JP2006237505A - Compound electromagnetic wave shield filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound electromagnetic wave shield filter having highly durable pigement, absorbability for near-infrared in a wide wavelength range, as well as excellent in optical transparency in a visible light range. <P>SOLUTION: The compound electromagnetic wave shield filter 10 has a mesh layer 3 including a mesh conductive layer 2 formed on the transparent base material 1, and further has the near-infrared ray absorbing layer 4 formed on at least the surface including the opening part of the mesh layer on the surface side with the mesh layer 3 formed on the transparent base material 1. The layer 4 comprises an ionizing-radiation-hardening-type transparent resin including a phthalocyanine compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electromagnetic wave shielding filter having optical transparency, and more particularly to an electromagnetic wave shielding filter having near infrared absorption performance as an optical filter function and particularly suitable for a display such as a PDP.

  In order to shield electromagnetic waves generated from various displays such as a PDP (plasma display panel) and a CRT (CRT) display, an electromagnetic wave shielding filter disposed on the front surface of the display is known. The electromagnetic wave shielding filter used for such applications requires light transmittance as well as electromagnetic wave shielding performance. However, in a case where an ITO (indium tin oxide) film is provided on the entire surface of a transparent substrate (see Patent Document 1, Patent Document 2, etc.), it is not possible to achieve both sufficient electromagnetic shielding performance and sufficient transparency. . Therefore, a metal foil such as a copper foil bonded to a transparent substrate made of a resin film with an adhesive is formed into a mesh-like conductor layer by etching (see Patent Document 3, etc.). . In addition, a mesh layer consisting only of a mesh-like conductor layer made of a metal layer or the like may be used. However, since metallic luster and rust are worrisome, usually a rust prevention layer, a blackening layer, etc. are further provided on the surface of the mesh-like conductor layer. It is also known to provide a mesh layer with a provided configuration.

  Further, a front filter or the like disposed in front of the display may be required to have near-infrared absorption performance that suppresses unnecessary near-infrared radiation from the display and prevents malfunction of the infrared device. The front filter is also required to be lightweight and thin. For this reason, when the electromagnetic wave shielding filter has only electromagnetic wave shielding performance with respect to the actual front filter, the electromagnetic wave shielding filter is further laminated and integrated with a resin film-based near infrared absorption filter with an adhesive, A device such as a composite electromagnetic shielding filter in which functions other than the electromagnetic shielding function are combined has been devised (see Patent Document 3, etc.).

  However, in consideration of further lightness, thinness, simplification of the manufacturing process, reduction of the constituent layers (leading to cost reduction, low haze, light transmittance improvement, etc.), the above configuration is There was room for improvement in the case where the near infrared absorption filter was laminated as an additional separate part.

  In view of this, a composite electromagnetic wave shielding filter having a configuration that does not require the lamination of an additional near-infrared absorption filter has also been proposed. For example, an adhesive for laminating with an adherend such as an antireflection filter or a front plate, or a resin layer constituting an electromagnetic wave shielding filter containing a near infrared absorber, for example, (1) to (4) have been proposed.

(1) Near-infrared absorption in an adhesive layer for laminating and laminating copper foil or the like to be a mesh-like conductor layer by etching on a transparent substrate, that is, an adhesive layer between the transparent substrate and the mesh layer Containing an agent (Patent Document 4).

(2) The portion of the adhesive layer for copper foil laminating as described above exposed at the mesh opening is roughened to prevent the light transmittance from being lowered, or the electromagnetic wave shielding filter is adhered to the adherend. For example, a near-infrared absorber is contained in the transparent resin layer filling the opening (Patent Document 4, Patent Document 5).

(3) A near-infrared absorber is contained in a flattening resin layer for filling the openings of the mesh layer and flattening surface irregularities due to the mesh layer (Patent Documents 4 and 5).

(4) To include a near infrared absorber in the adhesive layer between the transparent substrate and the mesh layer, and further to use the resin of this adhesive layer for adhesion to other adherends such as plastic plates. In addition, the resin of the adhesive layer is fluidized by being heated and pressed over the adherend and oozed out of the mesh, filling the mesh opening and contacting the adherend (Patent Document) 6).

  On the other hand, as a near-infrared absorbing layer applicable when imparting a near-infrared absorbing function necessary for a composite electromagnetic shielding filter to an electromagnetic shielding, a near-infrared absorbing dye blended in a transparent resin has been proposed. As this near-infrared absorbing dye, onium-based dyes such as diimmonium and aminium are often used because they have absorption in a wide near-infrared region. However, since onium dyes are deactivated and discolored in a resin having a reactive group, it has been difficult to apply them to a wide range of uses (for example, Patent Document 7: JP-A-10-180922). Further, metal complex dyes such as phthalocyanine dyes and dithiols are known as near infrared absorbing dyes that are stable among resins having reactive groups.

  Although phthalocyanine dyes are stable among resins having a reactive group, conventionally known ones absorb at 700 to 900 nm, and are combined with dyes having absorption in a wavelength region longer than 900 nm, such as the above diimonium dyes. Was almost. In addition, the absorption wavelength range of conventional phthalocyanine dyes is not necessarily optimal, and the absorption range is narrow due to the molecular structure. Therefore, near infrared absorption ability is realized in a wide wavelength range if multiple types of phthalocyanine dyes are not used. I can't. In order to give appropriate absorption in a wide near-infrared region, several kinds of dyes must be used, and there is a problem that the visible light transmittance is lowered.

On the other hand, metal complexes such as dithiol are stable among resins having reactive groups, and some have absorption in a relatively wide near-infrared region, but have poor solubility and usability problems (for example, Patent Document 8). : JP-A-2004-29436).
JP-A-1-278800 JP-A-5-323101 JP 2001-210988 A JP 2002-311843 A ([Claim 1], [Claim 2], [0030]) Japanese Patent No. 3473110 ([Claim 1] to [Claim 3], [0014]) JP-A-11-145679 ([Claim 6], [0007], [0020], [0024]) JP-A-10-180922 JP 2004-29436 A

  By the way, when the resin layer containing the near-infrared absorbing agent is an adhesive layer between the transparent base material and the mesh layer, volume shrinkage due to solvent drying is not an issue, so solution type thermosetting resin such as urethane resin Can be used. On the other hand, in the case where the resin layer is a transparent resin layer in which the opening of the mesh layer is filled, the mesh layer needs to be thicker than the adhesive layer for the purpose of planarization because the mesh layer is thick. Therefore, as the resin of the transparent resin layer, it is common to adopt an ultraviolet curable resin since it can be applied in a solvent-free type (Patent Document 4, Patent Document 5, Patent Document). 6).

  In addition, when a near-infrared absorber is contained in the adhesive layer between the transparent base material and the mesh layer, the near-infrared absorber effectively acts only on the exposed portion at the mesh layer opening, and the transparent base material and the mesh The portion where these layers are bonded to each other becomes a useless region that does not act effectively because of the opaque mesh layer. Therefore, a wasteful near-infrared absorber is used correspondingly, which is disadvantageous in terms of material cost. Similarly, the same can be said for the case where a near-infrared absorber is contained in the adhesive layer on which the electromagnetic wave shielding filter is adhered and laminated to another adherend. Therefore, the layer containing the near infrared absorber is preferably a transparent resin layer provided in an area where the contained near infrared absorber is used without waste, that is, in the opening of the mesh layer.

  Therefore, the present inventors used an ultraviolet curable resin as a transparent resin layer to be formed so as to fill the opening, and contained a near-infrared absorber in the transparent resin layer containing the infrared absorber. A composite electromagnetic wave shielding filter having a near-infrared absorbing layer as a layer was produced. Surprisingly, however, it has been found that the near-infrared absorption performance before curing the resin layer with ultraviolet light is even better. In other words, the original performance of the near-infrared absorber contained in the resin layer was not sufficiently exhibited after the resin was cured by ultraviolet irradiation. However, if it is made of a solvent-dried resin such as urethane resin that does not require UV curing, it cannot be formed to a thickness that can completely fill the mesh layer and flatten the surface.

  As described above, the problem of the present invention is that at least a mesh layer composed of a mesh-like conductor layer has at least a mesh in order to add near infrared absorption performance to an electromagnetic wave shield filter laminated on a transparent substrate. When a near-infrared absorber is contained in the transparent resin layer formed in the opening to form a composite electromagnetic wave shield filter, the performance of the near-infrared absorber that occurs when the resin layer containing the near-infrared absorber is cured is reduced. Is to prevent.

  And the further subject of the present invention is, during the curing and after curing of the resin layer containing the near-infrared absorber, while the durability of the pigment is high and has an absorption property for near-infrared rays in a wide wavelength range, It is an object of the present invention to provide a composite electromagnetic wave shielding filter that simultaneously has excellent light transmittance in the visible light region.

  In a composite electromagnetic shielding filter, a metal mesh is indispensable to obtain an electromagnetic shielding function, and an adhesive layer may be required to adhere or fix the metal mesh. Due to the presence of an adhesive or the like, when the resin layer containing the near-infrared absorber is cured and used after curing, discoloration or fading of the near-infrared absorbing dye, or alteration of the resin layer may occur. There was a problem that it was difficult to maintain good near-infrared absorption characteristics over a long period of time.

  In order to solve the above problems, in the present invention, a mesh layer including a mesh-like conductor layer is formed on a transparent substrate, and at least the mesh layer on the surface on which the mesh layer is formed on the transparent substrate. A composite electromagnetic wave shielding filter having a near infrared absorbing layer formed on a surface including the opening of the above, wherein the near infrared absorbing layer is at least three of the following four types of phthalocyanine compounds (A) to (D): The composition of an ionizing radiation curable transparent resin comprising

  By adopting such a configuration, the transparent resin layer containing the near-infrared absorbing agent employs an ionizing radiation curable resin for the resin, so that a solventless coating that can be formed thick is also possible. The near-infrared absorbing performance of the near-infrared absorbing agent does not deteriorate before and after curing by irradiation with ionizing radiation, and the original performance of the near-infrared absorbing agent is obtained. Moreover, since the layer containing the near infrared absorber is not a transparent adhesive layer that is interposed between the transparent base material and the mesh layer and adhesively laminates them, the mesh layer is between the transparent base material and the mesh layer. There is no need to waste the near-infrared absorber in that area. In addition, since the transparent resin layer containing the near infrared absorber may be formed only at the opening portion of the mesh that realizes light transmittance, it is possible to use the necessary minimum near infrared absorber without waste. is there.

