JP2011191735A - Anti-reflective film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-reflective film of a single layer structure and having sufficient anti-reflection performance, with excellent antistatic performance, heat resistance and abrasion resistance. <P>SOLUTION: The anti-reflective film is configured by directly laminating low-refractive index layer on a transparent base film. The low-refractive index layer is a cured matter of a coating solution for low-refractive index layer containing a complex consisting of: (a) multifunctional (meth)acrylate; (b) hollow silica particles, and (c) π-conjugated conductive polymer and dopant. The coating solution for low-refractive index layer contains per 100 pts.mass multifunctional (meth)acrylate (a), 40-250 pts.mass hollow silica fine particles (b) and 1-25 pts.mass complex (c), and the mass ratio of the π-conjugated conductive polymer to dopant in the complex is set to 1:1-1:5. Polythiophenes, polypyrroles or polyanilines are preferred as the π-conjugated conductive polymer, and polyanion is preferred as the dopant. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antireflection film which is applied to, for example, a plasma display panel (PDP), a liquid crystal display panel (LCD) and the like, has a sufficient antireflection performance with a single layer structure, and is excellent in antistatic performance.

  2. Description of the Related Art In recent years, electronic image display devices (electronic displays) such as plasma display panels and liquid crystal display panels have made remarkable progress for television and monitor applications and have become widespread. As these electronic image display devices are increased in size, there is a problem that visibility is reduced due to reflection of external light. Therefore, a method is generally adopted in which an antireflection film formed by providing an antireflection layer on the surface of a transparent substrate film is bonded to the display surface to enhance visibility.

  Furthermore, in order to prevent dust and the like from adhering to the display surface due to static electricity, these antireflection films are required to have antistatic performance. For example, an antireflection film having a low refractive index layer comprising hollow silica fine particles and polyfunctional (meth) acrylate is known (see Patent Document 1). However, although the antireflection film described in Patent Document 1 is excellent in antireflection performance, in order to impart antistatic performance, a hard coat layer or antistatic layer having antistatic performance is used as a transparent base film and a low refractive index. It is necessary to provide it between the layers, and as a result of increasing the number of coatings, productivity is lowered.

  Further, π-conjugated conductive polymers are used as industrial materials such as various antistatic agents and electrode materials because they exhibit good conductivity. This π-conjugated conductive polymer is imparted with high conductivity by doping a substance called a dopant. For example, a coating agent composition containing a complex composed of a π-conjugated conductive polymer and a dopant and a polyfunctional (meth) acrylate is known (see Patent Document 2).

  However, a complex composed of a π-conjugated conductive polymer and a dopant has a high refractive index of about 1.5, and therefore is not suitable as a material for forming a low refractive index layer. Typically used as a material for forming. Therefore, although antistatic performance is excellent, when it is intended to impart antireflection performance, a coating layer containing a complex composed of a π-conjugated conductive polymer and a dopant and a polyfunctional (meth) acrylate is used. On top of this, it is necessary to provide at least one antireflection layer. In that case, since the number of times of coating increases, productivity decreases. In addition, antireflection films are required to have sufficient heat resistance and scratch resistance during production and use.

JP 2005-99778 A JP 2008-222850 A

  An object of the present invention is to provide an antireflection film having a single layer structure and sufficient antireflection performance, excellent antistatic performance, and excellent heat resistance and scratch resistance.

  In order to achieve the above object, an antireflection film according to a first invention is an antireflection film in which a low refractive index layer is directly laminated on a transparent substrate film, and the low refractive index layer Contains (a) a polyfunctional (meth) acrylate, (b) a hollow silica fine particle, and (c) a complex composed of a π-conjugated conductive polymer and a dopant, and (a) 100 mass of a polyfunctional (meth) acrylate. (B) 40 to 250 parts by mass of hollow silica fine particles and (c) 1 to 25 parts by mass of a complex composed of a π-conjugated conductive polymer and a dopant, and (c) a π-conjugated conductive polymer And a cured product of a coating solution for a low refractive index layer in which the mass ratio of the π-conjugated conductive polymer and the dopant in the composite composed of the dopant is set to 1: 1 to 1: 5.

The antireflection film of the second invention is characterized in that, in the first invention, the π-conjugated conductive polymer is a polythiophene.
The antireflection film of the third invention is characterized in that, in the second invention, the polythiophene is poly (3,4-ethylenedioxythiophene).

The antireflection film of a fourth invention is characterized in that, in the first invention, the π-conjugated conductive polymer is a polypyrrole or a polyaniline.
The antireflection film of the fifth invention is characterized in that, in the invention described in any one of the first to fourth inventions, the dopant is a polyanion.

  The antireflection film of a sixth invention is characterized in that, in the fifth invention, the polyanion is polystyrene sulfonic acid.

According to the present invention, the following effects can be exhibited.
In the antireflection film of the first invention, the low refractive index layer is directly laminated on the transparent substrate film. The low refractive index layer is for a low refractive index layer containing (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a complex composed of a π-conjugated conductive polymer and a dopant. It is a cured product of the coating liquid. The coating solution for the low refractive index layer comprises (b) 40 to 250 parts by mass of hollow silica fine particles and (c) a π-conjugated conductive polymer and a dopant per 100 parts by mass of (a) polyfunctional (meth) acrylate. 1 to 25 parts by mass of the composite, and (c) the mass ratio of the π-conjugated conductive polymer and the dopant in the composite consisting of the π-conjugated conductive polymer and the dopant is 1: 1 to 1: 5. Is set.

