JP2008152199A - Antiglare antireflection film, polarizing plate and display apparatus each using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antiglare antireflection film which is used for a liquid crystal display or the like, has excellent productivity because of a single layer type, by which high antireflection performance (reduction in a refractive index) can be obtained even when film thickness is sufficiently large in order to obtain coating film strength (abrasion resistance and pencil hardness) and further which is excellent in perceptivity when used for a display apparatus and to provide a polarizing plate and the display apparatus each using the antiglare antireflection film. <P>SOLUTION: The antiglare antireflection film has an antiglare antireflection layer on a transparent film base material. The antiglare antireflection layer is formed of an application composition containing a 1st resin, a 2nd resin and at least one kind of particulate among porous and hollow particulates. The 1st resin and the 2nd resin respectively have functional groups reacting with each other and difference between surface tension of the resins:Δγ is ≥1.8 dyne/cm and ≤30.0 dyne/cm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antiglare antireflection film, a polarizing plate using the same, and a display device.

  Conventionally, a phenomenon has been known in which the reflectance is reduced by coating the surface of a transparent object with a transparent film having a low refractive index. Visibility can be improved by providing an antireflection film using such a phenomenon on the display surface of the image display device. The antireflection film has a single layer structure in which a low refractive index layer is provided on the display surface, or one or more intermediate to high refractive index layers are provided on the display surface in order to improve the antireflection performance. There is a multilayer structure in which a low refractive index layer is provided thereon. Single-layer antireflection film has a simpler layer structure than multilayer type, so it is superior in productivity and cost performance. On the other hand, it is difficult to improve antireflection properties compared with multilayer antireflection film. Met.

In addition, as a method of reducing the reflectance, there is a method of reducing the refractive index of the low refractive index layer, and a low refractive index material or a method of reducing the refractive index by increasing the number of voids has been proposed.
Japanese Patent Laid-Open No. 2001-167637 JP 2002-225866 A JP 2003-236970 A JP 2003-240906 A JP 2003-255103 A In JP-A-2001-233611, the above-mentioned Patent Document 1 and Patent Document 2 include hollow fine particles such as hollow silica having cavities therein in a binder containing an inorganic component obtained from a hydrolyzed polycondensate of alkoxysilane. Dispersed low refractive index layers are disclosed. This low refractive index layer has the same effect as a low refractive index layer having a large number of microvoids, and the microvoids are protected by a hard outer shell such as silica. Have.

  On the other hand, for example, Patent Documents 3 to 5 disclose techniques using a fluorine-based resin as a binder component having a low refractive index. The coating film made of such a binder containing fluorine atoms has a lower refractive index as the fluorine atom content is higher. Moreover, when the fluorine atom content of a coating film becomes high, antifouling property will improve.

  In Patent Document 6, a coating liquid composed of a monomer containing functional groups that are cured by ionizing radiation or heat in the molecule is applied to the surface of the substrate, dried, and then the monomer is cured by heat, resulting in low refraction. It is disclosed to form a rate layer.

  However, in the techniques of Patent Document 1 and Patent Document 2 described above, a hard coating film is formed by a binder containing an inorganic component, but on the other hand, since it is brittle against an impact from the outside, the coating film strength, particularly scratch resistance is high. There was a problem of being inferior. In addition, in the case of a single-layer type antireflection film, particularly when the amount of hollow fine particles such as hollow silica is reduced, the coating strength can be obtained, but the antireflection performance (lower refractive index) cannot be obtained. Further, when the thickness of the antireflection film is increased, it is effective for imparting coating film strength. However, since hollow fine particles such as hollow silica are buried in the film, the surface is hollow such as hollow silica. The fine particles are not uniformly distributed and do not contribute to lowering the refractive index of the surface, making it difficult to satisfy the antireflection performance (lower refractive index) and the coating film strength in a well-balanced manner.

  Moreover, in the technique of the said patent documents 3-5, when the fluorine atom content in a coating film became high, there existed a problem that the hardness and intensity | strength of a coating film fell.

  Furthermore, in the technique of the above-mentioned patent document, if the amount of silica particles added is increased to some extent, the aggregation of silica particles occurs and the strength of the coating film is reduced. The appearance of a string-proof antireflection film having an antireflection film excellent in strength has been desired.

  The object of the present invention is to solve the above-mentioned problems of the prior art and to provide excellent productivity and excellent coating strength (scratch resistance, pencil hardness) for the string-proof antireflection film due to the single layer type. Anti-reflection film having anti-glare property with high anti-reflection performance (lower refractive index) and excellent visibility when used in a display device, and polarizing plate using the same And providing a display device.

  As a result of intensive research in view of the above points, the inventor of the present invention combined the specific resin configuration with the porous or hollow fine particles inside, so that the porous or hollow fine particles are unevenly distributed upward, The upper part has a lower refractive index, and it is possible to achieve both anti-glare and anti-reflective properties in a single layer, providing high anti-reflective performance (lower refractive index) and visibility when used in display devices. In addition, the inventors have found that an antireflection film having an excellent antiglare property is obtained, and have completed the present invention.

  In order to achieve the above object, the invention of the antiglare antireflection film according to claim 1 is an antiglare antireflection film having an antiglare antireflection layer on a transparent film substrate, and is antiglare. The antireflection layer includes a first resin and a second resin having functional groups that react with each other and having a difference in surface tension between the resins: Δγ of 1.8 dyne / cm or more and 30.0 dyne / cm or less, and porous And a coating composition comprising at least one kind of fine particles having cavities.

  The invention of the antiglare antireflection film according to claim 2 is the antiglare antireflection film according to claim 1, wherein the first resin is a hydroxyl group-containing resin and the second resin is a melamine resin. It is a feature.

  The invention of the antiglare antireflection film according to claim 3 is the antiglare antireflection film according to claim 1, wherein the first resin is a carboxyl group-containing resin and the second resin is an epoxy group-containing resin. It is characterized by being.

  The invention of an anti-glare antireflection film according to claim 4 is the anti-glare antireflection film according to any one of claims 1 to 3, wherein the fine particles having a porous or hollow shape are hollow silica. It is characterized by being fine particles.

  The invention of the antiglare antireflection film according to claim 5 is the antiglare antireflection film according to any one of claims 1 to 4, wherein the film thickness of the antiglare antireflection layer is It is characterized by being 1.0 μm or more and 30.0 μm or less.

  The invention of an antiglare antireflection film according to claim 6 is the antiglare antireflection film according to any one of claims 1 to 5, wherein the transparent film substrate is a cellulose ester film. It is characterized by that.

  The invention of a polarizing plate according to claim 7 is characterized in that the antiglare antireflection film according to any one of claims 1 to 6 is used on one surface.

  The invention of a display device according to an eighth aspect is characterized by using the antiglare antireflection film according to any one of the first to sixth aspects.

  The invention of a display device according to a ninth aspect uses the polarizing plate according to the seventh aspect.

  The invention of the antiglare antireflection film according to claim 1 is an antiglare antireflection film having an antiglare antireflection layer on a transparent film substrate, and the antiglare antireflection layer has a function of reacting with each other. Difference in surface tension of the resin having a group: Δγ is 1.8 dyne / cm or more and 30.0 dyne / cm or less, and at least of the fine particles having a porosity and a cavity According to the invention of the antiglare and antireflection film according to claim 1, the resin composition is combined with fine particles having a porous or hollow inside. In this way, porous or hollow fine particles are unevenly distributed upward, the refractive index of the upper part of the layer is lowered, and it is possible to achieve both anti-glare property and anti-reflective property in one layer, and high anti-reflective performance (low refraction property). Rate) and single layer type Therefore, it is excellent in productivity, and even when the film thickness is sufficient to obtain coating film strength (abrasion resistance, pencil hardness), high antireflection performance (lower refractive index) can be obtained and further used for a display device. There is an effect that the visibility at the time is also excellent.

  The invention of the antiglare antireflection film according to claim 2 is the antiglare antireflection film according to claim 1, wherein the first resin is a hydroxyl group-containing resin and the second resin is a melamine resin. Therefore, according to the invention of the antiglare antireflection film of claim 2, the above-described effects are exhibited.

  The invention of the antiglare antireflection film according to claim 3 is the antiglare antireflection film according to claim 1, wherein the first resin is a carboxyl group-containing resin and the second resin is an epoxy group-containing resin. In particular, according to the invention of the antiglare antireflection film of claim 3, the above-described effects are exhibited.

  The invention of an anti-glare antireflection film according to claim 4 is the anti-glare antireflection film according to any one of claims 1 to 3, wherein the fine particles having a porous or hollow shape are hollow silica. According to the invention of the antiglare antireflection film according to claim 4, particularly high antireflection performance (lower refractive index) can be obtained and the coating strength (abrasion resistance, pencil hardness) can be obtained. There is also an effect.

  The invention of the antiglare antireflection film according to claim 5 is the antiglare antireflection film according to any one of claims 1 to 4, wherein the film thickness of the antiglare antireflection layer is According to the invention of the antiglare antireflection film of claim 5, particularly excellent coating strength (scratch resistance, pencil hardness) and high antireflection performance ( There is an effect of lowering the refractive index.

  The invention of an antiglare antireflection film according to claim 6 is the antiglare antireflection film according to any one of claims 1 to 5, wherein the transparent film substrate is a cellulose ester film. Therefore, according to the invention of the antiglare antireflection film of claim 6, the above-described effects are particularly obtained.

  The invention of the polarizing plate of claim 7 uses the antiglare antireflection film having high antireflection performance (low refractive index) according to any one of claims 1 to 6 on one surface. Therefore, according to the invention of the polarizing plate of claim 7, when this is used for a display device, there is an effect that the reflection of light does not matter and the visibility is excellent.

  Since the invention of the display device of claim 8 uses the antiglare antireflection film having the high antireflection performance (lower refractive index) according to any one of claims 1 to 6, According to the display device of the present invention, there is an effect that the reflection of light is not concerned and the visibility is excellent.

  The invention of the display device of claim 9 uses a polarizing plate using the antiglare antireflection film having high antireflection performance (low refractive index) according to claim 7 on one surface, and the present invention. According to the display device, there is an effect that the reflection of light is not concerned and the visibility is excellent.

  Next, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

(Anti-glare antireflection layer)
An antiglare antireflection film according to the present invention is an antiglare antireflection film having an antiglare antireflection layer on a transparent film substrate, and the antiglare antireflection layer has functional groups that react with each other. And the difference in surface tension of the resin: Δγ is 1.8 dyne / cm or more and 30.0 dyne / cm or less, and at least one kind of fine particles having pores and cavities It is formed from the coating composition containing microparticles | fine-particles.

  According to the anti-glare antireflection film of the present invention, the porous or hollow fine particles are unevenly distributed above the layer by combining the specific resin configuration and the fine particles of the porous or hollow inside, and above the layer. The refractive index is lowered, and both antiglare and antireflection properties can be achieved in a single layer.

  The anti-glare property as used in the present invention means that the reflected image is lowered by blurring the outline of the image reflected on the surface, and the reflected image is used when an image display device such as a liquid crystal display, an organic EL display or a plasma display is used. It is intended to prevent you from worrying about the reflection. By providing appropriate unevenness on the surface, such a property can be provided.

  As a method for forming such irregularities, there are processing on a transparent film substrate, application of an antiglare layer, and the like.

  Examples of the concavo-convex shape referred to in the present invention include structures selected from right cones, oblique cones, pyramids, oblique pyramids, wedge shapes, convex polygons, hemispheres, and the like, and structures having these partial shapes. Note that the hemispherical shape does not necessarily have a true spherical shape, and may be an ellipsoidal shape or a more deformed convex curved shape. Moreover, the prism shape, the lenticular lens shape, and the Fresnel lens shape in which the ridge line of the concavo-convex shape extends linearly can also be mentioned. The slope from the ridge line to the valley line may be flat, curved, or a combination of both.

  The roughness of the concavo-convex shape of the antiglare antireflection layer has an arithmetic average roughness (Ra) defined by JIS B 0601: 2001 of 60 to 700 nm, preferably 80 to 400 nm. Here, when the roughness (Ra) of the concavo-convex shape is less than 60 nm, the antiglare effect is weak, and when the roughness (Ra) of the concavo-convex shape exceeds 700 nm, an impression that is too rough is visually observed. The arithmetic average roughness (Ra) is preferably measured with an optical interference type surface roughness measuring instrument, and can be measured using, for example, an optical interference type surface roughness meter RST / PLUS (manufactured by WYKO).

  Furthermore, in order to impart antiglare properties, the following method and a method of forming an uneven shape on the surface of the transparent film substrate described later may be used in combination.

(1) A method in which a negative shape having a desired shape is formed on a roll or master, and the shape is given by embossing.

(2) A method in which a negative mold having a desired shape is formed on a roll or a master, a thermosetting resin is filled into the negative mold, and the film is peeled off from the negative mold after heat curing.

(3) A negative shape of a desired shape is formed on a roll or master, and after applying ultraviolet or electron beam curable resin to fill the recess, the transparent film substrate is coated on the intaglio via a resin solution. A method in which a cured resin and a transparent film substrate to which it is adhered are peeled off from a negative mold by irradiation with ultraviolet rays or electron beams.

(4) A solvent casting method in which a negative shape having a desired shape is formed on a casting belt and the desired shape is imparted during casting.

(5) A method in which a resin that is cured by light or heating is relief printed on a transparent substrate, and is cured by light or heating to form irregularities.

(6) A method in which a resin that is cured by light or heating is printed on the surface of the transparent film substrate by an ink jet method, and the surface of the transparent film substrate is made uneven by curing by light or heating.

(7) A method in which a resin that is cured by light or heating is printed on the surface of the transparent film substrate by an ink jet method, and is cured by light or heating to form a concavo-convex shape, and further covered with a transparent resin layer.

(8) A method of cutting the surface with a machine tool or the like.

(9) A method in which particles of various shapes such as spheres and polyhedrons are pushed in and integrated so as to be partially buried in the surface of the transparent film substrate to make the surface of the transparent film substrate uneven.

(10) A method in which particles of various shapes such as spheres and polygons are dispersed in a small amount of binder and applied to the surface of the transparent film substrate to make the surface of the transparent film substrate uneven.

(11) A method in which a binder is applied to the surface of a transparent film substrate, and particles of various shapes such as spheres and polygons are dispersed thereon to make the surface of the transparent film substrate uneven.

(12) A method of forming irregularities by pressing a mold against the surface of a transparent film substrate. Specifically, the method described in JP-A-2005-156615.

  Among the above methods, among the methods of forming a concavo-convex shape on the surface in combination, a method of forming a negative type and a combination with an ink jet method are effective.

  Next, a coating composition for forming an antiglare antireflection layer will be described.

(Porous or hollow fine particles)
From the viewpoint of the object effect of the present invention, the coating composition for forming an antiglare antireflection layer contains fine particles having a porous or void, in other words, containing fine particles having a porous or hollow inside. And By containing fine particles having such a porous or hollow inside, the fine particles are unevenly distributed above the layer, the refractive index is lowered near the outermost surface, and antireflection properties are imparted.

  The reflectance for calculating the antireflection property can be measured with a spectrophotometer. At that time, after roughening the measurement-side back surface of the sample, the light absorption treatment is performed using a black spray, and then the reflected light in the visible light region (400 to 700 nm) is measured. The reflectance is preferably as low as possible, but the average value in the visible light region wavelength is preferably 1.5% or less, and the minimum reflectance is 1.5% or less, more preferably 1.0% or less. Is preferred. Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light.

  Examples of the porous or hollow fine particles include cross-linked polymethyl methacrylate fine particles, fine particles obtained by crosslinking acrylic and styrene, and hollow silica fine particles.

  Examples of the polymethyl methacrylate fine particles include polymethyl methacrylate fine particles (average particle size of 8 μm) manufactured by Sekisui Chemical Co., Ltd., and fine particles obtained by crosslinking acrylic and styrene include, for example, acrylic / styrene crosslinked fine particles (average particle size of 0.1 μm) manufactured by Nippon Paint. 5 μm), and commercial products such as the same acrylic / styrene crosslinked fine particles (average particle size 1 μm). These fine particles having a porous or hollow interior are preferably hollow silica fine particles from the viewpoint of the objective effect.

  Next, hollow silica fine particles (hereinafter also simply referred to as hollow fine particles) will be described.

  The hollow fine particles are (I) composite particles comprising porous particles and a coating layer provided on the surface of the porous particles, or (II) having a cavity inside, and the contents are a solvent, a gas or a porous substance It is a hollow particle filled with.

  The hollow particles are particles having cavities inside, and the cavities are surrounded by particle walls. The cavity is filled with contents such as a solvent, a gas, or a porous material used at the time of preparation. The average particle size of such hollow fine particles is 5 to 200 nm, preferably 10 to 70 nm. The particle diameter of the hollow fine particles is preferably monodispersed with a coefficient of variation of 1 to 40%.

  The average particle diameter of the hollow silica fine particles used in the present invention can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc.

  The average particle diameter of the hollow fine particles to be used is appropriately selected according to the thickness of the transparent film of the low refractive index layer to be formed, and is 3/2 to 1/10, preferably 2/3 to the film thickness of the transparent film. 1/10 is desirable. These hollow fine particles are preferably used in a state dispersed in an appropriate medium. As a dispersion medium, water, alcohol (for example, methanol, ethanol, isopropyl alcohol) and ketone (for example, methyl ethyl ketone, methyl isobutyl ketone, acetone), ketone alcohol (for example, diacetone alcohol), propylene monomethyl ether, propylene glycol monomethyl ether acetate Etc. are preferred.

  The thickness of the coating layer of the composite particles or the thickness of the particle walls of the hollow particles is 1 to 40 nm, preferably 1 to 20 nm, more preferably 2 to 15 nm. In the case of composite particles, if the thickness of the coating layer is less than 1 nm, the particles may not be completely covered, and the coating liquid component can easily enter the composite particles to reduce the internal porosity. However, the effect of lowering the refractive index may not be obtained sufficiently. In addition, when the thickness of the coating layer exceeds 20 nm, the coating liquid component does not enter the inside, but the porosity (pore volume) of the composite particles is lowered and the effect of lowering the refractive index cannot be sufficiently obtained. Sometimes. In the case of hollow particles, when the particle wall thickness is less than 1 nm, the particle shape may not be maintained, and even when the thickness exceeds 20 nm, the effect of lowering the refractive index may not be sufficiently exhibited. is there.

The coating layer of the composite particles or the particle wall of the hollow particles is preferably composed mainly of silica. Moreover, components other than silica may be contained, and specifically, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O _3. , MoO ₃ , ZnO ₂ , WO ₃ and the like. Examples of the porous particles constituting the composite particles include those made of silica, those made of silica and an inorganic compound other than silica, and those made of CaF ₂ , NaF, NaAlF ₆ , MgF, and the like.

Of these, porous particles made of a composite oxide of silica and an inorganic compound other than silica are particularly suitable. Examples of inorganic compounds other than silica include Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , SnO ₂ , CeO ₂ , P ₂ O ₃ , Sb ₂ O ₃ , MoO ₃ , ZnO ₂ and WO ₃ . 1 type or 2 or more types can be mentioned.

In such porous particles, the molar ratio: MO _X / SiO ₂ is 0.0001 to 1.0 when silica is represented by SiO ₂ and inorganic compounds other than silica are represented by oxide conversion (MO _X ). Preferably, it is desirable to be in the range of 0.001 to 0.3.

Here, porous particles having a molar ratio of MO _X / SiO ₂ of less than 0.0001 are difficult to obtain, and even if obtained, particles having a small pore volume and a low refractive index are obtained. Absent. In addition, when the molar ratio of the porous particles: MO _X / SiO ₂ exceeds 1.0, the ratio of silica decreases, so that the pore volume increases and it is difficult to obtain a low refractive index. There is.

  The pore volume of such porous particles is desirably in the range of 0.1 to 1.5 ml / g, preferably 0.2 to 1.5 ml / g. If the pore volume is less than 0.1 ml / g, particles having a sufficiently reduced refractive index cannot be obtained. If the pore volume exceeds 1.5 ml / g, the strength of the fine particles is lowered, and the strength of the resulting coating may be lowered. is there.

  In addition, the pore volume of such porous particles can be determined by a mercury intrusion method. Examples of the contents of the hollow particles include a solvent, a gas, and a porous substance used at the time of preparing the particles. The solvent may contain an unreacted particle precursor used when preparing the hollow particles, the catalyst used, and the like. Moreover, what consists of a compound illustrated by said porous particle as a porous substance is mentioned. These contents may be composed of a single component or may be a mixture of a plurality of components.

  As a method for producing such hollow fine particles, for example, the method for preparing composite oxide colloidal particles disclosed in paragraphs [0010] to [0033] of JP-A-7-133105 is suitably employed. Specifically, when the composite particles are composed of silica and an inorganic compound other than silica, hollow fine particles are produced from the following first to third steps.

First Step: Preparation of Porous Particle Precursor In the first step, a silica raw material and an alkaline aqueous solution of an inorganic compound raw material other than silica are separately prepared in advance, or a silica raw material and an inorganic compound raw material other than silica are prepared. A mixed aqueous solution is prepared, and this aqueous solution is gradually added to an alkaline aqueous solution having a pH of 10 or more with stirring according to the composite ratio of the target composite oxide to prepare a porous particle precursor.

  As the silica raw material, alkali metal, ammonium or organic base silicate is used. Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate. Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. The ammonium silicate or the organic base silicate includes an alkaline solution obtained by adding ammonia, a quaternary ammonium hydroxide, an amine compound or the like to a silicic acid solution.

  In addition, alkali-soluble inorganic compounds are used as raw materials for inorganic compounds other than silica. Specifically, an oxo acid of an element selected from Al, B, Ti, Zr, Sn, Ce, P, Sb, Mo, Zn, W, etc., an alkali metal salt or alkaline earth metal salt of the oxo acid, ammonium And salts and quaternary ammonium salts. More specifically, sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate, and sodium phosphate are suitable.

Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required. The aqueous solution finally has a pH value determined by the type of inorganic oxide and the mixing ratio thereof. There is no restriction | limiting in particular in the addition rate of the aqueous solution at this time. In the production of composite oxide particles, a dispersion of seed particles can be used as a starting material. Here, the seed particles are not particularly limited, but inorganic oxides such as SiO ₂ , Al ₂ O ₃ , TiO ₂ or ZrO ₂ or fine particles of these composite oxides are used. Can be used. Furthermore, the porous particle precursor dispersion obtained by the above production method may be used as a seed particle dispersion. When using a seed particle dispersion, the pH of the seed particle dispersion is adjusted to 10 or higher, and then an aqueous solution of the compound is added to the above-mentioned alkaline aqueous solution while stirring. Also in this case, it is not always necessary to control the pH of the dispersion. When seed particles are used in this way, it is easy to control the particle size of the porous particles to be prepared, and particles with uniform particle sizes can be obtained.

  The silica raw material and the inorganic compound raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or seed particles. It grows on the top and particle growth occurs. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.

The composite ratio of silica and an inorganic compound other than silica in the first step is that the inorganic compound relative to silica is converted to an oxide (MO _X ), and the molar ratio of MO _X / SiO ₂ is 0.05 to 2.0, Preferably it is in the range of 0.2-2.0. Within this range, the pore volume of the porous particles increases as the proportion of silica decreases. However, even when the molar ratio exceeds 2.0, the pore volume of the porous particles hardly increases. On the other hand, when the molar ratio is less than 0.05, the pore volume becomes small. When preparing the hollow particles, the molar ratio of MO _X / SiO ₂ is preferably in the range of 0.25 to 2.0.

Second step: Removal of inorganic compound other than silica from porous particles In the second step, at least an inorganic compound other than silica (elements other than silicon and oxygen) is obtained from the porous particle precursor obtained in the first step. Selectively remove some. As a specific removal method, the inorganic compound in the porous particle precursor is dissolved and removed using a mineral acid or an organic acid, or is contacted with a cation exchange resin for ion exchange removal.

  The porous particle precursor obtained in the first step is a particle having a network structure in which silicon and an inorganic compound constituent element are bonded through oxygen. By removing the inorganic compound (elements other than silicon and oxygen) from the porous particle precursor in this way, porous particles having a larger porosity and a larger pore volume can be obtained. Further, if the amount of removing the inorganic oxide (elements other than silicon and oxygen) from the porous particle precursor is increased, the hollow particles can be prepared.

  In addition, prior to removing inorganic compounds other than silica from the porous particle precursor, fluorine-substituted, obtained by dealkalizing an alkali metal salt of silica into the porous particle precursor dispersion obtained in the first step. It is preferable to add a silicic acid solution containing an alkyl group-containing silane compound or a hydrolyzable organosilicon compound to form a silica protective film. The thickness of the silica protective film may be 0.5 to 40 nm, preferably 0.5 to 15 nm. Even if the silica protective film is formed, since the protective film in this step is porous and thin, it is possible to remove inorganic compounds other than silica described above from the porous particle precursor. .

  By forming such a silica protective film, inorganic compounds other than silica described above can be removed from the porous particle precursor while maintaining the particle shape. Further, when forming the silica coating layer described later, the pores of the porous particles are not blocked by the coating layer, and therefore the silica coating layer described later is formed without reducing the pore volume. Can do. Note that when the amount of the inorganic compound to be removed is small, the particles are not broken, and thus it is not always necessary to form a protective film.

  Further, when preparing hollow particles, it is desirable to form this silica protective film. When preparing the hollow particles, the inorganic compound is removed to obtain a hollow particle precursor composed of a silica protective film, a solvent in the silica protective film, and an undissolved porous solid content. When a coating layer to be described later is formed on the precursor, the formed coating layer becomes a particle wall to form hollow particles.

The amount of the silica source added for forming the silica protective film is preferably small as long as the particle shape can be maintained. If the amount of the silica source is too large, the silica protective film becomes too thick, and it may be difficult to remove inorganic compounds other than silica from the porous particle precursor. As a hydrolyzable organosilicon compound used for forming a silica protective film,
Formula _{R n Si (OR ') 4} -n
[Wherein R, R ′ represents a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, an acrylic group, and n = 0, 1, 2, or 3]
The alkoxysilane represented by these can be used. In particular, tetraalkoxysilanes such as fluorine-substituted tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is added to the dispersion of the porous particles, and the alkoxysilane is hydrolyzed. The produced silicic acid polymer is deposited on the surface of the inorganic oxide particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of the porous particle precursor is water alone or when the ratio of water to the organic solvent is high, a silica protective film can be formed using a silicic acid solution. When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the dispersion, and at the same time an alkali is added to deposit the silicic acid solution on the surface of the porous particles. In addition, you may produce a silica protective film together using a silicic acid liquid and the said alkoxysilane.

Third step: Formation of silica coating layer In the third step, the porous particle dispersion prepared in the second step (in the case of hollow particles, the hollow particle precursor dispersion) contains a fluorine-substituted alkyl group-containing silane compound. By adding a hydrolyzable organosilicon compound or silicic acid solution, the surface of the particles is coated with a polymer such as a hydrolyzable organosilicon compound or silicic acid solution to form a silica coating layer.

The hydrolyzable organosilicon compound used for forming the silica coating layer has the general formula as described above.
R _n Si (OR ′) _4-n
[Wherein R, R ′ represents a hydrocarbon group such as an alkyl group, an aryl group, a vinyl group, an acrylic group, and n = 0, 1, 2, or 3]
The alkoxysilane represented by these can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.

  As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilane, pure water, and alcohol is used as a dispersion of the porous particles (in the case of hollow particles, a hollow particle precursor). In addition, the silicic acid polymer produced by hydrolyzing alkoxysilane is deposited on the surface of the porous particles (in the case of hollow particles, hollow particle precursors). At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the dispersion. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.

  When the dispersion medium of porous particles (in the case of hollow particles, the hollow particle precursor) is water alone or a mixed solvent with an organic solvent and the mixed solvent has a high ratio of water to the organic solvent, silicic acid You may form a coating layer using a liquid. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.

  The silicic acid solution is added to the dispersion of porous particles (in the case of hollow particles, hollow particle precursors), and at the same time, alkali is added to the porous particles (in the case of hollow particles, hollow particles). Precursor) is deposited on the surface. In addition, you may use a silicic acid liquid for the coating layer formation in combination with the said alkoxysilane. The addition amount of the organosilicon compound or silicic acid solution used for forming the coating layer only needs to be sufficient to cover the surface of the colloidal particles, and the finally obtained silica coating layer has a thickness of 1 to 40 nm, Preferably, it is added in an amount of 1 to 20 nm in a dispersion of porous particles (in the case of hollow particles, a hollow particle precursor). When the silica protective film is formed, the organosilicon compound or the silicate solution is added in such an amount that the total thickness of the silica protective film and the silica coating layer is in the range of 1 to 40 nm, preferably 1 to 20 nm. Is done.

  Next, the dispersion liquid of the particles on which the coating layer is formed is heat-treated. By the heat treatment, in the case of porous particles, the silica coating layer covering the surface of the porous particles is densified, and a dispersion of composite particles in which the porous particles are coated with the silica coating layer is obtained. In the case of a hollow particle precursor, the formed coating layer is densified to form hollow particle walls, and a dispersion of hollow particles having cavities filled with a solvent, gas, or porous solid content is obtained.

  The heat treatment temperature at this time is not particularly limited as long as it can close the fine pores of the silica coating layer, and is preferably in the range of 80 to 300 ° C. When the heat treatment temperature is less than 80 ° C., the fine pores of the silica coating layer may not be completely closed and densified, and the treatment time may take a long time. Further, when the heat treatment temperature exceeds 300 ° C. for a long time, fine particles may be formed, and the effect of lowering the refractive index may not be obtained.

  The refractive index of the inorganic fine particles thus obtained is as low as less than 1.42. Such inorganic fine particles are presumed to have a low refractive index because the porosity inside the porous particles is maintained or the inside is hollow.

  From the viewpoint of low refractive index properties and film strength, the content of fine particles having a porous or hollow inside is preferably 0.01 to 500 parts by mass, more preferably 0.1 to 100 parts by mass of the resin solid content. It is -100 mass parts, Most preferably, it is 1-50 mass parts.

  Moreover, as the hollow fine particles, those in which a polymer having a hydrocarbon main chain is covalently bonded to the surface of silica can also be used. Specific examples include compounds described in JP-A-2006-257308.

  Next, the first resin and the second resin contained from the viewpoint of the object effect of the present invention will be described.

  1st resin and 2nd resin are compositions which form the resin layer which has an uneven | corrugated shape on the surface by drying the coating film obtained by apply | coating on a transparent film base material. For example, a coating composition described in JP-A-2006-3647 is preferably used. It is considered that the first resin and the second resin are localized on the basis of the difference in surface tension after applying the coating composition.

  As the first resin and the second resin, resins having functional groups that react with each other are used. The resin layer is cured by the reaction between the functional group of the first resin and the functional group of the second resin.

  Examples of combinations of such functional groups include, for example, a combination of a hydroxyl group and an imino group, a methylol group, and an alkoxide group of a melamine resin, a combination of a hydroxyl group and a (block) isocyanate group, and a hydroxyl group and an acid (anhydride) group. Combinations, combinations of hydroxyl groups and silanol groups, combinations of epoxy groups and carboxyl groups, combinations of epoxy groups and amino groups, combinations of epoxy groups and hydroxyl groups, combinations of epoxy groups and silanol groups, oxazoline groups and carboxyl groups And combinations of different functional groups such as a combination of an active methylene group and an acryloyl group. The "functional group that reacts with each other" here means that the reaction does not proceed or the reaction rate is slow only by mixing only the first resin and the second resin, but they react with each other by mixing the catalyst together. Something to do is also included. Examples of the catalyst that can be used here include a photoinitiator, a radical initiator, an acid / base catalyst, and a metal catalyst.

  As the first resin and the second resin, a resin having a difference between the surface tension of the first resin and the surface tension of the second resin: Δγ of 1.8 dyne / cm or more and 30.0 dyne / cm or less is used. The difference from the surface tension: Δγ is preferably 1.8 dyne / cm or more and 15.0 dyne / cm or less. More preferably, Δγ is 1.8 dyne / cm or more and 5.0 dyne / cm or less, and further preferably Δγ is 1.8 dyne / cm or more and 2.5 dyne / cm or less.

  Here, if the difference from the surface tension: Δγ is less than 1.8 dyne / cm, it is not preferable because a sufficient uneven shape formed based on the difference in surface tension cannot be obtained. Further, when the difference from the surface tension: Δγ exceeds 30.0 dyne / cm, it is not preferable because a uniform state in the solution state cannot be maintained and the stability is lowered.

  Difference between the surface tension of the first resin and the surface tension of the second resin: Based on the difference in surface tension after applying the coating composition to the transparent film substrate by using a resin having Δγ within the above range. The first resin and the second resin are localized, and a resin layer having random irregularities on the surface is obtained.

  In the above, the surface tension is generally a force for minimizing the area of the interface between different phases. The first resin and the second resin used in the present invention have a very high viscosity as compared with liquids such as water. Therefore, it is very difficult to measure the surface tension of the resin as it is by the ring method (hanging ring method) or the like. Therefore, in the present invention, the surface tension of the first resin and the second resin is determined by measuring the surface tension of a specific solvent, and then preparing a solution in which the resin is dissolved in the solvent at a concentration of 40% by mass of the resin solid content. The surface tension is measured and the difference between the surface tension of the first resin and the surface tension of the second resin: Δγ is measured by calculating a value obtained by subtracting the surface tension value of the solvent from the obtained measurement value. . In such a method, the surface tension can be measured using, for example, a dynamometer manufactured by Big Mallincklot International.

  The first resin and the second resin used in the present invention are considered to be localized due to different surface tensions in the drying process. And in a hardening process, since the surface tension of each resin differs, cohesion force will also differ, and it is thought that the resin layer which has an unevenness | corrugation on the surface by this is formed. Since the coating composition for forming an antiglare layer of the present invention has irregularities formed based on the surface tension of the resin used in this way, the surface shape of the irregular resin layer of the present invention should have special regularity. It becomes a random uneven shape. For this reason, there is an advantage that there is no inconvenience such as moiré due to the interference of light, which may occur in irregularities having regularity.

  As described above, the first resin and the second resin react with each other. Therefore, in the concavo-convex resin layer obtained by the present invention, the first resin and the second resin are not in a completely separated state in terms of components, and the abundance of each resin component is uneven. It will be in the state.

  As for the coating composition for forming an antiglare layer in the present invention, specific embodiments are exemplified. As the first resin (a-1), a hydroxyl group-containing resin is preferable, and an acrylic resin, an olefin resin, a polyether resin, and a polyester are used. More preferred is a hydroxyl group-containing resin having at least one skeleton selected from the group consisting of a resin, a polycarbonate resin, a polyamide resin, and a polyurethane resin.

  As the second resin (b-1), it is preferable to use a melamine resin. In this case, the hydroxyl group of the first resin (a-1) and the imino group, methylol group and / or alkoxide group of the second resin (b-1) react to form a crosslink and cure.

  Examples of the olefin resin that can be used as the first resin (a-1) include (meth) acrylic resins, for example, resins obtained by polymerization or copolymerization of (meth) acrylic monomers, (meth) acrylic monomers and other ethylenically unsaturated compounds. Resins that are copolymerized with a monomer having a double bond, such as polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ionomer, ethylene / vinyl alcohol copolymer, ethylene / chloride. A vinyl copolymer etc. are mentioned.

  The polyether resin that can be used as the first resin (a-1) is a resin containing an ether bond in the molecular chain, and examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  The polyester resin that can be used as the first resin (a-1) is a resin containing an ester bond in the molecular chain, and examples thereof include unsaturated polyester resins, alkyd resins, and polyethylene terephthalate.

  The polycarbonate resin that can be used as the first resin (a-1) is 4,4-dioxydiallylalkane-based polycarbonate including 4,4-dihydroxydiphenyl-2,2-propane (common name, bisphenol A). Among them, polycarbonate of 4,4-dihydroxydiphenyl-2,2-propane is particularly preferable, and those having a number average molecular weight of about 15,000 to 80,000 are preferable. Examples of the polycarbonate resin include Panlite L-1225, L-1250, and K-1300 manufactured by Teijin Chemicals Limited.

  The polyamide resin that can be used as the first resin (a-1) has an acid amide bond (—CONH—) in the molecular chain, such as ε-caprolactam, 6-aminocaproic acid, ε-enantolactam, Polycondensates such as 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, laurolactam, α-pyrrolidone, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and diamine A polymer comprising a polycondensation product with a dicarboxylic acid such as adipic acid or sebacic acid, a copolymer thereof, or a blend of these polymers or copolymers can be mentioned. Preferably, ε-caprolactam, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, laurolactam, a polymer comprising a polycondensate of hexamethylenediamine and adipic acid, or a copolymer thereof, Alternatively, it is a blend of these polymers and copolymers.

  Examples of the polyurethane resin that can be used as the first resin (a-1) include resins having a urethane bond in the molecular chain.

  Furthermore, the copolymer of said resin can also be used as 1st resin (a-1).

  The hydroxyl value (OH value) of the first resin (a-1) is preferably 10 to 400. When the OH value of the first resin (a-1) is less than 10, curing may be insufficient, resulting in a decrease in film formability (resin layer forming ability) and a decrease in chemical resistance of the resulting resin layer. There is. On the other hand, when the OH value of the first resin (a-1) exceeds 400, the flexibility of the resulting resin layer may be lowered and the mechanical strength may be lowered due to the crosslinking density becoming too high. .

  Of the first resin (a-1), a (meth) acrylic resin having a hydroxyl group is particularly preferably used in the present invention. This is because this resin can form a resin layer having a better uneven surface in a combination using a melamine resin as the second resin (b-1).

  In this embodiment, the melamine resin that can be used as the second resin (b-1) is generally a resin having various surface tension values.

  In the present invention, a second resin (b-1) made of a melamine resin having a difference from the surface tension of the first resin (a-1): Δγ of 1.8 or more, preferably 2 or more is used. And as 2nd resin (b-1), it is more preferable to use resin which has surface tension lower than the surface tension of said 1st resin (a-1).

  As the melamine resin constituting the second resin (b-1), commercially available ones can be used, for example, purchased from Nippon Cytec Industries, Ltd., Dainippon Ink, Mitsui Toatsu, etc. Can do.

  As another specific embodiment of the coating composition for forming an antiglare layer of the present invention, it is preferable to use a carboxyl group-containing resin as the first resin (a-2).

  On the other hand, it is preferable to use an epoxy group-containing resin as the second resin (b-2). In this case, the carboxyl group of the first resin (a-2) reacts with the epoxy group of the second resin (b-2) to form a crosslink and cure. As a resin that can be used as the first resin (a-2), an acrylic resin, for example, a resin obtained by polymerizing or copolymerizing a (meth) acrylic monomer, or a (meth) acrylic monomer and another ethylenically unsaturated double bond An acrylic resin such as a resin copolymerized with a monomer having a carboxyl group on its skeleton is particularly preferable.

  Here, the acid value of the first resin (a-2) is preferably 20 to 400, and more preferably 50 to 250. When the acid value of the first resin (a-2) is less than 20, curing may be insufficient, resulting in a decrease in film formability (resin layer forming ability) and a decrease in chemical resistance of the resulting resin layer. There is. On the other hand, when the acid value of 1st resin (a-2) exceeds 400, there exists a possibility that the fall of the flexibility of the resin layer obtained by the crosslinking density becoming high too much, and the fall of mechanical strength may arise. is there.

  In the above embodiment of the present invention, examples of the epoxy group-containing resin that can be used as the second resin (b-2) include bisphenol type epoxy resins and epoxy group-containing acrylic resins. Is preferred. In the present specification, “epoxy group-containing resin” refers to a resin having an epoxy group, and the structure of the skeleton of the resin is not limited.

In the present invention, as an epoxy group-containing resin that can be used as the second resin (b-2), for example, 30 to 70% by mass of a radical polymerizable monomer having an epoxy group, 10 to 50% by mass of a radical polymerizable monomer having a hydroxyl group. %, And a copolymer obtained by copolymerizing a monomer composition containing the remaining amount of other radical polymerizable monomers.

  Examples of the radical polymerizable monomer having an epoxy group include glycidyl (meth) acrylate, 3,4 epoxycyclohexanylmethyl methacrylate, and the like. Examples of the radical polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, Plaxel FM-1 (manufactured by Daicel Corporation), and the like. Examples of other radical polymerizable monomers include styrene, α-methylstyrene, acrylic acid esters (for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid-n, i, and t-butyl, acrylic acid 2 Ethyl hexyl, lauryl acrylate, etc.), methacrylic acid esters (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n, i, and t-butyl, 2-ethylhexyl methacrylate, lauryl methacrylate, etc.) , Acrylamide, methacrylamide and the like. These may be used alone or in combination of two or more. An epoxy group-containing resin is obtained by polymerizing these monomers in the presence of a radical polymerization initiator such as t-butylperoxy-2-ethylhexanoate or dimethyl 2,2'-azobisisobutyrate. be able to.

  Among the second resins (b-2) made of these epoxy resins, the difference between the surface tension of the second resin (b-2) and the surface tension of the first resin (a-2): Δγ is 1 .8 or more, preferably 2 or more. And it is preferable to use 2nd resin (b-2) which consists of an epoxy resin which has surface tension lower than the surface tension of said 1st resin (a-2).

  The epoxy resin used as the second resin (b-2) is preferably an epoxy resin having an epoxy equivalent of 100 to 5000, and more preferably an epoxy resin having an epoxy equivalent of 160 to 2000.

  In any of the above embodiments, the weight average molecular weight of the first resin is preferably 500 to 500,000, particularly 1000 to 100,000. When the weight average molecular weight of the first resin exceeds 500,000, the polymer viscosity is increased, and workability and the like may be deteriorated. On the other hand, when the weight average molecular weight of the first resin is less than 500, localization may be insufficient. The weight average molecular weight can be determined by a gel permeation chromatography method (GPC method).

  Moreover, it is preferable that the weight average molecular weights of 2nd resin are 200-500,000, especially 400-100,000. When the weight average molecular weight of the second resin exceeds 500,000, the polymer viscosity is increased, and workability and the like may be deteriorated. On the other hand, when the weight average molecular weight of the second resin is less than 200, localization may be insufficient. This weight average molecular weight can also be determined by a gel permeation chromatography method (GPC method).

  The solvent to be used is not particularly limited, and is appropriately selected in consideration of the material of the portion serving as a base for coating, the binder resin, the coating method, and the like.

  Specific examples of the solvent include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol diethyl ether, and the like Ether solvents: ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methyl lactate, methyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Ester solvents such as nomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, γ-butyrolactone; amide solvents such as dimethylformaldehyde, dimethylacetamide, N-methylpyrrolidone; propylene carbonate, dimethyl carbonate, diethyl carbonate Carbonate solvents such as n-butane, n-hexane, cyclohexane, etc .; alcohols such as i-propanol, i-butanol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether And system solvents. Among these solvents, ester solvents, ether solvents, and alcohol solvents are preferable, and these solvents can be used alone or in admixture of two or more. Further, the coating composition for forming an antiglare layer of the present invention may be an aqueous coating composition. Accordingly, an aqueous solvent may be used.

  The first resin and the second resin are preferably used in a range of 10/90 to 90/10 expressed by a solid content mass ratio of the resin (first resin / second resin), and 70/30 to 40/60. It is more preferable to use in the range of. By using in such a ratio, a resin layer having a good uneven surface and excellent in physical strength can be obtained.

  The refractive index of the first resin and the second resin in the coating composition for forming the antiglare antireflection layer may be the same or different, and a preferable refractive index difference is 0.00 to 0.50, more preferably Is 0.01-0.30.

