JP2010151887A - Filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive filter for display that is shiny and transparent and has high reflection preventing property and foreign substance masking property. <P>SOLUTION: This filter for display has a conductive mesh having an uneven structure on a substrate, and a hard coat layer containing particles is stacked on the conductive mesh. The thickness (Et) of the conductive mesh is smaller than 3 μm, the thickness (Ht) of the hard coat layer is 3 μm or greater, and the average particle diameter of the particles is 60% or more to thickness (Ht), 100%, of the hard coat layer. The content of the particles is 3-18 mass% to the all components, 100 mass%, of the hard coat layer, and the hard coat layer has an uneven structure originating from that of the conductive mesh. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a display filter mounted on the screen of a display device such as a CRT, an organic EL display, a liquid crystal display, and a plasma display, and more specifically, for a display having glossiness and transparency and preventing reflection. Regarding filters.

  One of the performances required for a display is prevention of reflection of external light such as a fluorescent lamp. As a conventional method for preventing reflection, it is generally known to provide an antiglare layer containing particles on a substrate. If the effect of preventing the reflection is to be improved, there is a problem that the glossiness and transparency of the display image are lowered.

  On the other hand, thin and large-screen plasma displays and liquid crystal displays with a screen size of 40 inches or more, and even 50 inches or more are popular. These thin and large-screen displays are not only used for image viewing but also for interior decoration. Also plays a role as a figurine.

  In such a situation, the decrease in glossiness is a factor that greatly impairs the interior decoration due to the roughness of the screen when the display is turned off, as well as the reduction in image quality when the display is turned on. It was.

  Conventionally known filters for displays are optical functional films in which an antireflection layer or near infrared shielding layer is provided on a plastic film, and plastic films in which a conductive layer (electromagnetic wave shielding layer) is provided ( And an electromagnetic wave shielding film) are laminated via an adhesive layer.

  In recent years, with the reduction in the price of displays, the price of filters for displays has been inevitably reduced. The price can be reduced by using only one plastic film for the display filter composed of two films as described above. In order to further reduce the cost, it is effective to reduce the thickness of the conductive mesh (for example, to reduce the thickness of the conductive mesh to less than 3 μm).

  As one aspect of the above-described display filter comprising a single plastic film, a display in which a conductive layer is provided on a plastic film and functional layers such as a hard coat layer, an antireflection layer, and an antiglare layer are laminated thereon. Filters have been proposed (Patent Documents 1 to 3).

  Patent Documents 1 to 3 described above provide an antiglare layer containing particles on a conductive mesh.

Also proposed is a display filter that has an anti-glare effect (prevention of reflection of fluorescent lamps) by providing a hard coat layer having an uneven shape corresponding to the uneven shape of the conductive mesh on the conductive mesh. (Patent Documents 4 and 5).
JP 2007-140282 A JP 2007-243158 A WO2008 / 029709 JP 2008-216734 A JP 2008-216770 A

  However, the configurations described in Patent Documents 1 to 3 are such that an antiglare layer containing particles that are conventionally known is laminated on a conductive mesh, and only glare and reflection are caused. It imparts the original effect of the antiglare layer for the purpose of prevention.

  As described above, the antiglare layer containing particles has a problem that the glossiness and transparency of the display image are lowered if the effect of preventing reflection is to be improved. The same problem may occur in the antiglare layer formed.

  Patent Documents 4 and 5 describe that the hard coat layer laminated on the conductive mesh has an uneven shape corresponding to the uneven shape of the conductive mesh. That is, Patent Documents 4 and 5 describe a hard coat layer having an uneven structure derived from an uneven structure of a conductive mesh.

  However, Patent Documents 4 and 5 do not describe that a hard coat layer having a thickness of 3 μm or more is formed on a conductive mesh having a thickness of less than 3 μm.

  A hard coat layer is applied and formed on a conductive mesh with a thickness of less than 3 μm, and the concave / convex shape is sufficient to prevent the reflection of the hard coat layer and the effect of concealing foreign matter, which will be described later. In order to form a concavo-convex structure derived from the structure, the thickness of the hard coat layer needs to be less than 3 μm, and when the thickness of the hard coat layer is less than 3 μm, there is a problem that the hard coat property is insufficient. Moreover, the foreign substance concealment property described below may not be sufficiently exhibited when the thickness of the hard coat layer laminated on the conductive mesh is 3 μm.

  Further, as in Patent Documents 1 to 5, a conductive mesh is disposed on the viewing side (viewer side) from the base material (plastic film), and a thin film such as a hard coat layer or an antireflection layer is formed on the conductive mesh. However, the display filter having only the functional layer has a problem that minute foreign matters considered to be caused by the conductive mesh are easily noticeable. That is, the so-called foreign matter concealing property, which makes it difficult to see minute foreign matters that are considered to occur during the production of the conductive mesh, is one of the important characteristics.

  SUMMARY OF THE INVENTION In view of the above-described problems associated with the prior art, the present invention has an object to provide a low-cost display filter that has glossiness and transparency and prevents reflection, and the present invention. An object of the present invention is to provide a display filter that suppresses the visibility of minute foreign matter (increasing foreign matter concealment) that occurs when a conductive mesh is arranged on the viewing side from the base material. An object of the present invention is to provide a display filter capable of enhancing the function for interior decoration of a thin large-screen display.

The above object of the present invention has been basically achieved by the following invention.
1) A display filter having a conductive mesh having a concavo-convex structure on a substrate, and a hard coat layer containing particles laminated on the conductive mesh,
The conductive mesh has a thickness (Et) of less than 3 μm,
The hard coat layer has a thickness (Ht) of 3 μm or more,
The average particle size of the particles is 60% or more with respect to 100% of the thickness (Ht) of the hard coat layer,
Containing 3% by mass to 18% by mass of the particles with respect to 100% by mass of all components of the hard coat layer,
The display-use filter, wherein the hard coat layer has an uneven structure derived from an uneven structure of a conductive mesh.
2) The display filter as described in 1) above, wherein a height difference (D) of the uneven structure formed on the hard coat layer is 0.5 μm to 5 μm.
3) The display filter according to 1) or 2), wherein a center line average roughness Ra of the hard coat layer is 150 nm or more and less than 500 nm.
4) The display filter according to any one of 1) to 3), wherein an average particle diameter of the particles is 3 μm to 20 μm.
5 The display according to any one of 1) to 4) above, wherein a ratio (Ht / Et) of the thickness (Ht) of the hard coat layer to the thickness (Et) of the conductive mesh is 1.5 or more. Filter.

  ADVANTAGE OF THE INVENTION According to this invention, the filter for a display which has glossiness and transparency, and was excellent in the prevention of a reflection, and the foreign material concealment property can be provided at low cost. Furthermore, the function for interior decoration can be enhanced by mounting the display filter of the present invention on a thin large screen display.

  The display filter of the present invention has a conductive mesh having a concavo-convex structure on a substrate, and has a hard coat layer containing particles on the conductive mesh. The hard coat layer is preferably laminated directly on the conductive mesh, and particularly preferably formed directly on the conductive mesh.

  It is important that the conductive mesh according to the present invention has a thickness (Et) of less than 3 μm. As a result, the price of the display filter can be reduced, and at the same time, the coating stability when the hard coat layer is formed is further improved. In addition, when the thickness (Et) of the conductive mesh is as small as less than 3 μm, the raw material cost for manufacturing the conductive mesh is naturally reduced, but the production speed and production stability in the manufacturing process are reduced. Is improved. Furthermore, a conductive mesh having a high-definition mesh pattern with a line width of less than 10 μm can be manufactured easily and stably.

