JP2010072039A - Antireflection film and electronic image display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film which is applied to the surface of a plasma display (PDP), a liquid crystal display (LCD) or the like, has very low luminous reflectance, has a mild reflection color tone, and prevents the occurrence of interference fringes, and further to provide an electronic image display using the antireflection film. <P>SOLUTION: The antireflection film is constituted by laminating a hard coat layer, a high refractive index layer and a low refractive index layer in this order on a polyester film via an adhesive layer. Film thickness of the adhesive layer is 5 to 30 nm, refractive index difference between the polyester film and the hard coat layer is ≤0.02, a refractive index of the high refractive index layer is 1.70 to 1.90 and a refractive index of the low refractive index layer is 1.28 to 1.36. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is applied to the surface of a plasma display (PDP), a liquid crystal display (LCD), etc., and has an extremely low visibility reflectance, a gentle reflection color, and an antireflection property that suppresses the generation of interference fringes. The present invention relates to a film and an electronic image display device using the film.

  In recent years, electronic displays are widely used for televisions and monitors. In particular, displays are becoming thinner and larger, and plasma displays, liquid crystal displays, organic EL displays, and the like are attracting attention. These large displays are required to have less reflection of light emitted from an external light source such as a fluorescent lamp in order to improve visibility.

  Therefore, a method is generally known in which an antireflection film formed by providing an antireflection layer on the surface of a transparent base film is bonded to the display surface for use. These antireflection films are required to have a gentle reflection color (= the reflection color does not become tight) due to the problem of color reproducibility as well as improvement in visibility.

For example, by defining the refractive index and thickness of the hard coat layer, high refractive index layer, and low refractive index layer, respectively, the reflectance in each of the short wavelength region, medium wavelength region, and long wavelength region can be kept low. An antireflection film with a gentle color has been proposed. (For example, see Patent Document 1)
However, in the configuration defined in Patent Document 1, the refractive index of the high refractive index layer is 1.60 to 1.70, the thickness is defined to 120 to 140 nm, and the refractive index of the low refractive index layer is 1.38 to 1. .45, the thickness is defined as 70 to 90 nm, and the refractive index of the low refractive index layer is not so low, so that sufficient antireflection performance is not obtained.
Further, a polyethylene terephthalate (PET) film mainly used as a transparent substrate film has a refractive index of 1.65, and a hard coat layer having a refractive index defined in Patent Document 1 is applied on the PET film. When processed, a refractive index difference of 0.10 to 0.20 occurs between the PET film and the hard coat layer. Since reflection of light occurs at the interface between layers having different refractive indexes, rainbow-colored unevenness (interference fringes) becomes noticeable when the film is viewed under a fluorescent lamp or the like due to interference of reflected light generated at the interface between the two.

In addition, a gentle antireflection film having a reflection color composed of an antistatic layer and a low refractive index layer has been proposed. (For example, see Patent Document 2)
However, as in Patent Document 1, sufficient antireflection performance has not been obtained, and when an attempt is made to obtain sufficient antireflection performance, the color of reflected light becomes large and color unevenness occurs. That is, it is suggested that the color of the reflected color becomes tight.

JP 2005-99119 A JP 2008-3122 A

  The present invention is intended to solve the background art as described above, an antireflection film having a very low visibility reflectance, a gentle reflection color, and suppressing the occurrence of interference fringes, and the same An object of the present invention is to provide an electronic image display device using the.

  In order to achieve the above object, the antireflection film of the first invention of the present invention comprises a hard coat layer, a high refractive index layer and a low refractive index layer in this order on a polyester film via an adhesive layer. In the laminated antireflection film, the thickness of the adhesive layer is 5 to 30 nm, the refractive index difference between the polyester film and the hard coat layer is within 0.02, and the refractive index of the high refractive index layer Is 1.70 to 1.90, and the refractive index of the low refractive index layer is 1.28 to 1.36.

  The antireflective film of the second invention of the present invention is the antireflective film of the first invention, wherein the low refractive index layer has a film forming property, a fluorine-containing compound having a polymerizable double bond, and a void ratio of the hollow portion. Modified hollow silica fine particles obtained by modifying hollow silica fine particles having a mean particle size of 10 to 100 nm with a silane coupling agent having a polymerizable double bond, and the fluorine-containing compound and the above The proportion of the modified hollow silica fine particles is 40 to 80% by mass of the fluorine-containing compound and 60 to 20% by mass of the modified hollow silica fine particles.

（式中、Ｚは（メタ）アクリロイルオキシ基であり、Ｒ¹は炭素数１〜４のアルキレン基であり、Ｒ²は水素原子、メチル基又はエチル基である。） The antireflection film of the third invention of the present invention is the antireflective film according to the first or second invention, wherein the modified hollow silica fine particles are subjected to hydrothermal treatment and are represented by the following chemical formula (1). It is modified by a silane coupling agent and has a thermal mass decrease of 2 to 10% by mass when the temperature is increased from room temperature to 500 ° C. at a rate of temperature increase of 10 ° C./min. .

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.)

The antireflection film of the fourth invention of the present invention is the invention according to any one of the first to third inventions, wherein the hard coat layer contains conductive metal oxide fine particles, whereby 1.0E + 10 ⁸ Ω to It has a surface resistivity of 1.0E + 10 ¹² Ω.

  An electronic image display device according to a fifth aspect of the present invention is characterized by having the antireflection film according to any one of the first to fourth aspects on a display surface.

According to the present invention, the following effects can be exhibited.
The antireflective film of the first invention of the present invention comprises a polyester film and a hard coat layer, wherein a hard coat layer, a high refractive index layer and a low refractive index layer are laminated on the polyester film in this order via an adhesive layer. And the refractive index of the high refractive index layer is 1.70 to 1.90, and the refractive index of the low refractive index layer is 1.28 to 1.36. By setting the refractive index of each layer in this way, the reflectance in the visibility wavelength range (light wavelength 500 nm to 650 nm) can be made extremely low, the waveform of the reflection spectrum becomes flat, and the color of the reflected color Can be calm. Therefore, by sticking to the display surface of an electronic image display device such as a plasma display (PDP) or liquid crystal display (LCD), reflection of light emitted from an external light source such as a fluorescent lamp is suppressed, and visibility is improved. At the same time, good color reproducibility and good video can be provided. Moreover, since the refractive index difference between the polyester film and the hard coat layer is set within 0.02, and the film thickness of the adhesive layer is set as thin as 5 to 30 nm, it is based on the refractive index difference. The adhesion between the polyester film and the hard coat layer can be improved while suppressing the generation of interference fringes.

  In the antireflective film of the second invention of the present invention, the low refractive index layer has film-forming properties, the fluorine-containing compound having a polymerizable double bond is 40 to 80% by mass, and the porosity of the hollow portion Is contained in 60 to 20% by mass of modified hollow silica fine particles of 40 to 45%, so that the antireflection performance can be improved. Since the modified hollow silica fine particles are modified with a silane coupling agent having a polymerizable double bond, the polymerizable double bond of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized. As a result, the hollow silica fine particles are integrally bonded to the fluorine-containing compound, and the scratch resistance of the cured film can be improved. Furthermore, since the average particle diameter of the modified hollow silica fine particles is 10 to 100 nm, a transparent film can be formed.

  In the antireflection film of the third invention of the present invention, the modified hollow silica fine particles are subjected to hydrothermal treatment, so that the outer shell is densified and moisture is hardly adsorbed on the surface of the cured film. Furthermore, when the hollow silica fine particles are modified by the silane coupling agent represented by the chemical formula (1) and the temperature is increased from room temperature to 500 ° C. at a temperature increase rate of 10 ° C./min, the thermal mass reduction is 2 to 10%. Since it is a mass% thing, compatibility with a fluorine-containing compound becomes favorable and can improve the abrasion resistance of a cured film.

The antireflection film of the fourth invention of the present invention has a surface resistivity of 1.0E + 10 ⁸ Ω to 1.0E + 10 ¹² Ω because the hard coat layer contains conductive metal oxide fine particles. Therefore, adhesion of foreign matters such as dust due to static electricity can be prevented.

  Since the image display device of the fifth invention of the present invention is provided with the antireflection film according to any one of the first to fourth on the display surface, the reflection of any of the first to fourth inventions. The effect by a preventive film can be exhibited.

  The antireflection film of the present invention uses a polyester film as a base material (base layer), and in that order (A) an adhesive layer, (B) a hard coat layer, (C) a high refractive index layer, (D) a low The refractive index layer is laminated.

First, the base material (base layer) used for this invention is demonstrated.
As the base film used in the present invention, a polyester film such as polyethylene terephthalate (PET, n = 1.65) which is excellent in terms of ease of molding, availability and cost is employed. Moreover, the thickness of this polyester film becomes like this. Preferably it is 25-400 micrometers, More preferably, it is 50-200 micrometers. When this film thickness is less than 25 μm or more than 400 μm, the handleability at the time of manufacture and use of the antireflection film is unfavorable. The polyester film may contain various additives. Examples of such additives include ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants, flame retardants, and the like.

Next, the (A) adhesive layer provided on the polyester film will be described.
The (A) adhesive layer in the present invention has a function of improving the adhesion between the polyester film and the (B) hard coat layer described later without adversely affecting optically. The thickness of the adhesive layer is 5 to 30 nm, preferably 10 to 20 nm. As long as the adhesion between the polyester film and the hard coat layer can be increased, a known resin layer having an arbitrary refractive index as an adhesive is used. Applicable. When the film thickness of the adhesive layer is less than 5 nm, the adhesion between the polyester film and the hard coat layer cannot be maintained. On the other hand, when the film thickness of the adhesive layer exceeds 30 nm, for example, a commercially available adhesive layer is provided. In the polyester film, a thick adhesive layer has an optical adverse effect, so that interference fringes increase.