  In addition, organic fine particles selected from polymethyl methacrylate, polystyrene, and melamine polymer, and silica fine particles may be contained. The average particle diameter of these fine particles is preferably in the range of 5 nm to 30 μm. Furthermore, it is preferably 10 nm to 15 μm. The average particle diameter can be measured by, for example, a laser diffraction particle size distribution measuring apparatus.

  Moreover, as content of microparticles | fine-particles, 0.01-500 mass parts is preferable with respect to 100 mass parts of resin solid content from dispersibility and the stability of a coating composition, More preferably, 0.1-100 mass parts And particularly preferably 1 to 30 parts by mass.

  As specific examples of organic fine particles selected from polymethyl methacrylate, polystyrene, benzoguanamine, and melamine polymer, polymethyl methacrylate-based fine particles include, for example, Soken Chemical Co., Ltd .; MX150, MX300, Nippon Shokubai Co., Ltd .; MA1004, MA1006, MA1010, Epostor MX (emulsion), grade: MX020W, MX030W, MX050W, MX100W), manufactured by Sekisui Plastics; MBX series (MBX-8, MBX12), and also containing fluorine-containing polymethylmethacrylate fine particles But it ’s okay. Fluorine-containing polymethyl methacrylate fine particles are fine particles formed from fluorinated acrylate or fluorinated methacrylate from monomers or polymers, fine particles formed from fluorine-containing acrylic acid, fluorine-containing methacrylic acid, fluoroacrylic acid or fluoromethacrylic acid. . Specific examples include commercial products such as Nippon Paint: FS-701, Negami Kogyo: MF-0043.

  Examples of the polystyrene-based fine particles include commercially available products such as those manufactured by Soken Chemical; SX series (SX-130H, SX-200H, SX-350H), Sekisui Plastics; SBX series (SBX-6, SBX-8). It is done. Moreover, the microparticles | fine-particles which styrene and the acryl bridge | crosslinked are mentioned.

  Examples of the melamine polymer-based fine particles include a product made by Nippon Shokubai; a benzoguanamine / melamine / formaldehyde condensate (trade name: eposter, grade; M30, product name: eposter GP, grade; H40 to H110), a product made by Nippon Shokubai; Commercially available products such as condensates (trade name: eposter, grade; S12, S6, S, SC4), manufactured by Nissan Chemical Industries, Ltd .; melamine resin / silica composite particles (trade name: Optobeads) can be mentioned.

  Examples of the silica fine particles include trade names such as those manufactured by Nippon Aerosil Co., Ltd .; Aerosil 200, 200V, 300, manufactured by Degussa; Aerosil OX50, TT600, manufactured by Fuji Silysia Chemical;

  The fine particles may be used alone or in combination of two or more. The fine particles may be added in any state such as powder or emulsion.

  Other fine particles include benzoguanamine-based fine particles, for example, Nippon Shokubai Co., Ltd .: benzoguanamine-formaldehyde condensate (trade name: Eposter, Grades; L15, M05, MS, SC25), polyurethane-based fine particles (for example, Daiichi Seika's dimic beads) And ethylene / methyl methacrylate copolymer.

  Furthermore, ultraviolet curable resin composition such as silicone resin powder, polystyrene resin powder, polycarbonate resin powder, polyolefin resin powder, polyester resin powder, polyamide resin powder, polyimide resin powder, or polyfluorinated ethylene resin powder In addition, a crosslinked resin particle component described in JP-A No. 2000-241807 can also be added.

  Moreover, various other additives can be added as needed. Examples of such additives include rheology control agents such as waxes such as polyethylene wax and polypropylene wax, surface conditioners (leveling agents) such as acetylene diols, coupling agents, plasticizers, and dispersants. . Examples of the leveling agent include fluorine-based or silicone surfactants and polyoxyethylene oleyl ether compounds described in the later-described low refractive index layer.

  As a polyoxyethylene oleyl ether compound, it is a compound generally represented by general formula (I).

General formula _{(I) C 18 H 35 -O} (C 2 H 4 O) n H
In the formula, n represents 2 to 40.

  The average addition number (n) of ethylene oxide with respect to the oleyl part is 2 to 40, preferably 2 to 10. The compound of general formula (I) can be obtained by reacting ethylene oxide and oleyl alcohol.

  Specific products include Emulgen 404 [polyoxyethylene (4) oleyl ether], Emulgen 408 [polyoxyethylene (8) oleyl ether], Emulgen 409P [polyoxyethylene (9) oleyl ether], Emulgen 420 [polyoxy Ethylene (13) oleyl ether], Emulgen 430 [polyoxyethylene (30) oleyl ether] or more, Kao Corporation, NOFLEEAO-9905 [polyoxyethylene (5) oleyl ether] manufactured by NOF Corporation. In addition, the number in () represents the number n.

  In addition, inorganic fine particles and metal oxides may also be included. Specifically, titanium oxide, aluminum oxide, tin oxide, indium oxide, indium oxide-tin (ITO), zinc oxide, zirconium oxide, magnesium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined silicic acid Mention may be made of calcium, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate.

  The thickness of the antiglare antireflection layer is not limited from the viewpoint of coating strength and antireflection properties, but is usually 0.5 to 50 μm, particularly preferably 1 to 30 μm. The antiglare antireflection layer may be composed of a single layer or a plurality of layers.

  The antiglare antireflection layer is a coating process for applying the antiglare antireflection layer forming coating composition to a transparent film substrate, a drying process for drying the obtained coating film, and a dried coating film is cured. And a curing step.

  The method for applying the coating composition for forming the antiglare antireflection layer to the substrate is not particularly limited, and is appropriately selected depending on the coating composition to be used and the situation of the coating process. For example, various coating methods such as wire bar coating, spin coating, roll coating, screen printing, spray coating, gravure coating, and an inkjet method described later can be employed.

  Moreover, it is preferable that application | coating is drawn out from the state wound up in roll shape with the transparent film base material width | variety mentioned later of 1.4-4m, performs application | coating, and after drying and hardening processing, it is wound up in roll shape. .

  The drying step is preferably performed by vacuum drying. It is considered that the solvent contained in the coating composition can be removed by drying under reduced pressure, and the first resin and the second resin can be localized well.

  By curing the coating film in which the first resin and the second resin are localized in the drying step, the uneven resin layer is formed. Examples of the curing method include a method of thermosetting by heating, a method of curing by irradiation with light such as an electron beam or ultraviolet rays, and the like. In the case of thermosetting, the heating temperature is preferably 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 150 ° C.

  The heating time varies depending on the heating temperature, but a range of 3 to 300 minutes is appropriate. Or after winding up once, the method of carrying out an aging process for about 1 to 20 days at the temperature of about 50-100 degreeC may be used.

In the case of curing by light irradiation, exposure of the irradiation light is preferably from ^{10mJ / cm 2 ~10J / cm 2} , and more preferably ^{50mJ / cm 2 ~1J / cm 2} . Although the wavelength range of the light irradiated here is not particularly limited, light having a wavelength in the ultraviolet region is preferably used.

  Further, the antiglare antireflection layer may contain an active energy ray curable resin. Or it can also laminate | stack as another layer.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active rays such as ultraviolet rays or electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and the active energy ray curable resin layer is cured by irradiation with an active ray such as an ultraviolet ray or an electron beam. It is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and a resin curable by ultraviolet irradiation is preferable.

  As the ultraviolet curable resin, for example, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, or an ultraviolet curable epoxy resin is preferable. Used. Of these, ultraviolet curable acrylate resins are preferred.

  The UV curable acrylic urethane resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxyl group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used.

  For example, a mixture of 100 parts Unidic 17-806 (Dainippon Ink Chemical Co., Ltd.) and 1 part Coronate L (Nihon Polyurethane Co., Ltd.) is preferably used.

  Examples of UV curable polyester acrylate resins include those which are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with polyester polyols. JP-A-59-151112 Those described in the publication can be used.

  Specific examples of the ultraviolet curable epoxy acrylate resin include an epoxy acrylate as an oligomer, a reactive diluent and a photopolymerization initiator added thereto, and reacted to form an oligomer. Those described in Japanese Patent No. 105738 can be used.

  Specific examples of UV curable polyol acrylate resins include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, etc. Can be mentioned.

  Specific examples of photopolymerization initiators for these ultraviolet curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photopolymerization initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the ultraviolet curable resin composition is 0.1 to 20 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the composition.

  Examples of the resin monomer may include general monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, and styrene as monomers having one unsaturated double bond. Moreover, as a monomer having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate, Examples include pentaerythritol tetraacrylic ester.

  Examples of commercially available ultraviolet curable resins that can be used in the present invention include ADEKA OPTMER KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (Asahi Denka Co., Ltd.) Manufactured by company); KEIEI Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS- 101, FT-102Q8, MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10, DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (manufactured by Daicel UC Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC-5102, RC- 5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (Dainippon Ink & Chemicals, Inc.); 340 clear (manufactured by China Paint Co., Ltd.); Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries Co., Ltd.); SP-1509 , SP-1507 (manufactured by Showa Polymer Co., Ltd.); RCC-15C (manufactured by Grace Japan Co., Ltd.), Aronix M-6100, M-8030, M-8060 (manufactured by Toagosei Co., Ltd.); NK Hard B-420 , B-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Other examples include ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and isobornyl acrylate.

As a light source for curing an ultraviolet curable resin by a photocuring reaction to form a cured film layer, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually 5 to 500 mJ / cm ² , preferably 5 to 150 mJ / cm ² , and particularly preferably 20 to 100 mJ / cm ² .

  Moreover, when irradiating actinic radiation, it is preferable to carry out while applying tension | tensile_strength in the conveyance direction of a film, More preferably, it is performing applying tension | tensile_strength also in the width direction. The tension to be applied is preferably 30 to 300 N / m. The method for applying tension is not particularly limited, and tension may be applied in the transport direction on the back roll, or tension may be applied in the width direction or biaxial direction by a tenter. This makes it possible to obtain a film having further excellent flatness.

  The coating composition for the antiglare antireflection layer may contain a solvent, or may be appropriately contained and diluted as necessary. Examples of organic solvents contained in the coating liquid include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), esters It can be appropriately selected from among organic solvents (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or a mixture thereof can be used. Propylene glycol monoalkyl ether (1 to 4 carbon atoms of the alkyl group) or propylene glycol monoalkyl ether acetate ester (1 to 4 carbon atoms of the alkyl group) is 5% by mass or more, more preferably 5 to 80%. It is preferable to use the organic solvent containing at least mass%.

(Example of unevenness formation by inkjet method)
The antiglare antireflection layer of the present invention can also be formed uneven by an ink jet method.

  The convex structure part may be formed by applying the composition for forming an antiglare antireflection layer as an ink liquid by an ink jet method, or on the convex structure part formed with a coating liquid having an actinic radiation curable resin. It can also be used as an overcoat layer, or it can be used as a coating solution for forming a convex structure portion by an ink jet method and then overcoating the convex structure portion.

  FIG. 1 is a schematic diagram showing the formation of a convex structure by an ink jet method and the overcoat with a transparent resin layer.

  FIG. 2 is a cross-sectional view showing an example of an inkjet head that can be used in the inkjet method used in the present invention.

  2A is a cross-sectional view of the inkjet head 10, and FIG. 2B is an enlarged view taken along line AA in FIG. 2A. In the figure, 11 is a substrate, 12 is a piezoelectric element, 12b is a driving piezoelectric element, 12a is a non-driving piezoelectric element, 13 is a flow path plate, 13a is an ink flow path, 13b is a wall, 14 is a common liquid chamber component, 14a is a common liquid chamber, 15 is an ink supply pipe, 16 is a nozzle plate, 16a is a nozzle, 17 is a drive circuit printed board (PCB), 18 is a lead portion, 19 is a drive electrode, 20 is a groove, and 21 is a protective plate , 22 are fluid resistances, 23 and 24 are electrodes, 25 is an upper partition, 26 is a heater, 27 is a heater power source, 28 is a heat transfer member, and 30 is an ink jet head.

  In the integrated inkjet head 30, the laminated piezoelectric element 12 having the electrodes 23 and 24 is grooved in the direction of the flow path 13a corresponding to the flow path 13a, so that the groove 20 and the driving piezoelectric element 12b. And non-driving piezoelectric element 12a. The groove 20 is filled with a filler. The flow path plate 13 is joined to the piezoelectric element 12 subjected to the groove processing through the upper partition wall 25. That is, the upper partition 25 is supported by the non-driving piezoelectric element 12a and the wall 13b that separates the adjacent flow path. The width of the driving piezoelectric element 12b is slightly narrower than the width of the flow path 13a. When the driving piezoelectric element 12b selected by the driving circuit on the driving circuit printed board (PCB) is applied with a pulsed signal voltage, the driving piezoelectric element 12b. The element 12b changes in the thickness direction, and the volume of the flow path 13a changes via the upper partition wall 25. As a result, ink droplets are ejected from the nozzles 16a of the nozzle plate 16.

  Heaters 26 are bonded to the flow path plate 13 via heat transfer members 28, respectively. The heat transfer member 28 is provided around the nozzle surface. The heat transfer member 28 is intended to efficiently transfer the heat from the heater 26 to the flow path plate 13, carry the heat from the heater 26 to the vicinity of the nozzle surface, and warm the air in the vicinity of the nozzle surface. A material with good conductivity is used. For example, metals such as aluminum, iron, nickel, copper, and stainless steel, or ceramics such as SiC, BeO, and AlN are preferable materials.

  When the piezoelectric element is driven, the piezoelectric element is displaced in a direction perpendicular to the longitudinal direction of the flow path, and the volume of the flow path is changed. By the change in volume, ink droplets are ejected from the nozzle. The piezoelectric element is given a signal that keeps the flow path volume constantly reduced, and after the displacement of the selected flow path in the direction of increasing the flow volume, the displacement that reduces the flow volume again is applied. By applying a pulse signal to be applied, ink is ejected as ink droplets from a nozzle corresponding to the flow path.

  FIG. 3 is a schematic view showing an example of an inkjet head unit and a nozzle plate that can be used in the present invention.

  3A is a sectional view of the head portion, and FIG. 3B is a plan view of the nozzle plate. In the figure, 10 is a transparent film substrate, 31 is an ink droplet, 32 is a nozzle, and 29 is an actinic ray irradiation part. The ink droplet 31 ejected from the nozzle 32 flies in the direction of the transparent film substrate 10 and adheres. The ink droplets landed on the transparent film substrate 10 are irradiated with actinic rays from an actinic ray irradiating unit disposed upstream thereof and are cured. Reference numeral 35 denotes a back roll for holding the transparent film substrate 10.

  In the present invention, as shown in FIG. 3B, the nozzles of the inkjet head unit are preferably arranged in a staggered manner, and are preferably provided in multiple stages in parallel in the transport direction of the transparent film substrate 10. . It is also preferable to apply fine vibrations to the ink jet head portion during ink ejection so that ink droplets land randomly on the transparent substrate. Thereby, generation | occurrence | production of an interference fringe can be suppressed. The fine vibration can be given by a high frequency voltage, a sound wave, an ultrasonic wave or the like, but is not particularly limited thereto.

  As the method for forming the convex structure portion used in the present invention, it is preferable to use an ink jet method in which small droplets of ink are formed from multiple nozzles. FIG. 4 shows an example of an ink jet system that can be preferably used in the present invention.

  4, FIG. 4A shows a method (line head) in which an inkjet head 30 is arranged in the width direction of the transparent film substrate 10 and a convex structure portion is formed on the surface of the transparent film substrate 10 while being conveyed. 4B shows a method (flat head method) in which the inkjet head 30 moves in the sub-scanning direction and forms a convex structure portion on the surface thereof. FIG. , A method of forming a convex structure portion on the surface of the transparent film substrate 10 while scanning in the width direction (capstan method), and any method can be used. In view of the above, the line head method is preferable. In addition, 29 described in FIGS. 4A to 4C is an actinic ray irradiation unit used when an actinic ray curable resin described later is used as the ink.

  Moreover, in this invention, you may provide another actinic ray irradiation part in the downstream of the conveyance direction of the transparent film base material of Fig.4 (a), FIG.4 (b), and FIG.4 (c).

  In the present invention, in order to form fine irregularities, the ink droplet is preferably 0.1 to 100 pl, more preferably 0.1 to 50 pl, and particularly preferably 0.1 to 10 pl. By ejecting ink droplets under the above conditions, fine irregularities having a major axis of dots of 1 to 30 μm and a dot height of 0.1 to 10 μm can be obtained.

  In addition, the viscosity of the ink droplets is preferably 0.1 to 20 mPa · s at 25 ° C., more preferably 0.5 to 10 mPa · s.

  A transparent resin layer can also be applied so as to cover the convex structure formed by the inkjet method.

  The transparent resin layer includes the first resin, the second resin, the active energy ray curable resin, the photopolymerization initiator, the photoreaction initiator, the photosensitizer, and the heat according to the present invention described in the section of the antiglare coating composition. An ink composition is prepared by appropriately using a curable resin, a thermoplastic resin, an ultraviolet absorber, fine particles, a solvent, and the like, and further applied on the convex structure portion by an arbitrary application method.

  FIG. 5 is a schematic diagram of an uneven surface forming apparatus using an uneven roller. In the same figure, a resin solution prepared in advance is cast on a casting belt 52 from a die 51, and a web (a film containing a residual solvent after casting a dope on a metal support is called a web). After forming and peeling, a concavo-convex surface is formed on the web by the concavo-convex-type roller 53 for forming the concavo-convex surface and the back roll 54 facing the concavo-convex roller 53. Subsequently, a concavo-convex surface is formed on the back surface of the web by the concavo-convex surface forming uneven roller 53 ′ having a concavo-convex shape on the opposite surface of the web and the back roll 54, and then the web is stretched by the tenter 55. The film is dried by the next film drying device 56 and wound by the winding roll 57.

  Further, the uneven surface formation may be performed after the tenter 55 in FIG. 5, in the drying device 56 in FIG. 5, or after the drying is finished. In FIG. The concavo-convex roller and the back roll are arranged to form the concavo-convex, but a plurality of concavo-convex rollers and a back roll may be used.

  FIG. 6 shows a schematic view of the uneven surface forming apparatus in the drying apparatus. In this case, the amount of residual solvent is significantly lower than in the case of FIG. 5, but the surface temperature of the transparent support can be set to a desired temperature by controlling the heating conditions with the drying device, so that the unevenness can be accurately performed. There is an advantage that it can be formed. Since the other points in FIG. 6 are the same as those in FIG. 5, the same reference numerals are given to the same parts in the drawing.

  After returning the film to room temperature, a concavo-convex surface forming apparatus using a concavo-convex roller can be used in another line. However, in this case, if the residual solvent or temperature is low, the concavo-convex surface formation is not stable. In addition, there is a risk of dust and foreign matter adhering to the concave / convex processing by the concave / convex roller, and it is preferable to perform it in the film forming process as shown in FIGS. It is preferable that irregularities are easily formed.

  As the concavo-convex type roller used for the formation of the concavo-convex surface, it is possible to select and apply as appropriate to fine rugged and rough rugged, pattern, mat shape, lenticular lens shape, concave or convex portion consisting of part of a spherical surface, prism shape Can be used in which the embosses for forming the irregularities are regularly or randomly arranged. For example, a concave portion or a convex portion formed of a part of a sphere having a diameter of a convex portion or a concave portion of 5 to 100 μm and a height of 0.1 to 2 μm can be mentioned, and these may combine large unevenness and small unevenness.

  The material of the concavo-convex roller and the back roll can be metal, stainless steel, carbon steel, aluminum alloy, titanium alloy, ceramic, hard rubber, reinforced plastic, or a combination of these materials. From this point, the concavo-convex roller is preferably a metal. In particular, ease of cleaning and durability are also important, and it is preferable to use a stainless uneven roller. Particularly preferably, the surface-side uneven shape is formed of a metal material and a ceramic material for the viewing side, and the surface uneven shape is formed of a rubber material for the back side. By using concavo-convex rollers made of different materials, concavo-convex shapes having slightly different concavo-convex shapes (shapes such as peaks, valleys, and ridge lines) can be formed, and glare can be effectively prevented.

  Further, the surface may be subjected to water repellency or water repellency treatment. As a method of forming a desired concavo-convex surface on the concavo-convex roller, it can be formed by using an etching method, a sand blasting method, a mechanical processing method, a mold, or the like. As the back roll, hard rubber or metal is preferably used.

  The surface temperature T1 of the concavo-convex roller is T2 + 10 ° C. to T2 + 55 ° C., preferably T2 + 30 ° C. to T2 + 50 ° C., with respect to the thermal deformation temperature T2 of the resin used. The heat distortion temperature T2 is a value measured according to ASTM D-648.

  When the surface temperature T1 of the concavo-convex roller is lower than the thermal deformation temperature T2, it becomes difficult to form a fine concavo-convex shape. If the surface temperature T1 exceeds 55 ° C. than the heat distortion temperature T2, the flatness of the resulting film tends to deteriorate. The surface temperature T1 of the concavo-convex roller can be controlled by setting the temperature of the concavo-convex roller itself, the ambient temperature, the film temperature for forming the concavo-convex, the residual solvent amount of the film, and the concavo-convex formation speed. The temperature of the concavo-convex roller itself can be controlled by circulating a temperature-controlled gas or liquid medium in the concavo-convex roller. For example, it is selected in accordance with the type of resin and the uneven shape to be formed in the range of 40 to 300 ° C., preferably 50 to 250 ° C. At that time, it is preferable to prevent the residual solvent in the film from foaming, and even if the surface of the concavo-convex roller is at a temperature equal to or higher than the boiling point of the residual solvent, foaming can be prevented if the concavo-convex formation speed is high. . For example, the unevenness can be formed at a speed of 10 m / min or more.

