 ≦ z ≦ 30.

  In the copolymer (A), the unit (Y) other than the unit (X) and the unit (Z) has adhesion to the substrate, solubility in a solvent, and compatibility with other coating liquid compositions. In order to impart various properties such as transparency, it may be introduced as appropriate, but the amount of units (Y) introduced is too low in the ratio of units (X), resulting in sufficient scratch resistance and antifouling durability. It is preferable to select appropriately within a range that does not make it difficult to obtain properties and transparency. Therefore, the range of the preferable molar fraction of the unit (Y) is 0 ≦ y ≦ 40, and more preferably 0 ≦ y ≦ 15.

  Table 1 shows specific examples of the copolymer (A) useful in the present invention, but the present invention is not limited thereto. In addition, the number in Table 1 represents the mole fraction of each polymerization unit.

In addition, the abbreviation in Table 1 represents the following.
MMA: Polymerized unit derived from methyl methacrylate n-BuMA: Polymerized unit derived from n-butyl methacrylate X: Unit containing polysiloxane structure Y: Polymerized unit based on any vinyl monomer Z: Represented by the above general formula (5) Polymer unit x: mole fraction of X y: mole fraction of Y z: mole fraction of Z

[Synthesis of polysiloxane structure-containing copolymer (A)]
The polysiloxane structure-containing copolymer (A) used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. At this time, it can be synthesized by a known operation such as a batch system, a semi-continuous system or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972. Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable.

Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, It may be a single organic organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, or a mixture of two or more thereof, or a mixed solvent with water.

  The polymerization temperature needs to be set in relation to the molecular weight of the copolymer (A) to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but in the range of 50 to 120 ° C. Polymerization is preferably performed.

  When introducing a polysiloxane moiety using a polymer initiator, other radical initiators can be used in combination as required.

  Examples of the radical initiator that can be used in combination include diacyl peroxides such as acetyl peroxide and benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide; Dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide; peroxy esters such as t-butyl peroxyacetate and t-butyl peroxypivalate; azobisisobutyronitrile, azobisisovalero Azo compounds such as nitrile; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; perfluoroethyl iodide, perfluoropropyl iodide Zido, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2 -(Perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyl Octyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methylde L) Ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane And iodine-containing fluorine compounds such as octafluoro-1,4-diiodobutane and dodecafluoro-1,6-diiodohexane;

  The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  The radical polymerization initiator may be used in combination with an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite, and an organic reducing agent such as cobalt naphthenate and dimethylaniline, as necessary.

  As a reprecipitation solvent for the obtained copolymer, water, isopropanol, hexane, methanol, and a mixed solvent thereof are preferable.

[Component (B): Compound having at least one ethylenically unsaturated group in one molecule]
As a preferred embodiment of the compound (B) having at least one ethylenically unsaturated group in one molecule,
(1) a fluorine-containing compound having at least one ethylenically unsaturated group in one molecule;
(2) a monomer having two or more ethylenically unsaturated groups (preferably used together with inorganic fine particles having a hollow structure),
And so on. Thereby, the layer obtained by the curable composition of the present invention is:
Compared to a conventional low refractive index layer using magnesium fluoride or calcium fluoride, an optical film having excellent scratch resistance and thus excellent scratch resistance can be obtained even when used as the outermost layer.

[(1) Fluorine-containing compound having at least one ethylenically unsaturated group in one molecule]
Preferable examples of the fluorine-containing compound having at least one ethylenically unsaturated group in one molecule include a copolymer of a fluorine-containing monomer and a monomer having a functional group containing an ethylenically unsaturated group.

(Fluorine-containing copolymer)
The fluorine-containing copolymer has a lower refractive index than a normal polymer not containing fluorine, and is suitable for a curable composition for a low refractive index layer. On the other hand, the polysiloxane structure-containing copolymer (A) has a function of improving scratch resistance and imparting antifouling properties by imparting slipperiness. By both, the curable composition preferably used for the low refractive index layer of the antireflection film excellent in scratch resistance and antifouling property is realized. Two or more types of fluorine-containing copolymers may be used. Moreover, you may use together with the compound (B) which has at least 1 other ethylenically unsaturated group in 1 molecule, such as the said polyfunctional (meth) acrylate monomer.

  The fluorine-containing copolymer used in the present invention preferably has a structure represented by the general formula (4).

General formula (4):

In the general formula (4), Rf ⁴¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ⁴² represents a fluorine-containing alkyl group having a linear, branched or alicyclic structure having 1 to 30 carbon atoms, and an ether bond You may have. L ⁴¹ represents a single bond or a divalent linking group, and R ⁴¹ represents a hydrogen atom or a methyl group. A ⁴¹ represents a polymerized unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. B ⁴¹ represents a structural unit containing a polysiloxane structure in the main chain or side chain. a to d each represent a mole fraction (%) of each structural unit, and satisfy values of 30 ≦ a + b ≦ 95, 5 ≦ a ≦ 90, 0 ≦ b ≦ 70, 5 ≦ c ≦ 50, and 0 ≦ d ≦ 90. Represents. Preferably, 35 ≦ a + b ≦ 70, 30 ≦ a ≦ 60, 0 ≦ b ≦ 30, 10 ≦ c ≦ 50, 0 ≦ d ≦ 50, particularly preferably 40 ≦ a + b ≦ 60, 40 ≦ a ≦. 55, 0 ≦ b ≦ 20, 15 ≦ c ≦ 50, 0 ≦ d ≦ 40. However, a + b + c + d = 100 (mol%). e represents the mass fraction (%) of polymerized units B in the copolymer, and 0 ≦ e <20. Preferably 0 ≦ e <10, particularly preferably 0 ≦ e <5.

{Polymerized units represented by general formulas (6 ′) and (7 ′)}
First, the polymer unit represented by the following general formula (6 ′) and the polymer unit represented by the following general formula (7 ′) in the fluorine-containing copolymer represented by the general formula (4) of the present invention. explain.

General formula (6 ′):

Formula (7 ′):

Rf ⁴¹ and Rf ⁴² in the general formulas (6 ′) and (7 ′) are represented by the general formulas (6) and (7) of the polysiloxane structure-containing copolymer (A) of the component (A). The same as Rf ³¹ and Rf ³² in the polymerized unit derived from the fluorinated vinyl monomer.

  Although the preferable example of the polymerization unit represented by the said General formula (6 ') in the fluorine-containing copolymer represented by General formula (4) of this invention below is shown, this invention is not limited to these. .

  Although the preferable example of the polymerization unit represented by the said General formula (7 ') in the fluorine-containing copolymer represented by General formula (4) of this invention below is shown, this invention is not limited to these. .

{Polymerized unit represented by formula (8)}
Next, the polymer unit represented by the following general formula (8) in the fluorine-containing copolymer represented by the general formula (4) of the present invention will be described.

General formula (8):

In the general formula (8), L ⁴¹ represents a single bond or a divalent linking group, and R ⁴¹ represents a hydrogen atom or a methyl group.

Preferred examples of the linking group L ⁴¹ include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * _{- (CH 2) 6 -O -} **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, - CONH- (CH 2) 3 -O - **, * - CH ₂ CH (OH) CH ₂ —O— *, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a (meth) acryloyl group. Represents the connecting part on the side). R ⁴¹ represents a hydrogen atom or a methyl group, and is more preferably a hydrogen atom from the viewpoint of curing reactivity.

The method for introducing the (meth) acryloyl group into the fluorine-containing copolymer is not particularly limited, but for example:
(1) After synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid chloride, (meth) acrylic anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride, etc. How to act,
(2) A method of allowing (meth) acrylic acid to act on the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid,
(3) A method of allowing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and a (meth) acryloyl group to act on the polymer having the nucleophilic group,
(4) A method of allowing (meth) acrylic acid to act after synthesizing a polymer having an epoxy group,
(5) A method of causing a compound having both an epoxy group such as glycidyl methacrylate and a (meth) acryloyl group to act on a polymer having a carboxyl group,
(6) A method in which dehydrochlorination is performed after polymerizing a vinyl monomer having a 3-chloropropionic acid ester moiety,
Etc.

  Among these, in the present invention, it is preferable to introduce a (meth) acryloyl group by the method (1) or (2), particularly for a polymer containing a hydroxyl group.

In the introduction of the (meth) acryloyl group into the fluorine-containing copolymer, by adjusting the introduction amount, the hydroxyl group of the copolymer can be completely substituted with the (meth) acryloyl group, It can also be substituted with a (meth) acryloyl group. The same introduction is possible for a copolymer having a functional group other than a hydroxyl group.

  Although the preferable example of the polymerization unit represented by the said General formula (8) in the fluorine-containing copolymer represented by General formula (4) of this invention below is shown, this invention is not limited to these.

{Polymerized units A ⁴¹ based on any vinyl monomer}
Next, the polymerization unit A ⁴¹ based on an arbitrary vinyl monomer in the fluorine-containing copolymer represented by the general formula (4) of the present invention will be described. A ⁴¹ may be a single species or a plurality of species.

In the general formula (4), A ⁴¹ represents a polymer unit based on an arbitrary vinyl monomer, and is not particularly limited as long as it is a structural unit based on a monomer copolymerizable with hexafluoropropylene. It can be appropriately selected from various viewpoints such as adhesion to a substrate, Tg of a polymer (contributing to film hardness), solubility in a solvent, transparency, slipperiness, and dust / antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose.

The vinyl monomer unit that can be used in combination with A ⁴¹ is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.); acrylic acid esters (methyl acrylate, methyl acrylate, acrylic acid) Ethyl, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate); methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.); styrene derivatives (styrene, p-hydroxy) Methyl styrene, p-methoxy styrene, etc.); fluorinated vinyl ethers {however, excluding the polymer unit represented by the general formula (7 ′)}; vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.); Esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.); unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.); acrylamides (N, N-dimethylacrylamide, N- t-butylacrylamide, N-cyclohexylacrylamide, etc.); methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  Among the vinyl monomers that can be used in combination, from the viewpoint of further lowering the refractive index, it is preferable to introduce vinyl ethers or fluorine-containing vinyl ethers (however, excluding the polymer unit represented by the general formula (7 ′)). .