  As the method for forming the adhesive layer (A), a method of applying a coating liquid containing a water-dispersible or water-soluble polyester resin as an adhesive on the polyester film and then drying it is preferable. Regardless of water solubility, it is preferable to use a polyester resin, particularly a copolyester resin, as the adhesive for forming the adhesive layer. The copolyester resin means a polyester resin obtained by a polycondensation reaction between a plurality of dicarboxylic acids and a plurality of polyols or a transesterification reaction between a plurality of esters and a plurality of polyols. This copolyester resin is formed by a polycondensation reaction of a dicarboxylic acid and a polyol.

Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer An acid etc. are mentioned. In addition to the dicarboxylic acid, a sulfonic acid metal base-containing dicarboxylic acid may be added to impart water dispersibility.
Examples of the polyol include ethylene glycol, propylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 1,4-butanediol, dipropylene glycol, 1,6-hexanediol, and xylene glycol. However, it is not limited to these.

Moreover, you may add a filler, a wax, etc. to the coating liquid containing the said copolyester resin in order to provide blocking resistance and slipperiness.
Examples of the filler include silica, titanium oxide, calcium carbonate, calcium silicate, barium sulfate, calcium phosphate, aluminum oxide, magnesium oxide, zinc oxide, and tin oxide. Among these, it is preferable to select one that does not settle in the coating solution. These fillers usually have an average particle size of 20 to 60 nm. When the average particle size is less than 20 nm, sufficient blocking resistance and slipping properties may not be obtained, and when it exceeds 60 nm, the filler tends to fall off.
As the wax, water-dispersible or water-soluble waxes such as carnauba wax, candelilla wax, rice wax, wood wax, palm wax, montan wax, ozokerite, ceresin wax, paraffin wax, polyethylene glycol, polypropylene glycol and the like are preferable. .

In order to further improve the scratch resistance, it is preferable to add a crosslinking agent to the adhesive layer (A).
As said crosslinking agent, an oxazoline, an epoxy compound, a melamine compound, an isocyanate compound, a coupling agent etc. can be used, Of these, an oxazoline is preferable. As the oxazolines, a polymer containing an oxazoline group is preferable. This is obtained by copolymerization with an addition polymerizable oxazoline group-containing monomer alone or with another monomer. Examples of the addition polymerizable oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. The other monomer is not particularly limited as long as it is a monomer copolymerizable with an addition-polymerizable oxazoline group-containing monomer, and includes acrylic acid esters, unsaturated carboxylic acids, unsaturated nitriles, Examples thereof include unsaturated amides, vinyl esters, vinyl ethers, α-olefins, halogen-containing α, β-unsaturated monomers, α, β-unsaturated aromatic monomers, and the like.

  Furthermore, in order to provide this (A) adhesive layer on the said polyester film, it is performed by coating the said coating liquid on the single side | surface or both surfaces of a polyester film. The application can be carried out at any stage, but it is preferably carried out during the production process of the polyester film. As a coating method, any known coating method can be used. Examples thereof include a gravure coating method, a roll brush method, a spray coating method, an air knife method, a coil bar method, and a dip coating method.

Next, the (B) hard coat layer used on one surface of the polyester film will be described.
The (B) hard coat layer in the present invention has a difference between the refractive index of the polyester film and the refractive index of 0.02 or less, and can be used for the hard coat layer as long as the surface hardness and scratch resistance can be improved. All resins can be used, and it is particularly preferable that the resin is formed from a material containing an ionizing radiation curable resin and metal oxide fine particles.
Here, the metal oxide fine particles mean metal oxides having an average particle diameter of preferably 150 nm or less, more preferably 10 to 150 nm. When this average particle diameter exceeds 150 nm, the fine particles become too large, resulting in a loss of transparency of the hard coat layer.
By reducing the reflected light by making the difference between the refractive index of the hard coat layer and the refractive index of the polyester film within 0.02 as described above, interference fringes generated by interference of the reflected light can be reduced. it can. On the other hand, when the difference in the refractive index between the polyester film and the hard coat layer exceeds 0.02, the reflected light at the interface between the polyester film and the hard coat layer becomes strong, so that the interference fringes become strong and inappropriate. It is.

  The ionizing radiation curable resin particularly preferable as the (B) hard coat layer is a resin that undergoes a curing reaction when irradiated with active energy rays such as ultraviolet rays and electron beams, and the type thereof is not particularly limited. . Specifically, for example, monofunctional (meth) acrylate [in the present specification, (meth) acrylate means a generic name including both acrylate and methacrylate. ], Starting materials such as polyfunctional (meth) acrylates and reactive silicon compounds such as tetraethoxysilane. Among these, from the viewpoint of achieving both productivity and hardness, a composition containing an ultraviolet curable polyfunctional acrylate as a main component is preferable. The composition containing such an ultraviolet curable polyfunctional acrylate is not particularly limited, and is commercially available as, for example, a mixture of two or more known ultraviolet curable polyfunctional acrylates, or an ultraviolet curable hard coat material. And the like.

  The ultraviolet curable polyfunctional acrylate is not particularly limited. For example, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, tetramethylol methane triacrylate, trimethylol propane triacrylate, 1,6-hexanediol diacrylate. An acrylic derivative of a polyfunctional alcohol such as 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, polyethylene glycol diacrylate, polyurethane acrylate, or the like is preferable.

Moreover, when the metal oxide fine particles added to the ionizing radiation curable resin are dispersed in the ionizing radiation curable resin to form a coating film, there is a difference in refractive index between the polyester film and the hard coat layer. Those that can be adjusted to 0.02 or less are selected.
Examples of the metal oxide constituting the metal oxide fine particles include ITO (indium-tin composite oxide, refractive index 2.0), ATO (antimony-tin composite oxide, refractive index 2.1), tin oxide ( (Refractive index 2.0), antimony oxide (refractive index 2.1), zinc oxide (refractive index 2.1), zirconium oxide (refractive index 2.1), titanium oxide (refractive index 2.4) and aluminum oxide ( At least one selected from the group consisting of refractive index 1.6) is preferred. Of these, tin oxide and antimony oxide are particularly preferable in terms of particle dispersibility, average particle diameter, availability, and production cost.
Moreover, the addition amount of the metal oxide fine particles to the ionizing radiation curable resin is about 1 to 400 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

  Furthermore, other components can be further added to the ionizing radiation curable resin as long as the effects of the present invention are not impaired. 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. Further, any amount of solvent can be added as long as it is dried after film formation in the wet coating method.

  Moreover, the formation method of such a (B) hard-coat layer is not specifically limited, General wet-coating methods, such as a roll-coating method, a coil bar method, a die-coating method, are employ | adopted. The formed layer can be subjected to a curing reaction by heating or irradiation with active energy rays such as ultraviolet rays and electron beams, as necessary.

Next, (C) the high refractive index layer will be described.
The refractive index of the (C) high refractive index layer in the present invention is 1.70 to 1.90. When the refractive index is less than 1.70, the reflectance in the short wavelength region is high. On the other hand, when it exceeds 1.90, the reflectance in the long wavelength region is high. It is not flat (becomes V-shaped) and the color of the reflected color becomes tight. That is, when the reflection spectrum becomes V-shaped, a complementary color having a wavelength at the bottom of the V-shape can be seen. Therefore, if the wavelength at the bottom of the V-shape shifts due to film thickness unevenness when forming the coating film, various colors appear depending on the location and color unevenness occurs.

The material constituting the (C) high refractive index layer is not particularly limited, and an inorganic material or an organic material can be used. Examples of the inorganic material include fine particles such as zinc oxide, titanium oxide, cerium oxide, aluminum oxide, tantalum oxide, yttrium oxide, ytterbium oxide, zirconium oxide, indium tin oxide, and antimony-containing tin oxide. On the other hand, as the organic material, for example, a material obtained by polymerizing and curing a composition containing a polymerizable monomer having a fluorene skeleton can be used.
The average particle size of the fine particles of the inorganic material preferably does not greatly exceed the thickness of the layer, and is particularly preferably 0.1 μm or less. When the average particle size is increased, the optical performance is deteriorated such as scattering, which is not preferable. Further, the surface of the fine particles can be modified with various coupling agents as required. Examples of the various coupling agents include organically substituted silicon compounds, metal alkoxides such as aluminum, titanium, zirconium, and antimony, and organic acid salts.

Next, (D) the low refractive index layer will be described.
The refractive index of the (D) low refractive index layer in the present invention is 1.28 to 1.36. When the refractive index of this low refractive index layer exceeds 1.36, the overall reflectance becomes high and sufficient antireflection performance cannot be obtained. On the other hand, when the refractive index is less than 1.28, it is difficult to form a sufficiently hard layer.

Examples of the material constituting the (D) low refractive index layer include inorganic substances such as silicon oxide, lanthanum fluoride, magnesium fluoride, and cerium fluoride, a single or mixture of fluorine-containing organic compounds, or the weight of fluorine-containing organic compounds. Compositions containing coalescing can be used. Further, a monomer containing no fluorine (abbreviated as a non-fluorine monomer) or a polymer can be used as a binder. Among these, silicon oxide-based fine particles, particularly hollow silica fine particles and fluorine-containing organic compounds are particularly preferable because of their low refractive index.
More preferably, the low refractive index layer has (d1) film-formability, a fluorine-containing compound having a polymerizable double bond, a void ratio of 40 to 45%, and an average particle diameter of 10 to 10%. (D2) modified hollow silica fine particles obtained by modifying hollow silica fine particles of 100 nm with a silane coupling agent having a polymerizable double bond, and the ratio of the fluorine-containing compound to the modified hollow silica fine particles is a fluorine-containing compound Is 40 to 80% by mass, and the modified hollow silica fine particles are 60 to 20% by mass.