  When a hard coat layer is laminated on a conductive mesh with a thickness of less than 3 μm, and a concavo-convex structure derived from the concavo-convex structure of the conductive mesh is formed on the hard coat layer, the anti-reflection effect and foreign substance concealment are fully manifested. In order to form such a concavo-convex structure, the thickness of the hard coat layer has conventionally been required to be less than 3 μm. However, the hard coat layer having a thickness of less than 3 μm has a problem that the hard coat property is insufficient. Moreover, in the hard coat layer having a thickness of less than 3 μm, there is a problem that the concealability of the fine foreign matter (making the fine foreign matter difficult to see) that is considered to have occurred during the production of the conductive mesh is not sufficiently exhibited.

  Therefore, even when a hard coat layer with a thickness of 3 μm or more is laminated on a conductive mesh with a thickness of less than 3 μm, we have intensively studied a hard coat layer that sufficiently exhibits reflection prevention and foreign substance concealment. The present invention has been achieved.

  That is, the present invention is a display filter having a conductive mesh having a concavo-convex structure on a substrate, and a hard coat layer containing particles laminated on the conductive mesh, the thickness of the conductive mesh (Et) is less than 3 μm, the thickness (Ht) of the hard coat layer is 3 μm or more, and the average particle diameter of the particles is 60% or more with respect to 100% of the thickness (Ht) of the hard coat layer, The particles are contained 3% by mass to 18% by mass with respect to 100% by mass of all components of the hard coat layer, and the hard coat layer has an uneven structure derived from the uneven structure of the conductive mesh.

(Hard coat layer)
In the hard coat layer according to the present invention, particles having an average particle size of 60% or more with respect to 100% of the thickness (Ht) of the hard coat layer are 3% by mass to 18% by mass with respect to 100% by mass of all components of the hard coat layer. %contains. When the hard coat layer having the above-described configuration is laminated on the conductive mesh having a thickness (Et) of less than 3 μm with a thickness of 3 μm or more, the hard coat layer has an uneven structure derived from the uneven structure of the conductive mesh. As a result, it is possible to obtain a hard coat layer that sufficiently exhibits a reflection preventing effect and a foreign matter concealing effect. When the average particle diameter of the particles contained in the hard coat layer is less than 60% with respect to 100% of the thickness (Ht) of the hard coat layer, the hard coat layer has a sufficient uneven structure derived from the uneven structure of the conductive mesh. Therefore, the effect of preventing reflection and the effect of concealing foreign matter are not sufficiently exhibited.

  The ratio of the average particle diameter (P) of the particles contained in the hard coat layer to the hard coat layer thickness (Ht) of 100%, that is, ((P / Ht) × 100) is 60% or more as described above. Although it is important that it is present, it is preferably 70% or more, more preferably 80% or more, and particularly preferably 90% or more. The upper limit of the ratio is preferably 200% or less, preferably 180% or less, more preferably 160% or less, and particularly preferably 150% or less.

  When the ratio ((P / Ht) × 100) is 60% or more, a concavo-convex structure derived from the concavo-convex structure of the conductive mesh is easily formed on the hard coat layer, and the reflection prevention property is improved. Shielding is improved. On the other hand, when it exceeds 200%, glossiness and transparency are lowered, and the clarity of the image on the display may be lowered, or the interior decoration may be lowered, which is not preferable.

  Specifically, the average particle size of the particles contained in the hard coat layer of the present invention is preferably 3 μm or more, more preferably 3.5 μm or more, further preferably 4 μm or more, and particularly preferably 5 μm or more. The upper limit of the average particle diameter of the particles is preferably 20 μm or less, more preferably 15 μm or less, further preferably 12 μm or less, and particularly preferably 10 μm or less.

  When the average particle size of the particles contained in the hard coat layer is 3 μm or more, a concavo-convex structure derived from the concavo-convex structure of the conductive mesh is easily formed on the hard coat layer, and reflection prevention and foreign matter shielding properties are improved. . On the other hand, when the average particle size of the particles contained in the hard coat layer is larger than 20 μm, the glossiness and transparency may be lowered, the sharpness of the display image may be lowered, and the interior decoration may be lowered. Absent.

  Here, the average particle diameter of the particles is a volume average and can be measured, for example, by a laser scattering method using a laser diffraction particle diameter measuring apparatus.

  As particles contained in the hard coat layer, known particles made of inorganic materials (inorganic particles) and particles made of organic materials (organic particles) can be used. Particles are preferably used. Examples of the inorganic particles include silica beads, and examples of the organic particles include plastic beads.

  Among the above plastic beads, those having excellent transparency are preferable. Specific examples include acrylic particles (polymethyl methacrylate, crosslinked polymethyl methacrylate, etc.), styrene particles (polystyrene, crosslinked polystyrene, etc.), acrylic Examples thereof include styrene-based particles (such as methyl methacrylate-styrene copolymer), urethane-based particles (such as urethane acrylate), and melamine-based particles. In the present invention, acrylic particles particularly excellent in transparency are preferably used.

  The shape of the particles used in the present invention is preferably spherical (true spherical, ellipsoidal, etc.), more preferably true spherical.

  The hard coat layer of the present invention contains 3% by mass to 18% by mass of the above particles with respect to 100% by mass of all components of the hard coat layer. When the content of the particles contained in the hard coat layer is less than 3% by mass with respect to 100% by mass of all components of the hard coat layer, the uneven structure derived from the conductive mesh is not sufficiently formed in the hard coat layer, The effect of preventing reflection and hiding foreign matter cannot be obtained. On the other hand, if it exceeds 18% by mass, the glossiness and the transparency are lowered, the image clarity of the display is lowered, and the interior decoration and the surface quality are lowered.

  In particular, particles having an average particle diameter of 60% or more with respect to 100% of the thickness (Ht) of the hard coat layer exceed 18% by mass with respect to 100% by mass of all components of the hard coat layer. When it is contained in the hard coat layer, convex portions formed by particles are also formed in the opening portions of the conductive mesh, and thus cannot be distinguished from the convex portions formed on the fine lines of the conductive mesh. That is, as a result of the formation of the concavo-convex structure as a whole, the glossiness and transparency are greatly reduced, and the image clarity, interior decoration, and surface quality of the display are significantly reduced.

  The content of particles in the hard coat layer is preferably 3.5% by mass or more, more preferably 4% by mass or more, and particularly preferably 4.5% by mass with respect to 100% by mass of all components of the hard coat layer. % Or more. The upper limit of the content of the particles is preferably 15% by mass or less, more preferably 12% by mass or less, and particularly preferably 10% by mass or less with respect to 100% by mass of all the components of the hard coat layer.

It is important that the thickness (Ht) of the hard coat layer according to the present invention is 3 μm or more. By setting the thickness of the hard coat layer to 3 μm or more, high hard coat properties can be obtained. Moreover, the foreign substance concealment property is further improved by setting the thickness of the hard coat layer on which the uneven structure derived from the uneven structure of the conductive mesh is 3 μm or more.
The hard coat property of the hard coat layer can be represented by pencil hardness defined by JIS K5600-5-4 (1999). In the hard coat layer according to the present invention, the pencil hardness is preferably H or higher, and more preferably 2H or higher. The upper limit is about 9H.

  The thickness of the hard coat layer according to the present invention is preferably 3.5 μm or more, preferably 4 μm or more, particularly preferably 4.5 μm or more, from the viewpoint of obtaining high hard coat properties and improving the foreign matter concealing property. . The upper limit of the thickness of the hard coat layer is preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. If the thickness of the hard coat layer exceeds 12 μm, curling is likely to occur, and it is difficult to form an uneven structure of a conductive mesh on the hard coat layer. In the present invention, the thickness of the hard coat layer means the thickness of the hard coat layer at the center of gravity of the opening of the conductive mesh, that is, the distance from the base material to the surface of the hard coat layer at the center of gravity of the opening of the conductive mesh. To do.

