JP2009285859A - Norbornene resin film having reflection preventive layer, and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene resin film having a reflection preventive layer, allowing efficient production, capable of restraining sufficiently a crack from being generated, and usable favorably as a reflection preventive film useful when applied in a wavelength plate. <P>SOLUTION: This norbornene resin film having the reflection preventive layer has the reflection preventive layers laminated with three or more of layers with refractive indexes different between adjacent fellow layers and having reflection preventive ability, on both faces of a base material film containing a norbornene polymer, and each layer having the reflection preventive ability is formed using a UV curable material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a norbornene-based resin film having an antireflection layer, which is useful as an antireflection film, and uses thereof. More specifically, the present invention relates to a film having a multilayer antireflection layer on both sides of a norbornene-based polymer, a wavelength plate for an optical pickup module having the same, and an optical pickup module having the wavelength plate.

  The antireflection film with an antireflection layer formed on a plastic film prevents reflection of external light in various display elements such as liquid crystal display panels, film-type liquid crystal elements, touch panels, cold cathode ray tube panels, and plasma displays. Widely used to improve image quality. Particularly in a liquid crystal display panel, the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate.

  The antireflection layer of the antireflection film is usually formed by depositing a metal oxide or the like on a film serving as a base material (see Patent Documents 1 and 2). However, the production of the antireflection layer by vapor deposition has a problem of poor productivity. Further, the antireflection layer formed by vapor deposition has a problem that cracks are likely to occur in the antireflection layer when the base film contracts due to heat history or the like, and improvement has been demanded.

The present applicant has proposed to produce an antireflection film having excellent scratch resistance using a curable resin composition containing particles as a technique for obtaining an antireflection layer by a method other than vapor deposition ( (See Patent Document 3). However, as an antireflection film used for various display elements and the like, higher optical performance and heat resistance are required, and an antireflection film that can be manufactured with higher productivity has been required.
Japanese Patent Laid-Open No. 5-135115 JP-A-8-110406 JP 2005-89536 A

  An object of the present invention is to provide a norbornene-based resin film having an antireflection layer that can be efficiently produced, the occurrence of cracks is sufficiently suppressed, and can be suitably used as an antireflection film useful for wave plate applications. .

  The norbornene-based resin film having an antireflection layer of the present invention is obtained by laminating three or more layers having an antireflection ability, in which the refractive indexes of adjacent layers are different, on both surfaces of a base film containing a norbornene-based polymer. The antireflection layer is formed, and the layer having the antireflection ability is formed using a UV curable material.

  In such a norbornene-based resin film having the antireflection layer of the present invention, it is preferable that the refractive indexes of the layers having the nth antireflection ability from the side close to both surfaces of the base film are equal to each other.

In the norbornene-based resin film having the antireflection layer of the present invention, the base film is preferably a stretched film.
The norbornene-based resin film having the antireflection layer of the present invention has a wavelength 55 of the base film.
The in-plane retardation at 0 nm is preferably 80 to 850 nm.

  The norbornene-based resin film having the antireflection layer of the present invention is a resin obtained by (co) polymerizing a monomer containing a norbornene-based polymer containing at least one compound represented by the following formula (I) It is preferable that

〔式（Ｉ）中、Ｒ¹〜Ｒ⁴は、各々独立に水素原子；ハロゲン原子；酸素、窒素、イオウまたはケイ素を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１５の炭化水素基、極性基もしくはその他の１価の有機基を表す。あるいはＲ¹とＲ²もしくはＲ³とＲ⁴が相互に結合してアルキリデン基を形成していてもよく、Ｒ¹とＲ²、Ｒ³とＲ⁴またはＲ²とＲ³とが相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合して多環構造を形成してもよい。）を形成してもよい。形成される炭素環または複素環は芳香環でもよいし非芳香環でもよい。また、ｘは０または１〜３の整数であり、ｙは０または１である。〕。

[In the formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon, 1 Represents a hydrocarbon group, polar group or other monovalent organic group of ˜15. Alternatively, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ^4, or R ² and R ³ are bonded to each other. Thus, a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X is 0 or an integer of 1 to 3, and y is 0 or 1. ].

  In the norbornene-based resin film having an antireflection layer of the present invention, at least one layer having antireflection ability is a low refractive index layer having a refractive index of 1.4 or less at a wavelength of 589 nm, and hollow silica ultrafine particles It is preferable to contain.

  In the norbornene-based resin film having an antireflection layer of the present invention, at least one antireflection ability layer is a high refractive index layer having a refractive index of 1.7 or more at a wavelength of 589 nm, and is composed of zirconia, titania, five It is preferable to contain one or more ultrafine particles selected from the group consisting of tantalum oxide and niobium pentoxide.

  The norbornene-based resin film having the antireflection layer of the present invention has a low refractive index layer having a refractive index of 1.4 or less at a wavelength of 589 nm and a high refractive index layer having a refractive index of 1.7 or more at a wavelength of 589 nm. It is preferable to have an antireflection layer laminated adjacently.

The norbornene-based resin film having the antireflection layer of the present invention preferably has a gas barrier layer containing a layered clay compound between the base film and the antireflection layer.
The norbornene-based resin film having the antireflection layer of the present invention preferably has a layer having antireflection ability formed by a dip coating method.

  The method for producing a norbornene resin film having an antireflection layer according to the present invention is a method for producing a norbornene resin film having an antireflection layer according to the present invention, wherein a layer having antireflection ability is formed by a dip coating method. It is characterized by including the process to perform.

The wave plate for an optical pickup module of the present invention is characterized by having a norbornene resin film having the antireflection layer of the present invention. The optical pickup module of the present invention includes the wavelength plate for an optical pickup module of the present invention.

  According to the present invention, the norbornene-based resin film having an antireflection layer, which is excellent in antireflection ability, excellent in heat resistance, manufactured with excellent productivity, and useful for uses such as a wave plate, and the film are used. It is possible to provide a wavelength plate for an optical pickup module and an optical pickup module.

Hereinafter, the present invention will be specifically described.
The norbornene-based resin film having an antireflection layer of the present invention (hereinafter also referred to as an antireflection film) is obtained by laminating three or more layers having antireflection ability on both surfaces of a base film containing a norbornene polymer. An antireflection layer.

Base film The base film constituting the antireflection film of the present invention contains a norbornene-based polymer.
As the norbornene-based polymer, a monomer containing a compound having a norbornene skeleton can be (co) polymerized, and a hydrogenated polymer can be used without limitation. Those modified with a functional group can also be used.

  In the present invention, the norbornene-based polymer (co) polymerizes a monomer containing at least one compound represented by the following formula (I) (hereinafter also referred to as “specific monomer (I)”). It is preferable that the resin is obtained as described above.

