JP2009192922A - Filter for image display apparatus, and image display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filter for an image display apparatus, which has desired optical filter functions demanded for the image display apparatus, such as near IR absorption and external light reflection prevention, high transparency and electromagnetic wave shielding function, and obtains an image of high contrast by preventing image whitening under an external light incident environment. <P>SOLUTION: The filter 100 for the image display apparatus comprises: a layer configuration constituted by laminating an electromagnetic wave shielding filer 20 having a patterned electromagnetic shielding layer 4 on a rear face side transparent substrate 5; and a surface adjustment filter 10 having a surface side transparent substrate 2 and a surface adjustment layer 1 via a surface side transparent tacky adhesive layer 3 on the electromagnetic shielding layer 4, and laminating a rear face side transparent tacky adhesive 6 on the rear face side transparent substrate 5, wherein, the electromagnetic shielding layer 4 includes a metal fine particle binding body and a nickel columnar integrated crystal layer having a light diffusive irregular surface on the outermost surface covering the surface thereof, and includes an absorbent in either one or two layers of the surface side transparent tacky adhesive layer 3 or rear face side transparent tacky adhesive layer 6. The image display device is also provided which uses this filter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a filter for an image display device and an image display device using the same, and is particularly suitable as a filter for a plasma display panel (hereinafter sometimes referred to as “PDP”), and optical such as near infrared absorption. The present invention relates to a filter for an image display device that has a filter function and has high visible light transmittance, excellent transparency, and shields electromagnetic waves, and an image display device using the same.

In recent years, PDPs have attracted attention as image display devices (referred to as displays) become larger and thinner.
Since PDP uses plasma discharge for light emission, unnecessary electromagnetic waves in the 30 MHz to 1 GHz band may leak to the outside and affect other devices (for example, remote control devices, information processing devices, etc.). Therefore, a film-like electromagnetic wave shielding member for shielding (shielding) electromagnetic waves that leak while maintaining the transparency of image light on the front side (observer side) of the plasma display panel used in the plasma display device. It is common to provide it.
Electromagnetic wave shielding member materials that can be used for the front surface of plasma displays include silver sputtered thin films and copper mesh, but silver sputtered thin films are expensive and cover the entire surface, so visible light (line) Poor compatibility between transparency and electromagnetic wave shielding. Since the copper mesh has an opening, the transparency is high. However, since the copper foil is etched by photolithography to create a mesh shape, many materials are thrown away and it is difficult to reduce the cost.
In recent years, electromagnetic wave shielding members have been proposed in which a conductive paste or ink containing a catalyst for electroless plating is printed on a transparent substrate by pattern printing such as gravure, and copper is deposited on the transparent substrate to form a fine line pattern. (Patent Documents 1 and 2), it can be said that the method is more economical and more productive than the copper foil etching method.
In the specification of the present application, when simply referring to “electromagnetic wave” without any notice, the electromagnetic wave in a broad sense has a frequency (long wavelength) band lower than the infrared band, and mainly the MHz to GHz band or the like. The one in the vicinity. Infrared, visible light, and ultraviolet light are used in a meaning that does not include them.

On the other hand, in the electromagnetic wave shielding member, the surface is generally blackened in order to prevent invisibility and to improve the contrast and prevent whitening of the image in the environment of incident external light such as sunlight and illumination light. It is.
As a conventional blackening treatment method, for example, a method of performing black copper-cobalt alloy plating on copper plating, a method of pattern printing using a black additive or a black additive such as carbon black on a conductive paste, etc. (Patent document 3) etc. are mentioned.
However, in the method of performing black copper-cobalt alloy plating or the like, two layers of plating are performed, which has a problem in productivity or economy, and pattern printing is performed using a black additive in the conductive paste. In the method, the black additive is added, thereby causing a problem that printability of printing ink is deteriorated or conductivity is lowered.
In addition to electromagnetic waves in the above frequency band, the PDP has unnecessary radiation such as near infrared rays, emission spectrum light of neon atoms (also called neon light), and it is necessary to absorb and shield these. In addition, if extraneous light such as sunlight or illumination light is reflected and reflected on the screen, the extraneous light is reflected, the screen is whitened, and the image contrast is lowered. It was. In order to satisfy these requirements, filters for image display devices having various configurations in which an electromagnetic wave shielding filter and various optical filters having a desired function have been created and combined have been proposed. Among them, a layered structure as shown in FIG. 1 is often used as a preferred form.

JP 2001-102792 A Japanese Patent Laid-Open No. 11-174174 JP 2000-13088 A

  It is an object of the present invention to have a desired optical filter function, high transparency, and electromagnetic wave shielding function required for an image display device such as near-infrared absorption and anti-reflection of external light, and image whitening in an external light incident environment. It is an object of the present invention to provide a filter for an image display device that obtains a high-contrast image and an image display device using the same.

  The present inventor has conducted extensive research to solve the above problems in a filter for an image display device having a specific structure (see FIG. 1) in which an optical filter having a desired function and an electromagnetic wave shielding filter are laminated. As a result, the outermost surface of the surface-coated nickel columnar crystal aggregate comprises a metal fine particle binder obtained by binding metal fine particles with a binder resin and a nickel columnar crystal aggregate layer covering the surface of the metal fine particle binder. It has been found that the above problem can be solved by having an electromagnetic wave shielding layer that is a light diffusive fine uneven surface. The present invention has been completed based on such findings.

That is, the present invention provides an electromagnetic wave shielding filter having a patterned electromagnetic wave shielding layer on the back surface side transparent substrate, and the surface side transparent adhesive layer on the electromagnetic wave shielding layer of the electromagnetic wave shielding filter. A surface adjustment filter having a surface adjustment layer selected from an antireflection layer, an antiglare layer, or a hard coating layer on the side transparent substrate, and the surface side transparent substrate side faces the electromagnetic wave shielding layer In this way, the electromagnetic wave shielding filter has a layer structure in which a back side transparent adhesive layer is laminated on the back side transparent base material of the electromagnetic wave shielding filter, and the electromagnetic wave shielding layer is composed of metal fine particles in which metal fine particles are bound by a binder resin. A binder and a nickel columnar crystal aggregate layer covering the surface of the metal fine particle binder, the outermost surface of the surface-coated nickel columnar crystal aggregate layer has a light diffusive fine irregular surface, Surface side transparency In any one or two layers of the pressure-sensitive adhesive layer or the back side transparent pressure-sensitive adhesive layer, any one selected from a near-infrared absorber, a neon light absorber, a toning agent, or an ultraviolet absorber. A filter for an image display device comprising the above absorbent,
The present invention also provides an image display device using the image display device filter.

  According to the present invention, an image display that has a desired optical filter function such as a near-infrared absorption function, high transparency, and an electromagnetic wave shielding function, and that prevents whitening of the image in an external light incident environment and obtains a high-contrast image. An apparatus filter and an image display apparatus using the same can be provided.