  Further, from the viewpoint of uniformly and stably coating and forming the hard coat layer on the conductive mesh and from the viewpoint of foreign matter concealment, the ratio of the thickness of the hard coat layer (Ht) to the thickness of the conductive mesh (Et). (Ht / Et) is preferably 1.5 or more, more preferably 1.8 or more, and particularly preferably 2.0 or more. The upper limit of the ratio (Ht / Et) is preferably 5.0 or less, more preferably 4.5 or less, and particularly preferably 4 or less, because an uneven structure of a conductive mesh is difficult to be formed on the hard coat layer if the upper limit is too large. 0 or less is preferable.

  In the present invention, the hard coat layer has a concavo-convex structure derived from the concavo-convex structure of the conductive mesh, that is, the concavo-convex structure of the conductive mesh, that is, the fine lines (convex portions) constituting the conductive mesh, and the fine lines and fine lines. It means that the convex part of the hard coat layer is formed on the fine line of the conductive mesh using the enclosed opening part (concave part), and the concave part of the hard coat layer is formed in the opening part of the conductive mesh.

  FIG. 1 is a schematic cross-sectional view showing an example of a state in which a hard coat layer is laminated on a conductive mesh. FIG. 1 shows a state in which a hard coat layer 3 containing particles 4 is laminated on a conductive mesh. In FIG. 1, a convex portion in the concavo-convex structure of the hard coat layer 3 is formed on the fine line (convex portion) 2 of the conductive mesh, and the hard coat is applied to the opening portion (between the fine line and the fine line) of the conductive mesh. A recess is formed in the concavo-convex structure of the layer 3. Reference numeral 1 denotes a base material.

  By forming the concavo-convex structure derived from the concavo-convex structure of the conductive mesh on the hard coat layer according to the present invention, even if the hard coat layer in the opening of the conductive mesh is relatively smooth, the outer surface of a fluorescent lamp, etc. Reflection of light is effectively prevented, and the hard coat layer in the opening is smoothed to provide gloss and transparency, display transparency of the display is good, and interior decoration and surface quality are improved. To do.

  The hard coat layer according to the present invention preferably has a center line average roughness Ra of 150 nm or more, more preferably 200 nm or more, and particularly preferably 210 nm or more. The upper limit of the center line average roughness Ra of the hard coat layer is preferably less than 500 nm, and more preferably less than 400 nm.

  In the present invention, it is preferable that the center line average roughness Ra of the hard coat layer formed with the concavo-convex structure derived from the concavo-convex structure of the conductive mesh is 150 nm or more because the effect of preventing reflection is enhanced. On the other hand, if the center line average roughness Ra of the hard coat layer is 500 nm or more, the glossiness and transparency may be lowered, the image clarity of the display may be lowered, and the interior decoration and surface quality may be lowered. It is not preferable.

Moreover, in the concavo-convex structure formed on the hard coat layer (the concavo-convex structure derived from the concavo-convex structure of the conductive mesh), the height difference (D) of the concavo-convex structure is preferably in the range of 0.5 to 5 μm.
The height difference (D) of the concavo-convex structure is a vertical distance between the vertex 5 of the convex portion of the hard coat layer and the lowest point 6 of the concave portion in FIG.

  As described above, when the height difference (D) of the concavo-convex structure formed on the hard coat layer (the concavo-convex structure derived from the concavo-convex structure of the conductive mesh) is 0.5 μm or more, the effect of preventing reflection and foreign matter concealment are achieved. Since an effect becomes high, it is preferable. The height difference (D) is preferably 0.6 μm or more. On the other hand, if the height difference (D) becomes too large, the glossiness and transparency may be lowered, and the image clarity of the display may be lowered or the interior decoration may be lowered. Therefore, the height difference (D) Is preferably 5 μm or less, more preferably 4 μm or less, and particularly preferably 3 μm or less.

  The vertex 5 of the convex portion in the hard coat layer is the vertex 5 on the straight line passing through the center of gravity of the opening of the conductive mesh and parallel to the thin line of the conductive mesh, and The lowest part of the recess is the lowest point 6. For example, in the case of a grid-like conductive mesh preferably used in the present invention, the apex 5 of the convex portion exists on each of the four sides surrounding the opening, and the height difference (D) also exists. For the height difference (D) of the structure, the largest value among them is adopted. In this way, the height difference (D) in one certain opening is obtained. By performing this operation on 10 arbitrarily selected openings and averaging, the height difference of the concavo-convex structure in the present invention ( D) is obtained.

  The height difference (D) of the concavo-convex structure can be performed using a laser microscope (for example, “VK-9700” manufactured by Keyence Corporation).

  The hard coat layer concerning this invention can contain a monomer, an oligomer, and a polymer as a resin component. Examples of such resin components include thermosetting resins or photocurable resins such as acrylic resins, silicon resins, melamine resins, urethane resins, alkyd resins, and fluorine resins. In view of the balance of productivity and the like, an acrylic resin is preferably applied.

  The hard coat layer containing an acrylic curable resin as a resin component can be obtained, for example, by curing a curable composition containing a polyfunctional (meth) acrylate compound. Here, the polyfunctional (meth) acrylate compound is a general term for a polyfunctional acrylate compound and a polyfunctional methacrylate compound. In the following description, “(meth)...” Has the same meaning as described above.

  Below, the hard-coat layer formed by hardening the curable composition containing said polyfunctional (meth) acrylate compound as one of the preferable aspects of a hard-coat layer is demonstrated.

  As the polyfunctional (meth) acrylate compound, a polyfunctional (meth) acrylate compound having 3 to 10 (meth) acryloyl groups in the molecule is preferably used.

  Specific examples of such polyfunctional (meth) acrylate compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Pentaerythritol 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 isophor Such as emissions diisocyanate urethane prepolymer and the like. These compounds can be used alone or in combination of two or more.

  The use ratio of the polyfunctional (meth) acrylate compound is preferably in the range of 30 to 90% by mass and in the range of 40 to 80% by mass with respect to 100% by mass of all components (excluding the organic solvent) of the curable composition. Is more preferable.

  In addition to the above polyfunctional (meth) acrylate compound, a compound having 1 to 2 ethylenically unsaturated groups in the molecule for the purpose of relaxing the rigidity of the hard coat layer or reducing shrinkage during curing. It is preferable to use together. Here, the ethylenically unsaturated group is, for example, a (meth) acryloyl group or a vinyl group.

  Examples of the compound having two ethylenically unsaturated groups in the molecule include the following compounds (a) to (f).

  (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.

  (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.

  (C) Polyhydric alcohol (meth) acrylic acid diesters: pentaerythritol di (meth) acrylate.

  (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.

  (E) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and two alcoholic hydroxyl group-containing compounds in advance with a hydroxyl group-containing (meth) acrylate further reacted with two ( Urethane (meth) acrylates having a (meth) acryloyloxy group.

  (F) Epoxy (meth) acrylates having two (meth) acryloyloxy groups in a molecule obtained by reacting a compound having two epoxy groups in the molecule with acrylic acid or methacrylic acid.

  Compounds having one ethylenically unsaturated group 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) acrylate, polypropylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N-vinylpyrrolidone, N-bi -3-methyl pyrrolidone, or the like can be used N- vinyl-5-methyl pyrrolidone. These compounds may be used alone or in combination.