〔式（Ｉ）中、Ｒ¹〜Ｒ⁴は、各々独立に水素原子；ハロゲン原子；酸素、窒素、イオウまたはケイ素を含む連結基を有していてもよい置換または非置換の炭素原子数１〜１５の炭化水素基、極性基もしくはその他の１価の有機基を表す。あるいはＲ¹とＲ²もしくはＲ³とＲ⁴が相互に結合してアルキリデン基を形成していてもよく、Ｒ¹とＲ²、Ｒ³とＲ⁴またはＲ²とＲ³とが相互に結合して炭素環または複素環（これらの炭素環または複素環は単環構造でもよいし、他の環が縮合して多環構造を形成してもよい。）を形成してもよい。形成される炭素環または複素環は芳香環でもよいし非芳香環でもよい。また、ｘは０または１〜３の整数であり、ｙは０または１である。〕
前記特定単量体（Ｉ）を含む単量体を（共）重合して得られた樹脂としては、好ましくは、次のような（共）重合体が挙げられる。
（１）前記特定単量体（Ｉ）の開環重合体。
（２）前記特定単量体（Ｉ）と共重合性単量体との開環共重合体。
（３）上記（１）又は（２）の開環（共）重合体の水素添加物。

[In the formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon, 1 Represents a hydrocarbon group, polar group or other monovalent organic group of ˜15. Alternatively, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ^4, or R ² and R ³ are bonded to each other. Thus, a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X is 0 or an integer of 1 to 3, and y is 0 or 1. ]
Preferred examples of the resin obtained by (co) polymerizing the monomer containing the specific monomer (I) include the following (co) polymers.
(1) A ring-opening polymer of the specific monomer (I).
(2) A ring-opening copolymer of the specific monomer (I) and a copolymerizable monomer.
(3) A hydrogenated product of the ring-opening (co) polymer of (1) or (2) above.

Specific monomer (I) may be used independently and may use 2 or more types together.
Certain preferred among the monomer (I), the above formula (I), R ¹ to and R ³ are hydrogen atoms or 1 to 10 carbon atoms, more preferably 1-4, particularly preferably 1 to 2 carbon A hydrogen group, R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group, and x Is 0 or an integer of 1 to 3, and y is 0 or 1. The specific monomer (I) is preferable in that the norbornene-based polymer obtained has a high glass transition temperature and excellent mechanical strength.

  Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group, and these polar groups are connected via a linking group such as a methylene group. It may be bonded. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a norbornene-based polymer having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting norbornene polymer, which is preferable. Further, the specific monomer (I where n is 0) ) Is preferred because of its easy synthesis.

In the above formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group, In particular, the moisture absorption of the resulting norbornene polymer means that this alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the formula — (CH ₂ ) _n COOR is bonded. It is preferable at the point which can make property low.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of the specific monomer (I) and (2) a ring-opening copolymer of the specific monomer (I) and the copolymerizable monomer are obtained. The ring polymerization reaction is performed in the presence of a metathesis catalyst.

This metathesis catalyst includes (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), group IIB elements (eg, Zn, Cd, Hg, etc.), group IIIA elements (eg, B, Al, etc.), group IVA elements (eg, Si, Sn, Pb, etc.), or group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond. In this case, additives such as alcohols, aldehydes, ketones and amines may be added to increase the activity of the catalyst.

<Solvent for polymerization reaction>
Solvents used in the ring-opening polymerization reaction (solvents constituting molecular weight regulator solutions, solvents for specific monomers and / or metathesis catalysts) include alkanes, cycloalkanes, aromatic hydrocarbons, halogenated alkanes, halogens Aryl, saturated carboxylic acid esters, ethers and the like, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.

The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. it can.
<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. It is preferable to do.

  (2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of an unsaturated hydrocarbon polymer containing two or more carbon-carbon double bonds in the main chain, such as a conjugated diene compound, a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, or polynorbornene. The specific monomer may be subjected to ring-opening polymerization.

  The ring-opening (co) polymer obtained as described above can be used as it is, but obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer (3) Hydrogenated (co) polymers are preferred because they are excellent in heat resistance colorability and light resistance and can improve the durability of the retardation film.

<Hydrogenation catalyst>
For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, by adding a hydrogenation catalyst to the ring-opening polymer solution and allowing hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, to act at 0 to 200 ° C., preferably 20 to 180 ° C. Done.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light. When used as the transparent film of the present invention, stable characteristics can be obtained over a long period of time.

  The ring-opening (co) polymer obtained as described above can be stabilized by adding additives such as known antioxidants and ultraviolet absorbers. Further, additives such as a lubricant can be added for the purpose of improving processability.

The hydrogenated (co) polymer used as the norbornene polymer used in the present invention preferably has a gel content of 5 wt% or less contained in the hydrogenated (co) polymer, Further, it is particularly preferably 1% by weight or less.

The preferred molecular weight of the norbornene-based polymer used in the present invention is the intrinsic viscosity [η] _inh 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g, and the number in terms of polystyrene measured by gel permeation chromatography (GPC). The average molecular weight (Mn) is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 20,000 to 300. It is preferable to use those having a molecular weight of 30,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

Intrinsic viscosity [η] _inh, used by a number average molecular weight and weight-average molecular weight is in the above range, the heat resistance of a norbornene-based polymer, water resistance, chemical resistance, and mechanical properties, as the anti-glare film of the present invention The balance with the stability of the optical characteristics is good.

  The glass transition temperature (Tg) of the norbornene polymer used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. Stabilizes optical property changes of the resulting norbornene polymer film, prevents thermal deterioration of the resin when heated to near Tg, such as stretching, and changes the environment when used in an optical pickup module This is because the change in phase difference is sufficiently suppressed.

The photoelastic coefficient (C _P ) is preferably 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 80 (× 10 ⁻¹² Pa ⁻¹ ), and particularly preferably 0 to 50 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 30 (× 10 ⁻¹² Pa ⁻¹ ), and most preferably 0 to 20 (× 10 ⁻¹² Pa ⁻¹ ). This is to minimize the change in phase difference due to the stress generated when the antireflection layer is laminated, the stress generated when the antireflection layer is fixed to the optical pickup module, and the environmental change during use.

  The norbornene-based polymer used in the present invention is composed of (1) to (2) a ring-opening (co) polymer as described above, or (3) a hydrogenated product of a ring-opening (co) polymer. Further, it can be further stabilized by adding a known antioxidant, ultraviolet absorber or the like. Moreover, in order to improve workability, the additive used in conventional resin processings, such as a lubricant, can also be added.

  The norbornene-based polymer used in the present invention may be stabilized by adding a known antioxidant or ultraviolet absorber. Moreover, additives such as a lubricant may be added for the purpose of improving processability.

  The base film used in the present invention contains the norbornene-based polymer described above. As the base film used in the present invention, a film or sheet formed from the above cyclic olefin resin by a known method such as a melt molding method or a solution casting method (solvent casting method) can be used. Of these, the solvent casting method is preferred from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable.

  The thickness of the base film used in the present invention, that is, the norbornene-based polymer film is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 10 to 250 μm, and particularly preferably 50 to 200 μm. This is to ensure good handling and facilitate winding into a roll.

The thickness distribution of the base film (norbornene polymer film) used in the present invention is usually within ± 20%, preferably within ± 10%, more preferably within ± 5%, and particularly preferably ± with respect to the average value. Within 3%.