FIG. 1 is a cross-sectional view showing a layer structure of a filter for an image display device of the present invention. In addition, the scales in each drawing including FIG. 1 are appropriately changed from the actual values in the vertical and horizontal dimension ratios and the dimension ratios between the respective layers, while being easy to illustrate.
In FIG. 1, the upper side is the viewer (viewer) side, and the lower side is the image display device side. The filter 100 for an image display device of the present invention includes a surface adjustment layer 1, a surface side transparent base material 2, a surface side transparent adhesive layer 3, an electromagnetic wave shielding layer 4, a back side transparent base material 5, The back side transparent adhesive layer 6 is laminated in this order.
Among these constituent layers, the surface adjustment layer 10 is constituted by the surface adjustment layer 1 and the front surface side transparent base material 2, and the electromagnetic wave shielding filter 20 is constituted by the electromagnetic wave shielding layer 4 and the back surface side transparent base material 5. The

  Usually, in the manufacturing process, first, the surface adjustment filter 10 and the electromagnetic wave shielding filter 20 are configured. After that, the surface side transparent base material 2 side of the surface adjustment filter 10 and the electromagnetic wave shielding layer 4 side of the electromagnetic wave shielding filter 20 are laminated via the surface side transparent adhesive layer 3 therebetween. In addition, the back surface side transparent adhesive layer 6 is laminated on the surface of the electromagnetic wave shielding filter 20 on the back surface side transparent base material 5 side. Thus, the image display device filter 100 is configured. In addition, either the lamination | stacking (lamination | stacking of the surface side transparent adhesive layer 3) process with the surface adjustment filter 10 and the electromagnetic wave shielding filter 20 and the lamination | stacking process of the back surface side transparent adhesive layer 6 can be performed before and after. Or it is also possible to advance both processes simultaneously. These can be realized by appropriately selecting a known lamination technique.

The obtained image display device filter 100 is laminated on the viewer side of the image display device or the image display device substrate 200 using the back-side transparent adhesive layer 6. When the image display device filter 100 is laminated with the image display device or the image display device substrate 200 to form an image display device front plate (also referred to as a plate-like image display device filter). This is further installed on the observer side of the main body of the image display device.
In the present invention, the surface adjustment layer 1 is selected from any one of an antireflection layer, an antiglare layer, and a hard coating layer. To prevent the reflection of extraneous light from the reflection of extraneous light on the outermost surface, whitening, and reduction in image contrast, either an antireflection layer or an antiglare layer is selected. If it is not necessary to prevent reflection of extraneous light, the hardest coating layer is selected because it is necessary to protect the outermost surface from scratches and contamination at a minimum. In addition, it can be said that the antireflection layer or the antiglare layer also substantially serves as the function of the hard coating layer.

In the present invention, either one or two of the front surface side transparent adhesive layer 3 and the rear surface side transparent adhesive layer 6 is subjected to unnecessary or extraneous radiation from the image display device. In order to absorb and remove or adjust the color tone of image light, one or more absorbers selected from near infrared absorbers, neon light absorbers, toning agents, and ultraviolet absorbers are included. .
Furthermore, in the present invention, as a new configuration, in order to prevent whitening of the image in an environment where external light is incident and to obtain a high-contrast image, an electromagnetic wave shielding layer is used as shown in FIG. It consists of a metal fine particle binder 7 bound by a resin 7a and a nickel columnar crystal aggregate layer 8 covering the surface of the metal fine particle binder, and the outermost surface of the surface-coated nickel columnar crystal aggregate layer is light diffusing. The structure is formed with a fine uneven surface.

Here, the metal fine particle binder and the surface-coated nickel columnar crystal aggregate layer having the fine irregular surface cooperate to realize conductivity sufficient to exhibit a sufficient electromagnetic wave shielding function. In addition, the surface-coated nickel columnar crystal aggregate layer having the fine uneven surface functions as a so-called blackening layer, and absorbs extraneous light, and even if it does not absorb and reflects as a diffuse reflection, it is visually recognized by the observer. To reduce reflected light. This reduces adverse effects of external light such as image whitening due to external light, image contrast reduction, and reflection of external light. That is, the combination of the metal fine particle binder 7 and the nickel columnar crystal aggregate layer 8 employed in the present invention has both the effect of reducing the adverse effect of extraneous light and the conductivity as compared with the conventionally known blackening layer. Excellent in properties.
As described above, the effect of reducing the adverse effects of extraneous light is also exhibited by the antireflection layer or the antiglare layer, but it is difficult to completely reduce these layers alone. By using the surface-coated nickel columnar crystal aggregate in combination, a better effect of reducing the adverse effect of extraneous light can be achieved. Further, in the case where the scratch resistance of the outermost surface is designed with the highest priority, when a hard coating layer is adopted as the surface adjustment layer, the antireflection property or the antiglare property must be sacrificed. For this reason, in the present invention, the combination of the fine metal particle binder 7 and the nickel columnar crystal aggregate layer 8 is essential.

As in the case shown in FIG. 1, the observer observes an object such as a PDP from the surface adjustment filter 10 side through the image display device filter 100. By taking such a configuration, the observer When viewed, it is possible to see an image having excellent transparency with a transmission color tone not showing blue, near infrared rays being effectively absorbed, and high visible light transmittance.
The filter for an image display device of the present invention preferably has a visible light transmittance of 40% or more at a wavelength of 380 to 780 nm and a near infrared transmittance of 20% or less at a wavelength of 800 to 1100 nm. When the visible light transmittance is 40% or more, even when it is used as a near-infrared absorbing electromagnetic wave shielding filter of an image display device such as a PDP, sufficient luminance can be given and the image is not darkened. From the above viewpoint, the visible light transmittance is particularly preferably 60% or more. On the other hand, when the near-infrared transmittance is 10% or less, peripheral electronic devices do not malfunction due to near-infrared rays generated from the PDP main body. From the above viewpoint, the near infrared transmittance is preferably 10% or less.

First, the surface adjustment filter 10 will be described. The surface adjustment filter 10 is formed by forming the surface adjustment layer 1 on the observer side surface of the surface side transparent substrate 2 as described above. When an anti-glare layer (Anti Glare layer, AG layer) is adopted as the surface adjustment layer 1, various known forms can be adopted, but a preferred form is the observer side surface of the surface side transparent substrate 2 Or an ionizing radiation curable resin and / or a thermosetting resin as a binder on the surface of the transparent substrate 2 on the surface side, and an inorganic filler or an organic filler (light diffusion as light diffusing particles). Agent), and forms this into a coating film.
As the resin used for the binder, when surface strength is desired as the surface layer, a curable acrylic resin or the above-mentioned ionizing radiation curable resin is preferably used, and the “function as a hard coating layer is combined. Is also possible.
Examples of the inorganic filler include silica particles having an average particle diameter of about 0.5 to 10 μm, and aggregates of colloidal silica particles with an amine compound having an average particle diameter of about 0.5 to 10 μm. be able to.
Examples of the organic filler include melamine resin particles, acrylic resin particles, acrylic-styrene copolymer particles, polycarbonate particles, polyethylene particles, polystyrene particles, and benzoguanamine resin particles. These organic fillers usually have an average particle size of about 2 to 10 μm.
These light diffusing particles may be used alone or in combination of two or more. The content in the antiglare layer is usually 2 to 15% by mass, preferably 3 to 8%. % By mass.

Moreover, the anti-glare layer 5 can also be formed by sticking the anti-glare film which provided the fine unevenness | corrugation on the surface to the surface of a base material. Such an antiglare film is finely coated on the surface by a hot press method using an embossed plate or a sand blast method on a substrate such as a polyethylene terephthalate film, a polycarbonate film, or a triacetyl cellulose film having a thickness of about 15 to 250 μm. Unevenness is formed.
The thickness of the antiglare layer is not particularly limited, but usually about 0.07 to 20 μm is preferable. Further, when the average interval between the irregularities of the antiglare layer is Sm, the average inclination angle of the irregularities is θa, and the ten-point average roughness of the irregularities is Rz, Sm is 60 to 250 μm, and θa is 0 It is preferable that the angle is 3 ° to 1.0 ° and Rz is 0.3 to 1.0 μm.