First, the (d1) fluorine-containing compound will be described.
Fluorine atoms (hereinafter also simply referred to as fluorine) have a very low polarizability, so that fluorine-containing monomers have a low molecular energy after film formation because the cohesive force of the molecules is small. It has the property of being scarce. Here, the film formability represents a property that a cured film (hereinafter also simply referred to as a film) is formed from a fluorine-containing curable coating liquid without being repelled when applied onto a substrate such as a synthetic resin film. A film that can form a uniform film with a certain thickness at the stage where a fluorine-containing curable coating liquid containing a solvent is applied to a substrate and heated to remove the solvent is judged to have good film formability. For example, the critical surface tension when the trifluoromethyl group is oriented is 6 dyn / cm, whereas the tetrafluoroethylene group is 18 dyn / cm, so that fluorine can be formed in the form of a methylene fluoride group or a fluorinated methine group. By introducing it, the film forming property is improved. Further, from the viewpoint of increasing the cohesive force of molecules, a technique of polymerizing is also effective.
Accordingly, (d1) the fluorine-containing compound having film-forming properties and having a polymerizable double bond includes (a) a structure in which fluorine atoms are introduced into the molecule as methylene fluoride groups or fluorinated methine groups. And (a) a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond.

  Moreover, since the cured film formed from the (d1) fluorine-containing compound has a higher refractive index and a higher antifouling property as the fluorine atom content is higher, the fluorine content in the fluorine compound is 40 to 80. It is mass%, Preferably it is 50-70 mass%, More preferably, it is 55-70 mass%. When the fluorine content is less than 40% by mass, the effect of lowering the refractive index and lowering the reflectance of the cured film obtained cannot be obtained. On the other hand, if it exceeds 80% by mass, the fluorine atom content in the cured film is too high, so that the strength and hardness of the film are lowered, and the scratch resistance and abrasion resistance of the surface of the cured film are insufficient.

The (a) fluorine-containing monomer having a structure in which a fluorine atom is introduced into the molecule as a methylene fluoride group or a fluorinated methine group has almost all the fluorine atoms in the molecule as a methylene fluoride group or a fluorinated methine group. All known monomers can be used as long as they are introduced monomers. That is, the polymerizable double bond may be either one (monofunctional) monomer, two or more (polyfunctional) monomers, or a mixture thereof.
These fluorine-containing compounds can increase the strength and hardness of the cured film, and can improve the scratch resistance and wear resistance of the film surface. Among the fluorine-containing compounds, a fluorine-containing polyfunctional (meth) acrylic acid ester is preferable because a crosslinked structure can be formed and the strength and hardness of the cured film are high. In this specification, both acrylic and methacrylic are referred to as (meth) acrylic.
Specific examples of the fluorine-containing polyfunctional (meth) acrylic acid ester include, for example, 1,3-bis {(meth) acryloyloxy} -2,2-difluoropropane, 1,4-bis {(meth) acryloyloxy}. -2,2,3,3-tetrafluorobutane, 1,5-bis {(meth) acryloyloxy} -2,2,3,3,4,4-hexafluoropentane, 1,6-bis {(meta ) Acryloyloxy} -2,2,3,3,4,4,5,5-octafluorohexane, 1,7-bis {(meth) acryloyloxy} -2,2,3,3,4,4, 5,5,6,6-decafluoroheptane, 1,8-bis {(meth) acryloyloxy} -2,2,3,3,4,4,5,5,6,6,7,7-dodeca Fluorooctane, 1,9-bis {(meth) acrylo Ruoxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorononane, 1,10-bis {(meth) acryloyloxy} -2 , 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane, 1,11-bis {(meth) acryloyloxy} -2 , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10-octadecafluoroundecane, 1,12-bis {(meth) acryloyl Oxy} -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11-eicosafluorododecane, 1, 8-bis {(meth) acryloyloxy} -2,7-dihydroxy 4,4,5,5-tetrafluorooctane, 1,7-bis {(me ) Acryloyloxy} -2,8-dihydroxy 4,4,5,5-tetrafluorooctane, 2,7-bis {(meth) acryloyloxy} -1,8-dihydroxy 4,4,5,5-tetrafluoro Octane, 1,10-bis {(meth) acryloyloxy} -2,9-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis {(meth) acryloyl Oxy} -2,10-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 2,9-bis {(meth) acryloyloxy} -1,10-dihydroxy 4,4 5,5,6,6,7,7-octafluorodecane, 1,2,7,8-tetrakis {(meth) acryloyloxy} -4,4,5,5-tetrafluorodecane, 1,2,8 , 9-Tetra Kiss {(meth) acryloyloxy} -4,4,5,5,6,6-hexafluorononane, 1,2,9,10-tetrakis {(meth) acryloyloxy} -4,4,5,5 6,6,7,7-octafluorodecane, 1,2,10,11-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8,8-deca Fluoroundecane, 1,2,11,12-tetrakis {(meth) acryloyloxy} -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane, 1, 10-bis (α-fluoroacryloyloxy) -2,9-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, 1,9-bis (α-fluoroacryloyloxy) -2 , 10-Dihydroxy 4,4,5,5,6 , 6,7,7-octafluorodecane, 2,9-bis (α-fluoroacryloyloxy) -1,10-dihydroxy 4,4,5,5,6,6,7,7-octafluorodecane, , 2,9,10-tetrakis (α-fluoroacryloyloxy) -4,4,5,5,6,6,7,7-octafluorodecane, 1,2,11,12-tetrakis (α-fluoroacryloyl) Oxy) -4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorododecane, 1,12-bis {(meth) acryloyloxy} -3,10-dihydroxy-5 5,6,6,7,7,8,8-octafluorododecane and the like. In use, these are used alone or as a mixture.
These fluorine-containing polyfunctional (meth) acrylic acid esters are produced by a known method, for example, a ring-opening reaction between a corresponding fluorine-containing epoxy compound and (meth) acrylic acid, a corresponding fluorine-containing polyhydric alcohol or the above-mentioned It is produced by an esterification reaction of a fluorine-containing (meth) acrylic acid ester having a hydroxyl group (hydroxyl group) obtained as an intermediate by a ring-opening reaction and (meth) acrylic acid chloride.

In addition, the (a) fluorine-containing reactive polymer that is soluble in the solvent and has a polymerizable double bond has a main chain derived from the fluorine-containing ethylenic monomer and has a reactive group for crosslinking and curing. is there. As the solvent, ester solvents such as ethyl acetate and propyl acetate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alcohol solvents such as isopropyl alcohol and 2-butanol are preferable. Examples of the reactive group include a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and an epoxy group. Such a fluorine-containing reactive polymer that is soluble in a solvent and has a polymerizable double bond has a high molecular weight, so it has good film forming properties while containing fluorine, and is crosslinked and cured using reactive groups after film formation. By doing so, a solvent-insoluble cured film can be obtained.
This solvent-soluble fluorine-containing reactive polymer having a polymerizable double bond has a content of groups having a polymerizable double bond of usually 1 to 20% by mass, preferably 5 to 15% by mass, Weight) The average molecular weight is usually 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 2,000 to 200,000. As this fluorine-containing reactive polymer, a known fluorine-containing reactive polymer (for example, one disclosed in re-published patent WO02 / 018457) is used.

  The content (ratio) of the fluorine-containing compound having (d1) film-forming properties and having a polymerizable double bond is 40 to 40 in the total amount (solid content) with (d2) modified hollow silica fine particles described later. It is 80 mass%, and it is preferable that it is 40-60 mass%. When the content of the fluorine-containing compound is less than 40% by mass, the strength and hardness of the cured film tends to decrease, and the scratch resistance on the film surface is insufficient. On the other hand, when the content is more than 80% by mass, the content of the modified hollow silica fine particles is relatively reduced, the overall balance is deteriorated, the scratch resistance on the coating surface is insufficient, and the reflectance of the coating is also increased.

Next, (d2) modified hollow silica fine particles will be described.
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, and the average particle diameter is about 10 to 100 nm. The thickness of the outer shell is about 1 to 60 nm, the porosity of the hollow portion is 40 to 45%, and the refractive index is a low refractive index of 1.20 to 1.29. In addition, since the hollow portion contains air having a refractive index of 1.0, the film formed by curing the fluorine-containing curable coating liquid can be reduced in refractive index and reflectance, The scratch resistance and wear resistance of the coating can be improved by inorganic fine particles called silica fine particles. When the void ratio of the hollow portion is less than 40%, the amount of air in the hollow portion is reduced, and it becomes impossible to reduce the refractive index and reflectivity of the coating. On the other hand, when the void ratio of the hollow portion exceeds 45%, it is necessary to make the outer shell thin in order to increase the void ratio, which makes it difficult to manufacture.
Furthermore, since the outer shell of normal hollow silica fine particles does not have a dense shell, it tends to adsorb moisture, and if water droplets are left on the film containing the hollow silica fine particles, the moisture will be adsorbed and visible. A spot (water mark) is made. On the other hand, since the hollow silica fine particles used in this embodiment are hydrothermally treated to densify the outer shell, it becomes difficult for moisture to be adsorbed on the silica surface. Will improve.
In addition, since the modified hollow silica fine particles used in this embodiment are modified with a silane coupling agent having a polymerizable double bond, an excellent effect that is not found in ordinary silica fine particles or hollow silica fine particles, that is, including The effect that it is excellent in compatibility with a fluorine compound can be expressed. For this reason, when the modified hollow silica fine particles are mixed with a fluorine-containing compound, aggregation of the modified hollow silica fine particles can be suppressed, and a film having no transparency and excellent transparency can be obtained. Further, in the film, the polymerizable double bond of the silane coupling agent and the polymerizable double bond of the fluorine-containing compound are copolymerized (chemically bonded) to form a strong film, so that the film has scratch resistance and abrasion resistance. The sex can be improved dramatically.