Hereinafter, preferred examples of the polymerization unit A ⁴¹ based on an arbitrary vinyl monomer in the fluorine-containing copolymer represented by the general formula (4) of the present invention will be shown, but the present invention is not limited thereto.

(Structural unit B ⁴¹ containing polysiloxane structure in main chain or side chain)
Next, the fluorine-containing copolymer of the general formula (4) of the present invention, the structural unit B ⁴¹ containing a polysiloxane structure in the main chain or side chain is described.

  As the main chain polysiloxane partial structure, a structure represented by the following general formula (9) is particularly preferable.

General formula (9):

In the general formula (9), R ^{411 to} R ⁴¹⁴ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 5. Examples include a methyl group and an ethyl group), and an aryl group (having a carbon number). 6 to 10 are preferable, and examples thereof include a phenyl group and a naphthyl group, an alkoxycarbonyl group (preferably having a carbon number of 2 to 5. Examples include a methoxycarbonyl group and an ethoxycarbonyl group), or a cyano group. An alkyl group and a cyano group are preferable, and a methyl group and a cyano group are particularly preferable.

R ^{415 to} R ⁴²⁰ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 5. Examples include a methyl group and an ethyl group), and a haloalkyl group (a fluorinated alkyl having 1 to 5 carbon atoms). A trifluoromethyl group and a pentafluoroethyl group), or a phenyl group, preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

  r1 and r2 each independently represents an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. r3 and r4 each independently represents an integer of 0 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. p2 represents an integer of 10 to 1000, preferably an integer of 20 to 500, and particularly preferably an integer of 50 to 200.

  There is no particular limitation on the method for introducing the polysiloxane partial structure into the main chain. For example, an azo group-containing polysiloxane amide described in JP-A-6-93100 {commercially available "VPS-0501", "VPS-1001" (Trade name), a method using a polymer type initiator such as Wako Pure Chemical Industries, Ltd .; a polymerization initiator, a reactive group derived from a chain transfer agent (for example, a mercapto group, a carboxyl group, a hydroxyl group, etc.) And then reacting with a polysiloxane containing one or both terminal reactive groups (eg, epoxy group, isocyanate group, etc.); copolymerizing cyclic siloxane oligomer such as hexamethylcyclotrisiloxane by anionic ring-opening polymerization Among them, a method using an initiator having a polysiloxane partial structure is easy and preferable.

  Next, the side chain polysiloxane partial structure will be described. The polysiloxane partial structure generally has a repeating siloxane moiety represented by the following general formula (10).

General formula (10):

In general formula (10), R ⁴²¹ and R ⁴²² may be the same or different and each represents an alkyl group or an aryl group. As an alkyl group, C1-C4 is preferable and a methyl group, a trifluoromethyl group, an ethyl group etc. are mentioned as an example. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable. p3 represents an integer of 10 to 500, preferably 10 to 350, and particularly preferably 10 to 250.

The fluorine-containing copolymer having a polysiloxane structure represented by the general formula (10) in the side chain is, for example, “JA Appl. Polym. Sci.”, 2000, p. 78 (1955), as disclosed in JP-A-56-28219 and the like, a reactive group having reactivity with a polymer having a reactive group such as an epoxy group, a hydroxyl group, a carboxyl, or an acid anhydride group. Polymer reaction of polysiloxanes (for example, “Silaplane” series, manufactured by Chisso Corporation etc.) having one end at one end (for example, amino group, mercapto group, carboxyl group, hydroxyl group, etc. with respect to epoxy group, acid anhydride group) It can be synthesized by a method of polymerizing a polysiloxane-containing silicon macromer, and both methods can be preferably used. In the present invention, a method of introducing by polymerization of silicon macromer is more preferable.

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

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

The mass average molecular weight (Mw) of the fluorine-containing copolymer represented by the general formula (4) is preferably 10 ³ to 10 ⁶ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁵ , and particularly preferably. Is the case of 10 ⁴ to 10 ⁵ .

  Table 2 shows specific examples of polymers useful in the present invention, but the present invention is not limited thereto.

In addition, the abbreviation in Table 2 represents the following.
Q: Polymerized unit represented by the above general formula (6 ′) N: Polymerized unit represented by the above general formula (7 ′) O: Polymerized unit represented by the above general formula (8) M1: Any vinyl monomer Polymer unit A ⁴¹ based on
SS: Structural unit B ⁴¹ containing polysiloxane structure in main chain or side chain
a: mole fraction of Q b: mole fraction of N c: mole fraction of O d: mole fraction of M1 e: mass fraction of SS with respect to the mass of the entire other structural unit Mw: mass average molecular weight

[Synthesis of Component (B) Fluorinated Copolymer]
The fluorine-containing copolymer represented by the general formula (4) used in the present invention can be synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. . Moreover, it is compoundable by well-known operations, such as a batch type, a semi-continuous type, and a continuous type.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972. Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable.

  Solvents used in the solution polymerization method are, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, Each of various organic solvents such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol may be used alone or as a mixture of two or more kinds, or as a mixed solvent with water. Good.

  The polymerization temperature must be set in relation to the molecular weight of the fluorine-containing copolymer to be produced (component (B)), the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher. It is preferable to perform the polymerization in the range of ° C.

  The reaction pressure can be appropriately selected, but is usually 0.01 to 10 MPa, preferably 0.05 to 5 MPa, more preferably about 0.1 to 2 MPa. The reaction time is about 5 to 30 hours.

  When introducing a polysiloxane moiety using a polymer initiator, other radical initiators can be used in combination as required.

  Examples of the radical initiator that can be used in combination include diacyl peroxides such as acetyl peroxide and benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide and cumene hydroperoxide; Dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide; peroxy esters such as t-butyl peroxyacetate and t-butyl peroxypivalate; azobisisobutyronitrile, azobisisovalero Azo compounds such as nitrile; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; perfluoroethyl iodide, perfluoropropyl iodide Zido, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- (perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2 -(Perfluorodecyl) ethyl iodide, heptafluoro-2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyl Octyl iodide, 2- (perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methylde L) Ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H, 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane And iodine-containing fluorine compounds such as octafluoro-1,4-diiodobutane and dodecafluoro-1,6-diiodohexane;

  The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

The radical polymerization initiator may be used in combination with an inorganic reducing agent such as sodium hydrogen sulfite and sodium pyrosulfite, and an organic reducing agent such as cobalt naphthenate and dimethylaniline, as necessary.

  As a reprecipitation solvent for the obtained copolymer, water, isopropanol, hexane, methanol, and a mixed solvent thereof are preferable.

[(2) Monomer having two or more ethylenically unsaturated groups]
Yet another preferred embodiment includes a monomer having two or more ethylenically unsaturated groups. Examples of monomers having two or more ethylenically unsaturated groups include esters of polyhydric alcohols and (meth) acrylic acid {eg, ethylene glycol di (meth) acrylate, 1,4-dichlorohexane diacrylate, penta Erythritol tetra (meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, 1,3,5-cyclohexanetriol trimethacrylate, polyurethane polyacrylate, polyester polyacrylate, etc.}, vinylbenzene Conductors (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloyl ethyl ester, 1,4-divinylcyclohexanone, etc.), vinyl sulfones (eg, divinyl sulfone), acrylamides (eg, methylene bisacrylamide) and Methacrylamide is included.

  Among these, an acrylate or methacrylate monomer having at least three functional groups, and further an acrylate monomer having at least five functional groups are preferable from the viewpoint of film hardness, that is, scratch resistance. A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate is commercially available and is particularly preferably used.

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

  In addition to the monomer having two or more ethylenically unsaturated groups, a crosslinked structure may be introduced into the binder by the reaction of the crosslinkable group. 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. The binder having these crosslinkable functional groups can form a crosslinked structure by heating after coating.

  A monomer having two or more ethylenically unsaturated groups and a monomer into which a crosslinking functional group has been introduced do not have a low refractive index as compared with the fluorine-containing copolymer. However, when used in combination with particles having voids therein (hollow particles), a sufficiently effective refractive index can be obtained as a low refractive index layer of an antireflection film which is a preferred example of the optical film of the present invention. Specific examples of the hollow particles are described in the silica-based particles described in JP-A-2002-79616. The particle refractive index is preferably 1.15 to 1.40, more preferably 1.20 to 1.30.

  Among the curable compositions of the present invention, component (A) {a structural unit having a polysiloxane structure represented by the general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain. Containing copolymer} and component (B) {compound having at least one ethylenically unsaturated group in one molecule}, the amount of component (A) is 0 with respect to 100 parts by mass of component (B). It is preferable to mix | blend so that it may become 1-40 mass parts, and it is still more preferable to mix | blend so that it may become 1-15 mass parts. When the blending ratio of the component (A) is 40 parts by mass or less, problems such as deterioration of scratch resistance and deterioration of the surface state do not occur. Moreover, if it is 0.1 mass part or more, since required antifouling performance can be obtained, it is preferable to set it as the said range.

[Component (C): Organosilane compound, hydrolyzate of the organosilane compound and / or partial condensate thereof]
In addition to the polysiloxane structure-containing copolymer (A) and the compound (B) having at least one ethylenically unsaturated group in one molecule, the curable composition of the present invention includes an organosilane compound or the organosilane compound. It is preferable to use a hydrolyzate of a silane compound and / or a partial condensate thereof (component C) in combination.

[Organosilane compound]
As the organosilane compound, an organosilane represented by the following general formula (2-0) produced in the presence of at least one of an acid catalyst and a metal chelate compound is preferably used. Next, this organosilane compound will be described in detail.

Formula (2-0):
_{^{(R 20) m0 -Si (X}} 21) 4-m0

In General Formula (2-0), R ²⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, hexyl group, t-butyl group, s-butyl group, hexyl group, decyl group, hexadecyl group and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X ²¹ represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (an alkoxy group having 1 to 5 carbon atoms is preferable, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I and the like), and an R ²² COO group ( R ²² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as a CH ₃ COO group, a C ₂ H ₅ COO group, etc., preferably an alkoxy group, particularly preferably a methoxy group or an ethoxy group. It is.