  For this reason, the anti-reflective action is exhibited by the function of the low refractive index layer, and an anti-reflection film is attached to the display surface of an electronic image display device such as a plasma display panel or a liquid crystal display panel, thereby allowing an external light source such as a fluorescent lamp to Visibility of irradiated light can be suppressed and visibility can be improved. At the same time, since the low refractive index layer contains a composite composed of a π-conjugated conductive polymer and a dopant, an antistatic effect is exhibited, and an antireflection film is bonded to the display surface of an electronic image device. In addition, adhesion of dust and the like to the display surface due to static electricity can be suppressed. In addition, the scratch resistance of the antireflection film can be improved mainly based on the properties of the cured product of (a) polyfunctional (meth) acrylate.

  In addition, (c) the mass ratio of the π-conjugated conductive polymer and the dopant in the complex composed of the π-conjugated conductive polymer and the dopant is set to 1: 1 to 1: 5, so that In addition to exhibiting excellent electrical conductivity, it is possible to exhibit good heat resistance.

  In the antireflection film of the second invention, since the π-conjugated conductive polymer is a polythiophene, in addition to the effects of the first invention, good conductivity can be expressed with a smaller content. it can.

  In the antireflection film of the third invention, since the polythiophene is poly (3,4-ethylenedioxythiophene), in addition to the effect of the second invention, good conductivity is achieved with a smaller content. In addition to being able to express, the material is readily available.

  In the antireflection film of the fourth invention, since the π-conjugated conductive polymer is polypyrrole or polyaniline, in addition to the effect of the first invention, good conductivity is expressed with a smaller content. can do.

  In the antireflection film of the fifth invention, since the dopant is a polyanion, in addition to the effects of the invention according to any one of the first to fourth, the good conductivity is expressed with a smaller content. can do.

  In addition to the effects of the fifth invention, the antireflection film of the sixth invention can exhibit good conductivity with a smaller content and easily obtain materials since the polyanion is polystyrene sulfonic acid. It is possible.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The antireflection film of this embodiment is configured by directly laminating a low refractive index layer on a transparent substrate film. The low refractive index layer is a coating for a low refractive index layer containing a composite comprising (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a π-conjugated conductive polymer and a dopant. It is a liquid cured product (cured film). The coating solution for the low refractive index layer is composed of (b) 40 to 250 parts by mass of hollow silica fine particles and (c) a π-conjugated conductive polymer and a dopant per 100 parts by mass of (a) polyfunctional (meth) acrylate. 1 to 25 parts by mass, and the mass ratio of the π-conjugated conductive polymer and the dopant in the composite (c) is set to 1: 1 to 1: 5.

Next, components of the antireflection film will be described in order.
<Transparent substrate film>
The transparent base film used for the antireflection film is not particularly limited as long as it has transparency, but preferably has a refractive index (n) in the range of 1.55 to 1.70 in order to suppress light reflection. . As a material for forming such a transparent substrate film, for example, polyester such as polyethylene terephthalate (PET, n = 1.65), polycarbonate (PC, n = 1.59), polyarylate (PAR, n = 1. 60) and polyethersulfone (PES, n = 1.65) are preferred. Of these, a polyester film, particularly a polyethylene terephthalate film, is preferable in terms of ease of molding.

The thickness of the transparent substrate film is preferably 25 to 400 μm, more preferably 50 to 200 μm. In addition, various additives may be contained in the transparent base film. Examples of such additives include ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants, flame retardants, and the like. Moreover, in order to improve the adhesiveness of a transparent base film and a low refractive index layer, you may provide a well-known interference prevention layer between a transparent base film and a low refractive index layer. The interference prevention layer can be formed on the surface of the transparent substrate film by a known method during the production of the transparent substrate film, or a commercially available product of a transparent substrate film on which an interference prevention layer has been formed in advance is used. You can also.
<Low refractive index layer>
The low refractive index layer contains (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a complex composed of a π-conjugated conductive polymer and a dopant (conductive polymer, complex). It is a cured product of the coating solution for the low refractive index layer. The thickness of the low refractive index layer is preferably kλ / 4 because surface reflection is reduced by light interference and the transmittance is improved. Here, λ represents a wavelength of light of 400 to 650 nm, and k represents 1 or 3. Thus, the antireflection effect can be further enhanced by setting the thickness of the low refractive index layer to kλ / 4. In this case, when k is 1, antireflection performance (luminosity reflectance) is improved, and when k is 3, scratch resistance is improved.

The refractive index of the low refractive index layer is preferably 1.20 to 1.44. When the refractive index is less than 1.20, the content of the polyfunctional (meth) acrylate is reduced, so that it is difficult for the low refractive index layer to have sufficient coating strength. On the other hand, when the refractive index exceeds 1.44, sufficient antireflection performance cannot be obtained.
[Multifunctional (meth) acrylate]
The polyfunctional (meth) acrylate is a resin that causes a curing reaction when irradiated with active energy rays such as ultraviolet rays and electron beams, and the type thereof is not particularly limited. From the viewpoint of improving the strength and scratch resistance of the coating film, polyfunctional (meth) acrylate is used instead of monofunctional (meth) acrylate. Here, the monofunctional (meth) acrylate indicates a resin having one acryloyl group (CH ₂ ═CHCO—) or methacryloyl group (CH ₂ ═C (CH ₃ ) CO—) in the molecule, and is polyfunctional. (Meth) acrylate refers to a resin having two or more acryloyl groups or methacryloyl groups in the molecule.

