JP2006122889A - Production method of coating film, anti-reflecting film and its production method, polarizing plate using the anti-reflecting film, and image displaying device using these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a high-productivity, high-quality anti-reflecting film. <P>SOLUTION: In an anti-reflecting film production method, a coating liquid is applied onto a web W, which is supported by a backup roller 11 and travels continuously, by using a slot die to form at least one layer having a film thickness of ≤200 nm in a dried state and having a lower refractive index than that of the web. An edge lip on the downstream side in the web traveling direction has a land length in the web traveling direction ILO of 30-100 μm, and a space between an edge lip 18a on the upstream side in the web traveling direction and a web surface is set so as to be 30-120 μm larger than a space between the edge lip 18b on the downstream side in the web traveling direction and the web surface. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for producing a coating film, an antireflection film and a method for producing the same, a polarizing plate using the film, and a polarizing plate using the film, The present invention relates to the image display device used.

With the high performance and widespread use of information communication equipment and AV equipment, the demand for parts using thin films on the order of 10 nm to 100 nm is rapidly expanding, and there is a need to create such thin films with high productivity. It is growing. The thin film is often used as an optical component, and a thin film having such an optical function is generally called an optical thin film. The optical thin film has an optical film thickness (optical film thickness nd = physical film thickness × refractive index) of about ¼ to 1 times the visible light wavelength, and various functions can be achieved by laminating the optical thin film as a single layer or multiple layers. You can have it. Main products using optical thin films include bandpass filters, dichroic mirrors, dichroic filters, cold mirror filters, beam splitters, antireflection films, near infrared cut filters, laser mirrors, ND filters, and the like.

  Antireflection films having antireflection films are used in various image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). Yes. Antireflection films are also used for glasses and camera lenses.

  As such an antireflection film, a multilayer film in which a transparent thin film of metal oxide is laminated has been conventionally used. The reason for using a plurality of transparent thin films is to prevent reflection of light in a wavelength range as wide as possible in the visible range.

  These metal oxide transparent thin films are formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method, which is a kind of physical vapor deposition method. However, a transparent thin film of metal oxide has excellent optical properties as an antireflection film, but a film formation method by vapor deposition or sputtering is low in productivity and is not suitable for mass production.

  On the other hand, it replaces with a vapor deposition method and the method of forming an antireflection film by application | coating of an inorganic fine particle is proposed (patent documents 1-5). Among these, Patent Document 1 has a configuration of an antireflection layer having fine pores and fine inorganic particles, and the antireflection layer is formed by coating. The fine pores are formed by performing an activated gas treatment after the application of the layer and releasing the gas from the layer.

  Patent Document 2 discloses a structure of an antireflection film in which a support, a high refractive index layer, and a low refractive index layer are laminated in this order, and an antireflection film in which an intermediate refractive index layer is provided between the support and the high refractive index layer. The configuration is disclosed. This low refractive index layer is formed by application of a polymer or inorganic fine particles.

Patent document 3 is a proposal of the content which apply | coats an antireflection layer by the die-coating method. Patent Documents 4 and 5 are proposals that apply an antireflection layer by a die coating method, and can apply a thin layer with high accuracy by devising the structure of the die.
Japanese Patent Publication No. 60-59250 JP 59-50401 A JP 7-151904 A JP 2003-200097 A JP 2003-211052 A

  However, when an antireflection film is formed by a coating method, since the coating is applied in a very thin film thickness region of about ½ to ¼ of the visible light wavelength, the film thickness deviation has a large film thickness unevenness on the order of several nm. End up. Furthermore, since a slight film thickness unevenness of each layer becomes a color unevenness and the color is greatly shifted and detected as unevenness by visual observation, a coating technique for accurately controlling the film thickness is very important. The main places where film thickness unevenness occurs in the production process of the antireflection film are the coating part and the drying part after coating.

  On the other hand, the dip coating method, the micro gravure method, the reverse roll coating method and the like have been mainly used so far as the coating method of the antireflection film.

  However, in the dip coating method, vibration of the coating liquid in the liquid receiving tank is unavoidable, and stepped unevenness is likely to occur. Further, in the reverse roll coating method and the micro gravure method, stepped unevenness is likely to occur due to roll eccentricity and deflection related to coating. Furthermore, in the microgravure method, coating amount unevenness is likely to occur due to the manufacturing accuracy of the gravure roll and the change with time of the roll and the blade due to the contact between the blade and the gravure roll.

  Further, since these coating methods are post-measuring methods, it is relatively difficult to ensure a stable film thickness. Therefore, in these coating methods, it is difficult to increase the coating speed beyond a certain speed, and although the productivity is higher than that of the vapor deposition method or the like, the high productivity inherent in coating is not fully utilized.

  On the other hand, since the die coating method of Patent Document 3 described above is a pre-measuring application method, it has an advantage of high film thickness stability. However, since coating is performed using a generally used die configuration, it is possible to realize only high speed comparable to the above-described various coating methods. Specifically, in a thin layer coating such as an antireflection layer, film thickness unevenness occurs in a direction perpendicular to and parallel to the transport direction of the transparent support, and it is difficult to maintain film thickness stability. .

  On the other hand, in the above-described die coating methods of Patent Documents 4 and 5, a thin layer can be applied with high accuracy by devising the configuration of the die.

  However, even if coating is performed with the configuration shown in these patent documents, depending on the type of liquid, it is difficult to perform coating at high speed, and sometimes coating itself is impossible. Furthermore, even when the WET film thickness becomes stable during high-speed coating, a good surface shape may not be obtained due to film thickness unevenness that occurs in the immediately subsequent drying process.

  When an organic solvent is included in the coating liquid, especially when an uneven film thickness of several nanometers generated in the coating and drying process is visually recognized as a surface failure, such as an antireflection film, Causes significant product quality degradation.

In the drying process, a hot air drying method is usually used. Although this hot air drying method is excellent in drying efficiency, the air is applied directly or through a porous plate, a rectifier plate, etc. As a result, the thickness of the coating layer becomes uneven and unevenness occurs, or the evaporation rate of the solvent on the coating surface becomes non-uniform due to convection, and so-called crushed skin occurs, resulting in a uniform coating layer. There is a problem that can not be. In addition, it is possible to obtain a good surface condition by adjusting the conditions of the wind blown on the coating film and lowering the evaporation speed, but if the coating speed is lowered to increase productivity, the drying is completed. Therefore, it is not a preferable method for improving productivity.

  The present invention has been made in view of such circumstances, and an object thereof is to provide a method for producing a coating film and a method for producing an antireflection film, which are excellent in high-definition drawing properties, antireflection properties and antiglare properties. And Another object of the present invention is to provide a method for producing an antireflection film that has higher productivity than vapor deposition and other coating methods and high film thickness uniformity.

  In order to achieve the above object, the present invention according to claim 1 is directed to applying a coating liquid using a slot die onto a transparent support that is continuously supported by a backup roller, and a film thickness in a dry state. In the method for producing an antireflection film, in which at least one layer having a refractive index lower than that of the transparent support is formed at 200 nm or less, the transparent support running of the tip lip downstream in the transparent support running direction The direction land length is 30 to 100 μm, and the gap between the upstream end lip on the upstream side of the transparent support traveling direction and the surface of the transparent support is defined as the front end lip on the downstream side in the transparent support traveling direction and the transparent support. It is characterized by being set larger by 30 to 120 μm than the gap with the body surface.

  That is, as a result of intensive studies to solve the above problems, the inventor of the present invention is able to stably stabilize a thin layer of 200 nm or less like an antireflection film without film thickness unevenness by using a coating device in which the shape of the slot die is devised. The present inventors have found a novel method for producing an antireflective film that can be applied.

The present invention according to claim 2 has a viscosity of 20.0 mPa · sec or less when the coating liquid is applied, and the amount of the coating liquid applied on the transparent support is 2.0 to 5.0 ml. / M ² . Thus, a favorable surface shape can be obtained by further specifying the amount and viscosity of the coating solution applied to the transparent support.

That is, the present invention is useful when the amount of the coating solution applied to the transparent support is 20 ml / m ² or less, but in order to stably apply a film thickness of 200 nm or less, A particularly good surface shape can be obtained when the amount of the coating solution to be applied is ² to 5 ml / m ² . If the amount of the coating solution is less than 2 ml / m ^2, it is difficult to apply the entire surface, and if it exceeds 5 ml / m ² , unevenness due to disturbance of drying occurs.

  According to the third aspect of the present invention, a medium refractive index layer, a high refractive index layer, and a low refractive index layer are formed in this order from the transparent support side, and substantially three layers having different refractive indexes are formed. It is characterized by. Thus, it can be set as a high quality antireflection film by setting it as substantially 3 layers.

In the present invention according to claim 4, for the design wavelength λ (= 400 to 680 nm) of the antireflection film, the medium refractive index layer is represented by the following (formula 1), and the high refractive index layer is represented by the following ( Formula 2) is characterized in that the low refractive index layer satisfies the following (Formula 3).
λ / 4 × 0.80 <n1d1 <λ / 4 × 1.00 (Formula 1)
λ / 2 × 0.75 <n2d2 <λ / 2 × 0.95 (Formula 2)
λ / 4 × 0.95 <n3d3 <λ / 4 × 1.05 (Formula 3)
(In formula 1, n1 is the refractive index of the medium refractive index layer, d1 is the layer thickness (nm) of the medium refractive index layer, and in formula 2, n2 is the refractive index of the high refractive index layer, (d2 is the layer thickness (nm) of the high refractive index layer. In Formula 3, n3 is the refractive index of the low refractive index layer, and d3 is the layer thickness (nm) of the low refractive index layer.)
In the present invention according to claim 5, the refractive index n1 of the medium refractive index layer is 1.60 to 1.65, the high refraction, with respect to the transparent support having a refractive index of 1.45 to 1.55. The refractive index n2 of the refractive index layer is 1.85 to 1.95, and the refractive index n3 of the low refractive index layer is 1.35 to 1.45.

  The present invention according to claim 6 is characterized in that the layer having a lower refractive index than the transparent support or the low refractive index layer comprises a thermosetting and / or ionizing radiation curable fluorine-containing resin.

  In the present invention according to claim 7, the high refractive index layer contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium, and has a refractive index. It is 1.55 to 2.40.

  The present invention according to claim 8 is characterized by having at least one hard coat layer between the transparent support and a layer having a lower refractive index than the transparent support or the low refractive index layer. . Thus, it can be set as a high quality anti-reflective film by having a hard-coat layer.

  The present invention according to claim 9 is characterized in that one or more layers constituting the antireflection film are continuously formed without being wound up. Such continuous formation improves productivity.

  The present invention according to claim 10 is an antireflection film comprising at least one layer obtained by the production method according to any one of claims 1 to 9.

  The present invention according to claim 11 is a method for producing a coating film formed by applying a coating liquid using a slot die so that a continuously running web has a film thickness in a dry state of 200 nm or less. The land length in the web traveling direction of the tip lip on the downstream side of the slot die in the web traveling direction is set to 30 μm or more and 100 μm or less, and the wind turbulence near the coating surface is prevented by a dryer having a casing surrounding the web immediately after coating. Then, the coating film manufacturing method is characterized in that drying is performed by a drying apparatus that dries while keeping the solvent vapor on the coating surface side being dried at a high concentration.

  The present invention according to claim 12 is the coating film according to claim 11, wherein a condenser for condensing and recovering the solvent in the coating solution is provided on the coating surface side of the running position of the web in the dryer. It is a manufacturing method.

  The present invention according to claim 13 is the method for producing a coating film according to claim 12, wherein the condenser is provided with a cooling mechanism and temperature control is possible.

  According to a fourteenth aspect of the present invention, there is provided a coating film manufacturing method formed by applying a coating liquid using a slot die so that a continuously running web has a film thickness in a dry state of 200 nm or less. The web run direction land length of the tip lip on the downstream side of the web direction of the slot die is set to 30 μm or more and 100 μm or less, and the surface of the coating film is moved along the surface of the coating film. It is a method for producing a coated film, characterized in that the coating film is dried by a drying apparatus that is moved while moving at a relative speed of −0.1 m / second to 0.1 m / second relative to the speed.

The present invention according to claim 15 is a coating film formed by applying a coating solution to a continuously running web using a slot die so that the film thickness in a dry state is 200 nm or less and then drying with a drying apparatus. In the manufacturing method of
The land length in the web traveling direction of the tip lip on the downstream side in the web traveling direction of the slot die is 30 μm or more and 100 μm or less,
In addition, while the web is transported through the drying device, the organic solvent gas evaporated from the coating liquid applied to the web is released to the exhaust chamber through the hole of the air conditioning member, and enters the exhaust chamber. The coating film manufacturing method is characterized in that drying is performed using a drying device that exhausts the gas of the organic solvent to the outside through an exhaust pipe.

  According to a sixteenth aspect of the present invention, the clearance between the leading lip on the upstream side in the web running direction of the slot die and the web surface is made larger than the clearance between the leading lip on the downstream side of the web and the web. 16. The method for producing a coating film according to claim 11, wherein the coating film is produced.

  According to the seventeenth aspect of the present invention, the gap between the tip lip on the upstream side in the web running direction of the slot die and the web surface is 30 μm or more and 120 μm or less than the gap between the tip lip on the downstream side of the web and the web. It is enlarged in the range of this.

In the present invention according to claim 18, the overall length of the drying device is such that the coating film is transported in the drying device for 2 seconds or more, and the evaporation rate of the coating solution solvent in the drying device is 0. The method for producing a coating film according to any one of claims 11 to 17, wherein the coating film is at least ³ g / (m ² · sec).

  The present invention according to claim 19 is a coating film produced by the coating film manufacturing method according to any one of claims 11 to 18.

  The present invention according to claim 20 is characterized in that the coating film according to claim 19 has a dry film thickness of 200 nm or less and at least one layer having a lower refractive index than the transparent support as the web. It is an antireflection film characterized by having.

  The present invention according to claim 21 is a polarizing plate characterized in that the antireflection film according to claim 10 or 20 or the coating film according to claim 19 is attached to at least one surface of the polarizing film. It is.

  The present invention according to claim 22 is an optical compensation film having optical anisotropy, wherein the antireflection film according to claim 10 or 20 or the coating film according to claim 19 is adhered to one surface of the polarizing film. Is attached to the other surface of the polarizing film.

  The present invention according to claim 23 is an image display device comprising the antireflection film according to claim 10 or 20 or the coating film according to claim 19.

  The present invention according to claim 24 is an image display device comprising the polarizing plate according to claim 21 or 22.

  As described above, according to the present invention, it is possible to provide a high-quality and high-quality coating film and antireflection film.

  Hereinafter, preferred embodiments of an antireflection film according to the present invention, a method for producing the same, a polarizing plate using the film, and an image display device using them will be described in detail with reference to the accompanying drawings.

[Configuration of antireflection film]
FIG. 1 is a schematic cross-sectional view showing a basic layer structure of an antireflection film according to the present invention. The antireflection film has a layer structure in the order of a transparent support (1), a hard coat layer (2), a medium refractive index layer (3), a high refractive index layer (4), and a low refractive index layer (5). .

  Such an antireflection film having a five-layer structure has an optical film thickness of each of the medium refractive index layer (3), the high refractive index layer (4), and the low refractive index layer (5), that is, the refractive index and the film thickness. It is described in the above-mentioned Patent Document 2 that it is preferable that the product of is approximately λ / 4 or a multiple of the design wavelength λ.

  However, in order to realize the reflectance characteristic of the present invention with low reflectance and reduced color of reflected light, the middle refractive index layer (3) is particularly described below for the design wavelength λ (= 400 to 680 nm). (Equation 1), the high refractive index layer (4) must satisfy the following (Equation 2), and the low refractive index layer (5) must satisfy the following (Equation 3). The design wavelength λ is desirably 400 to 600 nm, more desirably 450 to 550 nm, and most desirably 475 to 525 nm.

[Equation 1]
λ / 4 × 0.80 <n1d1 <λ / 4 × 1.00 (Formula 1)
[Equation 2]
λ / 2 × 0.75 <n2d2 <λ / 2 × 0.95 (Formula 2)
[Equation 3]
λ / 4 × 0.95 <n3d3 <λ / 4 × 1.05 (Formula 3)
In the above formulas, n1 is the refractive index of the medium refractive index layer (3), d1 is the layer thickness (nm) of the medium refractive index layer (3), and n2 is the refractive index of the high refractive index layer (4). D2 is the layer thickness (nm) of the high refractive index layer (4), n3 is the refractive index of the low refractive index layer (5), and d3 is the layer thickness (nm) of the low refractive index layer (5). ).

  Further, for a transparent support having a refractive index of 1.45 to 1.55 such as triacetylcellulose (refractive index: 1.49), n1 is 1.60 to 1.65, and n2 is 1. .85 to 1.95, n3 must have a refractive index of 1.35 to 1.45, for example, a refractive index of 1.55 to 1.65 made of polyethylene terephthalate (refractive index: 1.66). N1 is 1.65 to 1.75, n2 is 1.85 to 2.05, and n3 is 1.35 to 1.45.

  When the material of the medium refractive index layer (3) or the high refractive index layer (4) having the above refractive index cannot be selected, a layer having a refractive index higher than the set refractive index and a layer having a low refractive index It is known that a layer that is optically equivalent to the medium refractive index layer (3) or the high refractive index layer (4) having a set refractive index can be formed using the principle of an equivalent film in which a plurality of layers are combined. It can also be used to realize the reflectance characteristics of the present invention.

  In the present invention, “substantially three layers” includes an antireflection layer composed of terms having different refractive indexes of four layers and five layers using such an equivalent film.

  Further, when a hard coat layer (2) is applied on the transparent support (1) or the transparent support (1) and a low refractive index layer (5) is laminated as a refractive index layer, an antireflection film is obtained. It can be used suitably.

  As shown in FIG. 2 to FIG. 7, the high refractive index layer (4) is further applied on the transparent support (1) or the hard coat layer (2) on the transparent support (1). Even if the low refractive index layer (5) is laminated, it can be suitably used as an antireflection film.

  The hard coat layer (2) may have antiglare properties. The antiglare property may be formed by dispersion of matte particles as shown in FIG. 6 or may be formed by surface shaping by a method such as embossing as shown in FIG.

[Explanation of materials for each layer]
<Base film>
As a base film used for the antireflection film of the present invention, the following transparent support can be used. The base film is also called a web. A plastic film is preferably used as the transparent support (1). Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl It includes methacrylate and polyether ketone.

  In particular, triacetylcellulose is preferably used when the antireflection film of the present invention is used as one side of a surface protective film of a polarizing plate for use in a liquid crystal display device, an organic EL display device or the like. As the triacetyl cellulose film, a known film such as TAC-TD80U (manufactured by Fuji Photo Film Co., Ltd.) or a film disclosed in the public technical report number 2001-1745 is preferably used.

  In addition, polyethylene terephthalate or polyethylene naphthalate is preferable when it is used by being attached to a glass substrate or the like for use in a flat CRT or PDP.

  The light transmittance of the transparent support (1) is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support (1) is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support (1) is preferably 1.4 to 1.7.

  Although the thickness of the transparent support body (1) of this invention is not specifically limited, 30-150 micrometers is preferable, 40-130 micrometers is more preferable, 70-120 micrometers is still more preferable.

[Hard coat layer]
The hard coat layer (2) is provided on the surface of the transparent support (1) in order to impart physical strength (also referred to as scratch resistance) to the antireflection film. In particular, it is preferably provided between the transparent support (1) and the high refractive index layer (4).

  The hard coat layer (2) is preferably formed by a crosslinking reaction or a polymerization reaction of a photocurable and / or thermosetting compound. For example, a coating composition containing polyester (meth) acrylate, polyurethane (meth) acrylate, polyfunctional monomer, polyfunctional oligomer or hydrolyzable functional group-containing organometallic compound is coated on the transparent support (1) and cured. It can be formed by subjecting a functional compound to a crosslinking reaction or a polymerization reaction.

  The curable functional group is preferably a photopolymerizable functional group, and the hydrolyzable functional group-containing organometallic compound is preferably an organic alkoxysilyl compound. Specifically, the same content as that of the matrix binder of the high refractive index layer (4) described later can be mentioned.

  A more preferred embodiment is to use a polymerizable compound that cures by radical polymerization reaction and cationic polymerization reaction. The polymerizable compound may contain a radical polymerizable group and a cationic polymerizable group in the same molecule, or may be a compound contained in different molecules and a mixture of both.

  A multilayer antireflection film composed of a curable film formed from a curable composition mainly containing these polymerizable compounds makes it possible to form the surface irregularities uniformly and stably by embossing. These are presumed to be due to appropriate action of thermoelastic deformation of the hard coat layer (2).

  Preferred embodiments of the curable composition include both a crosslinkable polymer containing a repeating unit represented by the following (Chemical Formula 1) and a compound containing two or more ethylenically unsaturated groups in the same molecule. And a curable composition that contains and cures by polymerizing both the ring-opening polymerizable group and the ethylenically unsaturated group in the crosslinkable polymer.

この化学式１において、ａ^１ 及びａ^２ は、各々同じでも異なってもよく、水素原子、脂肪族基、―ＣＯＯＲ_１、又は−ＣＨ_２ ＣＯＯＲ_１ を表す。Ｒ_１ は炭化水素基を表す。Ｐは、開環重合性基を含む一価の基又はエチレン性不飽和基を表す。Ｌは、単結合又は二価の連結基を表す。

In the chemical formula 1, a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ₁ , or —CH ₂ COOR ₁ . R ₁ represents a hydrocarbon group. P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group. L represents a single bond or a divalent linking group.