  The ratio of the compound having 1 to 2 ethylenically unsaturated groups in one molecule is suitably in the range of 5 to 40% by mass with respect to 100% by mass of all components of the curable composition, The range of 10-40 mass% is preferable.

  Further, as a modifier of the hard coat layer, an antifoaming agent, a thickening agent, an antistatic agent, an organic polymer compound, an ultraviolet absorber, a light stabilizer, a dye, a pigment or a stabilizer can be used. Can be contained in the curable composition within a range that does not impair the reaction by active rays or heat.

  In the present invention, as a method of curing the curable composition, for example, a method of irradiating ultraviolet rays or an electron beam as an active ray, a high-temperature heating method, or the like can be used. It is preferable to add a photopolymerization initiator or a thermal polymerization initiator to the curable 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 amount of the photopolymerization initiator or thermal polymerization initiator used is suitably in the range of 0.01 to 10% by mass with respect to 100% by mass of all components of the curable composition. 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.

  In order to prevent thermal polymerization when forming the hard coat layer and dark reaction during storage, the curable composition further includes a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or 2,5-t-butyl hydroquinone. Can be added. The addition amount of the thermal polymerization inhibitor is preferably in the range of 0.005 to 0.05 mass% with respect to 100 mass% of all components of the curable composition.

  Examples of the actinic rays used for curing the curable composition include ultraviolet rays, electron beams and radiation (α rays, β rays, γ rays, etc.), and practically, ultraviolet rays are simple and preferable. 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 expensive and requires an operation under an inert gas, but it does not have to contain a photopolymerization initiator or a photosensitizer in the curable composition. It is advantageous.

  Examples of the heat source required for thermosetting the curable composition include a steam heater, an electric heater, an infrared heater, and a far infrared heater. The curable composition can be heated by blowing air or an inert gas heated to 140 ° C. or higher to the substrate or the coating film using these heat sources. Of these, heating with air at 200 ° C. or higher is preferable, and heating with nitrogen at 200 ° C. or higher is more preferable for increasing the curing rate.

  As a curing method for the curable composition, from the viewpoint of imparting high hardness to the hard coat layer and from the viewpoint of productivity, a method of irradiating actinic rays is preferable, and a method of irradiating ultraviolet rays is particularly preferable. Therefore, the hard coat layer of the present invention is preferably a hard coat layer cured by irradiating an ultraviolet curable curable composition with ultraviolet rays.

  The hard coat layer can also serve as a high refractive index layer described later by increasing the refractive index. Examples of means for increasing the refractive index of the hard coat layer include a method in which the hard coat layer contains metal oxide fine particles described later or a high refractive index organic compound described later.

(Antireflection layer)
In the present invention, an antireflection layer can be further laminated on the hard coat layer. Examples of the antireflection layer include a configuration in which a high refractive index layer and a low refractive index layer are laminated so that the low refractive index layer is the outermost surface, or a configuration having only a low refractive index layer.

The refractive index of the high refractive index layer is preferably in the range of 1.50 to 1.80, more preferably in the range of 1.55 to 1.75, and particularly preferably in the range of 1.60 to 1.70.
Further, the refractive index of the low refractive index layer (including the case of the laminated structure and the case of only the low refractive index layer) is preferably in the range of 1.20 to 1.45, and is preferably in the range of 1.25 to 1.40. More preferred.

  The high refractive index layer can be formed by curing a curable composition containing a polyfunctional (meth) acrylate compound in the same manner as the hard coat layer. The refractive index can be increased by incorporating metal oxide fine particles and / or a high refractive index organic compound in such a curable composition.

  Examples of the metal oxide fine particles include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, tin oxide-doped indium oxide (ITO), and antimony-doped tin oxide ( ATO), aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, and the like. These metal oxide fine particles may be used alone or in combination. The content of the metal oxide fine particles is preferably in the range of 30 to 90 mass with respect to 100 mass% of all components of the curable composition.

  Examples of the high refractive index organic compound include resins containing halogen atoms other than fluorine (for example, resins containing bromine atoms, resins containing chlorine atoms, resins containing iodine atoms), resins containing sulfur atoms, and resins containing nitrogen atoms. , A resin containing a phosphorus atom, a resin containing an aromatic ring (for example, a resin containing a fluorene skeleton, a resin containing a phenyl group, etc.). Among these, resins containing an aromatic ring are preferable, and examples thereof include acrylic resins having a 9,9-bisphenoxyfluorene skeleton and acrylic resins having a biphenyl group. The content of the high refractive index organic compound is preferably in the range of 10 to 70% by mass with respect to 100% by mass of all components of the curable composition.

  The thickness of the high refractive index layer is preferably in the range of 0.02 to 0.2 μm, and more preferably in the range of 0.05 to 0.15 μm.

  As a preferred embodiment of the low refractive index layer, a constitution mainly composed of a siloxane polymer bonded with silica-based fine particles can be employed. The term “bond” as used herein means a state in which the silica component of the silica-based fine particles and the siloxane polymer in the matrix are reacted and homogenized. A siloxane polymer formed by combining with silica-based fine particles once forms a silanol compound by a known hydrolysis reaction with a polyfunctional silane compound in a solvent and an acid catalyst in the presence of the silica-based fine particles. It can be obtained by utilizing the reaction.

  As such a polyfunctional silane compound, a polyfunctional fluorine-containing silane compound or a polyfunctional fluorine-free silane compound can be used. From the viewpoint of lowering the refractive index and antifouling properties, the polyfunctional fluorine-containing silane is used. A compound is preferably used.

  Examples of the polyfunctional fluorine-containing silane compound include trifluoromethylmethoxysilane, trifluoromethylethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, and tridecasilane. Trifunctional fluorine-containing silane compounds such as fluorooctyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltriethoxysilane, and bifunctional fluorine-containing silane compounds such as heptadecafluorodecylmethyldimethoxysilane However, from the viewpoint of surface hardness, trifluoromethylmethoxysilane, trifluoromethylethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropylto Silane is preferably used.

  Examples of the polyfunctional fluorine-free silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methyltrimethoxysilane, and methyltrimethoxysilane. Ethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Trifunctional silanes such as methoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxysilane Compound, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-amino Propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3-methacryloxypropyldimethoxy Bifunctional silane compounds such as silane and octadecylmethyldimethoxysilane, tetrafunctional silane compounds such as tetramethoxysilane and tetraethoxysilane, etc. There may be mentioned vinyltrimethoxysilane in terms of surface hardness, 3-methacryloxypropyl trimethoxy silane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane is preferably used.

  The silica-based fine particles are preferably silica-based fine particles having an average particle diameter of 1 nm to 200 nm, and silica-based fine particles having an average particle diameter of 1 nm to 70 nm are particularly preferably used. When the average particle diameter is less than 1 nm, the bond with the matrix material becomes insufficient and the hardness may be lowered. On the other hand, if the average particle diameter exceeds 200 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. The average particle size of the silica-based fine particles is a number average particle size as observed with a transmission electron microscope.

  As the silica-based fine particles, those having a cavity inside are particularly preferably used in order to reduce the refractive index.

  Examples of such silica-based fine particles having cavities therein include silica-based fine particles having a hollow portion surrounded by an outer shell, porous silica-based fine particles having a large number of hollow portions, and the like. Such silica fine particles having cavities therein can be produced, for example, by the method disclosed in Japanese Patent No. 3272111.

The volume occupied by cavities in the silica-based fine particles, that is, the porosity is preferably 5% or more, and more preferably 30% or more. The porosity can be measured using, for example, a mercury porosimeter (trade name: Bore Sizer 9320-PC2, manufactured by Shimadzu Corporation).
Further, the refractive index of the silica-based fine particles themselves having cavities therein is preferably 1.20 to 1.40, and more preferably 1.20 to 1.35.