Specific examples of the base film used in the present invention include a product name “Arton” manufactured by JSR Corporation.
As a base film used for the antireflection film of the present invention, a film stretched as necessary is suitably used. Specifically, it can be produced by a known uniaxial stretching method or biaxial stretching method. That is, a horizontal uniaxial stretching method by a tenter method, a compression stretching method between rolls, a longitudinal uniaxial stretching method using rolls having different circumferences, a biaxial stretching method in which horizontal uniaxial and longitudinal uniaxial are combined, a stretching method by an inflation method, etc. Can be used.

  The base film used in the present invention is also preferably a film having a function as a retardation film. In this case, the in-plane retardation at a wavelength of 550 nm of the base film is 80 to 850 nm, preferably 100 to 400 nm, More preferably, the thickness is 100 to 200 nm.

Antireflective layer The antireflective layer constituting the antireflective film of the present invention is formed by laminating three or more layers having antireflective ability, in which adjacent layers have different refractive indexes, and the base film Formed on both sides. Preferably, the antireflection film of the present invention comprises an antireflection layer in which three or more layers having antireflection ability are formed on both sides of the base film symmetrically with the base film interposed therebetween. Have. That is, in the antireflection film of the present invention, the antireflection layers formed on both sides of the base film are composed of three or more layers having antireflection ability, and the nth antireflection from the side closer to both sides of the base film. It is preferable that the refractive indexes of the layers having a function are equal to each other.

  The antireflection layer is desirably formed by a dip coating method using a UV (ultraviolet) curable material, preferably a UV curable material containing inorganic fine particles. When the antireflection layer is formed by the dip coating method, an antireflection layer that is symmetrical between the front and the back is easily obtained, which is preferable.

The antireflection layer preferably has at least one of a low refractive index layer and a high refractive index layer as a layer having antireflection ability, more preferably has a low refractive index layer and a high refractive index layer, and has a low refractive index. It is preferable to have a refractive index layer and a high refractive index layer alternately. The antireflection layer according to the present invention is
You may have a middle refractive index layer.

-Low refractive index layer The low refractive index layer constituting the antireflection film of the present invention is a layer formed of a low refractive index material, and preferably has a refractive index of 1.45 or less, preferably 1.4 at a wavelength of 589 nm. Hereinafter, it is more preferably 1.38 to 1.25.

Examples of the UV curable material for forming the low refractive index layer include a fluororesin-based paint containing a hydroxyl group-containing fluoropolymer, an unsaturated compound obtained by reacting an isocyanate group-containing unsaturated compound and a hydroxyl group-containing fluoropolymer. Any known material capable of forming a low refractive index layer, which can be applied by a dip coating method, such as a coating composition containing a saturated group-containing fluorinated vinyl polymer, can be used. Examples include UV curable resin compositions that include components (A), (B), and (C) as essential components, and that can further include the following components (D), (E), and (F) as optional components.
(A) an ethylenically unsaturated group-containing fluoropolymer (B) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or at least one (meth) acryloyl group Containing fluorine-containing (meth) acrylate compound (C) Silica-based particle (D) Compound that generates active species upon irradiation with active energy ray (E) Organic solvent (F) Other additives About these components This will be described below.

(A) Ethylenically unsaturated group-containing fluorine-containing polymer The ethylenically unsaturated group-containing fluorine-containing polymer is a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It is obtained by reacting a fluoropolymer with an isocyanate group / hydroxyl molar ratio of 1.1 to 1.9.
(A1) A compound containing one isocyanate group and at least one ethylenically unsaturated group As a compound containing one isocyanate group and at least one ethylenically unsaturated group, The compound is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group.

Moreover, since the curable resin composition mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
As such a compound, 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate may be used singly or in combination of two or more.
(A2) Hydroxyl-containing fluoropolymer The hydroxy-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
(A) A structural unit represented by the following formula (1).
(B) A structural unit represented by the following formula (2).
(C) A structural unit represented by the following formula (3).

［式（１）中、Ｒ¹はフッ素原子、フルオロアルキル基又は−ＯＲ²で表される基（Ｒ²はアルキル基又はフルオロアルキル基を示す）を示す］

[In formula (1), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

［式（２）中、Ｒ³は水素原子又はメチル基を、Ｒ⁴はアルキル基、−(ＣＨ₂)_x−ＯＲ⁵若しくは−ＯＣＯＲ⁵で表される基（Ｒ⁵はアルキル基又はグリシジル基を、ｘは０又は１の
数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[In the formula (2), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

［式（３）中、Ｒ⁶は水素原子又はメチル基を、Ｒ⁷は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］
上記水酸基含有含フッ素重合体は、硬化後の塗膜の表面滑り性や塗膜の耐擦傷性を付与するためにポリシロキサンセグメントを有するアゾ基含有ポリシロキサン化合物により導入される構造単位、水酸基含有含フッ素重合体の溶剤への溶解性が向上させるために乳化作用を有する構造単位を含んで構成することも好ましい。

[In formula (3), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]
The hydroxyl group-containing fluoropolymer is a structural unit introduced by an azo group-containing polysiloxane compound having a polysiloxane segment in order to impart surface slipperiness and scratch resistance of the coating film after curing, hydroxyl group-containing In order to improve the solubility of the fluorinated polymer in a solvent, it is also preferable to include a structural unit having an emulsifying action.

The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).
(D) A structural unit represented by the following formula (4).

［式（４）中、Ｒ¹⁸は乳化作用を有する基を示す］
式（４）において、Ｒ¹⁸の乳化作用を有する基としては、疎水性基及び親水性基の双方を有し、かつ、親水性基がポリエチレンオキサイド、ポリプロピレンオキサイド等のポリエーテル構造である基が好ましい。

[In formula (4), R ¹⁸ represents a group having an emulsifying action]
In the formula (4), the group having an emulsifying action of R ¹⁸ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

  Examples of the group having such an emulsifying action include a group represented by the following formula (5).

［式（５）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］
構造単位（ｄ）は、反応性乳化剤を重合成分として用いることにより導入することができる。このような反応性乳化剤としては、下記式（６）で表される化合物が挙げられる。

[In formula (5), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]
The structural unit (d) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (6).

［式（６）中、ｎ、ｍ及びｕは、上記式（５）と同様である］
水酸基含有含フッ素重合体は、ゲルパーミエーションクロマトグラフィーで、テトラヒドロフランを溶剤として測定したポリスチレン換算数平均分子量が通常５，０００〜５００，０００、好ましくは１０，０００〜３００，０００、より好ましくは１０，０００〜１００，０００である。

[In the formula (6), n, m and u are the same as in the above formula (5)].
The hydroxyl group-containing fluorine-containing polymer has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000, preferably 10,000 to 300,000, more preferably 10 measured by gel permeation chromatography using tetrahydrofuran as a solvent. , 100,000 to 100,000.

The content of the component (A) in the UV curable resin composition forming the low refractive index layer is not particularly limited, but is usually 3 to 90% by weight with respect to the total amount of the composition other than the organic solvent. , Preferably 5 to 80% by weight, more preferably 10 to 60% by weight. When the amount of the component (A) is within the above range, it is possible to achieve both sufficient coating strength and a low refractive index.
(B) a polyfunctional (meth) acrylate compound containing at least two (meth) acryloyl groups and / or a fluorine-containing (meth) acrylate compound (B1) containing at least one (meth) acryloyl group Polyfunctional (meth) acrylate compound containing two or more (meth) acryloyl groups At least two or more (meth) acryloyl group-containing polyfunctional (meth) acrylate compounds are obtained by curing a curable resin composition. It is used to increase the coating strength of the resulting cured product and the antireflection film using it.