Next, the crosslinkable polymer containing the repeating unit represented by Chemical Formula 1 will be described in detail. In Chemical Formula 1, a ¹ and a ² represent a hydrogen atom, an aliphatic group, preferably an alkyl group having 1 to 4 carbon atoms, —COOR ₁ , or —CH ₂ COOR ₁ . R ₁ represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

  L is a single bond or a divalent linking group, preferably a single bond, -O-, an alkylene group, an arylene group, * -COO-, * -CONH-, * -OCO-, or * -NHCO-. (Here, * means linking to the main chain on the * side).

  P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group. The monovalent group containing a ring-opening polymerizable group is a monovalent group having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, etc. Among them, cationic ring-opening polymerization of a heterocyclic compound Is preferred.

  Examples of the monovalent group including a ring-opening polymerizable group include a monovalent group including a vinyloxy group or an imino ether ring such as an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, or an oxazoline ring. Among these, a monovalent group including an epoxy ring, an oxetane ring and an oxazoline ring is particularly preferable, and a monovalent group including an epoxy ring is most preferable.

  When P represents an ethylenically unsaturated group, preferred ethylenically unsaturated groups include acryloyl group, methacryloyl group, styryl group, and vinyloxycarbonyl group.

  The crosslinkable polymer containing the repeating unit represented by Chemical Formula 1 of the present invention is preferably synthesized simply by polymerizing the corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction.

  Although the preferable specific example of the repeating unit represented by Chemical formula 1 is shown as Chemical formula 2 below, this invention is not limited to these.

本発明の化学式１で表される繰り返し単位のうち、より好ましい例としては、エポキシ環を有するメタクリレート又はアクリレートから誘導される繰り返し単位であり、その中でも特に好ましい例としてグリシジルメタクリレート、グリシジルアクリレートから誘導されるＥ−１、Ｅ−３を挙げることができる。

Among the repeating units represented by the chemical formula 1 of the present invention, a more preferable example is a repeating unit derived from a methacrylate or acrylate having an epoxy ring. Among them, a particularly preferable example is derived from glycidyl methacrylate or glycidyl acrylate. E-1 and E-3.

  In addition, the crosslinkable polymer containing the repeating unit represented by the chemical formula 1 of the present invention may be a copolymer composed of a plurality of types of repeating units represented by the chemical formula 1, and among them, in particular, E-1, E- Curing shrinkage can be more effectively reduced by using any one of the three copolymers.

  The crosslinkable polymer containing a repeating unit represented by Chemical Formula 1 of the present invention may be a copolymer containing a repeating unit other than Chemical Formula 1. In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or to control the content of the ring-opening polymerizable group of the crosslinkable polymer, a copolymer containing a repeating unit other than the chemical formula 1 can be used. As a method for introducing a repeating unit other than the chemical formula 1, a method of introducing a corresponding monomer by copolymerization is preferable.

  When a repeating unit other than the formula 1 is introduced by copolymerizing a corresponding vinyl monomer, preferably used monomers include esters derived from acrylic acid or α-alkyl acrylic acid (for example, methacrylic acid). Or amides (for example, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropane) Sulfonic acid, acrylamide propyl trimethyl ammonium chloride, methacrylamide, diacetone acrylamide, acryloyl morpholine, N-methylol acrylamide, N-methylol methacrylamide, alkyl ester (meta Acrylate (as alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, octafluoropentyl (meth) acrylate, cyclohexyl (meth ) Acrylate, cyclopentyl (meth) acrylate, 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-ylmethyl (meth) acrylate 3-methyl-2-norbornylmethyl (Meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.), acrylic acid or α-alkyl acrylic acid (acrylic acid, methacrylic acid) , Itaconic acid, etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimides (N-phenylmaleimide, etc.) Maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg butadiene, cyclopentadiene, isoprene), aromatic vinyl compounds (eg styrene, p-chlorostyrene, t-butylstyrene) , Α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl -N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chloride, vinyl alcohol Ethers (e.g. methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like.

  Two or more of these vinyl monomers may be used in combination. Vinyl monomers other than these are listed in Research Disclosure No. Those described in 19551 (1980, July) can be used.

  In the present invention, esters derived from acrylic acid or methacrylic acid, amides, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

  A repeating unit having a reactive group other than the ring-opening polymerizable group or the ethylenically unsaturated group as a repeating unit other than the chemical formula 1 can also be introduced. In particular, when it is desired to increase the hardness of the hard coat layer (2) or to improve the adhesion between layers when another functional layer is used on the substrate or the hard coat, a reactive group other than the ring-opening polymerizable group. A method of forming a copolymer containing is preferable. As a method for introducing a repeating unit having a reactive group other than the ring-opening polymerizable group, a method of copolymerizing a corresponding vinyl monomer (hereinafter referred to as “reactive monomer”) is simple and preferable.

  Although the preferable specific example of a reactive monomer is shown below, this invention is not limited to these.

<Preferable specific example of reactive monomer>
Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N -Methylol group-containing vinyl monomers (for example, N-methylol acrylamide, N-methylol methacrylamide, etc.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halides Vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate) ), Acid anhydride-containing vinyl monomers (eg maleic anhydride), formyl group-containing vinyl monomers (eg acrolein, methacrolein), sulfinic acid group-containing vinyl monomers (eg potassium styrenesulfinate), active methylene-containing vinyl monomers ( Examples thereof include acetoacetoxyethyl methacrylate), amino group-containing monomers (for example, allylamine), alkoxysilyl group-containing monomers (for example, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltrimethoxysilane), and the like.

  In the crosslinkable polymer containing the repeating unit represented by Chemical Formula 1 of the present invention, the proportion of the repeating unit represented by Chemical Formula 1 is 30% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass. Hereinafter, it is particularly preferably 70% by mass or more and 100% by mass or less.

  When the repeating unit other than chemical formula 1 does not have a crosslinking reactive group, the hardness decreases if the content is too large, and when it has a crosslinking reactive group, the hardness may be maintained, but curing shrinkage increases. Or brittleness may worsen.

  In particular, when a molecular weight decrease such as dehydration or dealcoholization occurs during a crosslinking reaction, such as when a copolymer of an alkoxysilyl group-containing monomer (for example, methacryloyloxypropyltrimethoxysilane) and a repeating unit represented by Chemical Formula 1 is used. Curing shrinkage tends to increase.

  When a repeating unit having a crosslinking reactive group that undergoes a crosslinking reaction with a decrease in molecular weight is introduced into a crosslinkable polymer containing a repeating unit represented by Chemical Formula 1 of the present invention, it is represented by Chemical Formula 1. The preferable ratio in which the repeating unit is contained is 70 to 99% by mass, more preferably 80 to 99% by mass, and particularly preferably 90 to 99% by mass.

  The preferred molecular weight range of the crosslinkable polymer containing the repeating unit represented by Chemical Formula 1 is from 1,000 to 1,000,000, more preferably from 3,000 to 200,000, and most preferably from 5,000 to 100,000. It is as follows. In addition, the said mass mean molecular weight is measured by GPC method and is a polystyrene conversion value.

  A compound containing two or more ethylenically unsaturated groups in the same molecule that can be used in the present invention will be described. Preferred types of ethylenically unsaturated groups are acryloyl group, methacryloyl group, styryl group and vinyl ether group, particularly preferably methacryloyl group or acryloyl group, particularly preferably acryloyl group.

  Although the compound containing an ethylenically unsaturated group should just have two or more ethylenically unsaturated groups in a molecule | numerator, More preferably, it is three or more. Among them, a compound having an acryloyl group is preferable, and a compound called a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule or a molecule called urethane acrylate, polyester acrylate or epoxy acrylate. An oligomer having several acrylate groups and a molecular weight of several hundred to several thousand can be preferably used. Specifically, the same thing as the polyfunctional monomer of the high refractive index layer (4) mentioned later is mentioned.

  These polymerizable compounds are preferably used in combination with a polymerization initiator, and specific examples thereof include those described in the high refractive index layer (4) described later.

  The hard coat layer (2) preferably contains inorganic fine particles having an average primary particle size of 300 nm or less. The average particle size of the primary particles is more preferably 10 to 150 nm, still more preferably 20 to 100 nm. The average particle diameter here is a mass average diameter. By setting the average particle size of the primary particles to 200 nm or less, the hard coat layer (2) that does not impair the transparency can be formed.

  The inorganic fine particles have functions of increasing the hardness of the hard coat layer (2) and suppressing curing shrinkage of the coating layer. It is also added for the purpose of controlling the refractive index of the hard coat layer (2).

  Specific examples of the composition of the hard coat layer (2) include those described in JP-A Nos. 2002-144913, 2000-9908 and WO0 / 46617.

  The content of the inorganic fine particles in the hard coat layer (2) is preferably 10 to 90% by mass and more preferably 15 to 80% by mass with respect to the total mass of the hard coat layer (2).

  The high refractive index layer (4) can also serve as the hard coat layer (2). When the high refractive index layer (4) also serves as the hard coat layer (2), the fine inorganic particles are finely dispersed using the method described in the high refractive index layer (4), and are contained in the hard coat layer (2). It is preferable to form them.

  The film thickness of the hard coat layer (2) can be appropriately designed depending on the application. The film thickness of the hard coat layer (2) is preferably 0.2 to 15 μm, more preferably 0.5 to 12 μm, and particularly preferably 0.7 to 10 μm.

  The strength of the hard coat layer (2) is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.

  Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

[High refractive index layer]
The high refractive index layer (4) of the present invention typically has a refractive index of 1.55 to 2.40, which is formed by applying a curable composition containing at least high refractive index inorganic compound fine particles and a matrix binder. It consists of a sex membrane. The refractive index is preferably 1.65 to 2.30, and more preferably 1.80 to 2.00. The refractive index of the high refractive index layer (4) of the present invention is 1.55 to 2.40, which is a so-called high refractive index layer or a medium refractive index layer. In the present specification below, This layer may be collectively referred to as a high refractive index layer.

[Composition for high refractive index layer]
[High refractive index particles]
The high refractive index inorganic fine particles contained in the high refractive index layer (4) of the present invention preferably have a refractive index of 1.80 to 2.80 and an average primary particle size of 3 to 150 nm. Particles having a refractive index of less than 1.80 are not preferable because the effect of increasing the refractive index of the film is small, and particles having a refractive index of more than 2.80 are colored. Further, particles having an average primary particle diameter exceeding 150 nm are not preferable because the haze value when a film is formed is high, and the transparency of the film is impaired, and if it is less than 3 nm, it is difficult to maintain a high refractive index.

  In the present invention, more preferred inorganic fine particles are those having a refractive index of 1.90 to 2.80 and primary particles having an average particle diameter of 3 to 100 nm, and more preferably a refractive index of 1.90 to 2.80. And the average particle diameter of a primary particle is a particle | grain of 5-80 nm.

  Specific examples of preferable high refractive index inorganic fine particles include oxides or composite oxides such as Ti, Zr, Ta, In, Nd, Sn, Sb, Zn, La, W, Ce, Nb, V, Sm, and Y, and sulfide. The particle | grains which have an object as a main component are mentioned. Here, the main component refers to a component having the largest content (mass%) among the components constituting the particles.

  In the present invention, particles mainly composed of an oxide or composite oxide containing at least one metal element selected from Ti, Zr, Ta, In, and Sn are preferred. The inorganic fine particles used in the present invention may contain various elements in the particles.

  Examples thereof include Li, Si, Al, B, Ba, Co, Fe, Hg, Ag, Pt, Au, Cr, Bi, P, and S. In the case of tin oxide and indium oxide, it is preferable to contain elements such as Sb, Nb, P, B, In, V, and halogen in order to increase the conductivity of the particles, and in particular, about 5 to 20% by mass of antimony oxide. What was contained is most preferable.

  Particularly preferred are inorganic fine particles mainly containing titanium dioxide containing at least one element selected from Co, Zr, and Al (hereinafter sometimes referred to as “specific oxide”). In particular, the preferred element is Co.

  The total content of Co, Al, and Zr with respect to Ti is preferably 0.05 to 30% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.2 to 7% by mass with respect to Ti. %, Particularly preferably 0.3 to 5% by mass, most preferably 0.5 to 3% by mass.

  Co, Al, and Zr are present inside or on the surface of inorganic fine particles mainly composed of titanium dioxide. These are more preferably present inside the inorganic fine particles mainly composed of titanium dioxide, and most preferably present both inside and on the surface. These specific metal elements may exist as oxides.

  Further, as another preferable inorganic particle, a double oxide of titanium element and at least one metal element (hereinafter also abbreviated as “Met”) selected from metal elements whose oxide has a refractive index of 1.95 or more The particles and the double oxide include inorganic fine particles doped with at least one metal ion selected from Co ions, Zr ions, and Al ions (sometimes referred to as “specific double oxide”). It is done.

  Here, Ta, Zr, In, Nd, Sb, Sn, and Bi are preferable as the metal element of the metal oxide having a refractive index of 1.95 or more. In particular, Ta, Zr, Sn, and Bi are preferable. The content of the metal ions doped in the double oxide is preferably within a range not exceeding 25 mass% with respect to the total amount of metal [Ti + Met] constituting the double oxide from the viewpoint of maintaining the refractive index. More preferably, it is 0.05-10 mass%, More preferably, it is 0.1-5 mass%, Most preferably, it is 0.3-3 mass%.

  The doped metal ion may exist as either a metal ion or a metal atom, and appropriately exists from the surface to the inside of the double oxide. It is preferably present both on the surface and inside.

  The inorganic fine particles used in the present invention preferably have a crystal structure or an amorphous structure. The crystal structure is preferably mainly composed of rutile, a mixed crystal of rutile / anatase, or anatase, and particularly preferably a rutile structure. Thereby, the inorganic fine particles of the specific oxide or specific double oxide of the present invention are 1.90 to 2.80, preferably 2.10 to 2.80, more preferably 2.20 to 2.80. It is possible to have a refractive index of Moreover, the photocatalytic activity of titanium dioxide can be suppressed, and the weather resistance of the high refractive index layer (4) of the present invention can be remarkably improved.

  A conventionally known method can be used as a method of doping the above-described specific metal element or metal ion. For example, methods described in JP-A-5-330825, JP-A-11-263620, JP-A-11-512336, European Patent No. 0335773, etc., ion implantation methods (for example, Shunichi Gonda, Jun Ishikawa) 3. Eiji Kamijo, “Ion beam applied technology” (CMC Co., Ltd., published in 1989, Yasushi Aoki, Surface Science, Vol.18, (5), pp.262, 1998, Shoichi Anbo, etc. Science, Vol. 20 (2), pp60, 1999 and the like).

  The inorganic fine particles used in the present invention may be surface treated. In the surface treatment, the surface of the particles is modified using an inorganic compound and / or an organic compound, the wettability of the surface of the inorganic particles is adjusted to make fine particles in an organic solvent, and the composition for forming a high refractive index layer Dispersibility and dispersion stability can be improved.

Examples of inorganic compounds that can be modified by physicochemical adsorption on the particle surface include inorganic compounds containing silicon (such as SiO ₂ ) and inorganic compounds containing aluminum (Al ₂ O _3). , Al (OH) ₃ ), inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O ₄ etc.), inorganic compounds containing zirconium (ZrO ₂ , Zr (OH) ₄ etc.), iron And inorganic compounds containing Fe (such as Fe ₂ O ₃ ).

  Moreover, the surface modifier of inorganic fillers, such as a conventionally well-known metal oxide and an inorganic pigment, can be used for the example of the organic compound used for surface treatment. For example, it is described in “Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation”, Chapter 1 (Technical Information Association, 2001).

  Specifically, an organic compound having a polar group having an affinity for the surface of the inorganic particles can be used. Such organic compounds include compounds referred to as coupling compounds. Examples of the polar group having affinity with the inorganic particle surface include a carboxyl group, a phosphono group, a hydroxy group, a mercapto group, a cyclic acid anhydride group, and an amino group, and a compound containing at least one kind in the molecule is preferable. .

  For example, long chain aliphatic carboxylic acids (eg stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, etc.), polyol compounds (eg pentaerythritol triacrylate, dipentaerythritol pentaacrylate, ECH (epichlorohydrin) modified glycerol triacrylate) Etc.), phosphono group-containing compounds (for example, EO (ethylene oxide) -modified phosphate triacrylate, etc.), alkanolamines (ethylenediamine EO adducts (5 mol), etc.).

  As a coupling compound, a conventionally well-known organometallic compound is mentioned, A silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc. are contained. Of these, a silane coupling agent is most preferable. Specific examples include compounds described in paragraph numbers “0011” to “0015” in JP-A-2002-9908 and 2001-310423.

  Two or more kinds of these surface treatments can be used in combination.

  As the oxide fine particles used in the present invention, fine particles having a core / shell structure that forms a shell made of an inorganic compound using the fine oxide particles as a core are also preferable. The shell is preferably an oxide composed of at least one element selected from Al, Si, and Zr. Specifically, for example, the contents described in JP-A-2001-166104 can be mentioned.

  The shape of the inorganic fine particles used in the present invention is not particularly limited, but is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, or an indefinite shape. The inorganic fine particles of the present invention may be used alone or in combination of two or more.

(Dispersant)
In order to use the inorganic particles used in the present invention as stable predetermined ultrafine particles, it is preferable to use a dispersant together. The dispersant is preferably a low molecular compound or a high molecular compound having a polar group having an affinity for the surface of the inorganic fine particles.

Examples of the polar group include a hydroxy group, a mercapto group, a carboxyl group, a sulfo group, a phosphono group, an oxyphosphono group, a -P (= O) (R ₁ ) (OH) group, and a -OP (= O) (R ₁ ) (OH) group, amide group (—CONHR ₂ , —SO ₂ NHR ₂ ), cyclic acid anhydride-containing group, amino group, quaternary ammonium group and the like.

Here, R ₁ represents a hydrocarbon group having 1 to 18 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxy group) Ethyl group, cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, cyclohexyl group, etc.). R ₂ represents a hydrogen atom or the same content as R 1.

  In the polar group, the group having a dissociable proton may be a salt thereof. The amino group and quaternary ammonium group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, and more preferably a tertiary amino group or a quaternary ammonium group.

The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is an aliphatic group having 1 to 12 carbon atoms (such as those having the same contents as the group of R ₁ above). It is preferable.

  The tertiary amino group may be a ring-forming amino group containing a nitrogen atom (for example, a piperidine ring, a morpholine ring, a piperazine ring, a pyridine ring, etc.), and the quaternary ammonium group is a cyclic amino group. Or a quaternary ammonium group. In particular, an alkyl group having 1 to 6 carbon atoms is more preferable.

  The polar group of the dispersant according to the present invention is preferably an anionic group having a pKa of 7 or less or a salt of these dissociating groups. In particular, a carboxyl group, a sulfo group, a phosphono group, an oxyphosphono group, or a salt of these dissociating groups is preferable.

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. As the crosslinkable or polymerizable functional group, an ethylenically unsaturated group (for example, (meth) acryloyl group, allyl group, styryl group, vinyloxy group carbonyl group, vinyloxy group, etc.) capable of addition reaction / polymerization reaction by radical species, And cationically polymerizable groups (epoxy groups, thioepoxy groups, oxetanyl groups, vinyloxy groups, spiroorthoester groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, preferably ethylene. An unsaturated group, an epoxy group, or a hydrolyzable silyl group.

  Specifically, for example, compounds described in paragraph Nos. [0013] to [0015] in JP-A No. 11-153703, Patent No. US6110858B1, JP-A No. 2002-276069, and JP-A No. 2001-310423. Etc.

  The dispersant used in the present invention is also preferably a polymer dispersant. In particular, polymer dispersants containing an anionic group and a crosslinkable or polymerizable functional group are exemplified, and these functional groups are the same as those described above.

  The amount of the dispersant used relative to the inorganic fine particles is preferably in the range of 1 to 100% by mass, more preferably 3 to 50% by mass, and most preferably 5 to 40% by mass. Two or more dispersants may be used in combination.

(Dispersion medium)
In the present invention, the dispersion medium used for wet dispersion of inorganic fine particles can be appropriately selected from water and organic solvents, and is preferably a liquid having a boiling point of 50 ° C. or higher, and has a boiling point of 60 to 180 °. More preferably, the organic solvent is in the range of C.

  The dispersion medium is preferably used at a ratio of 5 to 50% by mass of the total dispersion composition containing inorganic fine particles and a dispersant. More preferably, it is a ratio of 10 to 30% by mass. Within this range, dispersion proceeds easily, and the resulting dispersion is in a viscosity range with good workability.

  Examples of the dispersion medium include alcohols, ketones, ester amides, ethers, ether esters, hydrocarbons, halogenated hydrocarbons and the like.

  Specifically, alcohols (eg, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.), ketones (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.), Esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, Methyl chloroform, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone, etc.), ethers (eg, dioxane, tetra Dorofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.), ether alcohols (e.g., 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol and the like).

  Two or more of them may be mixed and used. Preferred dispersion media include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol. A coating solvent system mainly comprising a ketone solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) is also preferably used.

(Inorganic fine particles)
When the curable coating composition for forming the high refractive index layer (4) of the present invention is a composition in which inorganic ultrafine particles having an average particle diameter of 100 nm or less are dispersed, the stability of the liquid of the composition is improved. The cured film formed from this curable coating composition has an inorganic fine particle uniformly dispersed in an ultrafine particle state in the matrix of the cured film, and has a high refractive index film with uniform optical properties and transparency. Achieved. The size of the ultrafine particles present in the matrix of the cured film is preferably in the range of an average particle size of 3 to 100 nm, more preferably 5 to 100 nm. In particular, 10 to 80 nm is most preferable.

  Furthermore, it is preferable that large particles having an average particle diameter of 500 nm or more are not included, and it is particularly preferable that large particles having an average particle diameter of 300 nm or more are not included. Thereby, the specific uneven | corrugated shape mentioned above can form the cured film surface.

