JP2010134002A - Filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide, at a low cost, a filter for display that has electromagnetic wave shielding property, and sufficient reflection preventing performance without reducing transmission image clearness. <P>SOLUTION: The filter for display has a conductive layer including a conductive mesh on a transparent substrate and a resin layer stacked on the conductive layer. The thickness of the conductive mesh is 8 μm or less. The resin layer contains particles (A) having an average particle diameter of 1-20 μm and particles (B) having an average particle diameter of 300 nm or shorter, and the center line average roughness Ra of the resin layer is 100 nm or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a display filter mounted on a screen of a display device such as an organic EL display, a liquid crystal display, and a plasma display. More specifically, the present invention has excellent electromagnetic shielding properties, anti-reflection properties, and transmitted image clarity. The present invention relates to a low-cost display filter.

  A display such as an organic EL display, a liquid crystal display, and a plasma display (hereinafter referred to as PDP) is a display device capable of clear full color display. A display is usually provided with a front filter (display filter) on the viewing side of the display for the purpose of preventing reflection of external light and reflection, shielding electromagnetic waves generated from the display, and protecting the display. In particular, PDP generates strong electromagnetic waves due to its structure and operating principle, and there is concern about the effects on human bodies and other devices, and display filters with electromagnetic wave shielding and antireflection functions are usually used. ing.

  A general display filter is an electromagnetic wave shield in which an optical functional film having an antireflection function, a color adjustment function, a near infrared ray blocking function, and the like on a base material and a conductive layer (electromagnetic wave shielding layer) on the base material is provided. It is formed by laminating a film with an adhesive layer.

  In recent years, with the reduction in the price of displays, the price of filters for displays has been inevitably reduced. For the display filter comprising two films as described above, the cost can be reduced by using only one substrate.

  As one configuration of a display filter composed of only one substrate, functional layers such as a hard coat layer and an antireflection layer are arranged so as to cover a conductive layer having a conductive mesh formed on the substrate. An embodiment is mentioned. The conductive mesh is preferably used because a conductive layer having a low resistance can be obtained at a relatively low cost compared to a metal thin film formed by sputtering or vacuum deposition.

  Patent Document 1 proposes to directly form a functional layer such as a hard coat layer or an antireflection layer on the above-described conductive layer having a conductive mesh.

  On the other hand, the performance required for a display is becoming stricter year by year, and the demand for a filter for a display is becoming higher. In particular, in order to further improve image quality characteristics, high contrast, suppression of interference fringes, prevention of reflection on display surfaces such as fluorescent lamps, etc. have been strongly demanded.

As a method for preventing reflection, it is known to apply a transparent paint containing fine particles on a substrate to form fine irregularities on the surface (Patent Documents 2 and 3).
JP 2007-243158 A JP-A-2005-316450 JP 2006-195305 A

  In order to uniformly coat and form a functional layer on a conductive layer having a conductive mesh, it is necessary to increase the thickness of the functional layer to some extent. In order to prevent reflection, when a functional layer containing fine particles is provided on the conductive layer with a relatively large thickness, a sufficient uneven structure may not be formed, and the reflection prevention effect may not be sufficiently obtained. is there. If relatively large fine particles are contained in a relatively large amount in order to form a sufficient concavo-convex structure in the functional layer, there arises a new problem that transmitted image clarity is lowered.

  Accordingly, an object of the present invention is to provide a display filter that has electromagnetic wave shielding properties and has sufficient anti-reflection performance without deteriorating transmitted image clarity at low cost. It is to provide.

The above object of the present invention has been basically achieved by the following invention.
1) A display filter having a conductive layer containing a conductive mesh on a transparent substrate, and a resin layer laminated on the conductive layer,
The thickness of the conductive mesh is 8 μm or less,
The resin layer contains particles (A) having an average particle size of 1 to 20 μm and particles (B) having an average particle size of 300 nm or less, and the center line average roughness Ra of the resin layer is 100 nm or more. This is a display filter.
2) The display filter according to 1), wherein the resin layer has a single layer or a laminated structure of two or more layers including at least a hard coat layer.
3) The display filter according to 2), wherein the hard coat layer contains the particles (A) and the particles (B).
4) The filter for display according to any one of 1) to 3), wherein the uneven average interval Sm of the resin layer is in a range of 30 to 120 μm.
5) The display filter according to any one of 1) to 4), wherein the resin layer has a laminated structure including a hard coat layer and an antireflection layer.
6) Further described in any one of 1) to 5) above, further comprising a functional layer having at least one function selected from the group consisting of a near infrared ray blocking function, a color tone correction function, an ultraviolet ray blocking function, and a Ne cut function. Display filter.

  ADVANTAGE OF THE INVENTION According to this invention, the filter for a display which has electromagnetic wave shielding property and sufficient reflection prevention performance, without reducing a transmitted image clearness can be provided at low cost.

  The display filter of the present invention has a resin layer on a conductive layer including a conductive mesh having a thickness of 8 μm or less. The resin layer contains particles (A) having an average particle diameter of 1 to 20 μm and particles (B) having an average particle diameter of 300 nm or less, and the center line average roughness Ra of the resin layer is adjusted to 100 nm or more. Therefore, it is possible to sufficiently prevent the reflection without reducing the clearness of the transmitted image. In the following description, the particles (A) are referred to as fine particles (A), and the particles (B) are referred to as ultrafine particles (B).

  Inclusion of only fine particles (A) having an average particle diameter of 1 to 20 μm in the resin layer reduces the reflection, but on the other hand, the transmitted image clarity is reduced. Therefore, the present invention has further found that the transmitted image clarity is improved by adding ultrafine particles (B) having an average particle diameter of 300 nm or less to the resin layer.

  When the resin layer containing the fine particles (A) having a relatively large average particle diameter contains the ultrafine particles (B) having a smaller average particle diameter, the uneven structure 1 of the resin layer formed by the fine particles (A) is used. Since each one becomes a steep protrusion, the flat portion increases as compared with the case where the ultrafine particles (B) are not contained. Therefore, the scattering of light from the display panel is suppressed, and it is considered that the clearness of the transmitted image can be maintained while having sufficient reflection prevention performance.

  The difference between the uneven structure of the resin layer formed by using the fine particles (A) and the ultrafine particles (B) in combination with the uneven structure of the resin layer formed only of the fine particles (A), which is a feature of the present invention. Will be described. FIG. 1 is a schematic enlarged cross-sectional view of a concavo-convex structure of a resin layer formed by using the fine particles (A) and ultrafine particles (B) of the present invention in combination, and FIG. 2 is formed only by the fine particles (A). It is the model expanded sectional view of the uneven structure of the resin layer.

  1 and 2, a resin layer 3 is laminated so as to cover a conductive mesh 2 formed on a transparent substrate 1. The resin layer 3 in FIG. 1 includes fine particles (A) indicated by reference numeral 4 and ultrafine particles (B) indicated by reference numeral 5, and the convex structure of the resin layer formed by the fine particles (A) is as follows. The shape is relatively steep. In contrast, the resin layer in FIG. 2 does not include the ultrafine particles (B), and the convex portions of the resin layer formed only by the fine particles (A) indicated by reference numeral 4 have a comparatively gentle shape. ing.

  Although the mechanism by which the steep convex portion is formed by using the fine particle (A) and the ultrafine particle (B) is not clear, the region between the convex portion and the convex portion is formed by forming the steep convex portion. It is considered that the ratio of the flat portion F in the image becomes larger, which contributes to the improvement of the transmitted image sharpness. In the case of a comparatively gentle convex structure as shown in FIG. 2, the ratio of the flat part F in the region between the convex part is small because the slope of the convex part has a tail. .

  Further, by laminating a resin layer containing fine particles (A) on a conductive layer containing a conductive mesh, the appearance defects caused by the presence of minute foreign matters or exogenous foreign matters considered to be caused by the conductive mesh are concealed ( It has been found that the yield during production can be greatly improved by concealing defects on the conductive mesh.

  Furthermore, in the resin layer coating step, by containing the ultrafine particles (B) in the resin layer coating solution, the precipitation of the fine particles (A) can be prevented, and the stability of the coating solution over time is improved. It has been improved, and it has become possible to stably perform continuous coating for a long time.

  The display filter according to the present invention has been found to be able to prevent reflection without deteriorating the sharpness of the transmitted image by making the surface structure of the resin layer laminated on the conductive layer as described above. Is. Furthermore, the resin layer laminated on the conductive layer is a functional layer having a hard coat function or an antireflection function, whereby the cost of the display filter can be reduced.

(Resin layer)
The resin layer used for the display filter of the present invention is disposed on a conductive layer including a conductive mesh having a thickness of 8 μm or less. By making the resin layer according to the present invention a functional layer having a hard coat function or an antireflection function, the cost of the display filter can be reduced.

  The resin layer according to the present invention is preferably disposed on one outermost surface side of the display filter so as to be the outermost surface on the viewer side (viewing side) when the display filter is mounted on the plasma display. .

  The resin layer according to the present invention may be a single layer or a laminated structure of two or more layers. The resin layer of the present invention preferably includes at least a hard coat layer. When the resin layer is a single layer, it is preferably a hard coat layer, and when the resin layer has a laminated structure of two or more layers, it is preferably a laminated structure of a hard coat layer and an antireflection layer. The antireflection layer may be a low refractive index layer alone, or a laminated structure of a high refractive index layer and a low refractive index layer (the low refractive index layer is disposed on the outermost surface side of the display filter). The high refractive index layer, the middle refractive index layer, and the low refractive index layer (the low refractive index layer is disposed on the outermost surface side of the display filter) may be laminated in this order. Also good. In the case of the laminated structure of the hard coat layer and the antireflection layer, the antireflection layer is disposed on the outermost surface side of the display filter. The display filter of the present invention is used by being installed in a PDP television or the like so that the resin layer side is the viewer side with respect to the conductive layer and the transparent base material side is the display side with respect to the conductive layer.

  The resin layer contains fine particles (A) having an average particle diameter of 1 to 20 μm and ultrafine particles (B) having an average particle diameter of 300 nm or less. When the resin layer has a laminated structure of two or more layers, it is important that the fine particles (A) and the ultrafine particles (B) are contained in the same layer. In the case where the resin layer has a laminated structure of two or more layers, if only one of the plurality of layers constituting the resin layer contains the fine particles (A) and the ultrafine particles (B), the intended effect of the present invention is achieved. However, two or more layers containing the fine particles (A) and the ultrafine particles (B) may be laminated. In the laminated structure having two or more resin layers, it is preferable that the layer containing the fine particles (A) and the ultrafine particles (B) is only one layer.

  In the present invention, the resin layer preferably includes at least a hard coat layer, and the hard coat layer contains fine particles (A) and ultra fine particles (B).

  The center line average roughness Ra (hereinafter simply referred to as Ra) of the resin layer according to the present invention is 100 nm or more. The Ra of the resin layer can be controlled by adjusting the average particle size and content of the fine particles (A) contained in the resin layer.

  For example, when the resin layer is composed of a single hard coat layer, Ra of the hard coat layer becomes Ra of the resin layer, and the resin layer is composed of the hard coat layer and the antireflection layer (the antireflection layer is used for the display filter). In the case of the laminated structure of the uppermost surface side), Ra of the antireflection layer becomes Ra of the resin layer.

  In the case where the resin layer has the laminated structure of the hard coat layer and the antireflection layer (the antireflection layer is disposed on the outermost surface side of the display filter), the hard coat layer is composed of fine particles (A) and ultrafine particles. It is preferable that (B) is contained and the antireflection layer does not contain fine particles (A). Since the antireflection layer is usually laminated with a very thin film of several hundred nm or less, even if the antireflection layer is laminated on the hard coat layer, the Ra of the antireflection layer substantially follows the Ra of the hard coat layer. By controlling Ra of the hard coat layer, Ra as the resin layer can be controlled.

  As described above, the resin layer according to the present invention contains fine particles (A) having an average particle diameter in the range of 1 to 20 μm. Here, the average particle diameter is a volume average and can be measured, for example, by a laser scattering method using a laser diffraction particle diameter measuring apparatus. The fine particles (A) are contained in order to form a concavo-convex structure in the resin layer and have a center line average roughness Ra of 100 nm or more.

  The average particle diameter of the fine particles (A) according to the present invention is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 8 μm, and particularly preferably in the range of 3 to 7 μm. When the average particle size of the fine particles (A) is less than 1 μm, sufficient anti-reflection performance cannot be obtained, while when the average particle size exceeds 10 μm, the transmitted image sharpness decreases.

  The content of the fine particles (A) according to the present invention is preferably in the range of 0.5 to 20% by mass, preferably 1 to 15% by mass with respect to 100% by mass of all the components of the layer containing the fine particles (A). The range is more preferable, the range of 2 to 10% by mass is further preferable, and the range of 3 to 8% by mass is particularly preferable. When the content of the fine particles (A) is less than 0.5% by mass, the reflection preventing performance may be insufficient. On the other hand, when the content exceeds 20% by mass, the transmitted image clarity may be deteriorated. .

  Moreover, there exists a preferable range in the relationship between the thickness (Hr; μm) of the resin layer and the average particle diameter (D; μm) of the fine particles (A) contained in the resin layer. That is, the average particle diameter (D) of the fine particles (A) is preferably in the range of 0.4 × Hr to 1.5 × Hr, more preferably in the range of 0.5 × Hr to 1.3 × Hr, especially 0. The range of .6 × Hr to 1.2 × Hr is preferred.

  When the average particle diameter (D) of the fine particles (A) is smaller than 0.4 × Hr, the reflection preventing effect and the defect concealing effect applied to the conductive mesh may be reduced, whereas 1.5 If it exceeds xHr, a rough feeling may be seen on the surface of the filter, and therefore neither is preferable. Here, the thickness (Hr) of the resin layer means the total thickness (μm) of the resin layer, and when the resin layer has a laminated structure, it means the total thickness of a plurality of layers. Here, as shown in FIG. 1, the thickness of the resin layer refers to the lowest portion of the resin layer in the cross-sectional enlarged photograph of one opening of the conductive mesh (the region surrounded by the fine lines of the conductive mesh). It is the distance from the transparent substrate to the resin layer surface, and is a value measured and averaged for any five openings.

  The shape of the fine particles (A) according to the present invention may be spherical, such as a true sphere or an ellipse, or may be a non-true sphere. A preferable shape of the fine particles (A) is a true sphere.

  Examples of the material of the fine particles (A) according to the present invention include inorganic and organic materials, and those formed of organic materials are preferable. Moreover, the thing excellent in transparency is good. Specific examples of the fine particles (A) include silica beads for inorganic materials and plastic beads for organic materials. Specific examples of the plastic beads include acrylic beads, styrene beads, melamine beads, and polyethylene beads. In the present invention, it is preferable to use acrylic beads having excellent transparency.