Examples of the compound (B1) include neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and caprolactone-modified dipentaerythritol. Mention may be made of hexa (meth) acrylate.
(B2) Fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group At least one fluorine-containing (meth) acrylate compound containing (meth) acryloyl group is a curable resin composition. It is used to lower the refractive index of.

  The compound (B2) is not particularly limited as long as it is a fluorine-containing (meth) acrylate compound containing at least one (meth) acryloyl group. As such an example, one kind of perfluorooctylethyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, or a combination of two or more kinds can be given.

The content of the component (B) in the UV curable resin composition forming the low refractive index layer is not particularly limited, but is usually 5 to 90% by weight with respect to the total amount of the composition other than the organic solvent. The value is preferably in the range of 10 to 80% by weight, more preferably 15 to 60% by weight. When the component (B) is contained within the above range, the cured coating film has a low refractive index and sufficient coating film strength.
(C) Particles mainly composed of silica (C1) Particles mainly composed of silica The UV curable resin composition forming the low refractive index layer has an antireflection ability of the cured product of the curable resin composition. For the purpose of improving, particles containing silica as a main component are blended. As the particles containing silica as a main component, known particles can be used, and as long as the shape is spherical, not only ordinary colloidal silica but also hollow particles, porous particles, and core / shell type particles. From the viewpoint of reducing the refractive index of the composition, hollow particles and porous particles are preferable, hollow particles are more preferable, and hollow ultrafine particles are particularly preferable. In the present invention, the ultrafine particles mean those having a particle diameter of about 1 to 100 nm. Moreover, not only spherical shape but an indeterminate shape particle | grains may be sufficient. Colloidal silica having a number average particle size determined by a dynamic light scattering method of 1 to 100 nm, a solid content of 10 to 40% by weight, and a pH of 2.0 to 6.5 is preferable. In particular, particles having a particle diameter of about 10 to 50 nm are more preferable in terms of productivity of silica particles themselves and light scattering during coating film formation.

  As a commercial product of particles mainly composed of silica, for example, Snowtex O (manufactured by Nissan Chemical Industries, Ltd.) (number average particle diameter determined by dynamic light scattering method 7 nm, solid content 20% by weight, pH 2.7) ), Snowtex OL (number average particle diameter determined by dynamic light scattering method: 15 nm, solid content: 20% by weight, pH 2.5), and the like.

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule include, for example, those having NH ₂ groups as reactive groups, those having OH groups, those having isocyanate groups, those having thiocyanate groups, epoxy groups And those having a thiol group. A preferred compound is 3-mercaptopropyltrimethoxysilane.

The particles containing silica as a main component are preferably those which have been surface-treated with an organic compound containing a polymerizable unsaturated group (hereinafter sometimes referred to as “specific organic compound”). By such surface treatment, the coating strength of a cured product obtained by curing the UV curable resin composition forming the low refractive index layer used in the present invention can be improved.
(C2) Specific organic compound The specific organic compound (C2) that can be used for the surface treatment of the particles (C1) containing silica as a main component is a polymerizable compound containing a polymerizable unsaturated group in the molecule.

  The polymerizable unsaturated group is not particularly limited, but preferred examples include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, maleate group, and acrylamide group. Can be mentioned.

This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
The specific organic compound (C2) further includes [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) in the molecule. -NH-], [-NH-C (= O) -NH-], [-NH-C (= S) -NH-], and [-S-C (= S) -NH-] It is preferable that it contains the group chosen more. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.

Such a specific organic compound (C2) is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group generation”). The compound is sometimes referred to as a “compound”, and specifically, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable. The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

In the UV curable resin composition forming the low refractive index layer, the content of the particles (C) mainly composed of silica is usually preferably 1 to 90% by weight with respect to the total amount of the composition other than the organic solvent, 5 to 80 weight% is more preferable, 10 to 70 weight% is further more preferable, and 20 to 60 weight% is especially preferable. When the component (C) is within the above range, a cured coating film having sufficient hardness can be obtained.
(D) Compound that generates active species upon irradiation with active energy rays A compound that generates active species upon irradiation with active energy rays such as ultraviolet rays is used to cure a UV curable resin composition that forms a low refractive index layer. Used.

  Examples of compounds that generate active species upon irradiation with active energy rays such as ultraviolet rays (hereinafter referred to as “photopolymerization initiators”) include photoradical generators that generate radicals as active species. In the present invention, it is preferable to use ultraviolet rays as active energy rays from the viewpoint of having a constant energy level, a high curing rate, and a relatively low irradiation apparatus, and being compact.

The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, and still more preferably based on the total amount of the composition other than the organic solvent. May be 0.1 to 15% by weight. When the amount of the photopolymerization initiator is within the above range, the curing reaction proceeds sufficiently and the scratch resistance of the cured coating film is excellent.
(E) Organic solvent It is preferable to further add an organic solvent to the UV curable resin composition forming the low refractive index layer. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. Examples of such an organic solvent include one kind or a combination of two or more kinds such as methyl isobutyl ketone, methyl ethyl ketone, methanol, ethanol, t-butanol, and isopropanol.

The amount of the organic solvent is not particularly limited, and may be an amount that can form a coating film by the dip coating method, but the amount of the ethylenically unsaturated group-containing fluoropolymer is 100 parts by weight. On the other hand, the amount is preferably 100 to 100,000 parts by weight. This is because when the addition amount is less than 100 parts by weight, it may be difficult to adjust the viscosity of the UV curable resin composition forming the low refractive index layer, while the addition amount is 100,000 weights. This is because the storage stability of the UV curable resin composition forming the low refractive index layer may be reduced, or the viscosity may be excessively lowered and handling may be difficult.
(F) Additive In the UV curable resin composition forming the low refractive index layer, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, as long as the objects and effects of the present invention are not impaired. Additives such as wettability improvers, surfactants, plasticizers, UV absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than component (C), pigments, dyes, etc. It is also preferable.

Formation of Low Refractive Index Layer The low refractive index layer is preferably formed from a UV curable resin composition comprising the above components. The UV curable resin composition forming the low refractive index layer that can form the antireflection layer of the present invention comprises the (A) ethylenically unsaturated group-containing fluoropolymer, the (B) component, and (C). Add component (D), component (E), organic solvent, and (F) additive, respectively, as necessary,
It can be prepared by mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the polymerization initiator.

The curing condition of the UV curable resin composition for forming the low refractive index layer is not particularly limited. For example, when an active energy ray is used, the exposure amount is within a range of 0.01 to 10 J / cm ² . It is preferable to set the value of.

This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is. For these reasons, the exposure dose is more preferably set to a value in the range of 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

  The low refractive index layer is a cured product obtained by providing a coating film of the UV curable resin composition forming the low refractive index layer described above on a base film by a dip coating method, and curing it by irradiation with active energy rays. It is comprised suitably from. In the antireflection film of the present invention, the low refractive index layer may be provided directly on the base film, and is provided via one or more layers such as a gas barrier layer, a high refractive index layer, and a medium refractive index layer. May be.