Moreover, as a method of roughening the surface of the surface-side transparent base material 2, a method of forming a rough surface directly on the surface of the base material 2 by a sandblasting method, an embossing method, or the like, and a surface of the base material 2 In addition, a method of forming a porous film having a sea-island structure can be exemplified. Also in this case, it is preferable that Sm is 60 to 250 μm, θa is 0.3 to 1.0 degree, and Rz is 0.3 to 1.0 μm.
In addition, said Sm, (theta) a, and Rz are based on JISB06011994, For example, it can measure with a surface roughness measuring device ("SE-3400" by Kosaka Laboratory).
When an antireflection layer (Anti Reflection layer, AR layer) is employed as the surface adjustment layer 1, it is preferable to form an antireflection layer on the surface of the surface side transparent substrate 2 to prevent reflection of external light. .
The antireflection layer generally has a single layer of a low refractive index layer or a multilayer structure in which a low refractive index layer and a high refractive index layer are alternately laminated so that the low refractive index layer is positioned at the uppermost layer. The film is formed by a dry film formation method such as vapor deposition or sputtering, or by using a wet film formation method such as coating.
The refractive index of the low refractive index layer and the high refractive index layer is not particularly limited as long as there is a difference in refractive index between these layers, but the refractive index of the low refractive index layer is preferably 1.45 or less. . When the refractive index is within this range, sufficient antireflection performance can be obtained.

As a material constituting the low refractive index layer, silicon oxide, fluoride, fluorine-containing resin or the like is used. Specifically, SiO ₂ (refractive index n = 1.45), MgF ₂ (refractive index n = 1). .4), LiF (refractive index n = 1.4), 3NaF · AlF ₃ (refractive index n = 1.4), AlF ₃ (refractive index n = 1.4), Na ₃ AlF ₆ (refractive index n = 1.33). In the present invention, a material in which these inorganic materials are finely divided and dispersed in a binder resin such as a thermosetting resin or ionizing radiation curable resin is preferable because the low refractive index layer 5 can be easily provided.
As a method of forming the low refractive index layer, first, the above-described materials are diluted with a solvent, for example, a wet coating method in which the material is formed by spin coating, roll coating, printing, vacuum deposition, sputtering, plasma CVD, ion plating, or the like. It can be obtained by applying a low refractive index layer-forming material by a vapor phase method, etc., and then drying and curing with heat, ionizing radiation (in the case of ultraviolet rays, use the above-mentioned photopolymerization initiator), etc. it can.

  Further, fine particles having voids may be used for the low refractive index layer. The fine particles having voids form a structure in which fine particles are filled with gas and / or a porous structure containing gas, and are in inverse proportion to the gas occupancy ratio in the fine particles compared to the original refractive index of the fine particles. It means fine particles having a reduced refractive index. Depending on the form, structure, aggregation state, and dispersion state of the fine particles within the coating film, fine particles capable of forming a nanoporous structure inside and / or at least part of the surface are also included. The fine particles having voids may be either inorganic or organic, and examples thereof include metals, metal oxides, and resins, and preferably silicon oxide (silica) fine particles.

Furthermore, a material in which a sol obtained by dispersing ultrafine silica particles of 5 to 30 nm in water or an organic solvent and a fluorine-based film forming agent can be used. The sol in which the ultrafine silica particles of 5 to 30 nm are dispersed in water or an organic solvent is obtained by a method of dealkalizing alkali metal ions in alkali silicate salt by ion exchange or the like, or neutralizing alkali silicate salt with mineral acid. A known silica sol obtained by condensing active silicic acid known by the method, etc., a known silica sol obtained by condensing alkoxysilane with hydrolysis in an organic solvent in the presence of a basic catalyst, and the above-mentioned An organic solvent-based silica sol (organosilica sol) obtained by substituting water in the aqueous silica sol with an organic solvent by a distillation method or the like is used. These silica sols can be used in both aqueous and organic solvent systems. In producing the organic solvent-based silica sol, it is not necessary to completely replace water with the organic solvent. The silica sol contains solids 0.5 to 50 wt% concentration as SiO _2. Various structures such as a spherical shape, a needle shape, and a plate shape can be used for the structure of the ultrafine silica particles in the silica sol.
In the filter for an image display device of the present invention, both the low refractive index layer and the antiglare layer can be provided.

In the present invention, if the hard coating layer has transparency and shows a hardness of “H” or higher in the pencil hardness test specified by JISK5600-5-4 (1999), the hard coating layer is constituted. The material to be used is not particularly limited.
Usually, it is formed as a resin cured layer, and as the curable resin to be used, an ionizing radiation curable resin, other known curable resins, or the like may be appropriately employed according to the required performance. As the ionizing radiation curable resin, the same ones as described above can be used. The hard coating layer can be formed on the surface-side transparent substrate 2 by a wet film formation method such as coating by diluting the above material with a solvent as necessary. Although the thickness of a hard coating layer is not specifically limited, The range of 1-20 micrometers is preferable and the range of 3-5 micrometers is more preferable.
In addition, from the viewpoint of improving the stain resistance, a stainproof layer can be further provided on the hard coating layer. A coating composition in which a silicone compound, a fluorine compound, or the like is appropriately added to a binder resin is applied and formed on a hard coating film.
In addition, when the filter for an image display device of the present invention is used as a contamination-preventing layer, it prevents or adheres to dust and contaminants due to inadvertent contact and environmental contamination. However, it may be a layer formed for easy removal. 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.

There is no restriction | limiting in particular as the surface side transparent base material 2 and the back surface side transparent base material 5, It can select suitably from well-known resin films or glass as base materials, such as a conventional antireflection filter and an anti-glare filter, and can be used.
Examples of the resin film include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin resins such as polyethylene, polypropylene, polymethylpennorbornene resin, and cycloolefin resin; methyl poly (meth) acrylate, poly (meta ) Acrylic resins such as ethyl acrylate; PVC resins such as polyvinyl chloride and polyvinylidene chloride; Cellulosic resins such as diacetyl cellulose, triacetyl cellulose, and acetyl cellulose butyrate; Polysulfone resins such as polysulfone and polyether sulfone; Polyamide resin; polyether ether ketone; fluororesin; polycarbonate resin and the like.
Among these, a polyester film is preferable because of excellent balance of transparency, transparency, mechanical strength, heat resistance, cost, and the like, and a polyethylene terephthalate film is particularly preferable.
Further, glass substrates such as soda glass, potash glass, and borosilicate glass are also preferable from the viewpoint of optical characteristics and mechanical characteristics.

The surface side transparent base material 2 and the back side transparent base material 5 may be either transparent or translucent, and may be colored, but for PDP, colorless and transparent are preferable.
The thickness of these base materials is not particularly limited and may be determined according to the intended use. However, in the case of a transparent resin film, it is usually in the range of about 10 to 500 μm, preferably 15 to 250 μm. Moreover, when it is a transparent resin plate or a glass plate, about 1-5 mm is usually suitable. Moreover, when using the said resin film as a base material, in order to improve the adhesiveness with the layer provided in the surface, surface treatment is given by the oxidation method, the uneven | corrugated method, etc. on one side or both surfaces as needed. be able to. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected depending on the type of substrate, but in general, the corona discharge treatment method is preferable from the viewpoints of effects and operability.