  In order to disperse the high refractive index inorganic particles in the size of ultrafine particles not containing coarse particles in the above range, for example, a wet dispersion method using a medium having an average particle diameter of less than 0.8 mm together with the dispersant Achieved with a method of dispersing in

  Examples of the wet disperser include conventionally known ones such as a sand grinder mill (eg, a bead mill with pins), a dyno mill, a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. In particular, a sand grinder mill, a dyno mill, and a high-speed impeller mill are preferable for dispersing the oxide fine particles of the present invention in ultrafine particles.

  As the media used together with the disperser, the average particle size is less than 0.8 mm, and when the average particle size is within this range, the above-mentioned inorganic fine particle size is 100 nm or less and the particle size is uniform. Fine particles can be obtained. The average particle size of the media is preferably 0.5 mm or less, more preferably 0.05 to 0.3 mm.

  Moreover, as a medium used for wet dispersion, beads are preferable. Specific examples include zirconia beads, glass beads, ceramic beads, steel beads, etc., and 0.05 to 0.2 mm from the viewpoint of durability and ultrafine particle formation such that the beads are not easily broken during dispersion. Zirconia beads are particularly preferred.

  The dispersion temperature in the dispersion step is preferably 20 to 60 ° C, more preferably 25 to 45 ° C. When dispersed in ultrafine particles at a temperature in this range, re-aggregation and precipitation of the dispersed particles do not occur. This is presumably because the dispersant is appropriately adsorbed on the inorganic compound particles and does not cause poor dispersion stability due to desorption of the dispersant from the particles at room temperature.

  By using the dispersion method described above, a high refractive index film excellent in refractive index uniformity, film strength, adhesion to an adjacent layer and the like that do not impair transparency is preferably formed.

  Moreover, you may implement a preliminary dispersion process before the said wet dispersion | distribution process. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  Furthermore, the dispersion particles in the dispersion satisfy the above-mentioned range of the average particle diameter and the monodispersibility of the particle diameter, and in the separation treatment with beads in order to remove coarse aggregates in the dispersion. It is also preferable to arrange the filter medium so as to be microfiltered. The filter medium for fine filtration preferably has a filtration particle size of 25 μm or less.

  The type of filter medium for microfiltration is not particularly limited as long as it has the above performance, and examples thereof include a filament type, a felt type, and a mesh type. The material of the filter medium for finely filtering the dispersion is not particularly limited as long as it has the above-described performance and does not adversely affect the coating solution. Examples thereof include stainless steel, polyethylene, polypropylene, and nylon.

(Matrix of high refractive index layer)
The high refractive index layer (4) contains at least high refractive index inorganic ultrafine particles and a matrix. According to a preferred embodiment of the present invention, the matrix of the high refractive index layer is at least one of (i) an organic binder, or (ii) an organometallic compound containing a hydrolyzable functional group and a partial condensate of the organometallic compound. It is formed by curing after applying a composition for forming a high refractive index layer containing.

(I) Organic binder As the organic binder,
(A) a conventionally known thermoplastic resin;
(B) A combination of a conventionally known reactive curable resin and a curing agent, or
(C) A combination of a binder precursor (such as a curable polyfunctional monomer or polyfunctional oligomer described below) and a polymerization initiator,
The binder formed from is mentioned.

  A coating composition for forming a high refractive index layer is prepared from a dispersion containing the binder forming component (a), (b) or (c) above, a high refractive index composite oxide fine particle and a dispersant. After apply | coating a coating composition on a transparent support body and forming a coating film, it hardens | cures by the method according to the component for binder formation, and a high refractive index layer (4) is formed.

  The curing method is appropriately selected according to the type of the binder component. For example, a crosslinking reaction or a polymerization reaction of a curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer) is performed by at least one of heating and light irradiation. The method to make it occur is mentioned. Especially, the method of forming the binder which hardened | cured the crosslinking reaction or the polymerization reaction of the curable compound by irradiating light using the combination of said (c) is preferable.

  Furthermore, it is preferable that the dispersing agent contained in the dispersion liquid of the high refractive index composite oxide fine particles is subjected to a crosslinking reaction or a polymerization reaction at the same time or after the coating composition for forming the high refractive index layer.

  The binder in the cured film produced in this way is, for example, the above-mentioned dispersant and the curable polyfunctional monomer or polyfunctional oligomer that is the precursor of the binder undergoes a crosslinking or polymerization reaction, and the binder contains the dispersant. An anionic group is incorporated.

  Further, since the binder in the cured film has a function in which the anionic group maintains the dispersion state of the inorganic fine particles, the crosslinked or polymerized structure imparts a film forming ability to the binder and contains high refractive index inorganic compound fine particles. The physical strength, chemical resistance, and weather resistance in the cured film can be improved.

  Examples of the thermoplastic resin include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, polyvinyl chloride copolymer resin, polyacrylic resin, polymethacrylic resin, and polyolefin resin. , Urethane resin, silicon resin, imide resin and the like.

  Moreover, it is preferable to use the said reaction curable resin, ie, a thermosetting resin, and / or an ionizing radiation curable resin. Thermosetting resins include phenolic resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea co-condensation resin, silicon resin, polysiloxane Examples thereof include resins.

  Examples of ionizing radiation curable resins include radical polymerizable unsaturated groups ((meth) acryloyloxy groups, vinyloxy groups, styryl groups, vinyl groups, etc.) and / or cationic polymerizable groups (epoxy groups, thioepoxy groups, vinyloxy groups). , Oxetanyl group, etc.), for example, relatively low molecular weight polyester resin, polyether resin, (meth) acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol Examples include polyene resins.

  As needed for these reaction curable resins, crosslinking agents (epoxy compounds, polyisocyanate compounds, polyol compounds, polyamine compounds, melamine compounds, etc.), polymerization initiators (azobis compounds, organic peroxide compounds, organic halogen compounds, oniums) Conventionally known compounds such as curing agents such as UV photoinitiators such as salt compounds and ketone compounds) and polymerization accelerators (organic metal compounds, acid compounds, basic compounds, etc.) are used. Specific examples include compounds described by Fuzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” (Taisei, 1981).

  Hereinafter, a method for forming a cured binder by crosslinking or polymerizing a curable compound by light irradiation using the combination of (c), which is a preferable method for forming a cured binder, will be mainly described.

  The functional group of the photocurable polyfunctional monomer or polyfunctional oligomer may be either radically polymerizable or cationically polymerizable.

  Examples of the radical polymerizable functional group include an ethylenically unsaturated group such as a (meth) acryloyl group, a vinyloxy group, a styryl group, and an allyl group, and among them, a (meth) acryloyl group is preferable.

  It is preferable to contain a polyfunctional monomer containing two or more radically polymerizable groups in the molecule.

  The radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds. Preferably, it is a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule. Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof, and copolymers thereof.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide-modified products and caprolactone-modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2- Acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  Examples of the radical polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Examples thereof include esters of saturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds.

  Also, addition reaction products of unsaturated carboxylic acid esters and amides having nucleophilic substituents such as hydroxyl group, amino group and mercapto group with monofunctional or polyfunctional isocyanates and epoxies, polyfunctional carboxylic acids A dehydration condensation reaction product with an acid or the like is also preferably used.

  A reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene or the like instead of the unsaturated carboxylic acid.

  Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like.

  Polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids, for example, as described in paragraph numbers [0026] to [0027] of JP-A-2001-139663, for example. The compound of this is mentioned.

  Examples of other polymerizable esters include, for example, vinyl methacrylate, allyl methacrylate, allyl acrylate, aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, and JP-A-57-196231. Those having an aromatic skeleton as described in JP-A-2-226149 and those having an amino group as described in JP-A-1-165613 are also preferably used.

  Specific examples of polymerizable amides formed from an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis- (meth) acrylamide, 1,6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris ( Examples include meth) acrylamide, xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, it has a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule (Japanese Patent Publication No. 48-41708), urethane acrylates (Japanese Patent Publication No. 2-16765), and an ethylene oxide skeleton. Urethane compounds (Japanese Patent Publication No. 62-39418, etc.), polyester acrylates (Japanese Patent Publication No. 52-30490, etc.), and further described in Japan Adhesion Association Vol. 20, No. 7, pages 300-308 (1984). These photocurable monomers and oligomers can also be used.

  These radical polymerizable polyfunctional monomers may be used in combination of two or more.

  Next, a cation polymerizable group-containing compound (hereinafter also referred to as “cation polymerizable compound” or “cation polymerizable organic compound”) that can be used for forming the binder of the high refractive index layer (4) will be described.

  As the cationically polymerizable compound used in the present invention, any compound that causes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used. Examples include epoxy compounds, cyclic thioether compounds, cyclic ether compounds, spiro orthoester compounds, vinyl ether compounds, and the like. In the present invention, one or more of the above cationic polymerizable organic compounds may be used.

  As the cationically polymerizable group-containing compound, the number of cationically polymerizable groups in one molecule is preferably 2 to 10, particularly preferably 2 to 5. The molecular weight of the compound is 3000 or less, preferably in the range of 200 to 2000, particularly preferably in the range of 400 to 1500. If the molecular weight is too small, volatilization during the film formation process becomes a problem, and if it is too large, the compatibility with the composition for forming a high refractive index layer is deteriorated.

  Examples of the epoxy compound include aliphatic epoxy compounds and aromatic epoxy compounds.

  Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and the like. Can do.

  In addition to the above epoxy compounds, for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxide stearate, octyl epoxide stearate, epoxidized linseed oil, epoxidized polybutadiene, etc. Can be mentioned.

  Examples of the alicyclic epoxy compound include polyglycidyl ether of polyhydric alcohol having at least one alicyclic ring, or unsaturated alicyclic ring (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc. ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.

  Moreover, as an aromatic epoxy compound, the mono- or polyglycidyl ether of the monovalent | monohydric or polyhydric phenol which has at least 1 aromatic nucleus, or its alkylene oxide adduct can be mentioned, for example. Examples of these epoxy compounds include compounds described in paragraphs [0084] to [0086] of JP-A-11-242101, and paragraphs [0044] to [0046] of JP-A-10-158385. And the compounds described.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable in consideration of fast curability. In the present invention, one of the above epoxy compounds may be used alone, but two or more may be used in appropriate combination.

  Examples of the cyclic thioether compound include compounds in which the epoxy ring is a thioepoxy ring.

  Specific examples of the compound containing an oxetanyl group as a cyclic ether include the compounds described in paragraphs [0024] to [0025] in JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.

  Examples of the spiro orthoester compound include compounds described in JP 2000-506908 A.

  Examples of vinyl hydrocarbon compounds include styrene compounds, vinyl group-substituted alicyclic hydrocarbon compounds (vinylcyclohexane, vinylbicycloheptene, etc.), and compounds described in the radical polysynthetic monomers (compounds whose V1 is equivalent to -O-) , Propenyl compounds (Journalof Polymer Science: Part A: Polymer Chemistry, Vol. 32, 2895 (1994) and the like), alkoxy allene compounds (Journalof PolymerScience: Part A: PolymerCV, 19: PolymerChem. Part A: Polymer Chemistry, Vol. 34, 1015 (1996), special No. 2002-29162), isopropenyl compounds (Journalof PolymerScience: Part A: Polymer Chemistry, Vol. 34, 2051 (1996) description, etc.), and the like.

  Two or more kinds may be used in appropriate combination.

  The polyfunctional compound of the present invention is preferably a compound containing at least one of each selected from the above radical polymerizable group and cationic polymerizable group in the molecule. Examples thereof include compounds described in paragraphs [0031] to [0052] in JP-A-8-277320, compounds described in paragraph [0015] in JP-A-2000-191737, and the like. The compounds used in the present invention are not limited to these.

  The radical polymerizable compound and the cationic polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 to More preferably, it is contained at a ratio of 30:70.

  Next, the polymerization initiator used in combination with the binder precursor in the combination (c) will be described in detail. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

  The polymerization initiator (L) of the present invention is a compound that generates radicals or acids by light and / or heat irradiation. The photopolymerization initiator (L) used in the present invention preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the near infrared region can also be used.

  First, the compound (L1) that generates radicals will be described in detail. The compound (L1) that generates radicals preferably used in the present invention refers to a compound that initiates and accelerates polymerization of a compound having a polymerizable unsaturated group by generating radicals by irradiation with light and / or heat.

  A known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

  Examples of the compound that generates radicals include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, amine compounds (described in Japanese Patent Publication No. 44-20189), organic halogenated compounds, carbonyls, and the like. Examples include photo radical polymerization initiators such as compounds, metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, and disulfone compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A 63-298339, M.M. P. Hut "Journal of Heterocyclic Chemistry" 1 (No3), (1970) "and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: S-triazine compound.

  More preferred are s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Examples of other organic halogen compounds include ketones, sulfides, sulfones and nitrogen-containing heterocycles described in paragraphs [0039] to [0048] of JP-A-5-27830.

  Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 (published by Technical Information Association, 1991), paragraph numbers [0015] to [0016] of JP-A-8-134404, The compounds described in paragraph Nos. [0029] to [0031] of JP-A No. 11-217518 can be mentioned, and benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, and benzoin isobutyl ether Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, benzyldimethyl ketal, and acylphosphine oxide.

  Examples of the organic peroxide compound include compounds described in paragraph [0019] of JP-A No. 2001-139663.

  Examples of the metallocene compound include various titanocene compounds described in JP-A-2-4705 and JP-A-5-83588, iron-arene complexes described in JP-A-1-304453, JP-A-1-152109, and the like. Is mentioned.

  Examples of the hexaarylbiimidazole compounds described in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And various compounds.

  Examples of the organic borate compounds include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Mention may be made of the organic borate compounds described. Examples thereof include the compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539.

  As other organic boron compounds, organic boron such as JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. Specific examples include transition metal coordination complexes and the like.

  Examples of the sulfone compound include compounds described in JP-A-5-239015, and examples of the disulfone compound include those represented by general formulas (II) and (III) described in JP-A 61-166544. Compounds and the like.

  These radical generating compounds may be used alone or in combination of two or more. As addition amount, it is 0.1-30 mass% with respect to the whole quantity of a radically polymerizable monomer, Preferably it is 0.5-25 mass%, Most preferably, it can add at 1-20 mass%. Within this range, the temporal stability of the composition for a high refractive index layer is highly polymerizable without problems. “Latest UV Curing Technology”, Technical Information Association, 1991, p. Various compound examples are also described in 159 and are useful in the present invention.

  Commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 819, 907, 1870 (CGI-403 / Irg184 = 7/3 mixed initiator, 500) manufactured by Ciba Specialty Chemicals Co., Ltd. , 369, 1173, 2959, 4265, 4263), OXE01), etc., and Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, manufactured by Nippon Kayaku Co., Ltd. , ITX, QTX, BTC, MCA, etc.), Esacure manufactured by Sartomer (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like are preferable examples.

  Next, the acid generator (L2) that can be used as the photopolymerization initiator (L) will be described in detail. Examples of the acid generator (L2) include known compounds such as a photo-initiator for photocationic polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a known acid generator used in a microresist, and the like. A mixture thereof may be mentioned.

  Examples of the acid generator (L2) include organic halogenated compounds and disulfone compounds. Specific examples of these organic halogen compounds and disulfone compounds are the same as those described for the compound generating a radical.

  Examples of the onium compounds include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like. For example, paragraph numbers [0058] to [0058] of [JP-A-2002-29162] [0059] and the like.

  In the present invention, the acid generator (L2) that is particularly preferably used includes onium salts. Among them, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are used for photosensitivity at the start of photopolymerization, and material stability of the compound. From the point of property etc., it is preferable.

  Specific examples of the onium salt that can be suitably used in the present invention include, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, and JP-A-2000-71366. Diaryl iodonium salt or triaryl sulfonium salt described in paragraph numbers [0010] to [0011] of the book, sulfonium salt of thiobenzoic acid S-phenyl ester described in paragraph number [0017] of JP-A-2001-288205, Examples include onium salts described in paragraph numbers [0030] to [0033] of JP-A-2001-133696.

  Other examples of the acid generator include organic metal / organic halides described in paragraphs [0059] to [0062] of JP-A-2002-29162, and a photoacid generator having an o-nitrobenzyl type protecting group. And compounds such as compounds that generate photosulfonic acid to generate sulfonic acid (iminosulfonate, etc.).

  These acid generators may be used alone or in combination of two or more. These acid generators are added in a proportion of 0.1 to 20% by mass, preferably 0.5 to 15% by mass, particularly preferably 1 to 10% by mass, based on 100% by mass of the total mass of the cationic polymerizable monomer can do. When the addition amount is in the above range, it is preferable from the viewpoint of stability of the composition for high refractive index, polymerization reactivity and the like.

  The composition for high refractive index of the present invention is 0.5 to 10% by mass of the radical polymerization initiator and 1 to 10% by mass of the cationic polymerization initiator with respect to the total mass of the radical polymerizable compound and the cationic polymerizable compound. It is preferable to contain in the ratio. More preferably, it contains 1 to 5% by mass of a radical polymerization initiator and 2 to 6% by mass of a cationic polymerization initiator.

  In the composition for high refractive index of the present invention, when a polymerization reaction is carried out by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

  Moreover, when performing a polymerization reaction by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together.

  The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength range of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Furthermore, a value having absorption in the region of 750 to 1400 nm and a molecular extinction coefficient of 20000 or more is preferable.

  Moreover, it is more preferable that there is a trough of absorption in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent. As the near-infrared spectral sensitizer, various pigments and dyes known as near-infrared absorbing pigments and near-infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber.

  Commercially available dyes and literature (for example, “Chemical Industry”, May 1986, P. 45-51, “Near-Infrared Absorbing Dye”, “Development and Market Trends of Functional Dyes in the 90s”, Chapter 2.3. (1990) CMC), “special function pigments” (edited by Ikemori and Piladani, 1986, issued by CMC Corporation), J. Am. FABIAN, Chem. Rev., 92, pp 1197 to 1226 (1992), a catalog published in 1995 by Nippon Sensitive Dye Research Institute, Exciton Inc. Known dyes described in the laser dye catalog or patent issued in 1989.

(Ii) Organometallic compound containing a hydrolyzable functional group As a matrix of the high refractive index layer (4) used in the present invention, a coating film by a sol-gel reaction using an organometallic compound containing a hydrolyzable functional group It is also preferable to form a cured film after formation. Examples of the organometallic compound include compounds composed of Si, Ti, Zr, Al and the like. Examples of the hydrolyzable functional group include an alkoxy group, an alkoxycarbonyl group, a halogen atom, and a hydroxyl group, and an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group is particularly preferable.

  Preferred organometallic compounds are organosilicon compounds represented by the following chemical formula 3 and partial hydrolysates (partial condensates) thereof. In addition, it is a well-known fact that the organosilicon compound represented by Chemical Formula 3 is easily hydrolyzed and subsequently undergoes a dehydration condensation reaction.

化学式３において、Ｒ^ａは、置換又は無置換の炭素数１〜３０脂肪族基又は炭素数６〜１４アリール基を表す。Ｘは、ハロゲン原子（塩素原子、臭素原子等）、ＯＨ基、ＯＲ_２基、ＯＣＯＲ_２ 基を表す。ここで、Ｒ_２ は置換又は無置換のアルキル基を表す。ｍは０〜３の整数を表す。ｎは１〜４の整数を表す。ｍとｎの合計は４である。但し、ｍが０の場合は、ＸはＯＲ_２基又はＯＣＯＲ_２ 基を表す。

In Chemical Formula 3, R ^a represents a substituted or unsubstituted aliphatic group having 1 to 30 carbon atoms or an aryl group having 6 to 14 carbon atoms. X represents a halogen atom (a chlorine atom, a bromine atom or the like), an OH group, an OR ₂ group, or an OCOR ₂ group. Here, R ₂ represents a substituted or unsubstituted alkyl group. m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. However, when m is 0, X represents an OR ₂ group or an OCOR ₂ group.

In the chemical formula 3, the aliphatic group represented by ^Ra preferably has 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, benzyl group, phenethyl group). Cyclohexyl group, cyclohexylmethyl, hexenyl group, decenyl group, dodecenyl group, etc.). More preferably, it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms.

^Examples of the aryl group for R ^a include phenyl, naphthyl, anthranyl, and the like, and is preferably a phenyl group.

  Although there is no restriction | limiting in particular as a substituent, Halogen (fluorine, chlorine, bromine, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), Aryl groups (phenyl, naphthyl, etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl, etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy, etc.), aryloxy (phenoxy, etc.), alkylthio groups (methylthio) , Ethylthio etc.), arylthio group (phenylthio etc.), alkenyl group (vinyl, 1-propenyl etc.), alkoxysilyl group (trimethoxysilyl, triethoxysilyl etc.), acyloxy group (acetoxy, (meth) acryloyl etc.), alkoxy Carbonyl group (methoxycarbonyl, ethoxycarbonyl) Bonyl etc.), aryloxycarbonyl group (phenoxycarbonyl etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl etc.), acylamino group (acetylamino, benzoylamino) , Acrylicamino, methacrylamino and the like).

  Among these substituents, more preferred are a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group ((meta ) Acryloyl), a polymerizable acylamino group (acrylamino, methacrylamino). These substituents may be further substituted.

R ₂ represents substituted or unsubstituted alkyl. The explanation of the substituent in the alkyl group is the same as R1.

m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4. m is preferably 0, 1, 2 and particularly preferably 1. When m is 0, X represents an OR ₂ group or an OCOR ₂ group.

  The content of the compound of Chemical Formula 3 is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, and particularly preferably 30 to 50% by mass of the total solid content of the high refractive index layer (4).

  Specific examples of the compound of Chemical Formula 3 include compounds described in paragraph numbers [0054] to [0056] of JP-A No. 2001-166104.