（式中、Ｚは（メタ）アクリロイルオキシ基であり、Ｒ¹は炭素数１〜４のアルキレン基であり、Ｒ²は水素原子、メチル基又はエチル基である。） Further, in order to enhance the effect of modification, (d2) modified hollow silica fine particles are modified with a silane coupling agent having a polymerizable double bond represented by the following chemical formula (1), and the temperature rise rate is 10 ° C./min. It is preferable that the thermal mass decrease when the temperature is raised from room temperature to 500 ° C. is 2 to 10% by mass.

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.)

The (d2) modified hollow silica fine particles will be further described. The modified hollow silica fine particles are obtained by surface-treating the surface of the hollow silica fine particles having an average particle diameter of 5 to 100 nm and a specific surface area of 50 to 1000 m ² / g with a silane coupling agent. It is manufactured by. Specifically, an organosilyl group (monoorganosilyl group, diorganosilyl group or triorganosilyl group) is formed on the surface of the hollow silica fine particle by a hydrolysis reaction between the silanol group on the surface of the hollow silica fine particle and the silane coupling agent. In addition to bonding, the surface has an organic group directly bonded to a large number of silicon atoms.
Further, since the hollow portion (cavity) is larger than that of normal hollow silica fine particles, the refractive index of the cured film is 1 by combining the modified hollow silica fine particles having a low refractive index with a fluorine-containing compound having a high fluorine content. .28 to 1.32, which can realize a lower refractive index and lower reflectance than conventional cured films.

The content (ratio) of the (d2) modified hollow silica fine particles is 20 to 60% by mass and 40 to 60% by mass in the total amount (solid content) with the (d1) fluorine-containing compound. desirable. When this proportion is less than 20% by mass, the content of the modified hollow silica fine particles is reduced, and it becomes impossible to reduce the refractive index and the reflectance of the resulting film, and the scratch resistance is insufficient. . On the other hand, when it exceeds 60% by mass, the excessive modified hollow silica fine particles cannot react with the (d1) fluorine-containing compound, and the modified hollow silica fine particles remain, and on the contrary, the film surface lacks scratch resistance.
As a result of the copolymerization and bonding of the (meth) acryloyloxy group contained in the silane coupling agent of the modified hollow silica fine particles and the polymerizable double bond of the fluorine-containing compound, the function of the modified hollow silica fine particles and the fluorine content The function of the compound is expressed synergistically and continuously.

Specifically, the hollow silica fine particles used as the raw material for the (d2) modified hollow silica fine particles can be produced through the following first to fifth steps.
That is, in the first step, an aqueous solution of silicate or acidic silicic acid solution and an alkali-soluble inorganic compound aqueous solution are added to an alkaline aqueous solution having a pH of 10 or higher, or an alkaline aqueous solution having a pH of 10 or higher in which seed particles are dispersed as required. At the same time, a core particle dispersion in which the molar ratio of silica and inorganic compound other than silica is in the range of 0.3 to 1.0 is prepared.
Subsequently, in the second step, a silica source is added to the core particle dispersion to form a first silica coating layer on the core particle surface.
Next, in the third step, an acid is added to the dispersion liquid on which the first silica coating layer is formed to remove part or all of the elements constituting the core particles. Next, in the fourth step, an aqueous alkali solution and an organosilicon compound or a partial hydrolyzate thereof are added to the dispersion of the hollow silica fine particles obtained in the third step, and the second silica coating layer is added to the hollow silica fine particles. Form.
Further, it is preferable to add a fifth step of hydrothermally treating the hollow silica fine particle dispersion obtained in the fourth step.

The hydrothermal treatment is a modification treatment of hollow silica fine particles performed in the presence of high-temperature water. By this hydrothermal treatment, hollow silica fine particles having a dense outer shell can be obtained. By densifying the outer shell, it becomes difficult for moisture to be adsorbed and the water resistance of the hollow silica fine particles can be improved. As a result, (d2) modified hollow silica fine particles obtained by modifying the hollow silica fine particles (D1) The water resistance of a film obtained by curing a fluorine-containing curable coating liquid combined with a fluorine-containing compound can be improved. Further, by densifying the outer shell, the thickness of the outer shell can be reduced and the porosity of the hollow portion can be increased.
As conditions for this hydrothermal treatment, the treatment temperature is preferably 200 to 280 ° C., the treatment time is preferably 5 to 20 hours, and more preferably 10 to 20 hours. When the treatment temperature is less than 200 ° C., the hydrothermal treatment is not sufficiently performed, and the outer shell of the hollow silica fine particles tends to be insufficiently densified. On the other hand, when the temperature exceeds 280 ° C., the outer shell of the hollow silica fine particles is not further densified, and the hollow silica fine particles are aggregated. In addition, when the treatment time is less than 5 hours, the outer shell of the hollow silica fine particles cannot be sufficiently densified, which is not preferable. On the other hand, when the time exceeds 20 hours, the outer shell of the hollow silica fine particles is not further densified, and the productivity of the hollow silica fine particles is lowered, which is industrially undesirable.

  The modification of the hollow silica fine particles with the silane coupling agent is performed as follows. For example, a silane coupling agent is added to and mixed with hollow silica fine particles dispersed in an organic solvent, and distilled water is added to this mixture to carry out ordinary hydrolysis and condensation reactions. The solid content of the hollow silica fine particles is preferably 1 to 70% by mass, and more preferably 15 to 40% by mass. In this case, the order of adding the silane coupling agent is not particularly limited. The content of distilled water to be mixed is desirably 3 to 5 times by mass with respect to the silane coupling agent. The operation for carrying out the hydrolysis reaction and the condensation reaction is carried out by refluxing the organic solvent for 3 to 7 hours under normal pressure with stirring.

  The production method of the modified hollow silica fine particles (d2) will be further described. An organosol having a silica concentration of 1 to 70% by mass is prepared, and a silane coupling agent and an alkali catalyst are added within a range of 30 to 300 ° C. The silane coupling agent is reacted with the hollow silica fine particles under the condition that the water content is 0.1 to 50% by mass with respect to the amount. In the method for producing an organosol, a silica sol composed of hollow silica fine particles prepared using water as a dispersion medium is solvent-substituted to obtain an organosol.

  Examples of the silane coupling agent include γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, and γ-acryloyloxypropyltriethoxysilane. Content of a silane coupling agent is 1-50 mass parts normally with respect to 100 mass parts of hollow silica fine particles, Preferably it is 3-25 mass parts. If the content is less than 1 part by mass, the proportion of the untreated hollow silica fine particles increases, and the yield of the (d2) modified hollow silica fine particles is unfavorably reduced. If the content exceeds 50 parts by mass, the silane coupling agent is excessive. Thus, an excessive silane coupling agent remains, which is not preferable.

  The organic solvent is not particularly limited as long as it does not adversely affect the surface coating of the hollow silica fine particles by the silane coupling agent. As examples of such organic solvents, alcohols, glycols, esters, ketones, nitrogen compounds, aromatics, and the like can be used. Specific examples of organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycol, butanol and ethylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, aromatic hydrocarbons such as toluene and xylene, dimethyl Examples include amides such as formamide, dimethylacetamide, N-methylpyrrolidone and the like. Of these, alcohols such as methanol, ethanol and isopropyl alcohol are preferred. An organic solvent can be used individually or in mixture of 2 or more types. The resulting modified hollow silica fine particles can be isolated by centrifugation or the like, but can also be subjected to a subsequent step while the organic solvent is present.

The kind of the alkali catalyst is not particularly limited, and ammonia, an alkali metal hydroxide, an amine compound, and the like are preferably used. These alkali catalysts may be added in the form of an aqueous solution. The content of the alkali catalyst is not particularly limited, and is preferably 20 to 2000 ppm based on the organosol in which the hollow silica fine particles are dispersed, although it depends on the type of the alkali catalyst. When this content is less than 20 ppm, the reaction of the silane compound on the surface of the hollow silica fine particles may not sufficiently proceed. On the other hand, when it exceeds 2000 ppm, the dispersibility when the hollow silica fine particles are dispersed in the fluorine-containing compound may be deteriorated due to the excess alkali catalyst, and there is a problem that the alkali catalyst remains in the composition. There are things to do.
The water content in the reaction solution is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, based on the silica content. If the moisture content is in the range of 10 to 50% by mass, the surface of the hollow silica fine particles reacts with the silane coupling agent to effect surface treatment effectively. When the water content is less than 10% by mass, the surface treatment efficiency is low and stable surface treatment is not performed, and when it exceeds 50% by mass, the tendency of the silane coupling agents to react with each other increases, resulting in the surface treatment of the hollow silica fine particles. It becomes insufficient.

  The reaction temperature when the silane coupling agent is reacted with the hollow silica fine particles is preferably in the temperature range of 30 ° C. to less than the boiling point of the organic solvent, and 30 to 300 ° C. considering the case where the reaction is performed using a pressure vessel. It is preferable that When the reaction temperature is less than 30 ° C., the reaction rate is slow and not practical. On the other hand, if it exceeds 300 ° C., it exceeds the boiling point of the solvent of the organosol, and the evaporation of the solvent may cause an increase in the water content, which is not preferable.