  1st invention is a composite electromagnetic wave shielding filter which has electromagnetic wave shielding performance and near-infrared absorption performance, Comprising: The mesh layer containing a mesh-like conductor layer is formed on a transparent base material, Furthermore, in the said transparent base material, It is a composite electromagnetic wave shielding filter in which a near-infrared absorbing layer is formed on at least the surface of the side on which the mesh layer is formed including the opening of the mesh layer, and the near-infrared absorbing layer comprises the following four types of phthalocyanine compounds: The present invention relates to a composite electromagnetic shielding filter comprising an ionizing radiation curable transparent resin comprising at least three of (A) to (D).

（式〔Ｉ〕中、Ａ^１〜Ａ^１６は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、ヒドロキシスルホニル基、アミノスルホニル基、あるいは窒素原子、硫黄原子、酸素原子またはハロゲン原子を含んでも良い炭素数１〜２０の置換基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。Ｍ^１は、酸化バナジウムまたは銅を表す。）
第２の発明は、第１または第２の発明において、複合電磁波シールドフィルタがディスプレイの観察側に配置されていることを特徴とする、プラズマディスプレイに関するものである。 Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.
A second invention relates to a plasma display according to the first or second invention, wherein the composite electromagnetic wave shielding filter is disposed on the viewing side of the display.

  According to the composite electromagnetic wave shielding filter of the present invention, a transparent resin layer containing a near-infrared absorber for imparting near-infrared absorbing performance can be easily ionized to a thickness that can flatten surface irregularities due to the mesh layer. Even if a radiation curable resin is used, the near infrared absorption performance is not lowered when the transparent resin layer is formed, and the original performance of the near infrared absorber can be obtained. In addition, since the transparent resin layer may be formed only with the mesh openings, it is possible to use a necessary near-infrared absorber without waste. In particular, in the present invention, since not only an electron beam but also ultraviolet rays can be used as ionizing radiation, the resin can be cured by an inexpensive and simple ultraviolet irradiation device.

  And in the present invention, since it contains at least three of the four types of phthalocyanine compounds as a near-infrared absorbing dye, the durability of the dye is high, while having an absorption property for near-infrared rays in a wide wavelength range, Provided is a composite electromagnetic wave shielding filter that also has excellent light transmittance in the visible light region.

The best mode for carrying out the present invention will be described below with reference to the drawings.
First, FIG. 1 is sectional drawing which shows two examples as a basic form example about the composite electromagnetic wave shield filter by this invention.

  The composite electromagnetic wave shielding filter 10 of FIG. 1 (A) is the most basic form, and a mesh layer 3 including at least a mesh-like conductor layer 2 is laminated on a transparent substrate 1. With a configuration in which a near-infrared absorbing layer 4 made of an ionizing radiation-curable resin transparent to visible light cured with ionizing radiation and containing a near-infrared absorbing agent is laminated on the entire surface including the opening and its opening. is there. The composite electromagnetic wave shielding filter 10 in FIG. 1B further includes a transparent substrate including the region of the opening of the mesh layer 3 between the transparent base material 1 and the mesh layer 3 in addition to the configuration in FIG. The transparent adhesive layer 5 is provided on the entire surface of the material 1.

〔Overview〕
The composite electromagnetic wave shielding filter of the present invention is compared with a conventional electromagnetic wave shielding filter in which a mesh layer composed of at least a mesh-like conductor layer is laminated on a transparent substrate, and an opening of the mesh layer is filled with a transparent resin layer. In addition to making the transparent resin layer a resin layer of ionizing radiation curable resin cured with ionizing radiation, by containing three or more specific near infrared absorbers, near infrared absorbing performance as well as electromagnetic shielding performance This is a composite electromagnetic wave shielding filter characterized in that the functions are combined to provide a function. The “ionizing radiation” in the present invention includes both ultraviolet rays and electron beams.

The formation method of the mesh layer which consists of a mesh-like conductor layer etc. on a transparent base material is not limited, What is necessary is just to employ | adopt conventionally well-known various methods suitably. For example, a method for forming the mesh-like conductor layer is typically described as a method of forming an opening in a mesh shape by etching after bonding a metal foil to a transparent substrate via a transparent adhesive layer. is there. In addition, the near-infrared absorbing layer made of a transparent resin containing the above-mentioned near-infrared absorbing dye is used as an adhesive layer, and other optical filters other than the near-infrared absorbing filter, such as an antireflection filter and an antiglare filter. A functional layer for imparting a function according to the application, such as a color adjustment filter, or a protective film, an optical article such as a front substrate that is a component of the display itself, and the adherend. You may make it function as a layer for carrying out adhesion lamination. In addition, you may laminate | stack these functional layers through another adhesive bond layer on a near-infrared absorption layer. A conventionally known adhesive may be appropriately employed for the adhesive layer.
Hereinafter, the composite electromagnetic wave shielding filter of the present invention will be described in order from the transparent substrate 1 for each layer.

(Transparent substrate)
The transparent substrate 1 is a layer for reinforcing a mesh layer generally having a low mechanical strength. Therefore, as long as it has light transmittance as well as mechanical strength, it may be selected and used depending on the application, taking into account heat resistance, insulation, etc. as appropriate. Specific examples of the transparent substrate include a resin plate, a resin sheet (or a film, the same applies hereinafter), a glass plate, and the like.

  Examples of transparent resins used as resin plates and resin sheets include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, terephthalic acid-isophthalic acid-ethylene glycol copolymer, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer. Polyester resins such as nylon 6, polyamide resins such as nylon 6, polyolefin resins such as polypropylene and polymethylpentene, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and styrene-acrylonitrile copolymer, triacetyl Examples thereof include cellulose resins such as cellulose, imide resins, and polycarbonate resins.

  In addition, these resins are used as a single or a plurality of types of mixed resins (including polymer alloys) as a resin material, and as a layer, they are used as a single layer or a laminate of two or more layers. In the case of a resin sheet, a uniaxially stretched or biaxially stretched sheet is more preferable in terms of mechanical strength.

  Moreover, you may add additives, such as a ultraviolet absorber, a filler, a plasticizer, an antistatic agent, in these resins suitably as needed.

  Further, as glass of the glass plate, there are quartz glass, borosilicate glass, soda lime glass, etc. More preferably, the thermal expansion coefficient is small, the dimensional stability and the workability in high-temperature heat treatment are excellent, and the alkali component in the glass Non-alkali glass that does not contain any of them can be used, and it can also be used as an electrode substrate as a front substrate of a display.

  The thickness of the transparent substrate is not particularly limited as long as it depends on the application. When the transparent substrate is made of a transparent resin, it is usually about 12 to 1000 μm, preferably 50 to 700 μm, more preferably 100. ˜500 μm is desirable. On the other hand, when a transparent base material is a glass plate, about 1-5 mm is usually suitable. In any material, if the thickness is less than the above, the mechanical strength is insufficient, causing warping, sagging, breakage, etc. If the thickness exceeds the above, it becomes excessive performance and high cost, and thinning is difficult. .

  In addition, as the transparent substrate, a sheet (or film), a plate, or the like made of these inorganic materials, organic materials, or the like can be applied. It may be combined with the front substrate which is one component, but in the form using the composite electromagnetic wave shielding filter as the front filter disposed in front of the front substrate, the sheet is more preferable than the plate in terms of thinness and lightness. Needless to say, the resin sheet is superior to the glass plate in that it is excellent and does not break.

  In addition, the transparent base material is in the form of a continuous belt-like sheet at least in the initial stage of production, such as formation of a mesh-like conductor layer, in that the composite electromagnetic wave shielding filter can be continuously produced to improve productivity. It is preferable to handle.

  In this respect, a resin sheet is a preferable material for the transparent substrate, but among the resin sheets, in particular, polyester resin sheets such as polyethylene terephthalate and polyethylene naphthalate, and cellulose resin sheets are transparent, In view of heat resistance, cost, etc., a polyethylene terephthalate sheet is more preferable. In addition, although the transparency of a transparent base material is so good that it is high, Preferably the light transmittance which becomes 80% or more by visible light transmittance | permeability is good.

  In addition, a transparent substrate such as a resin sheet is appropriately coated on the surface thereof with known easy processes such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, and alkali treatment. An adhesion treatment may be performed.

[Mesh layer: Mesh-like conductor layer]
The mesh-like conductor layer 2 is a layer responsible for the electromagnetic wave shielding function, and even if it is opaque itself, the mesh-like shape has an opening so that both electromagnetic wave shielding performance and light transmittance are achieved. This is an essential layer of the mesh layer 3 having a mesh shape. In addition to the mesh-like conductor layer 2, the mesh layer 3 retains the mesh-like shape of the mesh-like conductor layer that is the origin of the shape characteristics of the mesh layer, so that the rust prevention described later The layer 6 and the blackened layer 7 are also regarded as constituent layers of the mesh layer. Accordingly, in the cross-sectional view of FIG. 1, only the essential mesh-like conductor layer 2 is explicitly indicated as the mesh layer 3, but the mesh layer in the case of having a rust prevention layer or a blackening layer provided as necessary. It is a conceptual drawing including.