  In the high refractive index layer (4), the organic binder preferably has a silanol group. When the binder has a silanol group, the physical strength, chemical resistance, and weather resistance of the high refractive index layer (4) are further improved.

  A silanol group is, for example, a binder precursor (such as a curable polyfunctional monomer or polyfunctional oligomer), a polymerization initiator, a high refractive index inorganic fine particle as a binder forming component constituting a coating composition for forming a high refractive index layer. An organosilicon compound represented by Chemical Formula 3 having a cross-linkable or polymerizable functional group is blended with the coating composition together with a dispersant contained in the dispersion liquid, and the coating composition is coated on a transparent support. The dispersant, the polyfunctional monomer, the polyfunctional oligomer, and the organosilicon compound represented by Chemical Formula 3 can be introduced into the binder by a crosslinking reaction or a polymerization reaction.

  The hydrolysis / condensation reaction for curing the organometallic compound is preferably performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as oxalic acid, acetic acid, formic acid, trifluoroacetic acid, methanesulfonic acid and toluenesulfonic acid, inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia , Organic bases such as triethylamine and pyridine, metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium and tetrabutoxytitanate, metal chelate compounds of β-diketones and β-ketoesters, and the like. Specifically, for example, compounds described in paragraph numbers [0071] to [0083] in JP-A No. 2000-275403 can be mentioned.

  The ratio of these catalyst compounds in the composition is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, and more preferably 0.5 to 10% by mass with respect to the organometallic compound. The reaction conditions are preferably adjusted as appropriate depending on the reactivity of the organometallic compound.

  In the high refractive index layer (4), the matrix preferably has a specific polar group. Specific polar groups include anionic groups, amino groups, and quaternary ammonium groups. Specific examples of the anionic group, amino group and quaternary ammonium group are the same as those described for the dispersant.

  The matrix of the high refractive index layer having a specific polar group is, for example, blended with a coating composition for forming a high refractive index layer, a dispersion containing high refractive index inorganic fine particles and a dispersant, and as a cured film forming component, A combination of a binder precursor having a specific polar group (such as a curable polyfunctional monomer or polyfunctional oligomer having a specific polar group) and a polymerization initiator, a specific polar group, and a cross-linked or polymerizable functional group At least one of the organosilicon compounds represented by the chemical formula 3 having the formula, and further, if desired, a monofunctional monomer having a specific polar group and a cross-linkable or polymerizable functional group is blended, and the coating composition is transparent Applying the above-mentioned dispersant, monofunctional monomer, polyfunctional monomer, polyfunctional oligomer, and / or organosilicon compound represented by Chemical Formula 3 by crosslinking or polymerization reaction on a support. Ri is obtained.

  The monofunctional monomer having a specific polar group functions as a dispersion aid for inorganic fine particles in the coating composition. Furthermore, after coating, a uniform dispersion of inorganic fine particles in the high refractive index layer (4) can be achieved by crosslinking or polymerization reaction with a dispersant, a polyfunctional monomer or polyfunctional oligomer, or a polymerization reaction. The high refractive index layer (4) excellent in physical strength, chemical resistance and weather resistance can be produced.

  It is preferable that the usage-amount with respect to the dispersing agent of the monofunctional monomer which has an amino group or a quaternary ammonium group is 0.5-50 mass%, More preferably, it is 1-30 mass%. If the binder is formed by crosslinking or polymerization reaction at the same time as or after the coating of the high refractive index layer (4), the monofunctional monomer can function effectively before the coating of the high refractive index layer (4).

  Further, the matrix of the high refractive index layer (4) of the present invention corresponds to (b) of the organic binder described above, and is cured and formed from a conventionally known organic polymer containing a crosslinked or polymerizable functional group. Can be mentioned. The polymer after the formation of the high refractive index layer preferably has a structure that is further crosslinked or polymerized.

Examples of the polymer include polyolefin (made of saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. Of these, polyolefins, polyethers, and polyureas are preferable, and polyolefins and polyethers are more preferable. The mass average molecular weight of the organic polymer before curing is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 3 × 10 ³ to 1 × 10 ⁵ .

  The organic polymer before curing is preferably a copolymer having a repeating unit having a specific polar group as described above and a repeating unit having a crosslinked or polymerized structure. The ratio of the repeating unit having an anionic group in the polymer is preferably 0.5 to 99% by mass, more preferably 3 to 95% by mass, and 6 to 90% by mass in all repeating units. Most preferred. The repeating unit may have two or more anionic groups which may be the same or different.

  When the repeating unit having a silanol group is included, the proportion is preferably 2 to 98 mol%, more preferably 4 to 96 mol%, and most preferably 6 to 94 mol%.

  When the repeating unit having an amino group or a quaternary ammonium group is included, the proportion is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass.

  In addition, even if the silanol group, the amino group, and the quaternary ammonium group are contained in the repeating unit having an anionic group or the repeating unit having a crosslinked or polymerized structure, the same effect can be obtained.

  The ratio of the repeating unit having a crosslinked or polymerized structure in the polymer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and most preferably 8 to 60% by mass.

  The matrix formed by crosslinking or polymerizing the binder is preferably formed by applying a coating composition for forming a high refractive index layer on a transparent support and performing crosslinking or polymerization reaction simultaneously with or after application.

In the high refractive index layer (4) of the present invention, other compounds can be appropriately added depending on applications and purposes. For example, when the low refractive index layer (5) is provided on the high refractive index layer (4), the refractive index of the high refractive index layer (4) is preferably higher than the refractive index of the transparent support. If (4) contains atoms such as aromatic rings, halogenated elements other than fluorine (for example, Br, I, Cl, etc.), S, N, P, etc., the refractive index of the organic compound will increase, so these are included. A binder obtained by a crosslinking or polymerization reaction such as a curable compound to be used can also be preferably used.
(Other composition of high refractive index layer)
In the high refractive index layer (4) of the present invention, other compounds can be appropriately added depending on applications and purposes. For example, the refractive index of the high refractive index layer (4) is preferably higher than the refractive index of the transparent support, and the high refractive index layer (4) has a halogenated element other than an aromatic ring or fluorine (for example, Br, I, Cl, etc.), a binder obtained by a crosslinking or polymerization reaction such as a curable compound containing atoms such as S, N, and P can also be preferably used.

  For the high refractive index layer (4), in addition to the above components (inorganic fine particles, polymerization initiator, sensitizer, etc.), resin, surfactant, antistatic agent, coupling agent, thickener, anti-coloring agent , Colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductive metal fine particles, etc. Can also be added.

[Medium refractive index layer]
The antireflection film of the present invention preferably has a two-layer structure in which the high refractive index layer (4) is composed of different refractive indexes. That is, the low refractive index layer (5) formed by applying the composition by the above method is formed on the high refractive index layer (4) having a higher refractive index than the high refractive index layer (4 ) And an intermediate refractive index layer (3) having a refractive index intermediate between the refractive index of the support and the refractive index of the high refractive index layer (4) is formed on the opposite side of the low refractive index layer (5). A three-layer laminated structure is preferred. As described above, the refractive index of each refractive index layer is relative.

  The material constituting the middle refractive index layer (3) of the present invention may be any conventionally known material, but the same material as the high refractive index layer (4) is preferred. The refractive index is easily adjusted by the type and amount of inorganic fine particles, and a thin layer having a thickness of 30 to 500 nm is formed in the same manner as described in the high refractive index layer (4). More preferably, the film thickness is 50 to 300 nm.

[Low refractive index layer]
The low refractive index layer (5) is formed by a cured film of a copolymer having a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as essential constituent components. preferable. A curing agent such as polyfunctional (meth) acrylate, a filler of inorganic fine particles or organic fine particles is preferably used together with the copolymer from the viewpoint of achieving both low refractive index and film hardness.

  The refractive index of the low refractive index layer (5) is preferably 1.20 to 1.49, more preferably 1.25 to 1.48, and 1.30 to 1.46. Particularly preferred.

  The thickness of the low refractive index layer (5) is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer (5) is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer (5) is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher at a load of 500 g in a pencil hardness test according to JIS K5400.

  In order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. The angle is more preferably 95 ° or more, and particularly preferably 100 ° or more.

  The copolymer used for the low refractive index layer (5) of this invention is demonstrated below.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3. -Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers Of these, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino acids Of monomers having a group or a sulfo group (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into the structural unit by a polymer reaction (for example, by acting an acrylic acid chloride on a hydroxy group) Guidance Possible), and the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers that do not contain fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents, film transparency, and the like. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers ( Methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tert-butylacrylamide, - cyclohexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  A preferred embodiment of the copolymer used in the present invention includes a compound represented by the following chemical formula 4.

化学式４において、Ｌは炭素数１〜１０の連結基を表す。この連結基は、好ましくは炭素数１〜６の連結基であり、より好ましくは２〜４の連結基である。また、この連結基は、直鎖であっても分岐構造を有していてもよく、環構造を有していてもよく、Ｏ、Ｎ、Ｓから選ばれるヘテロ原子を有していてもよい。

In Chemical Formula 4, L represents a linking group having 1 to 10 carbon atoms. This linking group is preferably a linking group having 1 to 6 carbon atoms, and more preferably a linking group having 2 to 4 carbon atoms. The linking group may be linear or branched, may have a ring structure, and may have a heteroatom selected from O, N, and S. .

  Preferred examples include *-(CH2) 2-O-**, *-(CH2) 2-NH-**, *-(CH2) 4-O-**, *-(CH2) 6-O-. **, *-(CH2) 2-O- (CH2) 2-O-**, * O-CONH- (CH2) 3-O-**, * -CH2 CH (OH) CH2-O-** * -CH2CH2OCONH (CH2) 3-O-** (* represents a linking site on the polymer main chain side, and ** represents a linking site on the (meth) acryloyl group side). m represents 0 or 1;

  In Chemical Formula 4, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In Chemical Formula 4, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Adhesion to a substrate, Tg of a polymer (Contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc. May be.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  In Chemical Formula 4, x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  A particularly preferred embodiment of the copolymer used in the present invention is a compound represented by the following chemical formula 5.

化学式５において、Ｘ、ｘ、ｙは、化学式４と同じ意味を表し、好ましい範囲も同じである。

In Chemical Formula 5, X, x, and y have the same meaning as in Chemical Formula 4, and the preferred range is also the same.

  In Chemical Formula 5, n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.

  In Chemical Formula 5, B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said Chemical formula 4 is mentioned.

  In Chemical Formula 5, z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  The copolymer represented by the chemical formula 4 or 5 can be obtained, for example, by introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  Although the preferable specific example of the copolymer useful by this invention is shown below, this invention is not limited to these.

本発明に好ましく用いられる共重合体の合成は、種々の重合方法、たとえば、溶液重合、沈澱重合、懸濁重合、塊状重合、乳化重合によって水酸基含有重合体等の前駆体を合成した後、前記高分子反応によって（メタ）アクリロイル基を導入することにより行なうことができる。重合反応は回分式、半連続式、連続式等の公知の操作で行なうことができる。

The copolymer preferably used in the present invention is synthesized by synthesizing a precursor such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. It can be carried out by introducing a (meth) acryloyl group by a polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  As described above, from the viewpoint of film hardness of the low refractive index layer (5), it is not always advantageous to add an additive such as a curing agent, but interfacial adhesion to the high refractive index layer (4), etc. From the above viewpoint, a curing agent such as a polyfunctional (meth) acrylate compound, a polyfunctional epoxy compound, a polyisocyanate compound, an aminoplast, a polybasic acid, or an anhydride thereof may be added.

  When adding these, it is preferable that it is the range of 0-30 mass% with respect to the total solid of a low refractive index layer membrane | film | coat, It is more preferable that it is the range of 0-20 mass%, 0-10 It is particularly preferable that the mass range.

  In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, known silicone-based or fluorine-based antifouling agents, slipping agents, and the like can be appropriately added. When these additives are added, it is preferably added in the range of 0 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0 to 10% by mass. Particularly preferred is 0 to 5% by mass.

  The radical polymerization initiator may be in any form of generating radicals by the action of heat or generating radicals by the action of light.

  As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.

  Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p-nitrobenzenediazonium Etc.

  When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays.

  Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included.

  Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photoradical polymerization initiators.

  The amount of the compound that initiates radical polymerization by the action of heat or light may be an amount that can initiate the polymerization of the carbon-carbon double bond, but generally the total amount in the composition for forming a low refractive index layer is not limited. 0.1-15 mass% is preferable with respect to solid content, More preferably, it is 0.5-10 mass%, Most preferably, it is a case of 2-5 mass%.

  The solvent contained in the low refractive index layer coating liquid composition is not particularly limited as long as the composition containing the fluorinated copolymer is uniformly dissolved or dispersed without causing precipitation. These solvents can also be used in combination. Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl). Alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

  The low refractive index layer (5) contains, in addition to the fluorine-containing compound, a filler (for example, inorganic fine particles and organic fine particles), a silane coupling agent, a slip agent (silicone compound such as dimethyl silicone), a surfactant and the like. can do. In particular, it is preferable to contain inorganic fine particles, a silane coupling agent, and a slip agent.

  Next, the inorganic fine particles that can be contained in the low refractive index layer (5) of the present invention are described below.

The coating amount of the inorganic fine particles is preferably 1 to 100 mg / ^{m 2,} more preferably 5-80 mg / ^{m 2,} more preferably from 10~60mg / ^{m 2.} If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

  Since the inorganic fine particles are contained in the low refractive index layer (5), it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost. The average particle size of the silica fine particles is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer (5).

  That is, when the thickness of the low refractive index layer (5) is 100 nm, the particle size of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably spherical, but there is no problem even if it is indefinite.

  Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to further reduce the refractive index increase of the low refractive index layer (5) by one layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, if the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is expressed by the following formula 4.
[Equation 4]
^{x = (4πa 3/3)} / (4πb 3/3) × 100

The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.

  If the hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Refractive index particles do not hold.

  The refractive index of these hollow silica particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (5) (referred to as “silica fine particles having a small size particle size”) is used. It is preferably used in combination with “large-sized silica particles”.

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

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

  Silica fine particles are treated by physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed.

  Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.

  The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer (5) in order to perform surface treatment before the preparation of the layer coating solution, but is further added as an additive during the preparation of the layer coating solution. Thus, it is preferably contained in the layer.

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

  What has been described above for the silica fine particles is also applicable to other inorganic particles.

  As the silane coupling agent, a compound represented by the following chemical formula and / or a derivative compound thereof can be used.

(X) n-Si- (OR) m
In the above chemical formula, X represents an organic functional group, and R represents an alkyl group. Of these, preferred is a silane coupling agent containing a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group or an acylamino group in X, and particularly preferred is an epoxy group, It is a silane coupling agent containing a polymerizable acyloxy group ((meth) acryloyl) and a polymerizable acylamino group (acrylamino, methacrylamino). m represents an integer of 0 to 3. n represents an integer of 1 to 4. The sum of m and n is 4.

  Particularly preferred among the compounds represented by the above chemical formula are compounds having a (meth) acryloyl group as a cross-linkable or polymerizable functional group in X, such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethyl. And methoxysilane.

  As the slip agent, dimethyl silicone and a fluorine-containing compound into which a polysiloxane segment is introduced are preferable.

[Other layers]
The laminated antireflection film may further be provided with a moisture proof layer, an antistatic layer, a primer layer, an undercoat layer, a protective layer, a shield layer, and a sliding layer. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Outline of Method for Forming Antireflection Film]
Each layer of the antireflection film having a multilayer structure is formed by a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a die coating method, a wire bar coating method, a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294). According to the description, it can be formed by coating, but it is preferably coated by a die coating method, and more preferably by using a new die coater described later.

  In this case, two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,789, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

  In the antireflection film of the present invention, at least the high refractive index layer (4) and the low refractive index layer (5) are laminated, so that bright spot defects are easily noticeable when foreign matter such as dust or dust is present. The bright spot defect in the present invention is a defect that can be seen by reflection on the coating film as described above, and can be detected by an operation such as black coating on the back surface of the antireflection film after coating. The bright spot defects that can be visually observed are generally 50 μm or more. When there are many bright spot defects, the yield at the time of manufacture will fall and a large-area antireflection film cannot be manufactured.

  In the antireflection film of the present invention, the number of bright spot defects is 20 or less per square meter, preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

  In order to continuously produce the antireflection film of the present invention, a process of continuously feeding a roll-shaped support film, a process of applying and drying a coating liquid, a process of curing a coating film, and a support having a cured layer A step of winding the body film is performed.

  The film support is continuously sent out from the roll-shaped film support to the clean room. In the clean room, the static electricity charged on the film support is removed by an electrostatic charge-off device, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating liquid is applied onto the film support in the coating chamber installed in the clean room, and the applied film support is sent to the drying chamber and dried.

  The film support having the dried coating layer is fed from the drying chamber to the radiation curing chamber, irradiated with radiation, and the monomer contained in the coating layer is polymerized and cured. Further, the film support having a layer cured by radiation is sent to a thermosetting chamber and heated to complete the curing, and the film support having the layer that has been completely cured is wound up into a roll shape.

  The above-described steps may be performed every time each layer is formed, or a plurality of coating chambers-drying chambers-radiation curing chambers-thermosetting chambers may be provided to form each layer continuously. It is preferable to form each layer continuously from the viewpoint of productivity.

  An example of the configuration of an apparatus for continuously applying each layer is shown in FIG. This apparatus includes a film forming unit (on a support) between a feeding device 1 for continuously feeding a roll-shaped support film (hereinafter referred to as “web”) W and a winding device 2 for winding the web W. (Units for forming a coating film) 100, 200, 300, and 400 are installed as many as necessary.

  The apparatus shown in FIG. 8 is an example of a configuration in which four layers are continuously applied without winding up, but it is of course possible to change the number of film forming units in accordance with the layer configuration.

  The film forming unit 100 includes a process 101 for applying a coating liquid, a process 102 for drying a coating film, and a process 103 for curing the coating film. The other film forming units 200, 300, and 400 have the same configuration. The step of applying the coating liquid, the step of drying the coating film, and the step of curing the coating film will be described in detail below.

Using an apparatus in which three film forming units are installed, the roll-shaped web W coated with the hard coat layer (2) is continuously sent out, the medium refractive index layer (3), the high refractive index layer (4), It is more preferable that the low refractive index layer (5) is sequentially applied by each film forming unit and then wound, and the roll-shaped web W is formed using the apparatus shown in FIG. 8 in which four film forming units are installed. It is further possible to continuously feed and wind up the hard coat layer (2), the medium refractive index layer (3), the high refractive index layer (4), and the low refractive index layer (5) after being sequentially applied by each film forming unit. preferable.
[Preparation before application]
In order to produce an antireflection film with few bright spot defects in the present invention, as described above, it is necessary to precisely control the degree of dispersion of the high refractive index ultrafine particles in the coating material for the high refractive index layer, and Examples include microfiltration operation. Similarly, each layer forming the antireflection layer is formed on the web W before the coating process in the coating unit and the drying process performed in the drying chamber are performed in a highly clean air atmosphere, and before the coating is performed. It is preferable that dust and dust are sufficiently removed.

  The air cleanliness in the coating process and the drying process is preferably class 10 (353 particles / (cubic meter) or less of 0.5 μm or more) based on the standard of air cleanliness in the US Federal Standard 209E. More preferably, the number of particles is 1 (35.5 particles / 0.5 m or more). Moreover, it is preferable that air cleanliness is high also in sending out, winding-up parts, etc. other than a coating-drying process.

  As a dust removal method used in a dust removal step as a pre-process for coating, a method described in Japanese Patent Application Laid-Open No. 59-150571, a method of pressing a nonwoven fabric, a blade or the like on the web surface, described in Japanese Patent Application Laid-Open No. 10-309553 A method of blowing air with high cleanliness at high speed to peel off deposits from the web surface and sucking it with a suction port close thereto, as described in JP-A-7-333613. For example, a dry dust removal method such as a method of peeling off and adhering the deposits (manufactured by Shinkosha, New Ultra Cleaner, etc.) can be used.

  In addition, a method of introducing a web into a cleaning tank and peeling off deposits with an ultrasonic vibrator, described in Japanese Patent Publication No. 49-13020, after supplying a cleaning liquid to the web, spraying and sucking high-speed air As described in JP-A-2001-38306, a wet dust removing method such as a method in which a web is continuously rubbed with a roller wetted with a liquid and then a liquid is sprayed onto the rubbed surface to perform cleaning. be able to. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.

  In addition, it is particularly preferable to remove static electricity on the web before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and application is preferably 1000 V or less, more preferably 300 V or less, and even more preferably 100 V or less.

  The requirements necessary for preparing the coating solution are described below.

[Dispersion medium for coating]
When preparing the coating solution for each layer of the hard coat layer and the low refractive index layer of the present invention, the following dispersion solvents can be used. The dispersion medium for coating is not particularly limited. You may use individually or in mixture of 2 or more types.

  Preferred dispersion media include aromatic hydrocarbons such as toluene, xylene and styrene, chlorinated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene, methane derivatives such as monochloromethane, ethane derivatives such as monochloroethane, and the like. Chlorinated aliphatic hydrocarbons, alcohols such as methanol, isopropyl alcohol and isobutyl alcohol, esters such as methyl acetate and ethyl acetate, ethers such as ethyl ether and 1,4-dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples include ketones such as cyclohexanone, glycol ethers such as ethylene glycol monomethyl ether, alicyclic hydrocarbons such as cyclohexane, aliphatic hydrocarbons such as normal hexane, and mixtures of aliphatic or aromatic hydrocarbons.

  Among these solvents, a dispersion medium for coating prepared by alone or mixing two or more ketones is particularly preferable.