  The refractive index of the fine particles (A) according to the present invention is preferably 1.35 to 1.70, more preferably 1.40 to 1.65, and even more preferably 1.45 to 1.60. The refractive index difference between the resin constituting the resin layer and the fine particles (A) is preferably 0.1 or less, more preferably 0.07 or less, and further preferably 0.05 or less, from the viewpoint of transmitted image clarity. 0 is most preferred. By setting such a particle refractive index and refractive index difference, light scattering in the fine particles (A) in the resin layer is suppressed, and the clarity of the transmitted image can be improved.

  The variation coefficient of the particle size distribution of the fine particles (A) according to the present invention is preferably in the range of 3 to 50%. When the variation coefficient of the particle size distribution of the fine particles (A) is less than 3%, coating unevenness tends to occur. When the variation coefficient exceeds 50%, the particle size greatly varies, and the surface feels rough due to the fine particles. Gets worse. The variation coefficient of the particle size distribution can be obtained from an image analysis method, a Coulter counter method, a centrifugal sedimentation method, a dynamic light scattering method, a laser diffraction scattering method, or the like.

  The resin layer concerning this invention contains the ultrafine particle (B) whose average particle diameter is 300 nm or less with the above-mentioned fine particle (A). The average particle size of the ultrafine particles (B) according to the present invention is preferably 200 nm or less, more preferably 140 nm or less, further preferably 60 nm or less, and particularly preferably 30 nm or less. The substantial lower limit of the average particle diameter of the ultrafine particles (B) is about 1 nm. When the average particle diameter of the ultrafine particles (B) exceeds 300 nm, it does not contribute to the improvement of transmitted image sharpness, but may rather decrease.

  The content of the ultrafine particles (B) according to the present invention is preferably in the range of 0.5 to 50% by mass, based on 100% by mass of all the components of the layer containing the ultrafine particles (B), and 1 to 40 masses. % Is more preferable, further 3 to 30% by mass is preferable, and 5 to 20% by mass is particularly preferable. When the content of the ultrafine particles (B) is less than 0.5% by mass, the effect of improving the clarity of the transmitted image is small. On the other hand, when the content of the ultrafine particles (B) exceeds 50% by mass, It is not preferable because the resin layer becomes brittle.

  Examples of the ultrafine particles (B) according to the present invention include silica, alumina, and metal oxide. Examples of the silica include colloidal silica (silica sol) and gas phase method silica. Examples of the metal oxide include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, and oxidation. Examples thereof include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide, gallium-doped zinc oxide, and fluorine-doped tin oxide. Among these, silica, alumina, titanium oxide, antimony oxide, zirconium oxide, ITO, and ATO are preferable, and silica is particularly preferably used.

  In the present invention, the average particle diameter of the ultrafine particles (B) is an average particle diameter determined by observation with a transmission electron microscope.

  The Ra of the resin layer according to the present invention is 100 nm or more, preferably 150 nm or more, more preferably 200 nm or more, and particularly preferably 300 μm or more. The upper limit of Ra of the resin layer is preferably 1000 nm or less, more preferably 900 nm or less, still more preferably 800 nm or less, and particularly preferably 700 nm or less.

  When the Ra of the resin layer is less than 100 nm, there is no effect of preventing reflection, while when it exceeds 1000 nm, the transmitted image sharpness tends to decrease.

  Moreover, in the uneven | corrugated average space | interval Sm of a resin layer, a preferable range exists from a viewpoint of reflection prevention and a transmitted image clearness. Specifically, the unevenness average interval Sm of the resin layer is preferably in the range of 30 to 120 μm, more preferably in the range of 40 to 110 μm, further preferably in the range of 50 to 100 μm, and particularly preferably in the range of 60 to 90 μm. When the unevenness average interval Sm of the resin layer is less than 30 μm, the outline of the reflected image becomes clear and the reflected image becomes easy to see, and when it exceeds 120 μm, the clarity of the transmitted image may be deteriorated.

The uneven average spacing Sm of the resin layer can be controlled by adjusting the content of the fine particles (A).
(Conductive layer)
Display filters are provided with various conductive layers from the standpoint of antistatic properties. In particular, plasma display panels generate strong leakage electromagnetic waves from the panel due to their structure and operating principle, and conductive meshes are used to shield them. A conductive layer such as is used. In recent years, the influence of electromagnetic waves leaking from electronic equipment on the human body and other equipment has been studied. For example, in Japan, it is required to keep within the reference value by VCCI (voluntary control council for interference by processing equipment electronic office machine). It has been. Specifically, in VCCI, the radiated electric field intensity is less than 50 dBμV / m in class A indicating the regulation value for business use, and less than 40 dBμV / m in class B indicating the regulation value for consumer use. Since the electric field strength exceeds 50 dBμV / m (in the case of 40 inch diagonal type) in the 20 to 90 MHz band, it cannot be used for home use in this state. For this reason, a display filter in which an electromagnetic wave shielding layer (conductive layer) is arranged is used for the plasma display panel.

  As described above, in order for the electromagnetic wave shielding layer to exhibit electromagnetic wave shielding performance, electrical conductivity is required, and the electrical conductivity necessary for electromagnetic wave shielding of the plasma display panel is 3Ω / □ or less, preferably 1Ω / □, in terms of surface resistance. Hereinafter, it is more preferably 0.5Ω / □ or less. Therefore, in the display filter of the present invention having a conductive layer, the conductivity of the conductive layer is preferably 3Ω / □ or less in terms of surface resistance, more preferably 1Ω / □ or less, and even more preferably 0.5Ω / □. □ Below. Also, the lower the sheet resistance, the better the electromagnetic shielding properties are improved, but the practical lower limit is considered to be about 0.01Ω / □.

  In the display filter of the present invention, by using a conductive mesh as the conductive layer, the transmittance of the display filter is increased while sufficiently reducing the sheet resistance, and light from the conductive layer to the viewer side is increased. Reflection can be suppressed.

  In order to improve electromagnetic shielding properties, it is necessary to increase the thickness of the conductive mesh to some extent, but conversely, if the thickness is too large, the transmitted image sharpness tends to decrease, and the coating of the resin layer The applicability may decrease, and application stripes and unevenness may occur. In addition, when a hard coat layer is used as the resin layer, it may be difficult to process due to curling.

  From such a viewpoint, it is important that the thickness of the conductive mesh according to the present invention is 8 μm or less. The thickness of the conductive mesh according to the present invention is preferably 7 μm or less, and more preferably 5 μm or less. The lower limit of the thickness of the conductive mesh is preferably 0.5 μm or more and more preferably 1 μm or more from the viewpoint of ensuring sufficient electromagnetic shielding properties.

  If the thickness of the conductive mesh exceeds 8 μm, the coating property of the resin layer is lowered, and it becomes difficult to stably form a resin layer having a uniform surface roughness in the surface.

  The pitch of the conductive mesh in the present invention is preferably in the range of 50 to 500 μm, more preferably in the range of 75 to 450 nm, and still more preferably in the range of 100 to 350 μm. When the pitch of the conductive mesh is less than 50 μm, the transmittance tends to decrease, and when it exceeds 500 μm, the conductivity tends to decrease, which is not preferable.

  Here, the pitch of the conductive mesh is the interval between the portions where the conductive mesh does not exist (opening portions surrounded by the thin lines of the conductive mesh). Specifically, one opening portion and the opening portion. And the distance between the centers of gravity of adjacent openings sharing one side.

  The line width of the conductive mesh according to the present invention is preferably in the range of 3 to 30 μm, and more preferably in the range of 5 to 20 μm. When the line width of the conductive mesh is less than 3 μm, the electromagnetic wave shielding property tends to be lowered. On the other hand, when the line width exceeds 30 μm, the transmittance of the display filter tends to be lowered.

  The aperture ratio of the conductive mesh greatly affects the transmittance of the display filter. The opening ratio of the conductive mesh is the ratio of the total area of the opening to the sum of the total area of the mesh portion (thin line portion) in plan view and the total area of the opening in plan view. Is determined by the line width and pitch. In the present invention, the opening ratio of the conductive mesh is preferably 60% or more, more preferably 70% or more, and particularly preferably 80% or more. The upper limit of the aperture ratio is preferably 95% or less, and more preferably 93% or less.

  The aperture ratio of the conductive mesh can be measured, for example, as follows.

  Using a digital microscope (VHX-200) manufactured by Keyence Corporation, the surface is observed at a magnification of 200 times, and there is a conductive mesh using its luminance extraction function (histogram extraction, luminance range setting 0-170). Binarize into a portion that does not (opening) and a portion where the conductive mesh exists, and then, using the area measurement function, calculate the entire area and the area of the opening, and calculate the opening area as the entire area. The aperture ratio is obtained by dividing.

  Specifically, it is preferable to calculate the aperture ratio at 20 arbitrary locations from one sample having a size of 20 cm × 20 cm and set the average value.

  The shape of the mesh pattern of the conductive mesh (the shape of the opening) is, for example, a lattice mesh pattern formed of a quadrangle such as a square, a rectangle, or a rhombus, a triangle, a pentagon, a hexagon, an octagon, or a dodecagon. Examples thereof include a mesh pattern made of a polygon, a mesh pattern made of a circle and an ellipse, a mesh pattern made of the composite shape, and a random mesh pattern. Among these, a lattice mesh pattern made of a tetragon and a mesh pattern made of a hexagon are preferable, and a regular mesh pattern is more preferably used.

  When the mesh pattern is, for example, a lattice mesh pattern, the mesh pattern line is at a certain angle with respect to the line in which the pixels are arranged so as not to cause moire due to the interaction with the display pixels arranged side by side. It is preferable to have (bias angle). Since the bias angle that does not cause moire changes depending on the pixel pitch and the pitch / line width of the mesh pattern, the bias angle is appropriately set according to these conditions.

  In the display filter of the present invention, the conductive layer containing the conductive mesh is formed on a transparent substrate. As the transparent substrate, various films obtained by a solution casting method or a melt casting method are preferably used. Details of the transparent substrate will be described later.

  In the display filter of the present invention, a known method can be used as a method of forming the conductive mesh layer on a transparent substrate or the like. For example, 1) A method of printing a conductive ink in a pattern on a transparent substrate. 2) Method of performing plating after pattern printing with ink containing catalyst core of plating, 3) Method of using conductive fiber, 4) Method of patterning after bonding metal foil on transparent substrate with adhesive, 5 Examples thereof include a method of patterning after forming a metal thin film on a transparent substrate by vapor deposition or plating, 6) a method using a photosensitive silver salt, and 7) a method of laser ablating the metal thin film. However, it is not limited to these.

  The manufacturing method of said electroconductive mesh is demonstrated in detail.

  1) The method of printing a conductive ink in a pattern on a transparent substrate is a method of printing the conductive ink in a pattern on a transparent substrate by a known printing method such as screen printing or gravure printing.

  2) A method of performing plating after pattern printing with ink containing catalyst nuclei for plating is, for example, printing in a pattern using a catalyst ink made of a palladium colloid-containing paste and immersing this in an electroless copper plating solution. Electroless copper plating, followed by electrolytic copper plating, and further by electrolytic plating of a Ni-Sn alloy to form a conductive mesh pattern.

  3) A method using conductive fibers is a method in which a knitted fabric made of conductive fibers is bonded through an adhesive or an adhesive.

  4) The method of patterning after laminating a metal foil on a transparent substrate with an adhesive was performed by laminating a metal foil (copper, aluminum, nickel, etc.) on the transparent substrate via an adhesive or an adhesive. Thereafter, a resist pattern is produced from the metal foil using a photolithography method or a screen printing method, and then the metal foil is etched. As a method for forming the above resist pattern, a photolithography method is preferable, and the photolithography method is a method of applying a photosensitive resist on a metal foil or laminating a photosensitive resist film, adhering a pattern mask, and exposing, This is a method of forming an etching resist pattern by developing with a developing solution, and further eluting metals other than the pattern portion with an appropriate etching solution to form a desired conductive mesh.

  5) A method of patterning after forming a metal thin film on a transparent substrate by vapor deposition or plating is performed by using a metal thin film (copper, aluminum, silver, gold, palladium, indium, tin, or A metal made of an alloy of silver and other metals) is formed by vapor deposition such as vapor deposition, sputtering, ion plating, or plating, and this metal thin film is formed by photolithography or screen printing. This is a method of etching a metal thin film after producing a resist pattern using it. As a method of forming the above resist pattern, a photolithography method is preferable, and the photolithography method is a method of applying a photosensitive resist on a metal thin film or laminating a photosensitive resist film, adhering a pattern mask, and exposing, This is a method of forming an etching resist pattern by developing with a developing solution, and further eluting metals other than the pattern portion with an appropriate etching solution to form a desired conductive mesh. In this method, it is preferable to form a metal thin film on a transparent substrate without using an adhesive or a pressure-sensitive adhesive.

  6) A method using a photosensitive silver salt is a method in which a silver salt emulsion layer such as silver halide is coated on a transparent substrate, and after photomask exposure or laser exposure, development processing is performed to form a silver mesh. is there. The formed silver mesh is preferably further plated with a metal such as copper or nickel. This method is described in WO 2004/7810, JP-A 2004-221564, JP-A 2006-12935, and the like, and can be referred to.

  7) The method of laser ablating a metal thin film is a method of producing a metal thin film mesh pattern by laser ablation of a metal thin film formed on a transparent substrate in the same manner as in 5) above.

  Laser ablation means that when a solid surface that absorbs laser light is irradiated with laser light with a high energy density, the bonds between the irradiated parts are broken and evaporated, causing the solid surface of the irradiated part to break. It is a phenomenon that is cut away. By utilizing this phenomenon, the solid surface can be processed. Since laser light is highly straight and condensing, it is possible to selectively process a fine area about 3 times the wavelength of the laser light used for ablation, and high processing accuracy is obtained by the laser ablation method. I can do it.

  The laser used for such ablation can be any laser having a wavelength that is absorbed by the metal. For example, a gas laser, a semiconductor laser, an excimer laser, or a solid laser using a semiconductor laser as an excitation light source can be used. A second harmonic light source (SHG), a third harmonic light source (THG), or a fourth harmonic light source (FHG) obtained by combining these solid-state lasers and a nonlinear optical crystal can be used.

  Among such solid-state lasers, an ultraviolet laser having a wavelength of 254 nm to 533 nm is preferably used from the viewpoint of not processing a plastic film. Among them, it is preferable to use a solid-state laser SHG (wavelength 533 nm) such as Nd: YAG (neodymium: yttrium, aluminum, garnet), more preferably a solid laser THG (wavelength 355 nm) ultraviolet laser such as Nd: YAG. .

  As a laser oscillation method, any type of laser can be used. From the viewpoint of processing accuracy, a pulse laser is preferably used, and a Q-switch type pulse laser having a pulse width of ns or less is more preferable.