  It is preferable to control the temperature of the back roll in the same manner, and it is preferable to set the temperature to be equal to or lower than that of the uneven roller.

  The roll pressure at the time of forming the unevenness is appropriately determined from a linear pressure of 5 to 500 N / cm, more preferably from 30 to 500 N / cm in consideration of the type of the thermoplastic resin, the shape of the unevenness to be formed, the temperature, and the like. .

(High refractive index layer, low refractive index layer)
In the present invention, a low refractive index layer, a high refractive index layer, or the like can be formed on the reflective antiglare layer. Next, the low refractive index layer will be described.

(Low refractive index layer)
The refractive index of the low refractive index layer is lower than the refractive index of the transparent film substrate as a support, and is preferably in the range of 1.30 to 1.45 at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is preferably 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and even more preferably 30 nm to 0.2 μm.

  The composition for forming a low refractive index layer preferably contains two types of silica fine particles, one of which is the aforementioned hollow silica fine particle having a porous or hollow interior, and the other one type of silica fine particle. The silica fine particles are not particularly limited, but are preferably colloidal silica in the present invention, and the average particle size of the colloidal silica is 1.1 to less than 20 times the average particle size of the hollow silica fine particles. preferable.

  The low refractive index layer may contain two types of hollow silica fine particles having different average particle diameters.

  The content of the hollow silica fine particles having a porous or hollow interior in the low refractive index layer is preferably 10 to 50% by mass, particularly 10 to 40% by mass. In order to obtain the effect of lowering the refractive index, the content is preferably 15% by mass or more, and when it exceeds 40% by mass, the binder component is decreased and the film strength may be insufficient. Most preferably, it is 20-40 mass%.

(Colloidal silica)
The colloidal silica preferably used in the present invention is obtained by dispersing silicon dioxide in a colloidal form in water or an organic solvent, and is not particularly limited but has a spherical shape, a needle shape, or a bead shape. The low refractive index layer of the antireflection film of the present invention contains at least two kinds of silica-based fine particles having different average particle diameters, and the average particle diameter of the other silica-based fine particles is 1 with respect to the average particle diameter of one particle. .1 to less than 20 times. Particularly preferably, the colloidal silica has an average particle size of preferably 1.1 to less than 20 times the average particle size of the hollow fine particles, and more preferably 1.5 to 5.0 times. Therefore, the average particle diameter of colloidal silica is preferably in the range of 50 to 300 nm. The particle size of colloidal silica is preferably monodispersed with a coefficient of variation of 1 to 40%. The average particle diameter can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. However, when the ratio between the average particle size of colloidal silica and the average particle size of the hollow fine particles is obtained, the same measurement method must be used.

  The colloidal silica as described above used in the present invention is commercially available, and examples thereof include the Snowtex series manufactured by Nissan Chemical Industries, the Cataloid-S series manufactured by Catalytic Chemical Industries, and the Rebacil series manufactured by Bayer. Further, colloidal silica cation-modified with alumina sol or aluminum hydroxide, or beaded colloidal silica in which primary particles of silica are connected in a bead shape by connecting particles with divalent or higher metal ions is also preferably used. Examples of the beaded colloidal silica include Nissan Chemical's Snowtex-AK series, Snowtex-PS series, and Snowtex-UP series.

  When colloidal silica is contained, the content in the low refractive index layer is preferably 10 to 60% by mass, and more preferably 30 to 60% by mass with respect to the solid content in the low refractive index layer. In order to obtain the effect of lowering the refractive index, it is preferably 30% by mass or more, and when it exceeds 40% by mass, the binder component is decreased and the film strength becomes insufficient.

  The total content of at least two kinds of fine particles contained in the low refractive index layer is 10 to 80% by mass, preferably 15 to 70% by mass, and particularly preferably 20 to 60% by mass. In addition, the content ratio when the two kinds of particles are contained is in the range of 1: 0.1 to 10, and the content ratio of the hollow fine particles and the colloidal silica is particularly selected from the viewpoint of the reflectance reduction effect and the surface hardness. However, 1: 0.8-5 is more preferable.

(binder)
The low refractive index layer preferably contains 5 to 80% by mass of binder as a whole. The binder has a function of adhering silica fine particles and maintaining the structure of the low refractive index layer including voids. The usage-amount of a binder is adjusted so that the intensity | strength of a low refractive index layer can be maintained, without filling a space | gap. Examples of the binder include an organosilicon compound represented by the following general formula (2), a hydrolyzate thereof, or a polycondensate thereof.

General formula (2) Si (OR) ₄
In formula, R is an alkyl group, Preferably it is a C1-C4 alkyl group.

  As specific compound compounds, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  The low refractive index layer may contain a silane coupling agent as a binder. Silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltri Ethoxysilane, γ- (β-glycidyloxyethoxy) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ- Acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N- Examples include β- (aminoethyl) -γ-aminopropyltrimethoxysilane and β-cyanoethyltriethoxysilane.

  Examples of silane coupling agents having a disubstituted alkyl group with respect to silicon include dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, and γ-glycidyloxypropylmethyldiethoxysilane. Γ-glycidyloxypropylmethyldimethoxysilane, γ-glycidyloxypropylphenyldiethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldi Ethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimeth Shishiran, .gamma.-mercaptopropyl methyl diethoxy silane, .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, methyl vinyl dimethoxy silane, and methyl vinyl diethoxy silane.

  Among these, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltrimethoxysilane having a double bond in the molecule. Γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-methacryloyloxypropylmethyldiethoxy having a disubstituted alkyl group with respect to silicon Silane, methylvinyldimethoxysilane and methylvinyldiethoxysilane are preferred, and γ-acryloyloxypropyltrimethoxysilane and γ-methacryloyloxyp Particularly preferred are propyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane and γ-methacryloyloxypropylmethyldiethoxysilane.

  Two or more coupling agents may be used in combination. In addition to the silane coupling agents shown above, other silane coupling agents may be used. Other silane coupling agents include alkyl esters of orthosilicate (eg, methyl orthosilicate, ethyl orthosilicate, n-propyl orthosilicate, i-propyl orthosilicate, n-butyl orthosilicate, sec-butyl orthosilicate, orthosilicate). Acid t-butyl) and its hydrolyzate.

  Examples of other binders for the low refractive index layer include polyvinyl alcohol, polyoxyethylene, polymethyl methacrylate, polymethyl acrylate, diacetyl cellulose, triacetyl cellulose, nitrocellulose, polyester, alkyd resin, and fluoroacrylate.

(solvent)
The coating composition for a low refractive index layer according to the present invention preferably contains an organic solvent. Specific examples of organic solvents include alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate). , Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Group hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  It is preferable that the solid content concentration in the coating composition for the low refractive index layer is 1 to 4% by mass. By making the solid content concentration 4% by mass or less, uneven coating is less likely to occur, and 1% by mass or more. By doing so, the drying load is reduced.

(Fluorine or silicone surfactant)
The low refractive index layer preferably contains a fluorine-based or silicone-based surfactant. Inclusion of the surfactant is effective for reducing coating unevenness and improving the antifouling property of the film surface.

  Fluorosurfactants include perfluoroalkyl group-containing monomers, oligomers, and polymers as the core, and include derivatives such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, and polyoxyethylene. It is done.

  Commercially available products may be used as the fluorosurfactant, for example, Surflon “S-381”, “S-382”, “SC-101”, “SC-102”, “SC-103”, “SC-104”. (All manufactured by Asahi Glass Co., Ltd.), Florard "FC-430", "FC-431", "FC-173" (all manufactured by Fluorochemicals-Sumitomo 3M), Ftop "EF352", "EF301", " EF303 "(both manufactured by Shin-Akita Kasei Co., Ltd.), Schwego Fureer" 8035 "," 8036 "(all manufactured by Schwegman)," BM1000 "," BM1100 "(all manufactured by BM Himmy), Mega For example, “F-171” and “F-470” (both manufactured by Dainippon Ink and Chemicals, Inc.) can be used.

  The fluorine content of the fluorosurfactant in the present invention is 0.05 to 2% by mass, preferably 0.1 to 1% by mass. The above-mentioned fluorosurfactants can be used alone or in combination of two or more, and can be used in combination with other surfactants.

  The silicone oil or silicone surfactant will be described.

  Silicone oils used in the present invention can be broadly classified into straight silicone oils and modified silicone oils depending on the type of organic groups bonded to silicon atoms. Here, the straight silicone oil refers to one in which a methyl group, a phenyl group, or a hydrogen atom is bonded as a substituent. A modified silicone oil is one having a component that is secondarily derived from a straight silicone oil. On the other hand, it can be classified from the reactivity of silicone oil. These are summarized as follows.

Silicone oil Straight silicone oil 1-1. Non-reactive silicone oil: dimethyl, methylphenyl substitution, etc. 1-2. Reactive silicone oil: methyl hydrogen substitution, etc. Modified silicone oil: Modified silicone oil was born by introducing various organic groups into dimethyl silicone oil 2-1. Non-reactive silicone oil: alkyl, alkyl / aralkyl, alkyl / polyether, polyether, higher fatty acid ester substitution, etc. Alkyl / aralkyl-modified silicone oil: a part of methyl group of dimethyl silicone oil is a long-chain alkyl group or phenylalkyl group Silicone oil substituted with Polyether-modified silicone oil: Silicone polymer surfactant with hydrophilic polyoxyalkylene introduced into hydrophobic dimethyl silicone Higher fatty acid-modified silicone oil: Higher part of methyl group of dimethyl silicone oil Silicone oil substituted with fatty acid ester Amino-modified silicone oil: Silicone oil having a structure in which a part of methyl group of silicone oil is substituted with aminoalkyl group Epoxy-modified silicone oil: Siri Silicone oil with a structure in which part of the methyl group of corn oil is substituted with an epoxy group-containing alkyl group Carboxyl-modified or alcohol-modified silicone oil: A structure in which a part of the methyl group of silicone oil is substituted with a carboxyl group or a hydroxyl group-containing alkyl group Silicone oil having 2-2. Reactive silicone oil: amino, epoxy, carboxyl, alcohol substitution, etc. Of these, polyether-modified silicone oil is preferably added. The number average molecular weight of the polyether-modified silicone oil is, for example, 1,000 to 100,000, preferably 2,000 to 50,000. When the number average molecular weight is less than 1,000, the drying property of the coating film On the contrary, when the number average molecular weight exceeds 100,000, it tends to be difficult to bleed out on the surface of the coating film.

  Specific products include Nihon Unicar Corporation L-45, L-9300, FZ-3704, FZ-3703, FZ-3720, FZ-3786, FZ-3501, FZ-3504, FZ-3508, FZ-. 3705, FZ-3707, FZ-3710, FZ-3750, FZ-3760, FZ-3785, FZ-3785, Y-7499, Shin-Etsu Chemical KF96L, KF96, KF96H, KF99, KF54, KF965, KF968, KF56, KF995, KF351, KF351A, KF352, KF353, KF354, KF355, KF615, KF618, KF945, KF6004, FL100, and the like.

  The silicone surfactant used in the present invention is a surfactant obtained by substituting a part of the methyl group of the silicone oil with a hydrophilic group. The position of substitution includes a side chain of silicone oil, both ends, one end, both end side chains, and the like. Examples of the hydrophilic group include polyether, polyglycerin, pyrrolidone, betaine, sulfate, phosphate, and quaternary salt.

  As the silicone surfactant, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene is preferable.

  A nonionic surfactant is a generic term for surfactants that do not have a group capable of dissociating into ions in an aqueous solution. In addition to a hydrophobic group, a hydrophilic group includes a hydroxyl group of a polyhydric alcohol, a polyoxyalkylene chain (poly Oxyethylene) or the like as a hydrophilic group. The hydrophilicity becomes stronger as the number of alcoholic hydroxyl groups increases and as the polyoxyalkylene chain (polyoxyethylene chain) becomes longer. The nonionic surfactant according to the present invention is characterized by having dimethylpolysiloxane as a hydrophobic group.

  When a nonionic surfactant composed of dimethylpolysiloxane with a hydrophobic group and polyoxyalkylene with a hydrophilic group is used, unevenness of the low refractive index layer and antifouling property of the film surface are improved. It is thought that the hydrophobic group made of polymethylsiloxane is oriented on the surface and forms a film surface that is not easily soiled. This effect cannot be obtained by using other surfactants.

  Specific examples of these nonionic surfactants include, for example, silicone surfactants manufactured by Nippon Unicar Co., Ltd., SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ- 2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164, FZ-2166, FZ-2191, etc. are mentioned.

  Moreover, SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, etc. are mentioned.

  In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. It is preferably a linear block copolymer. Since the main chain skeleton has a long chain length and a linear structure, it is excellent. This is considered to be due to the fact that one activator molecule can be adsorbed on the surface of the silica fine particle at a plurality of locations so as to cover the surface of the silica fine particle by being a block copolymer in which hydrophilic groups and hydrophobic groups are alternately repeated.

  Specific examples include silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208, and FZ-2222 manufactured by Nippon Unicar Co., Ltd.

  Among these silicone oils or silicone surfactants, those having a polyether group are preferred.

  Further, surfactant BYK series, BYK-300 / 302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, manufactured by BYK Japan 325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-340, BYK-344, BYK-370, BYK-375, BYK-377, BYK-352, BYK-354, BYK-355 / 356, BYK-358N / 361N, BYK-357, BYK-390, BYK-392, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-Silclean3700, dimethyl silicone series manufactured by GE Toshiba Silicone, XC96-723, YF380 , It can be preferably used XF3905, YF3057, YF3807, YF3802, YF3897.

  Other surfactants may also be used in combination. For example, anionic surfactants such as sulfonates, sulfates, phosphates, etc., and ethers having polyoxyethylene chain hydrophilic groups Type, ether ester type nonionic surfactants and the like may be used in combination.

  In the present invention, these silicone oils or silicone surfactants are preferably used in the low refractive index layer and the layer adjacent to the low refractive index layer, specifically, the antiglare layer and the high refractive index layer. When the low refractive index layer is the outermost surface layer of the antireflection film, it not only improves the water repellency, oil repellency and antifouling properties of the coating film, but also exhibits an effect on the scratch resistance of the surface. The content in the coating solution for the low refractive index layer is preferably 0.05 to 2.0% by mass from the viewpoint of crack resistance effect and coating unevenness.

(acid)
In the present invention, by adding an acid to the coating composition for the low refractive index layer, alkaline components such as ammonia are eluted from the inside of the hollow fine particles, and the coating composition for the low refractive index layer is prepared after the coating solution is prepared and applied. It is also possible to prevent the viscosity of the product from increasing.

  Examples of the acid to be added include known inorganic acids and organic acids. In the present invention, organic acids are preferable. Examples of the organic acid include acetic acid, formic acid, propionic acid, etc. Among them, acetic acid is preferable. The addition amount of the organic acid is an amount corresponding to an alkali component such as ammonia from the inside of the hollow fine particles, and an acid, for example, acetic acid, for example, 5 to 100 mass% is added to the solid content in the hollow fine particle dispersion. Depending on the concentration of the hollow fine particle dispersion, it is usually preferable to add the acid in the range of 0.5 to 30.0% by mass of the hollow fine particle dispersion.

(High refractive index layer)
Various functional layers can be provided between the transparent film substrate and the low refractive index layer. A typical example of the high refractive index layer will be described.

(Metal oxide fine particles of high refractive index layer)
The high refractive index layer preferably contains metal oxide fine particles. The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from the group consisting of Al, In, Sn, Sb, Nb, a halogen element, Ta and the like is doped with a trace amount of atoms. May be. A mixture of these may also be used. In the present invention, at least one metal oxide fine particle selected from among zirconium oxide, antimony oxide, tin oxide, zinc oxide, indium-tin oxide (ITO), antimony-doped tin oxide (ATO), and zinc antimonate is used. It is preferably used as a main component, particularly preferably zinc antimonate.

  The average particle size of primary particles of these metal oxide fine particles is preferably 10 to 200 nm, more preferably 10 to 150 nm. The average particle diameter of the metal oxide fine particles can be measured from an electron micrograph taken with a scanning electron microscope (SEM) or the like. You may measure by the particle size distribution meter etc. which utilize a dynamic light scattering method, a static light scattering method, etc. If the particle size is too small, aggregation tends to occur and the dispersibility deteriorates. If the particle size is too large, the haze is remarkably increased. The shape of the metal oxide fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a needle shape, or an indefinite shape.

  Specifically, the refractive index of the high refractive index layer is higher than the refractive index of the transparent film substrate as a support, and is preferably in the range of 1.50 to 1.90 at 23 ° C. and a wavelength of 550 nm. . As a means for adjusting the refractive index of the high refractive index layer, the kind and addition amount of the metal oxide fine particles are dominant, and therefore the refractive index of the metal oxide fine particles is preferably 1.80 to 2.60.

  The metal oxide fine particles may be surface-treated with an organic compound. By modifying the surface of the metal oxide fine particles with an organic compound, the dispersion stability in an organic solvent is improved, the dispersion particle size can be easily controlled, and aggregation and sedimentation over time can be suppressed. . For this reason, the surface modification amount with a preferable organic compound is 0.1-5 mass% with respect to metal oxide particle, More preferably, it is 0.5-3 mass%. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Among these, the silane coupling agent mentioned later is preferable. Two or more kinds of surface treatments may be combined.

  The thickness of the high refractive index layer containing metal oxide fine particles is preferably 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably 30 nm to 0.1 μm.

  The ratio of the metal oxide fine particles to be used and a binder such as an active energy ray curable resin, which will be described later, varies depending on the type and particle size of the metal oxide fine particles. On the other hand, the latter one is preferable.

  The amount of the metal oxide fine particles used in the present invention is preferably 5 to 85% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 75% by mass in the high refractive index layer. If the amount used is small, the desired refractive index and the effect of the present invention cannot be obtained, and if it is too large, the film strength is deteriorated.

  The metal oxide fine particles are supplied to a coating solution for forming a high refractive index layer in a dispersion state dispersed in a medium. As a dispersion medium for metal oxide particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Specific examples of the dispersion solvent include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ketone alcohol (eg, diacetone alcohol). , Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene) Chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, Tiger hydrofuran), ether alcohols (e.g., 1-methoxy-2-propanol), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable.

  The metal oxide fine particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  In the present invention, metal oxide fine particles having a core / shell structure may be further contained. One layer of the shell may be formed around the core, or a plurality of layers may be formed in order to further improve the light resistance. The core is preferably completely covered by the shell.

  As the core, titanium oxide (rutile type, anatase type, amorphous type, etc.), zirconium oxide, zinc oxide, cerium oxide, indium oxide doped with tin, tin oxide doped with antimony, or the like can be used.

  The shell is preferably formed of a metal oxide or sulfide containing an inorganic compound other than titanium oxide as a main component. For example, an inorganic compound mainly composed of silicon dioxide (silica), aluminum oxide (alumina) zirconium oxide, zinc oxide, tin oxide, antimony oxide, indium oxide, iron oxide, zinc sulfide, or the like is used. Of these, alumina, silica, and zirconia (zirconium oxide) are preferable. A mixture of these may also be used.

  The coating amount of the shell with respect to the core is 2 to 50% by mass as an average coating amount. Preferably it is 3-40 mass%, More preferably, it is 4-25 mass%. When the coating amount of the shell is large, the refractive index of the fine particles is lowered, and when the coating amount is too small, the light resistance is deteriorated. Two or more inorganic fine particles may be used in combination.

  The titanium oxide used as a core can use what was produced by the liquid phase method or the gaseous-phase method. As a method for forming the shell around the core, for example, US Pat. No. 3,410,708, Japanese Examined Patent Publication No. 58-47061, US Pat. No. 2,885,366, and US Pat. No. 3,437. No. 1,502, British Patent No. 1,134,249, US Pat. No. 3,383,231, British Patent No. 2,629,953, No. 1,365,999. Can be used.

(Active energy ray-curable resin)
The active energy ray curable resin is added as a binder for the metal oxide fine particles in order to improve the film formability and physical properties of the coating film. The active energy ray-curable resin has 2 functional groups that cause a polymerization reaction directly or indirectly by the action of a photopolymerization initiator by irradiation with ionizing radiation such as ultraviolet rays and electron beams as described above and below. One or more monomers or oligomers can be used. Examples of the functional group include a group having an unsaturated double bond such as a (meth) acryloyloxy group, an epoxy group, and a silanol group. Among these, radically polymerizable monomers and oligomers having two or more unsaturated double bonds can be preferably used. You may combine a photoinitiator as needed. Examples of such active energy ray-curable resins include polyfunctional acrylate compounds, and the like, and are composed of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. A compound selected from the group is preferred. Here, the polyfunctional acrylate compound is a compound having two or more acryloyloxy groups and / or methacryloyloxy groups in the molecule.

  Examples of the monomer of the polyfunctional acrylate compound include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethanetriacrylate. Acrylate, tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, glycerin triacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, Dipen Erythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetra Methylol methane trimethacrylate, tetramethylol methane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerin trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol te La methacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, isobornyl acrylate preferably. These compounds are used alone or in admixture of two or more. Moreover, oligomers, such as a dimer and a trimer of the said monomer, may be sufficient.

  The addition amount of the active energy ray-curable resin is preferably 15% by mass or more and less than 50% by mass in the solid content in the high refractive index composition.

  In order to accelerate the curing of the active energy ray-curable resin, a photopolymerization initiator and an acrylic compound having two or more polymerizable unsaturated bonds in the molecule are contained in a mass ratio of 3: 7 to 1: 9. Is preferred.

  Specific examples of the photopolymerization initiator include acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof, but are not particularly limited thereto.

(solvent)
Examples of the organic solvent used for coating the high refractive index layer include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol). , Benzyl alcohol, etc.), polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thio Diglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl ether, Lenglycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ether) Range amine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) ), Heterocyclic rings (for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide) , Sulfones (e.g., sulfolane), urea, acetonitrile, acetone and the like, and alcohols, polyhydric alcohols, and polyhydric alcohol ethers are particularly preferable.