  In the low refractive index layer, the refractive index of the low refractive index layer (refractive index of Na-D line, measurement temperature 25 ° C.), which is a cured product obtained by curing the UV curable resin composition, is 1.45 or less. It is preferable to set it as 1.4, more preferably 1.4 or less, and particularly preferably 1.38 to 1.25. When the refractive index of the low refractive index layer is in such a range, a sufficient antireflection effect can be obtained, and particularly when combined with a high refractive index film, a synergistic antireflection effect is easily obtained, which is preferable.

  When a plurality of low refractive index layers are provided, at least one of them may have a refractive index value within the above-mentioned range, and the other low refractive index layers have a value exceeding 1.45. It may be.

Examples of commercially available products suitably used as the UV curable resin composition that provides the low refractive index layer include JSR Opstar TU series.
The thickness of one layer of the low refractive index layer is not particularly limited, but is preferably 50 to 300 nm, for example. The reason for this is that when the thickness of the low refractive index layer is less than 50 nm, the adhesion to other antireflective layers and the like that are laminated may decrease, whereas the thickness exceeds 300 nm. This is because optical interference may occur and the antireflection effect may be reduced. Therefore, the thickness of one layer of the low refractive index layer is more preferably 50 to 250 nm, and further preferably 60 to 200 nm. In order to obtain higher antireflection properties, when a plurality of low refractive index layers are provided to form a multilayer structure, the total thickness is preferably 50 to 300 nm.

-High refractive index layer The high refractive index layer constituting the antireflection film of the present invention is a layer formed of a high refractive index material having UV curability, and preferably has a refractive index of 1.65 or more at a wavelength of 589 nm, Preferably it is 1.7 or more, More preferably, it is 1.7-2.0.

Although it does not restrict | limit especially as a UV curable resin composition for forming a high refractive index layer, As a film formation component, an epoxy-type resin, phenol-type resin, melamine-type resin, alkyd-type resin, cyanate It is preferable to include one kind alone or a combination of two or more kinds of resin, acrylic resin, polyester resin, urethane resin, siloxane resin and the like. If these resins are used, a strong thin film can be formed as the high refractive index layer, and as a result, the coating strength of the antireflection film can be remarkably improved.

  However, the refractive index of these resins alone is usually 1.45 to 1.62, which may not be sufficient to obtain high antireflection performance. Therefore, it is more preferable to blend high refractive index inorganic particles, for example, metal oxide particles. Moreover, as a hardening form, although the curable composition which can be thermosetting, ultraviolet curing, and electron beam curing can be used, the ultraviolet curable composition with favorable productivity is used more suitably.

  The thickness of the high refractive index layer is not particularly limited, but is preferably 50 to 3,000 nm, for example. The reason for this is that when the thickness of the high refractive index layer is less than 50 nm, the antireflection effect and adhesion to the substrate may be reduced when combined with the low refractive index layer, while the thickness is This is because if the thickness exceeds 3,000 nm, optical interference may occur and the antireflection effect may be reduced. Therefore, the thickness of the high refractive index layer is more preferably 50 to 1,000 nm, and further preferably 60 to 500 nm. In order to obtain higher antireflection properties, when a plurality of high refractive index layers are provided to form a multilayer structure, the total thickness may be set to 50 to 3,000 nm.

  The UV curable resin composition for forming the high refractive index layer constituting the antireflection film of the present invention is more preferably (A) a particle component and (B) a melamine compound having no polymerizable unsaturated group. And (C) a compound having two or more polymerizable unsaturated groups, and if necessary, an acid generator (D), a photopolymerization initiator (E), and other components such as a solvent and an additive The composition containing (F) is mentioned.

Hereinafter, each of these components constituting the UV curable resin composition for forming the high refractive index layer will be described.
(A) Particle component The (A) particle component constituting the high refractive index layer is at least one selected from the group consisting of zirconia, titania, tantalum pentoxide, niobium pentoxide, and ITO (tin-doped indium oxide). Fine particles are mentioned.

In the present invention, Si (OMe) ₃ of the compound represented by the following formula (7) is hydrolyzed as the total amount of the ultrafine particles or a part thereof, the surface hydroxyl groups of the ultrafine particles are reacted, and the polymerizable functional group of AcrylO is reacted. It is preferable to use ultrafine particles in which a group is bonded to the ultrafine particle surface.

In this case, it is preferable that the polymerizable functional group is bonded to the ultrafine particles of 10 to 100% by weight with respect to the total amount of the ultrafine particles, and more preferably the polymerizable functional group is bonded to the ultrafine particles of 50 to 100% by weight. By combining them, it is possible to achieve both coating film strength and high refractive index.
The average particle diameter of these ultrafine particles is preferably about 1 to 100 nm, more preferably about 5 to 50 nm.

  In the UV curable resin composition for forming the high refractive index layer, the amount (inclusive) of the particle component (A) is 5 to 90% by weight, with the total amount of the composition excluding the organic solvent being 100% by weight. It is preferably 15 to 85% by weight. If it is less than 5% by weight, it may not be possible to obtain a high refractive index. If it exceeds 90% by weight, the film formability may be insufficient. The content of the particle component (A) in the UV curable resin composition excluding the solvent is particularly preferably 65 to 90% by weight.

The amount of the particle component (A) means a solid content, and when the particle component (A) is used in the form of a solvent-dispersed sol, the blending amount does not include the amount of the solvent.
(B) Melamine compound having no polymerizable unsaturated group The melamine compound (B) having no polymerizable unsaturated group constituting the UV curable resin composition for forming the high refractive index layer is a cured product. It is suitably used for increasing the refractive index and improving the chemical resistance of the laminate.

  As a commercial item of such a compound (B), the Mitsui Cytec Co., Ltd. product name: Cymel 238, XV805, XM2819, Cymel 303; Sanwa Chemical Co., Ltd. Nikalac E-1201 etc. can be mentioned, for example. .

  The number average molecular weight of the compound (B) is preferably 300 to 20,000. More preferably, it is 300-5,000. If it is less than 500, chemical resistance of the resulting laminate may be insufficient, and if it exceeds 20,000, coatability may be insufficient.

Such a compound (B) may be used individually by 1 type, and may mix and use 2 or more types.
The content of the compound (B) in the UV curable resin composition for forming the high refractive index layer is preferably 0.01 to 50% by weight, preferably 100 to 50% by weight of the total composition excluding the organic solvent. More preferably, it is 1 to 40% by weight. If it is less than 0.01% by weight, the chemical resistance of the laminate may be inferior, and if it exceeds 50% by weight, the hardness of the cured product may be insufficient.

(C) Compound having two or more polymerizable unsaturated groups Component (C) constituting the UV curable resin composition for forming a high refractive index layer is a compound having two or more polymerizable unsaturated groups. is there. Component (C) is suitably used for enhancing the film-forming property of the composition and improving the coating film strength of the cured product of the composition of the present invention.