At least one of the pressure-sensitive adhesive compositions constituting the surface-side transparent pressure-sensitive adhesive layer 3 or the back-side transparent pressure-sensitive adhesive layer 6 includes a near-infrared absorber, a neon light absorber, a toning agent, or an ultraviolet absorber. Any one or more absorbers selected from the agents may be contained.
What is necessary is just to select suitably what has sufficient near-infrared absorptive performance and visible-light transmittance among well-known things as a near-infrared absorber. For example, organic near organic compounds such as phthalocyanine, imonium, diimonium, dithiol gold complex, cyanine compounds, azo compounds, polymethine compounds, quinone compounds, diphenylmethane compounds, triphenylmethane compounds, etc. Infrared absorbers, or inorganic near infrared absorbers composed of inorganic compounds such as metal oxides, metal borides and metal nitrides. Among these, an inorganic near-infrared absorber is preferable from the viewpoint of durability.

Examples of the metal oxide include tungsten oxide compounds, titanium oxide, zirconium oxide, tantalum oxide, niobium oxide, zinc oxide, ruthenium oxide, indium oxide, tin-doped indium oxide (ITO), tin oxide, and antimony-doped tin oxide ( ATO) and fine particles such as cesium oxide. In order to exhibit sufficient visible light transparency, the average particle diameter is preferably 380 nm or less, particularly the average particle diameter of 40 to 200 nm, which is the minimum wavelength of visible light.
As the metal boride, a multiboride metal compound is preferable, and specifically, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ). Yttrium boride (YB ₆ ), titanium boride (TiB ₆ ), zirconium boride (ZrB ₆ ), hafnium boride (HfB ₆ ), vanadium boride (VB ₆ ), tantalum boride (TaB ₆ ), boron Examples thereof include chromium bromide (CrB, CrB ₆ ), molybdenum boride (MoB ₆ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like.
Examples of the metal nitride include titanium nitride, niobium nitride, tantalum nitride, zirconium nitride, hafnium nitride, and vanadium nitride.
Among these, from the viewpoint of compatibility between high absorption of near infrared rays and high transmittance of visible light, and durability against changes in spectral transmittance characteristics under high humidity and high humidity conditions, tungsten oxide compounds In particular, a tungsten oxide compound represented by the following general formula (I) is preferable.

MxWyOz (I)
Here, the M element is at least one selected from the group consisting of Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, W represents tungsten, and O represents oxygen. .
Of the tungsten oxide compounds represented by the above general formula (I), cesium-containing tungsten oxide in which the M element is represented by Cs is particularly preferable because of its high near-infrared absorptivity.

In addition, in the above general formula (I), the added amount of the M element satisfies the relationship of 0.001 ≦ x / y ≦ 1.1 as the value of x / y based on the tungsten content. In particular, x / y is preferably in the vicinity of 0.33 from the viewpoint of suitable near infrared absorption ability. Further, when x / y is around 0.33, a hexagonal crystal structure is easily obtained, and the use of this crystal structure is also preferable in terms of durability.
The oxygen content in the general formula (I) preferably satisfies the relationship of 2.2 ≦ z / y ≦ 3.0 as the value of z / y based on the content of tungsten. More specifically, Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like can be mentioned.
The said inorganic near-infrared absorber may be used individually by 1 type, or can also use 2 or more types together.

In particular, it is important that the inorganic near-infrared absorber in the present invention has an average particle size of 40 to 200 nm. If the average particle size is less than 40 nm, the near-infrared absorptivity becomes insufficient. On the other hand, if the average particle size exceeds 200 nm, white turbidity occurs due to Mie scattering and the contrast decreases. In order to exhibit more preferable near infrared absorption performance, the average particle diameter is preferably 60 to 100 nm, and more preferably 70 to 80 nm.
In addition, the measurement of the average particle diameter in the present invention is obtained by taking an image with a transmission electron microscope, randomly extracting, for example, 50 inorganic near infrared absorbers, measuring the particle diameter, and averaging the results. is there. Moreover, when the shape of particle | grains is not spherical, it defines as what was calculated by measuring a major axis.

  As for content in the adhesive composition of the said near-infrared absorber, the range of 10-60 mass% (solid content conversion) is preferable. When it is 10% by mass or more, a sufficient near-infrared absorption effect is exhibited, and when it is 60% by mass or less, a sufficient amount of visible light can be transmitted. From the above viewpoint, the content of the near-infrared absorbent in the pressure-sensitive adhesive composition is more preferably in the range of 20 to 40% by mass (in terms of solid content).

  In the present invention, it can be said that it is particularly preferable to use an inorganic near-infrared absorber as described above. However, in such a case, within the range where the effects of the present invention can be obtained, other organic systems, metal complexes, etc. The near-infrared absorber can also be used in combination. For example, the aforementioned diimonium compounds can be used in combination.

  Further, in the present invention, when an inorganic compound such as a tungsten oxide compound is used as a suitable near-infrared absorber, and its average particle size is 40 to 200 nm, white turbidity and bluishness are added as new problems. It has been found that this causes coloration. The reason for this is unknown, but these inorganic compounds generally have a high refractive index (in the case of cesium-containing tungsten oxide, the refractive index is 2.5), and Rayleigh scattering by particles of a specific particle size and Presumably due to Mie scattering. In order to reduce this phenomenon, as a result of extensive studies by the present inventors, the gold oxide fine particles having a smaller particle diameter than the tungsten oxide compound particles in the pressure-sensitive adhesive layer containing the tungsten oxide compound particles. It has been found that it is preferable to mix a red pigment in a constituent layer of any of the filters for an image display device of the present invention. Such metal oxide fine particles are metal oxide fine particles having an average particle diameter of 5 to 30 nm, and the material itself is not limited as long as the effect of the present invention is achieved. In particular, in the case of near-infrared absorption of cesium-containing tungsten oxide, zirconium oxide and titanium oxide are preferable. These metal oxide fine particles can be used alone or in combination of two or more.

It is important that the metal oxide fine particles in the present invention have an average particle size of 5 to 30 nm. If the average particle diameter is less than 5 nm, the blue color of the transmitted color tone cannot be erased, and the effects of the present invention cannot be achieved. On the other hand, if the average particle diameter exceeds 30 nm, the bluishness of the transmitted color tone cannot be eliminated, and at the same time, white turbidity may occur. From the viewpoint of achieving the effect of the present invention at a higher level, the average particle diameter of the metal oxide fine particles is more preferably in the range of 10 to 20 nm.
The shape of the metal fine particles is not particularly limited, but a spherical shape is preferable.
In addition, the average particle diameter of the metal oxide fine particles is measured by a method using a transmission electron microscope as in the case of the inorganic near infrared absorber.

  It is preferable that content in the adhesive composition of the said metal oxide microparticles is 50-200 mass parts with respect to 100 mass parts of said inorganic near-infrared absorbers. When the amount is 50 parts by mass or more, the bluish color of the transmitted color tone can be eliminated. From the above viewpoint, the content of the metal oxide fine particles is more preferably in the range of 70 to 150 parts by mass with respect to 100 parts by mass of the inorganic near infrared absorber.

As such a red pigment, a red dye and a red pigment can be used.
There is no restriction | limiting in particular as a red dye, According to the objective, it can select suitably from well-known things, for example, C.I. I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 82, 87, 89, 92, 97, 106, 111, 114, 115, 134, 186, 249, 254 Acid dyes such as 289; C.I. I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 54, 59, 68, 69, 70, Basic dyes such as 73, 78, 82, 102, 104, 109, 112; I. Reactive dyes such as Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97; I. Solvent Red 111, 135, 179, etc. are mentioned.
The red pigment is not particularly limited and may be appropriately selected from known ones according to the purpose. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1, Permanent Carmine FBB (CI Pigment Red 146), Permanent Ruby FBH (CI Pigment Red 11), Fastel Pink B Supra (CI Pigment Red 81), etc. Is mentioned.
Each of the red dye and the red pigment may be used alone or in combination of two or more. A red dye and a red pigment may be used in combination.