  Moreover, 0.1-100 hours are preferable and, as for reaction time when making a silane coupling agent react with a hollow silica fine particle, 3-30 hours are more preferable. When the reaction time is shorter than 0.1 hour, the reaction may not proceed sufficiently, which is not practical. On the other hand, when the time is longer than 100 hours, no further improvement in yield or the like is observed, and it is not preferable to continue the reaction further. The hollow silica fine particles modified by the surface treatment may be further substituted with an organic solvent by the same method as described above, if necessary.

The average particle diameter of the (d2) modified hollow silica fine particles is 10 to 100 nm, and preferably 30 to 80 nm. Modified hollow silica fine particles having an average particle diameter in this range can form a transparent film. It is difficult to produce modified hollow silica fine particles having an average particle size of less than 10 nm. On the other hand, when the thickness exceeds 100 nm, light scattering is increased, and reflection is increased in the thin film, so that the antireflection function cannot be exhibited.
The specific surface area of the modified hollow silica fine particles is preferably 50~1000m ² / g for obtaining the dispersibility and stability of the modified hollow silica fine particles during or coalescing solvent, and more preferably 50 to 200 m ² / g . When the specific surface area is less than 50 m ² / g, it is difficult to obtain modified hollow silica fine particles having a low refractive index. On the other hand, when it exceeds 1000 m ² / g, the dispersion stability of the modified hollow silica fine particles is lowered, which is not desirable.

Furthermore, in (d2) modified hollow silica fine particles, the amount of the silane coupling agent bonded to the hollow silica fine particles by the modification treatment can be easily known by a thermal mass measurement method (TG). In this thermogravimetry analysis, the change in the mass of the sample due to the increase (or decrease) in the ambient temperature of the sample is measured with respect to the temperature. The mass change curve with respect to the temperature change is called a TG curve.
With respect to the modified hollow silica fine particles, thermal mass measurement is performed in a temperature range of 200 to 500 ° C. For example, a decrease in thermal mass when the temperature is increased from room temperature to 500 ° C at a temperature increase rate of 10 ° C / min is preferable Is 2 to 10% by mass, more preferably 3 to 10% by mass. In a film formed from a fluorine-containing curable coating liquid formed by blending modified hollow silica fine particles having a thermal mass reduction of less than 2% by mass, whitening occurs, and both scratch resistance and wear resistance are insufficient. On the other hand, when the thermal mass reduction exceeds 10% by mass, the reaction between particles is likely to occur, so that the stability of the modified hollow silica fine particles as a sol and the stability as a fluorine-containing cured coating liquid are unfavorable. .

  The water resistance of the cured film can be evaluated by the reflectance of the film. In a film having no or low water resistance, when water droplets are left on the film for 30 minutes, moisture is adsorbed and the refractive index increases, resulting in an increase in the reflectance of light on the film surface. On the other hand, in the film made of fluorine-containing curable coating liquid obtained by using the hydrosilica hollow silica fine particles, even if a water droplet is left on the film for 30 minutes, the reflection of light on the surface of the film before and after being left standing The rate change can be suppressed to 0.3% or less.

  In addition, a solvent may be contained in the fluorine-containing curable coating liquid as long as the reaction is not inhibited for the purpose of adjusting the viscosity of the coating liquid and surface leveling after coating. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol, 2-butanol and isobutanol, and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Further, in the fluorine-containing curable coating liquid, for the purpose of adjusting the fluorine content, polyfunctional (meth) acrylic acid ester not containing fluorine, such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate or the like can be blended at a ratio of 60% by mass or less. When this content exceeds 60% by mass, the refractive index of the film is increased, which is not preferable.

  The cured film is obtained by polymerizing and curing the fluorine-containing curable coating liquid with a high energy beam such as an electron beam, or polymerizing and curing the fluorine-containing curable coating liquid in the presence of a thermal decomposition type polymerization initiator or a photopolymerization initiator. Can be obtained. Among these, a method of applying a fluorine-containing curable coating liquid containing a photopolymerization initiator to the surface of the substrate and then irradiating it with ultraviolet rays in an inert gas atmosphere is preferable because it is simple and preferable.

  The photopolymerization initiator may be any as long as it has a polymerization initiating ability by ultraviolet irradiation. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- ON, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2- Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ′, 4,4′- Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Sandton, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like. These photopolymerization initiators can be used alone or as a mixture.

  It is preferable that content of these photoinitiators is 0.1-20 mass% with respect to solid content in a fluorine-containing curable coating liquid. When the content of the photopolymerization initiator is less than 0.1% by mass, the polymerization and curing of the fluorine-containing curable coating liquid is insufficient, and when it exceeds 20% by mass, the refractive index of the film after polymerization and curing is increased. Therefore, it is not preferable. The kind of ultraviolet lamp used for ultraviolet irradiation is not particularly limited as long as it is generally used. For example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like is used. .

  Moreover, as conditions for ultraviolet irradiation, the irradiation amount is preferably 10 mJ or more, and more preferably 100 mJ or more. The upper limit of the irradiation amount is determined according to a conventional method in this type of ultraviolet irradiation. When the irradiation dose is less than 10 mJ, sufficient hardness cannot be obtained for the film obtained after polymerization and curing. Further, post-curing by ultraviolet irradiation may be performed after the polymerization curing. In order to obtain good polymerization curability, it is preferable to suppress the oxygen concentration at the time of ultraviolet irradiation to 1000 ppm or less by blowing an inert gas such as nitrogen or argon at the time of polymerization curing and post-curing. The film thickness is preferably 50 to 200 nm. When this film thickness is less than 50 nm or exceeds 200 nm, the antireflection effect is lowered.

The antireflection film of the present invention can reduce reflection of a fluorescent lamp or the like coming from the background by being attached to the surface of an electronic image display device such as a cathode ray tube, a plasma display, or a liquid crystal display device.
Therefore, the electronic image display device of the present invention having such an antireflection film on the display surface can remarkably improve the visibility, thereby reducing eye fatigue and the like.

  Hereinafter, the embodiment will be described more specifically with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. In addition, the part in each example represents a mass part, and% represents mass%.

[Production Example 1, Preparation of Application Liquid as Adhesive for Forming Adhesive Layer (hereinafter referred to as Adhesive Application Liquid)]
(Production Example 1-1, Synthesis of Copolyester Resin (A))
100 parts by mass of dimethyl terephthalate, 100 parts by mass of dimethyl isophthalate, 30.3 parts by mass of ethylene glycol, 150 parts by mass of neopentyl glycol, 0.1 part by mass of zinc acetate and 0.1 part by mass of antimony trioxide are used in a transesterification reaction vessel. The resulting mixture was heated to 180 ° C. and reacted for 4 hours to conduct a transesterification reaction. Thereafter, 5 parts by mass of 5-sodium sulfoisophthalic acid was added, and an esterification reaction was performed at 240 ° C. for 1 hour. Next, the temperature was raised to 250 ° C., the inside of the system was reduced to 1 mmHg, and a polycondensation reaction was carried out for 2 hours to obtain a copolymerized polyester resin (A).

(Production Example 1-2, synthesis of crosslinking agent (B))
The flask was charged with 300 parts by mass of ion-exchanged water, heated to 60 ° C. under a nitrogen stream, and 0.3 parts by mass of ammonium persulfate and 0.3 parts by mass of sodium hydrogen nitrite were added. Thereafter, a mixture of 20.2 parts by mass of methyl methacrylate, 21.2 parts by mass of 2-isopropenyl-2-oxazoline, 45.5 parts by mass of polyethylene oxide methacrylic acid and 10.2 parts by mass of acrylamide was added dropwise over 4 hours. Stirring was continued for 1 hour after completion of the dropwise addition to obtain a 25% by mass aqueous dispersion of the crosslinking agent (B).

(Production Example 1-3, Preparation of Adhesive Coating Solution)
65 parts by mass of a 30% by mass aqueous dispersion of the copolyester resin (A), 40 parts by mass of a 25% by mass aqueous dispersion of the crosslinking agent (B) and 450 parts by mass of ion-exchanged water are mixed to form an adhesive. A coating solution was obtained.

[Production Example 2, production of adhesive layer laminated polyester film]
(Production Example 2-1, production of adhesive layer laminated polyester film A)
The biaxially stretched polyester film (polyethylene terephthalate film provided with an adhesive film on one side, manufactured by Toyobo Co., Ltd., Cosmo Shine A4100, thickness 100 μm, refractive index 1.65) is bonded to the surface without the adhesive film. The agent coating solution was applied by a gravure coating method. When the cross section of the film was observed by SEM, the thickness of the adhesive layer was 15 nm as a dry film thickness.

(Production Example 2-2, production of adhesive layer laminated polyester film B)
An adhesive coating solution was applied to the surface of the biaxially stretched polyester film used in Production Example 2-1 without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 5 nm.

(Production Example 2-3, production of adhesive layer laminated polyester film C)
An adhesive coating solution was applied to the surface of the biaxially stretched polyester film used in Production Example 2-1 without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 30 nm.

(Production Example 2-4, Production of Adhesive Layer Laminated Polyester Film D)
An adhesive coating solution was applied to the surface of the biaxially stretched polyester film used in Production Example 2-1 without an adhesive film by a gravure coating method. When the cross section of the film was observed by SEM, the film thickness of the adhesive layer was 40 nm. This adhesive layer thickness is outside the scope of the present invention.