When R ²⁰ or the X ²¹ there are a plurality, a plurality of R ²⁰ or X ²¹ may be different even in the same, respectively. m0 represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

The substituent contained in R ²⁰ is not particularly limited, but may be a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group, etc.), alkoxy group (methoxy group, ethoxy group) Group, i-propoxy group, hexyloxy group etc.), aryloxy group (phenoxy group etc.), alkylthio group (methylthio group, ethylthio group etc.), arylthio group (phenylthio group etc.), alkenyl group (vinyl group, 1-propenyl) Groups), acyloxy groups (acetoxy groups, acryloyloxy groups, methacryloyloxy groups, etc.), alkoxycarbons Groups (methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl groups (phenoxycarbonyl group, etc.), carbamoyl groups (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octyl) Carbamoyl group, etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like. These substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.

When there are a plurality of R ^{20 s} , at least one is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group. In this case, the compound represented by the general formula (2-0) is a vinyl polymer represented by the following general formula (2). It can be expressed as an organosilane compound having a functional substituent.

General formula (2):

In the general formula (2), R ²² represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. R ²² is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And a methyl group are particularly preferred.

U ²¹ represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

L ²¹ is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (for example, an ether group, an ester group, an amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number An arylene group having 6 to 20 carbon atoms and an alkylene group having 3 to 10 carbon atoms having a linking group therein are preferred, and an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group therein. More preferably, an unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

When X ²¹ there are a plurality, the plurality of X ²¹ may be different even in respectively the same. m1 represents 0 or 1, preferably 0.
R ²⁰ has the same meaning as R ^{20 in} formula (2-0), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group. .

X ²¹ has the same meaning as X ^{21 in} formula (2-0), 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 and an alkoxy group having 1 to 3 carbon atoms are more preferable, and a methoxy group is particularly preferable.

As the organosilane compound used in the present invention, those represented by the following general formula (2-1) are also preferred.
Formula ^{_{(2-1) :( R f 21 -L}} 22) m3 -Si (R 23) 4-m3

In the general formula (2-1), R _f ²¹ represents a linear, branched, or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. R _f ²¹ is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms. L ²² represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group. R ²³ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom. m3 represents an integer of 1 to 3.

Among the fluorine-containing organosilane compounds represented by the general formula (2-1), a fluorine-containing organosilane compound represented by the following general formula (2-2) is preferable.
Formula _{(2-2): C n F 2n} + 1 - (CH 2) r5 -Si (R 24) 3

In said general formula (2-2), n represents the integer of 1-10, 4-10 are preferable, r5 represents the integer of 1-5, and 1-3 are preferable. R ²⁴ represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom, preferably a methoxy group, an ethoxy group, or a chlorine atom.

  Two or more kinds of the compounds represented by general formulas (2-0), (2), (2-1) and (2-2) may be used in combination.

(Specific examples of organosilane compounds)
Although the specific example of a compound represented by general formula (2-0), (2), (2-1) or (2-2) below is shown, this invention is not limited to these.

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

[Hydrolyzate and / or partial condensate of organosilane compound]
The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst.

(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 and pyridine Organic bases such as: metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In the present invention, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids.

(Inorganic acids and organic acids)
Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant {pKa value (25 ° C.)} of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

(Metal chelate compound)
As the metal chelate compound, (wherein, R ⁵¹ represents an alkyl group having 1 to 10 carbon atoms) Formula R ⁵¹ OH alcohol and R ⁵² COCH ₂ COR ⁵³ (wherein represented by, R ⁵² is the number of carbon atoms 1 to 10 alkyl group, R ⁵³ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms) and selected from Zr, Ti and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination.

The metal chelate compound used in the present invention has the general formula Zr (OR ⁵¹ ) _s1 (R ⁵² COCHCOR ⁵³ ) _4-s1 , Ti (OR ⁵¹ ) _t1 (R ⁵² COCHCOR ⁵³ ) _4-t1 , and Al (OR ⁵¹ ). Those selected from the group of compounds represented by _u1 (R ⁵² COCHCOR ⁵³ ) _3-u1 are preferred, and they serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

R ⁵¹ and R ⁵² in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically an ethyl group, n-propyl group, i-propyl group, n-butyl group, s -A butyl group, a t-butyl group, an n-pentyl group or the like, or an aryl group such as a phenyl group. R ⁵³ is an alkyl group having 1 to 10 carbon atoms similar to R ⁵¹ and R ^52, and an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group. N-butoxy group, s-butoxy group, t-butoxy group and the like.
s1 represents an integer of 1 to 3, t1 represents an integer of 1 to 3, and u1 represents an integer of 1 or 2.

  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, diisopropoxybis (acetylacetonato) 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.

(Β-diketone compound and / or β-ketoester compound)
Moreover, it is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition of the present invention. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁵² COCH ₂ COR ⁵³ is used in the present invention, and acts as a stability improver of the curable composition of the present invention. Is. Here, R ⁵² represents an alkyl group having 1 to 10 carbon atoms, and R ⁵³ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁵² and R ⁵³ constitute a β- diketone compound and / or β- ketoester compound are the same as R ⁵² and R ⁵³ constituting the metal chelate compound.

Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-s-butyl, acetoacetic acid-
Examples include t-butyl, 2,4-hexane-dione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, and 5-methylhexanedione. . Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more.

  In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. The use of 2 mol or more is preferable because the storage stability of the resulting composition is improved.

  The organosilane compound may be added directly to the curable composition, but the organosilane compound is previously treated in the presence of a catalyst to prepare a hydrolyzate and / or partial condensate of the organosilane compound. The curable composition is preferably prepared using the obtained reaction solution (sol solution). In the present invention, first, a hydrolyzate and / or partial condensate of an organosilane compound and a metal chelate compound are added. It is preferable to prepare the composition to be contained, and apply a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound to the curable composition.

  Among the curable compositions of the present invention, component (C) {organosilane compound or hydrolyzate and / or partial condensate thereof of organosilane compound} and component (B) {1 ethylenically unsaturated group The compounding ratio of at least one compound in the molecule} is preferably such that the component (C) is 0.1 to 50 parts by mass with respect to 100 parts by mass of the component (B). It is still more preferable to mix | blend so that it may become -20 mass parts.

[Component (D): Polymerization initiator]
The curable composition of the present invention includes the component (A) polysiloxane structure-containing copolymer and the component (B) having at least one ethylenically unsaturated group in one molecule, as well as the component (D It is preferable to add a polymerization initiator which is The polymerization initiator (D) can be used without particular limitation as long as it is usually used, but is preferably a heat and / or ionizing radiation curable initiator.

  The SP value of the polymerization initiator of component (D) used in the present invention and the organosilane compound or hydrolyzate of the organosilane compound and / or its partial condensate as the component (C) are combined. The component (B) is preferably larger than the compound having at least one ethylenically unsaturated group in one molecule. This SP value difference makes it easy for the compound of component (B) to localize on the upper layer (outermost surface side) of the functional layer of the optical film of the present invention, in particular, the low refractive index layer of the antireflection film. It is considered that the component (D) and the component (C) are likely to be localized in the lower part (the side opposite to the outermost surface) of the low refractive index layer, and the polymerization proceeds efficiently. These are preferable because the transfer of the silicone component to the contact medium and the contamination of the production line can be sufficiently suppressed.

[SP value]
The SP value of a compound is a solubility parameter and is a numerical value of how easily it is soluble in a solvent, etc. It is synonymous with the polarity often used in organic compounds. Indicates that the polarity is large. As the SP value, a value calculated by the Fedors method can be used.

The polymerization initiator may have any structure of the polymerization initiator skeleton shown below. A compound in which the curable site of the organosilane compound is linked and bonded in the molecule to these polymerization initiators can also be used as the polymerization initiator, and the SP value of the linked and bonded compound is the compound of the above component (B). A larger effect has a similar effect. Further, as will be described later, a compound in which the curable site of the monomer containing an ethylenically unsaturated group is linked and bonded in the molecule can also be used as a polymerization initiator, and the SP value of this linked and bonded compound is the above component (B If it is larger than the compound (), the same effect is obtained.

[Ionizing radiation curable polymerization initiator skeleton]
The ionizing radiation curable polymerization initiator skeleton is a compound similar to a commonly used radical photopolymerization initiator, and is preferably a polyfunctional component of each copolymer (particularly component (B) used in the curable composition). It is preferable to have an initiator skeleton showing a value larger than the SP value of the (meth) acrylate and the (meth) acrylate group-containing fluorine-containing copolymer.

  Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxydimethyl-p-isopropylphenylketone, 1-hydroxycyclohexylphenyl Ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloro Acetophenone and the like are included.

  Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. It is.

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

  Examples of the borate salt include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin et al., “Rad Tech'98. Proceeding April”, pages 19-22, 1998 (Chicago). And the compounds described in paragraphs [0022] to [0027] of JP-A No. 2002-116539. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Examples include organoboron transition metal coordination complexes, and specific examples include ion complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of active esters include 1,2-octanedione, 1- [4- (phenylthio)-,
2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds and the like. Specifically, compounds described in Examples in JP-A No. 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

  Specific examples of the active halogens include Wakabayashi et al. “Bull Chem. Soc Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, and JP-A-5-27830. Publication, M.M. P. Examples include compounds described in Hutt's “Jurnal of Heterocyclic Chemistry”, Volume 1 (No. 3) (1970), and particularly, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Specific examples include s-triazine and oxathiazole compounds, 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-bromo-4-di ( Acetoxyethyl) aminophenyl] -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, Nos. In p14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, U.S. Pat. No. 4,701,399. Compounds such as 1-19 are particularly preferred.

Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl] titanium. .
Examples of coumarins include 3-ketocoumarin.
These initiators may be used alone or in combination.

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

  As a commercially available photo radical polymerization initiator, “KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC” manufactured by Nippon Kayaku Co., Ltd. , MCA), etc .; “Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263)” manufactured by Ciba Specialty Chemicals Co., Ltd .; “Esacure” manufactured by Sartomer Preferred examples include (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) "and the like, and combinations thereof.

(Photosensitizer)
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

  Examples of commercially available photosensitizers include “KAYACURE (DMBI, EPA)” manufactured by Nippon Kayaku Co., Ltd.