  As another preferred embodiment of the low refractive index layer in the present invention, a low refractive index layer obtained by curing a fluorine-containing compound and the above-described curable composition containing silica-based fine particles having voids therein can be mentioned.

  That is, a low refractive index layer can be formed by curing a curable composition containing a fluorine-containing compound and silica-based fine particles having cavities in a curable composition containing a polyfunctional (meth) acrylate compound. it can.

The curable composition containing said polyfunctional (meth) acrylate compound can take the structure similar to the curable composition in the above-mentioned hard-coat layer.
Examples of the fluorine-containing compound include a fluorine-containing monomer and a fluorine-containing polymer compound.

  Examples of the fluorine-containing monomer include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) ) Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, and other fluorine-containing (meth) acrylic acids Examples include esters.

  Examples of the fluorine-containing polymer compound include a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as constituent units. Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc. ), (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, and the like. As a monomer for imparting a crosslinkable group, in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc. ) Acrylate monomers (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.).

  The thickness of the low refractive index layer is preferably in the range of 0.01 to 0.2 μm, and more preferably in the range of 0.02 to 0.15 μm.

(Conductive mesh)
From the viewpoint of effectively shielding electromagnetic waves generated from the display, the conductive mesh according to the present invention preferably has a surface resistance of 3Ω / □ or less, more preferably 1Ω / □ or less, particularly 0.5Ω. / □ or less is preferable. A lower sheet resistance is preferable because the electromagnetic wave shielding property is improved, but a practical lower limit is considered to be about 0.01Ω / □.

  The display filter of the present invention has a conductive mesh on the substrate, but at least a portion corresponding to the image display area of the display only needs to be formed of a conductive mesh, and a portion corresponding to the outer periphery of the image display area is The conductive mesh may be used or the metal solid part may be used.

  It is important that the conductive mesh according to the present invention has a thickness (Et) of less than 3 μm. As a result, the price of the display filter can be reduced, and at the same time, the coating stability when the hard coat layer is formed is further improved. In addition, when the thickness (Et) of the conductive mesh is as small as less than 3 μm, the raw material cost for manufacturing the conductive mesh is naturally reduced, but the production speed and production stability in the manufacturing process are reduced. Is improved.

  The thickness (Et) of the conductive mesh according to the present invention is preferably smaller from the above viewpoint, specifically, it is preferably less than 2.6 μm, more preferably less than 2.2 μm, particularly It is preferable that it is less than 2.0 micrometers. The lower limit thickness of the conductive mesh is 0 from the viewpoint of forming a concavo-convex structure derived from the concavo-convex structure of the conductive mesh in the hard coat layer laminated on the conductive mesh, and from the viewpoint of ensuring electromagnetic shielding properties. 0.5 μm or more is preferable, and 1.0 μm or more is more preferable. Note that the conductive mesh having a concavo-convex structure means a general conductive mesh, and the convex portion of the concavo-convex structure is a thin line of the conductive mesh, and the concave portion of the concavo-convex structure is surrounded by the thin line portion of the conductive mesh. This is an opening.

  The electroconductive mesh concerning this invention can be manufactured with a well-known manufacturing method. For example, 1) A method of printing a conductive ink in a pattern on a substrate. 2) Method of plating after pattern printing with ink containing catalyst core of plating 3) Method of patterning after bonding metal foil on base material with adhesive 4) Vapor deposition method on base material Alternatively, a method of patterning after forming a metal thin film by plating. 5) A resin layer having a pattern opposite to the pattern of the conductive mesh is formed on the substrate with a peelable resin, and then the resin layer of the substrate is There are a method of laminating a metal thin film on the formed surface by a vapor deposition method and then peeling off the resin layer, 6) a method using a photosensitive silver salt, and 7) a method of laser ablating the metal thin film. Can be mentioned. Below, the manufacturing method of the electroconductive mesh of said 1) -7) is demonstrated.

  1) The method of printing the conductive ink in a pattern on the substrate is a method of printing the conductive ink in a pattern on the 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) The method of patterning after laminating a metal foil on a substrate with an adhesive is a method of laminating a metal foil (copper, aluminum, nickel, etc.) on the substrate via an adhesive or an adhesive, This metal foil is a method of etching a metal foil after producing a resist pattern using a photolithography method or a screen printing method. 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.

  4) A method of patterning after forming a metal thin film on a substrate by vapor deposition or plating is performed by using a metal thin film (copper, aluminum, silver, gold, palladium, indium, tin, or silver on the substrate). Other metal alloys) are formed by vapor deposition methods such as vapor deposition, sputtering, ion plating, etc., or plating methods, and this metal thin film is used by photolithography or screen printing. Then, after the resist pattern is prepared, the metal thin film is etched. 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.

  The conductive mesh of 5) is formed by first forming a resin layer having a pattern opposite to the pattern of the conductive mesh on a substrate with a releasable resin, and then the surface of the substrate on which the resin layer is formed. In addition, a metal thin film is laminated by a vapor deposition method, and then the resin layer is peeled off, and at the same time, the metal thin film on the resin layer is removed. Here, the vapor deposition method used for laminating metal thin films is the same as the vapor deposition method used in the method for producing a conductive mesh of 4) above.

  The conductive mesh manufacturing method is a method generally called lift-off, and a resin layer having a pattern opposite to that of the conductive mesh is formed on a substrate in advance using a resin that can be peeled off. In this method, a metal thin film is laminated on the formed side surface by a vapor deposition method, and then the resin layer having the reverse pattern is peeled off. When the resin layer having the reverse pattern is peeled off, the metal thin film on the resin layer is also peeled off at the same time, and the metal thin film in the portion where the resin layer does not exist remains on the substrate as it is. Is formed on the substrate. Therefore, in this manufacturing method, it is necessary to form the peelable resin layer in a pattern opposite to the conductive mesh.

  As the peelable resin used for the peelable resin layer formed in advance on the substrate, a resin soluble in a solvent is preferably used. As such a resin, a water-soluble resin, a resin soluble in an organic solvent, and a resin soluble in an alkali can be used. Among these resins, a water-soluble resin is preferable from the viewpoint of work environment and the like, and a water-soluble polymer resin is particularly preferably used.

  Examples of water-soluble polymer resins include polyvinyl pyrrolidone, polyvinyl alcohol, partially saponified polyvinyl alcohol, soluble starch, carboxymethyl starch, vinyl acetate-maleic acid alternating copolymer, and hydroxypropyl cellulose. One or a mixture of two or more molecular resins can be used.

  Examples of resins that are soluble in organic solvents include polyimide ether resins, polyamide resins, polyamideimide resins, polybenzimidazole resins, polyhydantoin resins, polyparaban resins, and solvent-soluble polyimide resins. Silicone grease or oil-based ink can also be used.

  As a method for forming a resin layer having a pattern opposite to that of the conductive mesh on a substrate using a releasable resin that is soluble in a solvent, a printing method, a photolithography method, or the like can be used. As a printing method, for example, various methods such as screen printing, inkjet, intaglio printing, relief printing, offset printing, gravure printing, flexographic printing, and the like can be used.

  Photolithography is a method in which a photoresist layer is stacked on a substrate, exposed through a photomask, or directly scanned and exposed with a laser, and developed to form a resist layer with a pattern opposite to the conductive mesh pattern. It is a method to do. As a method of laminating a photoresist layer on a substrate, for example, a method of attaching a resist film or a method of applying a liquid resist is used.