This polyfunctional (meth) acrylate is not particularly limited, and a known polyfunctional (meth) acrylate can be used. Moreover, in order to make the refractive index of a low refractive index layer lower, fluorine-containing polyfunctional (meth) acrylate can also be used. As the polyfunctional (meth) acrylate, for example, a bifunctional to hexafunctional acrylate is used.
(Hollow silica fine particles)
The hollow silica fine particles are fine particles in which silica (silicon dioxide, SiO ₂ ) is formed in a substantially spherical shape and has a hollow portion in the outer shell. The average particle diameter of the hollow silica fine particles is preferably 10 to 100 nm, more preferably 20 to 60 nm. When the average particle diameter of the hollow silica fine particles is smaller than 10 nm, it is not preferable because the production of the hollow silica fine particles becomes difficult. On the other hand, when the average particle size is larger than 100 nm, the light scattering in the low refractive index layer increases, the reflection increases in the thin film, and the antireflection function decreases.

As the hollow silica fine particles, commercially available particles dispersed in an organic solvent can be used as they are, or various commercially available silica powders can be dispersed in an organic solvent. The hollow silica fine particles can also be synthesized by a method for producing hollow spherical silica-based fine particles having a cavity inside the outer shell, as disclosed in, for example, JP-A-2006-21938. Based on this method, modified hollow silica fine particles (sol) of Production Example 1 described later are produced. In addition, modified hollow silica fine particles obtained by modifying the surface of the hollow silica fine particles with a silane coupling agent having a polymerizable double bond can also be used.
(Composite composed of π-conjugated conductive polymer and dopant)
The complex composed of a π-conjugated conductive polymer and a dopant refers to a π-conjugated conductive polymer doped with a dopant. Its refractive index is approximately 1.5. Even if a π-conjugated conductive polymer is used alone, conductivity is not exhibited, but doping with a dopant generates electrons that can move freely on the π-conjugated conductive polymer, and the conductivity is low. It will be obtained.

  The π-conjugated conductive polymer is a polymer compound having a π-conjugated structure (a structure in which double bonds are adjacent to each other with a single bond) in the molecular structure. Here, the polymer compound means a compound having a molecular weight of 10,000 or more. A well-known thing can be used as (pi) conjugated system conductive polymer. Of these, polythiophenes, polypyrroles or polyanilines are preferably used from the viewpoint of conductivity and stability in the external environment, and polythiophenes are particularly preferably used.

  Specific examples of polythiophenes include poly (3,4-ethylenedioxythiophene), poly (3-methylthiophene), poly (3,4-ethylenedioxythiophene), poly (3-hexyloxythiophene), poly (3-methyl-4-methoxythiophene) and the like.

  The dopant (dopant) generates electrons that can move freely on the π-conjugated conductive polymer by doping (complex formation) with the π-conjugated conductive polymer. It is a substance that develops conductivity in molecules. A well-known thing can be used for a dopant. Among these, it is particularly preferable to use a polyanion as a dopant from the viewpoint that the conductivity when the π-conjugated conductive polymer is doped can be further increased.

  A polyanion is a compound having an anionic group in the molecule. Specific examples of the polyanion include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient. The combination of the π-conjugated conductive polymer and the dopant is not particularly limited, but a combination of polythiophenes and polyanions is preferable from the viewpoint of conductivity and stability in the external environment.

  The combination of the π-conjugated conductive polymer and the dopant is not particularly limited, but a combination of polythiophenes and polyanions is preferable from the viewpoint of conductivity and availability of materials, and poly (3,4-ethylenedioxythiophene) and A combination of polystyrene sulfonic acids is more preferred.

  The mass ratio between the π-conjugated conductive polymer and the dopant needs to be 1: 1 to 1: 5. When the mass ratio of the π-conjugated conductive polymer and the dopant is smaller than 1: 1, the π-conjugated conductive polymer is not sufficiently doped, and the conductivity of the composite is lowered. On the other hand, when it is larger than 1: 5, the heat resistance of the composite deteriorates due to the influence of an excessive dopant. As a complex comprising a π-conjugated conductive polymer and a dopant, a commercially available product may be used, or a compound synthesized by a known method may be used. Further, an aqueous dispersion of a complex composed of a π-conjugated conductive polymer and a dopant may be used by replacing with an organic solvent.

  The content of the polyfunctional (meth) acrylate, the hollow silica fine particles, the composite composed of the π-conjugated conductive polymer and the dopant in the coating solution for the low refractive index layer is (a) 100 mass of polyfunctional (meth) acrylate. Per part, (b) 40 to 250 parts by mass of hollow silica fine particles and (c) 1 to 25 parts by mass of a composite composed of a π-conjugated conductive polymer and a dopant. When the content of the hollow silica fine particles is less than 40 parts by mass, sufficient antireflection performance of the antireflection film cannot be obtained, and when it is more than 250 parts by mass, the scratch resistance of the antireflection film is lowered. To do.