  The shape of the mesh-like conductor layer 2 as a mesh shape is not particularly limited, but a square shape is typical as the shape of the mesh opening. The shape of the opening is, for example, a triangle such as a regular triangle, a square such as a square, a rectangle, a rhombus, or a trapezoid, a polygon such as a hexagon, or a circle or an ellipse. The mesh has a plurality of openings having these shapes, and the openings are usually line-like line portions having a uniform width, and the openings and the openings are generally the same shape and the same size on the entire surface. To illustrate the specific size, the width of the line portion between the openings is 50 μm or less, preferably 20 μm or less in terms of the aperture ratio and the invisibility of the mesh. The size of the opening is [line interval or line pitch]-[line width]. In terms of [line interval or line pitch], it is 150 μm or more, preferably 200 μm or more. Is preferable.

  The bias angle (the angle formed between the mesh line portion and the outer periphery of the composite electromagnetic wave shield filter) may be appropriately set to an angle at which moiré is not likely to occur in consideration of the pixel pitch of the display and the light emission characteristics.

  Moreover, the area | region (mesh part 3A) which has a some opening part should just be an area | region which needs a light transmittance at least, Therefore, it does not need to be the whole surface. As an example, as illustrated in the plan view of FIG. 2, a portion that does not affect the image display around the four sides of the square composite electromagnetic wave shield filter 10 is formed into a frame shape, and the frame portion 3B is left without an opening. The form made into the mesh part 3A which has several opening part only inside is mentioned. The frame can be used for grounding. Note that the frame portion 3B may not be the entire periphery but only one side or the like. In addition, it is preferable to expose part or all of the frame part so that the grounding can be easily taken. For this purpose, the layer provided on the mesh layer such as the near-infrared absorbing layer is the part exposed at the frame part. It is preferable to provide the mesh portion 3A or the mesh portion 3A so as to partially cover the frame portion 3B.

  The mesh-shaped conductor layer 2 is typically formed by etching a metal foil, but other mesh layers are also significant in electromagnetic shielding performance. Therefore, in the present invention, the material and forming method of the mesh-like conductor layer are not particularly limited, and various mesh-like conductor layers in a conventionally known light-transmitting electromagnetic wave shielding filter can be appropriately employed. is there. For example, a mesh-like conductor layer is formed from the beginning on a transparent substrate using a printing method, a plating method, or the like, or initially, the entire surface is formed on a transparent substrate by a plating method. After forming the body layer, it may be a mesh-like conductor layer formed into a mesh shape by etching or the like.

  For example, when the mesh shape of the mesh-like conductor layer is formed by etching, it can be formed by patterning the metal layer laminated on the transparent base material by etching and opening the openings to form a mesh. To laminate a metal layer on a transparent substrate, the metal layer prepared as a metal foil is laminated to the transparent substrate with an adhesive, or the metal layer is deposited, sputtered, plated, etc. without using a laminating adhesive It can also be laminated on a transparent substrate using one or two or more physical or chemical forming methods. In addition, the mesh-like conductor layer by etching can also be formed into a mesh-like mesh-like conductor layer by patterning a single metal foil before lamination on a transparent substrate by etching. This single-layer mesh conductor layer is laminated on a transparent substrate with an adhesive or the like. Among these, a metal foil is laminated on a transparent substrate with an adhesive, and then meshed by etching after being easy to handle a mesh-like conductor layer with low mechanical strength and excellent in productivity. A mesh-like conductor layer that is processed and laminated on the transparent substrate via an adhesive is desirable.

  The mesh-like conductor layer is not particularly limited as long as it is a substance having sufficient conductivity to exhibit electromagnetic wave shielding performance, but usually a metal layer is preferable in terms of good conductivity, and the metal layer is as described above. It can be formed by vapor deposition, plating, metal foil lamination or the like. Examples of the metal material of the metal layer or the metal foil include gold, silver, copper, iron, nickel, and chromium. The metal of the metal layer may be an alloy, and the metal layer may be a single layer or multiple layers. For example, in the case of iron, low carbon steel such as low carbon rimmed steel and low carbon aluminum killed steel, Ni-Fe alloy, Invar alloy, and the like are preferable. On the other hand, when the metal is copper, it becomes copper or copper alloy, but as copper foil there are rolled copper foil and electrolytic copper foil, but from the point of thinness and its uniformity, adhesion with blackened layer, etc. Is preferably an electrolytic copper foil.

  In addition, the thickness of the conductor layer by a metal layer is about 1-100 micrometers, Preferably it is 5-20 micrometers. If the thickness is too thin, it will be difficult to obtain sufficient electromagnetic shielding performance due to an increase in electrical resistance, and if the thickness is too thick, it will be difficult to obtain a high-definition mesh shape. The side of the mesh disturbs the display angle of the display.

  Moreover, it is preferable that the surface of the metal layer used as a mesh-like conductor layer is a rough surface in order to improve the adhesiveness with adjacent layers, such as a transparent adhesive layer. For example, in the case of copper foil, a rough surface is obtained on the surface (the surface of the blackened layer) simultaneously with the formation of the blackened layer by the blackening treatment. The degree of the rough surface is 10-point average roughness Rz [JIS-B0601 compliant (1994 version)], preferably about 0.1 to 10 μm, more preferably 1.5 μm or less, still more preferably 0.5. ˜1.5 μm. If the roughness is less than this, the effect of roughening cannot be sufficiently obtained, and if the roughness is larger than this, bubbles tend to be embraced during application of an adhesive, a resist or the like.

[Mesh layer: Antirust layer]
The mesh layer 3 may be only the mesh-like conductor layer 2, but the mesh-like conductor layer made of a metal layer rusts and deteriorates during manufacturing, handling, etc., and may deteriorate the electromagnetic shielding performance. When it is necessary to prevent this, it is preferable to cover the surface of the mesh-like conductor layer with the antirust layer 6. Moreover, when the blackening layer mentioned later tends to rust, it is preferable to coat | cover including a blackening layer. The coating of the antirust layer may be performed on a surface selected in consideration of the manufacturing cost from one or more necessary surfaces among the front surface, the back surface, and the side surface of the mesh-like conductor layer. Therefore, the coating of the anticorrosive layer is only the front surface, only the back surface, both front and back surfaces (see, for example, FIG. 3A), only the side surface (both sides or one side), the front surface and both side surfaces, the back surface and both side surfaces, the front and back both surfaces and both side surfaces. Etc.

  In this specification, “surface” means a surface (surface above the drawing, transparent substrate) far from the transparent substrate of the target layer (here, the mesh-like conductor layer, the near-infrared absorbing layer, etc.). In the material, the upper surface of the drawing), the “back surface” is the surface of the layer of interest closer to the transparent substrate (the lower surface of the drawing, the lower surface of the transparent substrate is the lower surface of the drawing), and the “side surface” is the surface The surface connecting the back surface (surface facing the left-right direction of the drawing) will be referred to. In addition, when applied to a display application or the like, the viewer side surface may always be the back surface instead of the front surface defined in the present invention.

  The rust preventive layer is not particularly limited as long as it does not rust more easily than the mesh-like conductor layer coated with the rust preventive layer, such as an inorganic material such as metal, an organic material such as resin, or a combination thereof. In some cases, the blackened layer is also covered with a rust-preventing layer, so that the particles of the blackened layer can be prevented from falling off and deformed, and the blackness of the blackened layer can be increased. In this respect, when the mesh-like conductor layer is formed of a metal foil, when the blackened layer is provided on the metal foil on the transparent substrate by the blackening treatment, the blackened layer is prevented from falling off or being altered. In terms of meaning, it is preferably provided before lamination of the transparent substrate and the metal foil.

  The rust preventive layer 6 may be appropriately selected from conventionally known ones. For example, a metal compound such as a metal such as chromium, zinc, nickel, tin, copper or an alloy containing these metals, or a metal oxide containing these metals. Layer. These can be formed by a known plating method or the like. Here, if it shows an example of a rust prevention layer preferable at points, such as a rust prevention effect and adhesiveness, the chromium compound layer obtained by carrying out a chromate process after galvanization will be mentioned. In addition, the rust preventive layer made of this chromium compound layer has adhesion to a blackening layer made of a copper-cobalt alloy particle layer, which will be described later, and a transparent adhesive layer 5 (particularly a two-component curable urethane resin-based adhesive). Also excellent.

  In the case of chromium, chromate (chromate) treatment or the like may be used. The chromate treatment is carried out by bringing the chromate treatment solution into contact with the treated surface. This contact is not limited to coating methods such as roll coating, curtain coating, squeeze coating, pouring (single-sided contact), and electrostatic fogging. According to the chemical method, the dipping method, etc., double-sided contact is also possible. Moreover, what is necessary is just to dry, without washing with water after a contact. In addition, an aqueous solution containing chromic acid is usually used for the chromate treatment liquid. Specifically, “Alsurf (registered trademark) 1000” (manufactured by Nippon Paint Co., Ltd.), “PM-284” (Nippon Parkerizing Co., Ltd.) A processing solution such as a company can be used.

  In the chromate treatment, galvanization before the treatment is preferable in terms of adhesion and rust prevention effect. In addition, the rust preventive layer may contain a silicon compound such as a silane coupling agent in order to improve acid resistance during etching or acid cleaning.

  In addition, the thickness of a rust prevention layer is about 0.001-10 micrometers normally, Preferably it is 0.01-1 micrometer.

[Mesh layer: Blackened layer]
The blackening layer 7 can improve the contrast of the image in the bright room of the display. Some blackening layers have a roughened surface as described above and can improve adhesion. In terms of improving the contrast of the display image, the blackening layer is preferably provided on all surfaces of the mesh layer (mesh-like conductor layer itself or a mesh-like conductor layer already formed such as a rust prevention layer) that can be seen by the observer. However, if it is provided on one or more of the front, back and side surfaces, a corresponding effect can be obtained. Accordingly, the surface to be provided depends on the arrangement relationship between the composite electromagnetic wave shielding filter and the display, but only the front surface, only the back surface (see, for example, FIG. 3A), both the front and back surfaces, only the side surfaces (both sides or one side), Both side surfaces (see, for example, FIG. 3B), back surface and both side surfaces, front and back both surfaces, both side surfaces, and the like.