[Thermal radical polymerization initiator skeleton]
The thermal radical polymerization initiator skeleton is also a compound similar to a commonly used thermal radical polymerization initiator, preferably each copolymer used in a curable composition for forming a low refractive index layer, particularly a component. It is preferable to have an initiator skeleton showing a value larger than the SP value of the compound (B).

  As the thermal radical polymerization initiator, organic or inorganic peroxides, organic azo- and diazo compounds, and the like can be used.

Specifically, organic peroxides include benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, Ammonium persulfate, potassium persulfate, etc .; 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile), etc. as azo compounds; diazo Examples of the compound include diazoaminobenzene and p-nitrobenzenediazonium.
These initiators may be used alone or in combination.

  Specific examples of initiators that can be preferably used in the present invention and their SP values (calculated by the Fedors method) are shown below, but are not limited thereto.

  In addition, a monomer containing an ethylenically unsaturated group and a self-polymerization initiating compound in which polymerization initiation sites are linked and bonded in the molecule can also be suitably used as the polymerization initiator in the present invention. Such compounds are exemplified below.

  Further, specific compounds of the initiator that can be used in the present invention are shown below.

  Although there is no restriction | limiting in particular in the usage-amount of a polymerization initiator (D), It should be used in the range of 0.1-20 mass parts with respect to 100 mass parts of polysiloxane structure containing copolymer (A) used together. Is more preferable, and 1 to 10 parts by mass is more preferable.

  These polymerization initiator compounds may be used alone or in combination of two or more with other photosensitizers. Examples of such photosensitizers include those described above, and specifically include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone. Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.

[Component (E): Inorganic fine particles]
In the curable composition of the present invention, the polysiloxane structure-containing copolymer (A), the compound (B) having at least one ethylenically unsaturated group in one molecule, and the inorganic fine particles as the component (E) Is preferably added.

  The inorganic fine particles (E) to be contained in the functional layer of the optical film of the present invention, particularly the low refractive index layer of the antireflection film, desirably have a low refractive index, and include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.

[Silica fine particles]
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particle is equal to or greater than the above lower limit value, the effect of improving the scratch resistance is exhibited. If the particle size is equal to or smaller than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer and the appearance such as black tightening, integral reflection Since a problem such as deterioration of the rate does not occur, it is preferable to use a silica fine particle having a particle size within the above range. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

  In addition, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “silica fine particles with small size particle size”) is used as silica fine particles with the above particle size (“large size particles” It is preferably used in combination with “silica fine particles having a diameter”.

  Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.

  When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

The coating amount of the low refractive index particles is preferably 1 to 100 mg / m ^2, more preferably 5-80 mg / m ^2, more preferably from 10~60mg / m ^2. If the coating amount is not less than the lower limit value, the effect of improving the scratch resistance is exhibited. If the coating amount is not more than the upper limit value, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance This is preferable because there is no problem of deterioration.

(Hollow silica particles)
For the purpose of further reducing the refractive index, it is preferable to use hollow silica fine particles.

The refractive index of the hollow silica fine particles is preferably 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, if the radius of the cavity in the particle is r _i and the radius of the particle outer shell is r _o , the porosity x is expressed by the following formula (1).
Equation (1): x = (4πr i 3/3) / (4πr o 3/3) × 100
The porosity x of the hollow silica particles is preferably 10 to 60%, more preferably 20 to 60%.
Most preferably, it is 30 to 60%.

  If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Therefore, a low refractive index of 1.15 or more from the viewpoint of scratch resistance. Rate particles are preferred.

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

The coating amount of the hollow silica is preferably from 1 to 100 mg / m ^2, more preferably 5-80 mg / m ^2, more preferably from 10~60mg / m ^2. If the coating amount of the hollow silica is equal to or greater than the lower limit, the effect of lowering the refractive index and the effect of improving the scratch resistance are sufficiently exhibited. It is preferable because irregularities can be formed and defects such as black tightening and deterioration of integrated reflectance do not occur.

  The average particle diameter of the hollow silica is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, more preferably 40% or more and 60% or less of the thickness of the functional layer used, for example, the low refractive index layer. It is. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm. If the particle size of the silica fine particles is not less than the lower limit value, the ratio of the cavities will not be too small, so that the refractive index will be lowered, and if it is not more than the upper limit value, the surface of the low refractive index layer will be fine. This is preferable because it can form irregularities and does not cause the appearance of black tightening and the deterioration of the integrated reflectance.

  The hollow silica may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

  Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.

In the present invention, the specific surface area of the hollow silica is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be determined by the BET method using nitrogen.

  In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

  When the inorganic particles are silica, a coupling agent can be used. As the coupling agent, an alkoxy metal compound (for example, titanium coupling agent, silane coupling agent, etc.) is preferably used. Of these, treatment with a silane coupling agent is particularly effective.

  The above-mentioned coupling agent is used, for example, 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, but is further added as an additive during the preparation of the layer coating solution. It is preferably contained in the layer.

The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

  Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in International Publication No. 2004/017105 pamphlet. Two or more kinds of these surface treatments can be used in combination.

[Other additives]
In the curable composition of the present invention, various additives and / or an appropriate solvent can be added according to necessity. The concentration of the solid content of the curable composition to be obtained is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably. Is about 1 to 20% by mass.

  When the curable composition of the present invention is used for forming a low refractive index layer of an antireflection film, from the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer, a polyfunctional epoxy compound, a polyisocyanate A small amount of a curing agent such as a compound, aminoplast, polybasic acid or anhydride thereof may be added. When adding these, it is preferable to set it as the range of 30 mass% or less with respect to the total solid of a low-refractive-index layer film, It is more preferable to set it as the range of 20 mass% or less, The range of 10 mass% or less It is particularly preferable that

  Further, for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipping property, a well-known fluorine compound antifouling agent, slipping agent, etc. may be appropriately added in addition to the above organosilane compound. it can. 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 curable composition, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass.

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

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with a functional layer, for example, a low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited.

Although there is no restriction | limiting in particular in fluorine atom content in a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. . Examples of preferred fluorine-based compounds include "R-2020", "M-2020", "R-3833", "M-3833" (trade names) manufactured by Daikin Industries, Ltd .; Dainippon Ink and Chemicals, Inc. "Megafuck F-171", "Megafuck F-172", "Megafuck F-179A", "Defenser MCF-300" (named above), etc. manufactured by Co., Ltd. are mentioned, but it is limited to these. It is not something.

[Dustproofing agent, antistatic agent, etc.]
When the curable composition of the present invention is used for forming a functional layer of an optical film, particularly a low refractive index layer of an antireflection film, the curable composition is imparted with properties such as dust resistance and antistatic property. In order to achieve this, it is possible to appropriately add a known anti-dust agent such as a known cationic surfactant or polyoxyalkylene compound, and an antistatic agent. As for these dustproof agent and antistatic agent, the structural unit may be included in the silicone-based compound or the fluorine-based compound as a part of the function.

  When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass of the total solid content of the functional layer, for example, the low refractive index layer. %, And particularly preferably 0.1 to 5% by mass.

  Examples of preferable compounds include “Megafac F-150” (trade name) manufactured by Dainippon Ink & Chemicals, Inc., “SH-3748” (trade name) manufactured by Toray Dow Corning Co., Ltd. However, it is not limited to these.

  In addition, additives such as various silane coupling agents, surfactants, thickeners, and leveling agents may be appropriately added to the curable composition used for forming the low refractive index layer as necessary.

[Solvent for coating functional layer]
When the curable composition of the present invention is used as a coating liquid composition for forming a functional layer, particularly a low refractive index layer, the solvent used can dissolve or disperse each component, coating step Various solvents selected from the viewpoints of being easy to form a uniform surface in the drying step, ensuring liquid storage stability, having an appropriate saturated vapor pressure, and the like can be used. From the viewpoint of low load on drying, it is preferable to use a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed. .

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), and benzene (80.1 ° C.); Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogen; ethers such as diethyl ether (34.6 ° C.), diisopropyl ether (68.5 ° C.), dipropyl ether (90.5 ° C.), tetrahydrofuran (66 ° C.); ethyl formate (54.2 ° C.), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.); acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as Luketone, 79.6 ° C; methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols; cyano compounds such as acetonitrile (81.6 ° C.) and propionitrile (97.4 ° C.); carbon disulfide (46.2 ° C.) and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C.), dibutyl ether (142.4 ° C.), isobutyl acetate (118 ° C.), cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone {same as methyl isobutyl ketone (MIBK), 115.9 ° C.}, 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

<Optical film>
The optical film of the present invention has at least one functional layer formed by curing the curable composition of the present invention.

[Representative layer structure of optical film]
The optical film of the present invention is an optical film in which one or more functional layers are laminated on a support, and is composed of a single layer such as a hard coat film having only a hard coat layer or an antireflection film having only a low refractive index layer. Also, a multilayer structure such as an antireflection film laminated with a high refractive index layer / medium refractive index layer / low refractive index layer, a hard coat film laminated with an antistatic layer / hard coat layer, etc. may be used, but preferably Is a multi-layer configuration.

  Although the optical film of this invention is not specifically limited, It can also be used for the outermost surface of the display of an image display apparatus. In that case, it can be used in an image display device as it is or in the form of a polarizing plate combined with a polarizing film, but it is preferable to form a functional layer on a transparent support in advance and arrange it as an optical film in the image display device.

  The functional layer formed by curing the curable composition of the present invention is not particularly limited in use, but is an antifouling layer, a transparent conductive layer, a hard coat layer, an antiglare layer, a low refractive index layer, or the like. Are preferable, a low refractive index layer and a hard coat layer are more preferable, and a low refractive index layer is particularly preferable.

  The antireflection film, which is a typical embodiment of the optical film of the present invention, has a hard coat layer, which will be described later, on the support, if necessary, and is refracted so that the reflectance decreases due to optical interference. The layers are laminated in consideration of the rate, film thickness, number of layers, layer order, and the like. In the simplest configuration, the low-reflective antireflection film has a configuration in which only a low refractive index layer is coated on a support. In order to further reduce the reflectance, the antireflection layer is preferably composed of a high refractive index layer having a higher refractive index than that of the support and a low refractive index layer having a lower refractive index than that of the support. As a configuration example, two layers of a high refractive index layer / low refractive index layer from the support side, or three layers having different refractive indexes, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer, A layer having a refractive index lower than that of a high refractive index layer) / a high refractive index layer / a low refractive index layer are stacked in this order, and a stack of more antireflection layers is also proposed.