In the component (C), the number of polymerizable unsaturated groups must be 2 or more, and 3 or more is preferable from the viewpoint of film formability. When there is one polymerizable unsaturated group, the scratch resistance is lowered.
Specific examples of the component (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di ( Alkylene glycol di (meth) acrylates such as (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, trimethylolpropane trihydroxyethyl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa Poly (meth) acrylates of polyhydric alcohols such as (meth) acrylate and hydroxypivalate neopentyl glycol di (meth) acrylate;
Isocyanurate poly (meth) acrylates such as isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate;
Poly (meth) acrylates of cycloalkanes such as tricyclodecanediyldimethyldi (meth) acrylate;
Di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of alkylene oxide adduct of bisphenol A, ethylene oxide addition of hydrogenated bisphenol A Di (meth) acrylate, di (meth) acrylate of propylene oxide adduct of hydrogenated bisphenol A, di (meth) acrylate of alkylene oxide adduct of hydrogenated bisphenol A, bisphenol A diglycidyl ether and (meth) acrylic (Meth) acrylate derivatives of bisphenol A such as (meth) acrylate obtained from acids;
3,3,4,4,5,5,6,6-octafluorooctanedi (meth) acrylate, 3- (2-perfluorohexyl) ethoxy-1,2-di (meth) acryloylpropane, Nn And fluorine-containing (meth) acrylates such as -propyl-N-2,3-di (meth) acryloylpropyl perfluorooctylsulfonamide. These polyfunctional (meth) acrylate compounds can be used individually by 1 type or in mixture of 2 or more types.

  Among these polyfunctional (meth) acrylate compounds, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, etc. have many acryloyl groups contained in one molecule, and the crosslinking density A polyfunctional (meth) acrylate compound that can improve the thickness and give excellent film hardness is particularly preferred.

  The blending (content) amount of component (C) in the UV curable resin composition for forming the high refractive index layer is usually 3 to 80% by weight based on 100% by weight of the total composition excluding the organic solvent. 5 to 50% by weight is preferable, and 5 to 30% by weight is more preferable. If it is less than 3% by weight, the effect of addition may not be obtained. If it exceeds 80% by weight, it may not be possible to obtain a high hardness when cured.

In addition, in the UV curable resin composition for forming the high refractive index layer, in addition to the component (C), if necessary, a compound having a polymerizable unsaturated group in the molecule may be contained. Good.
(D) Acid generator In UV curable resin composition for forming a high refractive index layer, as needed, it is a compounding component other than the said reactive particle (A), a compound (B), and a compound (C). (D) An acid generator can be blended.

  Examples of such an acid generator (D) include those commonly used such as a compound that generates a cationic species thermally and a compound that generates a cationic species by radiation (light) irradiation. . These can be used individually by 1 type or in combination of 2 or more types.

  The amount of the acid generator (D) used as necessary in the present invention is preferably 0.01 to 20% by weight based on 100% by weight of the total composition excluding the organic solvent, 0.1% 10 to 10% by weight is more preferable. If it is less than 0.01% by weight, the film formability may be insufficient, and if it exceeds 20% by weight, a cured product with high hardness may not be obtained.

(E) Radical polymerization initiator In the UV curable resin composition for forming the high refractive index layer, the reactive particles (A), the compound (B), the compound (C), and the acid generation are generated as necessary. As a blending component other than the agent (D), a radical polymerization initiator (E) can be blended.

  Examples of such radical polymerization initiator (E) include those commonly used such as compounds (radiation (light) polymerization initiators) that generate active radical species by radiation (light) irradiation.

  The blending amount of the radical polymerization initiator (E) used as necessary in the UV curable resin composition for forming the high refractive index layer is 100% by weight based on the total amount of the composition excluding the organic solvent. 0.01 to 20% by weight is preferable, and 0.1 to 10% by weight is more preferable. If it is less than 0.01% by weight, the hardness of the cured product may be insufficient. If it exceeds 20% by weight, the cured product may not be cured to the inside (lower layer).

(F) Other components For the UV curable resin composition for forming the high refractive index layer, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, and a wettability improver are optionally added. , Surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes, and the like can be appropriately blended.

In addition, for the preparation of the UV curable resin composition, it is desirable to use a solvent selected in accordance with the blending component in an amount that provides an appropriate viscosity for film formation by the dip coating method.
Commercially available products suitably used as the UV curable resin composition that gives the high refractive index layer include JSR Opstar Z series.

Formation of High Refractive Index Layer The high refractive index layer that can form the antireflective layer of the antireflective film of the present invention is preferably formed from a UV curable resin composition comprising the above components. In the antireflection film of the present invention, the high refractive index layer may be provided directly on the base film, and is provided via one or more layers such as a gas barrier layer, a low refractive index layer, and a medium refractive index layer. May be. The UV curable resin composition for forming the high refractive index layer is formed on the above-mentioned base film by using the above-mentioned low birefringence layer or other layers as necessary, using a dip coating method. A coating film can be formed symmetrically through the material film, and this can be formed by UV curing.

The coating film formed from the UV curable resin composition for forming the high refractive index layer can be cured by radiation (light). In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited, and for gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

  The curing reaction of the coating film formed from the UV curable resin composition can be performed under an anaerobic condition such as nitrogen in an air atmosphere, and even when cured under an anaerobic condition. The product has excellent coating strength.

Specifically, the high refractive index layer may have a low birefringence layer or other layers by using a dip coating method with a UV curable resin composition for forming the high refractive index layer. It coats on both surfaces on a good base film, A coating film is formed, Preferably, after drying a volatile component at 0-200 degreeC, it can form by performing a hardening process with radiations, such as an ultraviolet-ray. When using radiation, it is preferable to use ultraviolet rays or electron beams. In such a case, the preferable irradiation amount of ultraviolet rays is 0.01 to 10 J / cm ² , more preferably 0.1 to ² J / cm ² . Moreover, the preferable irradiation conditions of an electron beam are a pressurization voltage of 10-300 KV, an electron density of 0.02-0.30 mA / cm < ² >, and an electron beam irradiation amount of 1-10 Mrad.

  The thus formed high refractive index layer has a high hardness and a high refractive index, and can form a coating film (film) excellent in coating film strength and adhesion to the substrate and the low refractive index layer. It has characteristics.

Antireflective film In the antireflective film of the present invention, each antireflective layer such as a low refractive index layer and a high refractive index layer is made of a UV-curable resin composition using a base film on which another layer may be formed in advance. Since it forms using the dip-coating method to immerse, each antireflection layer is formed by the structure used as object through a base film. In addition, about the thickness of each antireflection layer formed, since it depends also on the drying conditions at the time of coating-film formation, you may differ in both surfaces of a base film. In this invention, the antireflection film which has an antireflection layer on both surfaces of a base film is easily and efficiently formed by forming an antireflection layer by the dip coating method.

  Moreover, when providing a low-refractive-index layer and a high-refractive-index layer, since the more excellent antireflection effect is acquired, it is preferable to make the refractive index difference of both into 0.05 or more values. The reason for this is that when the refractive index difference between the low refractive index layer and the high refractive index layer is less than 0.05, a synergistic effect in these antireflective film layers cannot be obtained. This is because there is a case in which the lowering may occur. For this reason, it is more preferable to make the refractive index difference between the low refractive index layer and the high refractive index layer a value within the range of 0.1 to 0.5.