  In any case, the blackened layer may be a layer exhibiting a dark color such as black, and may be any layer that satisfies basic physical properties such as adhesion, and a known blackened layer can be appropriately employed.

  Therefore, as the blackening layer, an inorganic material such as a metal, an organic material such as a black colored resin, or the like can be used. For example, as the inorganic material, a metal compound such as a metal, an alloy, a metal oxide, or a metal sulfide is used. It is formed as a metal-based layer. As a method for forming the metal layer, various conventionally known blackening methods can be appropriately employed. Especially, the blackening process by a plating method is preferable at adhesiveness, uniformity, ease, etc. As a material for the plating method, for example, a metal such as copper, cobalt, nickel, zinc, molybdenum, tin, or chromium, a metal compound, or the like is used. These are superior to the case of cadmium or the like in terms of adhesion and blackness.

  When the mesh-like conductor layer is made of copper, such as copper foil, a preferable plating method for the blackening treatment for forming the blackened layer is a mesh-like conductor layer made of copper (because it is performed before forming the mesh shape). There is a cathodic electrodeposition plating method in which, if present, the previous conductor layer) is subjected to cathodic electrolysis in an electrolytic solution made of sulfuric acid, copper sulfate, cobalt sulfate or the like, and cationic particles are deposited. According to this method, the rough surface can be obtained simultaneously with the black color by the adhesion of the cationic particles. Copper particles and copper alloy particles can be used as the cationic particles. The copper alloy particles are preferably copper-cobalt alloy particles, and the average particle diameter is preferably 0.1 to 1 μm. A blackened layer composed of a copper-cobalt alloy particle layer is obtained by the copper-cobalt alloy particles. The cathodic electrodeposition method is also preferable in that the average particle size of the cationic particles to be adhered is adjusted to 0.1 to 1 μm. When the average particle diameter exceeds the above range, the density of the adhered particles is reduced, blackness is reduced and unevenness occurs, and particle falling off (powder falling) is likely to occur. On the other hand, even if the average particle diameter is less than the above range, the blackness is lowered. In the cathodic electrodeposition method, when the treatment is performed at a high current density, the treated surface becomes cathodic, and activated by reducing hydrogen generation, the adhesion between the copper surface and the cationic particles is remarkably improved.

  Moreover, as a blackening layer, black chrome, black nickel, a nickel alloy, etc. are preferable, and as this nickel alloy, they are a nickel-zinc alloy, a nickel-tin alloy, and a nickel-tin-copper alloy. In particular, the nickel alloy has a good degree of blackness and conductivity, can also impart a rust prevention function to the blackened layer (becomes a blackened layer and a rustproof layer), and can omit the rustproof layer. In addition, since the particles of the blackened layer are usually needle-like, the appearance is likely to change due to external force, but the blackened layer made of nickel alloy is difficult to deform and the appearance is difficult to change in the post-processing step. Benefits. In addition, the formation method of a nickel alloy as a blackening layer may be a known electrolytic or electroless plating method, and the nickel alloy may be formed after nickel plating.

(Transparent adhesive layer)
The transparent adhesive layer 5 is for adhering and fixing at least the mesh layer 3 composed of the mesh-like conductor layer 2 to the transparent base material 1 and is unnecessary and can be omitted depending on the method of forming the mesh-like conductor layer. It is also a layer. An example of a mesh-like conductor layer that requires the transparent adhesive layer 5 is a case where a metal foil that becomes the mesh-like conductor layer is bonded and fixed to a transparent substrate with an adhesive. In this case, as an adhesive for adhering the metal foil to the transparent substrate, a transparent adhesive is used so that the adhesive visible from the opening of the mesh layer made of the mesh-like conductor layer does not impair the light transmittance. There is a need. In particular, when a metal foil is laminated on a transparent base material and an opening is provided by etching and processed into a mesh shape, the adhesive is exposed in the entire area of the opening, so the transparency of the adhesive is required. The Therefore, it is preferable that the mesh-like conductor layer 2 made of metal foil is laminated on a transparent substrate via a transparent adhesive layer made of a transparent adhesive.

  In addition, as a specific lamination | stacking method of metal foil and a transparent base material, it does not specifically limit and a well-known lamination | stacking method is employ | adopted suitably, A transparent base material is a typical resin sheet in that. The field is generally dry lamination.

  The transparent adhesive used for the transparent adhesive layer is not particularly limited, and a known adhesive may be appropriately employed. For example, urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives and the like can be mentioned. Among them, urethane adhesives are preferable in terms of adhesive strength and the like. Such urethane adhesives include two-component curable urethane resin-based adhesives, and two-component curable urethane resin-based adhesives include various hydroxyl groups such as polyether polyol, polyester polyol, and acrylic polyol. It is an adhesive using a two-component curable urethane resin containing a containing compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

  The transparent adhesive layer is formed by applying a transparent adhesive to any one or both of a metal foil (before forming a mesh) or a transparent substrate by a known forming method, and then laminating them. It is formed by doing. Examples of the coating method include coating methods such as roll coating, comma coating, and gravure coating, and printing methods such as screen printing and gravure printing. In addition, although there is no restriction | limiting in particular in the thickness (at the time of drying) of a transparent adhesive bond layer, Usually, it is 0.1-20 micrometers, However, From points, such as adhesive force, cost, workability | operativity, it is 1-10 micrometers more preferably.

[Near-infrared absorbing layer]
The near-infrared absorbing layer 4 is a layer that imparts a near-infrared absorbing function as a composite electromagnetic wave shielding filter. This near-infrared absorbing layer is a transparent resin layer in which a specific near-infrared absorber is contained in a matrix made of a cured product of an ionizing radiation curable resin. The near infrared ray is a light ray adjacent to the visible light region and having a longer wavelength side than the visible light, and the near infrared ray to be noted in the present invention is a light ray having a wavelength of about 780 to 1100 nm. Further, as the near-infrared absorption performance, in general, in the wavelength region of 780 to 1100 nm, on average, it absorbs at least 50% or more, preferably 80% or more, more preferably 90% or more. desirable. In particular, when used as a composite electromagnetic shielding filter for a plasma display, near infrared absorption performance of 70% or more, more preferably 90% or more is desirable in the wavelength region of 800 to 950 nm.

  The near-infrared absorbing layer is formed by forming a transparent ionizing radiation curable resin composition to which a near-infrared absorbing agent is added as a non-cured material layer by a known layer forming means such as a coating method, and then the uncured material layer. It can be formed by irradiating an electron beam to cure the resin to form a cured product layer. In addition, you may add suitably well-known various additives, such as a dilution solvent and a stabilizer, in the said ionizing radiation resin composition as needed.

  Examples of the coating method include roll coating, comma coating, gravure coating, curtain coating, squeeze coating, pouring method, electrostatic atomization method, and dipping method. Further, as a layer forming means that can be partially formed in an arbitrary shape, for example, a printing method such as screen printing or gravure printing may be used.

Near-infrared absorber In the present invention, it is important to use at least three of the following four types of phthalocyanine compounds (A) to (D) as the near-infrared absorber.

（式〔Ｉ〕中、Ａ^１〜Ａ^１６は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、ヒドロキシスルホニル基、アミノスルホニル基、あるいは窒素原子、硫黄原子、酸素原子またはハロゲン原子を含んでも良い炭素数１〜２０の置換基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。Ｍ^１は、酸化バナジウムまたは銅を表す。）
本発明におけるフタロシアニン化合物（Ａ）〜（Ｄ）は、上記式〔Ｉ〕で表される化合物において、置換基Ａ^１〜Ａ^１６ならびにＭ^１に関する所定の条件が満たされる限りにおいて特に制限を受けないが、以下に具体的に記載する。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられる。この中では、特にフッ素原子および塩素原子が好ましい。 Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.
The phthalocyanine compounds (A) to (D) in the present invention are not particularly limited as long as the predetermined conditions regarding the substituents A ^{1 to} A ¹⁶ and M ¹ are satisfied in the compound represented by the formula [I]. Is specifically described below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are particularly preferable.