  After the metal thin film is laminated on the surface on which the resin layer having a pattern opposite to that of the conductive mesh is formed, the resin layer is peeled off. The resin layer is peeled off in a solvent in which the resin layer is soluble. And a method of spraying the solvent, and a method of physically detaching in combination with these methods, for example, a method of rubbing with a cloth, sponge, roller or the like can be applied.

  6) As a method using a photosensitive silver salt, there is a method in which a silver salt emulsion layer such as silver halide is coated on a substrate, followed by development after photomask exposure or laser exposure to form a silver mesh. . 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 substrate in the same manner as in 4) 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.

  Among the above-described methods for producing a conductive mesh, from the viewpoint that a conductive mesh having a thickness of less than 3 μm can be stably and easily produced and high electromagnetic shielding properties can be ensured, 2) and 4 above. ), 6) and 7) are preferably used, and from the viewpoints of coating properties when forming a hard coat layer and adhesion of the hard coat layer, 2), 4) and 7) above. The conductive mesh produced by the above production method is preferably used. In particular, the production method of 4) has good coating properties when forming a hard coat layer, and produces a high-definition conductive mesh at low cost. In particular, it is preferably used. Here, the high-definition conductive mesh refers to a conductive mesh having a line width of less than 10 μm.

  The production method 4) will be described in more detail.

  As a method of forming a metal thin film on a substrate, a vapor deposition method is preferably used, and it is particularly preferable to form a metal thin film only by the vapor deposition method. 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 wave 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 base material and a copper thin film. This improves the adhesion between the substrate and the copper thin film.

  Further, a metal compound such as a metal oxide, metal nitride, or metal sulfide can be laminated on the surface of the metal thin film by a vapor deposition method. This metal compound lamination is preferable because the blackening treatment described later can be omitted. Examples of such metal compounds include gold, platinum, silver, mercury, copper, aluminum, nickel, chromium, iron, tin, zinc, indium, palladium, iridium, cobalt, tantalum, antimony, titanium, and other metal oxides, nitriding Or sulfide.

  The thickness of the metal compound is preferably in the range of 5 to 200 nm, more preferably in the range of 10 to 100 nm. This metal compound layer constitutes a part of the metal thin film and further constitutes a part of the conductive mesh.

  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.

  Further, the resist layer for forming the etching resist pattern described above can be blackened by containing a black pigment such as carbon black or titanium black. The etching resist pattern formed with the black resist, which is the blackened resist layer, is preferably left on the conductive mesh without being removed, so that the blackening treatment described later can be omitted.

  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 the 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.

  Examples of the shape (opening shape) of the mesh pattern of the conductive mesh according to the present invention include, for example, a lattice mesh pattern formed of a quadrangle such as a square, a rectangle, and a rhombus, a triangle, a pentagon, a hexagon, an octagon, Examples thereof include a mesh pattern made of a polygon such as a dodecagon, 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.

  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 smaller than 3 μm, the electromagnetic wave shielding property tends to be lowered. On the other hand, when the line width is larger than 30 μm, the transmittance of the display filter tends to be lowered.

The pitch of the conductive mesh according to 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 75 to 350 μm.
If the pitch of the conductive mesh is smaller than 50 μm, the transmittance tends to decrease, and if it exceeds 500 μm, the conductivity tends to decrease, which is not preferable.

(Base material)
Although a substrate is used for the display filter of the present invention, the display filter of the present invention is preferably composed of only one substrate. A plastic film is preferably used as the substrate according to the present invention.

  Examples of the resin constituting the plastic film include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, cellulose resins such as triacetyl cellulose, polyolefin resins such as polyethylene, polypropylene, and polybutylene, acrylic resins, polycarbonate resins, arton resins, and epoxy resins. , Polyimide resin, polyetherimide resin, polyamide resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, and the like. Among these, a polyester resin, a polyolefin resin, and a cellulose resin are preferable, and a polyester resin is particularly preferably used. The thickness of the plastic film is suitably in the range of 50 to 300 μm, but is particularly preferably in the range of 80 to 250 μm from the viewpoint of cost and ensuring the rigidity of the display filter. Moreover, as a plastic film, the laminated | multilayer film which laminated | stacked the several layer can also be used.

  Further, as the base material, a plastic film on which an easy-adhesion layer for reinforcing adhesion (adhesion strength) with a conductive mesh, a hard coat layer, or a near-infrared shielding layer described later is laminated in advance is preferably used. That is, in the display filter of the present invention, a plastic film having an easy adhesion layer is preferably used as a substrate.

(Display filter)
The display filter of the present invention is preferably further provided with a layer having at least one function selected from a near-infrared shielding function, a color tone adjustment function, or a visible light transmittance adjustment function.

  The near-infrared shielding function is preferably adjusted so that the maximum value of light transmittance in the wavelength range of 800 to 1100 nm is 15% or less. The near-infrared shielding function may be imparted by kneading and dispersing a near-infrared absorber in a plastic film, a functional layer, or an adhesive layer described later, or a near-infrared shielding layer may be newly provided. The near-infrared shielding function can be imparted by using a near-infrared absorbing agent or by providing a layer that reflects near-infrared rays by metal free electrons such as a conductive thin film.

  In the present invention, there is an embodiment in which a near-infrared shielding layer formed by applying and drying a paint in which a near-infrared absorber is dispersed or dissolved in a resin binder is used, or an adhesive layer described later contains the near-infrared absorber. Preferably used.

  Near-infrared absorbers include organic near-infrared absorbers such as phthalocyanine compounds, anthraquinone compounds, dithiol compounds, diimonium compounds, or titanium oxide, zinc oxide, indium oxide, tin oxide, zinc sulfide, cesium-containing oxides An inorganic near infrared absorber such as tungsten can be used.

  When the above-described near-infrared shielding layer is newly provided, it can be provided by coating the base material between the base material and the conductive mesh or on the opposite surface of the base material from the conductive mesh. .

  In the case where the near infrared shielding function is imparted to the viewer side from the base material, it is preferable to use an inorganic near infrared absorber having excellent light resistance.

  The color tone adjustment function is a function for improving color purity and whiteness by absorbing light of a specific wavelength emitted from the display. In particular, it is preferable to shield orange light that lowers the color purity of red light emission, and it is preferable to include a dye having an absorption maximum in the wavelength range of 580 to 620 nm, for example, a tetraazaporphyrin-based dye. Furthermore, it is preferable to contain a dye having an absorption maximum at a wavelength of 480 to 500 nm in order to improve whiteness. For the color tone adjustment function, a layer containing a dye that absorbs light having the above-described wavelength may be newly provided, or a dye may be contained in the above-described near-infrared shielding layer, hard coat layer, or adhesive layer described later. .

  The visible light transmittance adjusting function is a function for adjusting the visible light transmittance, and can be adjusted by containing a dye or a pigment. The visible light transmittance adjusting function may be imparted to the base material, the near-infrared shielding layer, or an adhesive layer described later, or a transmittance adjusting layer may be newly provided.

  When a layer having the above-described color tone adjusting function and a layer having a visible light transmittance adjusting function are newly provided, these layers are between the base material and the conductive mesh, or the conductive mesh with respect to the base material. It can be provided on the opposite side.

  The display filter of the present invention can be attached to the display directly or via a known high-rigidity substrate such as a glass plate, an acrylic plate, or a polycarbonate plate. The display filter of the present invention is preferably provided with an adhesive layer for adhering to a display or a highly rigid substrate.

  The high-rigidity substrate is usually a substrate having a thickness of 0.5 to 5 mm, and the high-rigidity substrate is not included in the base material constituting the display filter of the present invention.