  It is preferable to laser ablate the metal thin film and the metal oxide layer after further forming a 0.01 to 0.1 μm metal oxide layer on the metal thin film (viewing side). As the metal oxide, metal oxides such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium, titanium, and tin can be used. However, copper oxide is used from the viewpoint of price and film stability. preferable. As a method for forming the metal oxide, a vacuum deposition method, a sputtering method, an ion plate method, a chemical vapor deposition method, an electroless method, an electrolytic plating method, or the like can be used.

  Among the above-described methods for producing a conductive mesh, a conductive mesh having a relatively small thickness (for example, a conductive mesh having a thickness of 8 μm or less) can be easily produced, and high electromagnetic shielding properties can be secured. The production methods 2), 5), 6) and 7) above are preferably used.

  Moreover, from the viewpoint of the coating properties of the resin layer and the adhesion between the resin layer and the conductive layer, the conductive mesh produced by the production methods 2), 5) and 7) above is preferably used. In particular, the production method 5) is particularly preferably used because the coating property of the resin layer is good and the production cost of the conductive mesh is low.

  The production method 5) will be described in more detail.

  As a method for forming a metal thin film on a transparent substrate, a vapor deposition method is preferred. Examples of the vapor deposition method include sputtering, ion plating, electron beam vapor deposition, vacuum vapor deposition, and chemical vapor deposition. Among these, sputtering and vacuum vapor deposition are preferable. As a metal for forming a metal thin film, an alloy or a multilayer of one or more of metals such as copper, aluminum, nickel, iron, gold, silver, stainless steel, chromium and titanium is used. can do. Among these, copper is preferably used from the viewpoints of obtaining good electromagnetic shielding properties, easy mesh pattern processing, and low cost.

  Moreover, when using copper as a metal of a metal thin film, it is preferable to use a nickel thin film with a thickness of 5-100 nm between a transparent base material and a copper thin film. Thereby, the adhesiveness of a transparent base material and a copper thin film improves.

  As a method for forming a resist pattern on the metal thin film, photolithography is preferably used. In such a photolithography method, a photosensitive resist layer is laminated on a metal thin film, the resist layer is exposed to a mesh pattern, developed to form a resist pattern, and then the metal thin film is etched to form a mesh pattern. In this method, the resist layer on the mesh is peeled and removed.

  As the photosensitive resist layer, a negative resist in which the exposed portion is cured or a positive resist in which the exposed portion is dissolved by development can be used. The photosensitive resist layer may be coated and laminated directly on the metal thin film, or a film made of a photoresist may be bonded. As a method for exposing the photoresist layer, there can be used a method of exposing with an ultraviolet ray or the like through a photomask, or a method of directly scanning and exposing using a laser.

  Etching methods include chemical etching methods. Chemical etching is a method in which a metal other than a metal portion protected by a resist pattern is dissolved and removed with an etching solution. Examples of the etching solution include a ferric chloride aqueous solution, a cupric chloride aqueous solution, and an alkaline etching solution.

  The conductive mesh according to the present invention is preferably blackened. By applying a blackening treatment, reflection from the viewer side and reflection from the display side due to the metallic luster of the conductive mesh can be reduced, and further reduction in image visibility can be reduced. An excellent display filter can be obtained.

  The conductive mesh does not necessarily need to have a mesh pattern other than the part that becomes the translucent part when it is installed on the display, that is, the part that is not the display part or the part that is hidden in the frame printing. For example, a solid metal foil may be used. In addition, if the solid portion that is not patterned is black, it can be used as frame printing for a display filter as it is.

(Lamination of resin layer)
In the present invention, the resin layer is laminated on the conductive layer including the conductive mesh, but it is preferable that the resin layer is laminated directly on the conductive layer. As a method for laminating the resin layers, it is preferable to apply a coating liquid (hereinafter simply referred to as a coating liquid) to be a resin layer.

  In coating, the viscosity (23 ° C.) of the coating liquid is preferably in the range of 1 to 50 mPa · s. By controlling the viscosity of the coating liquid within the above range, a surface structure effective for preventing reflection and preventing defects can be formed on the resin layer. When the viscosity of the coating liquid exceeds 50 mPa · s, the coating property is lowered, and coating stripes and coating unevenness may occur.

  Further, the solid content concentration in the coating liquid and the wet coating amount of the coating liquid are also preferably adjusted to the following ranges.

  The solid concentration in the coating liquid is preferably in the range of 10 to 80% by mass, more preferably in the range of 20 to 70% by mass, and particularly preferably in the range of 30 to 70% by mass.

Wet coating amount of the coating solution is preferably within a range from 1 to 50 g / ^{m 2,} more preferably in the range of 3~40g / ^{m 2,} in particular in the range of 5 to 30 g / ^{m 2} is preferred.

  Various coating methods such as reverse coating, gravure coating, rod coating, bar coating, die coating, or spray coating can be used as the coating method for the resin layer coating liquid. Among these, a gravure coating method and a die coating method are preferably used.

  In the present invention, the resin layer preferably includes a hard coat layer. The hard coat layer functions to prevent the display filter from being scratched, and in that sense, it is preferable that the hardness is sufficiently high.

  In order to obtain high hardness, it is preferable to use a polyfunctional polymerizable monomer as the resin component of the hard coat layer, and the specific gravity after curing of the hard coat layer formed thereby is preferably 1.2 or more. .3 or more is more preferable, and 1.4 or more is more preferable. Since the hardness tends to increase as the specific gravity after curing of the hard coat layer increases, the specific gravity after curing of the hard coat layer is preferably higher. The upper limit of the specific gravity of the hard coat layer is about 1.7.

  When the specific gravity is multiplied by the volume coating amount of the resin layer, the mass coating amount is obtained. Since the mass coating amount of the resin layer can be easily obtained by measuring the mass of the sample per unit area before and after coating, it is preferable for controlling and managing the manufacturing process.

For example, assuming that the thickness (A) of the conductive mesh is 5 μm, the opening ratio (C) of the conductive mesh is 85%, and the specific gravity after curing of the hard coat layer is 1.4, the theoretical volume coating amount of the resin layer ( B)
B = A × C = 5 × 0.85 = 4.25 cm ³ / m ² .

  In the present invention, as described above, the thickness of the conductive mesh is preferably 8 μm or less. When the thickness of the conductive mesh is larger than 8 μm, in the actual production process, the coating property when applying the resin layer on the conductive mesh is greatly reduced, and streaks and unevenness are generated on the coated surface of the resin layer. Cause. If coating stripes or unevenness occurs in the resin layer, it is fatal as a display filter.

When the thickness of the conductive mesh is larger than 8 μm, in order to ensure good coatability of the resin layer, the mass coating amount (after drying) of the resin layer is 17 g / m ² or more, and further 20 g / m. ^Two or more are necessary, and the productivity is greatly reduced due to an increase in drying time and curing time after coating. Furthermore, when the resin layer includes a hard coat layer, if the mass coating amount (in the case of a hard coat layer, the mass coating amount after curing) increases, curling on the display filter due to polymerization shrinkage during curing. And the problem that cracks occur in the hard coat layer.

Therefore, in the present invention, the mass coating amount of the resin layer is preferably 16 g / m ² or less, preferably 14 g / m ² or less, more preferably 10 g / m ² or less, and particularly preferably 9 g / m ² or less. From the viewpoint of securing the hardness of the resin layer, the lower limit of the mass coating amount of the resin layer is preferably 1 g / m ² or more, and more preferably 1.5 g / m ² or more. In addition, when the resin layer is a laminated structure, it is preferable that the mass coating amount of one layer on the most conductive layer side of the resin layer is in the above range.

Accordingly, in the present invention, the mass coating amount of the hard coat layer is preferably 16 g / m ² or less, preferably 14 g / m ² or less, more preferably 10 g / m ² or less, and particularly preferably 9 g / m ² or less. From the viewpoint of ensuring the hardness of the hard coat layer, the lower limit of the mass coating amount of the hard coat layer is preferably 1 g / m ² or more, and more preferably 1.5 g / m ² or more.

  Moreover, when using a hard-coat layer as a resin layer, when the centerline average roughness Ra of a resin layer becomes larger than 1000 nm, the abrasion resistance of a hard-coat layer may fall.

  Although the thickness of the resin layer can be controlled by adjusting the coating amount of the resin layer, the thickness of the resin layer is 15 μm or less from the viewpoint of production speed, raw material cost, curling properties of display filter, etc. Is preferable, 12 μm or less is more preferable, and 10 μm or less is particularly preferable. The lower limit of the thickness of the resin layer is preferably 1 μm or more, more preferably 1.5 μm or more, and particularly preferably 2 μm or more from the viewpoint of the film strength of the resin layer, coating stability, and the like.

  Further, the thickness of the resin layer is preferably in the range of 50 to 400%, more preferably in the range of 70 to 300%, with respect to 100% of the thickness of the conductive mesh. It is preferable to adjust. Here, the thickness of the resin layer is synonymous with the thickness (Hr) of the resin layer described above.

(Hard coat layer)
As described above, the resin layer of the present invention preferably includes at least a hard coat layer. Such a coat layer is a layer provided for preventing scratches. The hard coat layer preferably has high hardness, and the pencil hardness defined by JIS K5600-5-4 (1999) is preferably 1H or more, and more preferably 2H or more. The upper limit is about 9H.

Moreover, in order to simply evaluate the scratch resistance, a scratch resistance test using steel wool can be used. In this test method, the surface of the hard coat layer was subjected to 10 reciprocal rubbing at a stroke width of 10 cm and a speed of 30 mm / sec, applying a load of 250 g to # 0000 steel wool, and then visually observing the surface for scratching. Is evaluated in the following five stages.
5th grade: No scratches.
Fourth grade: 1 to 5 scratches.
3rd grade: 6 to 10 scratches.
Second grade: 11 or more scratches.
First grade: Countless scratches on the entire surface.

  In said test method, it is preferable that the hard-coat layer of this invention is tertiary or more, More preferably, it is quaternary or more.

  Examples of the hard coat layer component in the present invention include thermosetting or photocurable resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins. In view of the balance of cost, productivity and the like, an acrylate system is preferably applied.

  The acrylate hard coat film is composed of a cured composition containing polyfunctional acrylate as a main component. The polyfunctional acrylate is a monomer, oligomer or prepolymer having 3 (more preferably 4, more preferably 5) or more (meth) acryloyloxy groups in one molecule, and 3 in one molecule. The above (meth) acryloyloxy group (in the present specification, “... (meth) acryl ...” is abbreviated as “... acryl ...” or “methacryl ...”). The monomers, oligomers, and prepolymers having the above-mentioned) are represented by 3 or more (meth) acrylic acids in the polyhydric alcohol having 3 or more alcoholic hydroxyl groups in one molecule. And the like.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, Pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer Or the like can be used. These may be used alone or in combination of two or more.

  The use ratio of the monomer, oligomer or prepolymer having 3 or more (meth) acryloyloxy groups in one molecule is preferably 50 to 90% by mass with respect to 100% by mass of the hard coat layer constituting component. More preferably, it is 50-80 mass%.

  In addition to the above-mentioned compounds, it is preferable to use one or two functional acrylates together for the purpose of relaxing the rigidity of the hard coat layer or reducing shrinkage during curing. The monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule can be used without particular limitation as long as it is a normal monomer having radical polymerizability.

As the compound having two ethylenically unsaturated double bonds in the molecule, the following (a) to (f) (meth) acrylates and the like can be used. That is,
(A) C2-C12 alkylene glycol (meth) acrylic acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc.
(B) (Meth) acrylate diesters of polyoxyalkylene glycol: diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc.
(C) Polyhydric alcohol (meth) acrylic acid diesters: pentaerythritol di (meth) acrylate, etc.
(D) (Meth) acrylic acid diesters of ethylene oxide and propylene oxide adducts of bisphenol A or bisphenol A hydride: 2,2′-bis (4-acryloxyethoxyphenyl) propane, 2,2′-bis ( 4-acryloxypropoxyphenyl) propane, etc.
(E) Two or more in a molecule obtained by reacting a terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance with an alcoholic hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylates having a (meth) acryloyloxy group, and the like, and
(F) Epoxy (meth) acrylates having two or more (meth) acryloyloxy groups in the molecule obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid. Examples of the compound having one ethylenically unsaturated double bond in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, n- and i-propyl (meth) acrylate, n-, sec- and t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, hydroxyethyl (meth) ) Acrylate, polyethylene glycol mono (meth) a Chryrate, polypropylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N-vinylpyrrolidone, N-vinyl-3-methylpyrrolidone, N-vinyl -5-methylpyrrolidone and the like can be used. These monomers may be used alone or in combination of two or more.

  The proportion of the monomer having 1 to 2 ethylenically unsaturated double bonds in one molecule is preferably 10 to 40% by mass, more preferably 100% by mass with respect to the total amount of the hard coat layer constituent components. Is 20-40 mass%.

  In the present invention, as a modifier for the hard coat layer, a coating property improver, an antifoaming agent, a thickener, an antistatic agent, an organic lubricant, an organic polymer compound, an ultraviolet absorber, a light stabilizer, and a dye , Pigments or stabilizers can be used, and these are used as a composition component of the coating layer constituting the hard coat layer within a range that does not impair the reaction due to actinic radiation or heat. Properties can be improved.

  In the present invention, as a method for curing the hard coat composition, for example, a method of irradiating ultraviolet rays or the like as active rays, a high temperature heating method, or the like can be used. It is desirable to add a photopolymerization initiator or a thermal polymerization initiator to the coating composition.

  Specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylthio Sulfur compounds such as uranium disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more. Moreover, as a thermal polymerization initiator, a peroxide compound such as benzoyl peroxide or di-t-butyl peroxide can be used.

  The use amount of the photopolymerization initiator or thermal polymerization initiator is suitably 0.01 to 10% by mass with respect to 100% by mass of the total amount of the hard coat layer constituent components. When an electron beam or gamma ray is used as a curing means, it is not always necessary to add a polymerization initiator. Further, when thermosetting at a high temperature of 200 ° C. or higher, it is not always necessary to add a thermal polymerization initiator.

  The hard coat layer forming composition used in the present invention has a thermal polymerization prevention such as hydroquinone, hydroquinone monomethyl ether or 2,5-t-butyl hydroquinone in order to prevent thermal polymerization during production and dark reaction during storage. It is desirable to add an agent. The addition amount of the thermal polymerization inhibitor is preferably 0.005 to 0.05% by mass with respect to 100% by mass of the total amount of the hard coat layer constituent components.