Examples of the substituent having 1 to 20 carbon atoms that may contain a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Linear, branched or cyclic alkyl such as a group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Group, methoxymethyl group, phenoxymethyl group, diethylaminomethyl group, phenylthiomethyl group, benzyl group, p-chlorobenzyl group, p-methoxybenzyl group, etc. -Aryl groups such as methoxyphenyl group, pt-butylphenyl group, p-chlorophenyl group,
Methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, Cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, alkoxy group such as 2-ethylhexyloxy group, alkoxyalkoxy group such as methoxyethoxy group and phenoxyethoxy group, hydroxyalkoxy group such as hydroxyethoxy group, benzyloxy Group, aralkyloxy group such as p-chlorobenzyloxy group, p-methoxybenzyloxy group, phenoxy group, p-methoxyphenoxy group, pt-butylphenoxy group, p-chlorophenoxy group, o-aminophenoxy group, p-diethylaminoph Phenoxy aryloxy group such as a group,
Acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group Alkylcarbonyloxy groups such as n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3-heptylcarbonyloxy group, n-octylcarbonyloxy group, benzoyloxy group P-chlorobenzoyloxy group, p-methoxybenzoyloxy group, p-ethoxybenzoyloxy group, pt-butylbenzoyloxy group, p-trifluoromethylbenzoyloxy group, m-trifluoro B methylbenzoyl group, o--aminobenzoyl group, p- diethylamino benzoyloxy arylcarbonyloxy group such as a group,
Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, alkylthio group such as 2-ethylhexylthio group, benzylthio group, p-chlorobenzylthio group, aralkylthio group such as p-methoxybenzylthio group, phenylthio group, p-methoxyphenylthio Group, pt-butylphenylthio group, p-chlorophenylthio group, o-aminophenylthio group, o- (n-octylamino) phenylthio group, o- (benzylamino) phenylthio group, o- (methylamino) Phenylthio group, p-diethylaminophenylthio group, Chiruchio arylthio group such as a group,
Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec-butylamino group, di-n-pentylamino group, di-n-hexyl Alkyl group such as amino group, di-n-heptylamino group, di-n-octylamino group, phenylamino group, p-methylphenylamino group, pt-butylphenylamino group, diphenylamino group, di- arylamino groups such as p-methylphenylamino group, di-pt-butylphenylamino group, acetylamino group, ethyl Nylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino Group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino group, n-octylcarbonylamino group and other alkylcarbonylamino groups, benzoylamino group, p-chlorobenzoylamino Group, p-methoxybenzoylamino group, p-methoxybenzoylamino group, p-t-butylbenzoylamino group, p-chlorobenzoylamino group, p-trifluoromethylbenzoylamino group, m-trif Oro methylbenzoyl arylcarbonylamino group such as an amino group,
Hydroxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyl Alkoxycarbonyl groups such as oxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, methoxy Alkoxyalkoxycarbonyl groups such as ethoxycarbonyl group, phenoxyethoxycarbonyl group, hydroxyethoxycarbonyl group, benzyloxycarbonyl group, phenoxycarboni Group, p- methoxyphenoxy group, p-t-butyl phenoxy carbonyl group, p- chlorophenoxy carbonyl group, o- aminophenoxy group, p- diethylamino phenoxycarbonyl aryloxycarbonyl groups such as,
Aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group, n -Heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-sec Alkylaminocarbonyl such as -butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-n-octylaminocarbonyl group Group, phenylaminocarbonyl group, p-methylphenylaminocarbonyl group, pt-butylphenylaminocarbonyl group, diphenylaminocarbonyl group, di-p-methylphenylaminocarbonyl group, di-pt-butylphenylaminocarbonyl Arylaminocarbonyl groups such as groups,
Methylaminosulfonyl group, ethylaminosulfonyl group, n-propylaminosulfonyl group, n-butylaminosulfonyl group, sec-butylaminosulfonyl group, n-pentylaminosulfonyl group, n-hexylaminosulfonyl group, n-heptylaminosulfonyl Group, n-octylaminosulfonyl group, 2-ethylhexylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, di-n-butylaminosulfonyl group, di-sec-butylaminosulfonyl group Group, alkylaminosulfonyl group such as di-n-pentylaminosulfonyl group, di-n-hexylaminosulfonyl group, di-n-heptylaminosulfonyl group, di-n-octylaminosulfonyl group, phenylamino Aryl such as sulfonyl group, p-methylphenylaminosulfonyl group, pt-butylphenylaminosulfonyl group, diphenylaminosulfonyl group, di-p-methylphenylaminosulfonyl group, di-pt-butylphenylaminosulfonyl group An aminosulfonyl group etc. are mentioned.

Examples of the substituent that two adjacent substituents may be linked via a linking group include a substituent that forms a 5-membered ring or a 6-membered ring via a heteroatom represented by the following formula or the like. Can be mentioned.

The “substituent through sulfur atom” in the phthalocyanine compounds (A) and (B), or the “substituent through nitrogen atom” in the phthalocyanine compounds (C) and (D) includes an amino group, an aminosulfonyl group, Examples thereof include an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, and an arylcarbonylamino group. The absorption wavelength of phthalocyanine is usually about 600 to 750 nm. However, when a substituent via a sulfur atom or a nitrogen atom is introduced, the absorption becomes longer, and the absorption reaches 800 nm or more. To that end, at least four of A ^{1 to} A ¹⁶ are a substituent via a sulfur atom and / or a substituent via a nitrogen atom, more preferably eight or more are a substituent via a sulfur atom and / or It is a substituent through a nitrogen atom.

The near-infrared absorbing layer in the composite electromagnetic wave shielding filter according to the present invention includes at least three of the above four types of phthalocyanine compounds (A) to (D). That is, the near-infrared absorbing layer in the present invention includes, as the near-infrared absorbing layer, three kinds selected from those containing all of the four kinds of phthalocyanine compounds (A) to (D) and the four kinds of compounds. These phthalocyanine compounds are included. The selection method of the three kinds of phthalocyanine compounds, the combination of phthalocyanine compounds, the mixing ratio of each phthalocyanine compound, and the like are arbitrary. For example, in the present invention, in consideration of the specific contents of the substituents A ^{1 to} A ^{16 in} the phthalocyanine compound, the specific identification of the phthalocyanine compound thereby, particularly the infrared absorption characteristics, etc., combinations of phthalocyanine compounds, each phthalocyanine compound And the total blending amount of all phthalocyanine compounds can be determined. In addition, this invention does not exclude using together 2 or more types of compounds classified as the same kind of phthalocyanine compound. That is, for example, the case where two or more phthalocyanine compounds (A) belonging to the group of compounds classified as the phthalocyanine compound (A) are used in combination is not excluded. The same applies to the phthalocyanine compounds (B) to (D).

  In the present invention, the optical characteristics (for example, absorption wavelength) of the composite electromagnetic wave shielding filter are appropriately changed by appropriately changing the specific types and combinations of the phthalocyanine compounds, the blending amount of each phthalocyanine compound, or the blending ratio thereof. Area, light transmittance, etc.) can be arbitrarily controlled, and the most preferable near-infrared absorption filter according to the specific application, purpose, etc. of the composite electromagnetic wave shielding filter can be provided.

  Further, the near infrared absorbing layer may have a multilayer structure of two or more layers. In the case of a multilayer, the type, the combined ratio, the content, etc. of the near infrared absorbing agent may be changed for each layer. Although content of a near-infrared absorber should just be suitably determined according to a required characteristic, the thickness of a transparent resin layer, etc., for example, it is 0.1-10 mass% with respect to the resin part whole quantity of a transparent resin layer. Since the near-infrared absorbing layer is formed of a resin composition that is cured with ionizing radiation, there is an advantage that even if a near-infrared absorber having a low solubility is used, the required concentration can be obtained by the thickness of the layer.

As the ionizing radiation curable transparent resin constituting the near-infrared absorbing layer of the ionizing radiation curable resin, a known resin composition that can be cured by ionizing radiation irradiation can be used. Specifically, a prepolymer (so-called oligomer) can be used. And / or a composition in which monomers are appropriately mixed is preferably used. These prepolymers or monomers are used alone or in combination. Here, “ionizing radiation” in the present invention includes various kinds of electromagnetic waves, charged particle beams, and the like having an energy amount capable of crosslinking or polymerizing molecules. Electron beams are typical.

  Specifically, the prepolymer or monomer is a compound having a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group in the molecule. Become. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also included. For example, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. Moreover, the following (meth) acrylates are the meanings of an acrylate or a methacrylate similarly. In addition, the acrylate compound and the methacrylate compound are collectively referred to simply as an acrylate (compound) or an acrylate compound.

  Examples of prepolymers having radically polymerizable unsaturated groups include acrylate-based prepolymers such as polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth) acrylate. Etc. can be used. The molecular weight is usually about 250 to 100,000.

  As an example of a monomer having a radical polymerizable unsaturated group, in the case of an acrylate monomer, as a monofunctional monomer, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, Acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, carboxypolycaprolactone (meth) acrylate, etc. System monomers and (meth) acrylamide. In addition, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate as polyfunctional monomers , Bifunctional monomers such as tripropylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri ( Trifunctional monomers such as (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaeryth Penta (meth) acrylate, polyfunctional monomers such as four or more functional such as dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include a prepolymer of an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy compound, or a vinyl ether resin such as a fatty acid vinyl ether or an aromatic vinyl ether.

  Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of polyurethane by diol and diisocyanate.

  For curing the ionizing radiation curable resin, it is preferable to use ultraviolet rays or electron beams as ionizing radiation.

  Conventionally, as a flattening resin layer or a transparent resin layer that is used to fill the opening of the mesh layer, the volume of the resin shrinks due to solvent drying when forming the coating film because the mesh layer is thick. However, a solvent-drying type resin (for example, urethane resin) which is large and difficult to form is disadvantageous. In the present invention, since the ionizing radiation can be used for curing the resin, the near-infrared absorbing layer can be formed without the above-mentioned problem due to volume shrinkage.

  In curing the ionizing radiation curable resin, a method of using ultraviolet rays as ionizing radiation is advantageous in that an ultraviolet lamp that is simple and inexpensive can be used as an ultraviolet irradiation device.

  In curing the ionizing radiation curable resin, the method of using an electron beam as ionizing radiation maximizes the excellent characteristics of the above four types of phthalocyanine compounds (A) to (D) used in the present invention. This is advantageous for providing a higher degree of durability.

  Various electron beam accelerators such as Cockcroft-Walton type, Bandegraft type, resonant transformer type, insulated core transformer type, linear type, dynamitron type, high frequency type, etc. And an electron having an energy of 70 to 1000 keV, preferably 100 to 300 keV, and the irradiation dose is preferably about 5 to 300 kGy.

  By the way, the use of an ionizing radiation curable resin as the resin of the transparent resin layer is possible with solvent-free coating, is excellent in productivity, etc. by omitting solvent drying, and even if a certain amount of solvent is contained, solvent-free coating is possible. This is because coating close to the work is possible and large volume shrinkage due to solvent drying during coating film formation can be prevented. Moreover, since thick coating is possible, it is easy to flatten the surface close to a flat surface by filling the concave portion at the opening of the mesh layer laminated on the transparent base material, and the concave portion is completely filled to absorb near infrared rays. This is because it is easy to form a perfect plane on the surface of the layer. By such flattening, the composite electromagnetic wave shielding filter has a near-infrared absorbing layer, or in the composite electromagnetic wave shielding filter, the near-infrared absorbing layer. In the case of laminating using a functional layer such as a component and an appropriate adhesive or the like, an effect of preventing air bubbles from being engulfed by unevenness of the adhesive surface is also obtained. By providing such a planarizing function in the near infrared absorbing layer, the planarizing resin layer described in the prior art column can also be used in the near infrared absorbing layer.