[Coating liquid properties]
In the coating method of the present invention, the upper limit speed at which coating is possible is greatly affected by the liquid physical properties, so it is necessary to control the liquid physical properties, particularly the viscosity and surface tension at the moment of coating.

  The viscosity is preferably 20.0 mPa · sec or less, more preferably 10.0 mPa · sec or less, further preferably 5.0 mPa · sec or less, and most preferably 2.0 mPa · sec or less.

  Depending on the coating solution, the viscosity may change depending on the shear rate, and the above value indicates the viscosity at the shear rate at the moment of application. When a thixotropic agent is added to the coating solution, the viscosity is low when coating with high shear and the viscosity is high when drying where the coating solution is hardly sheared.

Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a web also affects the upper limit speed | rate which can be apply | coated. It is preferred that the amount of coating solution applied to the web is 2.0~5.0ml / ^{m 2.} Increasing the amount of the coating liquid applied to the web is preferable because the upper limit of the coating speed can be increased. However, if the amount of the coating liquid applied to the web is excessively increased, the load on drying increases. -It is preferable to determine the optimal amount of coating solution to be applied to the web according to the process conditions.

  The surface tension is preferably in the range of 15 to 36 mN / m. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating is possible decreases, so the range of 17 to 32 mN / m is more preferred, and the range of 19 to 26 mN / m is even more preferred.

[filtration]
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 10 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 5 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa (15 kgf / cm ² ) or less, more preferably 1.0 MPa (10 kgf / cm ² ) or less, and further 0.2 MPa (2 kgf / cm ² ) or less.

  The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.

It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.
[Coating process]
As a coating method of each layer of the antireflection film, a coating method using a slot die is preferable. Furthermore, as will be described later, the use of a slot die is more preferable because the occurrence of film thickness unevenness when applied at high speed is suppressed.

[Configuration of die coater]
FIG. 9 is a cross-sectional view of a coater using a slot die used in the practice of the present invention. The coater 10 applies a coating liquid 14 from the slot die 13 to the bead 14a on the web W that is continuously supported by the backup roller 11 to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section in cross section. For example, the pocket 15 may have a substantially circular shape as shown in FIG. 9 or a semicircular shape. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width.

  The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roller 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. In this land 18, the upstream side in the running direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

  FIG. 10 shows the cross-sectional shape of the slot die 13 in comparison with the conventional one, (A) shows the slot die 13 of the present invention, and (B) shows the conventional slot die 30. . In the conventional slot die 30, the distance between the upstream lip land 31a and the web W of the downstream lip land 31b is equal. In (B), reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the downstream side lip land length ILO is shortened, so that application with a wet film thickness of 20 μm or less can be accurately performed.

  The land length IUP of the upstream lip land 18a is not particularly limited, but a range of 100 μm to 1 mm is preferably employed. The land length ILO of the downstream lip land 18b is 30 μm or more and 100 μm or less, preferably 30 μm or more and 80 μm or less, more preferably 30 μm or more and 60 μm or less.

  If the land length ILO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip 17 is likely to be chipped, streaks are likely to occur in the coating film, and as a result, application becomes impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface.

  On the other hand, when the land length ILO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to perform thin layer coating.

  Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be reduced, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less.

  When the slot die 13 has an overbite shape, the gap GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

  FIG. 11 is a perspective view showing the slot die and its periphery in the coating process used in the practice of the present invention. On the side opposite to the side on which the web W travels, the decompression chamber 40 is installed at a position where it does not contact the web W so that sufficient decompression adjustment can be performed on the bead 14a. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency. There are gaps GB and GS between the back plate 40a and the web W, and between the side plate 40b and the web W, respectively. Exists.

  12 and 13 are cross-sectional views showing the decompression chamber 40 and the web W that are close to each other. The side plate 40b and the back plate 40a may be integrated with the chamber body as shown in FIG. 12, or are fastened to the chamber with screws 40c or the like so that the gap can be appropriately changed as shown in FIG. It may be a structure.

  Regardless of the structure, portions that are actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps GB and GS, respectively. The gap GB between the back plate 40a of the decompression chamber 40 and the web W is the distance from the uppermost end of the back plate 40a to the web W when the decompression chamber 40 is installed below the web W and the slot die 13 as shown in FIG. Indicates a gap.

  The gap GB between the back plate 40a and the web W is preferably set larger than the gap GL between the tip lip 17 of the slot die 13 and the web W. Thereby, it is possible to suppress a change in the degree of decompression in the vicinity of the bead due to the eccentricity of the backup roller 11.

  For example, when the gap GL between the tip lip 17 of the slot die 13 and the web W is not less than 30 μm and not more than 100 μm, the gap GB between the back plate 40 a and the web W is preferably not less than 100 μm and not more than 500 μm.

[Material and accuracy]
The longer the length in the web traveling direction of the tip lip 17 on the traveling direction side of the web W, the more disadvantageous it is for bead formation. If this length varies between arbitrary points in the slot die width direction, the bead is caused by a slight disturbance. Becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.

  Further, when the material of the tip lip 17 of the slot die is made of a material such as stainless steel, the length of the slot die tip lip 17 in the web running direction is set to 30 as described above. Even in the range of ˜100 μm, the accuracy of the tip lip 17 cannot be satisfied.

  Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip 17 of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less.

  Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.

  In order to achieve highly accurate coating, the length of the land on the web running direction side of the tip lip 17 and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of the two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness between the tip lip 17 and the backup roller 11 is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

[Application speed]
By achieving the accuracy of the backup roller 11 and the tip lip 17 as described above, the coating method employed in the present invention has high film thickness stability during high-speed coating. Furthermore, since the coating method employed in the present invention is a pre-measuring method, it is easy to ensure a stable film thickness even during high-speed coating.

  The coating method employed in the present invention can be applied at high speed and with good film thickness stability to a coating solution having a low coating amount such as the antireflection film of the present invention. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method and the micro gravure method, stepped unevenness is likely to occur due to roll eccentricity and deflection related to coating.

  Also, in the microgravure method, coating amount unevenness is likely to occur due to the manufacturing accuracy of the gravure roll and the change with time of the roll and blade due to the contact between the blade and the gravure roll. Moreover, since these application methods are post-measuring methods, it is difficult to ensure a stable film thickness. By using the production method of the present invention, it is preferable from the viewpoint of productivity to apply at a rate of 25 m / min or more.

<Drying process>
As a typical method for controlling the drying speed, a drying zone is provided immediately after the coating machine, and a drying process for controlling the drying speed by controlling the environment in the drying zone is provided. Some typical examples will be described below.

  For example, Japanese Patent Laid-Open No. 9-73016 describes the following method. Immediately after coating, a drying step for controlling the moving speed of the gas on the surface of the coating film so as to be a relative speed of −0.1 m / sec or more and 0.1 m / sec or less with respect to the moving speed of the coating film being conveyed And drying under control. The drying rate can be controlled by heating or cooling the coating film.

An example of the drying step will be described in detail with reference to FIG. While the web 110 is being transported, a coating film is formed on the surface of the web 110 by applying a coating solution using a coating machine 111. Although FIG. 14 shows a diagram of a wire bar coating machine as an example of a coating machine, in the present invention, the coating machine is not limited to a wire bar coating machine. A web 110 a having a coating film (hereinafter referred to as a coating web) 110 a is conveyed along the current plate 112 to the drying zone 113 and further conveyed to the heating zone 114. However, in the heating zone 114, drying for evaporating the residual solvent is also performed. In the present invention, the process from immediately after coating to the heating zone 114 is performed with as little wind as possible on the coating film. That is, the wind from the coating chamber air supply port (the wind speed and the wind direction which is substantially the same as the film conveyance speed) is introduced from the wire mesh 116 of the drying zone 113 after passing the current plate 112. The wind from the coating chamber air supply port is exhausted from the coating chamber exhaust port and is exhausted from the drying zone 113 through the exhaust plate 117 through the perforated plate 115 and the metal mesh 116. By arranging such a wire mesh or perforated plate, there is almost no sudden change in the wind speed and direction.

  The gap between the current plate 112 and the coating web 111a is generally 1 mm to 10 mm. The length of the rectifying plate 112 is preferably 1 m to 15 m. The temperature of the drying zone 113 is preferably 10 ° C to 50 ° C. By setting the conditions of the drying zone 113 as described above, a wind having a relative speed with respect to the moving speed (conveying speed) of the coating web 111a of −0.1 m / sec to 0.1 m / sec is applied during drying. It is preferable to apply to (that is, move the gas layer).

Japanese Patent Laid-Open No. 2001-170547 describes the following method, which can be preferably applied to the present invention. Immediately after coating, a drying zone is provided to surround the coating film surface by the drying zone, and further, a one-way flow of drying air flowing from one end side to the other end side in the long support width direction is generated. This drying air contains the same solvent gas as the dispersion medium contained in the coating film, and the drying speed can be controlled by controlling the wind speed and the content of the solvent gas. Further, the drying zone is divided into a plurality of divided zones, and the drying speed is controlled in more detail by adjusting the speed of drying air and the content of solvent gas in the one-way flow in each divided zone. be able to.

  15 is a side view of an example of the drying device 130 used in the present invention, and FIG. 16 is a plan view of the drying device 130 of FIG. 15 as viewed from above.

  The coating film drying apparatus 130 shown in FIGS. 15 and 16 includes a drying apparatus main body 132 that forms a drying zone in which the coating film is dried by passing the web 131 that runs continuously, and the width of the web 131 in the drying zone. Unidirectional airflow generating means pipes 133 to 139 for generating a unidirectional flow of drying air flowing from one end side to the other end side. The drying device 130 is provided immediately after the coating machine 140 that applies a coating solution containing an organic solvent to the traveling web 131.

  As the applicator 140, for example, a bar applicator provided with a wire bar 141 can be used, and an application liquid is applied to the lower surface of the web 131 that is supported by a plurality of backup rollers 142, 143, and 144. A coating film is formed. 15 and 16 show a wire bar coating machine as an example of a coating machine. However, in the present invention, the coating machine is not limited to a wire bar coating machine.

The drying apparatus main body 132 is provided immediately after the coating machine 140, is formed in a long rectangular box shape along the coating film surface side (the lower surface side of the web) of the traveling web 131, and is formed from each side of the box body. The side of the coated film surface side (the upper side of the box) is cut off. Thereby, the drying zone surrounding the coating film surface to be dried of the traveling coating web 131a is formed. The drying zone is divided into a plurality of drying zones 146a to 146g (seven division zones in this embodiment) by partitioning the drying apparatus main body 132 with a plurality of partition plates 145a to 145f orthogonal to the traveling direction of the coating web 131a. Is done. In this case, the partition plates 145a to divide the drying zones 146a to 146g.
The distance between the upper end of 145f and the coating film surface formed on the coating web 131a is preferably in the range of 0.5 mm to 12 mm, more preferably in the range of 1 mm to 10 mm. Each drying zone 146a to 146g is provided with unidirectional airflow generating means 133 to 139 (see FIG. 16).

The one-way airflow generating means 133 to 139 are mainly connected to the suction port formed on one side of the both sides of the drying apparatus main body 132 and the exhaust port formed opposite to the suction port on the other side. And exhaust means. Thus, by driving the exhaust means, the air sucked into the drying zones 146a to 146g from the suction port is exhausted from the exhaust ports, so that each drying zone 146a to 146g has one side in the width direction of the coating web 131a. Dry air flowing in one direction is generated from the end side (suction port side) to the other end side (exhaust port side). The unidirectional airflow generation means 133 to 139 can individually control the exhaust amount for each of the drying zones 146a to 146g by the exhaust means. The dry air sucked from the suction port is preferably air-conditioned air that has been air-conditioned at temperature and humidity. In addition, as the drying air sucked from the suction port, it is preferable that the concentration of the dispersion medium gas for applying the coating liquid is controlled in the drying air.

  Further, the width of the drying apparatus main body 132 is formed so as to be larger than the width of the web 131, and the opening portions on both sides of the drying zones 146a to 146g are provided with wind adjusting portions covered with the air adjusting plates 147 and 148, respectively. . This air conditioning portion secures a distance from the suction port to the coating film end and a distance from the coating film end to the exhaust port, and makes it easy for the drying air to be sucked into the drying zones 146a to 146g only from the suction port. In the drying zones 146a to 146g, a rapid flow of drying air is prevented. The length of the air conditioning portion, that is, the air conditioning plates 147 and 148, is preferably in the range of 50 mm or more and 150 mm or less on both the suction port side and the exhaust port side.

  Among the drying zones 146a to 146g, particularly the drying zone 146a closest to the coating machine 140 is dried immediately after the coating liquid is applied to the web 131, and fresh air outside the drying zone 146a, for example, the conditioned air described above is dried. It is important to make it difficult for the zone 146a to enter. For this purpose, the division zone 146a is disposed adjacent to the coating machine 140, and the position of the wire bar 141 and the position of the backup roller 143 of the coating machine 140 are adjusted in addition to the air conditioning plates 147 and 148 described above. It is preferable that the web 131 travels in the immediate vicinity of the drying zone 146a so that the open portion of the drying zone 146a is covered with the coated web 131a. In addition, it is preferable to provide a shielding plate 149 at a position opposite to the drying apparatus main body 132 with the coating web 131a interposed therebetween so that the stable running of the coating web 131a is not hindered by the air such as the air-conditioning wind.

  In JP 2003-93954 A, as in JP 2001-170547 A, a drying zone is installed immediately after coating, and a wind regulation plate having a plurality of holes facing the film surface of the coating film is installed. It shows that the drying rate can be controlled by controlling the aperture ratio of the holes and the distance between the coating film and the wind control plate.

  FIG. 17 is a side view of an example of the drying device 160 used in the present invention, and FIG. 18 is a top view of FIG. FIG. 19 is a cross-sectional view of a main part of the drying device 160 in FIG. In FIG. 18, an upper lid described later is removed.

  The drying device 160 applies a coating solution to the web 164 supported and transported by the transport rollers 161, 162, and 163 by the wire bar 166 of the coating device 165, and dries the coating film.

  The web on which the coating film is formed is referred to as a coating web 164a. The drying device 160 is used to dry the coating film, and includes seven drying zones 167, 168, 169, 170, 171, 172, and 173. 17, 18 and 19 show a wire bar coating machine as an example of a coating machine, but the coating machine used in the present invention is not limited to a wire bar coating machine. By sequentially passing through each of these drying zones 167 to 173, a gas of an organic solvent is generated from the coating liquid, and a coating film is formed on the coating web 164a.

  As shown in FIG. 18, exhaust ports 174, 175, 176, 177, 178, 179, 180 are provided on one side of the respective drying zones 167 to 173, and are connected to the exhaust device 181. The exhaust ports 174 to 180 can be individually exhausted by the exhaust device 181. On the other hand, ventilation openings 182, 183, 184, 185, 186, 187, and 188 are attached so that the atmosphere (air or other gas) can enter the drying zone. It has become. An exhaust pipe and an intake pipe (both not shown) are attached to each exhaust port and each ventilation port.

  FIG. 19 shows a cross-sectional view of the drying zone 168 among the seven drying zones. The drying zone 168 includes a drying zone body 168a and a wind regulation plate 190. The drying zone body 168a includes a passage chamber 191 through which the web 164 passes and an exhaust chamber 192 that exhausts the evaporated solvent gas. Further, the air conditioning plate 190 is provided so as to partition the passage chamber 191 and the exhaust chamber 192. An exhaust pipe 193 and an intake pipe 194 are attached to the exhaust chamber 192, and air (which may be other gas) is sent into the exhaust chamber 192 through the intake pipe 194. The intake pipe 194 and the exhaust pipe 193 are attached in the width direction of the web 164, and air flows in the width direction of the web 164 to form an air flow 195.

The aperture ratio, material, etc. of the air conditioning plate 190 are not particularly limited, but a wire net or punching metal having an aperture ratio of 50% or less is preferable, and the aperture ratio is more preferably 20% to 40%. Specifically, a wire mesh with 300 mesh and an aperture ratio of 30% can be used. Moreover, when the clearance gap between the coating-film surface 164b and the wind control board 190 is wide, an air eddy will generate | occur | produce and will cause the coating-film surface 164b to produce nonuniformity. Therefore, in order to control the flow of the wind, the gap C between the coating film surface 164b and the air conditioning plate 190 is preferably 3 mm to 30 mm, and more preferably 5 mm to 15 mm. Further, an upper lid 196 and side seals 197 and 198 which are seal members are attached in order to suppress unnecessary wind flow from the back surface of the web 164 (the surface on which the coating film is not formed) and the side. In addition, although the wire mesh is used for the air conditioning plate 190 in order to adjust the aperture ratio, the aperture ratio can be determined not only by the metal mesh but also by punch metal or the like. According to the drying step, the gas 199 in which the organic solvent in the coating film is evaporated (usually containing the evaporated solvent at a high concentration) 199 passes through the hole 190a of the air conditioning plate 190, and the coating surface. The air is exhausted from the exhaust pipe 193 uniformly in the width direction of the web by the drying air 195 in the exhaust chamber 192 passing through the opposite side of the air conditioning plate 190 with respect to 164 b and is discharged out of the drying zone 168. For this reason, a dry wind does not touch the coating-film surface 164b, and it is suppressed that a nonuniformity generate | occur | produces in the coating-film surface 164b.

  Also, as shown in FIG. 17, it is important that the drying zone 167 is installed immediately after the application liquid is applied to the web 164 so that the conditioned air in the fresh application chamber does not enter the drying device 160.

  In Japanese Patent Application Laid-Open No. 2003-106767, a condensing plate that is a plate-like member is installed almost in parallel with the traveling position immediately after coating, and the distance between the condensing plate and the coating film and the temperature of the condensing plate are controlled, It is shown that by providing a drying device that condenses and recovers the solvent, it is possible to dry without causing unevenness in film thickness due to drying. This method can also be applied to the present invention.

  FIG. 20A is a schematic view showing an example of a coating / drying line 210 for carrying out the coating film drying method of the present invention. The coating / drying line includes a delivery device 212 for feeding out the web 211, a backup roller 213, a coating die 214, a first drying device 215, a roller 216, a second drying device 217, rollers 218, 219, and a winder 220. ing. The web 211 is sent out from the transmitter 212. The web 211 is conveyed while being wound around the backup roller 213, and the application liquid is applied to the web 211 by the application die 214, so that the web 211 becomes the application web 211a.

  The first drying device 215 includes condensing plates 221 and 222 that are provided in parallel with the web 211 at a predetermined distance, and side plates that are hanged downward from the front and rear sides of the condensing plates 221 and 222. Thereby, when the solvent in the coating film is volatilized, the volatilized solvent is condensed on the condensing plates 221 and 222 and collected.

  In the first drying device 215, the solvent evaporates into the space between the application surface of the web 211 and the condensing plates 221 and 222, and the evaporated solvent is recovered from the condensing surfaces of the condensing plates 221 and 222. In order for the coated surface to be uniformly dried, an undisturbed boundary layer is formed between the coated surface and the condensing surfaces of the condenser plates 213 and 214, and uniform mass transfer and heat transfer must be performed. It is.

  However, natural thermal convection is generally known as an obstacle to uniform heat transfer between two planes having different temperatures as in the coating film drying apparatus. When thermal natural convection occurs, this boundary layer becomes unstable and disturbs the boundary layer, resulting in a non-uniform drying rate distribution. As a result, the coating film cannot be uniformly dried.

  Research on natural convection has been conducted for a long time, for example, Heat Transfer, vol.1 (1953) and Max Jacob (publisher: John Wiley & Sons) have experimental studies on natural convection in various cases. It has been introduced. The Chemical Engineering Handbook, Revised Sixth Edition, edited by the Society of Chemical Engineering (Publisher: Maruzen), presents research on natural convection all together.

These relate to vertical flat plates, horizontal square plates, inclined flat plates, horizontal cylindrical surfaces, inclined cylindrical surfaces, gaps sandwiched between vertical flat plates, gaps sandwiched between horizontal flat plates, and the like. As is clear from these studies, the shape of the solid surface greatly affects the amount of heat transfer.
However, these studies are mainly about plates or cylinders that are simply placed in the air. On the other hand, there are few studies on the problem between two planes, including the surface coated with coating liquid, where one side runs continuously, which is the subject of this study, and the conditions for the formation of a uniform boundary layer by suppressing natural convection Is not clear. In addition, since natural convection is convection caused by buoyancy of a fluid mass, the ratio of viscous force to buoyancy, the ratio of thermal diffusivity to momentum diffusivity, and the like are important. Each dimensionless number can be expressed in the following form.
Grasshof number = [thermal expansion coefficient × (T ₁ −T ₂ ) × L ³ × d ² × g] / δ ² ... (11)
Prandtl number = (specific heat capacity x δ) / thermal conductivity ··· Formula (12)
In general, equation (11) is called the Grashof number and equation (12) is called the Prandtl number. The relationship between these values and the occurrence of natural convection is only an empirical formula for a specific case. A value obtained by multiplying these two dimensionless numbers is generally called a Rayleigh number.

  In the coating / drying line 210 for carrying out the coating method according to the present invention, the distance between the web 211 and the condenser plates 221 and 222, the temperature of the condenser plates 221 and 222, and the coating film so that the Rayleigh number is less than 5000. By setting the temperature of the coating liquid, regardless of the type of solvent of the coating liquid, the shape of the condenser plates 221, 222, the arrangement angle of the condenser plates 221, 222, the traveling angle of the web 211, etc. A coating film is obtained. Moreover, when each condition is set so that the number of Rayleigh is less than 2000, the surface property of the coating film is further improved.

  The material used for condensing the solvent of the condensing plates 221 and 222 is not particularly limited, such as metal, plastic, wood, etc., but when the coating solution contains an organic solvent, it is resistant to the organic solvent. It is desirable to use some material or apply a coating to the surface.