The neon light absorber is added to absorb neon light emitted from the PDP, that is, an emission spectrum of neon atoms. The neon light absorber can suppress at least orange light emission from the PDP, and a bright red color can be obtained. Since the emission spectrum band of neon light has a wavelength of 550 to 640 nm, it is preferable that the spectral transmittance when functioning as a neon light absorption layer is designed to be 50% or less and further 25% or less at a wavelength of 590 nm.
As the neon light absorber, a dye having an absorption maximum in a wavelength region of at least 550 to 640 nm can be used. Specific examples of the dye include cyanine, oxonol, methine, subphthalocyanine or porphyrin. Of these, porphyrins are preferred. Among them, a tetraazaporphyrin-based dye as disclosed in Japanese Patent No. 3834479 is particularly preferable in terms of good dispersibility and good heat resistance, moisture resistance, and light resistance.
Although content of a neon light absorber is not specifically limited, It is preferable that it is 0.05-5 mass% in a neon light absorption layer. If the content is 0.05% by mass or more, a sufficient neon light absorbing function can be exhibited, and if it is 5% by mass or less, a sufficient amount of visible light can be transmitted.
The toning agent is provided for the purpose of improving the color purity of light emitted from the image display device, the color reproduction range, the surface color of the image display device when the power is turned off, and the like. That is, the color of the display filter is adjusted, and the color correction function is required for each display.

Examples of known dyes that can be used as color correction dyes include the dyes described in JP 2000-275432 A, JP 2001-188121 A, JP 2001-350013 A, JP 2002-131530 A, and the like. Can be suitably used. In addition, dyes such as anthraquinone, naphthalene, azo, phthalocyanine, pyromethene, tetraazaporphyrin, squarylium, and cyanine that absorb visible light such as yellow light, red light, and blue light. Can be used.
The content of the color correction dye is appropriately adjusted according to the color to be corrected and is not particularly limited. Usually, about 0.01-10 mass% is contained in the toning layer.

As the ultraviolet absorber, in addition to a narrowly defined ultraviolet absorber that shields by absorbing ultraviolet rays, an ultraviolet scattering agent that shields by scattering ultraviolet rays can be used.
As the ultraviolet absorber (in a narrow sense), salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like. Examples of benzophenone-based UV absorbers include 2,2′-dihydroxy-4- Methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzoto Azole, 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole and the like.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, and the like. Furthermore, as an example of a triazine ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as 1,3,5-triazine and 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy); 3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6 Bis (hydroxyphenyl) triazine compounds such as-(2,4-dimethylphenyl) -1,3,5-triazine; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4- Dibutoxyphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2- And tris (hydroxyphenyl) triazine compounds such as hydroxy-4- (3-butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-triazine.
In the present invention, the various ultraviolet absorbers may be used alone or in combination of two or more.

  As the ultraviolet scattering agent, inorganic materials such as metal oxide powder are mainly used. Examples of this ultraviolet scattering agent include powders obtained by atomizing titanium dioxide, zinc oxide, cerium oxide, etc., hybrid inorganic powders obtained by complexing titanium dioxide fine particles with iron oxide, and the surface of cerium oxide fine particles. Examples include hybrid inorganic powders coated with amorphous silica. Since the ultraviolet scattering effect and transparency are greatly affected by the particle diameter, in the present invention, the average particle diameter of the ultraviolet scattering agent is preferably 5 μm or less, particularly preferably in the range of 10 to 200 nm.

In the present invention, the resin in the pressure-sensitive adhesive composition used in the front-side transparent pressure-sensitive adhesive layer 3 or the back-side transparent pressure-sensitive adhesive layer 6 functions as a pressure-sensitive adhesive, and has an inorganic near-infrared absorber and metal oxide fine particles. It also fulfills the function of a binder for binding. Moreover, when using this adhesive composition as an adhesive layer so that it may explain in full detail later, what is excellent in the coating property to a base material, drying property, sclerosis | hardenability, etc. is preferable. Specifically, acrylic resins, rubber resins, polyester pressure-sensitive adhesives, and the like are preferable. These resins can be used alone or in combination of two or more.
For example, as the acrylic pressure-sensitive adhesive, a polymer obtained by polymerizing at least a monomer (monomer) of (meth) acrylic acid alkyl ester as a monomer can be used. As the polymer, it is common to use a copolymer of a (meth) acrylic acid alkyl ester monomer having an alkyl group having about 1 to 18 carbon atoms and a monomer having a carboxyl group. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid. Similarly, the following (meth) acrylates also mean acrylates or methacrylates.

Here, as specific examples of the homopolymer and the copolymer as the polymer using the monomer as described above, the following can be cited.
For example, homopolymers of the above (meth) acrylic acid alkyl ester monomers, that is, (meth) acrylic acid ester homopolymers include poly (meth) acrylate methyl, poly (meth) acrylate ethyl, poly (meth) acrylic And propyl acid, butyl poly (meth) acrylate, and octyl poly (meth) acrylate.
Examples of the copolymer composed of two or more acrylate monomers are, for example, methyl (meth) acrylate-ethyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate. Examples thereof include copolymers.
Also, a copolymer of one or more (meth) acrylic acid alkyl ester monomers and one or more other monomers can be used. As other monomers, (meth) acrylic acid alkyl ester, (meth) acrylic acid, itaconic acid, maleic acid having a hydroxyl group such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxy-3-phenyloxypropyl, etc. Examples thereof include vinyl monomers having a carboxyl group such as acid and fumaric acid, ethylene and styrene.
Specific examples of such a copolymer of one or more (meth) acrylic acid alkyl ester monomers and one or more other monomers include, for example, methyl (meth) acrylate-dihydroxyethyl (meth) acrylate. Copolymer, methyl (meth) acrylate- (meth) acrylic acid 2-hydroxy-3-phenyloxypropyl copolymer, methyl (meth) acrylate-styrene copolymer, methyl (meth) acrylate-ethylene copolymer, (Meth) acrylate methyl- (meth) acrylate 2-hydroxyethyl-styrene copolymer, (meth) methyl acrylate-butyl (meth) acrylate-butyl (meth) acrylate 2-hydroxyethyl-styrene copolymer It is done.

  About the manufacturing method of the adhesive composition of this invention, the said component may be mixed and there is no restriction | limiting in particular about the method. Furthermore, if necessary, various known additives such as isocyanate-based and epoxy-based crosslinking agents, tackifiers, silane coupling agents, diluent solvents, extender pigments and the like may be appropriately added.

  The pressure-sensitive adhesive composition used in the present invention can be suitably used for a pressure-sensitive adhesive layer of a functional filter such as an electromagnetic wave shielding filter, and by adding various absorbers described later, near-infrared absorption to the electromagnetic wave shielding filter. A function as a specific wavelength light absorption filter such as a filter can be provided.