  The antireflection film of the present invention preferably has a portion in which a low refractive index layer and a high refractive index layer are laminated adjacently, and more preferably has a refractive index of 1.4 or less at a wavelength of 589 nm. It is desirable to have a portion in which a certain low refractive index layer and a high refractive index layer having a refractive index of 1.7 or more at a wavelength of 589 nm are laminated adjacently.

  In the antireflection film of the present invention, an antireflection layer may be formed directly on the surface of the base film, and one or more layers such as a gas barrier layer are provided between the base film and the antireflection layer. You may have.

When the antireflection film of the present invention has a gas barrier layer between the base film and the antireflection layer, the gas barrier layer may be provided only on one side of the base film, or may be provided on both sides. Good. The gas barrier layer is not particularly limited, but preferably contains a layered clay compound. Specific examples of layered clay compounds include (muscovite), (Al, Mg) ₈ (Si ₄ O ₁₀ ) ₄ (OH) ₈ · 12H ₂ O (montmorillonite), (Mg, Li) ₃ Si ₄ O ₁₀ (OH) ₂ Na _0.3 · 4H ₂ O (hectorite), (Mg, Fe) ₃ (Al, Si) ₄ O ₁₀ (OH) ₂ (Ca _0.5 , Na) _0.3 · 4H ₂ O (saponite), ( Ca, Na) _0.3 Al ₂ (OH) ₂ (Al, Si) ₄ O ₁₀・ 4H ₂ O (Biderite), Fe ₂ (Al, Si) ₄ O ₁₀ (OH) ₂ Na _0.3・ nH ₂ O (Nontro) Night))).

In the antireflection film of the present invention, the base film has a high heat resistance, and the antireflection layer is formed using a UV curable material, so that the antireflection layer is formed by vapor deposition. Since it has a thermal expansion coefficient closer to that of the substrate film than the film, and the antireflection layer is less likely to crack, it can be suitably used even under conditions where heat history is applied.

  The antireflection film of the present invention can be suitably used for various display elements such as liquid crystal display panels, film-type liquid crystal elements, touch panels, cold cathode ray tube panels, and plasma displays. It can be suitably used even in a wet state. Furthermore, the antireflection film of the present invention is also suitable as an antireflection film constituting a wave plate for an optical pickup module.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description, “part” means “part by weight” unless otherwise specified.

In the following examples, the total light transmittance, haze value, spectral reflectance, phase difference, and thermal crack resistance were measured or evaluated by the following methods.
[Haze value]
Total light transmittance was measured using a haze meter “HGM-2DP type” manufactured by Suga Test Instruments Co., Ltd.

[Spectral reflectance]
Using a microspectroscopic reflectometer FE-3000 manufactured by Otsuka Electronics Co., Ltd., the reflectance from a wavelength of 380 nm to 780 nm was measured.

[Gas barrier properties]
The oxygen permeability was measured with a gas permeability measuring device BR-3 (manufactured by Toyo Seiki Co., Ltd.) according to JIS K7126.

[Heat resistance test]
Before and after holding a film sample fixed with a polyimide tape on a silicon wafer for 250 hours in a constant temperature layer of forced stirring type maintained at a constant temperature of 85 ° C. The presence or absence of cracks was observed with a 200 × optical microscope.

[Light resistance]
A semiconductor laser of 680 nm and 405 nm was irradiated at 100 mW / mm ² , and after 1000 hours, the irradiated portion was observed with a 200-fold optical microscope, and light resistance was evaluated according to the following criteria.

A: No change was observed before and after laser irradiation.
B: A slight change in surface shape was observed after laser irradiation.
C: Apparent surface shape change and / or white turbidity was observed after laser irradiation.

D: The film had a hole after laser irradiation.
[Refractive index]
Refraction with a wavelength of 589 nm using a spectroscopic ellipsometer FE-5000 manufactured by Otsuka Electronics Co., Ltd. using a coating sample obtained by spin-coating, solvent-drying and UV-curing each paint on a silicon wafer to a dry film thickness of 100 nm. The rate was measured.

[Production Example 1]
A transparent film made of a cyclic olefin resin, ARTON (registered trademark) FILM (manufactured by JSR Corporation, film thickness 100 μm) is heated in a tenter to Tg + 10 ° C. (175 ° C.) at a stretching speed of 300% / min. After stretching 1.3 times in the longitudinal direction of the film, it is cooled for about 1 minute in an atmosphere of Tg-20 ° C (145 ° C), further cooled at room temperature, and taken out from the tenter. A retardation film (1) was obtained. When the in-plane retardation of the obtained retardation film (1) was measured, it was 164 nm at a wavelength of 550 nm.

[Production Example 2]
A transparent film made of a cyclic olefin resin, ARTON (registered trademark) FILM (manufactured by JSR Corporation, film thickness 100 μm) is heated in a tenter to Tg + 10 ° C. (175 ° C.) at a stretching speed of 300% / min. After stretching 1.1 times in the longitudinal direction of the film, it is cooled for about 1 minute in an atmosphere of Tg-20 ° C. (145 ° C.), further cooled at room temperature, and taken out from the tenter. A retardation film (2) was obtained. When the in-plane retardation of the obtained retardation film (2) was measured, it was 101 nm at a wavelength of 550 nm.

[Production Example 3]
Hydrane WLS-201 (Dainippon Ink Chemical Co., Ltd.), which is a polyether-based urethane paint, was diluted to 3% using a methyl ethyl ketone / methanol mixed solvent (weight ratio 80/20) to prepare a primer coating solution.

[Production Example 4]
When the retardation films (1) and (2) obtained in Production Example 1 and Production Example 2 were subjected to corona treatment in the atmosphere at a discharge voltage of 100 W / m ² / min, both had a surface tension of 65 mN / m. It became.

[Production Example 5]
Each of the films obtained in Production Example 4 was cut into 75 mm × 100 mm with a cutter knife, and the primer coating solution prepared in Production Example 3 was dip-coated at a pulling speed of 300 mm / min with the film longitudinal direction as the working direction, and forced. It was made to dry at 100 degreeC for 3 minute (s) with the stirring type dryer. Furthermore, Unirex BHC-70 (manufactured by Blends), which is a gas barrier coating material having a solid content concentration of 5%, was dip coated. The dip coating conditions were an immersion time of 10 seconds and a lifting speed of 400 mm / min.

The coated film sample was dried at 100 ° C. for 3 minutes with a forced stirring dryer to obtain gas barrier films (1) and (2) having gas barrier layers on both sides.
The gas barrier properties and retardation of the gas barrier films (1) and (2) were measured and found to be 5 cc / m ² / day, 164 nm, and 4 cc / m ² / day, 101 nm, respectively.

[Preparation Example 1]
Low refractive index is obtained by adding isopropyl alcohol to JSR Opstar (registered trademark) (refractive index: 1.35, solid content concentration: 10%), which is a low refractive index material containing hollow silica ultrafine particles, and diluting to 3%. The rate coating material (A) was obtained.