  In addition, when the resin layer of the display filter of the present invention has a laminated structure in which a laminated film is further provided on the hard coat layer, the applicability and adhesiveness of the resin layer formed on the hard coat layer are inhibited. In that case, it is preferable to use an acrylic leveling agent in the hard coat layer. As such a leveling agent, “ARUFON-UP1000 series, UH2000 series, UC3000 series (trade name): manufactured by Toagosei Co., Ltd.” or the like is preferably used. The leveling agent is preferably added in an amount of 0.01 to 5 mass% with respect to 100 mass% of the total amount of the hard coat layer constituent components. In this way, by adding a leveling agent to the hard coat layer, for example, when a laminated film of a hard coat layer and an antireflection layer is used as the resin layer, the application name and adhesion of the antireflection layer formed on the hard coat layer Will be improved.

  Examples of the active rays used as necessary in the present invention include electromagnetic waves that polymerize acrylic vinyl groups such as ultraviolet rays, electron beams and radiation (α rays, β rays, γ rays, etc.). Ultraviolet light is convenient and preferred. As the ultraviolet ray source, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or the like can be used. Moreover, when irradiating actinic radiation, if it irradiates under a low oxygen concentration, it can harden | cure efficiently. Furthermore, the electron beam system is advantageous in that the apparatus is expensive and needs to be operated under an inert gas, but it is not necessary to include a photopolymerization initiator or a photosensitizer in the coating layer. is there.

  As the heat necessary for the thermosetting used in the present invention, steam heater, electric heater, infrared heater or far-infrared heater is used. The heat given by spraying on the base material and the coating film using is used. Among them, heat by air heated to 200 ° C. or higher is preferable, more preferably heat by nitrogen heated to 200 ° C. or higher. It is preferable because the curing rate is high.

  As a method for curing the hard coat layer, from the viewpoint of imparting a high altitude of the hard coat layer and from the viewpoint of productivity, a method of irradiating active rays is preferable, and a method of irradiating ultraviolet rays is particularly preferable. Therefore, the hard coat layer of the present invention is preferably an ultraviolet curable hard coat layer.

(Antireflection layer)
The antireflection layer can constitute the resin layer of the present invention. Such an antireflection layer has an antireflection film. Specifically, in the visible region, the refractive index is 1.5 or less, preferably 1.4 or less, such as a fluorinated transparent polymer resin or magnesium fluoride, Inorganic compounds such as metal oxides, fluorides, silicides, nitrides, sulfides, etc., with a single layer of silicon resin or silicon oxide thin film formed with an optical film thickness of 1/4 wavelength, etc. Or, there are two or more layers of thin films of organic compounds such as silicon resins, acrylic resins, fluorine resins, etc., but as a configuration that balances performance and cost, from the outermost layer to the low refractive index layer, Although a structure in which a high refractive index layer is laminated is preferable, in the present invention, even if an antireflection layer is not laminated or only a low refractive index layer is laminated, both the low refractive index layer and the high refractive index layer are laminated. May be laminated. This antireflection layer is usually laminated on the hard coat layer.

  The method for forming the antireflection layer is not particularly limited, but considering the balance between cost and performance, a method of applying a paint by wet coating is preferable. As the coating method of the paint, microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, flow coating method, etc. can be preferably used, but from the point of uniformity of coating thickness, microgravure coating Are preferably used. Next, after coating, each coating is formed by heating, drying, and curing with active rays such as heat or ultraviolet rays.

  The antireflection layer of the present invention is placed on the outermost surface of the display filter, for example, when a laminate comprising a hard coat layer and an antireflection layer is used as the resin layer. For this reason, since it is difficult to scratch when dust or the like adhering to the surface of the antireflection layer is wiped off with a cloth, it is preferable that the above-mentioned scratch resistance by steel wool is grade 3 or higher. More preferably, it is quaternary or higher.

  The antireflection layer in the present invention is not particularly limited as long as it has antireflection performance, but the following are particularly preferable embodiments of the antireflection layer, particularly preferable embodiments of the high refractive index layer, and particularly preferable low refractive index layers. The aspect of is shown.

  Particularly preferred antireflection layers in the present invention have (1) a minimum reflectance of 0.6% or less, (2) a maximum reflectance of 2.5% or less, and an absolute reflection spectrum of 5 ° at a wavelength of 400 to 700 nm. (3) The three conditions of the difference between the maximum reflectance and the minimum reflectance being less than 2.5% are satisfied. If the minimum reflectance exceeds 0.6%, the antireflection function becomes insufficient, which is not preferable. On the other hand, if the maximum reflectance exceeds 2.5%, the reflectance around 450 nm or around 700 nm increases, and the color tone of the reflected light becomes blue or red, which is not preferable. More preferably, the minimum reflectance is 0.5% or less, more preferably 0.3% or less, the maximum reflectance is 2.0% or less, the maximum reflectance and the minimum reflectance, By satisfying all that the difference of less than 2.0%, and further less than 1.5%, a flatter reflection spectrum and neutral color are preferable.

  In a particularly preferable antireflection layer, the refractive index of the low refractive index layer and that of the high refractive index layer are set so that the minimum reflectance and the maximum reflectance of the absolute reflection spectrum at a wavelength of 400 to 700 nm and the difference in reflectance are within the above ranges. Adjust as follows.

  The refractive index (nL) of the low refractive index layer is preferably 1.23-1.42, more preferably 1.34-1.38. Furthermore, the refractive index (nH) of the high refractive index layer is preferably 1.55 to 1.80, more preferably 1.60 to 1.75. Further, the difference in refractive index between the low refractive index layer and the high refractive index layer is preferably 0.15 or more.

It is also preferable to adjust the refractive index of the hard coat layer. The refractive index (nG) of the hard coat layer is preferably 1.45 to 1.55. Here, since the refractive index (nL) of the low refractive index layer and the refractive index (nH) of the high refractive index layer satisfy the following formulas (1) and (2), the minimum reflectance can be lowered. preferable.
(NH) = {(nL) × (nG)} ^1/2 ± 0.02 (1)
(NL) = {(nH) / (nG)} ^1/2 ± 0.02 (2)
In order for the antireflection layer to obtain a flatter reflection spectrum, the product (corresponding to the optical thickness) of the refractive index (nH) of the high refractive index layer and the thickness (dH) of the high refractive index layer in the aforementioned range. ) Is preferably a thickness (dH) that is 1.0 to 1.7 times the wavelength (λ) of visible light that is desired to prevent reflection, and more preferably 1.3 to 1. Six times is preferable. If it is less than 1.0 times, the difference between the maximum reflectance and the minimum reflectance also exceeds 2.5%, which is not preferable. On the other hand, if it exceeds 1.7 times, the minimum reflectance becomes higher than 0.6%, and the antireflection performance becomes insufficient. Here, the wavelength (λ) of visible light to be prevented from being reflected is arbitrarily selected as long as it is in the visible light range, but it is usually preferably in the range of 450 to 650 nm.

  In consideration of the range of the refractive index (nH) of the preferable high refractive index layer and the wavelength (λ) to be prevented from being reflected, in order to obtain a flatter reflection spectrum, the antireflective layer has a high refractive index layer. The thickness (dH) is in the range of 100 to 300 nm, preferably in the range of 100 to 200 nm.

  On the other hand, the preferable range of the thickness (dL) of the low refractive index layer of the present invention is the product of the refractive index (nL) of the low refractive index layer and the thickness (dL) of the low refractive index layer in the above range. The thickness (dL) is preferably 0.7 to 1.0 times 1/4 of the wavelength (λ) of visible light to be prevented from reflecting, and more preferably 0.75 to 0.95 times. Is preferred. Considering these, in the present invention, in order for the antireflection layer to obtain a flatter reflection spectrum, the thickness (dL) of the low refractive index layer is in the range of 70 to 160 nm. The thickness (dL) of the low refractive index layer is preferably in the range of 80 to 140 nm, more preferably 85 to 105 nm.

  Further, in order to obtain a flat reflection spectrum, the ratio (dH / dL) of the thickness (dH) of the high refractive index layer and the thickness (dL) of the low refractive index layer is 1.0 to 1.9. It is preferable to do. If it is less than 1.0, the maximum reflectance is higher than 2.5%, the difference between the maximum reflectance and the minimum reflectance is also over 2.5%, the reflection spectrum becomes V-shaped, Blue interference color appears. On the other hand, if it exceeds 1.9, a flat reflection spectrum can be obtained, but the minimum reflectance becomes higher than 0.6%, and the antireflection performance becomes insufficient. (DH / dL) is more preferably 1.1 to 1.8, and still more preferably 1.2 to 1.7, so that a flat reflection spectrum can be obtained and the minimum reflectance can be lowered.

  In the particularly preferred antireflective layer in the present invention, as a component of the high refractive index layer, in order to impart antistatic properties to the antireflective layer surface, metal compound particles are dispersed in the resin composition. preferable. A (meth) acrylate compound is used for the resin component. The (meth) acrylate compound is preferably radically polymerized by irradiation with actinic rays to improve the solvent resistance and hardness of the formed film. Furthermore, the (meth) acryloyl group has two or more polyfunctional (meth) The acrylate compound is particularly preferred in the present invention because of its improved solvent resistance. For example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanuric acid ester Trifunctional (meth) acrylates such as tri (meth) acrylate, pentafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.

  As the resin component, in order to improve the dispersibility of the metal compound particles, a (meth) acrylate compound having an acidic functional group such as a carboxyl group, a phosphate group, or a sulfonate group can be used. Specifically, examples of the acidic functional group-containing monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, and mono (2- (meta ) (Acryloyloxyethyl) acid phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, and other phosphoric acid (meth) acrylic acid esters, 2-sulfoester (meth) acrylates, and the like. In addition, (meth) acrylate compounds having a bond with polarity such as an amide bond, a urethane bond, and an ether bond can be used.

  As the metal compound particles used here, various conductive metal oxide particles are preferably used. Particularly preferred are tin-containing antimony oxide particles (ATO), zinc-containing antimony oxide particles, tin-containing indium oxide particles (ITO), zinc oxide / aluminum oxide particles, and antimony oxide particles. More preferably, tin-containing indium oxide particles (ITO) are used.

  As the conductive metal oxide particles, particles having an average particle size of 0.005 to 0.05 μm determined by observation with a transmission electron microscope are preferably used. The metal oxide fine particles can also be used as the ultrafine particles (B) described above.

  Constituent components of the high refractive index layer further contain conductive polymers such as polypyrrole, polythiophene, and polyaniline, and organometallic compounds such as metal alcoholates and chelate compounds for the purpose of further improving the conductivity effect. You can also.

  In forming the high refractive index layer, an initiator may be used to advance curing of the applied resin component. As the initiator, the applied binder component initiates or accelerates polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and conventionally known thioxanthone derivatives, azo compounds, diazo compounds, Various photopolymerization initiators such as aromatic carbonyl compounds, dialkylaminobenzoic acid esters, peroxides, acridine derivatives, phenazine derivatives and quinoxaline derivatives can be used. The amount of the photopolymerization initiator is usually preferably added in the range of 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total component of the high refractive index layer. In such a preferred range, photopolymerization is sufficiently fast and light irradiation for a short time may be sufficient to satisfy hardness and scratch resistance, while the coating film has functions such as conductivity, abrasion resistance, and weather resistance. There is no decline.

  Further, when the high refractive index layer is formed, an amine compound may be coexisted with the photopolymerization initiator in order to prevent a decrease in sensitivity due to oxygen inhibition. Furthermore, you may contain various additives, such as a polymerization inhibitor, a curing catalyst, antioxidant, a dispersing agent, a leveling agent, a silane coupling agent, as needed. In addition, for the purpose of improving the surface hardness, alkyl silicates and hydrolysates thereof, colloidal silica, dry silica, wet silica, titanium oxide and other inorganic particles, colloidally dispersed silica fine particles, and the like may be further included. it can.

  When the content (mass) of the resin component is (a) and the content (mass) of the metal compound particles is (b), the content ratio of the constituent components of the high refractive index layer is: The mass ratio [(a) / (b)] is preferably 10/90 to 30/70, more preferably 15/85 to 25/75. When the metal compound particles are within such a preferable range, the obtained film has sufficient transparency and good electrical conductivity, and on the other hand, various physical and chemical strengths of the obtained film do not deteriorate.

The plasma display panel filter is preferably subjected to antistatic treatment because dust easily adheres due to electrostatic charging and may be discharged and receive an electric shock when a human body comes into contact with it. In order to provide a desired level of antistatic property by the high refractive index layer, it is preferable to control the addition amount so that the surface resistance value of the layer is 1 × 10 ¹¹ Ω / □ or less, and further, 1 × It is preferable to control the amount of addition so that it becomes 10 ¹⁰ Ω / □ or less.

  The high refractive index layer is a layer having a total light transmittance of preferably 40% or more, and more preferably 50% or more from the viewpoint of sharpness and transparency.

  The high refractive index layer can be formed by preparing a coating liquid preferably dispersed with a solvent, applying the coating liquid on the hard coat layer, and then drying and curing.

  The solvent used in the formation of the high refractive index layer is formulated to improve coating or printing workability and to improve the dispersibility of the metal compound particles. Various known organic solvents can be used. In particular, in the present invention, an organic solvent having a boiling point of 60 to 180 ° C. is preferred from the viewpoint of viscosity stability and drying property of the composition, and among them, the organic solvent having an oxygen atom has an affinity for metal compound particles. It is preferable because it is good. Specific examples of the organic solvent include methanol, ethanol, isopropyl alcohol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether, cyclohexanone, and acetic acid. Preferable examples include butyl, isopropylacetone, methyl ethyl ketone, methyl isobutyl ketone, diacetylacetone, acetylacetone and the like. These may be used alone or in combination of two or more.

  Further, the amount of the organic solvent may be blended in any amount so that the composition has a viscosity with good workability according to the coating means and the printing means, but the solid content concentration of the composition is usually 60 mass. % Or less, preferably 50% by mass or less.

  As the preparation of the above-described composition for the high refractive index layer, any method can be adopted. Usually, metal compound particles are added to a solution in which a resin component is dissolved in an organic solvent, and a paint shaker or a ball mill is added. A method of dispersing by a dispersing machine such as a sand mill, three rolls, an attritor, a homomixer, etc., and then adding a photopolymerization initiator and dissolving uniformly is suitable.

  In a particularly preferred embodiment of the antireflection layer in the present invention, the low refractive index layer is obtained by coating a coating composition comprising silica fine particles having cavities therein, a siloxane compound, a curing agent, and a solvent. Is preferable because the refractive index can be lowered and the surface reflectance can be lowered.

  In order to improve the surface hardness and to improve the scratch resistance, the low refractive index layer preferably has a siloxane compound, which is a matrix material, and silica fine particles that are firmly bonded. It is preferable to react and bond the siloxane compound with the surface of the silica fine particles in advance at the stage of the composition.

  The coating composition for that purpose can be obtained by hydrolyzing the silane compound in a solvent with an acid catalyst in the presence of silica fine particles to form a silanol compound and then subjecting the silanol compound to a condensation reaction. As the silanol compound, one or more silane compounds selected from silane compounds represented by the following general formulas (1) to (5) are preferable.