[Production Example 3, preparation of hard coat layer coating solution]
(Production Example 3-1, preparation of hard coat layer coating solution A)
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, manufactured by Ishihara Sangyo Co., Ltd., SNS-10M) 83 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average functional group number 5.5, Nippon Kayaku Co., Ltd., DPHA) 75 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution A.

(Production Example 3-2, Preparation of Hard Coat Layer Coating Liquid B)
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, Ishihara Sangyo Co., Ltd., SNS-10M) 73 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average functional group number 5.5, Nippon Kayaku Co., Ltd., DPHA 78 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution B.

(Production Example 3-3, Preparation of Hard Coat Layer Coating Liquid C)
Antimony-doped tin oxide 30 mass% methyl ethyl ketone dispersion (antimony-doped tin oxide average particle size 98 nm, manufactured by Ishihara Sangyo Co., Ltd., SNS-10M) 57 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate) And pentafunctional dipentaerythritol pentaacrylate, average number of functional groups 5.5, Nippon Kayaku Co., Ltd., DPHA) 83 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass was stirred and mixed to obtain a hard coat layer coating solution C.

[Production Example 4, production of a film having a hard coat layer on the surface]
(Production Example 4-1, Production of Hard Coat Film A)
Spin coat the hard coat layer coating solution A obtained in Production Example 3-1 on the adhesive layer of the adhesive layer-laminated polyester film A obtained in Production Example 2-1 so that the dry film thickness is about 5 μm. After coating by the method, a hard coat film A was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.64.

(Production Example 4-2, Production of Hard Coat Film B)
Spin coat the hard coat layer coating solution A obtained in Production Example 3-1 on the adhesive layer of the adhesive layer-laminated polyester film B obtained in Production Example 2-2 so that the dry film thickness is about 5 μm. After coating by the method, a hard coat film B was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.64.

(Production Example 4-3, Production of Hard Coat Film C)
Spin coat the hard coat layer coating solution A obtained in Production Example 3-1 on the adhesive layer of the adhesive layer-laminated polyester film C obtained in Production Example 2-3 so that the dry film thickness is about 5 μm. After coating by the method, a hard coat film C was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (produced by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.64.

(Production Example 4-4, Production of Hard Coat Film D)
Spin coat the hard coat layer coating solution A obtained in Production Example 3-1 on the adhesive layer of the adhesive layer-laminated polyester film D obtained in Production Example 2-4 so that the dry film thickness is about 5 μm. After coating by the method, a hard coat film D was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.64. Since the adhesive layer-laminated polyester film D used in this example has a film thickness of the adhesive layer that is outside the scope of the present invention as described above, this hard coat film is also outside the scope of the present invention.

(Production Example 4-5, production of hard coat film E)
Spin the hard coat layer coating solution A obtained in Production Example 3-1 on the surface without an adhesive film of the biaxially stretched polyester film used in Production Example 2-1 so that the dry film thickness is about 5 μm. After coating by a coating method, a hard coat film E was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (produced by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.64. Since this hard coat layer does not interpose an adhesive layer, it is outside the scope of the present invention.

(Production Example 4-6, Production of Hard Coat Film F)
Spin coat the hard coat layer coating solution B obtained in Production Example 3-2 onto the adhesive layer of the adhesive layer-laminated polyester film A obtained in Production Example 2-1 so that the dry film thickness is about 5 μm. After coating by the method, hard coat film F was produced by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.63.

(Production Example 4-7, Production of Hard Coat Film G)
Spin coat the hard coat layer coating solution C obtained in Production Example 3-3 on the adhesive layer of the adhesive layer-laminated polyester film A obtained in Production Example 2-1 so that the dry film thickness is about 5 μm. After coating by the method, a hard coat film G was prepared by irradiating and curing 400 mJ of ultraviolet rays using an ultraviolet irradiation device (made by Eye Graphics, 120W high-pressure mercury lamp). The refractive index of the hard coat layer was 1.60. In the refractive index of the hard coat layer, the difference in refractive index from the polyester film is outside the scope of the present invention.

[Production Example 5, Preparation of High Refractive Index Layer Coating Solution]
(Production Example 5-1, Preparation of High Refractive Index Layer Coating Liquid A)
Zirconium oxide 25% by mass methyl ethyl ketone dispersion [trade name: “ZRMEK25WT% -F47”, manufactured by CI Chemical Co., Ltd.] 296 parts by mass, polyfunctional acrylate compound (hexafunctional dipentaerythritol hexaacrylate and pentafunctional dipenta Mixing with erythritol pentaacrylate, average functional number 5.5, Nippon Kayaku Co., Ltd., DPHA) 26 parts by mass and UV radical initiator (Ciba Specialty Chemicals Co., Ltd., Irgacure 184) 5 parts by mass Thus, a high refractive index layer coating solution A was obtained. The refractive index of the polymerized cured product of the coating liquid A (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.75.

(Production Example 5-2, Preparation of High Refractive Index Layer Coating Liquid B)
268 parts by mass of 25 mass% methyl ethyl ketone dispersion (trade name: “ZRMEK25WT% -F47”, manufactured by CI Kasei Co., Ltd.) of zirconium oxide, 33 parts by mass of DPHA, and 5 parts by mass of Irgacure 184 are mixed. Refractive index layer coating solution B was obtained. The refractive index of the polymerized cured product of the coating liquid B (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.70.

(Production Example 5-3, Preparation of High Refractive Index Layer Coating Liquid C)
Zirconium oxide 25 mass% methyl ethyl ketone dispersion [trade name: “ZRMEK25WT% -F47”, manufactured by CI Kasei Co., Ltd.] 348 parts by mass, DPHA 13 parts by mass, and Irgacure 184 5 parts by mass are mixed and stirred. The rate layer coating solution C was obtained. The refractive index of the polymerized cured product of the coating liquid C (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.90.

(Production Example 5-4, Preparation of High Refractive Index Layer Coating Liquid D)
Zirconium oxide 25 mass% methyl ethyl ketone dispersion [trade name: “ZRMEK25WT% -F47”, manufactured by CI Kasei Co., Ltd.] 244 parts by mass, DPHA 39 parts by mass, and Irgacure 184 5 parts by mass are stirred and mixed. The rate layer coating solution D was obtained. The refractive index of the polymerized cured product of the coating liquid D (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.67. Since the refractive index of this high refractive index layer is outside the scope of the present invention, this high refractive index layer coating solution D is for a comparative example.

(Production Example 5-5, Preparation of High Refractive Index Layer Coating Liquid E)
Zirconium oxide 25 mass% methyl ethyl ketone dispersion [trade name: “ZRMEK25WT% -F47”, manufactured by CI Kasei Co., Ltd.] 360 parts by mass, DPHA 10 parts by mass, and Irgacure 184 5 parts by mass are stirred and mixed. The rate layer coating solution E was obtained. The refractive index of the polymerized cured product of the coating liquid E (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.95. Since the refractive index of this high refractive index layer is outside the scope of the present invention, this high refractive index layer coating solution E is for a comparative example.

[Production Example 6, production of modified hollow silica sol]
(Production Example 6-1, Production of Modified Hollow Silica Sol α)
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. 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 content 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, 0.5% concentration of sodium sulfate 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 the 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 content concentration of 20%. .
As a fourth step, a mixture of an aqueous dispersion of silica-based fine particles (1) having a solid content concentration of 20%, pure water, ethanol and 28% aqueous ammonia is heated to 35 ° C., and then ethyl silicate (SiO 2 ₂ 28%) was added 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 size of 60 nm and a specific surface area of 110 m ² / g were dispersed (hereinafter referred to as “hollow silica sol A”).
Providing a hollow silica sol A (silica solid concentration of 20%) 200 g, an ultrafiltration membrane, subjected to solvent substitution to methanol, SiO ₂ minutes 20% of the organosol 100 g (water content relative to SiO ₂ minutes 0.5%). A 28% aqueous ammonia solution was added to the organosol so as to be 100 ppm as ammonia with respect to 100 g of the organosol, and mixed well. 3.6 g was added to prepare a reaction solution. This was heated to 50 ° C. and heated at 50 ° C. for 6 hours with stirring. After heating, cool the reaction solution to room temperature,
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 in which hollow silica fine particles were dispersed (hereinafter referred to as “modified hollow silica sol α”).

The average particle diameter, specific surface area and TG were measured by the following methods.
(Average particle size)
Using a particle size distribution measuring device (PAR-III, manufactured by Otsuka Electronics Co., Ltd.), the average particle size was measured by a dynamic light scattering method using laser light.
(Specific surface area)
A sample obtained by drying 50 ml of sol at 110 ° C. for 20 hours was measured by a nitrogen adsorption method (BET method) using a specific surface area measurement device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12).
(Differential thermal mass measurement method, TG / DTA)
Differential thermothermal mass simultaneous measurement was performed using a differential thermothermal mass simultaneous measurement apparatus (manufactured by Rigaku Corporation, Thermoplus TG8110). In addition, TG represents a thermogravimetry analysis (Thermogravimetry Analysis) and DTA represents a differential scanning calorimetry (differential scanning calorimetry). The measurement conditions are a temperature range of room temperature to 500 ° C. under a temperature rise rate of 10 ° C./min in an air atmosphere. In addition, about the sample for differential thermothermal mass simultaneous measurement methods (TG / DTA), after removing the solvent of the organosol prepared as mentioned above, it wash | cleans thoroughly with hexane, and it dries under reduced pressure after removing hexane. It dried with the machine and it used for the measurement as a powder sample.