  In the example shown in FIG. 1, the surface-side transparent adhesive layer 3 is formed by applying the above-mentioned adhesive composition onto the electromagnetic wave shielding layer 4, and the back-side transparent adhesive layer 6 is formed from the above-described adhesive pad composition. It is obtained by coating on the non-electromagnetic wave shielding layer non-formation surface side of the back side transparent substrate 5. As thickness of these adhesive layers 3 and 6, the range of 5-800 micrometers is preferable. When the thickness is 5 μm or more, the function as a pressure-sensitive adhesive can be sufficiently achieved, and sufficient adhesion to the glass substrate or the image display device 200 can be obtained, and the addition of a predetermined absorber can be used. Predetermined unwanted radiation such as infrared rays can be sufficiently absorbed. In particular, practically sufficient impact resistance can be imparted by setting the thickness to about 200 μm or more. On the other hand, if it is 800 μm or less, it is advantageous in terms of suppressing excessive quality and unnecessarily high raw material prices. From the above viewpoint, the thickness of the pressure-sensitive adhesive layer 4 is more preferably in the range of 10 to 500 μm, and particularly preferably in the range of 20 to 300. The absorption efficiency of predetermined unnecessary radiation such as near infrared rays can be controlled by changing the thickness of the pressure-sensitive adhesive layer 4.

Next, the electromagnetic wave shielding layer 4 will be described.
In the present invention, as shown in FIG. 2, the electromagnetic wave shielding layer 4 includes a metal fine particle binder 7 in which metal fine particles 7b are bound by a binder resin 7a, and a nickel columnar shape that covers the surface of the metal fine particle binder 7. The outermost surface of the surface-coated nickel columnar crystal aggregate layer 8 is a light diffusive fine uneven surface.

The electromagnetic wave shielding layer 4 is obtained by printing a metal paste in a predetermined pattern on the surface-side transparent substrate 2 and solidifying it by solvent drying or curing reaction, and the metal fine particles 7b are bound by the binder resin 7a. The porous metal fine particle binder 7 is preferably manufactured by subjecting it to electroless nickel plating and etching.
The predetermined pattern of the electromagnetic wave shielding layer 4 may be a mesh shape (lattice shape or net shape) or a stripe shape (a stripe shape or a parallel line group shape) usually employed for an electromagnetic wave shielding member. The line width and the inter-line pitch may be dimensions that are usually employed. For example, the line width is preferably 5 to 30 μm, the line pitch is 100 to 500 μm, the aperture ratio is 60 to 95%, and the mesh shape is preferably a square lattice from the viewpoint of light transmittance.
The thickness of the electromagnetic wave shielding layer 4 is as thin as possible within a range in which a desired electrical conductivity and a predetermined film strength can be ensured, from the viewpoint of cost and further elimination of air bubbles at the time of adhering an adhesive thereon. preferable. The thickness is preferably about 1 to 20 μm, and more preferably about 3 to 10 μm.

Here, the porosity of the metal fine particle binder is preferably 20 to 80%, and more preferably 30 to 70%. If the porosity is 20% or more, the exposed metal fine particles in the metal fine particle binder are not reduced, and the portion to be plated in the binder is not reduced, and the supply of plated metal ions to the inside of the binder is also possible. Easy. On the other hand, if the porosity is 80% or less, the strength of the electromagnetic wave shielding layer after plating is strong.
In the metal fine particle binder of the present invention, the constituent ratio of the metal fine particles and the binder resin is preferably 1 to 50 parts by mass, and preferably 3 to 30 parts by mass with respect to 100 parts by mass of the metal fine particles. Is more preferable.

The metal paste used for producing the metal fine particle binder is obtained by uniformly dispersing metal fine particles in a fluid (liquid) binder resin composition, and solidifying the metal fine particle binder (layer). Is formed. It is as follows.
As the metal fine particles, metal particles such as gold, silver, platinum, copper, iron, tin, nickel, aluminum, or composite metal particles can be used. These may be used alone or in combination. Here, metals such as gold, silver, and nickel exhibit conductivity that can be energized immediately after pattern printing, but metals that are easily oxidized in the air, such as copper, iron, and aluminum, are subjected to electrochemical treatment and chemicals after pattern printing. Conductivity that can be energized can be developed by performing treatment or the like. In particular, in the case of copper powder, the resistance of the oxide film on the surface is high, and the resistance of the binder is extremely high because the oxide films of the particles are in contact with each other. Therefore, it is essential to remove the oxide film on the surface by chemical treatment, etc., but this oxide film can be easily removed by immersing it in an acidic solution. It is only necessary to pass a bath. In this case, if copper powders are bonded by metal deposition, re-insulation by air oxidation does not proceed.
The particle size of the metal fine particles is preferably small enough to make a paste, and preferably has a particle size of 100 μm or less, but is preferably sufficiently smaller than the line width of the mesh pattern, and more preferably 10 μm or less. The shape is not particularly limited, such as spherical, spheroid, polyhedral, lump, scale, disk, fiber, or needle shape, and particles having various shapes, particle sizes, and the like may be used by appropriately mixing them. Good. In addition, the particle diameter is the maximum long diameter in the case of a spheroid in the case of a shape other than a sphere, the diameter of a circumscribed sphere in the case of a polyhedron, or the maximum diagonal length, and the longitudinal direction (long) in the case of a fibrous or needle shape. Axis length) etc. are evaluated.

The binder resin may be any resin that has adhesion to the metal fine particles and the base material and can maintain a stable coating film against the plating solution, such as acrylic resin, polyester resin, ethylene-vinyl acetate resin, urethane resin, phenol. Resins, epoxy resins, and the like can be used. As a method for imparting fluidity to the binder resin and solidifying the binder resin, the solid binder resin is typically dissolved or dispersed in a solvent to be in a fluid state, and the solvent is solidified by drying. Examples thereof include a method of solidifying a resin monomer or prepolymer that exhibits a fluid state in an uncured state by a curing reaction by crosslinking or polymerization.
As the solvent, an organic solvent which dissolves the binder resin and has a boiling point of about 100 to 250 ° C. can be used. If the boiling point is too low, the solvent is volatilized during paste preparation or pattern printing and the paste properties and the like change, resulting in inconvenience. If the boiling point is too high, drying after printing takes too much time.
In order to obtain a metal fine particle binder having a porosity of 20 to 80%, a metal paste having a solid content of 60 to 90% by mass and comprising 1 to 50 parts by mass of a binder resin with respect to at least 100 parts by mass of the metal fine particles. It is preferable that

The printing method for printing the metal paste in a pattern on the substrate does not particularly limit the effect of the present invention, and may be appropriately selected depending on the properties of the metal paste.
When using metal fine particles of nanometer size, the viscosity of the metal paste is generally low, and intaglio printing such as gravure printing, ink jet printing, flexographic printing, etc. are suitable, and when using metal fine particles of submicron to micron, generally metal The paste has a high viscosity, and intaglio printing such as gravure printing, flexographic printing, silk screen printing, and dispenser are suitable.
After printing, for example, when the metal paste is made of a solid resin solvent solution or dispersion, it is dried with hot air at about 80 to 150 ° C. to volatilize the solvent. Body) or prepolymer (oligomer) uncured product, the metal paste is solidified by causing a curing reaction by appropriate means such as ultraviolet irradiation, electron beam irradiation, heating, etc., and patterned on the substrate. A metal fine particle binder formed in the above is obtained.