  The obtained paint contains a siloxane compound that is a condensate of these silane compounds. Moreover, these silane compounds are hydrolyzed and may contain the silanol compound which is not condensed.

R ¹ Si (OR ⁶ ) ₃ (1)
R ¹ represents a fluoroalkyl group having 3 to 17 fluorine atoms. The number of fluorine in R ¹ is preferably 6-8. When the number of fluorine atoms per molecule is large, the hardness of the obtained film tends to decrease. The number of carbon atoms of R ¹ is preferably 3 to 10 because the scratch resistance of the obtained film can be increased. A carbon number of 3 is particularly preferred. R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, and may be the same or different. R ⁶ is more preferably a methyl group or an ethyl group. Use of the trifunctional silane compound represented by the general formula (1) is preferable because the refractive index of the resulting film can be lowered.

R ² Si (OR ⁷ ) ₃ (2)
R ² represents a group selected from a vinyl group, an aryl group, an alkenyl group, an acrylic group, a methacryl group, a methacryloxy group, a cyano group, an epoxy group, a glycidoxy group, an amino group, and a substituted product thereof. R ² having 2 to 10 carbon atoms is preferred because it can increase the scratch resistance of the resulting coating. R ⁷ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxyethyl group, or an acetyl group, and may be the same or different. R ⁷ is more preferably a methyl group or an ethyl group. Use of the trifunctional silane compound represented by the general formula (2) is preferable because the hardness of the resulting coating can be improved.

R ³ Si (OR ⁸ ) ₃ (3)
R ³ represents a group selected from hydrogen, an alkyl group, an aryl group, and substituents thereof. The number of carbon atoms of R ³ is preferably 1 to 6 because the scratch resistance of the resulting film can be increased. If R ³ exceeds 6 carbon atoms, the hardness of the resulting coating tends to decrease. R ⁸ represents a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different. R ⁸ is more preferably a methyl group or an ethyl group. Use of the trifunctional silane compound represented by the general formula (3) is preferable because the hardness of the resulting coating can be improved.

R ⁴ R ⁵ Si (OR ⁹ ) ₂ (4)
R ⁴ and R ⁵ each represent a group selected from hydrogen, an alkyl group, a fluoroalkyl group, an aryl group, an alkenyl group, a methacryloxy group, an epoxy group, a glycidoxy group, an amino group, and a substituent thereof. May be the same or different. As C4 of R < ⁴ >, R < ⁵ >, since 1-6 can improve the abrasion resistance of the obtained film, it is preferable. R ⁹ represents a methyl group, an ethyl group, a propyl group, an isopropyl group or an acetyl group, and may be the same or different. R ⁹ is more preferably a methyl group or an ethyl group. It is preferable to use a bifunctional silane compound represented by the general formula (4) because the flexibility of the resulting film can be improved.

Si (OR ¹⁰ ) ₄ (5)
R ¹⁰ represents a methyl group or an ethyl group, and may be the same or different. It is preferable to use a tetrafunctional silane compound represented by the general formula (5) because the hardness of the resulting film can be improved.

  These silane compounds represented by the general formulas (1) to (5) may be used alone or in combination of two or more.

  The content of the siloxane compound is preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass to 60% by mass with respect to the total amount of the film when the film is formed. It is preferable to contain a siloxane compound within this range because the refractive index of the coating can be lowered and the hardness of the coating can be increased. Therefore, the content of the siloxane compound in the coating is preferably in the above range with respect to all components except the solvent.

  Among these, in order to reduce the refractive index, the fluorine-containing silane compound represented by the general formula (1) is used as an essential component, and the silane compound represented by the general formulas (2) to (5) is selected. It is preferable to use a combination of one or more silane compounds. The amount of the silane compound represented by the general formula (1) is preferably 20% by mass to 80% by mass, and particularly preferably 30% by mass to 60% by mass with respect to the total amount of the silane compound. When the amount of the silane compound is less than 20% by mass, the reduction in the refractive index may be insufficient. On the other hand, when the amount of the silane compound exceeds 80% by mass, the hardness of the film may be lowered.

  Specific examples of the silane compounds represented by the general formulas (1) to (5) are shown below.

  Examples of the trifunctional silane compound represented by the general formula (1) include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoromethyltriacetoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyl. Triethoxysilane, trifluoropropyltriacetoxysilane, trifluoroacetoxyethyltrimethoxysilane, trifluoroacetoxyethyltriethoxysilane, trifluoroacetoxyethyltriacetoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane , Perfluoropropylethyltriacetoxysilane, perfluoropentylethyltrimethoxysilane, perfluoropentylethyltriethoxy Silane, Perfluoropentylethyltriacetoxysilane, Tridecafluorooctyltrimethoxysilane, Tridecafluorooctyltriethoxysilane, Tridecafluorooctyltripropoxysilane, Tridecafluorooctyltriisopropoxysilane, Heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyltriethoxysilane, and the like. Of these, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyltriethoxysilane are preferred from the viewpoint of the hardness of the resulting coating.

  Examples of the trifunctional silane compound represented by the general formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α- Glycidoxypro Rutrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltripropoxy silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycid Xylbutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid Xibutyltrimethoxy , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltri Methoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, β- (3,4-epoxycyclohexyl) propyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) pro Examples include pyrtriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane. Of these, vinyltrialkoxysilane and 3-methacryloxypropyltrialkoxysilane are preferred from the viewpoint of the hardness of the resulting coating.

  Examples of the trifunctional silane compound represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxy Silane, and the like. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of the hardness of the obtained film.

  Examples of the bifunctional silane compound represented by the general formula (4) include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylvinyldimethoxy. Silane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxy Silane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Methyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldi Ethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiacetoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiacetoxysilane, tri Fluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, trifluoropropylvinyldiacetoxysilane, heptadecafluorodecylme Examples include tildimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, and octadecylmethyldimethoxysilane. Of these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating.

  Examples of the tetrafunctional silane compound represented by the general formula (5) include tetramethoxysilane and tetraethoxysilane.

  As the silica fine particles used in the low refractive index layer, particles having a number average particle diameter of 1 nm to 50 nm are preferably used. When the number average particle diameter is less than 1 nm, the bonding with the matrix material becomes insufficient, and the hardness of the coating film may be lowered. On the other hand, when the number average particle diameter exceeds 50 nm, the generation of voids between particles caused by introducing a large amount of particles is reduced, and the effect of lowering the refractive index may not be sufficiently exhibited. Here, the average particle diameter of the silica fine particles can be determined by observation with a transmission electron microscope.

  The silica fine particles can also be used as the ultrafine particles (B) as long as the average particle diameter obtained by observation with a transmission electron microscope is 300 nm or less.

  Further, when the hard coat layer and the antireflection layer are laminated as the resin layer (the hard coat layer is the conductive layer side), and by controlling the Ra of the hard coat layer, the Ra of the resin layer is also controlled. When a large particle having a number average particle diameter exceeding 50 nm is added to the low refractive index layer of the antireflection layer, Ra on the outermost surface of the resin layer does not follow Ra of the hard coat layer, thereby preventing reflection. The particles in the layer may affect Ra on the outermost surface of the resin layer.

  The number average particle diameter of the silica fine particles used in the low refractive index layer is preferably smaller than the film thickness of the coating film to be formed. When the film thickness is exceeded, silica fine particles are exposed on the surface of the film, and not only the antireflection property is impaired, but also the surface hardness and stain resistance of the film are lowered.

  The silica fine particles used in the low refractive index layer are preferably silica fine particles having a silanol group on the surface in order to easily react with the siloxane compound of the matrix. In addition, silica fine particles having cavities inside are preferable for lowering the refractive index of the coating. Silica fine particles having no cavity inside generally have a refractive index lowering effect because the refractive index of the particles themselves is 1.45 to 1.50. On the other hand, since the silica fine particles having cavities inside have a refractive index of 1.20 to 1.40, the effect of lowering the refractive index by introduction is large. Examples of the silica fine particles having cavities therein include silica fine particles having cavities surrounded by an outer shell, and porous silica fine particles having a large number of cavities. Among these, when the hardness of the coating is taken into consideration, porous silica fine particles having high strength of the particles themselves are preferable. The refractive index of the fine particles is 1.20 to 1.40, more preferably 1.20 to 1.35. Moreover, the number average particle diameter of the silica fine particles having cavities therein is preferably 1 nm to 50 nm. The refractive index of the silica fine particles can be measured by the method disclosed in paragraph [0034] of JP-A-2001-233611. Silica fine particles having cavities therein are produced, for example, by the method described in paragraphs [0033] to [0046] of JP-A-2001-233611 and the method described in paragraph [0043] of Japanese Patent No. 3272111. can do. A commercially available product can also be used.

  The content of the silica fine particles used in the low refractive index layer is preferably 30% by mass to 80% by mass, particularly preferably 40% by mass to 70% by mass, based on the total amount of the film when the film is formed. . Therefore, it is preferable that the content of the silica fine particles in the coating is in the above-mentioned range with respect to all components except the solvent. When silica fine particles are contained in the coating within this range, not only the refractive index can be lowered, but also the hardness of the coating can be increased. When the content of the silica fine particles is less than 30% by mass, the refractive index lowering effect due to the voids between the particles is reduced. On the other hand, when the content of the silica fine particles exceeds 80% by mass, many island phenomena occur in the coating film, the hardness of the coating film decreases, and the refractive index becomes uneven depending on the location, which is not preferable.

  Further, as described above, the coating composition for forming the low refractive index layer is formed by hydrolyzing the silane compound in a solvent with an acid catalyst in the presence of silica fine particles, thereby forming the silanol compound. It can be obtained by condensation reaction of a silanol compound. In this hydrolysis reaction, an acid catalyst and water are added in a solvent over 1 to 180 minutes, and then reacted at room temperature to 80 ° C. for 1 to 180 minutes. It is preferable. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 70 ° C. Moreover, after obtaining a silanol compound by a hydrolysis reaction, it is preferable that the reaction solution is heated as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. In order to increase the degree of polymerization of the siloxane compound, it is possible to reheat or add a base catalyst.

  Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred. A preferable addition amount of these acid catalysts is preferably 0.05% by mass to 10% by mass, particularly preferably 0.1% by mass to 5% by mass, based on the total amount of silane compounds used in the hydrolysis reaction. %. If the amount of the acid catalyst is less than 0.05% by mass, the hydrolysis reaction may not proceed sufficiently. On the other hand, if the amount of the acid catalyst exceeds 10% by mass, the hydrolysis reaction may run away.

  The solvent is not particularly limited, but is determined in consideration of the stability, wettability, volatility, etc. of the coating composition. The solvent can be used not only as one type but also as a mixture of two or more types. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as lenglycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; dimethylformamide Amides such as dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, lactic acid Acetates such as methyl, ethyl lactate and butyl lactate; toluene, xylene, hexane, In addition to the aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl sulfoxide and the like.

  The amount of the solvent used during the hydrolysis reaction is preferably in the range of 50% by mass to 500% by mass, particularly preferably in the range of 80% by mass to 200% by mass, based on the total amount of silane compounds. When the amount of the solvent is less than 50% by mass, the reaction may run away and gel may occur. On the other hand, if the amount of the solvent exceeds 500% by mass, hydrolysis may not proceed.

  Moreover, as water used for a hydrolysis reaction, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the silane compound.

  Examples of the curing agent added for the purpose of curing the coating agent to form a low refractive index layer include various curing agents or three-dimensional crosslinking agents that accelerate the curing of the coating composition or facilitate the curing. . Specific examples of the curing agent include nitrogen-containing organic substances, silicon resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, melamine resins, polyfunctional acrylic resins, urea resins, and the like. One kind or two or more kinds may be added. Of these, metal chelate compounds are preferably used in view of the stability of the curing agent and the processability of the obtained film. Examples of the metal chelate compound used include a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and a magnesium chelate compound. Among these, for the purpose of lowering the refractive index, an aluminum chelate compound and / or a magnesium chelate compound having a low refractive index is preferable. These metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferable specific examples of the metal chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris ( Examples include aluminum chelate compounds such as acetylacetonate), and magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monosopropylate, and magnesium bis (acetylacetonate). . Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), and magnesium bis (ethylacetoacetate) are preferable. In view of storage stability and availability, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate) are particularly preferred. The amount of the curing agent added is preferably 0.1% by mass to 10% by mass, and particularly preferably 1% by mass to 6% by mass with respect to the total amount of silane compounds in the coating composition. Here, the total amount of the silane compound means an amount including all of the silane compound, its hydrolyzate and its condensate. When the content is less than 0.1% by mass, the hardness of the resulting coating is lowered. On the other hand, if the content exceeds 10% by mass, curing is sufficient and the hardness of the resulting coating is improved, but the refractive index is also increased, which is not preferable.

  Furthermore, it is preferable that a solvent having a boiling point of 100 to 180 ° C under atmospheric pressure and a solvent having a boiling point of less than 100 ° C under atmospheric pressure are used in the coating composition. By including a solvent having a boiling point of 100 to 180 ° C. under atmospheric pressure, the coating property of the coating liquid is improved, and a film having a flat surface can be obtained. Further, by including a solvent having a boiling point of less than 100 ° C. under atmospheric pressure, the solvent is effectively volatilized at the time of film formation, and a film having high hardness can be obtained. That is, a film having a flat surface and high hardness can be obtained.

  Specific examples of the solvent having a boiling point of 100 to 180 ° C. under atmospheric pressure include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethers such as propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3 -Methoxybutyl acetate, 3-methyl-3- Toxibutyl acetate, acetates such as methyl lactate, ethyl lactate and butyl lactate, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone, 2-heptanone, butanol, isobutylalcohol, pentano- , 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, alcohols such as diacetone alcohol, and aromatic hydrocarbons such as toluene and xylene Can be mentioned. These may be used alone or in combination. Among these, examples of particularly preferable solvents are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diacetone alcohol and the like.

  Examples of the solvent having a boiling point of less than 100 ° C. under atmospheric pressure include methanol, ethanol, isopropanol, t-butanol, methyl ethyl ketone, and the like. These may be used alone or in combination.

  The content of the total solvent in the coating composition is preferably in the range of 1300% by mass to 9900% by mass, particularly preferably in the range of 1500% by mass to 6000% by mass with respect to the total silane compound content. If the total solvent content is less than 1300% by mass or more than 9900% by mass, it becomes difficult to form a film having a predetermined film thickness. Here, the total amount of the silane compound means an amount including all of the silane compound, its hydrolyzate and its condensate.

(Other functional layers)
The display filter of the present invention preferably has a functional layer having at least one function selected from the group consisting of a near infrared blocking function, a color tone correction function, an ultraviolet blocking function, and a Ne cut function. These functional layers may be functional layers having a plurality of functions in one layer. The functional layer may be a stack of a plurality of layers.

  The functional layer constituting the display filter of the present invention will be described below.