[Typical layer structure of antireflection film]
The example of the preferable layer structure of the antireflection film of this invention is shown below.
-Support / low refractive index layer,
・ Support / Antistatic layer / Low refractive index layer,
・ Support / antiglare layer / low refractive index layer,
Support / antiglare layer / antistatic layer / low refractive index layer,
Support / antistatic layer / antiglare layer / low refractive index layer,
・ Support / hard coat layer / low refractive index layer,
Support / hard coat layer / antiglare layer / low refractive index layer,
Support / hard coat layer / antiglare layer / antistatic layer / low refractive index layer,
Support / hard coat layer / antistatic layer / antiglare layer / low refractive index layer,
Support / hard coat layer / high refractive index layer / low refractive index layer,
Support / hard coat layer / antistatic layer / high refractive index layer / low refractive index layer,
Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antiglare layer / high refractive index layer / low refractive index layer,
Support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Support / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / support / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer.

  As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, ATO, ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Layer structure of optical film other than antireflection film]
Other than the layer configuration of the antireflection film, examples of the layer configuration preferable as the optical film of the present invention are shown below.
・ Support / Antistatic layer,
・ Support / antiglare layer,
Support / antiglare layer / antistatic layer,
Support / antistatic layer / antiglare layer,
・ Support / hard coat layer,
・ Support / hard coat layer / antistatic layer,
・ Support / hard coat layer / antiglare layer,
Support / hard coat layer / antiglare layer / antistatic layer,
Support / hard coat layer / antistatic layer / antiglare layer,
・ Support / Antistatic layer / Hard coat layer,
・ Support / antiglare layer / hard coat layer,
・ Antistatic layer / support / hard coat layer,
-Antistatic layer / support / antiglare layer.

  Hereinafter, a basic configuration of an antireflection film suitable as one embodiment of the optical film of the present invention will be described with reference to the drawings.

  The cross-sectional view schematically shown in FIG. 1A is an antireflection film as an example of the optical film of the present invention. The antireflection film 1a has a layer structure in the order of a transparent support 2, a hard coat layer 3, a high refractive index layer 4, and a low refractive index layer 5 obtained by curing the curable composition of the present invention. The refractive index of the high refractive index layer 4 is preferably in the range of 1.50 to 2.00, and the refractive index of the low refractive index layer 5 is preferably in the range of 1.30 to 1.44.

  In the present invention, the hard coat layer may be provided separately from the high refractive index layer as described above, or may be a high refractive index hard coat layer having the function of the high refractive index layer. The hard coat layer may be a single layer or may be composed of a plurality of layers, for example, 2 to 4 layers. Further, the hard coat layer may be omitted. Accordingly, the hard coat layer shown in FIG. 1 is not essential, but it is preferable that any of these hard coat layers is applied to impart film strength. The low refractive index layer is coated on the outermost layer.

The cross-sectional view schematically shown in FIG. 1B is an antireflection film which is another example of the optical film of the present invention. The antireflection film 1b comprises a transparent support 2, a hard coat layer 3, a medium refractive index 6, a high refractive index layer 4, and a low refractive index layer (outermost layer) 5 obtained by curing the curable composition of the present invention. The layer structure is as follows. The transparent support 2, the medium refractive index layer 6, the high refractive index layer 4, and the low refractive index layer 5 have refractive indexes that satisfy the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer

  In the layer structure as shown in FIG. 1B, as described in JP-A-59-50401, the medium refractive index layer is represented by the following mathematical formula (2), and the high refractive index layer is represented by the following mathematical formula (3). It is preferable that the low refractive index layer satisfies the following mathematical formula (4) in that an antireflection film having more excellent antireflection performance can be produced.

Formula (2): (hλ / 4) × 0.7 <n ₁ d ₁ <(hλ / 4) × 1.3
Formula (3): (iλ / 4) × 0.7 <n ₂ d ₂ <(iλ / 4) × 1.3
Formula (4): (jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3

In equations (2)-(4), h is a positive integer (generally 1, 2 or 3), i is a positive integer (typically 1, 2 or 3), and j is a positive odd number (generally 1). ). n ₁ , n ₂ and n ₃ are the refractive indexes of the medium refractive index layer, the high refractive index layer and the low refractive index layer, respectively, and d ₁ , d ₂ and d ₃ are the medium refractive index layer, the high refractive index layer and the high refractive index layer, respectively. It is the layer thickness (nm) of the refractive index layer and the low refractive index layer. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

  In the layer configuration as shown in FIG. 1B, the medium refractive index layer is represented by the following mathematical formula (2-1), the high refractive index layer is represented by the following mathematical formula (3-1), and the low refractive index layer is represented by the following mathematical formula (4-1). It is particularly preferable that each of these is satisfied. Here, λ is 500 nm, h is 1, i is 2, and j is 1.

Formula (2-1): (hλ / 4) × 0.80 <n ₁ d ₁ <(hλ / 4) × 1.00
Formula (3-1): (iλ / 4) × 0.75 <n ₂ d ₂ <(iλ / 4) × 0.95
Formula (4-1): (jλ / 4) × 0.95 <n ₃ d ₃ <(jλ / 4) × 1.05

  The high refractive index, medium refractive index, and low refractive index described herein refer to the relative refractive index between layers. Moreover, in FIG.1 (b), the high refractive index layer is used as a light interference layer, and the antireflection film which has the very outstanding antireflection performance can be produced.

(Low refractive index layer)
The low refractive index layer in the antireflection film of the present invention will be described below.
The refractive index of the low refractive index layer of the antireflection film of the present invention is 1.20 to 1.49, preferably 1.30 to 1.44. Furthermore, the low refractive index layer preferably satisfies the following formula (4) as described above from the viewpoint of reducing the reflectance.

Formula (4): (jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3

In the formula, j, n ₃ , d ₃ and λ are as described above, and λ is a value in the range of 380 to 680 nm.
In addition, satisfy | filling the said Numerical formula (4) means that j (positive odd number, usually 1) which satisfy | fills Numerical formula (4) exists in the said wavelength range.

  The dynamic friction coefficient of the cured low refractive index layer surface is preferably 0.03 to 0.15, and the contact angle with water is preferably 90 to 120 °.

  The low refractive index layer in the present invention is preferably formed by coating and curing the curable composition of the present invention.

  The film thickness of the low refractive index layer is preferably 5 nm to 10 μm, more preferably 10 nm to 1 μm, and most preferably 30 nm to 500 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less.

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

[Material for hard coat layer]
(binder)
When the hard coat layer is the functional layer on the outermost surface of the optical film of the present invention, in addition to the hard coat layer material shown below, the polysiloxane structure which is the component (A) of the curable composition of the present invention It is preferred to add the containing copolymer. When the hard coat layer is not the functional layer on the outermost surface of the optical film of the present invention, it is preferable not to add the component (A).

  The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable resin. For example, it can be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a support and causing the polyfunctional monomer or polyfunctional oligomer to undergo a crosslinking reaction or a polymerization reaction. Among these, film strength, coating liquid, and the like are formed by curing a compound having at least one ethylenically unsaturated group in one molecule, which is component (B) of the curable composition of the present invention. It is preferable in terms of the stability of the coating film and the productivity of the coating film, and more preferably formed by curing a coating liquid composition containing a monomer containing two or more ethylenically unsaturated groups in one molecule. .

As the monomer having two or more ethylenically unsaturated groups in one molecule, those exemplified in the description of the component (B) of the curable composition of the present invention can be used. Esters of polyhydric alcohol and (meth) acrylic acid {for example, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate, etc.}, vinylbenzene and its derivatives (examples) Examples include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone, etc.), vinyl sulfone (eg divinyl sulfone), acrylamide (eg methylene bisacrylamide) and methacrylamide. It is done. Two or more of these monomers may be used in combination.
In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

  In order to make the formed film have a high refractive index, the monomer structure contains an aromatic ring, at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms. A high refractive index monomer or a monomer having a fluorene skeleton in the molecule may be selected.

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

  As described above, when the hard coat layer is the functional layer on the outermost surface of the optical film of the present invention, a polysiloxane structure-containing copolymer that is the component (A) of the curable composition of the present invention is added. Is preferred. In that case, the compounding ratio of the component (A) and the component (B) is such that the polysiloxane structure in the copolymer of the component (A) is 0.001 to 100 parts by mass of the compound of the component (B). It is preferable to mix | blend so that it may become 40 mass parts, and it is still more preferable to mix | blend so that it may become 0.01-15 mass parts. If the polysiloxane structure in the copolymer of the component (A) is 40 parts by mass or less with respect to 100 parts by mass of the compound of the component (B), the scratch resistance is deteriorated or the surface shape is deteriorated. In addition, since the necessary antifouling performance can be obtained if it is 0.001 part by mass or more, the blending ratio of component (A) and component (B) is within this range. It is preferable that

(Polymerization initiator)
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photoradical polymerization initiator or a thermal radical polymerization initiator. Examples of these polymerization initiators include the above-mentioned photo radical polymerization initiator and thermal radical polymerization initiator as the component (D) of the present invention.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums.

  Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included.

  Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether.

  Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  In addition, P. of “Latest UV Curing Technology”. Various examples are also described in 159 {Issuer: Kazuhiro Takasato, Issuer; Technical Information Association, Inc., published in 1991}, which is useful for the present invention.

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

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 are also as described above, and examples thereof include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

  As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used. Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides; hydrogen peroxide, peroxides as inorganic peroxides Ammonium sulfate, potassium persulfate, etc .; 2-azobisisobutyronitrile, 2-azobispropionitrile, 2-azobiscyclohexanedinitrile, etc. as azo compounds, diazoaminobenzene, p-nitrobenzenediazonium, etc. as diazo compounds be able to.

  The thermal radical initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.