[Back coat layer]
The antiglare and antiglare film of the present invention is preferably provided with a backcoat layer on the side opposite to the side on which the antiglare and antireflection layer of a transparent film substrate such as a cellulose ester film is provided. The back coat layer is provided in order to correct curl caused by providing an active energy ray-curable resin layer or other layers. That is, the degree of curling can be balanced by imparting the property of being rounded with the surface on which the backcoat layer is provided facing inward. The backcoat layer is preferably applied also as an antiblocking layer. In this case, it is preferable that fine particles are added to the backcoat layer coating composition in order to provide an antiblocking function.

  As fine particles added to the back coat layer, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, tin oxide, and oxidation. Mention may be made of indium, zinc oxide, ITO, hydrated calcium silicate, aluminum silicate, magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low haze, and silicon dioxide is particularly preferable.

  These fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). Zirconium oxide fine particles are commercially available, for example, under the names of Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) and can be used. Examples of the polymer include silicone resin, fluororesin, and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) Are commercially available and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large anti-blocking effect while keeping haze low. In the antiglare film used in the present invention, the dynamic friction coefficient on the back side of the active energy ray-curable resin layer is preferably 0.9 or less, particularly preferably 0.1 to 0.9.

  The fine particles contained in the backcoat layer are 0.1 to 50% by weight, preferably 0.1 to 10% by weight, based on the binder. When the back coat layer is provided, the increase in haze is preferably 1% or less, more preferably 0.5% or less, and particularly preferably 0.0 to 0.1%.

  Specifically, the back coat layer is formed by applying a composition containing a solvent for dissolving or swelling a cellulose ester film. The solvent to be used may include a solvent to be dissolved and / or a solvent to be swollen in addition to a solvent to be dissolved, a composition in which these are mixed at an appropriate ratio depending on the curl degree of the transparent resin film and the type of the resin, and This is done using the coating amount.

  In order to enhance the curl prevention function, it is effective to increase the mixing ratio of the solvent for dissolving the solvent composition to be used and / or the solvent for swelling, and to decrease the ratio of the solvent not to be dissolved. This mixing ratio is preferably (solvent to be dissolved and / or solvent to be swollen) :( solvent to be dissolved) = 10: 0 to 1: 9. Examples of the solvent for dissolving or swelling the transparent resin film contained in such a mixed composition include dioxane, acetone, methyl ethyl ketone, N, N-dimethylformamide, methyl acetate, ethyl acetate, trichloroethylene, methylene chloride, and ethylene chloride. , Tetrachloroethane, trichloroethane, chloroform and the like. Examples of the solvent that does not dissolve include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butanol, cyclohexanol, and hydrocarbons (toluene, xylene).

  These coating compositions are preferably applied to the surface of the transparent resin film with a wet film thickness of 1 to 100 μm using a gravure coater, dip coater, reverse coater, wire bar coater, die coater, spray coating, ink jet coating or the like. Is particularly preferably 5 to 30 μm. Examples of the resin used as the binder of the backcoat layer include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer. Polymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Vinyl polymer or copolymer, nitrocellulose, cellulose acetate propionate (preferably acetyl group substitution degree 1.2-2.3, propionyl group substitution degree 0.1-1.0), diacetyl cellulose, cellulose Cellulose derivatives such as acetate butyrate resin, maleic acid and / or Or acrylic acid copolymer, acrylic ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin Rubber resins such as polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene-butadiene resin, butadiene-acrylonitrile resin, Examples thereof include, but are not limited to, silicone resins and fluorine resins. For example, as an acrylic resin, Acrypet MD, VH, MF, V (manufactured by Mitsubishi Rayon Co., Ltd.), Hyperl M-4003, M-4005, M-4006, M-4202, M-5000, M-5001, M -4501 (manufactured by Negami Kogyo Co., Ltd.), Dialnal BR-50, BR-52, BR-53, BR-60, BR-64, BR-73, BR-75, BR-77, BR-79, BR- 80, BR-82, BR-83, BR-85, BR-87, BR-88, BR-90, BR-93, BR-95, BR-100, BR-101, BR-102, BR-105, BR-106, BR-107, BR-108, BR-112, BR-113, BR-115, BR-116, BR-117, BR-118, etc. (Mitsubishi Rayon Co., Ltd.) acrylic Fine methacrylic monomer are commercially available various homopolymers and copolymers, etc. was prepared as a raw material, it is also possible to select a preferred mono from this appropriate.

  Particularly preferred are cellulosic resin layers such as diacetylcellulose, triacetylcellulose, cellulose acetate propionate, and cellulose acetate butyrate.

  The order of coating the backcoat layer may be before or after coating the active energy ray-curable resin layer of the cellulose ester film, but when the backcoat layer also serves as an antiblocking layer, it is desirable to coat it first. . Alternatively, the backcoat layer can be applied in two or more steps.

[Transparent film substrate]
Below, the transparent film base material which can be used by this invention is demonstrated.

  The transparent film substrate used in the present invention is easy to manufacture, has good adhesion to the actinic radiation curable resin layer, is optically isotropic, and is optically transparent. Etc. are mentioned as preferable requirements.

  The transparent film substrate of the present invention is particularly preferably 1.4 to 4 m from the viewpoint of planarity.

  The term “transparent” as used in the present invention means that the visible light transmittance is 60% or more, preferably 80% or more, and particularly preferably 90% or more.

  Although it will not specifically limit if it has said property, For example, a cellulose-ester-type film, a polyester-type film, a polycarbonate-type film, a polyarylate-type film, a polysulfone (a polyethersulfone is also included) film, a polyethylene terephthalate, polyethylene Polyester film such as naphthalate, polyethylene film, polypropylene film, cellophane, cellulose diacetate film, cellulose triacetate, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Syndiotactic polystyrene film, polycarbonate film, cycloolefin Polymer film (Arton (manufactured by JSR), ZEONEX, ZEONOR (manufactured by ZEON CORPORATION)), polymethylpentene film, polyetherketone film, polyetherketoneimide film, polyamide film, fluororesin film, nylon film, poly A methyl methacrylate film, an acrylic film, a glass plate, etc. can be mentioned. Among them, cellulose triacetate film, polycarbonate film, and polysulfone (including polyethersulfone) are preferable, and in the present invention, cellulose ester film (for example, Konica Minoltack, product names KC8UX2MW, KC4UX2MW, KC8UY, KC4UNY, KC5UN, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4UEW, KC4FR-1, KC4FR-2 (manufactured by Konica Minolta Opto Corporation)) are from the viewpoint of manufacturing, cost, transparency, isotropy, adhesiveness, etc. Are preferably used. These films may be films produced by melt casting film formation or films produced by solution casting film formation.

(Cellulose ester)
In the present invention, it is preferable to use a cellulose ester film as the transparent film substrate. As the cellulose ester, cellulose acetate, cellulose acetate butyrate, and cellulose acetate propionate are preferable. Among these, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate propionate, and cellulose acetate butyrate are preferably used.

  In particular, when the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, X and Y are active ray curable resins on a transparent film substrate having a mixed fatty acid ester of cellulose in the following range A low reflection laminate having a layer and an antireflection layer is preferably used.

2.3 ≦ X + Y ≦ 3.0 0.1 ≦ Y ≦ 2.0
In particular, it is preferable that 2.4 ≦ X + Y ≦ 2.9 0.3 ≦ Y ≦ 1.5.

  When a cellulose ester is used as the transparent film substrate used in the present invention, the cellulose used as the raw material for the cellulose ester is not particularly limited, and examples include cotton linters, wood pulp (derived from coniferous trees, derived from hardwoods), kenaf, and the like. Can do. Moreover, the cellulose ester obtained from them can be mixed and used in arbitrary ratios, respectively. When the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride), these cellulose esters use an organic solvent such as acetic acid or an organic solvent such as methylene chloride, and It can be obtained by reacting with a cellulose raw material using a protic catalyst.

When the acylating agent is acid chloride (CH ₃ COCl, C ₂ H ₅ COCl, C ₃ H ₇ COCl), the reaction is performed using a basic compound such as an amine as a catalyst. Specifically, it can be synthesized with reference to the method described in JP-A-10-45804. In addition, the cellulose ester used in the present invention is obtained by mixing and reacting the amount of the acylating agent in accordance with the degree of substitution. In the cellulose ester, these acylating agents react with hydroxyl groups of cellulose molecules. Cellulose molecules are composed of many glucose units linked together, and the glucose unit has three hydroxyl groups. The number of acyl groups derived from these three hydroxyl groups is called the degree of substitution (mol%). For example, cellulose triacetate has acetyl groups bonded to all three hydroxyl groups of the glucose unit (actually 2.6 to 3.0).

  As the degree of substitution of the cellulose ester used in the present invention, the cellulose ester in which the 2-position, 3-position, and 6-position may be substituted with an acyl group on average, or the 6-position is more or less substituted is also preferably used. It is done. The substitution degree at the 6-position is preferably 0.7 to 0.97, more preferably 0.8 to 0.97.

  As the cellulose ester used in the present invention, a mixed fatty acid ester of cellulose in which a propionate group or a butyrate group is bonded in addition to an acetyl group such as cellulose acetate propionate, cellulose acetate butyrate, or cellulose acetate propionate butyrate Is particularly preferably used. The butyryl group that forms butyrate may be linear or branched.

  Cellulose acetate propionate containing a propionate group as a substituent has excellent water resistance and is useful as a film for liquid crystal image display devices.

  The measuring method of the substitution degree of an acyl group can be measured according to the rule of ASTM-D817-96.

  The number average molecular weight of the cellulose ester is preferably 70000 to 250,000, since it has high mechanical strength when molded and an appropriate dope viscosity, and more preferably 80000 to 150,000.

  These cellulose ester films are prepared by applying a cellulose ester solution (dope) generally called a solution casting film forming method onto, for example, an endless metal belt for infinite transfer or a support for casting of a rotating metal drum. It is preferable to manufacture the dope from a pressure die by casting (casting).

(Organic solvent)
As the organic solvent used for preparing these dopes, it is preferable that the cellulose ester can be dissolved and has an appropriate boiling point, such as methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2- Propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3 3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone, etc. DOO but can, methylene chloride organic halogen compounds such as chloride, dioxolane derivatives, methyl acetate, ethyl acetate, acetone, methyl acetoacetate, and the like are preferable organic solvents (i.e., good solvent), and as.

  Moreover, as shown in the following film forming process, it is used from the viewpoint of preventing foaming in the web when the solvent is dried from the web (dope film) formed on the casting support in the solvent evaporation process. The boiling point of the organic solvent is preferably 30 to 80 ° C. For example, the good solvent described above has a boiling point of methylene chloride (boiling point 40.4 ° C), methyl acetate (boiling point 56.32 ° C), acetone (boiling point 56.56 ° C). 3 ° C.), ethyl acetate (boiling point 76.82 ° C.) and the like.

  Among the good solvents described above, methylene chloride or methyl acetate having excellent solubility is preferably used.

  In addition to the organic solvent, it is preferable to contain 0.1 to 40% by mass of an alcohol having 1 to 4 carbon atoms. It is particularly preferable that the alcohol is contained at 5 to 30% by mass. After casting the dope described above onto a casting support, the solvent starts to evaporate and the alcohol ratio increases and the web (dope film) gels, making the web strong and peeling from the casting support. It is also used as a gelling solvent for facilitating the dissolution, and when these ratios are small, it also has a role of promoting the dissolution of the cellulose ester of the non-chlorine organic solvent.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol and the like.

  Of these solvents, ethanol is preferred because it has good dope stability, relatively low boiling point, good drying properties, and no toxicity. It is preferable to use a solvent containing 5 to 30% by mass of ethanol with respect to 70 to 95% by mass of methylene chloride. Methyl acetate can be used in place of methylene chloride. At this time, the dope may be prepared by a cooling dissolution method.

  Alternatively, methylene chloride and methyl acetate can be used in combination, for example, in a mass ratio of 10.1 to 3. It is preferable to further contain the alcohol described above.

(Plasticizer)
When a cellulose ester film is used for the antiglare film of the present invention, it is preferable to contain the following plasticizer. Examples of plasticizers include phosphate ester plasticizers, phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid plasticizers, glycolate plasticizers, citrate ester plasticizers, and polyesters. A plasticizer, a polyhydric alcohol ester plasticizer, or the like can be preferably used.

  For phosphate plasticizers, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenylbiphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc. For phthalate ester plasticizers, diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, butyl benzyl phthalate, diphenyl phthalate, dicyclohexyl phthalate, and other trimellitic acid plasticizers include tributyl trimellitate, triphenyl trimellitate, triethyl For pyromellitic acid ester plasticizers such as trimellitate, tetrabutylpyromellitate, In the case of glycolate plasticizers such as lupyromelitate and tetraethylpyromellitate, triacetin, tributyrin, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate, etc. Citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n- (2-ethylhexyl) citrate and the like can be preferably used. Examples of other carboxylic acid esters include trimethylolpropane tribenzoate, butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters.

  The polyhydric alcohol ester plasticizer is a plasticizer comprising an ester of a dihydric or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester.

  As the polyester plasticizer, a copolymer of a dibasic acid and a glycol such as an aliphatic dibasic acid, an alicyclic dibasic acid, or an aromatic dibasic acid can be used. The aliphatic dibasic acid is not particularly limited, and adipic acid, sebacic acid, phthalic acid, terephthalic acid, 1,4-cyclohexyl dicarboxylic acid, and the like can be used. As glycol, ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol and the like can be used. These dibasic acids and glycols may be used alone or in combination of two or more.

  The amount of these plasticizers used is preferably from 1 to 20% by mass, particularly preferably from 3 to 13% by mass, based on the cellulose ester, in terms of film performance, processability and the like.

(UV absorber)
For the antiglare film of the present invention, an ultraviolet absorber is preferably used. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having a small absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties.

  Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, oxybenzophenone compounds, benzotriazole compounds, triazine compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. For example, but not limited to.

  Specific examples of the benzotriazole-based ultraviolet absorbers include the following ultraviolet absorbers, but the present invention is not limited thereto.

UV-1: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole UV-2: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole UV-3 : 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole UV-4: 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl)- 5-Chlorobenzotriazole UV-5: 2- (2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl) benzotriazole UV-6: 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol)
UV-7: 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole UV-8: 2- (2H-benzotriazol-2-yl) -6 (Linear and side chain dodecyl) -4-methylphenol (TINUVIN171, manufactured by Ciba)
UV-9: Octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl- Mixture of 4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate (TINUVIN 109, manufactured by Ciba)
Moreover, although the following specific example is shown as a benzophenone series ultraviolet absorber, this invention is not limited to these.

UV-10: 2,4-dihydroxybenzophenone UV-11: 2,2'-dihydroxy-4-methoxybenzophenone UV-12: 2-hydroxy-4-methoxy-5-sulfobenzophenone UV-13: Bis (2-methoxy -4-hydroxy-5-benzoylphenylmethane)
As the ultraviolet absorber preferably used in the present invention, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber that are highly transparent and excellent in preventing the deterioration of the polarizing plate and the liquid crystal are preferable, and unnecessary coloring is less. A benzotriazole-based ultraviolet absorber is particularly preferably used.

  Moreover, the ultraviolet absorber whose distribution coefficient described in Unexamined-Japanese-Patent No. 2001-187825 is 9.2 or more improves the surface quality of a long film, and is excellent also in applicability | paintability. In particular, it is preferable to use an ultraviolet absorber having a distribution coefficient of 10.1 or more.

  Further, the polymer ultraviolet ray described in the general formula (1) or general formula (2) described in JP-A-6-148430 and the general formulas (2), (6), and (7) described in Japanese Patent Application No. 2000-156039. Absorbers (or UV absorbing polymers) are also preferably used. As a polymer ultraviolet absorber, PUVA-30M (manufactured by Otsuka Chemical Co., Ltd.) and the like are commercially available.

(Fine particles)
Moreover, in order to provide slipperiness to the cellulose ester film used in the present invention, the following fine particles can be used.

  As fine particles, examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, Mention may be made of magnesium silicate and calcium phosphate. Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.

  The average primary particle size of the fine particles is preferably 5 to 50 nm, and more preferably 7 to 20 nm. These are preferably contained mainly as secondary aggregates having a particle size of 0.05 to 0.3 μm. The content of these fine particles in the cellulose ester film is preferably 0.05 to 1% by mass, particularly preferably 0.1 to 0.5% by mass. In the case of a cellulose ester film having a multilayer structure by the co-casting method, it is preferable to contain fine particles of this addition amount on the surface.

  Silicon dioxide fine particles are commercially available under the trade names of, for example, Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). .

  Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.), and can be used.

  Polymer fine particles can also be used, and examples thereof include silicone resin, fluororesin, and acrylic resin. Among these, silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120 and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed under the trade name of and can be used.

  Among these, Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the cellulose ester film low. In the cellulose ester film used in the present invention, the dynamic friction coefficient on the back side of the active energy ray-curable resin layer is preferably 1.0 or less.

(Method for producing cellulose ester film)
The cellulose ester film of the present invention can be preferably used regardless of whether it is produced by a solution casting film forming method or a melt casting film forming method.

  Hereinafter, a method for producing a cellulose ester film will be described by taking a solution casting film forming method as an example.

  The cellulose ester film is produced by dissolving the cellulose ester and additives in a solvent to prepare a dope, casting the dope on a belt-like or drum-like metal support, and drying the cast dope as a web. It is performed by the process of carrying out, the process of peeling from a metal support body, the process of extending | stretching or maintaining width, the process of drying further, and the process of winding up the finished film.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. The concentration for achieving both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.

  The solvent used in the dope may be used alone or in combination of two or more, but it is preferable to use a mixture of a good solvent and a poor solvent of cellulose ester in terms of production efficiency, and there are many good solvents. This is preferable from the viewpoint of the solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as the solvent, the cellulose ester acetate ester (acetyl group substitution degree 2.4) and cellulose acetate propionate are good. As a solvent, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  As a method for dissolving the cellulose ester when preparing the dope, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  The heating temperature with the addition of the solvent is preferably higher from the viewpoint of the solubility of the cellulose ester. However, if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  A cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  Next, this cellulose ester solution is filtered using a suitable filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

A bright spot foreign substance is when two polarizing plates are placed in a crossed Nicol state, a cellulose ester film is placed between them, light is applied from the side of one polarizing plate, and observed from the side of the other polarizing plate. It is a point (foreign matter) where light from the opposite side appears to leak, and the number of bright spots having a diameter of 0.01 mm or more is preferably 200 / cm ² or less. More preferably, it is 100 pieces / cm < ² > or less, More preferably, it is 50 pieces / m < ² > or less, More preferably, it is 0-10 pieces / cm < ² > or less. Further, it is preferable that the number of bright spots of 0.01 mm or less is small.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Next, dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. A preferable metal support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to efficiently dry by changing the temperature of the metal support and the temperature of the drying air during the period from casting to peeling.

  In order for the cellulose ester film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Especially preferably, it is 20-30 mass% or 70-120 mass%.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Where M is the mass of a sample taken during or after production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying step of the cellulose ester film, the web is peeled off from the metal support, and further dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, Especially preferably, it is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  In order to produce the cellulose ester film for the antiglare antireflection film of the present invention, the web is stretched in the conveying direction where the amount of residual solvent of the web is just after peeling from the metal support, and both ends of the web are clipped. It is particularly preferable to perform stretching in the width direction by a tenter method of gripping with. The preferred draw ratio in both the machine direction and the transverse direction is 1.05 to 1.5 times, more preferably 1.05 to 1.3 times, and even more preferably 1.05 to 1.15 times. It is preferable that the area is 1.1 to 2 times by longitudinal and lateral stretching. This can be determined by the draw ratio in the longitudinal direction × the draw ratio in the transverse direction.

  In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 150 ° C, and more preferably from 50 to 140 ° C in order to improve dimensional stability.

  Although the film thickness of a cellulose-ester film is not specifically limited, 10-200 micrometers is used preferably. In particular, it was difficult to obtain an antireflection film excellent in flatness and hardness with a thin film of 10 to 70 μm, but according to the present invention, a thin antireflection film excellent in flatness and hardness was obtained, Moreover, since it is excellent also in productivity, it is especially preferable that the film thickness of a cellulose-ester film is 10-70 micrometers. More preferably, it is 20-60 micrometers. Most preferably, it is 30-60 micrometers. Moreover, the cellulose ester film made into the multilayer structure by the co-casting method can also be used preferably. Even when the cellulose ester has a multilayer structure, it has a layer containing an ultraviolet absorber and a plasticizer, and it may be a core layer, a skin layer, or both.

  As a method of forming an uneven shape having an arithmetic average roughness (Ra) of less than 50 to 1000 nm on the surface of the transparent film substrate, it is preferable to form the transparent film substrate by embossing, for example.

(Configuration of high refractive index layer and low refractive index layer)
Although the preferable laminated structure of an above described high refractive index layer and a low refractive index layer is shown below, it is not limited to these.

Transparent film substrate / antiglare antireflection layer / low refractive index layer Transparent film substrate / antiglare antireflection layer / high refractive index layer / low refractive index layer Transparent film substrate / antistatic layer / antiglare reflection Prevention layer / High refractive index layer / Low refractive index layer Further, the arithmetic average roughness (Ra) of the outermost surface when the high refractive index layer and the low refractive index layer are laminated is 40 to less than 500 nm, preferably 60 to 300 nm. It is preferable to do.

  The arithmetic average roughness (Ra) of the outermost surface can be measured using, for example, an optical interference type surface roughness meter: RST / PLUS (manufactured by WYKO).