In addition, when the content of the complex composed of the π-conjugated conductive polymer and the dopant is less than 1 part by mass, sufficient antistatic performance of the antireflection film cannot be obtained, and when the content is more than 25 parts by mass. Since the content of the polyfunctional (meth) acrylate is relatively reduced, the scratch resistance of the antireflection film is lowered.
(Diluted solvent)
Any solvent can be used for the coating liquid for the low refractive index layer. Specific examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol and methyl glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone and diacetone alcohol, methyl acetate, Examples thereof include esters such as ethyl acetate and butyl acetate, and ethers such as propylene glycol monomethyl ether, tetrahydrofuran and 1,4-dioxane.
(Other ingredients)
In addition, other components can be added to the coating solution for the low refractive index layer within a range not impairing the effects of the present invention. Examples of such other components include additives such as a polymer, a polymerization initiator, a polymerization inhibitor, an antioxidant, a dispersant, a surfactant, a light stabilizer, and a leveling agent.
<Method for forming low refractive index layer>
The method for forming the low refractive index layer on the surface of the transparent substrate film is not particularly limited, but the coating solution for the low refractive index layer is a coating method such as a roll coating method, a spin coating method, a coil bar method, a dip coating method, or a die coating method. The method of irradiating an ultraviolet-ray after apply | coating to the surface of a transparent base film by, etc. is mentioned. By such a method, the coating solution for the low refractive index layer is cured to obtain a cured product, and a low refractive index layer is formed. As a method for applying the coating solution for the low refractive index layer, a method capable of continuously forming the low refractive index layer such as a roll coating method is preferable from the viewpoint of productivity.

  In addition, before applying the coating solution for the low refractive index layer to the surface of the transparent substrate film by a coating method such as a roll coating method, a spin coating method, a coil bar method, a dip coating method, or a die coating method, A pretreatment such as a discharge treatment may be performed.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples. In addition, the part in each example shows a mass part and% represents the mass%.
[Production Example 1, production of modified hollow silica fine particles (sol)]
As a first step, a silica sol having an average particle diameter of 5 nm and a silica (SiO ₂ ) concentration of 20% and pure water were mixed to prepare a reaction mother liquor, which was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 1.17% sodium silicate aqueous solution as SiO ₂ and 0.83% sodium aluminate aqueous solution as alumina (Al ₂ O ₃ ) were simultaneously added to the reaction mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate and remained almost unchanged thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO ₂ .Al ₂ O ₃ primary particle dispersion (core particle dispersion) having a solid concentration of 20%.

Next, as a second step, this SiO ₂ · Al ₂ O ₃ primary particle dispersion is collected, pure water is added and heated to 98 ° C., and while maintaining this temperature, sodium sulfate having a concentration of 0.5% Was added. Subsequently, an aqueous solution of sodium silicate having a concentration of 1.17% as SiO ₂ and an aqueous solution of sodium aluminate having a concentration of 0.5% as Al ₂ O ₃ were added to form a composite oxide fine particle dispersion (first silica as a core particle). A fine particle dispersion having a coating layer was obtained. And this was wash | cleaned with the ultrafiltration membrane, and it was set as the complex oxide fine particle dispersion liquid of solid content concentration 13%.

  As a third step, pure water was added to the composite oxide fine particle dispersion, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, followed by dealumination. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and washed to obtain an aqueous dispersion of silica-based fine particles (1) having a solid concentration of 20%. .

As a fourth step, a mixed liquid of the silica-based fine particles (1) having a solid content concentration of 20% and pure water, ethanol and 28% ammonia water is heated to 35 ° C., and then ethyl silicate (SiO 2 ₂ was 28%) to form a silica coating (second silica coating layer). Subsequently, while adding 5 L of pure water, it was washed with an ultrafiltration membrane to prepare a dispersion of silica-based fine particles (2) having a solid concentration of 20%.

Finally, as a fifth step, the dispersion of silica-based fine particles (2) was hydrothermally treated again at 200 ° C. for 11 hours. Thereafter, it was washed with an ultrafiltration membrane while adding 5 L of pure water to adjust the solid content concentration to 20%. Then, using an ultrafiltration membrane, the dispersion medium of this dispersion was replaced with ethanol to obtain an organosol having a solid content concentration of 20%. This organosol was an organosol in which hollow silica fine particles having an average particle diameter of 60 nm and a specific surface area of 110 m ² / g were dispersed (hereinafter referred to as “hollow silica sol A”).

200 g of the hollow silica sol A (silica solid content concentration 20%) is prepared, and solvent replacement with methanol is performed with an ultrafiltration membrane, and 100 g of organosol having a SiO ₂ content of 20% (the water content is relative to the SiO ₂ content). 0.5%). Thereto, 28% aqueous ammonia solution was added to 100 g of the organosol so as to be 100 ppm as ammonia, mixed well, and then γ-acryloyloxypropyltrimethoxysilane [trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd. 3.6 g was added to obtain a reaction solution.