Form of near-infrared absorbing layer The surface of the near-infrared absorbing layer may basically be either a flat surface or a non-flat surface, and the near-infrared absorbing layer 4 illustrated in each of FIGS. (Surface on the upper side of the drawing) is drawn as a continuous flat surface including the opening region and the non-opening region of the mesh layer 3. This is a form in which a near-infrared absorbing layer is also present on the non-opening region of the mesh layer 3.

  In order to absorb the near infrared ray radiated from the display, the near infrared ray absorbing layer only needs to be present in the opening of the mesh layer, which is a portion that passes through the composite electromagnetic wave shielding filter. It is sufficient that a layer is formed at least in the opening. Further, the surface may be non-planar in terms of near infrared absorption performance. 4 is a cross-sectional view of FIG. 4 that conceptually illustrates some of other forms of the near-infrared absorption layer and the surface unevenness state thereof from this point of view.

  4A and 4B, the near-infrared absorbing layer 4 has a flat surface, and FIG. 4C has a non-flat surface. 4A and 4B also show a form in which the near-infrared absorbing layer 4 exists only in the opening of the mesh layer 3 and does not exist on the non-opening (immediately above the mesh layer).

  FIG. 4A shows a form in which the near-infrared absorbing layer 4 does not completely fill the opening, and the opening is a recess on the entire surface of the composite electromagnetic wave shielding filter 10. In FIG. 4A, the near-infrared absorbing layer 4 itself present in the opening has a flat surface. However, in practice, depending on the flow characteristics of the coating liquid, the center of the recess in the opening is used. Usually, it is a non-flat surface with a deep surface.

  4B shows that the near-infrared absorbing layer 4 completely fills the opening of the mesh layer 3 and fills up to the same height as the mesh layer, so that the non-opening of the mesh layer and the near-infrared absorbing layer The surface is a form that is a continuous flat surface with no steps.

  FIG. 4C shows that the near-infrared absorbing layer 4 is present in the entire region on the non-opening portion together with the opening portion of the mesh layer 3. This is a form in which the concave shape is left on the surface.

  In FIG. 1 and FIG. 3 and the like, the surface of the near-infrared absorbing layer 4 is a completely flat surface. However, these drawings are conceptual examples illustrating the layer structure, and the surface is (like the drawing). B) It may be a flat surface or it may be an uneven surface, and it is drawn as a flat surface including these.

  However, if the surface of the near-infrared absorbing layer is an uneven surface, the surface of the near-infrared absorbing layer (or the interface with the other layer in the case where another layer is further closely laminated) is used to transmit light that has passed through the opening. A flat surface is preferable in terms of optical characteristics that the path is bent. Moreover, in the point that a flat surface can be easily formed, even in a form in which a near infrared absorption layer is provided only in the opening, a form having the same thickness as the mesh layer as shown in FIG. 4B, and a mesh as shown in FIGS. The form which provides a near-infrared absorption layer also on the non-opening part of a layer is preferable.

  The flat surface may be a mirror surface but may not be a mirror surface. The flat surface has at least unevenness corresponding to the surface (horizontal) direction distribution of the thickness of the mesh layer (opening is low and valleys and non-opening is high and crests), and such unevenness, Or, even if there are other irregularities, when another adherend is laminated on the surface using an adhesive or the like, there is flatness that does not cause residual bubbles between them, In other words, it may be flatness that does not cause distortion of the display image or cloudiness (haze) due to light scattering. Therefore, even on a flat surface, for example, it may be a slow uneven surface corresponding to the mesh layer and it may be a mirror surface or a mat surface, and it is flat without a slow unevenness or steep unevenness depending on the mesh layer, In some cases, the mat surface has a fine mat-like fine unevenness. That is, the flat surface and the mirror surface are different concepts, and the mirror surface and the non-mirror surface are divided by fine unevenness that is finer than the flat surface and the non-flat surface.

  If the surface is a matte surface, the pyramid phenomenon (when the surface of the near-infrared absorbing layer is a mirror surface when winding a composite electromagnetic shielding filter in the form of a flexible sheet into a roll, it will be caught between the layers of the filter. The air that has escaped remains as bubbles without being escaped, and they are pressed into the filter by the tension at the time of winding, resulting in a microprojection defect with a pyramidal appearance on the surface of the filter. Advantages such as improved adhesion between layers during adhesion and adhesion lamination are obtained, and if there is a refractive index step at the interlayer interface due to fine irregularities on the surface, it can be made smooth and unnecessary light at the interface Reflection may be prevented.

  Including the cases of FIGS. 4A to 4C described above, the formation of the near-infrared absorbing layer is performed by supplying and applying the resin composition for forming the near-infrared absorbing layer intermittently. It is preferable to carry out by the intermittent coating method which consists of selectively supplying the resin composition and coating the mesh openings. Preferable specific examples of an apparatus suitable for such an intermittent coating method include those described in, for example, JP-A Nos. 2000-334355 and 2001-38276.

  The thickness of the near-infrared absorbing layer may be an appropriate thickness according to the near-infrared absorbing performance, the near-infrared absorbing agent content, the coating coating suitability when forming the near-infrared absorbing layer, the surface flattening suitability, etc. There is no particular limitation. For example, if you want to focus only on near-infrared absorption performance (or even a transparent function for the rough surface of the transparent adhesive layer exposed from the opening), it is necessary to provide only the opening and completely fill the opening. There is no. Therefore, for example, the thickness may be 1 μm or more. However, to satisfy the required near-infrared absorption performance, it is necessary to increase the content (ratio) of the near-infrared absorber in the transparent resin layer as the thickness is reduced. Further, in order to obtain a flat surface over the entire surface of the mesh layer if it also serves as a flattening resin layer, the near infrared ray including the non-opening portion of the mesh layer as illustrated in FIG. It is easy to form an absorption layer, and in such a case, the thickness of the near-infrared absorption layer differs between the opening portion of the mesh layer and the non-opening portion, and is equal to the thickness of the mesh layer at the opening portion of the mesh layer. Only thicker. In this case, in order to reliably cover the non-opening portion of the mesh layer with the near-infrared absorbing layer, for example, the portion may be 1 μm or more. However, in any case, if the thickness is too thick, the cost becomes high. Therefore, the thickest portion is preferably 100 μm or less (including the thickness of the mesh layer).

  In order to make the surface of the near-infrared absorbing layer into a desired uneven shape such as a flat surface, a matte surface, a mirror surface, etc., a shaping sheet may be used. The method of using the shaped sheet is, for example, from the top of the mesh layer laminated on the transparent substrate, while applying the coating liquid for forming the near-infrared absorbing layer and the coating film is liquid, After forming the surface shape formed on the surface of the coating film, such as by shaping the surface of the shaping sheet on the surface and solidifying the coating film, the shaping is performed. If the sheet is peeled off, the surface of the transparent resin layer can have a desired surface shape. Alternatively, if a state in which the coating film is plastically deformed by heating appears even after the coating is solidified, the shaped sheet may be peeled off after being formed by heating and pressurizing and shaping. In general, the resin is cured with ionizing radiation and solidified before peeling off the shaped sheet, and then the shaped sheet is peeled off.

  The shaped sheet can also be used as a protective sheet that is shipped as a product and peeled off at the customer's site while the near-infrared absorbing layer is not peeled off after curing.

  As the shaping sheet, there is no particular limitation as long as the surface can be shaped into a desired surface shape, such as a flat surface, and it has releasability from the coating film of the near infrared absorption layer, and an appropriate material is selected. Use it. In addition, if the ionizing radiation curable resin composition used as the near-infrared absorbing layer is cured by irradiating with an electron beam from the shaped sheet side, it is preferable to select one having transparency to the electron beam. As such a material, what consists of various resin sheets is mentioned.

  Examples of the resin sheet resin include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, Examples thereof include polyamide resins such as nylon 6, polyolefin resins such as polypropylene, polymethylpentene and cyclic polyolefin, imide resins and resins such as polycarbonate. Of these, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyolefin resins such as polypropylene and polynorbornene are usually preferred in terms of flatness, strength, releasability, electron beam transparency, heat resistance and cost. It is a good resin. From the viewpoint of mechanical strength, stretched sheets such as uniaxial stretching and biaxial stretching are preferred. As a specific example, a biaxially stretched polyethylene terephthalate sheet is optimal. The resin sheet has a thickness of about 10 to 1000 μm.

  In addition, the shaping surface of the shaping sheet is a flat surface, a mirror surface, and an uneven surface, the surface to be the shaping surface of the resin sheet is embossed, embossed, particles added into the resin sheet, Chemical etching or the like can be used.

  In addition, when the resin sheet alone is used as the shaping sheet, if the mold release property of the shaping surface is insufficient, a release layer made of a release material such as silicone may be formed on the shaping surface.

  Also, by adjusting the releasability of the shaping surface of the shaped sheet moderately (in a direction to reduce it when considering only releasability), the near infrared absorption layer at the mesh part of the mesh layer The shaped sheet is peeled off, and the shaped sheet can be peeled off together with the near-infrared absorbing layer at the frame portion. Thereby, the near-infrared absorption layer once formed also including the frame part can be removed together with the shaping sheet at the frame part to expose the frame part so that the frame part can be easily grounded. In order to adjust the releasability for this purpose, the wetting tension is preferably in the range of 35 to 45 mN / m (conforming to JIS K-6768), for example, with the wettability of the shaped surface as an index. In order to adjust the shaping surface to an appropriate releasability, for example, corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer coating treatment, preheat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, etc. An adhesion treatment may be performed.

  In addition, you may contain pigments other than a near-infrared absorber in a near-infrared absorption layer. For example, in order to prevent the coloring used in the near-infrared absorber to absorb in the visible light region, and the absorption is not uniform in the visible light region, and the white balance of the image is lost. In addition, a dye having absorption in other parts in the visible light region may be used in combination so that the light absorption becomes neutral (achromatic color). Alternatively, a neon light absorbing agent that suppresses neon emission emitted from the PDP and improves color reproducibility, a dye that suppresses unnecessary external light reflection, and the like.