  In the first drying device 215, the means for recovering the solvent condensed on the condensing plates 221 and 222, for example, provides grooves on the condensing surfaces of the condensing plates 221 and 222, and recovers the solvent using capillary force. The direction of the groove may be the traveling direction of the web 211 or may be a direction perpendicular to the traveling direction. When the condensing plates 221 and 222 are installed with an inclination, the grooves may be provided in a direction in which the solvent can be easily recovered.

  FIG. 20B shows a coating / drying line 225 of another embodiment. In addition, the same code | symbol is attached | subjected to the same location as the application | coating and drying line 210 of Fig.20 (a), and description is abbreviate | omitted. The first drying device 226 of the coating / drying line 225 is provided with a number of temperature adjusting rollers 227 capable of adjusting the temperature. By controlling the temperature of the temperature control roller 227, the coating film surface temperature of the coating web 221a is adjusted to make the volatilization amount of the organic solvent from the coating film as desired.

FIG. 21A shows a film product production line 230 to which the coating film production method of the present invention is applied. The prepared dope is cast from the casting die 231 onto the rotating drum 232 to form a casting film. After the cast film has a self-supporting property, it is peeled off as the web 234 while being supported by the peeling roller 233. Then, the web 234 is sent to the pre-drying chamber 226 where a large number of rollers 235 are provided, and is dried until the desired solvent content is obtained. Thereafter, the roller 237 is conveyed to the coating die 238. A coating apparatus is configured together with a backup roller 239 provided on the coating die 238 so as to face the web 234. Web 2
34 is conveyed while being wound around the backup roller 239, and a coating liquid is applied from the coating die 238 to form a coating web 234a on which a coating film is formed.

  The coating web 234a is sent to the drying device 240 and dried so that the coating film has a desired solvent amount. The drying device 240 is provided with condensing plates 241 and 242 to condense and recover the organic solvent gas volatilized from the coating film. Below the right end of the condensing plate 231, a bottle 243 for collecting the condensed solvent is provided, and the solvent is collected through the bottle 243.

  The coating web 234a delivered from the drying device 240 is conveyed by a roller 244 and sent to a drying chamber 246 provided with a number of rollers 245, and dried until the coating film has a desired solvent content. Finally, the coating web 234a is wound around a winder 247.

  In addition to the configuration in which the condenser plate 241 is used for the drying device 240, a configuration having a similar function, for example, a configuration using a perforated plate, a net, a scissors, a roll, or the like can be used. Moreover, you may use together with a collection | recovery apparatus as shown in US5694701 specification.

  The drying device 240 is preferably disposed as close as possible to the coating die 238 in order to prevent drying unevenness of the coating film due to the occurrence of natural convection immediately after the coating liquid is applied. Specifically, it is preferable that the inlet of the drying device 240 is located within 5 m from the coating die 238, more preferably within 2 m, and within 0.7 m. It is most preferable to arrange so as to be in the position. Further, the length of the drying device 240 is preferably set to a length that allows the coating film after coating to be placed in the drying device 240 for 2 seconds or more, more preferably 3 seconds or more, and further preferably 5 seconds or more. preferable.

  For the same reason, the traveling speed of the web 234 is preferably a speed at which the web 234 reaches the drying device 240 within 30 seconds after coating by the coating die 238, and reaches the drying device 240 within 20 seconds after coating. More preferred is speed.

  The larger the coating amount and the coating film thickness of the coating solution, the more easily the unevenness occurs because the flow inside the coating film is more likely to occur. However, if the drying device 240 is used, the coating amount and the coating film thickness are large. Even in the case, a sufficient effect can be obtained. If the thickness of the coating film is 0.001 mm to 0.08 mm (1 μm to 80 μm), the coating film can be dried uniformly and efficiently.

  If the running speed of the web 234 is too high, the boundary layer in the vicinity of the coating film is disturbed by the accompanying wind, which adversely affects the coating film. Therefore, the traveling speed of the web 234 is preferably set to 1 m / min to 100 m / min, and more preferably set to 5 m / min to 80 m / min.

  Since unevenness of the coating film is particularly likely to occur in the early stage of drying, it is preferable that the drying device 240 condenses and collects 70% or more of the solvent in the coating solution, and the remaining coating solution is dried in the post-drying chamber 246. What percentage of the solvent in the coating solution is condensed and recovered may be determined by comprehensively determining the influence on the drying unevenness of the coating film, production efficiency, and the like.

  In order to promote evaporation and condensation of the solvent in the coating solution, it is preferable to heat the coating web 234a, cool the condenser plates 241, 242 or both. For example, a cooling unit may be provided in the drying device 240, and a heating unit may be provided on the non-application surface side with the application web 234a interposed therebetween.

  In any case, it is desirable that the condenser plates 241 and 242 be temperature-controlled in order to control the drying speed of the coating film. The condenser plates 241 and 242 can be controlled in temperature, and if it is desired to cool, it is necessary to install equipment for cooling. For cooling, a water-cooled heat exchanger method using a refrigerant or the like, an air-cooled method using wind, a method using electricity, for example, a method using a Peltier element, or the like can be used.

  When it is desired to heat the coating web 234a, a heater can be provided on the anti-coating film side to heat it. Moreover, it can also heat by arrange | positioning the conveyance roll (heating roll) which can be heated up. In addition, you may heat using an infrared heater, a microwave heating means, etc.

  When determining the temperature of the coating web 234a and the condensing plates 241, 242, it should be noted that the evaporated solvent does not condense on a place other than the condensing plates 241, 242, such as the surface of the transport roll. It must be. For this reason, for example, this kind of dew condensation can be avoided by setting the temperature of the part other than the condenser plates 241 and 242 higher than the temperature of the condenser plates 241 and 242.

  The distance (interval) between the surface of the coating film and the surfaces of the condenser plates 241 and 242 needs to be adjusted to an appropriate distance in consideration of the desired coating film drying speed. Shortening the distance increases the drying speed, but is easily affected by the set distance accuracy. On the other hand, when the distance is increased, not only the drying speed is significantly reduced, but also natural convection due to heat occurs, resulting in drying unevenness.

  The distance between the surface of the coating film and the surfaces of the condensing plates 241 and 242 is such that the Rayleigh number indicated by a value obtained by multiplying the glassphos number indicated by the equation (11) and the Prandtl number indicated by the equation (12) is less than 5000. However, it is preferable to adjust in the range of 0.1 mm to 200 mm, more preferably in the range of 0.5 mm to 100 mm, and most preferably in the range of 5 mm to 10 mm.

  In the drying device 240, a large number of guide rollers 248 may or may not be provided on the opposite side of the condensing plates 241 and 242 across the coating web 234a.

  The first drying device does not necessarily have a linear shape as shown in FIG. 20, for example, a first drying having an arc shape as shown in the coating / drying lines 250 and 251 of FIGS. 22a and 22b. Devices 252 and 253 may be used. Further, a large drum may be provided, and a dryer may be disposed thereon. Note that the same portions as those in FIG. 20 are denoted by the same reference numerals, and description thereof is omitted. In the coating / drying lines 250 and 251 in FIG. 22, the arc-shaped first drying devices 252 and 253 are brought close to the coating die 214 to improve the solvent recovery efficiency.

  As the second drying device 217, a roller conveying dryer type or air floating dryer type drying device used as a conventional technique can be used. Any type of drying apparatus is common in that dried air is supplied to the surface of the coating film to dry the coating film.

  In addition, the method of drying a coating film only with a 1st drying apparatus without providing a 2nd drying apparatus can also be taken. FIG. 23, FIG. 24, and FIG. 25 are examples of configurations in which the coating film is dried only by the first drying device. Note that the same portions as those in FIG. 20 are denoted by the same reference numerals, and description thereof is omitted. Also apply. The main part of a drying line is illustrated.

  In the coating / drying line 260 of FIG. 23, the first drying device 261 is divided into a plurality of zones 261a, 261b, 261c, 261d, 261e. In each of the zones 261a to 261e, the distance between the condenser plates 262, 263, 264, 265, 266 and the coating film is changed stepwise. A large number of guide rollers 267 are provided on the opposite side of the condensing plates 262 to 266 across the coating web 211a.

  In the coating / drying line 270 of FIG. 24, the first drying device 271 is divided into a plurality of zones 271a to 271e. Further, in each of the zones 271a to 271e, the distance between the condenser plates 272 to 276 and the coating film changes stepwise. No guide roller is provided.

In the coating / drying line 280 of FIG. 25, the first drying device 281 is not divided into a plurality of zones, and the distance between each of the condenser plates 282 to 286 and the coating film is constant. A large number of guide rollers 287 are provided on the opposite side of the condensing plates 282 to 286 across the coating web 211a.
[Curing process of coated film]
In the present invention, the method for curing each layer of the antireflective film is preferably formed by applying a coating composition at the same time as coating or by a crosslinking reaction or polymerization reaction by light irradiation, electron beam irradiation or heating after coating. .

  When each layer of the antireflection film is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. By forming in an atmosphere having an oxygen concentration of 10% by volume or less, an outermost layer having excellent physical strength and chemical resistance can be obtained.

  The oxygen concentration is preferably 5% by volume or less, more preferably 1% by volume or less, particularly preferably the oxygen concentration is 0.5% by volume or less, and most preferably 0.1% by volume or less.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

  The light source for light irradiation may be any one in the ultraviolet light region or near infrared light region, and as a light source for ultraviolet light, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halides. Lamp, xenon lamp, sunlight, and the like. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam.

  Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.

  When using a near-infrared light source, it may be used in combination with an ultraviolet light source, or light may be irradiated from the substrate surface side opposite to the coating surface side. Thereby, the film hardening in the depth direction in the coating layer proceeds without delay with the vicinity of the surface, and a cured film having a uniform cured state is obtained.

Irradiation intensity of ultraviolet irradiation is preferably about 0.1~1000mW / cm ^2, irradiation amount on the coating film surface is preferably 10~1000mJ / cm ^2. Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.

  The antireflection film prepared as described above can be used for articles that require antireflection, particularly for polarizing plates and various image display devices described below.

[Polarizer]
When the antireflection film of the present invention is used as one side of the surface protective film of the polarizer, it is necessary to saponify the surface of the web opposite to the surface on which the antireflection layer is formed with an alkali. Specific means for the alkali saponification treatment can be selected from the following two.

  (1) After forming the antireflection layer on the web, the back surface of the web is saponified by immersing it in an alkaline solution at least once.

  (2) Before or after forming the antireflection layer on the web, by applying an alkaline liquid to the surface of the web opposite to the surface on which the antireflection film is to be formed, heating, washing and / or neutralizing, Only the back side of the web is saponified.

  (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.

  Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. In general, a polyvinyl alcohol film (hereinafter referred to as “PVA”) is preferably used as the iodine polarizer and the dye polarizer. PVA is usually saponified polyvinyl acetate, but modified PVA can also be used.

  A polarizing film is obtained by dyeing PVA. Examples of dyeing can be performed by any means such as a method of immersing a PVA film in an iodine-potassium iodide aqueous solution, application or spraying of iodine or a dye solution. In the process of producing a polarizing film by stretching PVA, it is preferable to use an additive that crosslinks PVA, for example, boric acids.

  The transmittance of the polarizing plate is preferably in the range of 30 to 50% and more preferably in the range of 35 to 50% in the light with a wavelength of 550 nm. The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.

[Image display device]
The antireflection film of the present invention, when used as one side of a polarizer surface protective film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB).

  When used in a transmissive or transflective liquid crystal display device, it is combined with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). By using it, a display device with higher visibility can be obtained.

  In addition, when a front plate such as an acrylic plate is disposed over the entire surface of the liquid crystal cell in the transmissive, reflective, and transflective liquid crystal display devices, not only the polarizing plate on the liquid crystal cell surface side, Adhering to the inside and / or outside of the front plate via an adhesive or the like is preferable because reflection at the interface can be reduced. Further, by combining with a λ / 4 plate, it can be used as a reflective or transflective LCD or a surface protection plate for an organic EL display.

  Furthermore, the antireflection layer of the present invention is formed on a transparent support such as PET and PEN, and the like, such as PDA, cell phone surface protection plate, touch panel, plasma display panel (PDP) and cathode ray tube display (CRT). It can be applied to various image display devices.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(Preparation of coating liquid for hard coat layer (HCL-1))
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.

  742.0 parts by mass of trimethylolpropane triacrylate (TMPTA, Nippon Kayaku Co., Ltd.), 277 parts by mass of poly (glycidyl methacrylate) having a weight average molecular weight of 15000, 728.0 parts by mass of methyl ethyl ketone, 503.0 parts by mass of cyclohexanone And 51.0 mass parts of photoinitiators (Irgacure 184, Nippon Ciba-Geigy Co., Ltd. product) were added and stirred. It filtered with the polypropylene filter with the hole diameter of 0.4 micrometer, and prepared the coating liquid (HCL-1) for hard-coat layers.

(Preparation of anti-glare hard coat layer coating solution (HCL-2))
284 parts by mass of commercially available zirconia-containing UV curable hard coat liquid (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, ZrO ₂ content of solid content of about 70%, polymerizable monomer, polymerization initiator) g, 86 parts by mass g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), 60 parts by mass g of methyl isobutyl ketone, and 17 parts by mass g of methyl ethyl ketone Diluted.

  Furthermore, 28.5 parts by mass of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred.

  Furthermore, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles (refractive index 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm was added to this solution at 10,000 rpm with a Polytron disperser. 30 parts by weight of a dispersion dispersed for 20 minutes was added, and then a 30% methyl ethyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index: 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) 95 parts by mass of a dispersion liquid dispersed at 10000 rpm for 30 minutes with a Polytron disperser was added and mixed and stirred to obtain a finished liquid.

  The finished solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare an antiglare hard coat layer coating solution (HCL-2).

(Preparation of coating solution for antiglare hard coat layer (HCL-3))
26.6128.0 parts by mass of PET-30 (trade name, pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd., refractive index 1.51) which is an ultraviolet curable resin, DPHA (also an ultraviolet curable resin) Product name, 1.41 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd., refractive index 1.51), 2.94 parts by mass of acrylic polymer, photocuring 1.35 parts by mass of Irgacure 184 (trade name, manufactured by Ciba Geigy Co., Ltd.) which is an initiator, acrylic-styrene beads (manufactured by Soken Chemical Co., Ltd., particle size of 3.5 μm) as the first translucent fine particles, 1.55 parts by weight of refractive index 1.55), styrene beads (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.60) as the second light-transmitting fine particles 4.65 parts by mass, 0.05% by mass of R-30 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) as a leveling agent, and the following fluorine-based surface modifier (Chemical Formula 11, FP-1) 0.05 parts by mass, 6.2 parts by mass of KBM-5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) which is an organosilane compound, 38.7 parts by mass of toluene, and 16.6 parts by mass of cyclohexanone Were sufficiently mixed to prepare a coating solution.

この塗布液を孔径３０μｍのポリプロピレン製フィルターでろ過して防眩性ハードコート層用塗布液（ＨＣＬ−３）を調製した。

This coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare an antiglare hard coat layer coating solution (HCL-3).

(Preparation of titanium dioxide fine particle dispersion A)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO2: Co3 O4: Al2 O3: containing cobalt and surface-treated with aluminum hydroxide and zirconium hydroxide: ZrO2 = 90.5: 3.0: 4.0: 0.5 weight ratio) was used.

  42 parts by mass of the following dispersant (Chemical Formula 12) and 702 parts by mass of cyclohexanone were added to 256 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion A having a weight average diameter of 70 nm.

（中屈折率層用塗布液（ＭＬ−１）の調製）
上記の二酸化チタン分散液Ａ５９．６質量部に、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物（ＤＰＨＡ）４０．７質量部、光重合開始剤（イルガキュア９０７）２．１９質量部、光増感剤（カヤキュアーＤＥＴＸ、日本化薬（株）製）０．８質量部、メチルエチルケトン２８０質量部及びシクロヘキサノン１０４９．０質量部を添加して攪拌した。

(Preparation of Medium Refractive Index Layer Coating Solution (ML-1))
In 59.6 parts by mass of the above titanium dioxide dispersion A, 40.7 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 2.19 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 0.8 parts by mass, 280 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred.

After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare an intermediate refractive index layer coating solution (ML-1). The coating solution had a viscosity of 1.5 mPa · sec, a surface tension of 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating solution for high refractive index layer (HL-1))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 36.6 parts by mass, a photopolymerization initiator (Irgacure 907) , Nippon Ciba-Geigy Co., Ltd.) 3.0 parts by mass, photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.0 part by mass, methyl ethyl ketone 535.0 parts by mass, and cyclohexanone 495 parts by mass Added and stirred.

The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-1) for a high refractive index layer. The coating solution had a viscosity of 1.6 mPa · sec, a surface tension of 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating solution for high refractive index layer (HL-2))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 36.7 parts by mass, a photopolymerization initiator (Irgacure 907) , Manufactured by Nippon Ciba-Geigy Co., Ltd.) 3.0 parts by mass, photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.0 part by mass, methyl ethyl ketone 267.0 parts by mass, and cyclohexanone 761.7 parts by mass Parts were added and stirred.

The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-2) for a high refractive index layer. The viscosity of this coating solution was 2.0 mPa · sec, the surface tension was 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating liquid for high refractive index layer (HL-3))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 36.7 parts by mass, a photopolymerization initiator (Irgacure 907) , Nippon Ciba-Geigy Co., Ltd.) 3.0 parts by mass, photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.0 part by mass, and cyclohexanone 1028.6 parts by mass were added and stirred. .

The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-3) for a high refractive index layer. The coating solution had a viscosity of 2.6 mPa · sec, a surface tension of 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating solution for high refractive index layer (HL-4))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 36.7 parts by mass, a photopolymerization initiator (Irgacure 907) , Nippon Ciba Geigy Co., Ltd.) 3.0 parts by mass, photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.0 part by mass, and methyl ethyl ketone 50.0 parts by mass were added and stirred. .

The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-4) for a high refractive index layer. The coating solution had a viscosity of 20.0 mPa · sec and a surface tension of 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating solution for high refractive index layer (HL-5))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) 36.7 parts by mass, a photopolymerization initiator (Irgacure 907) , Nippon Ciba-Geigy Co., Ltd.) 3.0 parts by mass, and photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.0 part by mass were added and stirred.

The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution (HL-5) for a high refractive index layer. The coating solution had a viscosity of 24.0 mPa · sec, a surface tension of 28 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-1))
203.2 parts by mass of a solution obtained by dissolving the following copolymer (chemical formula 13) in methyl ethyl ketone so as to have a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1.4 parts by mass, photoradical generator Irgacure 907 (trade name) 2.4 parts by mass, methyl ethyl ketone 764.6 parts by mass, and cyclohexanone 28.4 parts by mass were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-1). The viscosity of this coating solution was 0.61 mPa · sec, the surface tension was 24 mN / m, and the amount of the coating solution applied to the web W was 3.5 ml / m ² .

（低屈折率層用塗布液（ＬＬ−２）の調製）
上記の共重合体（化学式１３）をメチルエチルケトンに２３．７質量％の濃度になるように溶解した溶液４６８．８質量部、末端メタクリレート基含有シリコーン樹脂Ｘ−２２−１６４Ｃ（信越化学（株）製）３．３質量部、光ラジカル発生剤イルガキュア９０７（商品名）５．６質量部、メチルエチルケトン４９５．９質量部、及びシクロヘキサノン２６．４質量部を添加して攪拌した。

(Preparation of coating solution for low refractive index layer (LL-2))
468.8 parts by mass of a solution obtained by dissolving the above copolymer (Chemical Formula 13) in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 3.3 parts by mass, 5.6 parts by mass of photoradical generator Irgacure 907 (trade name), 495.9 parts by mass of methyl ethyl ketone, and 26.4 parts by mass of cyclohexanone were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-2). The coating solution had a viscosity of 1.0 mPa · sec, a surface tension of 24 mN / m, and the amount of the coating solution applied to the transparent support was 1.5 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-3))
355.5 parts by mass of a solution obtained by dissolving the above copolymer (Chemical Formula 13) in methyl ethyl ketone to a concentration of 23.7% by mass, a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 2.5 parts by mass, 4.2 parts by mass of photo radical generator Irgacure 907 (trade name), 610.5 parts by mass of methyl ethyl ketone, and 27.3 parts by mass of cyclohexanone were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-3). The viscosity of this coating solution was 0.76 mPa · sec, the surface tension was 24 mN / m, and the amount of the coating solution applied to the web W was 2.0 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-4))
142.2 parts by mass of a solution obtained by dissolving the above copolymer (Chemical Formula 13) in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 1.0 part by mass, 1.7 parts by mass of photoradical generator Irgacure 907 (trade name), 826.2 parts by mass of methyl ethyl ketone, and 28.9 parts by mass of cyclohexanone were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-4). The viscosity of this coating solution was 0.49 mPa · sec, the surface tension was 24 mN / m, and the amount of the coating solution applied to the web W was 5.0 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-5))
118.4 parts by mass of a solution obtained by dissolving the above copolymer (Chemical Formula 13) in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.8 parts by mass, 1.4 parts by mass of photo radical generator Irgacure 907 (trade name), 850.3 parts by mass of methyl ethyl ketone, and 29.1 parts by mass of cyclohexanone were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-5). The coating solution had a viscosity of 0.46 mPa · sec, a surface tension of 24 mN / m, and the amount of the coating solution applied to the web W was 6.0 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-6))
71.1 parts by mass of a solution obtained by dissolving the above copolymer (Chemical Formula 13) in methyl ethyl ketone to a concentration of 23.7% by mass, terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) ) 0.5 parts by mass, 0.8 parts by mass of photoradical generator Irgacure 907 (trade name), 898.1 parts by mass of methyl ethyl ketone, and 29.5 parts by mass of cyclohexanone were added and stirred.