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

  In addition to the monomer having two or more ethylenically unsaturated groups, a crosslinkable functional group is introduced into the polymer using a monomer having a crosslinkable functional group, and the crosslinkable functional group is reacted to react with the crosslinkable structure. It may be introduced into the 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.

  Further, the hard coat layer can contain mat particles for imparting antiglare properties and inorganic fine particles for increasing the refractive index, preventing cross-linking shrinkage, and increasing the strength as necessary.

(Matte particles)
For the purpose of imparting anti-glare properties, the hard coat layer is larger than inorganic fine particles and has an average particle size of 0.1 to 5.0 μm, preferably 1.5 to 3.5 μm, for example, inorganic compound particles or Resin particles can be contained.

  If the difference in refractive index between the matte particles and the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusion effect cannot be obtained, so 0.02 to 0.20 is preferable, and 0.04 to Particularly preferred is 0.10. Similarly to the refractive index, the amount of addition of the matting particles to the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusion effect cannot be obtained. % Is particularly preferred.

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

Two or more different kinds of mat particles may be used in combination.
When two or more kinds of mat particles are used, the difference in refractive index is preferably 0.02 or more and 0.10 or less in order to effectively exert the refractive index control by mixing the two, and 0.03 or more. Is particularly preferably 0.07 or less. Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder.

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

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

  The particle size distribution of the matte 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 has at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer and to reduce curing shrinkage. It is preferable to contain inorganic fine particles made of one kind of metal oxide and having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.

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

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 , ITO, SiO _{2 and the} like. 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 a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the fine particle surface is preferably used.

  The amount of these inorganic fine particles added is preferably 10 to 90% of the total mass of the hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.

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

  The bulk refractive index of the mixture of the binder and inorganic fine particles in the hard coat layer in the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within this range, the kind 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.

[Layers other than low refractive index layer / hard coat layer]
[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.

  As a method of forming the antiglare layer, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851; JP-A 2000-206317 As described, a method of forming by curing shrinkage of ionizing radiation curable resin due to a difference in ionizing radiation dose; weight ratio of good solvent to translucent resin by drying as described in JP-A-2000-338310 Is a method of forming unevenness on the coating film surface by gelling the translucent fine particles and the translucent resin while gelling; as described in JP-A-2000-275404, Methods for imparting surface irregularities are known, and these known methods can be used.

  The antiglare layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent. It is preferable that surface irregularities be formed by protrusions or protrusions formed by an aggregate of a plurality of particles.

  The antiglare layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties.

  The mat particles used for the antiglare layer may be the same as the mat particles used for the purpose of imparting antiglare property in the hard coat layer. The operation is the same.

As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either spherical or irregular.

Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an anti-glare antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” is derived from the fact that pixels are enlarged or reduced due to unevenness present on the surface of the antiglare and antireflection antireflection film, resulting in loss of luminance uniformity, but particles smaller than mat particles that impart antiglare properties. It can be greatly improved by using mat particles having a diameter different from that of the binder.

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

  The film thickness of the antiglare layer is preferably in the range of 1 to 10 μm, and more preferably in the range of 1.2 to 8 μm. If the film thickness of the antiglare layer is not less than the lower limit value, excellent hard properties can be imparted, and if the film thickness is not more than the upper limit value, there are problems such as curling and brittleness being deteriorated and workability being lowered. Since it does not occur, it is preferable to be within the above range.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.10 to 0.40 μm. If the center line average roughness is 0.40 μm or less, problems such as glare and whitening of the surface when external light is reflected hardly occur. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

  The surface hardness of the antiglare layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in the pencil hardness test.

[High refractive index layer, medium refractive index layer]
The antireflection film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to improve the antireflection property.

In the following specification, the high refractive index layer and the middle refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, medium refractive index layer, and low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support.
Furthermore, in this specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

  In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70-2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80.

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion.
The inorganic particles are preferably dispersed in the dispersion medium in the presence of a dispersant.

The high refractive index layer and the medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, the ionizing radiation-curable material described above). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support It is preferable that the coating composition is applied and cured 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.

  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 of maintaining the dispersion state of the inorganic particles by the anionic group, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder of the high refractive index layer is added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

  The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more kinds of inorganic particles may be used in combination in the high refractive index layer.

  When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.

  The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer, 30-200 nm is preferable, More preferably, it is 50-170 nm, Most preferably, it is 60-150 nm.

  The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

  The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

[Antistatic layer, conductive layer]
In the present invention, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the surface of the antireflection film. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. The antistatic layer can also be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is preferably from 10 ⁵ to 10 is ¹² Omega / □, more preferably 10 ⁵ to 10 ⁹ Omega / □ is the most be 10 ⁵ to 10 ⁸ Omega / □ is preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

  The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. Further, the transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

  The surface hardness of the antistatic layer in the present invention is preferably excellent, and the specific surface hardness of the antistatic layer is preferably a pencil hardness of 1 kg load, preferably H or more, and 2H or more. Is more preferably 3H or more, and most preferably 4H or more.

[Anti-fouling layer]
An antifouling layer can be provided on the outermost surface of the antireflection film of the present invention. The antifouling layer lowers the surface energy of the antireflection film and makes it difficult to attach hydrophilic or lipophilic stains.

  The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent.

  The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

  The thus formed optical film of the present invention preferably has a haze value of 3 to 70%, particularly preferably 4 to 60%. When the optical film has an antireflection function, the haze value is in the above range, and the average reflectance from 450 nm to 650 nm is preferably 3.0% or less, and is 2.5% or less. It is particularly preferred. When the antireflection film of the present invention has a haze value and an average reflectance within this range, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

  Layers other than the low refractive index layer described above, that is, a hard coat layer, an antiglare layer, a high refractive index layer, a medium refractive index layer, an antistatic layer, an antifouling layer, and the like, are also curable according to the present invention. It can form by hardening the said component (A), component (B), and component (C) which are the main components of a composition.

[Support]
As the transparent support of the optical film of the present invention, for example, an antireflection film, it is preferable to use a plastic film. As a polymer for forming a plastic film, cellulose ester {for example, triacetylcellulose, diacetylcellulose, typically “TAC-TD80U”, “TAC-TD80UF”, etc., manufactured by Fuji Photo Film Co., Ltd.}, polyamide, polycarbonate, Polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polyolefin, norbornene resin {“Arton” (trade name), manufactured by JSR Corporation}, amorphous polyolefin {“ZEONEX” (trade name), Japan ZEON Co., Ltd.}. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

  In addition, a cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure No. 2001-1745, published on March 15, 2001, the following. The cellulose acylate described here is also preferably used in the present invention.

[Saponification]
When the optical film of the present invention is used in an image display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the support of the optical film is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing film of the polarizing plate. Therefore, it is preferable in terms of cost to use the optical film of the present invention as it is for the protective film. .

  When the optical film of the present invention is disposed on the outermost surface of the display by providing an adhesive layer on one side or used as it is as a protective film for a polarizing plate, it is sufficiently adhered on the support. It is preferable to carry out a saponification treatment after forming the functional layer.

  The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkali solution, it is preferable to sufficiently wash with water so that the alkali component does not remain in the film, and to soak in a dilute acid to neutralize the alkali component. By performing the saponification treatment, the surface of the support opposite to the side having the outermost layer is hydrophilized.

  The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so when adhering to the polarizing film, it is difficult for dust to enter between the polarizing film and the optical film, thus preventing point defects due to dust. It is valid.

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

  Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is excellent in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the saponification treatment is performed up to the optical film surface, the surface is alkali-hydrolyzed and the membrane deteriorates. If it remains, it becomes a problem that it becomes dirty. In that case, although it becomes a special process, (2) is excellent.

(1) After forming the functional layer on the support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after forming the functional layer on the support, by applying an alkaline liquid to the surface opposite to the surface on which the functional layer of the optical film is formed, heating, washing and / or neutralizing, Only the back side of the film is saponified.

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

  First, a coating solution containing components for forming each layer is prepared. The coating solution is applied onto the support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, extrusion coating (see US Pat. No. 2,681,294). Heat and dry.

  Among these coating methods, the gravure coating method is preferable because a coating solution with a small coating amount such as each layer of an optical film can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method is more preferable because of high film thickness uniformity.

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

  In an optical film composed of a plurality of layers, two or more layers may be applied simultaneously. For the method of simultaneous application, US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, 3,526,528, and Harasaki Yuji, “Coating Engineering”, page 253, {Asakura Shoten (1973)}.

<Use of optical film>
〔Polarizer〕
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The optical film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. The manufacturing cost of a polarizing plate can be reduced because the optical film of the present invention also serves as a protective film. In addition, by using the optical film of the present invention, particularly the antireflection film, as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance and antifouling properties can be obtained.

[Polarizing film]
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used.

  A long polarizing film in which the absorption axis of the polarizing film is neither parallel nor perpendicular to the longitudinal direction is produced by the following method. That is, both ends of a continuously supplied polymer film are stretched by applying a tension while being held by a holding means and stretched at least 1.1 to 20.0 times in the film width direction. The longitudinal movement speed difference of the holding device is within 3%, and the angle formed by the film traveling direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. It can be produced by a stretching method in which the traveling direction is bent with both ends of the film held. In particular, those inclined at 45 ° are preferably used from the viewpoint of productivity.

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

(Image display device)
The image display device of the present invention uses the optical film, the antireflection film or the polarizing plate on the outermost surface of the display. For example, in the aspect used as one side of the surface protective film of the polarizing film, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device in a mode such as a cell (OCB).

In VA mode liquid crystal cell,
(1) In addition to a narrowly-defined VA mode liquid crystal cell (described in JP-A-2-176625) in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied. ,
(2) Liquid crystal cell ("SID97, Digest of tech. Papers" (Preliminary Collection), Vol. 28 (1997), p. 845},
(3) A liquid crystal cell of a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied {Procedures 58-59 (1998) ) Description} and
(4) Includes SURVAVAL mode liquid crystal cells (announced at "LCD International 98").