(Color tone correction layer)
A color correction layer having a color correction function, which is a kind of functional layer, is a layer containing a dye having a color correction function, and performs color correction of transmitted visible light to improve the image characteristics of the plasma display panel. Specifically, it is intended to achieve a high contrast and a clear color. Moreover, the transmittance of the entire display filter can be adjusted by the color tone correction layer, and it also plays a role of adjusting the reflection performance.

  The color tone correction is achieved by selectively absorbing visible light having a specific wavelength out of visible light transmitted through the display filter. Accordingly, the dye contained in the color tone correction layer selectively absorbs visible light having a specific wavelength, and the dye can be either a dye or a pigment. “Selectively absorb visible light having a specific wavelength” refers to specifically absorbing light in a specific wavelength region out of light in the visible light wavelength region (wavelength 380 to 780 nm). Here, the wavelength region specifically absorbed by the dye may be a single wavelength region or a plurality of wavelength regions.

  Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments and organic dyes such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, and metal complex-based materials, and inorganic pigments can be used. Among these, phthalocyanine-based and anthraquinone-based dyes are particularly preferable because of their good weather resistance. In addition, any one of the above-described dyes may be contained in the color correction layer, or two or more kinds may be contained.

  Further, the display filter may be required to have a transmission color of neutral gray or blue gray. This is because, when it is necessary to maintain or improve the light emission characteristics and contrast of the plasma display panel, white having a slightly higher color temperature than standard white may be preferred. The above dyes can also be applied to achieve such requirements.

  The color correction layer can take various forms as long as it contains a dye having a color correction capability. The color tone correction layer may be formed by a suitable method depending on the mode. For example, in the case of a mode in which a dye having a color tone correcting ability is contained in the pressure-sensitive adhesive, a color tone having a desired thickness is applied by adding a dye having a color tone correcting ability as a dye or pigment in the pressure-sensitive adhesive. A layer may be formed. Commercially available pressure-sensitive adhesives can be used as the pressure-sensitive adhesive, but preferred specific examples include acrylate copolymer, polyvinyl chloride, epoxy resin, polyurethane, vinyl acetate copolymer, styrene-acrylic. Mention may be made of pressure-sensitive adhesives such as copolymers, polyesters, polyamides, polyolefins, styrene-butadiene copolymer rubbers, butyl rubbers or silicone resins.

  In the case of a mode in which a color tone correction layer is formed by coloring a transparent base material and a transparent substrate, a dye having a color tone correction ability is used as a dye or a pigment as it is or dissolved in a solvent, and is applied and dried to obtain a desired color A color tone correction layer having a thickness may be formed. Solvents used for this purpose include ketone solvents such as cyclohexanone, ether solvents, ester solvents such as butyl acetate, ether alcohol solvents such as ethyl cellosolve, ketone alcohol solvents such as diacetone alcohol, toluene, etc. Aromatic solvents and the like.

  Further, when the color tone correction layer is a transparent base material containing a colorant having color tone correction ability, a thermoplastic resin as a raw material for the transparent base material is dissolved in a desired solvent, and the colorant having color tone correction ability is dyed Alternatively, a solution obtained by adding as a pigment may be applied and dried to form a color correction layer having a desired thickness. The solvent used here only needs to be able to dissolve the resin as a raw material and to dissolve or disperse the added dye or pigment. Solvents used for this purpose include ketone solvents such as cyclohexanone, ether solvents, ester solvents such as butyl acetate, ether alcohol solvents such as ethyl cellosolve, ketone alcohol solvents such as diacetone alcohol, toluene, etc. Aromatic solvents and the like.

  In a method for forming a color correction layer by applying a solution containing a dye having color tone correction ability, or a solution containing a dye having color tone correction ability and a raw material resin for a transparent substrate, the coating method may be, for example, a dip coating method. A roll coating method, a spray coating method, a gravure coating method, a comma coating method, a die coating method and the like can be selected. These coating methods can be continuously processed, and are more productive than batch-type vapor deposition methods. Alternatively, a spin coating method capable of forming a thin and uniform coating film can also be employed.

  The thickness of the color tone correction layer is preferably 0.5 μm or more in order to obtain a sufficient color tone correction capability. Moreover, 40 micrometers or less are preferable and it is especially preferable that it is 1-25 micrometers because it is excellent in light transmittance, more specifically visible light transmittance. When the thickness of the color correction layer is 40 μm or more, the solvent tends to remain when forming a color correction layer by applying a solution containing a desired dye, pigment, and transparent resin, and operations for forming the color correction layer It is not preferable because the property becomes difficult.

  When the color tone correction layer is a pressure-sensitive adhesive layer containing a colorant having a color tone correction ability or a transparent substrate containing a colorant having a color tone correction ability, the colorant is 0.1% relative to the pressure sensitive adhesive or the thermoplastic resin. The content is preferably at least 1% by mass, particularly preferably at least 1% by mass. Moreover, in order to maintain the physical properties of the pressure-sensitive adhesive layer or the transparent substrate, it is preferable to suppress the amount of the dye having a color tone correcting ability to 10% by mass or less.

(Near infrared blocking layer)
Next, a near-infrared blocking layer having a near-infrared blocking function, which is a type of functional layer, will be described. The near-infrared rays generated from the plasma display panel act on peripheral electronic devices such as a remote controller and a cordless phone to cause a malfunction. Therefore, it is necessary to cut the light in the near-infrared region to a level at which there is no practical problem. The problem wavelength region is 800 to 1000 nm, and the transmittance in the wavelength region is required to be 20% or less, preferably 10% or less. The near-infrared shielding layer is usually a pigment having a near-infrared absorption ability having a maximum absorption wavelength of 750 to 1100 nm for blocking near-infrared rays, specifically, polymethine, phthalocyanine, naphthalocyanine, metal complex, Aminium-based, imonium-based, diimonium-based, anthraquinone-based, dithiol-metal complex-based, naphthoquinone-based, indolephenol-based, azo-based, triallylmethane-based compounds, etc. are preferably applied, metal complex-based, aminium-based, phthalocyanine-based, Particularly preferred are naphthalocyanine and diimonium. In addition, when using the pigment | dye which has a near-infrared absorptivity, you may contain any 1 type and may contain 2 or more types.

  The structure, formation method, thickness, and the like of the near infrared absorption layer are the same as those of the color tone correction layer described above. The near-infrared absorbing layer may be the same layer as the color tone correcting layer, that is, the color tone correcting layer may contain a colorant having a color tone correcting ability and a colorant having a near infrared ray absorbing ability. You may provide the near-infrared shielding layer different from a layer. The amount of the near-infrared absorbing dye is preferably 0.1% by mass or more, particularly preferably 2% by mass or more, based on the binder resin, but the physical properties of the pressure-sensitive adhesive layer or transparent substrate containing the infrared absorber are preferred. In order to maintain this, it is preferable to keep the total amount of the dye having the color tone correcting ability and the near-infrared absorber to 10% by mass or less.

(Ne cut layer)
Next, a functional layer having a Ne cut function, which is a kind of functional layer, will be described. For the near-infrared shielding layer or color tone correction layer, an extra luminescent color (mainly in the wavelength region of 560 to 610 nm) from the discharge gas sealed in the plasma display panel, for example, a binary gas of neon and xenon, is selectively used. It is preferable to mix and contain one or more kinds of color correction agents for absorption / attenuation. By adopting such a dye structure, of the visible light emitted from the display screen of the plasma display panel, excess light due to the emission of the discharge gas is absorbed and attenuated. As a result, the visible light emitted from the plasma display panel is absorbed. The display color can be brought close to the display color of the display target, and a natural color tone can be displayed.

(UV blocking layer)
Next, an ultraviolet blocking layer having an ultraviolet blocking function, which is a kind of functional layer, will be described. In the display filter of the present invention, the ultraviolet blocking layer has a role of preventing the photodegradation of the dye contained in the color correction layer, the infrared blocking layer and the like located on the panel side of this layer. For the ultraviolet blocking layer, a transparent substrate containing an ultraviolet absorber, an adhesive layer, and the like are used.
Moreover, it is preferable that Tg of the layer containing a ultraviolet absorber is 60 degreeC or more, and it is more preferable that it is 80 degreeC or more. When a UV absorber is contained in a thermoplastic resin having a low Tg, the UV absorber may move to the pressure-sensitive adhesive interface or the adhesive interface, thereby hindering the stickiness or adhesiveness. If the Tg of the thermoplastic resin containing the ultraviolet absorber is 60 ° C. or more, the possibility of the ultraviolet absorber moving in the transparent substrate is reduced, and other components of the display filter, specifically, for example, When the transparent substrate, the color tone correction layer, or another transparent base material forming a part of the antireflection layer is bonded via the interlayer adhesive layer, the tackiness is not hindered.

  Examples of the resin having a Tg of 60 ° C. or more constituting the transparent substrate include polyethylene terephthalate, aromatic polyester typified by polyethylene naphthalate, nylon 6, aliphatic polyamide typified by nylon 66, aromatic polyamide, polycarbonate and the like. Illustrated. Among these, aromatic polyester is preferable, and polyethylene terephthalate that can form a biaxially stretched film excellent in heat resistance and mechanical strength is particularly preferable.

  Preferred examples of the ultraviolet absorber include salicylic acid compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, benzoxazinone compounds, and cyclic imino ester compounds, but at 380 nm to 390 nm. A benzoxazinone-based compound is most preferable from the viewpoint of ultraviolet blocking properties, color tone, and the like. These compounds may be used alone or in combination of two or more. Moreover, combined use of stabilizers, such as HALS (hindered amine light stabilizer) and antioxidant, is more preferable.

  Examples of benzoxazinone-based compounds that are preferable materials include 2-p-nitrophenyl-3,1-benzoxazin-4-one and 2- (p-bezoylphenyl) -3,1-benzoxazine-4. -One, 2- (2-naphthyl) -3,1-benzoxazin-4-one, 2-2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 '-( 2,6-naphthylene) bis (3,1-benzoxazin-4-one) and the like can be exemplified. The addition amount of these compounds is preferably 0.5 to 5% by mass in the base film.

  Moreover, it is preferable to use a cyanoacrylate-based tetramer compound in combination in order to impart further excellent light resistance. The cyanoacrylate tetramer compound is preferably contained in the base film in an amount of 0.05 to 2% by mass. The cyanoacrylate-based tetramer compound is a compound based on a tetramer of cyanoacrylate, such as 1,3-bis (2′cyano-3,3-diphenylacryloyloxy) -2, 2-bis-. (2 'cyano-3,3-diphenylacryloyloxymethylpropane). When used in combination with this, the aforementioned ultraviolet absorber is preferably 0.3 to 3% by mass in the base film.

  In the ultraviolet blocking layer, the transmittance at a wavelength of 380 nm is preferably 5% or less, so that the base material, the dye pigment, and the like can be protected from ultraviolet rays.

  The content of the ultraviolet absorber in the ultraviolet blocking layer is preferably 0.1 to 5% by mass, and more preferably 0.2 to 3% by mass. When the content of the ultraviolet absorber is 0.1 to 5% by mass, the ultraviolet ray incident from the viewer side of the display filter is absorbed, and the effect of preventing the light deterioration of the pigment contained in the color tone correction layer is excellent. And does not impair the strength of the transparent substrate or the adhesive layer.

  The method of adding the UV absorber to the UV blocking layer, particularly the transparent substrate, is not particularly limited, but the polymerization process of the thermoplastic resin, the kneading into the thermoplastic resin in the melting process before film formation, the biaxially stretched film Examples of impregnation are described. In particular, it is preferable to knead into the thermoplastic resin in the melting step before film formation in order to prevent a decrease in the polymerization degree of the thermoplastic resin. The kneading of the ultraviolet absorber at that time can be performed by a direct addition method of the powder of the agent, a master batch method in which a master polymer containing the agent in a high concentration is added to the film-forming polymer, or the like.

  The ultraviolet cut layer preferably has a thickness in the range of 5 to 250 μm, more preferably 50 to 200 μm, and still more preferably 80 to 200 μm. When the thickness of the ultraviolet absorbing layer is in the range of 5 to 250 μm, it is excellent in the effect of absorbing the ultraviolet rays incident from the viewer side of the display filter, and has light transmittance, specifically visible light transmittance. Are better.

(Adhesive layer)
In the present invention, an adhesive layer having adhesiveness may be used to bond the various functional layers described above or to bond a display filter to a display. The adhesive used at this time is not particularly limited as long as it is an adhesive that adheres two objects by its adhesive action, and an adhesive made of rubber, acrylic, silicon, or polyvinyl ether is used. it can.

  Furthermore, the pressure-sensitive adhesive is roughly classified into two types, a solvent-type pressure-sensitive adhesive and a solventless pressure-sensitive adhesive. Solvent-type pressure-sensitive adhesives excellent in dryness, productivity, and processability are still mainstream, but in recent years, they are changing to solvent-free pressure-sensitive adhesives in terms of pollution, energy saving, resource saving, safety, and the like. Among these, it is preferable to use an actinic radiation curable pressure sensitive adhesive that is a pressure sensitive adhesive that is cured in seconds by irradiation with actinic radiation and has excellent properties such as flexibility, adhesion, and chemical resistance.

  Specific examples of the actinic radiation curable acrylic pressure-sensitive adhesive can be referred to the Japan Adhesive Society, “Adhesive Data Book”, published by Nikkan Kogyo Shimbun, 1990, pages 83 to 88. It is not limited to. Hitachi Chemical Polymer Co., Ltd. (trade name XY (registered trademark) series, etc.), Toho Kasei Kogyo Co., Ltd. (trade name Hilock (registered trademark) series, etc.), stock, etc. Company Three Bond; (trade name Three Bond (registered trademark) series, etc.), Toa Gosei Chemical Industry Co., Ltd. (trade name Arontite (registered trademark) series, etc.), Cemedine Co., Ltd. ) Etc. can be used, but is not limited to these.

(Transparent substrate)
The transparent substrate in the present invention is usually used as a substrate for laminating an antireflection layer, a hard coat layer, an infrared cut layer, a conductive layer and the like. Moreover, the role as an ultraviolet-ray cut layer can also be played by adding an ultraviolet-absorption component.

  The transparent substrate in the present invention is a film capable of melt film formation or solution film formation. Specific examples thereof include films made of polyester, polyolefin, polyamide, polyphenylene sulfide, cellulose ester, polycarbonate, acrylate and the like. These films are preferably used as a base material for each functional layer in the present invention, but as a material for a transparent base material used for a surface forming a undulation structure, transparency, mechanical strength and dimensional stability are preferred. Examples of such materials include polyester, cellulose ester, and acrylic (polyacrylate). Among them, polyethylene terephthalate, polyethylene-2,6-naphthalate, and triacetyl cellulose are exemplified as suitable materials. can do. Among polyacrylates, a resin having a cyclic structure in the molecule is a suitable material excellent in optical isotropy. Examples of the resin having a cyclic structure in the molecule include an acrylic resin containing 10 to 50% by mass of a glutaric anhydride unit. However, polyester is particularly preferable as a material that has a balanced performance in all of the characteristics and can be applied to all the functional layer substrates in the present invention.