  The reflectance when the high refractive index layer and the low refractive index layer are laminated can be measured with a spectrophotometer in the same manner as described above. At that time, after roughening the back surface on the measurement side of the sample as described above, the reflected light in the visible light region (400 to 700 nm) is measured after performing light absorption using a black spray. The reflectance is preferably as low as possible, but the average value in the visible light wavelength is preferably 1.5% or less, and the minimum reflectance is preferably 1.5% or less, and more preferably 1.0% or less. Is preferred. Moreover, it is preferable to have a flat reflection spectrum in the wavelength region of visible light.

  In addition, the reflection hue on the polarizing plate surface when laminating a high refractive index layer and a low refractive index layer is often colored red or blue because the reflectance in the short wavelength region or long wavelength region is high. The color tone of light varies depending on the application, and when used on the outermost surface of an FPD television or the like, a neutral color tone is desired. In this case, generally preferred reflection hue ranges are 0.17 ≦ x ≦ 0.27 and 0.07 ≦ y ≦ 0.17 on the XYZ color system (CIE1931 color system).

  For the high refractive index layer and low refractive index layer, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, micro gravure coating method, inkjet method and extrusion coating method are used. And can be formed by coating.

  Moreover, when performing the said application | coating, it is preferable to take out from the state wound up in roll shape with the width | variety of a transparent film base material being 1.4-4 m, and to wind up in roll shape after drying and hardening processing.

  Further, the antiglare antireflection film in which the high refractive index layer and the low refractive index layer are laminated is preferably produced by a production method in which a heat treatment is performed at 50 to 160 ° C. in a state of being wound into a roll after application. . The period of the heat treatment may be appropriately determined depending on the set temperature. For example, if it is 50 ° C., it is preferably 3 days or more and less than 30 days, if it is 160 ° C., it is 10 minutes or more and 1 day or less. A range is preferred. Usually, it is preferably set at a relatively low temperature so that the heat treatment effect at the outside of the winding, the center of the winding, and the core is not biased, and is preferably performed at around 50 to 60 ° C. for about 7 days.

  In order to stably perform the heat treatment, it is necessary to perform in a place where the temperature and humidity can be adjusted, and it is preferable to perform in a heat treatment chamber such as a clean room without dust.

  When the anti-glare antireflection film is wound into a roll, the winding core is not particularly limited as long as it is a cylindrical core, but is preferably a hollow plastic core, and the plastic material can withstand the heat treatment temperature. A heat resistant plastic is preferable, and examples thereof include resins such as phenol resin, xylene resin, melamine resin, polyester resin, and epoxy resin. A thermosetting resin reinforced with a filler such as glass fiber is preferred.

  The number of windings on these winding cores is preferably 100 windings or more, more preferably 500 windings or more, and the winding thickness is preferably 5 cm or more.

  Thus, when performing the heat treatment in a state of winding the long antiglare antireflection film, it is preferable to rotate the roll, and the rotation is preferably performed at a speed of 1 rotation or less per minute. It may be continuous or intermittent. Moreover, it is preferable to perform rewinding of the roll once or more during the heating period.

  In order to rotate the long antiglare antireflection film wound around the core during the heat treatment, it is preferable to provide a dedicated turntable in the heat treatment chamber.

  In the case of intermittent rotation, it is preferable that the stop time is within 10 hours, the stop position is preferably made uniform in the circumferential direction, and the stop time is within 10 minutes. More preferred. Most preferred is continuous rotation.

  As for the rotation speed in continuous rotation, the time required for one rotation is preferably 10 hours or less, and if it is early, it becomes a burden on the apparatus, so the range of 15 minutes to 2 hours is substantially preferable.

  In the case of a dedicated carriage having a rotation function, it is preferable that the optical film roll can be rotated during movement and storage. In this case, rotation is effective as a countermeasure against black bands that occur when the storage period is long. Function.

(Surface treatment)
The surface of the antiglare antireflection layer is a cleaning method, alkali treatment method, flame plasma treatment method, high frequency discharge plasma method, electron beam method, ion beam method, sputtering method, acid treatment, corona treatment method, atmospheric pressure plasma method, etc. May be processed.

(Corona treatment method)
The corona treatment is a treatment performed by applying a high voltage of 1 kV or higher between the electrodes under atmospheric pressure and discharging it, using a device commercially available from Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be done. The intensity of the corona discharge treatment depends on the distance between the electrodes, the output per unit area, and the generator frequency. As one electrode (A electrode) of the corona treatment apparatus, a commercially available one can be used, but the material can be selected from aluminum, stainless steel and the like. The other is an electrode (B electrode) for holding a plastic film, and is a roll electrode installed at a certain distance from the A electrode so that the corona treatment is carried out stably and uniformly. A commercially available one can also be used, and the material is preferably a roll made of aluminum, stainless steel, or a metal thereof and lined with ceramic, silicone, EPT rubber, hyperon rubber, or the like. It is done. The frequency used for the corona treatment used in the present invention is a frequency of 20 to 100 kHz, and a frequency of 30 to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Occurs. The output of the corona treatment is 1 to 5 w · min. / M 2, but 2 to 4 w · min. An output of / m @ 2 is preferred. The distance between the electrode and the film is 5 to 50 mm, preferably 10 to 35 mm. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

(Alkaline treatment method)
The alkali treatment method is not particularly limited as long as it is a method in which a film provided with an antiglare layer is immersed in an aqueous alkali solution.

  As the aqueous alkali solution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonia solution or the like can be used, and an aqueous sodium hydroxide solution is particularly preferable.

  The alkali concentration of the aqueous alkali solution, for example, sodium hydroxide concentration is preferably 0.1 to 25% by mass, and more preferably 0.5 to 15% by mass.

  The alkali treatment temperature is usually 10 to 80 ° C, preferably 20 to 60 ° C. The alkali treatment time is 5 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The film after the alkali treatment is preferably sufficiently washed with water after neutralization with acidic water.

(Atmospheric pressure plasma method)
In the present invention, a discharge is formed by applying a high-frequency voltage having a frequency of 50 kHz to 150 MHz between opposing electrodes under atmospheric pressure or a pressure in the vicinity thereof, and the excitation gas formed by the discharge is converted into a transparent film substrate. It is preferable to form the antireflection layer by coating after contacting the surface of the film having the antiglare layer on the material or the transparent film substrate.

  The frequency is preferably 50 kHz to 27 MHz. The opposing electrodes are composed of a first electrode and a second electrode, and the frequency of the high-frequency voltage applied to any one of the electrodes is preferably 50 kHz to 150 MHz. Moreover, it is preferable that the frequency of the high frequency voltage applied to the first electrode is 1 to 200 kHz, and the frequency of the high frequency voltage applied to the second electrode is 800 kHz to 150 MHz.

  Hereinafter, the plasma discharge treatment performed under atmospheric pressure or a pressure in the vicinity thereof is also simply referred to as an atmospheric pressure plasma method.

  That is, the present invention provides a transparent film substrate or a film having an antiglare layer on the transparent film substrate, between the opposing electrodes constituted by the first electrode and the second electrode under atmospheric pressure or a pressure in the vicinity thereof, A high frequency voltage having a voltage component of the first frequency ω1 is applied to the first electrode, and a high frequency voltage having a voltage component of the second frequency ω2 is applied to the second electrode to form a discharge. After bringing the surface of the transparent film substrate into contact with the excited gas, an antireflection layer is formed thereon.

  As the atmospheric pressure plasma method applicable to the present invention, JP-A-11-133205, JP-A-2000-185362, JP-A-11-61406, JP-A-2000-147209, 2000-121804 are disclosed. The technology disclosed in the above can be referred to.

  The atmospheric pressure plasma method will be described below.

  First, the atmospheric pressure plasma method and apparatus useful for the present invention will be described.

  In the present invention, a gas is supplied to the discharge space (between the counter electrodes) at atmospheric pressure or in the vicinity thereof, a high-frequency voltage is applied to the discharge space, and the gas is excited into a plasma state. A transparent film substrate or the surface of a film having an antiglare layer on the transparent film substrate is exposed to a gas in a state. The high frequency voltage applied to the discharge space formed between the counter electrodes may be a high frequency of one frequency, or may be a high frequency of two or more frequencies.

  In the present invention, the atmospheric pressure plasma treatment is performed under atmospheric pressure or a pressure in the vicinity thereof, and the atmospheric pressure or the pressure in the vicinity thereof is about 20 to 110 kPa, so that the good effects described in the present invention can be obtained. Is preferably 93 to 104 kPa.

  In the present invention, the gas supplied between the counter electrodes (discharge space) is at least an excitation gas excited by a high-frequency voltage, or a gas that receives an excitation gas excited by a high-frequency voltage and its energy and enters a plasma state or an excited state. Including. The high frequency as used in the field of this invention means what has a frequency of at least 0.5 kHz.

  When plasma discharge treatment is performed with a high frequency voltage of one frequency (sometimes referred to as a one-frequency high-frequency voltage application method), or when plasma discharge treatment is performed with a high-frequency voltage of two frequencies (sometimes referred to as a two-frequency high-frequency voltage application method). The same electrodes can be used, and the apparatus itself is not significantly different. The difference is that there are two high-frequency power supplies and a filter associated therewith, and furthermore, a high-frequency voltage is applied from both electrodes of the counter electrode.

  In the case of the one-frequency high-frequency voltage application method useful in the present invention, one of the counter electrodes is a ground electrode, and the other is an application electrode. A high-frequency power source is connected to the application electrode, and the ground is grounded to the ground electrode. Has been.

  The thin film forming apparatus (atmospheric pressure plasma processing apparatus) of each of the 1-frequency high-frequency voltage application method and the 2-frequency high-frequency voltage application method will be described with reference to the drawings.

  FIG. 7 is a schematic view showing an example of a 1-frequency high-frequency voltage application type thin film forming apparatus useful for the present invention.

  A counter electrode is formed by an application electrode (square tube electrode) 136 for applying a high-frequency voltage inside the plasma discharge vessel 130 and a roll-type ground electrode 135 around which the transparent film substrate F is wound. . Any number of application electrodes 136 may be arranged. The gas G is supplied from the gas supply port 152 of the plasma discharge vessel 10, passes through a mesh for uniformizing the gas G, passes between the application electrodes 136 and along the inner wall of the application electrode and the plasma discharge vessel 131, and The discharge space 132 is filled with the gas G. A high frequency voltage is applied to the application electrode 136 by the high frequency power source 142, and the transparent film substrate F is exposed to the gas G excited in the discharge space 132. The frequency of the high frequency voltage to be applied is preferably 50 kHz or more. More preferably, it is in the range of 50 kHz to 150 MHz.

  If it is less than 50 kHz, the effect of the present invention cannot be obtained. Also, a frequency exceeding 150 MHz is not suitable for the present invention because it is difficult to form a discharge and complicated equipment is required, and because nonuniform processing occurs due to potential distribution generation, making it unsuitable for large area processing. Conceivable.

  While the transparent film substrate F is exposed to the excited gas G, the electrode is heated or cooled via the pipe from the electrode temperature adjusting means 160. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the longitudinal direction does not occur as much as possible.

  In the present invention, the transparent film substrate F is a transparent film transparent film substrate, that is, a transparent film substrate, a film in which an antiglare layer is applied on the transparent film substrate, or a high refractive index layer thereon. And / or a film coated with a medium refractive index layer.

  FIG. 8 is a schematic diagram showing another example of a two-frequency high-frequency voltage application type thin film forming apparatus useful for the present invention. In the same manner as in FIG. 7, the transparent film substrate F is subjected to plasma discharge treatment between the opposing electrodes (discharge space) 132 between the roll electrode (first electrode) 135 and the square tube electrode group (second electrode) 136. It is.

  In the discharge space (between the counter electrodes) 132 between the roll electrode (first electrode) 135 and the rectangular tube electrode group (second electrode) 136, the roll electrode (first electrode) 135 has a frequency from the first electrode 141. A high-frequency voltage V1 is applied to ω1, and a rectangular tube-type electrode group (second electrode) 136 is applied with a high-frequency voltage V2 having a frequency ω2 from the second power source 142.

  A first filter 143 is installed between the roll electrode (first electrode) 135 and the first power supply 141 so that the current from the first power supply 141 flows toward the roll electrode (first electrode) 135. The first filter is designed to make it difficult for the current from the first power source 141 to pass through and to easily pass the current from the second power source 142. Also, a second filter 144 is installed between the square tube electrode group (second electrode) 136 and the second power source 142 so that the current from the second power source flows toward the second electrode, The second filter 144 is designed to make it difficult for the current from the second power supply 142 to pass through and to easily pass the current from the first power supply 141. Here, being difficult to pass means that it preferably passes only 20% or less, more preferably 10% or less of the current. On the contrary, being easy to pass means preferably passing 80% or more of the current, more preferably 90% or more.

  In the present invention, any filter having the above properties can be used without limitation. For example, as the first filter, a capacitor of several tens to several tens of thousands pF or a coil of about several μH can be used according to the frequency of the second power source. As the second filter, a coil of 10 μH or more is used according to the frequency of the first power supply, and it can be used as a filter by grounding through these coils or capacitors.

  In the present invention, the roll electrode 135 may be the second electrode, and the rectangular tube electrode group 136 may be the first electrode. In any case, the first power source is connected to the first electrode, and the second power source is connected to the second electrode. Furthermore, the first power supply only needs to have the capability of applying a higher frequency voltage (V1> V2) than the second power supply. Further, it is sufficient that the frequency has an ability to satisfy ω1 <ω2.

  The gas G generated by the gas supply device 151 of the gas supply means 150 is introduced into the plasma discharge processing vessel 131 through the air supply port 152 while controlling the flow rate. The discharge space 132 and the plasma discharge treatment container 131 are filled with the gas G.

  The transparent film substrate F is unwound from the original winding (not shown) and conveyed, or is conveyed from the previous process, and accompanied by the nip roll 165 via the guide roll 164 and the transparent film substrate. Air is shut off and transferred to and from the rectangular tube electrode group 136 while being wound while being in contact with the roll electrode 135, and the roll electrode (first electrode) 135 and the rectangular tube electrode group (second electrode) 136 A voltage is applied from both sides to generate discharge plasma between the counter electrodes (discharge space) 132. The transparent film substrate F is exposed to a plasma state gas while being wound while being in contact with the roll electrode 135. The transparent film substrate F passes through the nip roll 166 and the guide roll 167, and is taken up by a winder (not shown) or transferred to the next step.

  Discharged treated exhaust gas G ′ is discharged from the exhaust port 153.

  During exposure to the plasma state gas, in order to heat or cool the roll electrode (first electrode) 135 and the rectangular tube electrode group (second electrode) 136, a medium whose temperature is adjusted by the electrode temperature adjusting means 160 is used. It sends to both electrodes through the piping 161 with the liquid feeding pump P, and adjusts temperature from the electrode inner side. Reference numerals 165 and 166 denote partition plates that partition the plasma discharge processing vessel 131 from the outside.

  In the present invention, the high-frequency voltage to be applied may be an intermittent pulse wave or a continuous sine wave, and is not limited to the applied voltage waveform. Sine waves are preferred for forming the thin film.

  In the present invention, the frequency of the high-frequency voltage applied to the first electrode is preferably 1 to 200 kHz, and the frequency of the high-frequency voltage applied to the second electrode is preferably 800 kHz or more.

Its power density in the 1~50W / cm ² (here, cm ² in the denominator is the area in which discharge is occurring.) And is more preferably 1.2~30W / cm ^2.

  Examples of the high-frequency power source useful in the present invention include 100 kHz * (manufactured by HEIDEN Laboratory), 200 kHz, 800 kHz, 2 MHz, 13.56 MHz, 27 MHz, and 150 MHz (all manufactured by Pearl Industry). In addition, * mark is HEIDEN Laboratory impulse high frequency power supply (100 kHz in continuous mode).

  In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state described below by applying such a voltage to the plasma discharge processing apparatus.

  FIG. 9 is a perspective view showing an example of the structure of the conductive metallic base material of the roll electrode and the dielectric material coated thereon.

  In FIG. 9, a roll electrode 135a is formed by covering a conductive metallic base material 135A and a dielectric 135B thereon. The inside is a hollow jacket, and the temperature is adjusted.

  FIG. 10 is a perspective view showing an example of the structure of the conductive metallic base material of the rectangular tube electrode shown in FIGS. 7 and 8 and the dielectric material coated thereon.

  In FIG. 10, a rectangular tube electrode 136a has a coating of a dielectric 136B similar to that of FIG. 9 on a conductive metallic base material 136A, and the structure of the electrode is a metallic pipe. , It becomes a jacket so that the temperature can be adjusted during discharge.

  In addition, the number of the rectangular tube-shaped electrodes is set to be plural along a circumference larger than the circumference of the roll electrode, and the discharge area of the electrodes is a full-square tube electrode surface facing the roll electrode 135. It is represented by the sum of the areas.

  The rectangular tube electrode 136a shown in FIG. 10 may be a cylindrical electrode, but the rectangular tube electrode has an effect of expanding the discharge range (discharge area) as compared with the cylindrical electrode, and thus is preferably used in the present invention. .

  9 and 10, a roll electrode 135a and a rectangular tube type electrode 136a are formed by spraying ceramics as dielectrics 135B and 136B on conductive metallic base materials 135A and 136A, respectively, and then sealing the inorganic compound. Is subjected to sealing treatment. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. Further, the dielectric layer may be a lining-processed dielectric provided with an inorganic material by glass lining.

  As the conductive metallic base materials 135A and 136A, a metal such as titanium or a titanium alloy, silver, platinum, stainless steel, aluminum, or iron, a composite material of iron and ceramics, or a composite material of aluminum and ceramics is used. Although it can mention, titanium or a titanium alloy is especially preferable for the reason mentioned below.

  The distance between the two electrodes (electrode gap) is determined in consideration of the thickness of the dielectric provided on the conductive metallic base material, the magnitude of the applied voltage, the purpose of using plasma, etc. The shortest distance between the dielectric surface when a dielectric is provided on one of the electrodes and the surface of the conductive metallic base material, and the distance between the dielectric surfaces when a dielectric is provided on both of the electrodes, In this case, the thickness is preferably from 0.1 to 20 mm, particularly preferably from 0.5 to 2 mm, from the viewpoint of uniform discharge.

  The plasma discharge treatment vessel is preferably a treatment vessel made of Pyrex (registered trademark) glass or the like, but may be made of metal as long as insulation from the electrode can be obtained. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

  The conductive metallic base material and dielectric useful in the present invention will be described in detail.

  An electrode used for such a high-power atmospheric pressure plasma method must be able to withstand severe conditions in terms of structure and performance. Such an electrode is preferably a metal base material coated with a dielectric.

In the dielectric-coated electrode used in the present invention, it is preferable that the characteristics match between various metallic base materials and dielectrics. One of the characteristics is linear thermal expansion between the metallic base material and the dielectric. The combination is such that the difference in coefficient is 10 × 10 ⁻⁶ / ° C. or less. It is preferably 8 × 10 ⁻⁶ / ° C. or lower, more preferably 5 × 10 ⁻⁶ / ° C. or lower, and further preferably 2 × 10 ⁻⁶ / ° C. or lower. The linear thermal expansion coefficient is a well-known physical property value of a material.

  Examples of the combination of the conductive metallic base material and the dielectric whose difference in linear thermal expansion coefficient is within this range include the following.

Metal matrix Dielectric (1) Pure titanium or titanium alloy Ceramic sprayed coating (2) Pure titanium or titanium alloy Glass lining (3) Stainless steel Ceramic sprayed coating (4) Stainless steel Glass lining (5) Composite material of ceramics and iron Ceramic sprayed coating (6) Ceramics and iron composite material Glass lining (7) Ceramics and aluminum composite material Ceramic sprayed coating (8) Ceramics and aluminum composite material Glass lining Here, in terms of the difference in coefficient of linear thermal expansion, The above (1) or (2) and (5) to (8) are preferable, and (1) is particularly preferable.

  In the present invention, titanium or a titanium alloy is particularly useful as the metallic base material from the above characteristics. By using titanium or a titanium alloy as the metal base material, the dielectric is used as described above, so that there is no deterioration of the electrode in use, especially cracking, peeling, dropping off, etc., and it can be used for a long time under harsh conditions. Can withstand.

  The metallic base material of the electrode useful for the present invention is a titanium alloy or titanium containing 70% by mass or more of titanium. In the present invention, the titanium alloy or titanium in the titanium can be used without any problem as long as it is 70% by mass or more, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, T15PB can be preferably used, and it contains lead in addition to the above-described atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin other than the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium have a thermal expansion coefficient that is about 1/2 smaller than that of stainless steel, such as AISI 316, and can be combined with a titanium alloy or a later-described dielectric applied on titanium as a metallic base material. Can withstand use at high temperature for a long time.

  On the other hand, as a required characteristic of the dielectric, specifically, an inorganic compound having a relative dielectric constant of 6 to 45 is preferable, and examples of such a dielectric include ceramics such as alumina and silicon nitride, Alternatively, there are glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  In addition, as one of the specifications that can withstand such high power as described above, the porosity of the dielectric is 10% by volume or less, preferably 8% by volume or less, preferably more than 0% by volume and 5% by volume or less. It is. The porosity of the dielectric can be measured by a BET adsorption method or a mercury porosimeter. In the examples described later, the porosity is measured using a dielectric fragment covered with a metallic base material by a mercury porosimeter manufactured by Shimadzu Corporation. High durability is achieved because the dielectric has a low porosity. Examples of the dielectric having such a void and a low void ratio include a high-density, high-adhesion ceramic spray coating by an atmospheric plasma spraying method described later. In order to further reduce the porosity, it is preferable to perform a sealing treatment.

  The above-mentioned atmospheric plasma spraying method is a technique in which fine powder such as ceramics, wire, or the like is put into a plasma heat source and sprayed onto a metallic base material to be coated as fine particles in a molten or semi-molten state to form a film. A plasma heat source is a high-temperature plasma gas in which a molecular gas is heated to a high temperature, dissociated into atoms, and energy is given to emit electrons. This plasma gas injection speed is high, and since the sprayed material collides with the metallic base material at a higher speed than conventional arc spraying or flame spraying, it is possible to obtain a coating film with high adhesion strength and high density. Specifically, reference can be made to a thermal spraying method for forming a heat shielding film on a high-temperature exposed member described in JP-A-2000-301655. By this method, the porosity of the dielectric (ceramic sprayed film) to be coated can be obtained.