This was heated to 50 ° C. and heated at 50 ° C. for 6 hours with stirring. After completion of the heating, the reaction solution was cooled to room temperature, and further the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an organosol composed of coated hollow fine particles having a SiO ₂ concentration of 20%. This organosol has an average particle size of 60 nm, a refractive index of 1.25, a porosity of 40 to 45%, a specific surface area of 130 m ² / g, and a mass reduction ratio by thermal mass measurement (TG) of 3.6%. It was an organosol (modified hollow silica fine particle sol) in which hollow silica fine particles were dispersed.
[Production Example 2, preparation of coating solution for low refractive index layer]
(Production Example 2-1, preparation of coating solution for low refractive index layer (L-1))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 1 part of a poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 1308 parts of isopropyl alcohol and 4308 parts of isopropyl alcohol were mixed to prepare a coating solution L-1 for a low refractive index layer.
(Production Example 2-2, Preparation of Coating Solution for Low Refractive Index Layer (L-2))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 2.5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 1188 parts of isopropyl alcohol were mixed to prepare a coating solution L-2 for a low refractive index layer.
(Production Example 2-3, preparation of coating solution for low refractive index layer (L-3))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts of (c) poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1 / 2.5 complex in terms of solid content, 5 parts, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-3 for a low refractive index layer.
(Production Example 2-4, Preparation of Coating Solution for Low Refractive Index Layer (L-4))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 7.5 parts of poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 1788 parts of isopropyl alcohol were mixed to prepare a coating solution L-4 for a low refractive index layer.
(Production Example 2-5, Preparation of Low Refractive Index Layer Coating Liquid (L-5))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 150 parts by weight conversion, (c) 10 parts by weight of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite, photopolymerization initiator [Ciba Specialty 12.5 parts of Chemicals Co., Ltd., trade name: Irgacure 907] and 3588 parts of isopropyl alcohol were mixed to prepare a coating solution L-5 for a low refractive index layer.
(Production Example 2-6, Preparation of Low Refractive Index Layer Coating Liquid (L-6))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 12.5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty 12.5 parts of Chemicals, Inc., trade name: Irgacure 907] and 3388 parts of isopropyl alcohol were mixed to prepare a coating solution L-6 for a low refractive index layer.
(Production Example 2-7, Preparation of Coating Solution for Low Refractive Index Layer (L-7))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 25 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. 12.5 parts manufactured by Trade Name: Irgacure 907] and 2388 parts isopropyl alcohol were mixed to prepare a coating solution L-7 for a low refractive index layer.
(Production Example 2-8, Preparation of Coating Solution for Low Refractive Index Layer (L-8))
(a) 100 parts of 1,10-diacryloyloxy-2,9-dihydroxy-4,4,5,5,6,6,7,7, -octafluorodecane [OD2H2A], (b) the above production example 150 parts of the modified hollow silica fine particle sol obtained in 1 in terms of solid content, and a composite of (c) poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content 12.5 parts, 12.5 parts of photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 3388 parts of isopropyl alcohol were mixed to obtain a coating solution L-8 for a low refractive index layer. Was prepared.
(Production Example 2-9, preparation of coating solution for low refractive index layer (L-9))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 233 parts, (c) 10 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. 16.7 parts made by trade name: Irgacure 907] and 4911 parts isopropyl alcohol were mixed to prepare a coating solution L-9 for a low refractive index layer.
(Production Example 2-10, preparation of coating solution for low refractive index layer (L-10))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 100 parts by weight conversion, (c) 6 parts by weight of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite, and photopolymerization initiator [Ciba Specialty 10 parts of Chemicals Co., Ltd., trade name: Irgacure 907] and 3110 parts of isopropyl alcohol were mixed to prepare a coating solution L-10 for a low refractive index layer.
(Production Example 2-11, Preparation of Coating Solution for Low Refractive Index Layer (L-11))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 67 parts, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 2664 parts of isopropyl alcohol were mixed to prepare a coating solution L-11 for a low refractive index layer.
(Production Example 2-12, preparation of coating solution for low refractive index layer (L-12))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 43 parts, (c) 4.3 parts of poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 2337 parts of isopropyl alcohol were mixed to prepare a coating solution L-12 for a low refractive index layer.
(Production Example 2-13, Preparation of Coating Solution for Low Refractive Index Layer (L-13))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1/1 in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd. , Trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-13 for a low refractive index layer.
(Production Example 2-14, preparation of coating solution for low refractive index layer (L-14))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 150 parts by weight, 5 parts by weight of a composite of (c) poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1/5, and a photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-14 for a low refractive index layer.
(Preparation of Production Example 2-15, coating liquid for low refractive index layer (L-15))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 2.5 parts of poly (3,4-ethylenedioxythiophene / polyvinylsulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 1188 parts of isopropyl alcohol were mixed to prepare a coating solution L-15 for a low refractive index layer.
(Production Example 2-16, Preparation of Coating Solution for Low Refractive Index Layer (L-16))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts of (c) poly (3,4-ethylenedioxythiophene) / polyacrylic acid ethylsulfonic acid = 1 / 2.5 complex in terms of solid content, 7.5 parts, photopolymerization initiator [Ciba -12.5 parts of Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 3788 parts of isopropyl alcohol were mixed to prepare a coating solution L-16 for a low refractive index layer.
(Production Example 2-17, Preparation of Coating Solution for Low Refractive Index Layer (L-17))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 25 parts of poly (3,4-ethylenedioxythiophene) / polyethyl acrylate sulfonate = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty 12.5 parts of Chemicals Co., Ltd., trade name: Irgacure 907] and 2388 parts of isopropyl alcohol were mixed to prepare a coating solution L-17 for a low refractive index layer.
(Production Example 2-18, preparation of coating solution for low refractive index layer (L-18))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polythienylmethylsulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 19.8 parts of isopropyl alcohol were mixed to prepare a coating solution L-18 for a low refractive index layer.
(Production Example 2-19, preparation of coating solution for low refractive index layer (L-19))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 1 part of a poly (3-methylthiophene) / polystyrenesulfonic acid = 1 / 2.5 complex in terms of solid content, a photopolymerization initiator [manufactured by Ciba Specialty Chemicals, (Trade name: Irgacure 907) and 4308 parts of isopropyl alcohol were mixed to prepare a coating solution L-19 for a low refractive index layer.
(Production Example 2-20, Preparation of Low Refractive Index Layer Coating Liquid (L-20))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 5 parts of poly (3-hexyloxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd. , Trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-20 for a low refractive index layer.
(Production Example 2-21, Preparation of Coating Solution for Low Refractive Index Layer (L-21))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 150 parts by weight conversion, (c) 10 parts by weight of poly (3-methyl-4methoxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 1588 parts of isopropyl alcohol and 3588 parts of isopropyl alcohol were mixed to prepare a coating solution L-21 for a low refractive index layer.
(Production Example 2-22, Preparation of Coating Solution for Low Refractive Index Layer (L-22))
(a) 100 parts of 1,10-diacryloyloxy-2,9-dihydroxy-4,4,5,5,6,6,7,7, -octafluorodecane [OD2H2A], (b) the above production example 150 parts of the modified hollow silica fine particle sol obtained in 1 in terms of solid content, and 12 parts of the composite of (c) poly (3-methyl-4methoxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content. .5 parts, 12.5 parts of photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 3388 parts of isopropyl alcohol were mixed to prepare a coating solution L-22 for low refractive index layer. Prepared.
(Production Example 2-23, preparation of coating solution for low refractive index layer (L-23))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts by weight, (c) 12.5 parts of poly (3-hexyloxythiophene) / polyethyl acrylate sulfonate = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty 12.5 parts of Chemicals, Inc., trade name: Irgacure 907] and 3388 parts of isopropyl alcohol were mixed to prepare a coating solution L-23 for a low refractive index layer.
(Production Example 2-24, Preparation of Low Refractive Index Layer Coating Liquid (L-24))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, 5 parts of a composite of (c) poly (2-methylaniline) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd., product Name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-24 for a low refractive index layer.
(Production Example 2-25, preparation of coating solution for low refractive index layer (L-25))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 5 parts of poly (3-isobutylaniline) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals, 12.5 parts of trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-25 for a low refractive index layer.
(Production Example 2-26, preparation of coating solution for low refractive index layer (L-26))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 150 parts by weight, 5 parts by weight of the composite of (c) poly (3-butylpyrrole) / polystyrene sulfonic acid = 1 / 2.5, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. Manufactured product, trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-26 for a low refractive index layer.
(Production Example 2-27, preparation of coating solution for low refractive index layer (L-27))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts by weight, (c) 5 parts of poly (3-methyl-4-hexyloxypyrrole) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 19.8 parts of isopropyl alcohol were mixed to prepare a coating solution L-27 for a low refractive index layer.
(Production Example 2-28, preparation of coating solution for low refractive index layer (L-28))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 5 parts of poly (oxy-1,4-phenylene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. 12.5 parts by trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-28 for a low refractive index layer.
(Production Example 2-29, preparation of coating solution for low refractive index layer (L-29))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 150 parts by weight, 12.5 parts of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907) and 4388 parts of isopropyl alcohol were mixed to prepare a coating solution L- for a low refractive index layer. 29 was prepared.
(Production Example 2-30, Preparation of Coating Solution for Low Refractive Index Layer (L-30))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 37.5 parts of a poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, a photopolymerization initiator [Ciba Specialty 12.5 parts of Chemicals Co., Ltd., trade name: Irgacure 907] and 1388 parts of isopropyl alcohol were mixed to prepare a coating solution L-30 for a low refractive index layer.
(Production Example 2-31, preparation of coating solution for low refractive index layer (L-31))
100 parts of (a) pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is solid 25 parts by weight, (c) 3.8 parts by weight of a poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite, and a photopolymerization initiator [Ciba 6.3 parts of Specialty Chemicals, trade name: Irgacure 907] and 2090 parts of isopropyl alcohol were mixed to prepare a coating solution L-31 for a low refractive index layer.
(Production Example 2-32, preparation of coating solution for low refractive index layer (L-32))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 400 parts, (c) 15 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 7175 parts of isopropyl alcohol were mixed to prepare a coating solution L-32 for a low refractive index layer.
(Production Example 2-33, Preparation of coating solution for low refractive index layer (L-33))
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 in terms of solid content 150 parts, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 0.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. 12.5 parts by trade name: Irgacure 907] and 3988 parts isopropyl alcohol were mixed to prepare a coating solution L-33 for a low refractive index layer.
(Production Example 2-34, Preparation of coating solution for low refractive index layer (L-34))
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) the modified hollow silica fine particle sol obtained in Production Example 1 is converted into solid content 150 parts, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrenesulfonic acid = 1 / 6.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals ( Co., Ltd., trade name: Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-34 for a low refractive index layer.
(Example 1-1)
A coating solution for low refractive index layer (L-1) prepared in Production Example 2-1 on a polyethylene terephthalate (PET) film (product name: A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm is used as an optical film. By applying a gravure coating method so that the thickness becomes kλ / 4 (k: 1, λ: 550 nm), drying, and then curing by irradiation with ultraviolet rays at an output of 400 mJ / cm ^{2 in} a nitrogen atmosphere, An antireflection film was produced.