In the present invention, the surface of the metal fine particle binder is coated with the nickel columnar crystal aggregate layer 8 (see FIG. 2) by subjecting the porous metal fine particle binder 7 to electroless nickel plating. Preferably, at least a part of the internal voids of the metal fine particle binder is also filled.
The nickel columnar crystal aggregate layer formed on the surface of the metal fine particle binder as the object to be plated is an aggregate of a large number of columnar crystals whose longitudinal direction (column length direction) is oriented in the thickness direction of the plating film. is there. Since it is such a columnar crystal aggregate, when it is etched, its surface is roughened to form a light diffusive fine uneven surface, and a black appearance is exhibited. Such a surface etching treatment can be obtained, for example, by etching only the vicinity of the outermost surface layer with a corrosive solution made of a ferric chloride aqueous solution.
Such columnar crystal aggregates can be formed by an electroless nickel plating solution treatment. Since columnar crystal aggregates are not formed by other plating solution treatments such as electrolytic nickel plating solution treatment and electroless copper plating solution treatment, a black appearance cannot be obtained even by etching treatment. Such columnar crystallization seems to require the presence of phosphorus based on hypophosphite contained in the electroless nickel plating solution (1-2 in the nickel columnar crystal aggregate layer). Contains about phosphorus by mass).
The thickness of the nickel columnar crystal aggregate layer covering the surface of the metal fine particle binder is preferably about 2 to 5 μm. When the film thickness is less than 2 μm, the effect of improving conductivity is insufficient. In addition, when the film thickness is 5 μm or more, the conductivity improving effect is saturated and the protrusion height of the electromagnetic wave shielding layer from the base material is increased. When the layers are laminated, bubbles are likely to be mixed into the adhesive layer.
Further, the nickel columnar crystal aggregate layer 8 has a black appearance, and white light of a display image and a decrease in contrast due to reflection of extraneous light such as sunlight and electric light from the surface of the electromagnetic wave shielding layer 4 having a metallic luster. It has the function to prevent. Therefore, the nickel columnar crystal aggregate layer 8 is a surface on the image observer side of the electromagnetic wave shielding layer 4, or a surface on the surface adjustment filter 10 side in the case of a filter for an image display device having a layer structure as shown in FIG. And the upper surface). Such a positional relationship can be naturally obtained by manufacturing according to the manufacturing process as described above.

FIG. 3 is a schematic cross-sectional view showing an intermediate member before electroless nickel plating according to another embodiment of the present invention.
In the intermediate member of the other embodiment, a primer layer 9 made of a liquid resin composition typified by ionizing radiation curable resin is formed on the surface-side transparent substrate 2, and a metal paste is intaglio-printed thereon. Then, the primer layer is cured, and then the primer layer 9 cured (or solidified) from the plate surface and the metal fine particle binder 7 constituting the electromagnetic wave shielding layer 4 are extracted together, so-called “pulling primer method” is applied. It is a member.
As shown in FIG. 3, the primer layer 9 in the intermediate member to which this “pulling primer method” is applied is a portion A (patterned electromagnetic wave shielding layer 4 formed with the metal fine particle binder 7 formed thereon. the thickness T _a of the same) in portions, the portion B where the metal fine particle binder body 7 is not formed (patterned electromagnetic shielding layer is not formed portion (opening) in the same) than the thickness T _B Is also big.

The primer layer 9 is provided on the surface side transparent substrate 2 with good adhesion. A layer of the metal fine particle binder 7 is provided on the primer layer 9 with good adhesion. Accordingly, the primer layer 9 is preferably a material having good adhesion to both the surface-side transparent base material 2 and the layer of the metal fine particle binder 7, and naturally, it is preferably transparent. . As a typical form, an ionizing radiation curable composition containing a liquid (fluid) ionizing radiation polymerizable compound in an uncured state is applied and cured (solidified).
As the ionizing radiation polymerizable compound, a monomer (monomer) and / or a prepolymer (or oligomer) that is polymerized and cured by a reaction such as crosslinking with ionizing radiation is used.

Examples of such monomers include radically polymerizable monomers such as methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentenyl (meth) ) Monofunctional (meth) acrylates such as acrylate, dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate And various (meth) acrylates such as polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Here, the expression (meth) acrylate means acrylate or methacrylate. Examples of the cationic polymerizable monomer include alicyclic epoxides such as 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate, glycidyl ethers such as bisphenol A diglycidyl ether, 4-hydroxybutyl vinyl ether And vinyl ethers, and oxetanes such as 3-ethyl-3-hydroxymethyloxetane.
Examples of such prepolymers include radically polymerizable prepolymers such as various (meth) acrylate prepolymers such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate, and unsaturated polyester prepolymers. Is mentioned. Other examples of the cationic polymerizable prepolymer include novolac type epoxy resin prepolymer and aromatic vinyl ether type resin prepolymer.
These monomers or prepolymers can be used alone or in combination with two or more types of monomers, two or more types of prepolymers, or one type of monomer, depending on the required performance, coating suitability, etc. A mixture of the above and one or more prepolymers can be used.

When ultraviolet rays or visible rays are employed as the ionizing radiation, a photopolymerization initiator is usually added. As a photopolymerization initiator, in the case of a radical polymerizable monomer or prepolymer, a compound such as a benzophenone-based, thioxanthone-based, or benzoin-based compound, or in the case of a cationic polymerization-based monomer or prepolymer, a metallocene-based compound, Aromatic sulfonium-based and aromatic iodonium-based compounds are used. These photopolymerization initiators are added in an amount of about 0.1 to 5 parts by mass with respect to 100 parts by mass of the composition comprising the monomer and / or prepolymer.
The ionizing radiation is typically ultraviolet rays or electron beams, but other than these, electromagnetic waves such as visible rays, X-rays and γ rays, or charged particle beams such as α rays can also be used.

In addition, the ionizing radiation curable composition may use various additives and modified resins for improving adhesion, durability, and imparting various physical properties. Examples of the additive include a heat stabilizer, a radical scavenger, a plasticizer, a surfactant, an antistatic agent, an antioxidant, an extender pigment, and a flame retardant. The surface-side transparent adhesive layer or the back-side transparent adhesive layer contains ultraviolet rays due to various circumstances such as deterioration of the absorbent due to the reaction between the absorbent and the adhesive, and deterioration of the adhesive properties due to the addition of the absorbent. If all of the absorber, neon light absorber, near-infrared absorber, or toning agent (chromatic dyes such as coloring dyes and coloring pigments) cannot be contained, they should not be included in these adhesives. Absorbent can be added to the primer layer. Alternatively, these absorbents can be contained in the three layers of the front-side transparent adhesive layer 3, the back-side transparent adhesive layer 6, and the primer layer 9 as appropriate. In this case, when all the absorbents are concentrated in a specific layer, the original function of the specific layer is deteriorated, or a problem due to the interaction between the specific layer and the absorbent (if present). Can be resolved). Of course, when all the absorbents can be added only in one or two of the front side transparent adhesive layer or the back side transparent adhesive layer, the primer layer contains these absorbents. There is no need to let them go.
This ionizing radiation curable composition may contain a solvent, but in this case, since a drying step is required after coating, it is preferable that the composition does not contain a solvent (non-solvent type).