The mixture was filtered through a PTFE filter having a pore diameter of 0.45 μm to prepare a coating solution for low refractive index layer (LL-5). The viscosity of this coating solution was 0.43 mPa · sec, the surface tension was 24 mN / m, and the amount of the coating solution applied to the web W was 10.0 ml / m ² .

(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, 119 parts of methyl ethyl ketone, 101 parts by weight of acryloyloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.), and 3 parts by weight of diisopropoxyaluminum ethyl acetoacetate were added. After mixing, 30 parts of ion exchange water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a.

  The mass average molecular weight of the sol liquid a was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution for low refractive index layer (LL-7))
JN-7228A containing a polysiloxane and a hydroxyl group-containing fluoropolymer (refractive index 1.42, solid content concentration 6%, manufactured by JSR Corporation) 14.9 parts by mass g, silica sol (silica, MEK-ST, average particle size) 15 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 0.61 parts by mass g, silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 0.79 parts by mass g, sol liquid a 0.41 parts by mass g, methyl ethyl ketone 3.1 parts by mass g, cyclohexanone 0.6 parts by mass g were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm. A coating solution for refractive index layer (LL-7) was prepared.

The coating solution had a viscosity of 0.61 mPa · sec, a surface tension of 24 mN / m, and the amount of the coating solution applied to the web W was 2.8 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-8))
JTA113 (trade name, refractive index 1.44, solid content concentration 6%, MEK solution, manufactured by JSR Corp.) 13.1 parts by mass g, colloidal, which has higher coating strength than JN-7228A described above Silica dispersion MEK-ST-L (trade name, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.31 parts by mass g, sol liquid a 0.59 parts by mass g, and methyl ethyl ketone 5 0.1 parts by mass g and 0.6 parts by mass of cyclohexanone were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for low refractive index layer (LL-8).

The coating solution had a viscosity of 0.66 mPa · sec m, a surface tension of 23.7 mN / m, and the amount of the coating solution applied to the web W was 2.8 ml / m ² .

(Preparation of dispersion A-1)
Hollow silica fine particle sol (Isopropyl alcohol silica sol, average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20% by mass, silica particle refractive index 1.31, prepared by changing the size according to Preparation Example 4 of JP-A-2002-79616 ) To 500 parts, 30 parts of acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 parts of diisopropoxyaluminum ethyl acetate were added and mixed, and then 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion A-1 was analyzed by gas chromatography, it was 1.5%.

(Preparation of coating solution for low refractive index layer (LL-9))
44.0 parts by mass of fluorine-containing copolymer P-3 (weight average molecular weight of about 50000) described in JP-A No. 2004-45462, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate with respect to 100 parts by mass of methyl ethyl ketone (DPHA, Nippon Kayaku Co., Ltd.) 6.0 parts by mass, terminal methacrylate group-containing silicone RMS-033 (Gelest) 3.0 parts by mass, photoradical generator Irgacure 907 (Ciba Specialty Chemicals) 3.0 parts by mass was added and dissolved. Thereafter, 195 parts by mass (39.0 parts by mass as silica + surface treatment agent solid content) and 17.2 parts by mass of sol liquid a (5.0 parts by mass as solid content) were added to dispersion (A-1). A coating solution for low refractive index layer (LL-9) was prepared by diluting with cyclohexanone and methyl ethyl ketone so that the solid content concentration of the entire coating solution was 6% by mass and the ratio of cyclohexanone and methyl ethyl ketone was 10:90.

The coating solution had a viscosity of 0.66 mPa · sec m, a surface tension of 23.7 mN / m, and the amount of the coating solution applied to the web W was 2.8 ml / m ² .

(Preparation of coating solution for low refractive index layer (LL-10))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 3.3 parts by mass, terminal methacrylate group-containing silicone RMS-033 (Gelest) 0.7 parts by mass, light Radical generator Irgacure 907 (Ciba Specialty Chemicals Co., Ltd.) 0.2 parts by mass was added and dissolved. Thereafter, 36.4 parts by mass of dispersion (A-1) and 6.2 parts by mass of sol liquid a were added. 290.6 parts by mass of methyl ethyl ketone and 9.0 parts by mass of cyclohexanone were added to prepare a coating solution for low refractive index layer (LL-10).

The coating solution had a viscosity of 0.66 mPa · sec m, a surface tension of 23.7 mN / m, and the amount of the coating solution applied to the web W was 2.8 ml / m ² .

(Die coater configuration)
The slot die 13 shown in FIG. 10 has an upstream lip land length IUP of 0.5 mm, a downstream lip land length ILO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and the length of the slot 16. The one with a length of 50 mm was used.

  The gap between the upstream lip land 18a and the web W is 50 μm longer than the gap between the downstream lip land 18b and the web W (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web W GL was set to 50 μm.

  Further, the gap GS between the side plate 40b and the web W of the decompression chamber 40 and the gap GB between the back plate 40a and the web W were both 200 μm.

Example 1
(Preparation of antireflection film)
On a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm, a hard coat layer coating solution (HCL-1) is applied at a coating speed of 25 m / min using the die coater. Applied. In application | coating of HCL-1, it changed into the clearance gap GL80micrometer of the downstream lip land 18b and the web W, and the pressure reduction degree of the pressure reduction chamber was 0.8 kPa.

Then, after drying at 80 ° C., using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, an illuminance of 400 mW / cm ^2, irradiation amount 500 mJ / cm ² of ultraviolet to cure the coated layer was irradiated, to form a hard coat layer having a thickness of 8μm (2).

  On the hard coat layer (2), the medium refractive index layer coating solution (ML-1) was coated at a coating speed of 25 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa.

Then, after drying at 100 ° C. for 30 seconds, using a 240 W / cm air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) while purging with nitrogen so that the oxygen concentration becomes 0.1 vol% or less, The coating layer was cured by irradiating with ultraviolet rays having an illuminance of 550 mW / cm ² and an irradiation amount of 550 mJ / cm ² to form a medium refractive index layer (refractive index 1.63, film thickness 64 nm).

  On the middle refractive index layer (3), a coating solution for high refractive index layer (HL-1) was applied at a coating speed of 25 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa.

Then, after drying at 100 ° C. for 30 seconds, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm while purging with nitrogen so that the oxygen concentration becomes 0.1 vol% or less. The film was irradiated with ultraviolet rays having an illuminance of 550 mW / cm ² and an irradiation amount of 550 mJ / cm ² to form a high refractive index layer (refractive index 1.90, film thickness 103 nm).

On the high refractive index layer, the low refractive index layer coating solution (LL-1) was applied at a coating speed of 25 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa. Then, after drying at 90 ° C. for 30 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. The film was irradiated with ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² to form a low refractive index layer (refractive index 1.45, film thickness 83 nm). In this way, an antireflection film was produced.

  In the above manufacturing process, the coating and drying processes are performed in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleaning described in JP-A-10-309553 is performed immediately before coating. The air was blown at a high speed to peel off the deposits from the surface of the web W, and the coating was performed while removing dust by a method of sucking with a suction port close to the web W. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

  The prepared antireflection film was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a 80 μm thick triacetyl cellulose film (TAC) A polarizing plate was prepared by adsorbing iodine to polyvinyl alcohol with a film obtained by saponifying TD80U (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions and adhering and protecting both sides of a polarizer prepared by stretching.

  The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF (made between the backlight and the liquid crystal cell) is replaced, the reflection of the background is extremely small, the color of the reflected light is remarkably reduced, and the display A display device with very high display quality in which in-plane uniformity was ensured was obtained.

(Example 2)
A gravure coater was used instead of the die coater, and an antireflection film was prepared in the same manner as in Example 1 except for the other conditions. Although coating was possible, streaks that occurred at equal intervals in the longitudinal direction of the web W (base) and stepwise unevenness that occurred in the width direction occurred. When a display device was created in the same procedure as in Example 1, uneven coloring was visually recognized in the display device, which was not at a high quality level.

(Examples 3 to 6)
An antireflection film was prepared by coating in the same manner as in Example 1 except that the downstream lip land length ILO of the coater 10 was changed to 10 μm, 30 μm, 100 μm, and 120 μm.

  The results are shown in Table 1. An antireflection film in which no surface failure occurs is obtained when the downstream lip land length ILO is in the range of 30 μm to 100 μm.

  In Example 3, streaky unevenness occurred in the longitudinal direction of the base.

  In Example 6, the bead 14a could not be formed at the same speed as in Example 1, and application was impossible. Application was possible by reducing the application speed to half, but streaky irregularities occurred in the longitudinal direction of the base.

  When using the antireflection film prepared in Examples 4 and 5 and producing a display device in the same procedure as in Example 1, the reflection of the background is extremely small, and the color of the reflected light is significantly reduced. Thus, a display device with very high display quality in which uniformity within the display surface was ensured was obtained.

  On the other hand, when the antireflection film obtained in Examples 3 and 6 was used and a display device was created in the same procedure as in Example 1, uneven coloring was visually recognized in the display device, which could not be said to be high quality. It was a level.

(Examples 7 to 10)
Coating was performed in the same configuration as in Example 1 except that the overbite length LO of the coater 10 was 0 μm, 30 μm, 120 μm, and 150 μm, and an antireflection film was prepared.

The results are shown in Table 1. An anti-reflection film that does not cause surface failure is obtained when the over bit length is in the range of LO 30 μm to 120 μm. Although application was possible in Example 7, stepped unevenness in the base width direction was seen in the surface shape. Is allowed.

  In Example 10, the bead 14a could not be formed at the same speed as in Example 1, and coating was impossible. Application was possible by reducing the application speed to half, but streaky irregularities occurred in the longitudinal direction of the base.

  Using the antireflection film prepared in Examples 8 and 9, and producing a display device in the same procedure as in Example 1, there is very little reflection of the background, the color of reflected light is significantly reduced, and Thus, a display device with very high display quality in which uniformity within the display surface was ensured was obtained.

  On the other hand, when the anti-reflection film obtained in Examples 7 and 10 was used and a display device was prepared in the same procedure as in Example 1, uneven coloring was visually recognized in the display device, which could not be said to be high quality. It was a level.

(Examples 11 to 15)
Coating is performed under the same conditions as in Example 1 except that LL-2, LL-3, LL-4, LL-5, and LL-6 are used instead of LL-1 as the coating solution for the low refractive index layer. The antireflection film was made.

The results are shown in Table 2. When the amount of the coating solution applied to the web W is 2 ml / m ² or more, the coating solution can be applied. However, when the amount is 1.5 ml / m ² , the entire surface cannot be applied uniformly, and an antireflection film is produced. I couldn't.

In addition, when the amount of the coating liquid applied to the web W is 6 ml / m ² and 10 ml / m ² , the coating is possible, but since the amount of the coating liquid is large, drying is not in time, and vertical streaks caused by the wind occur. Unevenness occurred on the entire surface.

  Using the antireflection film prepared in Examples 12 and 13 and producing a display device in the same procedure as in Example 1, the reflection of the background is extremely small, the color of the reflected light is significantly reduced, and Thus, a display device with very high display quality in which uniformity within the display surface was ensured was obtained.

  On the other hand, when the antireflection film obtained in Example 14 and Example 15 was used and a display device was created in the same procedure as in Example 1, uneven coloring was visually recognized in the display device, and what is high quality? It was a level I couldn't say.

(Examples 16 to 19)
The antireflective film is coated under the same conditions as in Example 1 except that HL-2, HL-3, HL-4, and HL-5 are used instead of HL-1 as the coating solution for the high refractive index layer. It was created.

  The results are shown in Table 3. The coating solution can be applied at a rate of 25 m / min up to a viscosity of 2 mPa · sec.

  HL-3 showing a viscosity of 2.6 mPa · sec could not be applied uniformly over the entire surface at 25 m / min, but a good antireflection film could be produced at 20 m / min.

  HL-4 showing a viscosity of 20 mPa · sec could not be applied uniformly over the entire surface at 25 m / min, but a good antireflection film could be produced at 3 m / min.

  HL-5 showing a viscosity of 24 mPa · sec could not be applied to the entire surface even when the coating speed was lowered.

  Using the antireflection film prepared in Example 16 and the antireflection film prepared by applying HL-3 at 20 m / min, a display device was prepared in the same procedure as in Example 1, and the background reflection was obtained. A display device with extremely high display quality in which there was very little dust, the color of reflected light was significantly reduced, and uniformity within the display surface was ensured was obtained.

(Example 20)
(Preparation of antireflection film)
(1) Application of anti-glare hard coat layer A triacetyl cellulose film (TAC-TD80UL, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unrolled in the form of a roll and applied for an anti-glare hard coat layer. (HCL-2) was coated at a coating speed of 25 m / min using the die coater. In the application of HCL-2, the gap GL between the downstream lip land 18b and the web W was changed to 80 μm, and the degree of vacuum in the vacuum chamber was 0.8 kPa.

After drying at 60 ° C. for 150 seconds, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm under a nitrogen purge, ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² are used. The coating layer was cured by irradiation to form a hard coat layer (2) having a thickness of 2.9 μm and wound up.

(2) Application of low refractive index layer The triacetyl cellulose film coated with the hard coat layer (2) is unwound again, and the low refractive index layer coating solution LL-7 is applied at 25 m / min using the die coater. Coating was performed at a coating speed. The degree of vacuum in the vacuum chamber was 0.8 kPa.

After drying at 120 ° C. for 150 seconds and further drying at 140 ° C. for 8 minutes, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge, the illuminance is 400 mW / cm. ^2. Irradiation with an irradiation amount of 600 mJ / cm ² was performed to form a low refractive index layer (5) having a thickness of 100 nm and wound up.

  In the above steps, the coating and drying steps are performed in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleaning described in JP-A-10-309553 is performed immediately before coating. The air was blown at a high speed to remove the deposits from the film surface, and the coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

  The prepared anti-reflection film was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a 80 μm thick triacetyl cellulose film ( A polarizing plate was prepared by adsorbing iodine to polyvinyl alcohol with a film obtained by saponifying TAC-TD80U (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions and adhering and protecting both sides of a polarizer prepared by stretching. .

  The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF (made between the backlight and the liquid crystal cell) is replaced, the reflection of the background is extremely small, the color of the reflected light is remarkably reduced, and the display A display device with very high display quality in which in-plane uniformity was ensured was obtained.

(Example 21)
(Preparation of antireflection film)
(1) Application of antiglare hard coat layer A triacetyl cellulose film (TD80U: trade name, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unrolled in a roll form and applied for an antiglare hard coat layer. Liquid HCL-3 was applied at a coating speed of 25 m / min using the die coater so that the dry film thickness was 7 μm.

  In application of HCL-3, the gap GL between the downstream lip land 18b and the web W was changed to 80 μm, and the degree of vacuum in the vacuum chamber was 0.8 kPa. After solvent drying at 110 ° C. for 10 seconds and at 50 ° C. for 20 seconds, under nitrogen purge (oxygen concentration of 200 ppm or less), UV irradiation is performed so that the integrated light amount becomes 55 mJ, photocuring, anti-glare A layer was formed and wound up.

(2) Application of low refractive index layer The triacetyl cellulose film coated with the antiglare layer is unwound again, and the coating liquid for low refractive index layer (LL-8) is dried so that the dry film thickness becomes 100 nm. Coating was performed at a coating speed of 25 m / min using a die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa.

  After drying at 120 ° C for 70 seconds, further drying at 110 ° C ° C for 10 minutes and thermosetting, under a nitrogen purge (oxygen concentration of 100 ppm or less), UV irradiation is performed so that the integrated light quantity becomes 120 mJ. Then, it was photocured to form an antireflection film coated with the low refractive index layer (5) and wound up.

  In the above steps, the coating and drying steps are carried out in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 just before the coating. The air was sprayed at a high speed to peel off the deposits from the film surface, and the coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

  The prepared antireflection film was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a 80 μm thick triacetyl cellulose film (TAC) A polarizing plate was prepared by adsorbing iodine to polyvinyl alcohol with a film obtained by saponifying TD80U (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions and adhering and protecting both sides of a polarizer prepared by stretching. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF (made between the backlight and the liquid crystal cell) is replaced, the reflection of the background is extremely small, the color of the reflected light is remarkably reduced, and the display A display device with very high display quality in which in-plane uniformity was ensured was obtained.

(Example 22)
(Preparation of antireflection film)
(1) Application of antiglare hard coat layer A triacetyl cellulose film (TD80U: trade name, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm is unrolled in a roll form and applied for an antiglare hard coat layer. Liquid HCL-3 was applied at a coating speed of 25 m / min using the die coater so that the dry film thickness was 7 μm.

  In application of HCL-3, the gap GL between the downstream lip land 18b and the web W was changed to 80 μm, and the degree of vacuum in the vacuum chamber was 0.8 kPa. After solvent drying at 110 ° C. for 10 seconds and at 50 ° C. for 20 seconds, under a nitrogen purge (oxygen concentration of 200 ppm or less), UV irradiation is performed so that the integrated light quantity becomes 55 mJ, photocuring, anti-glare A layer was formed and wound up.

(2) Application of low refractive index layer The triacetyl cellulose film coated with the antiglare layer is unwound again, and the low refractive index layer coating solution (LL-9) is applied at 25 m / min using the die coater. Applied at speed. The degree of vacuum in the vacuum chamber was 0.8 kPa. Then, after drying at 90 ° C. for 30 seconds, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. The film was irradiated with ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² to form a low refractive index layer (film thickness 95 nm). In this way, an antireflection film was produced.

  In the above steps, the coating and drying steps are carried out in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 just before the coating. The air was sprayed at a high speed to peel off the deposits from the film surface, and the coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

  The prepared antireflection film was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a 80 μm thick triacetyl cellulose film (TAC) A polarizing plate was prepared by adsorbing iodine to polyvinyl alcohol with a film obtained by saponifying TD80U (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions and adhering and protecting both sides of a polarizer prepared by stretching. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF (made between the backlight and the liquid crystal cell) is replaced, the reflection of the background is extremely small, the color of the reflected light is remarkably reduced, and the display A display device with very high display quality in which in-plane uniformity was ensured was obtained.

(Example 23)
An antireflection film was prepared by coating under the same conditions as in Example 22 except that LL-10 was used instead of LL-9 as the coating solution for the low refractive index layer.
When a display device was prepared using the antireflection film in the same procedure as in Example 22, the background reflection was extremely small, the color of the reflected light was significantly reduced, and the uniformity within the display surface was further improved. A display device with very high display quality was obtained.

(Comparative example)
By means of physical vapor deposition, a substantially middle refractive index layer consisting of two layers of titanium oxide (refractive index: 2.39) 25 nm and silicon oxide (refractive index 1.47) 25 nm is sequentially formed on the hard coat of Example 1 and oxidized. When an antireflective film was formed by forming a high refractive index layer made of titanium 46 nm and a low refractive index layer made of silicon oxide 97 nm, the reflected light was strongly colored reddish purple.

  Moreover, when the obtained antireflection film was used and a display device was prepared in the same procedure as in Example 1, the screen was strongly colored purple-red and the display quality was inferior.

(Example 101)
(Preparation of hard coat layer coating solution (HCL-1))
The same HCL-1 as in Example 1 was prepared and used.

(Preparation of anti-glare hard coat layer coating solution (HCL-2))
50.0 parts by mass of PETA (trade name, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd.), an ultraviolet curable resin, and Irgacure 184 (Ciba Specialty), a photocuring initiator・ Chemicals Co., Ltd. (2.0 parts by mass), cross-linked acrylic-styrene particles as first translucent fine particles (manufactured by Soken Chemical Co., Ltd., average particle size 3.5 μm, refractive index 1.55, 30) % Toluene dispersion) 13.3 parts by mass, crosslinked polystyrene particles as second light-transmitting fine particles (manufactured by Soken Chemical Co., Ltd., particle size 3.5 μm, refractive index 1.60, 30% toluene dispersion). 1.7 parts by weight of a polytron disperser used after dispersion at 10,000 rpm for 20 minutes) and 0.75 mass of FP-132, which is the following fluorine-based surface modifier (Chemical Formula 14) 10.0 parts by mass of KBM-5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), which is an organosilane compound, and 38.5 parts by mass of toluene were sufficiently mixed to prepare a coating solution. This coating solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare an antiglare hard coat layer coating solution (HCL-2).

（二酸化チタン微粒子分散液Ａの調整）
二酸化チタン微粒子分散液Ａは実施例１の二酸化チタン微粒子分散液Ａと全く同様にして調製した。

(Preparation of titanium dioxide fine particle dispersion A)
The titanium dioxide fine particle dispersion A was prepared in exactly the same manner as the titanium dioxide fine particle dispersion A of Example 1.

(Preparation of Medium Refractive Index Layer Coating Solution (ML-1))
ML-1 was prepared in exactly the same manner as ML-1 in Example 1.

(Preparation of coating solution for high refractive index layer (HL-1))
HL-1 was prepared in exactly the same manner as HL-1 in Example 1.

(Preparation of coating solution for low refractive index layer (LL-1))
LL-1 was prepared in exactly the same manner as LL-1 in Example 1.

(Preparation of sol solution a)
Sol solution a was prepared in exactly the same manner as Sol solution a of Example 1.

(Preparation of coating solution for low refractive index layer (LL-2))
JTA113 (trade name, refractive index 1.44, solid content concentration 6%, MEK solution, manufactured by JSR Corporation) 13.1 g, colloidal silica dispersion, which has higher coating strength than JN-7228A described above MEK-ST-L (trade name, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.31 g, the sol a0.59 g, methyl ethyl ketone 5.1 g, and cyclohexanone 0.6 g were added. After stirring, the mixture was filtered through a polypropylene filter having a pore diameter of 1 μm to prepare a coating solution for low refractive index layer (LL-2).