[Preparation Example 2]
Diluted to 3% by adding methyl isobutyl ketone to JSR Opstar (registered trademark) (refractive index 1.75, solid content concentration 50%), which is a high refractive index material containing zirconia ultrafine particles as a composition, A high refractive index coating material (B) was obtained.

[Example 1]
After the corona-treated retardation film (1) obtained in Production Example 4 was cut out in the same manner as in Production Example 5, the gas barrier coating material was used as a base film without dip coating. On this base film, the refractive index layer (A) formed using the low refractive index coating material (A) obtained in Preparation Example 1 under the conditions shown in Table 1, and the high refraction obtained in Preparation Example 2 Refractive index layers (B) formed using the coating material (B) were alternately formed and laminated to obtain an antireflection film (1) having a phase difference. Each time one layer was applied by a dip coater, each layer was dried in a solvent at 100 ° C. for 1 minute in the air and cured with an ultraviolet ray by irradiation with a metal halide lamp at 500 mJ / cm ² (200 mW / cm ² ). The refractive index of the refractive index layer (A) was 1.35, and the refractive index of the refractive index layer (B) was 1.75. For the antireflection film (1), the haze value, spectral reflectance, gas barrier properties, thermal crack resistance, and retardation before and after thermal crack resistance evaluation were measured. The results are shown in Table 1.

[Example 2]
An antireflection film (2) having a phase difference by alternately laminating a low refractive index layer and a high refractive index layer in the same manner as in Example 1 on the gas barrier film (1) obtained in Production Example 5 Got. The results of the same evaluation as in Example 1 are shown in Table 1.

[Example 3]
On the gas barrier film (2) obtained in Production Example 5, the refractive index layer (A) and the refractive index layer (B) are alternately formed and laminated in the same manner as in Example 1 under the conditions shown in Table 1, and the phase difference is determined. An antireflection film (3) was obtained. The results of the same evaluation as in Example 1 are shown together in Table 1.

[Comparative Example 1]
A high-refractive index material Nb ₂ O ₅ and a low-refractive index material SiO ₂ are alternately laminated on the gas barrier film (1) obtained in Preparation Example 5 using the vacuum deposition apparatus so as to have the film thicknesses shown in Table 1 and the phase difference. The antireflection film (a) having the following was obtained, but cracks occurred in the antireflection layer after the heat resistance test.

［実施例４］
市販品のＢＤ／ＤＶＤ／ＣＤドライブを分解し、ＢＤ対物レンズ手前にある水晶からなる反射防止膜付き位相差板を取り除き、実施例３で作製した位相差を有する反射防止フィルム（３）を３ｍｍ×４ｍｍに切り出したものをとりつけた後、再び、ＢＤ／ＤＶＤ／Ｃ
Ｄドライブとして組み立てたところ。分解以前の同等と初期特性が得られた。また、１００００時間連続で使用した時点でのドライブとしての不具合は観察されなかった。

[Example 4]
The commercially available BD / DVD / CD drive was disassembled, the phase difference plate with an antireflection film made of crystal in front of the BD objective lens was removed, and the antireflection film (3) having the retardation produced in Example 3 was 3 mm. After attaching the cut out to × 4mm, again BD / DVD / C
When assembled as a D drive. The same initial characteristics as before the decomposition were obtained. In addition, no malfunction as a drive when used continuously for 10,000 hours was observed.

Incidentally, the retardation film made of quartz had a thickness of 270 μm, whereas the thickness of the antireflection film (3) having the retardation obtained in Example 3 was 93 μm.
Furthermore, when removing the retardation plate made of quartz, cracks occurred at the corners of the retardation plate, whereas when the antireflection film (3) having the retardation was removed, the film was cracked. It never happened.

  The antireflection film of the present invention can be suitably used for various display elements such as liquid crystal display panels, film-type liquid crystal elements, touch panels, cold cathode ray tube panels, and plasma displays. It can be suitably used even in a wet state. Furthermore, the antireflection film of the present invention is also suitable as an antireflection film constituting a wave plate for an optical pickup module.

Claims (13)

On both surfaces of a base film containing a norbornene polymer, an antireflection layer is formed by laminating three or more layers having antireflective ability with different refractive indexes between adjacent layers,
A norbornene-based resin film having an antireflection layer, wherein the antireflection layer is formed using a UV curable material.   2. The norbornene-based resin film having an antireflection layer according to claim 1, wherein the refractive indexes of the nth layers having antireflection ability from the side closer to both surfaces of the base film are equal to each other.   The norbornene resin film having an antireflection layer according to claim 1 or 2, wherein the base film is a stretched film.   The norbornene-based resin film having an antireflection layer according to any one of claims 1 to 3, wherein an in-plane retardation at a wavelength of 550 nm of the substrate film is 80 to 850 nm. The norbornene-based polymer is a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (I): 5. A norbornene-based resin film having the antireflection layer according to claim 1;

[In the formula (I), R ^{1 to} R ⁴ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom which may have a linking group containing oxygen, nitrogen, sulfur or silicon, 1 Represents a hydrocarbon group, polar group or other monovalent organic group of ˜15. Alternatively, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form an alkylidene group, and R ¹ and R ² , R ³ and R ^4, or R ² and R ³ are bonded to each other. Thus, a carbocycle or a heterocycle (these carbocycles or heterocycles may be monocyclic structures or other rings may be condensed to form a polycyclic structure) may be formed. The formed carbocyclic or heterocyclic ring may be an aromatic ring or a non-aromatic ring. X is 0 or an integer of 1 to 3, and y is 0 or 1. ].   The at least one layer having antireflection ability is a low refractive index layer having a refractive index of 1.4 or less at a wavelength of 589 nm, and contains hollow silica ultrafine particles. A norbornene-based resin film having the antireflection layer as described above.   The layer having at least one antireflection ability is a high refractive index layer having a refractive index of 1.7 or more at a wavelength of 589 nm, and one kind selected from the group consisting of zirconia, titania, tantalum pentoxide and niobium pentoxide. The norbornene-based resin film having an antireflection layer according to claim 1, comprising the above ultrafine particles.   Having an antireflection layer in which a low refractive index layer having a refractive index of 1.4 or less at a wavelength of 589 nm and a high refractive index layer having a refractive index of 1.7 or more at a wavelength of 589 nm are laminated adjacently. A norbornene-based resin film having an antireflection layer according to any one of claims 1 to 7.   The norbornene-based resin film having an antireflection layer according to any one of claims 1 to 8, further comprising a gas barrier layer containing a layered clay compound between the base film and the antireflection layer.   The norbornene-based resin film having an antireflection layer according to any one of claims 1 to 9, wherein the layer having antireflection ability is formed by a dip coating method.   A method for producing a norbornene-based resin film having an antireflection layer according to any one of claims 1 to 10, comprising a step of forming a layer having antireflection ability by a dip coating method. A method for producing a norbornene-based resin film having a prevention layer.   A wave plate for an optical pickup module, comprising a norbornene-based resin film having the antireflection layer according to claim 1.   An optical pickup module comprising the wavelength plate for an optical pickup module according to claim 12.