  Examples of such polyester include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polypropylene naphthalate. Polyethylene terephthalate is most preferable in terms of performance and cost. Moreover, what mixed 2 or more types of polyester may be sufficient. Further, it may be a polyester in which these and other dicarboxylic acid components or diol components are copolymerized. In this case, in the film in which the crystal orientation is completed, the crystallinity is preferably 25% or more, more preferably Is preferably 30% or more, more preferably 35% or more. When the crystallinity is less than 25%, dimensional stability and mechanical strength tend to be insufficient. The degree of crystallinity can be measured by a Raman spectrum analysis method.

  When the above-described polyester is used, its intrinsic viscosity (measured in o-chlorophenol at 25 ° C. according to JIS K7367) is preferably 0.4 to 1.2 dl / g, more preferably 0.5 to 0.8 dl / g.

  The transparent substrate used in the present invention may be a composite film having a laminated structure of two or more layers. As the composite film, for example, a composite film that is substantially free of particles in the inner layer portion and provided with a layer containing particles in the surface layer portion, has particles in the inner layer portion, and has fine particles in the surface layer portion. The laminated body film etc. which were contained are mentioned. Further, the composite film may be a chemically different polymer or an identical polymer in the inner layer portion and the surface layer portion. However, when applying particles or the like, it is necessary to stop to such an extent that the transparency is not affected.

  When polyester is used as the transparent substrate in the present invention, the film is crystallized by biaxial stretching from the viewpoint of ensuring sufficient thermal stability, particularly dimensional stability and mechanical strength, and improving flatness. It is preferable that Here, the crystal orientation by biaxial stretching means that the thermoplastic resin film before unstretched, that is, before the completion of crystal orientation is preferably stretched about 2.5 to 5 times in the longitudinal direction and the width direction, respectively. Thereafter, the crystal orientation is completed by heat treatment, and it indicates a biaxial orientation pattern by wide-angle X-ray diffraction.

  Although the thickness of the transparent base material used by this invention is suitably selected according to the use used, from points, such as mechanical strength and handling property, Preferably it is 10-500 micrometers, More preferably, it is 20-300 micrometers. .

  The transparent substrate of the present invention may contain various additives, resin compositions, cross-linking agents and the like within a range that does not impair the effects of the present invention, particularly optical properties. For example, antioxidants, heat stabilizers, ultraviolet absorbers, organic and inorganic particles (for example, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, Metal fine powders, etc.), pigments, dyes, antistatic agents, nucleating agents, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins, epoxy resins, urea resins, phenol resins, silicone resins, rubber resins , Wax composition, melamine crosslinking agent, oxazoline crosslinking agent, methylolated, alkylolized urea crosslinking agent, acrylamide, polyamide, epoxy resin, isocyanate compound, aziridine compound, various silane coupling agents, various titanates Or the like can be mentioned a coupling agent.

  The transparent base material used in the present invention preferably has a total light transmittance of 90% or more and a haze of 1.5% or less. By applying such a material, the visibility and sharpness of the image can be improved. Can do.

  Further, the transparent substrate used in the present invention preferably has a transmission b value of 1.5 or less. If the transmission b value exceeds 1.5, the transparent base material itself appears slightly yellowish, which may impair the sharpness of the image.

The b value is a color specification method determined by the International Commission on Illumination (CIE). The b value represents saturation. If the b value is a positive sign, it is a yellow hue, and if it is a negative sign. Represents a blue hue. Further, the larger the absolute value, the larger the saturation of the color, and the brighter the color, and the smaller the absolute value, the smaller the saturation. When it is 0, it indicates an achromatic color. For example, colored pigments, organic pigments, dyes, and the like can be used as the pigments that can be realized by adding pigments, but because of excellent weather resistance, cadmium red, red rose, molybdenum red, Chrome Vermilion, Sankachrome, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine Blue, Bitumen Blue, Berlin Blue, Milori Blue, Cobalt Blue, Cerulean Blue, Cobalt Silica Blue, Cobalt Zinc Blue, Manganese Organic pigments such as violet, mineral violet, and cobalt violet are preferably used.
The transparent substrate used in the present invention is a transparent substrate having a primer layer (easy-adhesive layer, undercoat layer) for enhancing the adhesion (adhesive strength) to the conductive layer, the resin layer, or the functional layer described above. It is preferable that
(Transparent substrate)
The transparent substrate in the present invention imparts mechanical strength to the plasma display panel body, and an inorganic compound molded product or a transparent organic polymer molded product is used.

  As the inorganic compound molded article, preferably, glass, tempered or semi-tempered glass and the like are mentioned, and the thickness is usually in the range of 0.1 to 10 mm, more preferably 1 to 4 mm.

  The polymer molding may be transparent in the visible wavelength region, and specific examples thereof include polyethylene terephthalate (PET), polyethersulfone, polystyrene, polyethylene naphthalate, polyarylate, polyetheretherketone, polycarbonate. , Polypropylene, polyimide, triacetyl cellulose and the like. These transparent polymer molded products may be in the form of a plate (sheet) or a film as long as the main surface is smooth. When a sheet-like polymer molded product is used as a base material, since the base material is excellent in dimensional stability and mechanical strength, a transparent laminate excellent in dimensional stability and mechanical strength can be obtained. When it is required, it can be suitably used.

  In addition, since the transparent polymer film has flexibility and the functional layer can be continuously formed by a roll-to-roll method, when this is used, it is efficient and long. A laminate of functional layers can be produced over a large area. In this case, the thickness of the film is usually 10 to 250 μm. When the thickness of the film is less than 10 μm, the mechanical strength as a substrate is insufficient, and when the thickness exceeds 250 μm, the flexibility is insufficient, so that the film is not suitable for being wound with a roll.

  In the present invention, the mechanical strength can be obtained by using the glass which is a transparent substrate, but even when the glass is not used, the air gap with the plasma display panel is eliminated, so that the double image is eliminated. Because of the advantages, the present invention may or may not use a transparent substrate.

(Configuration of display filter)
The display filter of the present invention is a laminate in which the plurality of layers described above are laminated. Although the structural example is enumerated concretely, this invention is not limited to these. In the following configuration example, the layer on the left side is installed on the display so as to be on the viewing side.
(1) Hard coat layer + conductive layer + transparent substrate + ultraviolet blocking layer + color tone correction layer + near infrared blocking layer + adhesive layer + transparent substrate (2) Antireflection layer + hard coat layer + conductive layer + transparent substrate + UV blocking layer + color tone correction layer + near infrared blocking layer + adhesive layer + transparent substrate (3) Hard coat layer + conductive layer + transparent substrate + UV blocking layer + near infrared blocking layer + color correction layer + transparent substrate (4) Anti-reflective layer + hard coat layer + conductive layer + transparent substrate + UV blocking layer + near infrared blocking layer + color tone correction layer + transparent substrate (5) hard coat layer + conductive layer + transparent substrate + UV blocking layer + color tone correction Layer + near infrared blocking layer + adhesive layer (6) antireflection layer + hard coat layer + conductive layer + transparent substrate + ultraviolet blocking layer + color correction layer + near infrared blocking layer + adhesive layer (7) hard coat layer + conductive Layer + transparent substrate + UV blocking layer + near infrared blocking layer + color correction + Adhesive layer (8) anti-reflection layer + a hard coat layer + conductive layer + the transparent substrate + ultraviolet blocking layer + a near infrared ray blocking layer + color correction layer + adhesive layer

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Evaluation methods)
(1) Measurement of centerline average roughness Ra of resin layer Based on the method of JIS B0601-1982, surface roughness measuring instrument SE-3400 (Kosaka Co., Ltd.) was calculated based on the method of JIS B0601-1982. Measured using a laboratory.

About each sample, it measured about five or more arbitrary places from one filter of 20 cm x 20 cm size, and made the average value the value of Ra of the resin layer of the filter sample for a display, and the value of uneven | corrugated average space | interval Sm of a resin layer. In the measurement, the moving direction of the measuring needle was set so as to be parallel to the thin line of the conductive mesh and pass through the approximate center of the opening of the conductive mesh.
·Measurement condition:
Feeding speed: 0.5mm / S
Cut-off value λc;
When Ra is 100 nm or less, λc = 0.25 mm
When Ra is greater than 100 nm and less than or equal to 2000 nm, λc = 0.8 mm
Evaluation length: 8mm
In the measurement, first, measurement is performed at a cutoff value (λc) of 0.25 mm. As a result, if Ra is 100 nm, the value is adopted, and if Ra exceeds 100 nm, measurement is performed with a cutoff value (λc) of 0.8 mm, and the measurement result is adopted.
(2) Measurement of unevenness average interval Sm of resin layer According to the method of JIS B0601-1982, surface roughness measuring instrument SE-3400 (manufactured by Kosaka Laboratory Co., Ltd.) It measured using.

About each sample, it measured about five or more arbitrary places from one filter of 20 cm x 20 cm size, and made the average value the value of the uneven | corrugated average space | interval Sm of the resin layer of the filter sample for a display. In the measurement, the moving direction of the measuring needle was set so as to be parallel to the thin line of the conductive mesh and pass through the approximate center of the opening of the conductive mesh.
(3) Measurement of conductive mesh thickness A sample cross section was cut out with a microtome, and the cross section was observed with an electrolytic emission scanning electron microscope (Hitachi S-800, acceleration voltage 26 kV, observation magnification 3000 times). The thickness of the conductive mesh was measured.