  Another preferable specification that can withstand high power is that the thickness of the dielectric is 0.5 to 3 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

  In order to further reduce the porosity of the dielectric, it is preferable to further perform a sealing treatment with an inorganic compound on the sprayed film such as ceramics as described above. As the inorganic compound, metal oxides are preferable, and among them, those containing silicon oxide (SiOx) as a main component are particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment to promote the sol-gel reaction. Examples of the energy treatment include thermosetting (preferably 200 ° C. or lower), ultraviolet irradiation, and the like. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are repeated several times in succession, the mineralization is further improved and a dense electrode without deterioration can be obtained.

  When a ceramic sprayed coating is applied to a ceramic sprayed film using a metal alkoxide or the like of a dielectric-coated electrode as a sealing liquid, the content of the metal oxide after curing is 60 mol% or more when cured by a sol-gel reaction. Preferably there is. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the content of SiOx (x is 2 or less) after curing is preferably 60 mol% or more. The SiOx content after curing is measured by analyzing a fault of the dielectric layer by XPS.

  In the present invention, it is described in the present invention that the maximum height (Rmax) of the surface roughness defined by JIS B 0601: 2001 on the side in contact with at least the substrate of the electrode is adjusted to 10 μm or less. Although it is preferable from the viewpoint of obtaining an effect, the maximum value of the surface roughness is more preferably 8 μm or less, and particularly preferably adjusted to 7 μm or less. In this way, the dielectric surface of the dielectric-coated electrode can be polished to keep the dielectric thickness and the gap between the electrodes constant, the discharge state can be stabilized, and the heat shrinkage difference and residual Distortion and cracking due to stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric in contact with the substrate. Further, the arithmetic average roughness (Ra) defined by JIS B 0601: 2001 is preferably 0.5 μm or less, and more preferably 0.1 μm or less.

  In the dielectric-coated electrode used in the present invention, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The upper limit is 500 ° C.

  The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without breakdown. Such heat-resistant temperature can be applied by using the above-mentioned ceramic spraying or dielectric materials provided by layered glass linings with different amounts of bubbles, or within the range of the difference in linear thermal expansion coefficient between the metallic base material and the dielectric material below. This can be achieved by appropriately combining means for appropriately selecting the materials.

  In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage in a plasma discharge processing apparatus.

In the present invention, the power applied between the opposing electrodes is such that a power density of 1 to 50 W / cm ² , preferably 1.2 to 30 W / cm ² is supplied to the second electrode to excite the discharge gas and generate plasma. Generate and apply energy to the thin film forming gas to form a thin film.

  Here, regarding the method of applying the high frequency power source, either a continuous sine wave continuous oscillation mode called a continuous mode or an intermittent oscillation mode that performs ON / OFF intermittently called a pulse mode may be adopted, but at least On the second electrode side, a continuous sine wave is preferable because a denser and better quality film can be obtained.

  The discharge condition is that a high-frequency voltage is applied to the discharge space between the first electrode and the second electrode facing each other, and the high-frequency voltage is higher than the voltage component of the first frequency ω1 and the first frequency ω1. It is preferable to have at least a component obtained by superimposing a voltage component of frequency ω2.

  The high-frequency voltage becomes a component obtained by superimposing the voltage component of the first frequency ω1 and the voltage component of the second frequency ω2 higher than the first frequency ω1, and the waveform is on the sine wave of the frequency ω1. A sine wave waveform of ω1 is superimposed with a sine wave of high frequency ω2. It is not limited to a waveform in which a sine wave is superimposed, and both pulse waves may be used, one may be a sine wave and the other may be a pulse wave. Furthermore, it may have a third voltage component. However, in the present invention, as in the single-frequency high-frequency voltage application method, a continuous sine wave at least on the second electrode side can provide a denser and better quality film.

  In the present invention, the discharge start voltage refers to the lowest voltage that can cause discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) actually used. The discharge start voltage varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, and the like, but may be considered to be substantially the same as the discharge start voltage of the discharge gas alone.

  It is presumed that by applying a high-frequency voltage as described above between the counter electrodes (discharge space), discharge can be caused and high-density plasma can be generated.

  In the present invention, a specific method for applying a high-frequency voltage to the discharge space is to connect a first power source for applying a first high-frequency voltage having a frequency ω1 and a voltage V1 to the first electrode constituting the counter electrode. Then, a thin film forming apparatus (atmospheric pressure plasma processing apparatus) in which a second power source for applying a second high frequency voltage having a frequency ω2 and a voltage V2 is connected to the second electrode is used.

  Application of a high-frequency voltage from such two high-frequency power sources is necessary to start discharge of a discharge gas having a high discharge start voltage on the first frequency ω1 side, and the second frequency ω2 side is The important point is that it is necessary to increase the plasma density and form a dense and high-quality thin film.

  In the present invention, it is preferable to apply a high frequency voltage of about 1 to 200 kHz from the first electrode using the first power source and a high frequency voltage of about 800 kHz to 15 MHz from the second electrode using the second power source. . In this case, the applied high-frequency voltage of 1 to 200 kHz excites a discharge gas having a high discharge start voltage to generate plasma.

  Furthermore, it is preferable that the first power source has a capability of applying a higher frequency voltage than the second power source.

As another discharge condition in the present invention, a high-frequency voltage is applied between the first electrode and the second electrode facing each other, and the high-frequency voltage is applied to the first high-frequency voltage V1 and the second high-frequency voltage V2. When the discharge start voltage is IV,
V1 ≧ IV> V2 or V1> IV ≧ V2 is satisfied. More preferably,
V1>IV> V2 is satisfied.

  The definition of the high frequency and the discharge start voltage and the specific method for applying the high frequency voltage between the counter electrodes (discharge space) are the same as those described above.

  Here, the high frequency voltage (applied voltage) and the discharge start voltage are those measured by the following method.

Measuring method of high frequency voltages V1 and V2 (unit: kV / mm):
A high-frequency probe (P6015A) for each electrode part is installed, and the high-frequency probe is connected to an oscilloscope (Tektronix, TDS3012B) to measure the voltage.

Measuring method of discharge start voltage IV (unit: kV / mm):
A discharge gas is supplied between the electrodes, the voltage between the electrodes is increased, and a voltage at which discharge starts is defined as a discharge start voltage IV. The measuring instrument is the same as the above high-frequency voltage measurement.

  By adopting a discharge condition in which a high voltage is applied, even a discharge gas having a high discharge start voltage such as nitrogen gas can start the discharge gas and maintain a high density and stable plasma state.

  When the discharge gas is nitrogen gas according to the above measurement, the discharge start voltage IV is about 3.7 kV / mm. Therefore, in the above relationship, the first high-frequency voltage is set as V1 ≧ 3.7 kV / mm. By applying this, nitrogen gas can be excited to be in a plasma state.

  The discharge gas includes noble gases such as nitrogen, helium and argon, air, hydrogen, oxygen and the like. These may be used alone as a discharge gas or mixed, but nitrogen gas should be used. However, it is particularly preferable because a high economic efficiency of the discharge gas can be obtained as compared with the case where a rare gas such as helium or argon is used.

  The high-frequency power source installed in the atmospheric pressure plasma processing apparatus is the same as that described above, but is divided into a first power source (high-frequency power source) and a second power source (high-frequency power source) as follows.

  The following are mentioned as a 1st power supply.

High frequency power supply code Manufacturer Frequency A1 Shinko Electric 3kHz
A2 Shinko Electric 5kHz
A3 Kasuga Electric 15kHz
A4 Shinko Electric 50kHz
A5 HEIDEN Laboratory * 100kHz
A6 Pearl Industry 200kHz
In addition, * mark is HEIDEN Laboratory impulse high frequency power supply (100 kHz in continuous mode).

  Moreover, the following are mentioned as a 2nd power supply (high frequency power supply).

High frequency power supply symbol Manufacturer Frequency B1 Pearl Industry 800kHz
B2 Pearl Industry 2MHz
B3 Pearl Industry 13.56MHz
B4 Pearl Industry 27MHz
B5 Pearl Industry 150MHz
It is preferable that at least one of the counter electrodes includes gas supply means for supplying a discharge gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.

  7 and 8, the metal base material and the dielectric are not shown. However, similar to FIGS. 9 and 10, the metal base material of the electrode is covered with the same dielectric. Needless to say.

  The high-frequency voltage applied between the counter electrodes may be an intermittent pulse wave or a continuous sine wave, but in order to obtain the effect of the present invention, it is a continuous sine wave. Is preferred.

  In the present invention, the distance between the electrodes is determined in consideration of the thickness of the dielectric disposed on the metal base material of the electrodes, the magnitude of the applied voltage, and the like. The shortest distance between the dielectric when the dielectric is placed on one of the electrodes and the distance between the dielectrics when the dielectric is placed on both of the electrodes 0.5 to 20 mm is preferable, more preferably 0.5 to 5 mm, still more preferably 0.5 to 3 mm, and particularly preferably 1 mm ± 0.5 mm.

〔Polarizer〕
A polarizing plate using the antiglare antireflection film of the present invention will be described.

  The polarizing plate can be produced by a general method. The back surface side of the antireflection film of the present invention is subjected to alkali saponification treatment, and a completely saponified polyvinyl alcohol aqueous solution is used on at least one surface of a polarizing film prepared by immersing and stretching the treated antireflection film in an iodine solution. It is preferable to bond them together. The antireflection film may be used on the other surface, or another polarizing plate protective film may be used. In contrast to the antireflection film of the present invention, the polarizing plate protective film used on the other surface has an in-plane retardation (Ro) of 590 nm, a retardation of 20 to 70 nm, and a thickness direction retardation (Rt) of 100 to 400 nm. It is preferable that it is an optical compensation film (retardation film). These can be prepared, for example, by the methods described in JP-A No. 2002-71957 and Japanese Patent Application No. 2002-155395. Further, it is preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optically anisotropic layer formed by aligning a liquid crystal compound such as a discotic liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. Alternatively, an unoriented film having an in-plane retardation (Ro) of 0 to 5 nm at 590 nm and a thickness direction retardation (Rt) of -20 to +20 nm is also preferably used.

  By using in combination with the antiglare film of the present invention, a polarizing plate having excellent planarity and a stable viewing angle expansion effect can be obtained.

  As a polarizing plate protective film used on the back side, as a commercially available cellulose ester film, KC8UX2MW, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC4UEW, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC4FR-1, KC4F-1, -2 (manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are ones in which iodine is dyed on a system film and ones in which a dichroic dye is dyed, but it is not limited to this. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. A polarizing film having a thickness of 5 to 30 μm, preferably 8 to 15 μm, is preferably used. On the surface of the polarizing film, one side of the antireflection film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

(Image display device)
By incorporating the antiglare antireflection film surface of the polarizing plate using the antiglare antireflection film of the present invention on the viewing surface side of the image display device, various image display devices with excellent visibility can be produced. it can. The antireflection film of the present invention is a reflection type, transmission type, transflective type LCD or LCD of various drive systems such as TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used. In addition, the antireflection film of the present invention has significantly less color unevenness in the reflected light of the antireflection layer, and has a low reflectance and excellent flatness, and is a plasma display, field emission display, organic EL display, inorganic EL display, electronic It is also preferably used for various display devices such as paper. In particular, an image display device having a large screen of 30 or more screens has an effect that there is little color unevenness and wavy unevenness, and eyes are not tired even during long-time viewing.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
(Production of resin)
(Synthesis Example 1)
Preparation of acrylic resin solution 1 having a hydroxyl group 429 g of propylene glycol monopropyl ether (PFG) was charged into a 1 L reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen introduction tube, and the temperature was raised to 120 ° C. with stirring. . A monomer comprising 173.0 g of methyl methacrylate (MMA), 47.0 g of hydroxyethyl acrylate (HEA), 23.0 g of acrylic acid (AA) and 6.0 g of t-butylperoxy-2-ethylhexanoate And the solution containing a polymerization initiator was dripped over 3 hours using the dropping funnel.

After the completion of dropping, the mixture was kept at 120 ° C. for 30 minutes with stirring, and then a solution consisting of 1.0 g of t-butylperoxy-2-ethylhexanoate and 12.0 g of PFG was added dropwise over 30 minutes. After completion of the dropping, the reaction was continued by stirring at 120 ° C. for 2 hours to obtain a resin solution 1 having a nonvolatile content of 40.0% and a weight average molecular weight of 14,000. The obtained resin has a hydroxyl value of 180 and an acid value of 40, which can be used as the first resin in the present invention.

(Synthesis Example 2)
Preparation of Epoxy Group-Containing Acrylic Resin Solution 2 457.6 g of diethylene glycol dimethyl ether (DMDG) was introduced into a 1 L reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen introduction tube, and the temperature was raised to 120 ° C. with stirring. Monomer and polymerization consisting of 32.0 g of methyl methacrylate (MMA), 72.0 g of styrene (ST), 216.0 g of glycidyl methacrylate (GMA) and 6.4 g of t-butylperoxy-2-ethylhexanoate The solution containing the initiator was added dropwise using a dropping funnel over 3 hours.

 After the completion of dropping, the mixture was kept at 120 ° C. for 30 minutes with stirring, and then a solution composed of 1.0 g of t-butylperoxy-2-ethylhexanoate and 7.4 g of PFG was dropped over 30 minutes. After completion of the dropping, the reaction was continued by stirring at 120 ° C. for 2 hours to obtain a resin solution 2 having a nonvolatile content of 40.0% and a weight average molecular weight of 16,600. The resulting resin has an epoxy equivalent of 211, which can be used as the second resin in the present invention.

(Synthesis Example 3)
Preparation of the carboxyl group-containing acrylic resin solution 3 433 g of diethylene glycol dimethyl ether (DMDG) was introduced into a 1 L reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen introduction tube, and the temperature was raised to 120 ° C. with stirring. A monomer and a polymerization initiator comprising 155.9 g of styrene (ST), 52.4 g of n-butyl acrylate (NBA), 91.7 g of acrylic acid and 9.0 g of t-butylperoxy-2-ethylhexanoate. The solution containing was dropped over 3 hours using a dropping funnel. After the completion of dropping, the mixture was kept at 120 ° C. for 30 minutes with stirring, and then a solution consisting of 1.5 g of t-butylperoxy-2-ethylhexanoate and 6.9 g of PFG was added dropwise over 30 minutes. After completion of the dropping, the reaction was continued by stirring at 120 ° C. for 2 hours to obtain a resin solution 3 having a nonvolatile content of 40.0% and a weight average molecular weight of 10,000. The obtained resin has an acid value of 238, which can be used as the first resin in the present invention.

(Synthesis Example 4)
Preparation of acrylic resin solution 4 having hydroxyl group 433 g of propylene glycol monopropyl ether (PFG) was put into a 1 L reaction vessel equipped with a thermometer, a stirrer, a cooling tube and a nitrogen introduction tube, and the temperature was raised to 120 ° C. with stirring. . To this, 201.9 g of n-butyl methyl methacrylate (NBMA), 54.0 g of ethylhexyl methacrylate (EHMA), 41.8 g of hydroxyethyl methacrylate (HEMA), 2.3 g of methacrylic acid (MAA) and t-butylperoxy- A solution consisting of 6.0 g of 2-ethylhexanoate and containing a monomer and a polymerization initiator was added dropwise using a dropping funnel over 3 hours. After the completion of dropping, the mixture was kept at 120 ° C. for 30 minutes with stirring, and then a solution consisting of 1.5 g of t-butylperoxy-2-ethylhexanoate and 6.9 g of PFG was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was continued by stirring at 120 ° C. for 2 hours to obtain a resin solution 4 having a nonvolatile content of 40% and a weight average molecular weight of 14,000. The obtained resin has a hydroxyl value of 60 and an acid value of 5, which can be used as the first resin in the present invention.

(Measurement method of surface tension)
Surface tension and difference in surface tension: measurement of Δγ The surface tension of the resin prepared in the above synthesis example was measured by the following method. The surface tension difference: Δγ was determined by the following calculation.

Δγ = γ of first resin (PFG) −γ of second resin (PFG)
Measuring method A
Each resin was dissolved in a propylene glycol monopropyl ether (PFG) solvent so as to have a resin solid content of 40% by weight to prepare a solution for measuring surface tension. The surface tension of this solution was measured at 20 ° C. using a dynamometer manufactured by Big Mallincklot International. On the other hand, when the surface tension of the propylene glycol monopropyl ether (PFG) solvent was measured under the same conditions, it was 29.0 dyne / cm. A value obtained by subtracting the surface tension value of the propylene glycol monopropyl ether (PFG) solvent from the measured value for each resin was designated as γ (PFG) which is an approximate surface tension value of the resin component based on the PFG solvent.

Measurement method B
Each resin was dissolved in a diethylene glycol dimethyl ether (DMDG) solvent so that the resin solid content was 40% by weight to prepare a solution for measuring the surface tension. The surface tension of this solution was measured at 20 ° C. using a dynamometer manufactured by Big Mallincklot International. On the other hand, when the surface tension of the solvent was measured under the same conditions, the surface tension of the diethylene glycol dimethyl ether (DMDG) solvent was 32.0 dyne / cm, and the surface tension of the propylene glycol monopropyl ether (PFG) solvent was 29.0 dyne / cm. Met. The surface tension value of the diethylene glycol dimethyl ether (DMDG) solvent (32.0 dyne / cm) is subtracted from the above measured value for each resin, and then the difference between the surface tension of the DMDG solvent and the surface tension of the PFG solvent (3.0 dyne / cm) Γ (PFG), which is an approximate value of the surface tension of the resin component based on the PFG solvent, was calculated.

  The surface tension was measured by a measurement method using the same solvent as the solvent used when synthesizing the resin to be measured. Moreover, about the melamine resin, the surface tension was measured with the following measuring methods C.

Measuring method C
Each resin was dissolved in a propylene glycol monomethyl ether acetate (PGMAC) solvent so as to have a resin solid content of 40% by weight to prepare a solution for measuring the surface tension. The surface tension of this solution was measured at 20 ° C. using a dynamometer manufactured by Big Mallincklot International. On the other hand, when the surface tension of the solvent was measured under the same conditions, the surface tension of the propylene glycol monomethyl ether acetate (PGMAC) solvent was 31.0 dyne / cm, and the surface tension of the propylene glycol monopropyl ether (PFG) solvent was 29. It was 0 dyne / cm. By subtracting the surface tension value of propylene glycol monomethyl ether acetate (PGMAC) solvent from the above measured values for each resin, and then subtracting the difference (2.0 dyne / cm) between the surface tension of the PGMAC solvent and the surface tension of the PFG solvent. Γ (PFG), which is an approximate value of the surface tension of the resin component based on the PFG solvent, was calculated.

(Preparation of hollow silica fine particle 1 isopropyl alcohol dispersion)
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of 0.98 mass% sodium silicate aqueous solution as SiO ₂ and 9000 g of 1.02 mass% sodium aluminate aqueous solution as Al ₂ O ₃ were simultaneously added to the mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed 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 core particle dispersion having a solid content concentration of 20% by mass. [Step (a)]
1700 g of pure water is added to 500 g of this core particle dispersion and heated to 98 ° C., and while maintaining this temperature, a silicate solution (SiO ₂₎ obtained by dealkalizing a sodium silicate aqueous solution with a cation exchange resin. A dispersion of core particles in which 3000 g (concentration of 3.5% by mass) was added to form a first silica coating layer was obtained. [Step (b)]
Next, 1125 g of pure water is added to 500 g of the core particle dispersion liquid that has been washed with an ultrafiltration membrane to form a first silica coating layer having a solid concentration of 13% by mass, and concentrated hydrochloric acid (35.5%) is further added dropwise. The pH was adjusted to 1.0 and dealumination was performed. Next, the aluminum salt dissolved in the ultrafiltration membrane is separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and SiO ₂ · Al in which some of the constituent components of the core particles forming the first silica coating layer are removed. A dispersion of ₂ O ₃ porous particles was prepared [step (c)].

A mixture of 1500 g of the above porous particle dispersion, 500 g of pure water, 1,750 g of ethanol, and 626 g of 28% ammonia water is heated to 35 ° C., and then 104 g of ethyl silicate (SiO ₂ 28 mass%) is added, A first silica coating layer was formed. The surface of the porous particles was coated with a hydrolyzed polycondensate of ethyl silicate to form a second silica coating layer.

Next, a dispersion of hollow silica fine particles 1 having a solid content concentration of 20% by mass was prepared by replacing the solvent with isopropyl alcohol using an ultrafiltration membrane. The thickness of the first silica coating layer of the hollow silica fine particles was 3 nm, the average particle size was 45 nm, MO _X / SiO ₂ (molar ratio) was 0.0017, and the refractive index was 1.28. Here, the average particle diameter and the coefficient of variation of the particle diameter were measured by a dynamic light scattering method.

(Preparation of coating composition for forming antiglare antireflection layer)
23.0 parts of the epoxy group-containing acrylic resin solution 2 (second resin) of synthesis example 2 and 15.0 parts of the carboxyl group-containing acrylic resin solution 3 (first resin) of synthesis example 3 were mixed with methyl ethyl ketone 31. 0 copies,
In addition to 31.0 parts of propylene glycol monopropyl ether (PFG), mixing was performed, and 0.20 part of SF104E (Surfinol 104E, manufactured by Air Products Japan Co., Ltd.) was also added and mixed.

  Next, 30 parts by mass of the above-prepared hollow silica fine particle 1 isopropyl alcohol dispersion (average particle size 45 nm, particle size variation coefficient 30%) is added and mixed to prepare a coating composition for an antiglare antireflection layer. did.