[Other layers]
The composite electromagnetic wave shield filter of the present invention may have a configuration in which layers other than those described above are appropriately laminated as necessary. For example, for further imparting other functions that cannot be realized from the above-described layer configuration, such as surface protection, mechanical strength improvement, optical property improvement, etc., appropriately on the back surface side, the front surface side, or both of these surfaces with respect to the transparent substrate Is a layer. As these layers, for example, various known functional layers can be appropriately employed for conventional display applications. These can use a well-known thing suitably, such as a commercial item. Or you may form as a coating film. Further, it may be bonded and laminated to the front substrate of the display. At this time, in the embodiment in which the transparent resin layer is provided including the non-opening portion of the mesh layer, the transparent resin layer may function as an adhesive layer. Of course, an adhesive layer may be provided separately from the transparent resin layer.

  In such a composite electromagnetic wave shielding filter of the present invention, representative functional layers that can be appropriately used as necessary include neon light shielding functional layers, antireflection functional layers, antiglare functional layers, and antifouling functional layers. And an ultraviolet absorbing layer.

  The neon light shielding functional layer, the antireflection functional layer, the antiglare functional layer, the antifouling functional layer and the ultraviolet absorbing layer which are preferable in the present invention are described in detail below.

Antifouling layer The antifouling layer prevents or adheres to the surface of dust and contaminants due to inadvertent contact and environmental contamination when using a composite electromagnetic shielding filter. However, it is a layer formed for easy removal. For example, a fluorine-based coating agent, a silicon-based coating agent, a silicon / fluorine-based coating agent or the like is used, and among them, a silicon / fluorine-based coating agent is preferably applied. The thickness of these antifouling layers is preferably 100 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. When the thickness of these antifouling layers exceeds 100 nm, the initial value of antifouling properties is excellent, but the durability is inferior. 5 nm or less is the most preferable from the balance of antifouling property and its durability.

Neon light shielding layer The neon light shielding layer is for cutting unnecessary luminescence around 595 nm mainly emitted by excitation of neon gas in PDP, and neon light shielding dye and binder resin having an absorption maximum near this wavelength. In addition, it may be performed in the same manner as in the formation of the near-infrared absorbing layer, using other additives added as necessary. As the neon light-shielding dye, cyanine-based, oxonol-based, methine-based, subphthalocyanine-based, or porphyrin-based compounds can be preferably used, and porphyrin-based compounds are particularly preferable in terms of durability.

Antireflection layer The antireflection layer is typically one in which a high refractive index layer and a low refractive index layer are laminated in order, but there are also those having other laminated structures. The high refractive index layer is, for example, a thin film made of ZnO or TiO ₂ or a transparent resin film in which fine particles of these materials are dispersed. The low refractive index layer is a thin film made of MgF ₂ or SiO ₂ , a SiO ₂ gel film, or a transparent resin film containing fluorine or containing fluorine and silicon. Since the antireflection layer is laminated, it is possible to reduce reflection of unnecessary light such as external light on the laminated side, and to increase the contrast of the image or video of the applied display.

Anti- glare layer Anti-glare layer includes, for example, those in which beads such as polystyrene resin and acrylic resin having a diameter of about several μm are dispersed in a transparent resin. In addition, it is intended to prevent scintillation occurring at a specific position and direction of the display.

Ultraviolet absorption layer The ultraviolet absorption layer shields or controls ultraviolet rays contained in electrical or electronic devices and natural light. This makes it possible to further improve the durability of various resin materials and other constituent materials (for example, transparent resin materials and pigments) constituting the display.

  In the present invention, for example, an ultraviolet absorbing layer having a light transmittance of 40% or less, preferably 30% or less at all wavelengths in a region below 380 nm is provided between the antireflection layer and the near infrared absorbing layer. Can be provided. A near-infrared absorption filter in which such an ultraviolet absorption layer is formed is a preferred specific example of the present invention.

  The ultraviolet absorber may be contained in the above-mentioned transparent substrate, or may be provided as an independent layer containing the ultraviolet absorber, that is, an ultraviolet absorbing layer. The ultraviolet absorbing layer is, for example, an acrylic resin, polycarbonate resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, AS resin, polyester resin, vinyl acetate resin, polyvinyl butyral as a binder resin. A resin in which an ultraviolet absorber is added to a resin, PVPA, polystyrene resin, phenol resin, phenoxy resin, polysulfone, nylon, cellulose resin, cellulose acetate resin, etc. It is formed as a layer having a thickness of 1 to 30 μm, preferably 0.5 to 10 μm. In addition, when the ultraviolet absorbing layer is used as a filter, it is located on the outside side of the near infrared absorbing layer or contained in a layer located on the outside side, which causes deterioration of the near infrared absorbing agent in the near infrared absorbing layer. Preferred for protection.

<Plasma display>
The plasma display according to the present invention is characterized in that the above-mentioned composite electromagnetic wave shielding filter is arranged on the viewing side of the display.

  When the composite electromagnetic wave shielding filter according to the present invention is used for a PDP, it is installed on the front surface of the display to cut off electromagnetic waves and near infrared light emitted from the display. For this reason, if the visible light transmittance is low, the sharpness of the image is lowered. Therefore, the higher the visible light transmittance of the filter, the better. At least 30% or more, preferably 35% or more is necessary.

  The near infrared light cut region is designed to be 800 to 1000 nm where light is emitted from the PDP, and the light transmittance in that region is 30% or less.

  Hereinafter, the present invention will be described in more detail with reference to FIG. 2 and FIG. Note that the present invention is not limited by these descriptions.

Synthesis of phthalocyanine compound (A) In a 250 ml four-necked flask, 20 g (41 mmol) of 3- (4-chlorophenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile, 2 g of vanadium trichloride (13 Mmol), 2 g of octanol and 30 g of benzonitrile were charged and held for about 6 hours with stirring under reflux. Thereafter, 60 g of benzonitrile was added and the temperature was kept at 60 ° C., then 30 g (230 mmol) of 1- (2-aminoethyl) morpholine was added and stirred while maintaining at 60 ° C. for about 6 hours. The reaction solution was precipitated by a phthalonitrile method using a mixed solution of acetonitrile and water, and then vacuum-dried to obtain VOPc (PhS) ₈ {4-ClPhO} ₄ (OC ₄ H ₈ N (CH ₂ ) _2. 8 g of NH) ₄ was obtained (where Pc represents phthalocyanine, Ph represents phenyl, and so on). The maximum absorption wavelength when the phthalocyanine compound (A) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 925 nm.

Synthesis of phthalocyanine compound (B) 3- (4-chlorophenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile instead of 3-phenoxy-4,5-bis (4-methoxyphenylthio)- VOPc {4- (CH ₃ O) PhS} ₈ (PhO) ₄ (OC ₄ H ₈ N (CH ₂ ) is the same as that of the phthalocyanine compound (A) except that 22 g (41 mmol) of 6-fluorophthalonitrile is used. 10 g of ₂ NH) ₄ was obtained. The maximum absorption wavelength when the phthalocyanine compound (B) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 975 nm.

Synthesis of phthalocyanine compound (C) In a 250 ml four-necked flask, 20 g (34 mmol) of 3-phenoxy-4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile, 2 g of vanadium trichloride (13 Millimoles), and 30 ml of n-octanol, and the mixture was kept for about 4 hours with stirring at 170 ° C. while bubbling nitrogen. Thereafter, the mixture was cooled to room temperature, 15 g (136 mmol) of PhCH ₂ NH ₂ and 120 ml of benzonitrile were added, and the mixture was kept at 90 ° C. for about 5 hours. The reaction solution was cooled, precipitated by the phthalonitrile method, and then vacuum-dried to obtain 180 g of VOPc (2,5-Cl ₂ PhO) ₈ (PhO) ₄ (PhCH ₂ NH) ₄ . The maximum absorption wavelength when the phthalocyanine compound (C) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 878 nm.

Synthesis of phthalocyanine compound (D) CuPc (2,5-Cl ₂ PhO) ₈ (PhO) was carried out in the same manner as the synthesis of compound (C) except that 1 g (10 mmol) of copper chloride was used instead of vanadium trichloride. ) ₄ (PhCH ₂ NH) ₄ 180 g was obtained. The maximum absorption wavelength when the phthalocyanine compound (D) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 810 nm.
Production of Electromagnetic Shielding Filter In FIG. 3A, first, as a metal foil to be a mesh-like conductor layer 2, a continuous 10 μm thick in which a blackened layer 7 made of copper-cobalt alloy particles is formed on one surface. A strip-shaped electrolytic copper foil was prepared. Moreover, the transparent base material 1 prepared the 100-micrometer-thick continuous belt-shaped non-colored transparent biaxially-stretched polyethylene terephthalate film.

  And after carrying out zinc plating with respect to both surfaces of the said copper foil, the well-known chromate process was performed by the dipping method, and the antirust layer 6 was formed in both front and back surfaces. Next, a transparent two-component curable urethane resin comprising 12 parts by mass of a polyester polyurethane polyol having an average molecular weight of 30,000 and 1 part by mass of a xylene diisocyanate-based prepolymer on the transparent substrate on the blackened layer surface side of the copper foil. After dry laminating with an adhesive, it is cured at 50 ° C. for 3 days to obtain a continuous belt-like copper-clad laminated sheet having a transparent adhesive layer 5 having a thickness of 7 μm between the copper foil (rust preventive layer) and the transparent substrate. It was.

  Subsequently, the copper foil (the conductor layer, the blackening layer, and the rust prevention layer on the entire surface) is etched on the copper-laminated laminated sheet by using a photolithography method to prevent the rust prevention layer 6 and the mesh conductor layer. A mesh laminated sheet in which the mesh layer 3 composed of 2 and the blackening layer 7 was formed on the transparent substrate 1 was obtained.