  As described above, the adhesive layer can be provided with a near-infrared shielding function, a color tone adjusting function, or a visible light transmittance adjusting function. Moreover, it is a preferable aspect to provide the adhesive layer with an impact relaxation function for protecting the display from impact. In order to impart an impact relaxation function to the adhesive layer, the thickness of the adhesive layer is preferably 100 μm or more, and more preferably 300 μm or more. The upper limit thickness is preferably 3000 μm or less in consideration of the coating suitability of the adhesive layer.

  A well-known adhesive material or an adhesive material can be used for an adhesive layer. Examples of the adhesive material include acrylic, silicone, urethane, polyvinyl butyral, and ethylene-vinyl acetate. Adhesives include bisphenol A type epoxy resins, tetrahydroxyphenylmethane type epoxy resins, novolac type epoxy resins, resorcin type epoxy resins, polyolefin type epoxy resins and other epoxy resins, natural rubber, polyisoprene, poly-1, 2- (Di) enes such as butadiene, polyisobutene, polybutene, poly-2-heptyl-1,3-butadiene, poly-1,3-butadiene, polyoxyethylene, polyoxypropylene, polyvinyl ethyl ether, polyvinyl hexyl ether, etc. Polyesters such as polyethers, polyvinyl acetate, polyvinyl propionate, polyurethane, ethyl cellulose, polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile, polysulfone, phenoxy resin Etc., and the like.

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

(Evaluation methods)
(1) Measuring method of two-dimensional surface shape profile of hard coat layer Measured using a laser microscope VK-9700 (Keyence Co., Ltd.). First, using an observation / measurement software VK-H1V1, a sample having a size of 5 cm × 5 cm is set and measured so that the fine line of an arbitrary mesh of the conductive mesh is perpendicular to the center of the screen.

Next, the obtained measurement data is analyzed using analysis software VK-H1A1. First, image noise of measurement data is automatically removed, and the inclination when the object is slightly inclined at the time of measurement is corrected. Thereafter, profile analysis is performed in a direction perpendicular to the fine line of the center mesh. From the obtained profile, confirm whether there is a convex part of the hard coat layer on the fine wire of the mesh and whether there is a concave part of the hard coat layer in the opening of the conductive mesh. It was determined whether or not a concavo-convex structure derived from the concavo-convex structure of the conductive mesh was formed.
(2) Measuring method of center line average roughness Ra of hard coat layer The center line average roughness Ra of the hard coat layer was measured using a surface roughness measuring instrument SE-3400 (manufactured by Kosaka Laboratory Ltd.). .

Measurements were made at any five or more locations from one 20 cm × 20 cm sample, and the average value was taken as the Ra value of the hard coat layer. In the above measurement, set the direction of movement of the measuring needle so that it is parallel to the fine wire of the conductive mesh and almost through the center of the opening of the conductive mesh. Five measured values appearing in almost the same manner as the pitch of the sex mesh were adopted and averaged.
·Measurement condition:
Feeding speed: 0.5mm / S
Cut-off value λc;
When Ra is greater than 20 nm and less than or equal to 100 nm, 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
Ra: A parameter defined as Ra by a surface roughness measuring instrument SE-3400 (manufactured by Kosaka Laboratory Ltd.). It measured based on the method of JISB0601-1982.
(3) Measuring method of height difference (D) of uneven structure of hard coat layer Height difference (D) was measured using a laser microscope VK-9700 (Keyence Co., Ltd.). Measurements were made at 10 arbitrary locations from one 20 cm × 20 cm sample, and the average value was defined as the height difference (D).

  As a measuring method, using the observation / measurement software VK-H1V1, first, a sample of 5 cm × 5 cm size is set so that the upper and lower sides of the opening of the conductive mesh are parallel to the screen, and the center of gravity of one opening is measured. Install so that is at the center of the screen. The magnification is set such that the entire at least one opening of the conductive mesh enters. After focusing and setting the measurement height range, start measurement.

Next, the measurement data is analyzed using analysis software VK-H1A1. First, image noise of measurement data is automatically removed, and the inclination when the object is slightly inclined at the time of measurement is corrected. Thereafter, the line roughness is measured. At this time, an analysis line is set with a horizontal line and a vertical line passing through the center of gravity with respect to the screen. Various corrections (height smoothing → ± 12 simple average, slope correction → straight line (automatic)) are performed for each analysis line, and a undulation curve is obtained with a cutoff value λc = 0.08 mm (λs and λf are not set). Calculate and measure the maximum height Wz calculated based on the standard of JIS B0633-2001. The largest value of Wz obtained was defined as the height difference (D).
(4) Measuring method of conductive mesh thickness (Et) A sample cross section is cut out with a microtome, and the cross section is subjected to an electrolytic emission scanning electron microscope (S-800 manufactured by Hitachi, Ltd., acceleration voltage 26 kV, observation magnification 3000 times). And the thickness of the conductive mesh was measured.

Measurement was made at an arbitrary five locations from one 20 cm × 20 cm sample, and the average value was taken as the thickness of the conductive mesh.
(5) Measuring method of line width and pitch of conductive mesh Surface observation was performed at a magnification of 450 times using a digital microscope (VHX-200) manufactured by Keyence Corporation. Using the length measurement function, the pitch of the grid-like conductive mesh was measured. Measurements were made at 25 arbitrary locations from one 20 cm × 20 cm sample, and the average values were taken as the line width and pitch of the conductive 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.
(6) Measuring method of thickness (Ht) of hard coat layer Select 5 arbitrary openings from one sample of 20 cm × 20 cm size, cut out the sample cross section with a microtome, and cut the cross section with the electrolytic emission scanning electron microscope ( Hitachi Co., Ltd. S-800, acceleration voltage 15 kV, observation magnification 2000 times), the thickness of the hard coat layer at the center of gravity of the opening of the conductive mesh, that is, the distance from the base material to the hard coat layer surface Measure and average.
(7) Evaluation of antireflection effect Black paper (AC card # 300, manufactured by Oji Specialty Paper Co., Ltd.) with the display filter sample (20 cm × 20 cm) facing the viewing surface (low refractive index layer side). Paste on top. 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 at a distance of 30 cm from the 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: ○ (good)
-The outline of the reflected image is slightly blurred: △ (possible)
・ The outline of the reflected image is clearly visible: × (Not possible)
(8) Evaluation of foreign matter concealment property of a black paper (AC Card # 300 manufactured by Oji Specialty Paper Co., Ltd.) with the display filter sample (20 cm × 20 cm) facing the viewing surface side (low refractive index layer side). Paste on top. 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 visual recognition surface of the filter is visually observed from a distance of 30 cm in front, and it is evaluated whether or not a foreign substance is visually recognized on and near the fine line of the conductive mesh.
・ No foreign matter is visible at all or no more than 3 foreign matter is visible: ○ (possible)
・ 10 or more foreign objects are visible: × (impossible)
(9) Evaluation of pencil hardness of hard coat layer Pencil hardness was measured according to JIS K5600-5-4 (1999).
・ 2H or more: ○ (good)
・ H or more and less than 2H: △ (possible)
・ Less than H: × (impossible)
(10) Evaluation of interior decoration of display A front filter of a commercially available 50-inch size plasma display (plasma television) was removed, and display filters of Examples and Comparative Examples were attached. This plasma display was installed on the wall of an indoor room with an illuminance of 500 lux and a width of 25 square meters. With the display turned off, the glossiness of the display screen was visually evaluated to determine interior decoration. The evaluation criteria are shown below.
・ Glossy feeling and good interior decoration. : ○ (good)
・ Glossiness is slightly inferior, but interior decoration can be maintained: △ (possible)
・ There is no glossiness and the interior decoration is inferior. : × (Not possible)
(12) Evaluation of surface quality A filter sample for display (20cm x 20cm) 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: ○ (good)
・ Surface shape is uniform but slightly rough: △ (possible)
・ Sparsely convex and rough. ： × (Not possible)
(13) Average Particle Diameter of Particles Included in Hard Coat Layer The average particle diameter of the particles is measured using a laser diffraction particle diameter measuring device “MASTERSIZER 2000 (manufactured by MALVERN)”.