The resulting antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance by the methods described below, and the evaluation results are shown in Table 1.
(Visibility reflectance)
In order to remove the back surface reflection of the measurement surface, the back surface was roughened with sandpaper and painted with a black paint, and a light wavelength of 380 nm to 780 nm was measured with a spectrophotometer [trade name: U-best 560 manufactured by JASCO Corporation]. The 5 ° and −5 ° specular reflection spectra were measured. Viewing the tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z8701, using the spectral reflectance of the obtained light with a wavelength of 380 nm to 780 nm and the relative spectral distribution of the CIE standard illuminant D65. Sensitivity reflectance (%) was used.
(Surface resistivity)
The surface resistivity (Ω / □) of the antireflection film was measured using a digital insulation meter [manufactured by Toa DKK Co., Ltd., trade name: SM-8220]. In Tables 1 to 3, “RANGE OVER” means that the surface resistivity increased as it exceeded the measurement limit.
(3) Heat resistance The antireflection film was left in a thermostat set at 80 ° C., taken out from the thermostat after 1000 hours, and the surface resistivity was measured. Compared with the surface resistivity measured before putting in the thermostatic bath, it was marked with ○ when the increase in surface resistivity was suppressed within 2 digits, and when the surface resistivity was increased by 3 digits or more.
(4) Scratch resistance An anti-reflective film with # 0000 steel wool fixed to the tip of an eraser abrasion tester manufactured by Honko Seisakusho Co., Ltd. and a load of 2.5 N (250 gf) and 1 N (100 gf) applied. The surface scratches after 10 reciprocating rubs on the surface were visually observed and evaluated according to the following 6 grades A to E.