  Specifically, the etching was performed from masking to etching on the continuous belt-shaped copper-clad laminate sheet using a production line for a color TV shadow mask. That is, after applying an etching resist to the entire surface of the conductor layer of the copper-clad laminate sheet, a desired mesh pattern is closely exposed, developed, hardened, baked, and then blackened with a ferric chloride solution, an anticorrosive layer The copper foil was etched to form a mesh-shaped opening, and then washed with water, stripped of resist, washed, and dried sequentially. As shown in FIG. 2, the mesh shape of the mesh layer is a rectangular part of the mesh part 3 </ b> A whose line width is 10 μm, and whose line interval (pitch) is 300 μm. A bias angle of 49 degrees, defined as a minor angle with respect to the long side of the region. Further, the mesh of the mesh layer was etched so as to leave a frame portion 3B having a width of 15 mm with no opening on the outer periphery of the four sides when the continuous belt-like sheet was cut into a rectangular sheet having a desired size.

Production of Composite Electromagnetic Shielding Filter Next, the above-mentioned mesh laminated sheet once wound up is ionized by adding a near-infrared absorber to unwind and form a transparent resin layer 4 on the surface of the mesh layer 3 A coating liquid composed of a radiation curable resin composition was applied on a mesh (based on solid content) at a coating amount of 25 g / m ² by intermittent coating. The coating was performed up to a position where the frame portion moved 2.5 mm toward the entire inner periphery of the frame portion running in the width direction and the frame portions on both sides, and the outer side was not coated. The coating liquid was prepared by adding the above phthalocyanine to a UV-curable polycaprolactone-modified urethane acrylic resin containing 3% of a photopolymerization initiator (Darocur (registered trademark) 1173, manufactured by Nagase Sangyo Co., Ltd.) with respect to the resin content. Compound (A), phthalocyanine compound (B), phthalocyanine compound (C), and phthalocyanine compound (D) at a concentration per unit area in the transparent resin layer at the opening after coating formation with the above coating amount ( (Hereinafter also referred to as “area concentration”) are (A): 0.09 g / m ² , (B): 0.13 g / m ² , (C): 0.13 g / m ² , (D): 0.0. It is a coating liquid comprising a liquid resin composition which is contained at a ratio of 18 g / m ² and further diluted with an appropriate amount of an organic solvent (mixed solvent of methyl ethyl ketone: toluene = 1: 1 mass ratio).

  And after the said application | coating, as a shaping sheet | seat which shapes a flat surface with respect to the coating film after drying a solvent, a 50-micrometer-thick continuous belt-shaped commercially available biaxially-stretched polyethylene terephthalate film is the unadhesion-treated untreated surface. And laminated to the coating film. Thereafter, UV irradiation from the side of the shaped sheet (using a D bulb with a lamp output of 240 W / cm manufactured by Fusion UV Systems, a lamp output of 100%, a light source-coating distance of 60 mm, and a line speed of 5 m / min) After the coating film was cured, only the shaped sheet was peeled off to form the transparent resin layer 4 having a flat surface, and a composite electromagnetic wave shielding filter 10 as shown in FIG. 3A was obtained.

  3A is composed of transparent substrate 1 / transparent adhesive layer 5 / mesh layer 3 (rust prevention layer 6 / blackening layer 7 / mesh shape) in order from the transparent substrate 1 side. In the conductor layer 2 / rust prevention layer 6) / transparent resin layer 4, the observer side is configured to be the transparent substrate 1 side. “/” Indicates that the left and right layers are laminated and integrated. The transparent resin layer 4 is formed over the entire surface over both the mesh layer 3 and the opening, and the surface is a flat surface.

  Spectral characteristics of the obtained laminate before and after ultraviolet irradiation were measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) (FIG. 5 (a): before ultraviolet irradiation, FIG. 5 (b): ultraviolet irradiation. After) However, almost no spectral change was observed before and after ultraviolet irradiation, and the light transmittance at 800-1000 nm was 10% or less, and the near infrared rays were sufficiently blocked.

<Example 2>
Three phthalocyanine compound as a near-infrared absorbing ^{agent, (A): 0.13g / m} 2, (C): 0.13g / m 2, (D): except for using 0.18 g / ^{m 2} is carried out It carried out like Example 1. Spectral characteristics of the obtained laminate before and after ultraviolet irradiation were measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) (FIG. 6 (a): before ultraviolet irradiation, FIG. 6 (b): ultraviolet irradiation. After) However, there is almost no spectral change before and after UV irradiation, and the light transmittance at 1000-nm is slightly high, but the light transmittance at 800-950 nm with strong near-infrared radiation intensity from the PDP panel is 30% or less. The near infrared ray was sufficiently shielded.

<Example 3>
Example 2 The same as in Example 2 except that a photopolymerization initiator (Irgacure184 (registered trademark), manufactured by Ciba Specialty Chemicals Co., Ltd.) containing 3% of the resin content was used as the ultraviolet curable resin. I went there. As a result, although the spectral change before and after UV irradiation is slightly larger than that of Example 2, the light transmittance at 800-950 nm with strong near-infrared radiation intensity from the PDP panel is 30% or less, and the near-infrared rays are sufficiently shielded. (FIG. 7 (a): before ultraviolet irradiation, FIG. 7 (b): after ultraviolet irradiation).

<Example 4>
Instead of the ultraviolet resin, a 1 to 1 mass ratio resin of tetrahydrofurfuryl methacrylate (THF) and a urethane acrylate oligomer (UA) (no photopolymerization initiator) is used, and the electron is irradiated with an electron beam irradiation device as curing conditions. This was performed in the same manner as in Example 2 except that the coating was cured by irradiating the wire [acceleration voltage 175 kV, irradiation dose 30 kGy (3 Mrad)]. The spectral characteristics of the obtained laminate were almost the same as in Example 2, and almost no spectral change was observed before and after electron beam irradiation, and although the light transmittance near 1000 nm was slightly high, the near-infrared radiation intensity from the PDP panel was strong 800 The light transmittance at −950 nm was 30% or less and sufficiently shielded near infrared rays.

<Comparative Example 1>
The same procedure as in Example 1 was conducted except that 2 g of diimmonium (IR-022, manufactured by Nippon Kayaku Co., Ltd.) was used instead of the phthalocyanine compounds (A), (B), (C), and (D). . FIG. 8A shows the spectrum before curing of the coating film by UV irradiation, and FIG. 8B shows the spectrum after curing. The spectrum changed greatly between before and after curing, and the light transmittance in the near infrared region of 800 to 1000 nm exceeded 30%, and the near infrared shielding performance was remarkably deteriorated.

<Comparative example 2>
Two phthalocyanine compound as a near-infrared absorbing ^{agent, (C): 0.13g / m} 2, (D): except for using only 0.12 g / ^{m 2} was performed in the same manner as in Example 1. Although there is almost no spectral change before and after UV irradiation, 900-nm and beyond cannot be sufficiently shielded from 800-950 nm with strong near-infrared radiation intensity from the PDP panel, and the light transmittance reaches 70% at 950 nm (Fig. 9 (a): before ultraviolet irradiation, FIG. 9 (b): after ultraviolet irradiation).

Sectional drawing which illustrates the form example of the composite electromagnetic wave shield filter by this invention. The top view which illustrates the frame part provided in the circumference | surroundings of a mesh layer. Sectional drawing which illustrates some of the another example of a form of the composite electromagnetic wave shield filter by this invention. Sectional drawing which illustrates some of the position which provides a transparent resin layer, and its surface shape example. FIG. 5 shows the spectral characteristics of the composite electromagnetic shielding filter obtained in Example 1. FIG. 5 (a) shows the characteristics of the composite electromagnetic shielding filter before irradiation with ultraviolet rays, and FIG. The characteristics after subjecting the composite electromagnetic wave shielding filter to ultraviolet irradiation are shown. FIG. 6 shows the spectral characteristics of the composite electromagnetic wave shielding filter obtained in Example 2. FIG. 6 (a) shows the characteristics of the composite electromagnetic wave shielding filter before ultraviolet irradiation, and FIG. The characteristics after subjecting the composite electromagnetic wave shielding filter to ultraviolet irradiation are shown. FIG. 7 shows the spectral characteristics of the composite electromagnetic wave shielding filter obtained in Example 3. FIG. 7 (a) shows the characteristics of the composite electromagnetic wave shielding filter before ultraviolet irradiation, and FIG. The characteristics after subjecting the composite electromagnetic wave shielding filter to ultraviolet irradiation are shown. FIG. 8 shows the spectral characteristics of the composite electromagnetic wave shield filter obtained in Comparative Example 1. FIG. 8 (a) shows the characteristics of the composite electromagnetic wave shield filter before ultraviolet irradiation, and FIG. 8 (b) shows the same characteristics. The characteristic after attaching | subjecting a composite electromagnetic wave shield filter to ultraviolet irradiation is shown. FIG. 9 shows the spectral characteristics of the composite electromagnetic wave shielding filter obtained in Comparative Example 2. FIG. 9 (a) shows the characteristics of the composite electromagnetic wave shielding filter before ultraviolet irradiation, and FIG. The characteristics after subjecting the composite electromagnetic wave shielding filter to ultraviolet irradiation are shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent base material 2 Mesh-like conductor layer 3 Mesh layer 3A Mesh part 3B Frame part 4 Near-infrared absorption layer 5 Transparent adhesive layer 6 Rust prevention layer 7 Blackening layer 10 Composite electromagnetic wave shielding filter

Claims (2)

A composite electromagnetic shielding filter having electromagnetic shielding performance and near infrared absorption performance,
A mesh layer including a mesh-like conductor layer is formed on a transparent substrate, and further, near infrared absorption is performed on a surface including at least the mesh layer opening on the surface on which the mesh layer is formed on the transparent substrate. A composite electromagnetic shielding filter in which a layer is formed;
The near-infrared absorbing layer is made of an ionizing radiation curable transparent resin comprising at least three of the following four types of phthalocyanine compounds (A) to (D): .
Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.   A plasma display, wherein the composite electromagnetic wave shielding filter according to claim 1 is disposed on the viewing side of the display.

Images