  Further, the surface tensions of the epoxy group-containing acrylic resin solution 2 (second resin) of Synthesis Example 2 and the carboxyl group-containing acrylic resin solution 3 (first resin) of Synthesis Example 3 were measured by the measurement method B, respectively. Difference: Δγ was determined by the above calculation.

Surface tension measurement and difference: Δγ
Measured value of surface tension of first resin (Measurement method B): 33.5 dyne / cm
Surface tension γ (PFG) of the first resin: −1.5 dyne / cm
Measured value of surface tension of second resin (Measurement method B): 31.5 dyne / cm
Surface tension γ (PFG) of the second resin: −3.5 dyne / cm
Difference in surface tension: Δγ is 2.0 dyne / cm
<Preparation of transparent film substrate>
A transparent film substrate 1 of a transparent cellulose triacetate film (film thickness 80 μm) was produced as follows.

(Dope composition)
Cellulose triacetate (average degree of acetylation 61.0%) 100 parts by weight Triphenyl phosphate 8 parts by weight Ethylphthalyl ethyl glycolate 2 parts by weight Tinuvin 109 (manufactured by Ciba Specialty Chemicals) 1 part by weight Tinuvin 171 (Ciba 1 part by weight Methylene chloride 430 parts by weight Methanol 90 parts by weight The above materials are put into a closed container, kept at 80 ° C. under pressure and completely dissolved while stirring to obtain a dope composition. It was.

  Next, the dope composition is filtered, cooled and kept at 33 ° C., cast uniformly on a support made of a stainless steel band, and the solvent is evaporated until peeling is possible. The film was stretched 1.1 times in the width direction with a tenter, dried while being conveyed by a large number of rolls, wound with 10 μm height knurling provided at both ends, a film thickness of 80 μm, a width of 1.5 m, and a length. A transparent film substrate 1 (cellulose triacetate film) having a thickness of 3000 m was obtained.

  Further, a transparent film substrate 2 (cellulose triacetate film) having a film thickness of 40 μm, a width of 1.5 m, and a length of 5000 m was produced in the same manner as in the above case except that the film thickness was 40 μm.

(Preparation of antiglare antireflection film)
<Formation of antiglare antireflection layer>
The transparent film substrate 1 produced as described above is die-coated with the adjusted coating composition for an antiglare and antireflection layer, dried at 80 ° C., and then irradiated with 0.2 J / cm ² of ultraviolet light with a high pressure mercury lamp. An antiglare layer was provided so that the film thickness after irradiation and curing would be 8.0 μm.

<Formation of back coat layer>
On the opposite side of the surface on which the antiglare layer was applied, the following backcoat layer coating solution was die-coated so as to have a wet film thickness of 14 μm, dried at 85 ° C. and wound to provide a backcoat layer. 1 antiglare antireflection film was produced.

(Coating composition for back coat layer)
Acetone 30 parts by mass Ethyl acetate 45 parts by mass Isopropyl alcohol 10 parts by mass Diacetyl cellulose 0.6 parts by mass Ultrafine silica 2% acetone dispersion 0.2 parts by mass (Aerosil 200V manufactured by Nippon Aerosil Co., Ltd.)
Examples 2-7 and Comparative Examples 1-4
(Preparation of coating compositions for antiglare antireflection layers of Examples 2 to 6 and Comparative Examples 1 to 3)
In the same manner as in Example 1 except that the hollow silica fine particles 1 of the coating composition 1 for antiglare and antireflection layer 1 were changed to the compounds and addition amounts shown in Table 1, Examples 2 to 6 and Comparative Examples 1-3 coating compositions for the antiglare antireflection layer were prepared.

(Preparation of coating composition for antiglare antireflection layer of Example 7)
10.8 parts of methyl butylated melamine resin (molecular weight 700, second resin) and 22.5 parts of acrylic resin solution 1 (first resin) having a hydroxyl group of Synthesis Example 1 were mixed with 31.0 parts of methyl ethyl ketone as a solvent, acetic acid In addition to 31.0 parts of methyl, they were mixed, and then 0.20 part of SF104E (Surfinol 104E, manufactured by Air Products Japan Co., Ltd., additive) was also added and mixed. Next, 30 parts by mass of the prepared hollow silica fine particle 1 isopropyl alcohol dispersion (average particle size 45 nm, particle size variation coefficient 30%) is added and mixed, and the coating composition for the antiglare antireflection layer of Example 7 is mixed. Was prepared.

  Further, the surface tension of the methyl butylated melamine resin (second resin) was measured by the above measuring method C. Further, the surface tension of the acrylic resin solution 1 (first resin) having a hydroxyl group in Synthesis Example 1 was measured by the above-described measurement method A, and the difference in surface tension: Δγ was determined by the above calculation.

Surface tension measurement and difference: Δγ
Measured value of surface tension of first resin (Measurement method A): 30.4 dyne / cm
Surface tension γ (PFG) of the first resin: 1.4 dyne / cm
Measured value of surface tension of second resin (Measurement method C): 32.2 dyne / cm
Surface tension γ (PFG) of the second resin: −0.8 dyne / cm
Difference in surface tension: Δγ is 2.2 dyne / cm
(Preparation of coating composition for antiglare antireflection layer of Comparative Example 4)
10.8 parts of methylated melamine resin (molecular weight 550, second resin) and 22.5 parts of acrylic resin solution 1 (first resin) having a hydroxyl group of Synthesis Example 1 were added 31.0 parts of methyl ethyl ketone as a solvent, acetic acid In addition to 31.0 parts of methyl, they were mixed, and then 0.20 part of SF104E (Surfinol 104E, manufactured by Air Products Japan Co., Ltd., additive) was also added and mixed. Next, 30 parts by mass of the above-prepared hollow silica fine particle 1 isopropyl alcohol dispersion (average particle size 45 nm, particle size variation coefficient 30%) is added and mixed, and the antiglare antireflection layer coating composition of Comparative Example 4 is added. Was prepared.

  Further, the surface tension of the methylated melamine resin (second resin) was measured by the above measuring method C. Moreover, the surface tension of the acrylic resin solution 1 (first resin) having a hydroxyl group in Synthesis Example 1 was measured by the above-described measurement method A, and the difference in surface tension: Δγ was determined by the above calculation.

Surface tension measurement and difference: Δγ
Measured value of surface tension of first resin (Measurement method A): 30.4 dyne / cm
Γ of first resin (PFG): 1.4 dyne / cm
Measurement value of surface tension of second resin (Measurement method C): 33.0 dyne / cm
Γ (PFG) of the second resin: 0.0 dyne / cm
Difference in surface tension: Δγ is 1.4 dyne / cm
Next, the antiglare antireflection layer forming coatings of Examples 2 to 7 and Comparative Examples 1 to 4 shown in Table 1 below together with the coating composition for forming the antiglare antireflection coating of Example 1 are shown. Except having changed into the coating composition, it carried out similarly to the case of Example 1, and produced the anti-glare antireflection film of Examples 2-7 and Comparative Examples 1-4.

  Next, about each anti-glare antireflection film of the said Examples 1-7 and Comparative Examples 1-4, each performance was evaluated by the following items.

<Evaluation of antiglare antireflection film>
Abrasion resistance After anti-glare antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 were conditioned at 23 ° C. and a relative humidity of 60% for 2 hours, # 0000 steel wool (SW) A load of 1000 g / cm ² was applied to the sample, and the number of scratches per 1 cm width when 10 reciprocations were made was measured. In addition, the number of scratches is measured at a place where the number of scratches is the largest among the portions where the load is applied. 5 / cm or less is preferable, and 1 / cm or less is more preferable.

Pencil hardness The anti-glare antireflection films prepared in Examples 1 to 7 and Comparative Examples 1 to 4 above were prepared under the conditions of 25 ° C. and relative humidity of 60%. After adjusting the humidity for 2 hours, using a test pencil specified by JIS S 6006, according to the pencil hardness evaluation method specified by JIS K 5400, scratching was repeated 5 times with a pencil of each hardness using a 1 kg weight. The hardness of up to one scratch was measured. The higher the number, the higher the hardness.

Reflectance In order to prevent back surface reflection, the sample was affixed on a black acrylic plate with a baseless double-sided tape, and the reflectance was measured with a Konica Minolta spectrocolorimeter, CM-3700d.

Visibility evaluation As an index of visibility, reflection (antiglare property), sharpness, and transmission image clarity were evaluated.

[Reflection (anti-glare), sharpness]
Each sample was affixed on a monitor with a substrate-less double-sided tape, and 30 persons performed image sensory and sensory evaluation of sharpness, and the average score was obtained. Ten points are the best, with little reflection or high sharpness. One point is the worst. Seven or more points are acceptable levels.

(Transparency mapping)
The transmission image clarity at a comb width of 2.5 mm was measured with a image clarity measuring device ICM-IDP of Suga Test Instruments Co., Ltd. Transmission image clarity is a parameter that correlates with sharpness. The evaluation results are summarized in Table 2.

  As is clear from the results in Table 2 above, in the antiglare antireflection film produced in Examples 1 to 7 of the present invention, the first resin and the second resin have resins having functional groups that react with each other. The difference between the surface tension of the first resin and the surface tension of the second resin: a coating composition comprising at least two kinds of resins having Δγ of 2 dyne / cm or more and at least one kind of fine particles having a porous or hollow inside Since it has the anti-glare antireflection layer formed using the film, it can be seen that the film strength, reflectance, and visibility are all excellent.

  Moreover, it turns out that the anti-glare antireflection film of the present invention in which the fine particles whose inside is porous or hollow is the hollow silica fine particles exhibits particularly excellent performance.

  On the other hand, in the anti-glare antireflection film produced in Comparative Examples 1-4, it turns out that it is inferior about all of film | membrane intensity | strength, a reflectance, and visibility.

  In addition, except having used the transparent film base material 2 instead of the transparent film base material 1, it produced the anti-glare antireflection film like the case of the said Examples 1-7, and each anti-glare antireflection About the film, when the same evaluation as said case was implemented, the effect similar to the case of the anti-glare film of the said Examples 1-7 produced using the transparent film base material 1 was able to be confirmed.

Examples 8-14
In the production of the antiglare antireflection film of Example 1, Examples 8 to 8 were carried out in the same manner as in Example 1 except that the film thickness of the antiglare layer after curing was as shown in Table 3. 14 antiglare antireflection films were prepared.

Next, the antiglare antireflection films of Examples 8 to 14 were evaluated in the same manner as in Example 1. The obtained results are shown in Table 3. The evaluation results for the antiglare antireflection film of Example 1 are also shown in Table 3.

  As is clear from the results in Table 3 above, when the film thickness of the antiglare antireflection film is 1.0 μm or more and 30.0 μm or less, particularly excellent abrasion resistance, reflectance, and visibility, that is, antiglare property. (It is understood that reflection, sharpness, and transmission image clarity are obtained.

Example 15
In the production of the antiglare and antireflection film of Example 1, the coating composition 1 for forming the antiglare and antireflection layer was die-coated and temporarily dried at 40 ° C., and then the surface of the antiglare and antireflection layer was projected. An antiglare antireflection film of Example 15 was produced in the same manner as in Example 1 except that the film was embossed with a roll attached with, followed by main drying at 80 ° C.

  Next, the antiglare antireflection film of Example 15 was evaluated in the same manner as in Example 1. The obtained results are shown in Table 4 below.

Example 16
(Coating composition for hard coat layer)
The following composition was mixed and stirred to prepare a coating composition for a hard coat layer.

Acrylic monomer 35 parts by mass (dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku)
Trimethylolpropane triacrylate 13 parts by weight Photopolymerization initiator 1.9 parts by weight (Irgacure, Ciba Specialty Chemicals Co., Ltd.)
Silicon compound (manufactured by Big Chemie Japan) 0.1 parts by mass Propylene glycol monomethyl ether 25 parts by mass Methyl ethyl ketone 25 parts by mass The above materials were mixed and stirred to prepare a coating composition for a hard coat layer.

(Preparation of hard coat layer)
Next, on the surface of the transparent film substrate 1 of a cellulose triacetate film (film thickness 80 μm) (B side; surface in contact with a stainless steel band used in the casting film forming method; support side), for the above hard coat layer The coating composition is applied with a slit die, and the temperature and speed of the hot air are gradually increased and finally dried at 85 ° C., followed by UV irradiation with an irradiation intensity of 115 mJ / cm ² from the actinic ray irradiation part. A 3 μm hard coat layer was provided.

  Furthermore, the convex structure part liquid made of the coating composition for forming the antiglare and antireflection layer of Example 1 was ejected onto the above hard coat layer as an ink droplet by the following ink jet method at 4 pl, thermally dried, Irradiated with ultraviolet rays and cured to form a convex structure portion, and an antiglare antireflection film of Example 16 was produced. Moreover, the convex structure part height of this film was about 8 micrometers, and the convex structure part diameter was about 35 micrometers.

  As the ink jet emitting apparatus, a line head method (FIG. 4A) was used, and ten ink jet heads having 256 nozzles having a nozzle diameter of 3.5 μm were prepared. An ink jet head having the structure shown in FIG. 2 was used. The ink supply system is composed of an ink supply tank, a filter, a piezo-type ink jet head, and piping. The ink supply tank to the ink jet head section is insulated and heated (40 ° C.), and the emission temperature is 40 ° C. The driving frequency was 20 kHz.

Next, the antiglare antireflection film of Example 16 produced above was evaluated in the same manner as in Example 1. The obtained results are shown in Table 4 below.

  As is clear from the results in Table 4 above, according to the antiglare antireflection films of Examples 15 and 16, as in the case of Example 1, excellent scratch resistance, reflectance, and visibility, that is, It can be seen that antiglare properties (reflection, sharpness, and transmission image clarity) are obtained.

Examples 17-23 and Comparative Examples 5-8
(Preparation of polarizing film)
In order to produce a liquid crystal display panel, a polarizing film was first produced. That is, a polyvinyl alcohol film having a thickness of 120 μm was uniaxially stretched (temperature: 110 ° C., stretch ratio: 5 times). This was immersed in an aqueous solution composed of 0.075 g of iodine, 5 g of potassium iodide and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 68 ° C. composed of 6 g of potassium iodide, 7.5 g of boric acid and 100 g of water. This was washed with water and dried to obtain a polarizing film.

(Preparation of polarizing plate)
Then, according to the following Step 1 to Step 5, the polarizing film and the anti-glare antireflection film produced in Examples 1 to 7 and Comparative Examples 1 to 4 are a cellulose ester film / konica minol tuck having a commercially available retardation ( A polarizing plate was produced by attaching the antiglare antireflection layer to the outside on a Konica Minolta Opto Co., Ltd. product.

  Step 1: Dip in a 2 mol / L sodium hydroxide solution at 50 ° C. for 60 seconds, then wash with water and dry to obtain an antiglare antireflection film and a cellulose ester film having a saponified side to be bonded to a polarizing film. It was.

  Step 2: The polarizing film was immersed in a polyvinyl alcohol adhesive tank having a solid content of 2% by mass for 1 to 2 seconds.

  Step 3: In Step 1, the excess adhesive adhered to the polarizing film in Step 2 is gently wiped off, and the cellulose ester film treated in Step 1 and the antiglare antireflection layer are on the outside on this polarizing film. Laminated and arranged in the order of the treated antiglare antireflection film.

  Process 4: The polarizing film film arrange | positioned at the process 3 was bonded by the pressure of 20-30 N / cm <2>, and the conveyance speed at about 2 m / min.

  Step 5: The polarizing film and the antiglare film prepared in Step 4 were dried for 2 minutes in a dryer at 80 ° C. to prepare a polarizing plate.

(Production of liquid crystal display panel)
Next, the polarizing plate on the outermost surface of a commercially available liquid crystal display panel (NEC color liquid crystal display, MultiSync, LCD1525J: model name, LA-1529HM) was carefully peeled off, and the antiglare antireflection film prepared above was used here. The polarizing plates were bonded to produce liquid crystal display panels of Examples 17 to 23 and Comparative Examples 5 to 8, and the following were evaluated.

<Evaluation>
[Reflection (antiglare)]
The liquid crystal panels of Examples 17 to 23 and Comparative Examples 5 to 8 obtained as described above were placed on a desk having a height of 80 cm from the floor, and a daylight light straight tube on a ceiling portion having a height of 3 m from the floor. 10 sets of fluorescent lamps (FLR40S · D / MX, manufactured by Matsushita Electric Industrial Co., Ltd.) 40W × 2 were arranged as 1.5 sets at 10 m intervals. At this time, when the evaluator is in front of the liquid crystal panel display surface, the fluorescent lamp is arranged so that the fluorescent lamp comes to the ceiling from the evaluator's overhead to the rear. The liquid crystal panel was tilted by 25 ° from the vertical direction with respect to the desk, and a fluorescent lamp was reflected so that the visibility of the screen was evaluated as follows.

Reflection (Anti-Glare) Evaluation Rank 4: Does not bother with the reflection of the nearest fluorescent lamp, and can clearly read characters with a font size of 8 or less. 3: Reflection of a nearby fluorescent lamp is somewhat anxious However, I don't care about the distance and can read characters with a font size of 8 or less. 2: I'm worried about the reflection of a distant fluorescent light, and it is difficult to read characters with a font size of 8 or less. 1: Fluorescent light reflection is quite worrisome, and the portion of the reflection cannot read characters with a font size of 8 or less (clearness)
The clearness of images when moving images were displayed on each of the liquid crystal panels of Examples 17 to 23 and Comparative Examples 5 to 8 was visually evaluated according to the following criteria.

Sharpness evaluation rank 4: A fast moving image looks clear 3: A fast moving image sometimes looks slightly blurred 2: A non-moving image is clear but a moving image is unclear 1: Moving image, moving Both images are not clear (glare)
The liquid crystal panels of Examples 17 to 23 and Comparative Examples 5 to 8 produced above were projected with diffused light from a fluorescent lamp having a louver, and the surface glare was visually evaluated according to the following criteria.

Glitter evaluation rank 4: No glare is observed 3: Little glare is observed 2: Slight glare is observed 1: Clearly glare is observed

  As is clear from the results of Table 5 above, according to the liquid crystal panels of Examples 17 to 23 of the present invention, superior visibility (antiglare property, sharpness, compared with the liquid crystal panels of Comparative Examples 5 to 8). It can be seen that the image has glare.

It is the schematic diagram which showed the overcoat by the convex structure part formation by an inkjet method, and a transparent resin layer. It is sectional drawing which shows an example of the inkjet head which can be used for the inkjet method. It is the schematic which shows an example of an inkjet head part and a nozzle plate. It is a schematic diagram which shows an example of an inkjet system. It is the schematic of the uneven | corrugated surface forming apparatus using an uneven | corrugated roller. It is the schematic of the uneven surface forming apparatus in a drying apparatus. It is the schematic which shows an example of the thin film formation apparatus of a 1 frequency high frequency voltage application system useful for this invention. It is the schematic which shows an example of the thin film formation apparatus of a 2 frequency high frequency voltage application system useful for this invention. It is a perspective view which shows an example of the structure of the electroconductive metal base material of a roll electrode, and the dielectric material coat | covered on it. It is a perspective view which shows an example of the structure of the electroconductive metal preform | base_material of a rectangular tube type electrode, and the dielectric material coat | covered on it.

Explanation of symbols

10: Transparent film substrate 11: Substrate 12: Piezoelectric element 13: Channel plate 13a: Ink channel 13b: Wall 14: Common liquid chamber component 15: Ink supply pipe 16: Nozzle plate 16a: Nozzle 17: For driving Circuit printed board 18: Lead part 19: Drive electrode 20: Groove 21: Protection board 22: Fluid resistance 23, 24: Electrode 25: Upper partition wall 26: Heater 27: Heater power supply 28: Heat transfer member 29: Actinic ray irradiation part 30 : Inkjet head 31: droplet 32: nozzle 35: back roll 51: die 52: belt for casting 53: uneven roller 53 ′: uneven roller 54: back roller 55: tenter 56: film drying device 57: winding Roll 60: Static eliminator F: Transparent film substrate G: Discharge gas G ′: Excited discharge gas P: Liquid feed pump 135a: Roll electrode 135A 36A: metal base material 135A, 136B: dielectric 136a: prismatic electrode 130: atmospheric pressure plasma processing apparatus 131: atmospheric pressure plasma treatment chamber 132: discharge space 135: roll electrode (first electrode)
136: Square tube type electrode group (second electrode)
140: electric field applying means 141: first power supply 142: second power supply 143: first filter 144: second filter 150: gas supply means 151: gas generator 152: air supply port 153: exhaust port 160: electrode temperature adjusting means 161: Pipes 164, 167: Guide rolls 165, 166: Nip rolls 168, 169: Partition plates

Claims (9)

  An antiglare antireflection film having an antiglare antireflection layer on a transparent film substrate, the antiglare antireflection layer having functional groups that react with each other, and a difference in surface tension between resins: Δγ 1.8 dyne / cm or more and 30.0 dyne / cm or less, and a coating composition containing at least one kind of fine particles having porous and voids. An antiglare antireflection film characterized by comprising:   The antiglare antireflection film according to claim 1, wherein the first resin is a hydroxyl group-containing resin and the second resin is a melamine resin.   The antiglare antireflection film according to claim 1, wherein the first resin is a carboxyl group-containing resin and the second resin is an epoxy group-containing resin.   The antiglare antireflection film according to any one of claims 1 to 3, wherein the porous or hollow fine particles are hollow silica fine particles.   The antiglare antireflection film according to any one of claims 1 to 4, wherein the film thickness of the antiglare antireflection layer is from 1.0 µm to 30.0 µm.   The antiglare antireflection film according to any one of claims 1 to 5, wherein the transparent film substrate is a cellulose ester film.   A polarizing plate, wherein the antiglare antireflection film according to any one of claims 1 to 6 is used on one surface.   A display device using the antiglare antireflection film according to any one of claims 1 to 6.   A display device comprising the polarizing plate according to claim 7.

Images