(Production Example 6-2, Production of Modified Hollow Silica Sol β)
In Production Example 6-1, a dispersion of silica-based fine particles (2) was produced in the same manner as in Production 5-1, except that a hydrothermal treatment was performed at 200 ° C. for 1 hour to obtain an organosol having a SiO ₂ concentration of 20%. . This organosol was an organosol in which hollow silica fine particles having an average particle size of 50 nm and a specific surface area of 120 m ² / g were dispersed (hereinafter referred to as “hollow silica sol B”).
Except for using the hollow silica sol B as a raw material, the same procedure as in Modification Example 5-1 was performed to obtain an organosol composed of coated hollow fine particles having a SiO ₂ concentration of 20%. In this organosol, modified hollow silica fine particles having an average particle size of 50 nm, a refractive index of 1.30, a porosity of 30 to 35%, a specific surface area of 90 m ² / g, and a mass reduction ratio of TG of 3.2% are dispersed. Organosol (hereinafter referred to as “modified hollow silica sol β”). The average particle diameter, specific surface area and TG were measured by the above methods.

(Production Example 6-3, Production of Modified Hollow Silica Sol γ)
Except for using hollow silica sol A as a raw material and changing the content of γ-acryloyloxypropyltrimethoxysilane (trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) to 1.8 g, the same as in Production Example 5-1. Thus, an organosol made of coated hollow fine particles having a SiO ₂ concentration of 20% was obtained. This organosol has an average particle size of 60 nm, a specific surface area of 109 m ² / g, and a TG mass reduction ratio of 1.4% of hollow silica fine particles dispersed therein (hereinafter referred to as “modified hollow silica sol γ”). )Met.

[Production Example 7, production of fluorine-containing compound having a polymerizable double bond]
In a four-necked flask, 104 parts of perfluoro- (1,1,9,9-tetrahydro-2,5-bisfluoromethyl-3,6-dioxanonenol) and bis (2,2,3,3) , 4,4,5,5,6,6,7,7-dodecafluoroheptanoyl) peroxide 11 parts of 8% perfluorohexane. The hollow portion was purged with nitrogen, and then stirred at 20 ° C. for 24 hours under a nitrogen stream to obtain a highly viscous solid. A solution obtained by dissolving the obtained solid in diethyl ether was poured into perfluorohexane, followed by separation and vacuum drying to obtain a colorless and transparent polymer.
When this polymer was analyzed by 19F-NMR (nuclear magnetic resonance spectrum), 1H-NMR, and IR (infrared absorption spectrum), it was a fluorine-containing polymer having a hydroxyl group at the end of the side chain consisting of the structural unit of the allyl ether. The number average molecular weight measured by GPC (gel permeation chromatograph) was 72,000, and the mass average molecular weight was 118,000.
The obtained hydroxyl group-containing fluorine-containing allyl ether polymer (5 parts), methyl ethyl ketone (MEK) (43 parts), and pyridine (1 part) were charged into a four-necked flask and cooled to 5 ° C. or lower with ice. Subsequently, 1 part of α-fluoroacrylic acid fluoride dissolved in 9 parts of MEK was added dropwise over 10 minutes while stirring under a nitrogen stream. And the solution of the fluorine-containing reactive polymer was obtained as a fluorine-containing compound having a polymerizable double bond. The fluorine content of the fluorine-containing reactive polymer was 64%.
The obtained MEK solution had a solid content of 13%. As a result of analysis by 19F-NMR, the α-fluoroacryloyl group introduction rate was 40 mol%.

[Production Example 8, Preparation of low refractive index layer coating solution]
(Production Example 8-1, Preparation of Low Refractive Index Layer Coating Liquid A)
50 parts of the modified hollow silica sol α obtained in Production Example 6-1 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 7 in terms of solid content, 2-methyl- Low refractive index by mixing 5 parts of 1- [4-methylthiophenyl] -2-morpholinopropan-1-one [trade name: Irgacure 907, Ciba Specialty Chemicals Co., Ltd.] and 2000 parts of isopropyl alcohol. A layer coating solution A was obtained. The refractive index of the polymerized cured product of the coating liquid A (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.30.

(Production Example 8-2, Preparation of Low Refractive Index Layer Coating Liquid B)
45 parts of the modified hollow silica sol α obtained in Production Example 6-1 in terms of solid content, 1,12-bis {(meth) acryloyloxy} -3,10-dihydroxy 5,5,6,6,7, A low refractive index layer coating solution B was obtained by mixing 55 parts of 7,8,8-octafluorododecane (hereinafter abbreviated as OD2H2A) in terms of solid content, 5 parts of Irgacure 907 and 2000 parts of isopropyl alcohol. The refractive index of the polymerized cured product of the coating liquid B (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.36.

(Production Example 8-3, Preparation of Low Refractive Index Layer Coating Liquid C)
25 parts of the modified hollow silica sol α obtained in Production Example 6-1 in terms of solid content, 75 parts of OD2H2A in terms of solid content, 5 parts of Irgacure 907, and 2000 parts of isopropyl alcohol are mixed to apply a low refractive index layer. Liquid C was obtained. The refractive index of the polymerized cured product of the coating liquid C (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.40. Since the refractive index of the low refractive index layer is out of the scope of the present invention, the low refractive index layer coating liquid C is for a comparative example.

(Production Example 8-4, Preparation of Low Refractive Index Layer Coating Liquid D)
40 parts of the modified hollow silica sol α obtained in Production Example 6-1 in terms of solid content, 60 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 7 in terms of solid content, and 5 parts of Irgacure 907 Part and 2000 parts of isopropyl alcohol were mixed to obtain a low refractive index layer coating solution D. The refractive index of the polymerized cured product of the coating liquid D (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.32.

(Production Example 8-5, Preparation of Low Refractive Index Layer Coating Liquid E)
60 parts of the modified hollow silica sol α obtained in Production Example 6-1 in terms of solid content, 40 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 7 in terms of solid content, and 5 parts of Irgacure 907 Part and 2000 parts of isopropyl alcohol were mixed to obtain a low refractive index layer coating solution E. The refractive index of the polymerized cured product of the coating liquid E (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.28.

(Production Example 8-6, Preparation of Low Refractive Index Layer Coating Liquid F)
50 parts of the modified hollow silica sol β obtained in Production Example 6-2 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 7 in terms of solid content, and 5 parts of Irgacure 907 And 2000 parts of isopropyl alcohol were mixed to obtain a low refractive index layer coating solution F. The refractive index of the polymerized cured product of the coating liquid F (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.35.

(Production Example 8-7, Preparation of Low Refractive Index Layer Coating Liquid G)
50 parts of the modified hollow silica sol γ obtained in Production Example 6-3 in terms of solid content, 50 parts of the solvent-soluble fluorine-containing reactive polymer obtained in Production Example 7 in terms of solid content, and 5 parts of Irgacure 907 And 2000 parts of isopropyl alcohol were mixed to obtain a low refractive index layer coating solution G. The refractive index of the polymerized cured product of the coating liquid G (cured by irradiating with 400 mJ ultraviolet light in a nitrogen atmosphere) was 1.30.

<Example 1>
On the hard coat film A produced in Production Example 4-1, after applying the high refractive index layer coating solution A prepared in Production Example 5-1 by a spin coat method so that the dry film thickness is about 140 nm, Using an ultraviolet irradiation device (Eye Graphics, 120W high-pressure mercury lamp), it was cured by irradiation with 400 mJ ultraviolet rays in a nitrogen atmosphere. Furthermore, after applying the low refractive index layer coating solution A prepared in Production Example 8-1 by a spin coat method so that the dry film thickness is about 100 nm, an ultraviolet irradiation device (manufactured by Eye Graphics, 120W). Using a high-pressure mercury lamp, the film was cured by irradiation with 400 mJ ultraviolet light in a nitrogen atmosphere to obtain an antireflection film.
For the obtained antireflection film, the reflectance, ab chroma Cab *, scratch resistance, surface resistance value, adhesion, water resistance of the coating and evaluation of interference fringes were performed by the methods described below, and the results are shown. It is shown in 1.

(1) Measurement of reflectance A spectrophotometer [trade name: U-best, manufactured by JASCO Corporation] with a back surface roughened with sandpaper and a 5 ° specular reflection measuring device in order to remove the back surface reflection of the measurement surface. The reflectance was measured using V560]. From the obtained reflection spectrum, the visibility reflectance (%) for the C light source was calculated.
(2) Calculation of ab chroma Cab * Color space CIE1976L * a * b table defined in JIS Z8729 using the reflectance measured in the above (1) and the relative spectral distribution of CIE standard illuminant D65 based on JIS Z8720. the color system was calculated, it obtained a * value, b * ab chroma from the value Cab * = {(a *) 2 + (b *) 2} 1/2 was calculated.
(3) Evaluation of scratch resistance An anti-reflective film was fixed with # 0000 steel wool at the tip of an eraser abrasion tester manufactured by Honko Seisakusho and subjected to loads of 2.5N (250 gf) and 1N (100 gf). The scratches on the surface after the surface was rubbed back and forth 10 times 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 (4) Surface resistance value Measurement The surface resistance value of the antireflection film was measured using a digital insulation meter [manufactured by Toa DKK Co., Ltd., trade name: SM-8220].
(5) Adhesive evaluation The surface of the antireflection film was subjected to a cross-cut peeling tape test in accordance with JIS D0202-1998. After using cellophane tape (manufactured by Nichiban Co., Ltd., CT24) to adhere to the film, it was peeled off. Judgment is represented by the number of squares that do not peel out of 100 squares, and the case where peeling does not occur is 100/100, and the case where peeling completely occurs is represented as 0/100.
(6) Evaluation of water resistance of film After leaving distilled water for 30 minutes on the surface of the obtained film, water was wiped off with Kimwipe (Wiper S-200, manufactured by Crecia Co., Ltd.) The difference in reflectance at a light wavelength of 600 nm was measured on the surface of the film.
○: Reflectance difference is less than 0.3%, Δ: Reflectance difference is 0.3 to 0.5%, ×: Reflectance difference is greater than 0.5% (7) Evaluation of interference fringes Influence of back surface reflection In order to eliminate the problem, a sample was prepared by painting the surface opposite to the surface provided with the hard coat layer with a black paint. When the sample was visually observed using a three-wavelength fluorescent lamp as a light source in a dark room, the intensity of interference fringes was evaluated.
◎: Interference fringes are not visible, ○: Weak interference fringes are visible, ×: Strong interference fringes are visible

<Example 2>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that instead of the hard coat film A, the hard coat film B produced in Production Example 4-2 was used. The evaluation results are shown in Table 1.