  For a VA mode liquid crystal cell, a polarizing plate prepared by combining a biaxially stretched triacetyl cellulose film with the antireflection film of the present invention is preferably used. As for the method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

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

  In particular, for a TN mode or IPS mode liquid crystal display device, as described in Japanese Patent Application Laid-Open No. 2001-100043, an optical compensation film having an effect of widening the viewing angle is protected on the two sides of the polarizing film. By using it on the surface of the film opposite to the optical film of the present invention, a polarizing plate having an effect of an optical film (especially an antireflection film) and a viewing angle widening effect with the thickness of one polarizing plate is obtained. It is particularly preferable.

  The optical film of the present invention can also be used for a case cover, optical lens, spectacle lens, window shield, light cover, and helmet shield.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
In the following, examples other than Examples 4-2, 6-2, and 8-2 shall be read as “reference examples”.

<Preparation of antireflection film>
[Preparation of various coating solutions]
[Preparation of coating solution for antistatic layer]

{Coating solution for antistatic layer (AS-1)}
"Pertron C-4456-S7" 100 parts by mass Commercially available ATO-dispersed hard coat agent, manufactured by Nippon Pernox Co., Ltd., solid content: 45%
Cyclohexanone 30 parts by weight Methyl ethyl ketone 10 parts by weight “KBM-5103” 1.5 parts by weight Silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., 3-acryloxypropyltrimethoxysilane

  After stirring the mixed solution, it was filtered through a polypropylene filter having a pore size of 10 μm to prepare an antistatic layer coating solution (AS-1).

[Preparation of curable composition]
(Preparation of coating solution for hard coat layer)

Reference Example 1-1: Coating liquid for hard coat layer (HC-1)
“DPHA” 25.4 parts by mass Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Methyl isobutyl ketone 40.0 parts by mass Propylene glycol 6.3 parts by mass “Irgacure 184” 3 parts by weight Polymerization initiator, “KBM-5103” manufactured by Ciba Specialty Chemicals Co., Ltd. 5.2 parts by weight Silane coupling agent, “CAB-531-1” manufactured by Shin-Etsu Chemical Co., Ltd. 0.50 parts by weight Cellulose acetate butyrate, manufactured by Eastman Chemical Co., Ltd. Crosslinked poly (acryl-styrene) particles 21.0 parts by mass Copolymerization composition ratio = 50/50, refractive index 1.536, average particle size 3.5 μm, 30% by mass Methyl isobutyl ketone dispersion

  After stirring the mixed solution, it was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HC-1).

Reference Example 1-2: Coating liquid for hard coat layer (HC-2)
“DPHA” 25.4 parts by mass Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Methyl isobutyl ketone 40.0 parts by mass Propylene glycol 6.3 parts by mass “Irgacure 184” 3 parts by weight Polymerization initiator, Ciba Specialty Chemicals “KBM-5103 5.2 parts by weight Silane coupling agent, Shin-Etsu Chemical Co., Ltd.“ CAB-531-1 ”0.50 parts by weight Cellulose Acetate butyrate (separation 40,000), manufactured by Eastman Chemical Co., Ltd.

  After stirring the mixed solution, it was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution (HC-2).

Example 1-2: Coating liquid for hard coat layer (HC-3)
"KZ7973" 100 parts by mass Commercially available zirconia ultrafine particle dispersed hard coat agent, manufactured by JSR Corporation, solid content 50 mass%, refractive index 1.69
"Bright 20GNR4.6-EH" 0.1 parts by mass Conductive particles, manufactured by Nippon Chemical Industry Co., Ltd., benzoguanamine / melanin / formaldehyde condensate spherical powder plated with gold and nickel Polysiloxane structure / hydroxyl group-containing copolymer (P-1) 3 parts by mass

  After the mixed solution was stirred, it was filtered through a polypropylene filter having a pore diameter of 10 μm to prepare a conductive hard coat layer coating solution (HC-3).

Example 1-1: Coating liquid for hard coat layer (HC-4)
“PET-30” 540.0 parts by mass A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.
Polymethyl methacrylate solution (20% by mass) 300.0 parts by mass “Irgacure 184” 20.0 parts by mass Polymerization initiator, crosslinked polystyrene particles manufactured by Ciba Specialty Chemicals Co., Ltd. 17.0 parts by mass Average particle size 8. 0 μm, 30% by weight toluene dispersion Cross-linked poly (acryl-styrene) particles 133.0 parts by weight Average particle size 8.0 μm, 30% by weight toluene dispersion Toluene 47.0 parts by weight Cyclohexanone 98.0 parts by weight Silicone oil “X -22-164C "0.1 part by mass Polysiloxane structure / hydroxyl group-containing copolymer (P-1) 32.4 parts by mass After the above mixture was stirred, it was filtered through a polypropylene filter having a pore size of 10 μm, and a hard coat layer Coating solution (HC-4) was prepared.

[Preparation for low refractive index layer]
{Preparation of organosilane compound (sol solution a)}
The sol liquid a is prepared as follows.
A reactor equipped with a stirrer and a reflux condenser, 120 parts by mass of methyl ethyl ketone, 100 parts by mass of acryloyloxypropyltrimethoxysilane {“KBM-5103”, manufactured by Shin-Etsu Chemical Co., Ltd.}, 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate Part was added and mixed. Next, 30 parts by mass of ion-exchanged water was added to this and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a 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% by mass. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29% by mass.

(Preparation of hollow silica dispersion)
Hollow silica fine particle sol (isopropyl alcohol silica sol, average particle diameter 40 nm, shell thickness 6 nm, silica concentration 20 mass%, silica particle refractive index 1.30, size changed according to Preparation Example 4 of JP-A-2002-79616 1) 30 parts by mass of acryloyloxypropyltrimethoxysilane {"KBM-5103", manufactured by Shin-Etsu Chemical Co., Ltd.}, 2 parts by mass of trimethylmethoxysilane, and diisopropoxyaluminum ethyl acetate After adding 5 parts by mass and mixing, 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone.

  While adding cyclohexanone to 500 g of this dispersion so that the silica content was substantially constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. No foreign matter was generated in the dispersion, and the viscosity when the solid content concentration was adjusted to 26% by mass with cyclohexanone was 10 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained hollow silica dispersion was analyzed by gas chromatography, it was 1.0% by mass.

Examples 2-1 to 2-40 and comparative examples 2-1 to 2-4
{Coating liquids for low refractive index layer (Ln1) to (Ln44)}
The components shown in Table 3 below are mixed, dissolved in methyl ethyl ketone, adjusted to a solid content of 6% by mass, stirred, and then filtered through a polypropylene filter having a pore size of 10 μm (Ln1 to Ln44). Was made. The numbers in Table 3 represent parts by mass of the solid content of each component.

  In Table 3, colloidal silica represents “MEK-ST” manufactured by Nissan Chemical Industries, Ltd.

[Preparation of antireflection film]
Example 3-1
A triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} having a thickness of 80 μm is unwound in a roll form, and the above-described coating liquid for forming a hard coat layer (HC-1) is directly Using a gravure roll with a diameter of 180 mm / in and a gravure pattern with a depth of 40 μm and a doctor blade, a gravure roll was applied at a rotation speed of 30 rpm and a conveyance speed of 30 m / min. after drying, further by using "air-cooled Metal halide lamp" {manufactured by eye graphics Co., Ltd.} of 160 W / cm at an oxygen concentration of 0.1 vol% nitrogen purge, illuminance 400 mW / cm ^2, irradiation amount 110 mJ / cm ² The ultraviolet ray was irradiated to cure the coating layer, and a 6 μm thick hard coat layer was formed and wound up.

On the hard coat layer thus obtained, the antireflective film (101) is adjusted by using the coating solution for low refractive index layer (Ln1) so that the thickness of the low refractive index layer is 95 nm. Was made. The low refractive index layer was dried at 120 ° C. for 10 minutes, and the ultraviolet curing condition was an “air-cooled metal halide lamp” of 240 W / cm while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. Using an iGraphics Co., Ltd.}, an illuminance of 120 mW / cm ² and an irradiation amount of 240 mJ / cm ² was used.

Examples 3-2 to 3-40 and Comparative Examples 3-1 to 3-4
In Example 3-1, instead of using the low refractive index layer coating solution (Ln1), the low refractive index layer forming coating solutions (Ln2) to (Ln44) are used to form the low refractive index layer. In the same manner as in Example 3-1, antireflection films (102) to (144) were produced. Table 4 shows combinations of the hard coat layer forming composition and the low refractive index layer forming composition used for each of the obtained antireflection films.

Example 3-41
In Example 3-1, instead of using the hard coat layer forming coating solution (HC-1), the hard coat layer forming coating solution (HC-2) is used to form a low refractive index layer. Antireflection film (145) in the same manner as in Example 3-1, except that the low refractive index layer is formed using the low refractive index layer forming coating solution (Ln20) instead of using the coating liquid (Ln1). Was made. Table 4 shows combinations of the hard coat layer forming composition and the low refractive index layer forming composition used for each of the obtained antireflection films.

Examples 3-42 to 3-44
In Example 3-41, instead of using the low refractive index layer coating liquid (Ln20), the low refractive index layer is formed using the low refractive index layer forming coating liquid (Ln28), (Ln29), or (Ln38). Except doing it, it carried out similarly to Example 3-41, and produced the anti-reflective films (146)-(148), respectively. Table 4 shows combinations of the hard coat layer forming composition and the low refractive index layer forming composition used for each of the obtained antireflection films.

[Saponification treatment of antireflection film]
The obtained antireflection films (101) to (148) were treated and dried under the following saponification standard conditions.
(1) Alkaline bath: 1.5 mol / L sodium hydroxide aqueous solution, 55 ° C.-120 seconds (2) First washing bath: tap water, 60 seconds (3) Neutralization bath: 0.05 mol / L sulfuric acid, 30 ° C. -20 seconds (4) Second water washing bath: tap water, 60 seconds (5) Drying: 120 ° C.-60 seconds

[Evaluation of antireflection film]
The following evaluation was performed using the saponified antireflection film thus obtained. Table 4 shows the obtained results.

(Evaluation 1) Scratch resistance (1)-Steel wool resistance evaluation A rubbing test of each antireflection film sample was performed under the following conditions using a rubbing tester.
Evaluation environmental conditions: 25 ° C., 60% RH,
Rubbing material: Steel wool “No. 0000” (manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move. Then, a reciprocating rubbing motion under the following conditions was given.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / second,
Load: 200 g / cm ²
Tip contact area: 1 cm × 1 cm,
Number of rubbing: 10 round trips.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.