(Die coater configuration)
The slot die 13 shown in FIG. 10 has an upstream lip land length IUP of 0.5 mm, a downstream lip land length ILO of 50 μm, a length of the opening of the slot 16 in the web running direction of 150 μm, and the length of the slot 16. The one with a length of 50 mm was used. The gap between the upstream lip land 18a and the web 12 is 50 μm longer than the gap between the downstream lip land 18b and the web 12 (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web 12 is set. GL was set to 50 μm. Further, the gap GS between the side plate 40b and the web W and the gap GB between the back plate 40a and the web W of the decompression chamber 40 shown in FIG.

(Preparation of antireflection film)
With an ultrasonic dust remover, the surface of the application side of a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm is subjected to charge removal treatment, and then the hard coat layer coating liquid (HCL-1) is applied. Coating was performed at a coating speed of 30 m / min using the die coater. The degree of decompression of the decompression chamber 40 was 0.8 kPa. In the application of HLC-1 (hard coat layer coating solution), the gap GL between the downstream lip land 18b and the web W was changed to 80 μm. Immediately after application, initial drying was performed using the first drying device 215 shown in FIG. The total length of the first drying device 215 was 5 m. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coated web 211a initially dried by the first drying device 215 is dried at 80 ° C. using the second drying device 217, and then 160 W while purging with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. / Cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 500 mJ / cm ² to cure the coating layer, and a hard coat layer having a thickness of 8 μm Formed. On the above-mentioned hard coat layer, a medium refractive index layer coating solution (ML-1) was applied at a coating speed of 30 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa.

Immediately after applying the medium refractive index layer coating solution, initial drying was performed using the first drying device 215 shown in FIG. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coated web 211a initially dried by the first drying device 215 is then dried by using the second drying device 217 at 100 ° C. for 30 seconds, and then purged with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. While using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), the coating layer is cured by irradiating ultraviolet rays with an illuminance of 550 mW / cm ² and an irradiation amount of 550 mJ / cm ² , and a medium refractive index layer (Refractive index 1.63, film thickness 64 nm) was formed.

On the middle refractive index layer, a coating solution for high refractive index layer (HL-1) was applied at a coating speed of 30 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa. Immediately after application, initial drying was performed using the first drying device 215 shown in FIG. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coating web 211a initially dried by the first drying device 215 is then dried by using the second drying device 217 at 100 ° C. for 30 seconds, and then purged with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. On the other hand, using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays having an illuminance of 550 mW / cm ² and an irradiation amount of 550 mJ / cm ² were irradiated, and a high refractive index layer (refractive index of 1. 90, and a film thickness of 103 nm).

On the high refractive index layer, a coating solution for low refractive index layer (LL-1) was applied at 30 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa. Immediately after the application, initial drying was performed using the first drying device 215 shown in FIG. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coating web 211a initially dried by the first drying device 215 is then dried by using the second drying device 217 at 90 ° C. for 30 seconds, and then purged with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. While using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² were irradiated, and a low refractive index layer (refractive index 1. 45, film thickness 83 nm). Thus, the antireflection film 10 shown in FIG. 1 was produced.

  In the above steps, the coating and drying steps are carried out in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 just before the coating. The air was sprayed at a high speed to separate the deposits from the web surface, and the coating was carried out while removing dust by a method of sucking with a suction port close to the web. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

This antireflection film does not have any failure that occurs due to the coating process. Furthermore, although the drying speed immediately after coating was 0.3 [g / (m ² · s)] or more for each layer having a dry film thickness of 200 nm or less, film thickness unevenness due to the drying process is not visually recognized. It was an antireflection film with very high color uniformity. The drying speed was measured by collecting coating films at several points in the first drying device 215.

The prepared antireflection film 10 was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a triacetyl cellulose film (TAC) having a thickness of 80 μm. -TD80U, manufactured by Fuji Photo Film Co., Ltd.) was saponified under the same conditions, and iodine was adsorbed to polyvinyl alcohol, and both sides of a polarizer prepared by stretching were bonded and protected to prepare a polarizing plate. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. Made D-BE
When F is replaced with the polarizing plate on the viewing side (having between the backlight and the liquid crystal cell), the reflection of the background is extremely small, the color of the reflected light is significantly reduced, and the uniformity within the display surface As a result, a display device with extremely high display quality was obtained.

(Example 102)
An 80 μm-thick triacetylcellulose film (TD80U: trade name, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the antiglare hard coat layer coating solution HCL-2 has a dry film thickness of 7 μm. Using the die coater (see FIGS. 8 and 9), coating was performed at a coating speed of 30 m / min.

  In the application of HCL-2, the gap GL between the downstream lip land 18b and the web W was changed to 80 μm, and the degree of vacuum in the vacuum chamber was 0.8 kPa. Immediately after application, initial drying was performed using the first drying device 215 shown in FIG. The total length of the first drying device 215 was 5 m. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coating web 211a initially dried by the first drying device 215 is then dried at 110 ° C. for 10 seconds and at 50 ° C. for 20 seconds using the second drying device 217, and further under a nitrogen purge (oxygen concentration of 200 ppm or less). Then, UV irradiation was carried out so that the integrated light amount was 55 mJ, photocuring was performed, and an antiglare layer was formed and wound up.

The triacetyl cellulose film coated with the antiglare layer is unwound again, and the coating solution for low refractive index layer (LL-8) is applied at 30 m / min using the die coater so that the dry film thickness becomes 100 nm. Applied at speed. The degree of vacuum in the vacuum chamber was 0.8 kPa. Immediately after the application, initial drying was performed using the first drying device 215 shown in FIG. The total length of the first drying device 215 was 5 m. The condensing plates 221 and 222 in the first drying device 215 were arranged with a predetermined inclination angle such that the downstream side in the traveling direction was separated from the coating film. The coated web 211 a initially dried by the first drying device 215 is then 70 ° C. at 120 ° C. using the second drying device 217.
After drying for 2 seconds, it is further dried at 110 ° C. for 10 minutes and thermally cured, then under a nitrogen purge (oxygen concentration of 100 ppm or less), UV irradiation is performed so that the integrated light amount becomes 120 mJ, photocuring, and low refraction An antireflection film 30 (see FIG. 3) coated with a rate layer was formed and wound up.

  In the above steps, the coating and drying steps are carried out in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 just before the coating. The air was sprayed at a high speed to peel off the deposits from the film surface, and the coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

This antireflection film 30 does not have any failure caused by the coating process. Furthermore, although the drying speed immediately after coating was 0.3 [g / (m ² · sec)] or more for each layer having a dry film thickness of 200 nm or less, film thickness unevenness due to the drying process is not visually recognized. The anti-reflection film 30 had very high color uniformity.

The prepared antireflection film 30 was immersed in a 2.0 normal, 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and a triacetyl cellulose film (TAC) having a thickness of 80 μm. -TD80U, manufactured by Fuji Photo Film Co., Ltd.) was saponified under the same conditions, and iodine was adsorbed to polyvinyl alcohol, and both sides of a polarizer prepared by stretching were bonded and protected to prepare a polarizing plate. The thus-prepared polarizing plate is a liquid crystal display device of a notebook computer equipped with a transmission type TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the antireflection film side is the outermost surface. Made D-BE
When F is replaced with the polarizing plate on the viewing side (having between the backlight and the liquid crystal cell), reflection of the background is extremely small, the color of the reflected light is remarkably reduced, and the display surface is uniform. Thus, a display device with a very high display quality in which properties were ensured was obtained.

(Example 103)
The drying process installed immediately after application when applying each layer is the same as in Example 102, except that the drying apparatus 160 shown in FIG. 17 is changed from the one shown in the application / drying line 210 to perform initial drying. Then, an antireflection film (see FIG. 3) 30 was produced. In the drying device 160 shown in FIG. 17, the opening ratio of the air conditioning plate 190 is 25%, the distance C between the coating surface and the air conditioning plate is 10 mm, and the exhaust air velocity of each of the drying zones 167 to 173 is set to 0.1 m / second. . The total length of the drying device 160 was 5 m. This antireflection film 30 did not have any failure caused by the coating process. Furthermore, although the drying speed immediately after coating was 0.3 [g / (m ² · sec)] or more for each layer having a dry film thickness of 200 nm or less, film thickness unevenness due to the drying process is not visually recognized. It was an antireflection film with very high color uniformity. Using this antireflection film, a display device was produced in the same procedure as in Example 102. As a result, the background reflection was extremely small, the color of the reflected light was remarkably reduced, and the uniformity within the display surface was ensured. A display device with very high display quality was obtained.

(Example 104)
Coating is performed in the same manner as in Example 102 except that the drying process installed immediately after coating when applying each layer is changed from the coating / drying line 210 shown in FIG. 20 to the drying device shown in FIG. The antireflection film 30 was produced. In the drying process, the wind (5 mm × 1600 mm) from the wire mesh in the drying zone 113 after passing the current plate 112 (relative wind speed applied to the coating surface: 0.05 m / second in the transport direction) 25 ° C., 50% RH). The wind from the coating chamber air supply port is exhausted from the coating chamber exhaust port and is exhausted from the exhaust port 117 through the perforated plate 115 and the metal mesh 116.

This antireflection film 30 did not have any failure caused by the coating process. Furthermore, although the drying speed immediately after coating was 0.3 [g / (m ² · sec)] or more for each layer having a dry film thickness of 200 nm or less, film thickness unevenness due to the drying process is not visually recognized. It was an antireflection film with very high color uniformity. Using this antireflection film, a display device was produced in the same procedure as in Example 102. As a result, the background reflection was extremely small, the color of the reflected light was remarkably reduced, and the uniformity within the display surface was ensured. A display device with very high display quality was obtained.

[Comparative Example 101]
Example 102 Except for adopting a hot air drying method in which a non-application surface side is supported by a roll and dried by blowing air from an air nozzle on the application surface side as a drying step that is installed immediately after application when applying each layer. Application was performed in the same manner as described above to produce an antireflection film. As a result, wind was applied immediately after application, and the coated surface was disturbed, resulting in strong film thickness unevenness. The drying rate immediately after coating was 0.3 [g / (m ² · sec)] or more for each layer. Moreover, when the display apparatus was produced for the obtained anti-reflective film in the procedure similar to Example 102, the color nonuniformity was visually recognized in the display apparatus, and it could not be said that it was high quality.

[Comparative Example 102]
In the drying process that is installed immediately after application when applying each layer, the downstream side in the running direction of the condenser plate is separated from the coating film so that the evaporation rate of each layer is 0.15 [g / (m ² · sec)]. An antireflection film was produced by coating in the same manner as in Example 102 except that the film was arranged with a predetermined inclination angle.

In this experiment (Comparative Example 102), the evaporation rate of each layer is 0.15 [g / (m ² · sec)], which is less than 0.3 [g / (m ² · sec)]. The drying apparatus was left without being completely dried, and then the drying progressed rapidly, resulting in uneven film thickness. When a display device was produced using this antireflection film in the same procedure as in Example 102, color unevenness was visually recognized in the display device, which was not high quality.

[Comparative Example 103]
When applying each layer, coating was performed in the same manner as in Example 102 except that the total length of the drying step installed immediately after coating was 0.5 m, and an antireflection film was produced. In Comparative Example 103, since the total length of the drying process was short, the drying apparatus was left without being fully dried, and then the drying progressed rapidly, resulting in uneven film thickness. When a display device was produced using this antireflection film in the same procedure as in Example 102, color unevenness was visually recognized in the display device, which was not high quality.

[Comparative Example 104]
A gravure coater was used instead of using the die coater (see FIGS. 9 and 10), and an antireflection film was prepared in the same manner as in Example 102 except for the other conditions. Although coating was possible, film thickness unevenness due to coating occurred. When a display device was manufactured in the same procedure as in Example 102, the color unevenness was visually recognized in the display device, and it could not be said that the quality was high.

  Coating is carried out in the same manner as in Example 102 except that the downstream lip land length ILO is 10 μm (Comparative Example 105), 30 μm (Example 105), 100 μm (Example 106), and 120 μm (Comparative Example 106). A film was prepared. It has been found that an antireflection film free from surface defects can be obtained when the downstream lip land length ILO is in the range of 30 μm to 100 μm. In Comparative Example 105, film thickness unevenness caused by coating occurred in the longitudinal direction of the base. In Comparative Example 106, coating bead 14a could not be formed at the same speed as Example 102, and coating was impossible. When a display device was produced from the antireflection film produced in Example 105 and Example 106 in the same manner as in Example 101, the reflection of the background was extremely small, the color of the reflected light was remarkably reduced, and the display was further improved. A display device with very high display quality in which in-plane uniformity was ensured was obtained.

  On the other hand, when a display device was produced using the antireflection film obtained in Comparative Example 105 and Comparative Example 106 in the same procedure as in Example 102, color unevenness was visually recognized in the display device, and it could not be said that the quality was high.

[Comparative Example 107, Example 107, Example 108, Comparative Example 108]
Coating was performed in the same manner as in Example 102, except that the overcoating length LO of the die coater was 0 μm (Comparative Example 107), 30 μm (Example 107), 120 μm (Example 108), and 150 μm (Comparative Example 108). An antireflection film was produced. When the overbite length was in the range of 30 μm to 120 μm, an antireflection film free from surface defects was obtained. Although application was possible in Comparative Example 107, film thickness unevenness due to the application was recognized when the surface shape was seen.

  Further, in Comparative Example 108, the coating bead 14a could not be formed at the same speed as in Example 102, and coating was impossible. When a display device was produced from the antireflection film produced in Example 107 and Example 108 in the same manner as in Example 102, the reflection of the background was extremely small, the color of reflected light was remarkably reduced, and the display was further improved. A display device with very high display quality in which in-plane uniformity was ensured was obtained. On the other hand, when the antireflection film obtained in Comparative Example 107 and Comparative Example 108 was used to produce a display device in the same procedure as in Example 102, uneven coloring was visually observed in the display device, and it could not be said that the quality was high.

Sectional schematic diagram showing the basic layer structure of the antireflection film according to the present invention Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Cross-sectional schematic diagram showing an example of the layer structure of the antireflection film Explanatory drawing showing a configuration example of a device that continuously applies each layer Cross section of coater using slot die Expanded sectional view of the main part of the slot die The perspective view which shows a slot die and its periphery Sectional view showing the positional relationship between the vacuum chamber and the web Sectional view showing the positional relationship between the vacuum chamber and the web It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. FIG. 16 is a plan view of FIG. 15. It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is a top view of FIG. It is sectional drawing of FIG. It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is the schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is a principal part schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is a principal part schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is a principal part schematic of the apparatus of other embodiment used for the manufacturing method of the coating film which concerns on this invention. It is a table | surface which shows the result of Example 3 thru | or 6 and 7 thru | or 10. It is a table | surface which shows the result of Example 1 and 11 thru | or 15. It is a table | surface which shows the result of Example 1 and 16 thru | or 19.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Coater 11 ... Backup roller 13 ... Slot die 14 ... Coating liquid 14a ... Bead 14b ... Coating film 15 ... Pocket 16 ... Slot 17 ... Tip lip 18 ... Land 18a ... Upstream lip land 18b ... Downstream lip land W ... Web

Claims (24)

On a transparent support that is continuously supported by a backup roller, a coating solution is applied using a slot die, the film thickness in a dry state is 200 nm or less, and the refractive index is higher than that of the transparent support. In the method for producing an antireflection film in which at least one low layer is formed,
The front end lip of the front end lip on the downstream side in the running direction of the transparent support of the slot die is 30 to 100 μm, and the front end lip and the transparent support on the upstream side in the running direction of the transparent support. A method for producing an antireflection film, characterized in that a gap with a body surface is set to be 30 to 120 μm larger than a gap between a tip lip on the downstream side in the running direction of the transparent support and the surface of the transparent support. The viscosity at the time of application of the coating liquid is 20.0 mPa · sec or less, and the amount of the coating liquid applied on the transparent support is 2.0 to 5.0 ml / m ^2. The method for producing an antireflection film according to claim 1.   3. A medium refractive index layer, a high refractive index layer, and a low refractive index layer are formed in this order from the transparent support side, and substantially three layers having different refractive indexes are formed. The manufacturing method of the antireflection film as described in 1 .. For the design wavelength λ (= 400 to 680 nm) of the antireflection film, the medium refractive index layer represents the following (formula 1), the high refractive index layer represents the following (formula 2), and the low refractive index. 4. The method for producing an antireflection film according to claim 3, wherein the layers satisfy the following (Equation 3).
λ / 4 × 0.80 <n1d1 <λ / 4 × 1.00 (Formula 1)
λ / 2 × 0.75 <n2d2 <λ / 2 × 0.95 (Formula 2)
λ / 4 × 0.95 <n3d3 <λ / 4 × 1.05 (Formula 3)
(In formula 1, n1 is the refractive index of the medium refractive index layer, d1 is the layer thickness (nm) of the medium refractive index layer, and in formula 2, n2 is the refractive index of the high refractive index layer, (d2 is the layer thickness (nm) of the high refractive index layer. In Formula 3, n3 is the refractive index of the low refractive index layer, and d3 is the layer thickness (nm) of the low refractive index layer.)   For the transparent support having a refractive index of 1.45 to 1.55, the refractive index n1 of the medium refractive index layer is 1.60 to 1.65, and the refractive index n2 of the high refractive index layer is 1. The method for producing an antireflection film according to claim 4, wherein 85 to 1.95 and a refractive index n3 of the low refractive index layer is 1.35 to 1.45.   The layer having a refractive index lower than that of the transparent support or the low refractive index layer is made of a thermosetting and / or ionizing radiation curable fluorine-containing resin. The manufacturing method of the antireflection film as described in 1 ..   The high refractive index layer contains inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium, and has a refractive index of 1.55 to 2.40. The method for producing an antireflection film according to any one of claims 3, 4 and 6.   8. The apparatus according to claim 1, further comprising at least one hard coat layer between the transparent support and a layer having a lower refractive index than the transparent support or the low refractive index layer. The manufacturing method of the antireflection film as described in claim | item.   The method for producing an antireflection film according to any one of claims 1 to 8, wherein one or more layers constituting the antireflection film are continuously formed without winding.   An antireflection film comprising at least one layer obtained by the production method according to any one of claims 1 to 9. In the method of manufacturing a coating film formed by applying a coating liquid using a slot die so that the film thickness in a dry state is 200 nm or less on a continuously running web,
The land length in the web traveling direction of the tip lip on the downstream side in the web traveling direction of the slot die is 30 μm or more and 100 μm or less,
In addition, drying is performed by a drying apparatus that prevents the turbulence of the wind in the vicinity of the coating surface by a dryer having a casing surrounding the web immediately after coating, and that dries while keeping the solvent vapor on the coating surface side being dried at a high concentration. The manufacturing method of the coating film characterized by these.   The method for producing a coating film according to claim 11, wherein a condenser for condensing and recovering the solvent in the coating liquid is provided on the coating surface side of the running position of the web in the dryer.   The method for producing a coating film according to claim 12, wherein the condenser is provided with a cooling mechanism and temperature control is possible. In the method of manufacturing a coating film formed by applying a coating liquid using a slot die so that the film thickness in a dry state is 200 nm or less on a continuously running web,
The land length in the web traveling direction of the tip lip on the downstream side in the web traveling direction of the slot die is 30 μm or more and 100 μm or less,
And while moving the surface of the coating film along the surface of the coating film so that the gas has a relative speed of −0.1 m / second or more and 0.1 m / second or less with respect to the moving speed of the web. A method for producing a coating film, wherein the coating film is dried by a drying apparatus. In the method of manufacturing a coating film formed by applying a coating solution using a slot die so that the film thickness in a dry state is 200 nm or less on a continuously running web,
The land length in the web traveling direction of the tip lip on the downstream side in the web traveling direction of the slot die is 30 μm or more and 100 μm or less,
In addition, while the web is transported through the drying device, the organic solvent gas evaporated from the coating liquid applied to the web is released to the exhaust chamber through the hole of the air conditioning member, and enters the exhaust chamber. A method for producing a coating film, wherein drying is performed using a drying device that exhausts the gas of the organic solvent to the outside through an exhaust pipe.   The gap between the tip lip on the upstream side in the web running direction of the slot die and the web surface is made larger than the gap between the tip lip on the downstream side of the web and the web. The manufacturing method of the coating film as described in any one.   The gap between the tip lip on the upstream side in the web running direction of the slot die and the web surface is made larger in the range of 30 μm or more and 120 μm or less than the gap between the tip lip on the downstream side of the web and the web. The manufacturing method of the coating film of Claim 16. The total length of the drying apparatus is such that the coating film is transported in the drying apparatus for 2 seconds or more, and the evaporation rate of the coating solution solvent in the drying apparatus is 0.3 g / (m ² · sec) It is the above, The manufacturing method of the coating film as described in any one of Claims 11 thru | or 17 characterized by the above-mentioned.   A coating film produced by the coating film manufacturing method according to claim 11.   The coating film according to claim 19, wherein the coating film has a dry film thickness of 200 nm or less and has at least one layer having a refractive index lower than that of the transparent support as the web. .   21. A polarizing plate, wherein the antireflection film according to claim 10 or 20 or the coating film according to claim 19 is attached to at least one surface of the polarizing film.   The antireflection film according to claim 10 or 20 or the coating film according to claim 19 is attached to one surface of the polarizing film, and an optical compensation film having optical anisotropy is formed on the other surface of the polarizing film. A polarizing plate characterized by being attached.   An image display device comprising the antireflection film according to claim 10 or 20 or the coating film according to claim 19.   An image display device comprising the polarizing plate according to claim 21 or 22.

Images