<Example 3>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that instead of the hard coat film A, the hard coat film C produced in Production Example 4-3 was used. The evaluation results are shown in Table 1.

<Example 4>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that instead of the hard coat film A, the hard coat film F produced in Production Example 4-6 was used. The evaluation results are shown in Table 1.

<Example 5>
In Example 1, in place of the low-refractive index layer coating solution A, the antireflective treatment was performed in the same manner as in Example 1 except that the low-refractive index layer coating solution B prepared in Production Example 8-2 was used. A conductive film was prepared. The evaluation results are shown in Table 1.

<Example 6>
In Example 1, in place of the high refractive index layer coating solution A, the high refractive index layer coating solution B prepared in Production Example 5-2 was used, except that the antireflection was performed in the same manner as in Example 1. A conductive film was prepared. The evaluation results are shown in Table 1.

<Example 7>
In Example 1, in place of the high refractive index layer coating solution A, antireflection was performed in the same manner as in Example 1 except that the high refractive index layer coating solution C prepared in Production Example 5-3 was used. A conductive film was prepared. The evaluation results are shown in Table 1.

<Comparative Example 1>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that the hard coat film E produced in Production Example 4-5 was used instead of the hard coat film A. The evaluation results are shown in Table 1.

<Comparative example 2>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that instead of the hard coat film A, the hard coat film D produced in Production Example 4-4 was used. The evaluation results are shown in Table 1.

<Comparative Example 3>
In Example 1, an antireflection film was produced in the same manner as in Example 1 except that instead of the hard coat film A, the hard coat film G produced in Production Example 4-7 was used. The evaluation results are shown in Table 1.

<Comparative example 4>
In Example 1, in place of the low refractive index layer coating solution A, antireflection was performed in the same manner as in Example 1 except that the low refractive index layer coating solution C prepared in Production Example 8-3 was used. A conductive film was prepared. The evaluation results are shown in Table 1.

<Comparative Example 5>
In Example 1, in place of the high refractive index layer coating solution A, antireflection was performed in the same manner as in Example 1 except that the high refractive index layer coating solution D prepared in Production Example 5-4 was used. A conductive film was prepared. The evaluation results are shown in Table 1.

<Comparative Example 6>
In Example 1, in place of the high refractive index layer coating solution A, the antireflective treatment was performed in the same manner as in Example 1 except that the high refractive index layer coating solution E prepared in Production Example 5-5 was used. A conductive film was prepared. The evaluation results are shown in Table 1.

<Comparative Example 7>
On the hard coat film A produced in Production Example 4-1, the low refractive index layer coating solution A prepared in Production Example 8-1 was applied by spin coating so that the dry film thickness was about 100 nm, and then ultraviolet rays were applied. Using an irradiation apparatus (120W high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd.), 400 mJ ultraviolet rays were irradiated and cured in a nitrogen atmosphere to obtain an antireflection film.

  From the results shown in Table 1, in Examples 1 to 7, extremely low visibility reflectance could be achieved. In addition, the reflection spectrum was flat in the visibility wavelength range (light wavelength: 500 nm to 650 nm), the ab chroma Cab * for the CIE standard illuminant D65 was 5 or less, and the color of the reflected color was gentle. Furthermore, the evaluation about the scratch resistance could be maintained at B to C. Moreover, since the modified hollow silica sol α having excellent water resistance was used, the difference in reflectance after water marks could be suppressed to less than 0.3%. Moreover, since the film thickness of the adhesive layer was in the range of 5 to 30 nm, it was possible to sufficiently suppress the occurrence of interference fringes while maintaining the adhesion of the hard coat layer to the polyester film.

On the other hand, in Comparative Example 1, since the adhesive layer was not provided, the adhesion of the hard coat layer to the polyester film was quite poor, and the scratch resistance was also weak.
In Comparative Example 2, it was found that the interference fringes look strong because the thickness of the adhesive layer is thicker (40 nm) than specified in the present invention (5-30 nm).
Further, as in Comparative Example 3, even if the film thickness of the adhesive layer is within the range defined in the present invention (5 to 30 nm), the refractive index difference between the hard coat layer and the polyester film is defined in the present invention (0 It was found that the interference fringes look strong.
In Comparative Example 4, since the refractive index of the low refractive index layer exceeds (1.40 to 1.36) in the present invention (1.40), the visibility reflectance is high and sufficient antireflection performance is achieved. Was not obtained.
Further, in Comparative Example 5, the refractive index of the high refractive index layer does not satisfy the definition (1.70 to 1.90) in the present invention (1.67), and in Comparative Example 6, the refractive index of the high refractive index layer. Exceeds the specification (1.70 to 1.90) in the present invention (1.95), and in Comparative Example 7, since there is no high refractive index layer, all of them have a visibility wavelength range (light wavelength of 500 nm to 650 nm). Since the reflection spectrum was not flat (V-shaped), the ab chroma Cab * with respect to the CIE standard illuminant D65 was high, and the film had a tight reflection color.
In the above-mentioned patent document 1, it has been explained that the refractive index of the low refractive index layer is defined as 1.38 to 1.45, but the refractive index of the low refractive index layer is too high. As a result, the above-described explanation was supported.

<Example 8>
In Example 1, in place of the low-refractive index layer coating solution A, the antireflective treatment was performed in the same manner as in Example 1 except that the low-refractive index layer coating solution D prepared in Production Example 8-4 was used. A conductive film was prepared. The evaluation results are shown in Table 2.

<Example 9>
In Example 1, in place of the low refractive index layer coating solution A, the antireflective treatment was performed in the same manner as in Example 1 except that the low refractive index layer coating solution E prepared in Production Example 8-5 was used. A conductive film was prepared. The evaluation results are shown in Table 2.

<Example 10>
In Example 1, in place of the low refractive index layer coating solution A, antireflection was performed in the same manner as in Example 1 except that the low refractive index layer coating solution F prepared in Production Example 8-6 was used. A conductive film was prepared. The evaluation results are shown in Table 2.

<Example 11>
In Example 1, in place of the low refractive index layer coating solution A, the antireflective treatment was performed in the same manner as in Example 1 except that the low refractive index layer coating solution G prepared in Production Example 8-7 was used. A conductive film was prepared. The evaluation results are shown in Table 2.

From the results shown in Table 2, since the blending ratio of the fluorine-containing compound was increased in Example 8, the reflectance was slightly high, but the scratch resistance was excellent.
Further, in Example 9, since the blending ratio of the modified hollow silica sol α was increased, the scratch resistance was slightly weakened, but the antireflection performance was excellent.
On the other hand, in Example 10, since the modified hollow silica sol β having a high refractive index was used, the visibility reflectance was slightly increased. Moreover, since it did not have water resistance, the difference in reflectance due to water marks in the obtained film was 0.5% or more.
Further, in Example 11, although the modified hollow silica sol γ was modified, the weight reduction rate due to TG was lower than that of the modified hollow silica sol α of Examples 1 and 6, so that the scratch resistance was somewhat weak. It was.

Claims (5)

  In the anti-reflective film which laminated | stacked the hard-coat layer, the high refractive index layer, and the low-refractive-index layer in this order via the contact bonding layer on the polyester film, the film thickness of the said contact bonding layer is 5-30 nm, The said polyester The refractive index difference between the film and the hard coat layer is within 0.02, the refractive index of the high refractive index layer is 1.70 to 1.90, and the refractive index of the low refractive index is 1.28 to 1. An antireflective film, which is 1.36.   The low refractive index layer has a film forming property, a fluorine-containing compound having a polymerizable double bond, and hollow silica having a void ratio of 40 to 45% and an average particle diameter of 10 to 100 nm. Modified hollow silica fine particles modified with a silane coupling agent having a polymerizable double bond, and the ratio of the fluorine-containing compound to the modified hollow silica fine particles is 40 to 80% by mass of the fluorine-containing compound. The antireflection film according to claim 1, wherein the hollow silica fine particles are 60 to 20% by mass. The modified hollow silica fine particles are subjected to hydrothermal treatment and modified with a silane coupling agent represented by the following chemical formula (1), and the temperature is increased from room temperature to 500 ° C. at a temperature rising rate of 10 ° C./min. The antireflection film according to claim 1 or 2, wherein a decrease in thermal mass when the temperature is raised is 2 to 10% by mass.

(In the formula, Z is a (meth) acryloyloxy group, R ¹ is an alkylene group having 1 to 4 carbon atoms, and R ² is a hydrogen atom, a methyl group or an ethyl group.) The hard coat layer has a surface resistivity of 1.0E + 10 ⁸ Ω to 1.0E + 10 ¹² Ω by containing conductive metal oxide fine particles. 2. The antireflection film according to item 1.   An electronic image display device having the antireflection film according to any one of claims 1 to 4 on a display surface.