About each Example and the comparative example, it measured about five arbitrary places from one sample of 20 cm x 20 cm size, and made the average value the thickness of the electroconductive mesh.
(4) Measurement of line width and pitch of conductive mesh Surface observation was performed at a magnification of 450 times using a KEYENCE digital microscope (VHX-200). Using the length measurement function, the pitch of the grid-like conductive mesh was measured.
About each Example and the comparative example, it measured about arbitrary 25 places from one sample of 20 cm x 20 cm size, and made the average value the line | wire width and pitch of the electroconductive mesh. Note that the pitch of the conductive mesh is a distance between the centers of gravity of an opening having a mesh structure and an adjacent opening sharing one side with the opening.
(5) Viscosity measurement Using a Brookfield digital rheometer (DV-E), the spindle was set at LV1 and the rotation speed was set at 100 rpm, and the viscosity at 23 ° C. was measured. Each sample was measured 10 times, and the average value was taken as the viscosity of the hard coat layer paint.
(6) Refractive index measurement The raw material coating material of the layer used as a measuring object is apply | coated using a spin coater so that a dry film thickness may be set to 0.1 micrometer on a silicon wafer. Next, using Inert Oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.), the film is obtained by heat curing at 130 ° C. for 1 minute (curing conditions for the low refractive index layer). About the formed film, the refractive index in 633 nm is measured with a phase difference measuring apparatus (Nikon Co., Ltd. product: NPDM-1000).
(7) Measurement of the total thickness (Hr) of the resin layer For each of the examples and comparative examples, 5 arbitrary openings are selected from one sample of 20 cm × 20 cm size, and the sample cross section is cut out with a microtome. The distance from the transparent substrate at the lowest part of the resin layer to the surface of the resin layer was measured with an electrolytic emission scanning electron microscope (S-800 manufactured by Hitachi, Ltd., acceleration voltage 15 kV, observation magnification 2000 times). To average.
(8) Measurement of lamination thickness of resin layer The thickness of a relatively thin layer such as an antireflection layer in the structure of the resin layer is measured as follows. A cross section of the display filter sample is observed with a transmission electron microscope (H-7100FA type, manufactured by Hitachi) at an acceleration voltage of 100 kV. In the case of a filter using a glass substrate, it is peeled off from the glass for evaluation. Sample preparation uses an ultrathin section method. Observe at a magnification of 100,000 times and measure the thickness of each layer.
(9) Measurement of luminous transmittance With respect to the filter sample for display, using a spectrophotometer (manufactured by Shimadzu Corporation, UV3150PC), the transmittance with respect to incident light from the observer side (resin layer side) has a wavelength of 300 to 1300 nm. Measured in the range, the luminous transmittance in the visible light wavelength region (380-780 nm) is obtained.
(10) Evaluation of reflection The filter sample for display is placed on black paper (AC Card # 300 manufactured by Oji Specialty Paper Co., Ltd.) with the viewing surface side (resin layer side) facing up, and the four corners are transparent tape Secure with. Place the obtained sample in a dark room at a location 50 cm above the filter sample with a three-wavelength fluorescent lamp (National Parrook, three-wavelength daylight white (FL 15EX-N 15W)). The viewing surface of the filter is visually observed from a distance of 30 cm in front, and the sharpness of the contour of the fluorescent lamp image reflected on the viewing surface of the filter is evaluated.
・ The outline of the reflected image is unclear: ○
・ The outline of the reflected image is slightly blurred: △
-The outline of the reflected image is clearly visible: ×
Evaluation is performed by five people, evaluating one filter for each level, and adopting the most frequent determination result. If there are two determination results with the highest frequency, the worse evaluation result is adopted (if there are two determination results with the highest frequency, “◯” and “△”, “△”, “△” and “×” ”Is judged as“ × ”, and“ ○ ”and“ x ”are judged as“ × ”.)
(11) Evaluation of transmitted image clarity The adhesive layer side of the display filter sample is attached to a glass plate having a thickness of 2.5 mm. This sample is applied to a plasma TV (TH-42PX500, manufactured by Matsushita Electric Industrial Co., Ltd., but with a genuine filter removed) so that the glass side faces the plasma display panel. Install the panel surface and the filter viewing surface (resin layer) parallel to each other at a position where the distance to the outermost surface (resin layer outermost surface) of the filter is 20 mm. Display the pattern image. The pattern image is visually evaluated from a position obliquely 45 ° in the horizontal direction through the filter to determine the clarity of the transmitted image. Observation is performed at a distance of 30 cm from the position of 45 ° obliquely in the horizontal direction of the viewing surface of the filter. This evaluation method of observing from 45 ° obliquely in the horizontal direction is a method of more rigorously evaluating the transmitted image clarity than the method of observing from the front (90 °).
・ Transparent images are clearly visible: ○
・ Transmitted image is slightly blurred: △
・ Transparent image is blurred: ×
Evaluation is performed by five people, evaluating one filter for each level, and adopting the most frequent determination result. If there are two determination results with the highest frequency, the worse evaluation result is adopted (if there are two determination results with the highest frequency, “◯” and “△”, “△”, “△” and “×” ”Is judged as“ × ”, and“ ○ ”and“ x ”are judged as“ × ”.)
(12) Evaluation of defect concealment property A display filter sample (20 cm × 20 cm) is placed on a black paper (AC card # 300 manufactured by Oji Specialty Paper Co., Ltd.) with the viewing surface side (resin layer side) facing up. paste. Place the obtained sample in a dark room at a location 200 cm above the filter sample with a three-wavelength fluorescent lamp (National Parrook, three-wavelength daylight white (FL 15EX-N 15W)). The viewing surface of the filter is visually observed from a distance of 30 cm in front, and the point defects on the surface of the filter viewing surface are evaluated. Evaluation is carried out on 20 samples.
・ Number of point defects: 0/20: ○
-Number of point defects: 1-2 / 20 sheets: [Delta]
-Number of point defects: 3/20 or more: ×
Evaluation is performed by five people, evaluating one filter for each level, and adopting the most frequent determination result. If there are two determination results with the highest frequency, the worse evaluation result is adopted (if there are two determination results with the highest frequency, “◯” and “△”, “△”, “△” and “×” ”Is judged as“ × ”, and“ ○ ”and“ x ”are judged as“ × ”.)
(13) Evaluation of surface quality A filter sample for display (20 cm x 20 cm) is pasted on black paper (AC Card # 300 manufactured by Oji Specialty Paper Co., Ltd.) with the viewing surface side (resin layer side) facing up. wear. Place the obtained sample in a dark room at a location 200 cm above the filter sample with a three-wavelength fluorescent lamp (National Parrook, three-wavelength daylight white (FL 15EX-N 15W)). The filter viewing surface is visually observed from a distance of 30 cm in front, and the quality (roughness) of the filter viewing surface is visually evaluated.
-The surface shape is uniform and no rough feeling is seen: ○
・ Surface shape is uniform but slightly rough: △
・ Sparsely convex and rough. ： ×
Evaluation is performed by five people, evaluating one filter for each level, and adopting the most frequent determination result. If there are two determination results with the highest frequency, the worse evaluation result is adopted (if there are two determination results with the highest frequency, “◯” and “△”, “△”, “△” and “×” ”Is judged as“ × ”, and“ ○ ”and“ x ”are judged as“ × ”.)
<Fine particles (A)>
In this example, the following fine particles (A) were used.
Fine particles A1; acrylic particles having an average particle diameter of 6 μm (Chemisnow (registered trademark) MR series manufactured by Soken Chemical)
Fine particle A2: acrylic particle having an average particle diameter of 3 μm (Chemisnow (registered trademark) MX series manufactured by Soken Chemical)
Fine particles A3; acrylic particles having an average particle size of 5 μm (Chemisnow (registered trademark) MX series manufactured by Soken Chemical)
Fine particles A4; acrylic particles having an average particle diameter of 10 μm (Chemisnow (registered trademark) MX series, manufactured by Soken Chemical)
Fine particles A5; silica-based particles having an average particle size of 0.5 μm (Sea Catalysts (registered trademark) KE-P50 manufactured by Nippon Shokubai)
The average particle size of the fine particles (A) is measured using a laser diffraction particle size measuring device “MASTERSIZER2000 (manufactured by MALVERN)”.
<Ultrafine particles (B)>
In this example, the following ultrafine particles (B) were used.
Ultrafine particles B1; silica-based ultrafine particles having an average particle diameter of 12 nm (organosilica sol (registered trademark) MEK-ST manufactured by Nissan Chemical Industries)
Ultrafine particle B2; silica-based ultrafine particle having an average particle diameter of 50 nm (organosilica sol (registered trademark) IPA-ST-L manufactured by Nissan Chemical Industries)
Ultrafine particle B3; silica-based ultrafine particle having an average particle diameter of 100 nm (organosilica sol (registered trademark) IPA-ST-ZL manufactured by Nissan Chemical Industries)
The average particle size of the ultrafine particles (B) was obtained by photographing the silica sol at a magnification of 100,000 to 500,000 times using a transmission electron microscope (H-7100FA type manufactured by Hitachi, Ltd.). In the obtained photographic projection, the maximum diameters of arbitrary 50 particles are measured and averaged. The photographing magnification is appropriately selected according to the average particle diameter of the ultrafine particles (B).
[Example 1]
A display filter was prepared as follows.
<Preparation of conductive layer>
Using a catalyst ink made of a palladium colloid-containing paste on one side of an optical polyester film (Lumirror (registered trademark) manufactured by Toray Industries, Inc., thickness 100 μm), gravure printing is performed on a grid mesh pattern, which is electroless copper A conductive mesh was produced by immersing in a plating solution, performing electroless copper plating, subsequently performing electrolytic copper plating, and further performing electrolytic plating of a Ni-Sn alloy. This conductive mesh had a line width of 20 μm, a pitch of 300 μm, a thickness of 5 μm, and an aperture ratio of 87%.
<Preparation of hard coat layer>
A coating liquid containing 35 parts by mass of dipentaerythritol hexaacrylate, 12 parts by mass of N-vinylpyrrolidone, 3 parts by mass of methyl methacrylate, and 50 parts by mass of methyl ethyl ketone was prepared. 5% by mass of the fine particles (fine particles A1) are added to all components (excluding the solvent) of the hard coat layer, and the silica fine particles (ultrafine particles B1) having an average particle size of 12 nm as ultrafine particles (B). ) In terms of solid content was added in an amount of 20% by mass with respect to all the components of the hard coat layer (excluding the solvent) to prepare a paint for the hard coat layer. The viscosity of the coating liquid was 6 mPa · s.

This paint was applied onto the conductive mesh of the conductive layer obtained above using a micro gravure coater, dried at 80 ° C., cured by irradiation with ultraviolet rays 1.0 J / cm ² , and hard coat layer Formed. The thickness (Hr) of the hard coat layer was 6.1 μm.
<Preparation of near-infrared blocking layer having Ne cut function>
As a near-infrared absorbing dye, 14.5 parts by mass of KAYASORB (registered trademark) IRG-050 manufactured by Nippon Kayaku Co., Ltd., 8 parts by mass of eXcolor (registered trademark) IR-10A manufactured by Nippon Shokubai Co., Ltd. As an organic dye having a main absorption peak at 593 nm, TAP-2 manufactured by Yamada Chemical Industry Co., Ltd. was stirred and mixed in 2.9 parts by mass and 2000 parts by mass of methyl ethyl ketone and dissolved. This solution was stirred and mixed with 2000 parts by mass of Hals Hybrid (registered trademark) IR-G205 (solid content 29% solution) manufactured by Nippon Shokubai Co., Ltd. as a transparent polymer resin binder solution to prepare a paint.

The above-mentioned paint was applied to the surface of the optical polyester film opposite to the side on which the hard coat layer was formed using a die coater and dried at 120 ° C. to prepare a near-infrared shielding layer having a thickness of 10 μm.
<Preparation of color correction layer>
An organic color correction dye was contained in the acrylic transparent adhesive. The amount of dye added at each level was adjusted so that the final luminous transmittance of the filter was 40%. This pressure-sensitive adhesive was laminated on the near infrared ray blocking layer.
[Examples 2-8, Comparative Examples 1-4]
Display in the same manner as in Example 1 except that the types of fine particles (A) and ultrafine particles (B) added to the hard coat layer, the addition amount, and the thickness (Hr) of the hard coat layer are changed as shown in Table 1. A filter was prepared.
[Examples 9 to 13, Comparative Example 5]
Using the following conductive layer, except that the type of fine particles (A) and ultrafine particles (B) added to the hard coat layer, the addition amount, and the thickness (Hr) of the hard coat layer are changed as shown in Table 1. A display filter was produced in the same manner as in Example 1.
<Preparation of conductive layer>
On one side of an optical polyester film (Lumirror (registered trademark) manufactured by Toray Industries, Inc., thickness 100 μm), a nickel layer (thickness 0.02 μm) by vacuum deposition under a vacuum of 3 × 10 ⁻³ Pa at room temperature. Formed. Furthermore, a copper layer (thickness 3 μm) was formed thereon by a vacuum vapor deposition method at a room temperature and under a vacuum of 3 × 10 ⁻³ Pa. Thereafter, a photoresist film was laminated on the surface on the copper layer side, and the photoresist film was exposed and developed through a mask having a lattice mesh pattern, and then subjected to an etching treatment to produce a conductive mesh. Further, the conductive mesh was subjected to blackening treatment (oxidation treatment). This conductive mesh had a line width of 13 μm, a pitch of 300 μm, a thickness of 3 μm, and an aperture ratio of 89%.
[Examples 14 and 15]
A display filter of Example 14 was produced in the same manner as in Example 1 except that the following antireflection layer was laminated on the hard coat layer of Example 1.

Further, a display filter of Example 15 was produced in the same manner as in Example 6 except that the following antireflection layer was laminated on the hard coat layer of Example 9.
<Preparation of antireflection layer>
A commercially available high refractive index / antistatic coating (OPSR (registered trademark) TU4005 made by JSR) was diluted with isopropyl alcohol to a solid content concentration of 8% on the hard coat layer forming surface, and then applied with a micro gravure coater at 120 ° C. After drying for 1 minute, ultraviolet rays 1.0 J / cm ² were irradiated and cured to form a high refractive index layer having a refractive index of 1.65 and a thickness of 135 nm on the hard coat layer.

Next, the following coating material for the low refractive index layer was applied to the high refractive index layer forming surface with a micro gravure coater. Next, the film was dried and cured at 130 ° C. for 1 minute to form a low refractive index layer having a refractive index of 1.36 and a thickness of 90 nm on the high refractive index layer, thereby preparing an antireflection layer.
<Preparation of coating material for low refractive index layer>
95.2 parts by mass of methyltrimethoxysilane and 65.4 parts by mass of trifluoropropyltrimethoxysilane were dissolved in 300 parts by mass of propylene glycol monomethyl ether and 100 parts by mass of isopropanol.

  In this solution, a silica fine particle dispersion having a cavity inside the outer shell having a number average particle diameter of 50 nm (isopropanol dispersion type, solid content concentration 20.5%, manufactured by Catalyst Kasei Kogyo Co., Ltd.) 297.9 parts by mass, water 54 masses And 1.8 parts by mass of formic acid were added dropwise with stirring so that the reaction temperature did not exceed 30 ° C.

  After the dropwise addition, the obtained solution was heated at a bath temperature of 40 ° C. for 2 hours, and then the solution was heated at a bath temperature of 85 ° C. for 2 hours. The internal temperature was raised to 80 ° C. and heated for 1.5 hours. Until the polymer solution was obtained.

In the obtained polymer solution, 4.8 parts by mass of aluminum tris (acetyl acetate) (trade name: Aluminum Chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.) as an aluminum-based curing agent is dissolved in 125 parts by mass of methanol. Then, 1500 parts by mass of isopropanol and 250 parts by mass of propylene glycol monomethyl ether were added and stirred at room temperature for 2 hours to prepare a low refractive index paint.
[Comparative Example 6]
<Preparation of conductive layer>
As a transparent substrate, a copper foil (thickness: 10 μm) subjected to blackening on both sides was bonded to one side of an optical polyester film (Toray Lumirror (registered trademark), thickness: 100 μm) with an adhesive. A photoresist film was laminated on the surface of the copper foil, the photoresist film was exposed and developed through a mask having a lattice mesh pattern, and then subjected to an etching treatment to produce a conductive mesh. The obtained conductive mesh had a line width of 12 μm, a pitch of 100 μm, a thickness of 10 μm, and an aperture ratio of 75%.
<Preparation of hard coat layer>
A hard coat layer was applied and formed in the same manner as in Example 1 on the conductive mesh of the conductive layer obtained above. The thickness (Hr) of the obtained hard coat layer was 11.7 μm.
<Evaluation>
About each sample produced above, center line average roughness Ra of the resin layer, unevenness average interval Sm of the resin layer, reflection prevention, transmitted image clarity, defect concealment, and surface quality were evaluated. The results are shown in Table 1.

  From Table 1, in the examples of the present invention, the resin layer (hard coat layer) contains fine particles (A) and ultrafine particles (B), and the center line average roughness Ra of the resin layer is 100 nm or more, It can be seen that it is excellent in all of the anti-reflection, clearness of transmitted image, concealment of defects, and surface quality.

On the other hand, in Comparative Example 1, since the resin layer (hard coat layer) contains the fine particles (A) but does not contain the ultrafine particles (B), the transmitted image clarity was lowered.
In Comparative Example 2, since the average particle diameter of the fine particles (A) contained in the resin layer (hard coat layer) is less than 1 μm, the center line average roughness Ra of the resin layer is reduced, and the reflection preventing property and defects are reduced. Concealment was reduced.
In Comparative Example 3, since the resin layer (hard coat layer) contains the ultrafine particles (B) but does not contain the fine particles (A), the center line average roughness Ra of the resin layer becomes small, and the reflection occurs. Preventive properties and defect concealment properties were reduced.

  In Comparative Example 4, the resin layer (hard coat layer) contains fine particles (A) and ultrafine particles (B), but the thickness (Hr) of the resin layer is large, and the center line average roughness Ra of the resin layer is 100 nm. The anti-reflection effect was reduced.

  Comparative Example 5 contains fine particles (A), but because the average particle size of the ultrafine particles (B) was as large as 500 nm, the transmitted image clarity was reduced.

  In Comparative Example 6, since the thickness of the conductive mesh is as large as 10 μm, coating streaks and coating unevenness occur on the coated surface due to the deterioration of the coating property of the resin layer (hard coat layer), and an evaluation sample is obtained. I couldn't.

Schematic sectional view of an example of a resin layer containing fine particles (A) and ultrafine particles (B) of the present invention Schematic cross-sectional view of a comparative resin layer containing only fine particles (A)

Explanation of symbols

1 Base material 2 Conductive mesh 3 Resin layer 4 Fine particles (A)
5 Ultrafine particles (B)
Hr Resin layer thickness F Flat part

Claims (6)

A display filter having a conductive layer containing a conductive mesh on a transparent substrate, and a resin layer laminated on the conductive layer,
The thickness of the conductive mesh is 8 μm or less,
The resin layer contains particles (A) having an average particle size of 1 to 20 μm and particles (B) having an average particle size of 300 nm or less, and the center line average roughness Ra of the resin layer is 100 nm or more. This is a display filter.   The display filter according to claim 1, wherein the resin layer has a single layer structure or a laminated structure of two or more layers including at least a hard coat layer.   The display-use filter according to claim 2, wherein the hard coat layer contains the particles (A) and the particles (B).   The display-use filter according to any one of claims 1 to 3, wherein the uneven average interval Sm of the resin layer is in a range of 30 to 120 µm.   The display filter according to claim 1, wherein the resin layer has a laminated structure including a hard coat layer and an antireflection layer.   Furthermore, it has a functional layer which has a function layer which has at least 1 function chosen from the group which consists of a near-infrared shielding function, a color tone correction function, a ultraviolet-ray shielding function, and a Ne cut function. filter.

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