A: No scratch, A ′: 1-3 scratches, B: 4-10 scratches, C: 11-20 scratches, D: 21-30 scratches, E: 31 or more (Examples 1-2) Example 1-14)
In Example 1-1, instead of the coating solution for low refractive index layer (L-1), the coating solution for low refractive index layer (L-2 to L) prepared in Production Example 2-2 to Production Example 2-14 was used. An antireflection film was obtained in the same manner as in Example 1-1 except that -14) was used. The resulting antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance, and the results are shown in Table 1.

表１に示したように、実施例１−１〜実施例１−１４では、単層構成で十分な反射防止性能を有し、帯電防止性能にも優れ、かつ耐熱性及び耐擦傷性も良好な反射防止フィルムを得ることができた。
（実施例２−１〜実施例２−４）
実施例１−１において、低屈折率層用塗液（Ｌ−１）の代わりに、製造例２−１５〜製造例２−１８で調製した低屈折率層用塗液（Ｌ−１５〜Ｌ−１８）を用いた以外は実施例１−１と同様にして、反射防止フィルムを得た。得られた反射防止フィルムについて、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価を行い、それらの結果を表２に示した。

As shown in Table 1, in Examples 1-1 to 1-14, a single layer configuration has sufficient antireflection performance, excellent antistatic performance, and good heat resistance and scratch resistance. An antireflection film could be obtained.
(Example 2-1 to Example 2-4)
In Example 1-1, instead of the coating solution for low refractive index layer (L-1), the coating solution for low refractive index layer (L-15 to L) prepared in Production Example 2-15 to Production Example 2-18 was used. An antireflection film was obtained in the same manner as in Example 1-1 except that -18) was used. The obtained antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance, and the results are shown in Table 2.

表２に示したように、実施例２−１〜実施例２−４では、単層構成で良好な反射防止性能を有し、帯電防止性能が良く、かつ耐熱性及び耐擦傷性も良好な反射防止フィルムを得ることができた。
（実施例３−１〜実施例３−５）
実施例１−１において、低屈折率層用塗液（Ｌ−１）の代わりに、製造例２−１９〜製造例２−２３で調製した低屈折率層用塗液（Ｌ−１９〜Ｌ−２３）を用いた以外は実施例１−１と同様にして、反射防止フィルムを得た。得られた反射防止フィルムについて、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価を行い、それらの結果を表３に示した。

As shown in Table 2, Examples 2-1 to 2-4 have a single layer configuration and good antireflection performance, good antistatic performance, and good heat resistance and scratch resistance. An antireflection film could be obtained.
(Example 3-1 to Example 3-5)
In Example 1-1, instead of the coating solution for low refractive index layer (L-1), the coating solution for low refractive index layer (L-19 to L) prepared in Production Example 2-19 to Production Example 2-23 was used. An antireflection film was obtained in the same manner as in Example 1-1 except that -23) was used. The resulting antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance, and the results are shown in Table 3.

表３に示したように、実施例３−１〜実施例３−５では、単層構成で良好な反射防止性能を有し、帯電防止性能が良好で、かつ耐熱性及び耐擦傷性も良好な反射防止フィルムを得ることができた。
（実施例４−１〜実施例４−５）
実施例１−１において、低屈折率層用塗液（Ｌ−１）の代わりに、製造例２−２４〜製造例２−２８で調製した低屈折率層用塗液（Ｌ−２４〜Ｌ−２８）を用いた以外は実施例１−１と同様にして、反射防止フィルムを得た。得られた反射防止フィルムについて、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価を行い、それらの結果を表４に示した。

As shown in Table 3, Examples 3-1 to 3-5 have a single layer configuration and good antireflection performance, good antistatic performance, and good heat resistance and scratch resistance. An antireflection film could be obtained.
(Example 4-1 to Example 4-5)
In Example 1-1, instead of the coating solution for low refractive index layer (L-1), the coating solution for low refractive index layer (L-24 to L-L) prepared in Production Example 2-24 to Production Example 2-28 was used. An antireflection film was obtained in the same manner as in Example 1-1 except that -28) was used. The resulting antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance, and the results are shown in Table 4.