[Example 1]
A display filter was prepared as follows.
<Production of conductive mesh>
A nickel layer (thickness: 0.02 μm) was formed by sputtering on one side of an optical polyester film (Lumirror (registered trademark), manufactured by Toray Industries, Inc., thickness: 100 μm). Further, a copper layer (thickness: 2.5 μm) was formed thereon by a vacuum deposition method. Thereafter, a photoresist layer was applied and formed on the surface on the copper layer side, and the photoresist layer was exposed and developed through a mask of a lattice-like mesh pattern, and then subjected to 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 20 μm, a pitch of 300 μm, and a thickness of 2.5 μm.
<Formation of hard coat layer>
45 parts by mass of urethane acrylate (NK Oligo U-4HA manufactured by Shin-Nakamura Chemical Co., Ltd.), 45 parts by mass of dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.), 150 parts by mass of methyl isobutyl ketone, isopropyl alcohol 20 parts by mass, 4 parts by mass of a photopolymerization initiator (Ciba Specialty Chemicals (Irgacure 184)), and 1 part by mass of a leveling agent (“Polyflow KL-600” manufactured by Kyoeisha Chemical Co., Ltd.) with an average particle diameter of 8 μm A coating solution for forming a hard coat layer containing 5 parts by mass of acrylic particles was prepared.

This coating solution was coated on the conductive mesh produced above with a micro gravure coater, dried at 90 ° C., and then cured by irradiation with ultraviolet rays of 1.0 J / cm ² to form a hard coat layer. The thickness of this hard coat layer was 7 μm. The content ratio of the acrylic particles in the hard coat layer is 5% by mass with respect to 100% by mass of all components (excluding the organic solvent) of the hard coat layer.
<Lamination of near-infrared shielding layer>
A near-infrared shielding layer (phthalocyanine-based as a near-infrared absorbing dye) having an orange light shielding function on the PET film surface opposite to the conductive mesh and the hard coat layer of the PET film having the conductive mesh and the hard coat layer. A layer in which a paint obtained by mixing a dye, a diimonium dye, and a tetraazaporphyrin dye as an orange light absorbing dye in an acrylic resin was applied so that the dry film thickness was 12 μm was provided.
<Lamination of adhesive layer>
A UV curable urethane acrylate resin (Hybon (registered trademark) manufactured by Hitachi Chemical Co., Ltd.) was applied on a separate film with a slit die coater to a thickness of 100 μm, and then applied using a UV irradiation device. Then, a separate film was attached to obtain an adhesive layer sandwiched between the separate films. Next, an adhesive layer was laminated on the near-infrared shielding layer prepared above while peeling one of the separate films to obtain a display filter.
[Examples 2 to 10, Comparative Examples 1 to 5]
In the formation of the hard coat layer of Example 1, various hard coat layers were formed by changing the average particle diameter of the acrylic particles, the content of the particles, and the thickness of the hard coat layer.

  Table 1 shows the configurations of the hard coat layers in Examples 2 to 10 and Comparative Examples 1 to 5.

Except changing a hard-coat layer as shown in Table 1, it carried out similarly to Example 1, and produced the filter for displays of Examples 2-10 and Comparative Examples 1-5.
[Examples 11 to 14]
<Production of conductive mesh>
A nickel layer (thickness 0.02 μm) is formed by sputtering on one side of an optical polyester film (Lumirror (registered trademark) manufactured by Toray Industries, Inc., thickness 100 μm), and a copper layer (thickness 0.02 μm) is formed thereon by vacuum deposition. A thickness of 1.4 μm) was formed, and a copper nitride layer (thickness 0.08 μm) was further formed thereon by a sputtering method. Thereafter, a photoresist layer was applied and formed on the surface of the copper nitride layer, the photoresist layer was exposed and developed through a mask having a lattice mesh pattern, and then an etching process was performed to produce a conductive mesh. . This conductive mesh had a line width of 6 μm, a pitch of 100 μm, and a thickness of 1.5 μm.
<Formation of hard coat layer>
In the formation of the hard coat layer of Example 1, various hard coat layers were formed by changing the average particle diameter of the acrylic particles, the content of the particles, and the thickness of the hard coat layer. Table 1 shows the configuration of the hard coat layer in Examples 11 to 14.

Display filters of Examples 11 to 14 were produced in the same manner as Example 1 except that the hard coat layer was used on the conductive mesh.
(Evaluation)
Table 1 shows the evaluation results for each of the display filters prepared above.

  From the results of Table 1, it can be seen that the examples of the present invention are good or acceptable in all of the reflection preventing property, the foreign matter concealing property, the interior decoration property, the pencil hardness, and the surface quality.

  On the other hand, in Comparative Example 1, the average particle size of the particles contained in the hard coat layer is less than 60% with respect to 100% of the thickness of the hard coat layer, and the uneven structure is not sufficiently formed in the hard coat layer. It has poor intrusion prevention and foreign matter concealment.

  In Comparative Example 2, the thickness of the hard coat layer is less than 3 μm, and the foreign matter hiding property and pencil hardness are inferior.

  In Comparative Example 3, the concavo-convex structure derived from the concavo-convex structure of the conductive mesh is not formed in the hard coat layer, and the reflection preventing property and the foreign matter concealing property are inferior.

  In Comparative Example 4, since the hard coat layer contains more than 18% by mass of the particles, an uneven structure is formed in the opening, and the interior decoration and the surface quality are remarkably deteriorated.

  In Comparative Example 5, because the content of particles contained in the hard coat layer is less than 3% by mass, the hard coat layer does not have an uneven structure derived from the uneven structure of the conductive mesh, and the antireflection effect, and Foreign matter concealment is inferior.

The schematic cross section of an example of the filter for displays of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 2 Conductive mesh fine wire 3 Hard coat layer 4 Particle 5 Convex part top 6 Concave lowest point D Uneven structure height difference L Hard coat layer thickness

Claims (5)

A display filter having a conductive mesh having a concavo-convex structure on a base material, and a hard coat layer containing particles laminated on the conductive mesh,
The conductive mesh has a thickness (Et) of less than 3 μm,
The hard coat layer has a thickness (Ht) of 3 μm or more,
The average particle diameter of the particles is 60% or more with respect to 100% of the thickness (Ht) of the hard coat layer,
Containing 3% by mass to 18% by mass of the particles with respect to 100% by mass of all components of the hard coat layer,
And the said hard-coat layer has the uneven structure derived from the uneven structure of an electroconductive mesh, The filter for displays characterized by the above-mentioned.   The display filter according to claim 1, wherein a height difference (D) of the concavo-convex structure formed on the hard coat layer is 0.5 μm to 5 μm.   The display filter according to claim 1 or 2, wherein a center line average roughness Ra of the hard coat layer is 150 nm or more and less than 500 nm.   The display filter according to claim 1, wherein an average particle diameter of the particles is 3 μm to 20 μm.   The display filter according to claim 1, wherein a ratio (Ht / Et) of a thickness (Ht) of the hard coat layer and a thickness (Et) of the conductive mesh is 1.5 or more. .

Images