(Evaluation 2) Scratch Resistance (2) -Eraser Scratch Resistance Evaluation Using a rubbing tester, each antireflection film sample was subjected to a rubbing test under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rubbing material: A plastic eraser {"MONO" manufactured by Dragonfly Pencil Co., Ltd.) was fixed to the rubbing tip (1 cm x 1 cm) of the tester that was in contact with the sample.
Moving distance (one way): 4 cm, rubbing speed: 2 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm,
Number of rubbing: 100 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.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.
XX: Single-sided film is damaged.

(Evaluation 3) Evaluation of adhesion Using a sunshine weather meter “S-80” {manufactured by Suga Test Instruments Co., Ltd.}, each antireflection film sample after exposure for 200 hours with a sunshine carbon arc lamp, 60% RH was obtained. And humidity was adjusted for 2 hours under the conditions of a temperature of 25 ° C. and 60% RH. On the surface of each sample having the low refractive index layer, 11 vertical and 11 horizontal cuts are made at 1 mm intervals with a cutter knife in a grid pattern, and a total of 100 square squares are carved on the surface. A polyester adhesive tape “No. 31B” manufactured by Nitto Denko Corporation was attached. After 30 minutes, the tape was quickly peeled off in the vertical direction, and the number of squares peeled off was counted and evaluated according to the following four criteria. The same adhesion evaluation was performed 3 times and the average was taken.
A: No peeling was observed at 100 mm.
○: peeling of 1 to 2 mm was observed at 100 mm.
Δ: Peeling of 3 to 10 mm was observed at 100 mm (within tolerance).
X: Peeling of 11 mm or more was observed at 100 mm.

(Evaluation 4) “Magic Ink” Adhesion Evaluation As an index of surface contamination resistance, each antireflection film sample was conditioned at a temperature of 25 ° C. and 60% RH for 2 hours, and then “magic ink” (product) Name) was adhered, and the state when it was wiped off with a cleaning cloth was observed, and “magic ink” adhesion was evaluated as follows.
A: The mark of “magic ink” can be completely wiped off.
○: A trace of “magic ink” is visible.
Δ: A trace of “magic ink” is visible.
X: Traces of “magic ink” are hardly wiped off.

[Production of hard coat film]
Example 4-1
80 μm-thick triacetyl cellulose “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is rolled up and coated with an antistatic layer coating solution (AS-1). After drying for a minute, the coating layer was cured using an ultraviolet lamp with an irradiation part with an illuminance of 100 mW / cm ² and an irradiation amount of 100 mJ / cm ² to form an antistatic layer having a thickness of about 0.2 μm.

  On the antistatic layer, the hard coat layer coating solution (HC-3) prepared in Example 1-1 was applied, and subjected to a heat treatment and a curing treatment by ultraviolet irradiation to obtain a charge of about 5 μm in thickness. A preventive hard coat film (201) was produced. The conditions for the heat treatment and the curing treatment are 120 ° C., drying for 5 minutes, and ultraviolet irradiation under a nitrogen purge.

Example 4-2
80 μm-thick triacetyl cellulose “TAC-TD80U” (manufactured by Fuji Photo Film Co., Ltd.) is rolled up to form a hard coat layer coating solution (HC-4) prepared in Example 1-2. After drying at 90 ° C., the coating layer is cured with an ultraviolet lamp using an ultraviolet lamp with an illuminance of 100 mW / cm ² and an irradiation amount of 150 mJ / cm ² , and a hard antiglare layer having a thickness of 25 μm. A coated film (202) was produced.

[Saponification treatment and evaluation of hard coat film]
The obtained hard coat film was saponified in the same manner as in the case of the antireflection film, and then the saponified hard coat film obtained was evaluated in the same manner as the antireflection film. The results obtained are shown in Table 5.

  As is clear from this example, the antireflection films (Example 3-1) to (Example 3-44) of the present invention are antireflection films (Comparative Example 3-1) to (Comparative Example 3-4). It can be seen that since the polysiloxane copolymer (A) is contained, there is a clear difference in antifouling property, scratch resistance, and surprisingly adhesion. Furthermore, the antireflection film containing the sol liquid a in the low refractive index layer is more adhesive and less rubbed than the other antireflection films (Examples 3-8, 3-16, 3-25, 3-33). The antireflection film having high scratch resistance evaluation and containing fine particles such as hollow silica sol and colloidal silica “MEK-ST” in the low refractive index layer is more steel than the other antireflection films (Examples 3-17 and 3-34). Excellent wool scratch resistance and eraser scratch resistance evaluation.

  Moreover, the hard coat film with an antistatic layer of the present invention (Example 4-1) and the antiglare film (Example 4-2) also exhibited excellent scratch resistance, antifouling properties, and adhesion.

[Production of polarizing plate with optical film]
Example 5-1
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A polyvinyl alcohol adhesive is used for the antireflective film (101) prepared in Example 3-1 and the support (triacetylcellulose) side of the antireflective film becomes the polarizing film side. Affixed to one side of the polarizing film. Further, the disc surface of the discotic structural unit is inclined with respect to the support surface, and the angle formed by the disc surface of the discotic structural unit and the support surface changes in the depth direction of the optically anisotropic layer. Wide-view film SA with an optically anisotropic layer “Side-view film SA” {Fuji Photo Film Co., Ltd.} is saponified and attached to the other side of the polarizing film using a polyvinyl alcohol adhesive I attached. In this way, a polarizing plate with an optical film (HB-1) was produced.

Examples 5-2 to 5-44 and comparative examples 5-1 to 5-2
In Example 5-1, instead of using the antireflection film (101) produced in Example 3-1, antireflection produced in Examples 3-2-3-44 and Comparative Examples 3-1 to 3-4. Polarizing plates with optical film (HB-2) to (HB-48) were produced in the same manner as in Example 5-1, except that the films (102) to (148) were used.

Examples 6-1 and 6-2
In Example 5-1, instead of using the antireflection film (101) prepared in Example 3-1, the hard coat film (201) or (202) prepared in Example 4-1 or 4-2 is used. Except that, a polarizing plate with an optical film (HB-49) and (HB-50) was produced in the same manner as in Example 5-1.

[Production of image display device]
Examples 7-1 to 7-44 and Comparative Examples 7-1 to 7-2
Saponified antireflection films (101) to (148) prepared in Examples 3-1 to 3-44 and Comparative Examples 3-1 to 3-4 were obtained from NEC Corporation. An image surface device sample was prepared by pasting on a liquid crystal display surface of a personal computer “PC9821NS / 340W”.

Examples 8-1 and 8-2
In Example 7-1, instead of using the antireflection film (101) prepared in Example 3-1, the hard coat film (201) or (202) prepared in Example 4-1 or 4-2 is used. Except that, an image surface device sample was produced in the same manner as in Example 7-1.

  The polarizing plate with an optical film and the image display device produced as described above showed excellent scratch resistance, antifouling property and adhesion as compared with the comparative example, as in the case of the optical film attached thereto. .

FIG. 1 is a schematic cross-sectional view showing a layer structure when the antireflection film of the present invention is a composite film. FIG. 1A shows an example of a four-layer structure, and FIG.

Explanation of symbols

1a: Antireflection film 1b: Antireflection film 2: Transparent support 3: Hard coat layer 4: High refractive index layer 5: Low refractive index layer (outermost layer)
6: Medium refractive index layer

Claims (7)

An optical film having a hard coat layer on a transparent support, the hard coat layer being the outermost layer, and curing a curable composition containing the following components (A), (B), and (D) In the cured composition, the optical film is blended so that the component (A) is 0.001 to 40 parts by mass with respect to 100 parts by mass of the component (B).
(A) A copolymer containing a structural unit having a polysiloxane structure represented by the following general formula (1) in the main chain and a structural unit having an ethylenically unsaturated group in the side chain, 3) a copolymer represented by the polymer initiator method,
General formula (1):

{In General Formula (1), R ¹¹ and R ¹² represent a hydrogen atom, an alkyl group, or an aryl group. p represents an integer of 10 to 500. }
General formula (3):

{In General Formula (3), X ³¹ represents a unit containing a polysiloxane structure represented by General Formula (1). Y ³¹ represents a polymerized unit based on an arbitrary vinyl monomer, and may be a single unit or a plurality of types. L ³¹ represents a single bond or a divalent linking group, and the divalent linking group includes * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * —. _{(CH 2) 4 -O - **} , * - (CH 2) 6 -O - **, * - (CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- ( _{CH 2) 3 -O - **,} * - CH 2 CH (OH) CH 2 -O - **, * - CH 2 CH 2 OCONH (CH 2) 3 -O - **, or any one of the following formulas It is. In the formula, * represents a linking site on the copolymer main chain side, and ** represents a linking site on the (meth) acryloyl group side. R ³¹ and R ³² each independently represents a hydrogen atom or a methyl group. x to z each represents a mole fraction (%) of each structural unit, and represents values satisfying 50 ≦ x <100, 0 ≦ y ≦ 40, and 10 ≦ z ≦ 35.
(B) a monomer compound having two or more ethylenically unsaturated groups in one molecule;
(D) An ionizing radiation curable polymerization initiator.

The monomer constituting the Y ³¹ polymerization unit in the general formula (3) is methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate. 2. The optical film according to claim 1, which is a monomer selected from styrene, stearyl methacrylate, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, and methacrylonitrile.   The optical film of Claim 1 or 2 mix | blended so that the said component (A) may become 0.001-15 mass parts with respect to 100 mass parts of the said component (B) in the said hardening composition. .   The optical film according to claim 1, wherein the hard coat layer has an antiglare function.   The polarizing plate in which the optical film as described in any one of Claims 1-4 is used for one of the two protective films of the polarizing film in a polarizing plate.   The optical display as described in any one of Claims 1-4, or the image display apparatus in which the polarizing plate of Claim 5 is used for the outermost surface of a display.   An optical film manufacturing method comprising a hard coat layer as an outermost layer on a transparent support, wherein the hard coat layer is formed by curing the curable composition according to claim 1. A method for producing a film.

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