表４に示したように、実施例４−１〜実施例４−５では、単層構成で良好な反射防止性能を有し、帯電防止性能が良く、かつ耐熱性及び耐擦傷性も良好な反射防止フィルムを得ることができた。
（比較例１−１〜比較例１−６）
実施例１−１において、低屈折率層用塗液（Ｌ−１）の代わりに、比較例１−１では製造例２−２９で調製した低屈折率層用塗液（Ｌ−２９）を用い、比較例１−２では製造例２−３０で調製した低屈折率層用塗液（Ｌ−３０）を用い、比較例１−３では製造例２−３１で調製した低屈折率層用塗液（Ｌ−３１）を用い、比較例１−４では製造例２−３２で調製した低屈折率層用塗液（Ｌ−３２）を用い、比較例１−５では製造例２−３３で調製した低屈折率層用塗液（Ｌ−３３）を用い、比較例１−６では製造例２−３４で調製した低屈折率層用塗液（Ｌ−３４）を用いた以外は実施例１−１と同様にして、反射防止フィルムを得た。得られた反射防止フィルムについて、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価を行い、それらの結果を表５に示した。

As shown in Table 4, Examples 4-1 to 4-5 have a single layer configuration and good antireflection performance, good antistatic performance, and good heat resistance and scratch resistance. An antireflection film could be obtained.
(Comparative Example 1-1 to Comparative Example 1-6)
In Example 1-1, instead of the coating solution for low refractive index layer (L-1), in Comparative Example 1-1, the coating solution for low refractive index layer (L-29) prepared in Production Example 2-29 was used. In Comparative Example 1-2, the coating solution for low refractive index layer (L-30) prepared in Production Example 2-30 was used, and in Comparative Example 1-3, for low refractive index layer prepared in Production Example 2-31. Using the coating liquid (L-31), Comparative Example 1-4 used the coating liquid for low refractive index layer (L-32) prepared in Production Example 2-32, and Comparative Example 1-5 was Production Example 2-33. The coating solution for low refractive index layer (L-33) prepared in Step 1 was used, and in Comparative Example 1-6, the coating solution for low refractive index layer (L-34) prepared in Production Example 2-34 was used. An antireflection film was obtained in the same manner as in Example 1-1. The resulting antireflection film was evaluated for visibility reflectance, surface resistivity, heat resistance and scratch resistance, and the results are shown in Table 5.

表５に示したように、比較例１−１では、π共役系導電性高分子とドーパントからなる複合体を有していないことから、帯電防止性能が発現されないという結果に到った。また、比較例１−２では、π共役系導電性高分子とドーパントからなる複合体の含有量が多いため、相対的に多官能（メタ）アクリレートの含有量が減少し、耐擦傷性が悪化するという結果であった。比較例１−３では、中空シリカ微粒子の含有量が過少であるため、硬化膜の屈折率が十分に低下せず、視感度反射率が高くなって反射防止性能が劣るという結果を招いた。

As shown in Table 5, since Comparative Example 1-1 did not have a complex composed of a π-conjugated conductive polymer and a dopant, the antistatic performance was not exhibited. In Comparative Example 1-2, since the content of the complex composed of the π-conjugated conductive polymer and the dopant is large, the content of the polyfunctional (meth) acrylate is relatively decreased, and the scratch resistance is deteriorated. It was a result of doing. In Comparative Example 1-3, since the content of the hollow silica fine particles is too small, the refractive index of the cured film is not sufficiently lowered, resulting in high visibility reflectance and poor antireflection performance.

  Moreover, in Comparative Example 1-4, since the content of the hollow silica fine particles was excessive, the content of the polyfunctional (meth) acrylate was relatively decreased, and the scratch resistance was deteriorated. In Comparative Example 1-5, since the amount of the dopant is too small with respect to the π-conjugated conductive polymer, the π-conjugated conductive polymer is not sufficiently doped, resulting in low conductivity and antistatic properties. Declined. Furthermore, in Comparative Example 1-6, since the amount of the dopant was too much with respect to the π-conjugated conductive polymer, the heat resistance deteriorated due to the influence of the excessive dopant.

Claims (6)

An antireflection film comprising a low refractive index layer directly laminated on a transparent substrate film,
The low refractive index layer contains (a) a polyfunctional (meth) acrylate, (b) a hollow silica fine particle, and (c) a complex composed of a π-conjugated conductive polymer and a dopant; (B) Hollow silica fine particles 40 to 250 parts by mass and (c) π-conjugated system conductive polymer and dopant 1 to 25 parts by mass per 100 parts by mass of (meth) acrylate, and (c) π-conjugated A cured product of a coating solution for a low refractive index layer in which the mass ratio of the π-conjugated conductive polymer and the dopant in the composite comprising the conductive polymer and the dopant is set to 1: 1 to 1: 5 Antireflection film characterized by The antireflection film according to claim 1, wherein the π-conjugated conductive polymer is a polythiophene. The antireflection film according to claim 2, wherein the polythiophene is poly (3,4-ethylenedioxythiophene). The antireflection film according to claim 1, wherein the π-conjugated conductive polymer is polypyrrole or polyaniline. The antireflection film according to claim 1, wherein the dopant is a polyanion. 6. The antireflection film according to claim 5, wherein the polyanion is polystyrene sulfonic acid.