As a method for manufacturing the filter for an image display device as shown in FIG. 1, various known process sequences and processing methods may be appropriately combined, and there is no particular limitation. As an example of a typical production method, the metal paste is printed in a pattern on the back side transparent base material 5 by the above-described method, and solidified to bind the metal fine particles 7b with the binder resin 7a. The electromagnetic shielding layer 20 is obtained by applying the electroless nickel plating process and the etching process to the surface of the gold alloy fine particle binder 7 to cover the nickel columnar crystal aggregate layer 8, thereby obtaining the electromagnetic shielding filter 20.
On the other hand, a surface adjustment filter 10 is obtained in which the surface adjustment layer 1 such as an antireflection layer is provided on the surface side transparent substrate 2 by the known methods and materials as described above. In parallel, a pressure-sensitive adhesive composition for the surface-side transparent pressure-sensitive adhesive layer and a pressure-sensitive adhesive composition for the back-surface-side transparent pressure-sensitive adhesive layer, each containing a desired absorbent, are prepared. Next, a coating liquid for forming a pressure-sensitive adhesive layer for the surface-side transparent pressure-sensitive adhesive layer is applied on the electromagnetic wave shielding layer 4, dried and cured, and the surface-side transparent pressure-sensitive adhesive layer 3 is obtained. Next, the surface adjustment filter 10 is laminated on the surface of the surface side transparent pressure-sensitive adhesive layer so that the surface adjustment layer non-formation surface side of the surface side transparent base material 2 faces the electromagnetic wave shielding layer. After that, the back side transparent adhesive 5 is coated with a coating solution for forming the back side transparent adhesive layer on the non-electromagnetic wave shielding layer non-forming side, dried and cured, and then back side transparent adhesive The agent layer 6 is formed. Thus, the image display filter of the present invention having the layer structure as shown in FIG. 1 is obtained.
The pressure-sensitive adhesive layer-forming coating solution can be prepared by adding an appropriate solvent at a predetermined ratio to the pressure-sensitive adhesive composition as necessary, and dissolving or dispersing the solvent.

Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride, methanol, ethanol, propanol, butanol, and 1-methoxy. Examples include alcohols such as 2-propanol; ketones such as acetone, methyl ethyl ketone, 2-pentanone, methyl isobutyl ketone, and isophorone; esters such as ethyl acetate and butyl acetate; and cellosolv solvents such as ethyl cellosolve.
Moreover, as various additives which can be added here, antioxidant, a ultraviolet absorber, a light stabilizer, a leveling agent, an antifoamer etc. are mentioned, for example.
The concentration and viscosity of the coating solution are not particularly limited as long as the concentration and viscosity can be coated.

  As a method for coating the coating liquid on the back side transparent substrate 5 and the electromagnetic wave shielding layer 4, a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, A comma coat, a gravure coat method, etc. can be used. After applying and forming a coating film, an adhesive layer is formed by drying.

  The filter for an image display device of the present invention is suitable for an image display device such as a plasma display (PDP), a cathode ray tube display (CRT), or a liquid crystal display (LCD), and particularly suitable for a plasma display.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Production Example 1
Byron 200 (manufactured by Toyobo Co., Ltd.) by silk screen printing on one surface of a transparent substrate 2 made of biaxially stretched polyethylene terephthalate (PET) having a thickness of 100 μm and a size of 500 mm × 500 mm. (Polyester-based binder resin 7a) 57.5 parts by weight of DBE (manufactured by DuPont; dibasic acid ester) (solvent) 27.5 parts by weight of the solution was dissolved in 27.5 parts by weight of gold fine particles 7b and silver powder with a particle size of 5 μm 67.5 parts A metal paste having portions uniformly dispersed was printed in a lattice pattern. This was dried with hot air at 120 ° C. to evaporate DBE, and a porosity of 41% in a square lattice pattern with a line width of 20 μm, a pitch of 300 μm and a thickness of 10 μm on a PET substrate (mercury porosimeter (Shimadzu Corporation) An intermediate member on which the metal fine particle binder 7 measured by Autopore IV9520) was formed was obtained.
The thickness of the metal fine particle binder layer of the intermediate member was 10 μm, and the surface resistance was 1.0Ω / □.

Production Example 2
The surface-side transparent base material 2 made of a long roll-wrapped PET film having a width of 1000 mm and a thickness of 100 μm, which has been subjected to easy adhesion treatment on one side, is unrolled, and uncured and fluidized ionization for forming the primer layer 9 on the easy adhesion treatment surface. The radiation curable composition was applied and formed to a thickness of 8 μm. The application method employs a normal gravure reverse method, and the ionizing radiation curable composition includes 40 parts by mass of an epoxy acrylate prepolymer, 53 parts of a monofunctional monomer (non-hydrophilic monofunctional acrylate monomer mixture comprising phenoxyethyl acrylate). 3 parts by weight of trifunctional monomer (ethylene oxide modified isocyanuric acid triacrylate) and 1 part by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 (Ciba Specialty Chemicals)) as a photoinitiator are used. did. Although the ionizing radiation curable primer layer after application showed fluidity when touched, it did not flow down from the PET film.
On the other hand, a scale having an average particle diameter of about 2 μm as metal fine particles 7 b is formed on the plate surface of a metal intaglio roll formed with concave portions that form a square lattice mesh pattern having a line width of 20 μm, a line pitch of 300 μm, and a plate depth of 10 μm. A metal paste consisting of 93 parts by mass of silver particles, 7 parts by mass of thermoplastic polyester urethane resin as the binder resin 7a, and 25 parts by mass of butyl carbitol acetate as a solvent is applied with a pick-up roll, and a metal paste other than in the recesses with a doctor blade The metal paste was filled only in the recess. A meniscus-shaped dent was formed on the surface of the metal paste filled in the recess.
Then, a PET film with a primer layer is provided between the intaglio roll filled with the metal paste in the recess and the nip roll, and the ionizing radiation curing is performed by the pressing force (biasing force) of the nip roll against the intaglio roll. The primer layer is allowed to flow into the recess of the metal paste existing in the recess, and the metal paste and the ionizing radiation curable primer layer are brought into close contact with each other, and a part of the primer enters and mixes in the metal paste. It was.

Thereafter, ultraviolet rays are irradiated by a UV lamp made of a mercury lamp, and the primer layer made of the ionizing radiation curable composition is cured (solidified). Due to the curing of the primer layer, the metal paste in the recesses of the intaglio roll comes into close contact with the primer layer 9, and then the film and the cured primer layer are peeled off from the intaglio roll, and the metal paste is transferred and formed on the primer layer. The The transfer film thus obtained was passed through a drying zone at 110 ° C. to evaporate the solvent of the silver paste and solidified to form a metal fine particle binder layer 7 having a mesh pattern on the primer layer 9. . The thickness of the metal fine particle binder layer 7 at this time (thickness difference between the mesh pattern portion where the conductive material layer is formed and the other portion) is 9 μm, and the silver paste in the concave portion of the plate is The transition was performed at a high transition rate (the transition rate defined by the ratio of (the height of the transferred metal paste / the depth of the plate recess)) (9/10) × 10 = 90%. Moreover, neither disconnection nor shape defect was seen.
The thickness of the metal fine particle binder layer of the intermediate member was 9 μm, and the surface resistance was 1.0Ω / □.

Example 1
(1) Preparation of pressure-sensitive adhesive composition Content of cesium tungsten oxide (Cs0.33WO3) as a near-infrared absorber in an acrylic pressure-sensitive adhesive having an acid value of 6.8 (trade name: SK2094, manufactured by Soken Chemical Co., Ltd.) 10% by mass of 18.5% by mass of MIBK dispersion (trade name: YMF-02, average dispersed particle size of 800 nm or less, manufactured by Sumitomo Metal Mining Co., Ltd.) was added, and a tetraazaporphyrin-based dye (neon light absorber) 0.009% by weight of a trade name TAP-2 Yamada Chemical Co., Ltd., and 0.005% by weight of a coloring pigment (trade name Plast red 8320 Arimoto Chemical Co., Ltd.) added as a toning glaze, and as an ultraviolet absorber. 0.4% by mass of a benzotriazole compound was added. Further, 40% by mass of MIBK is added and stirred and mixed. A curing agent (trade name: E-5XM, manufactured by Soken Chemical Co., Ltd.) was added thereto to prepare a pressure-sensitive adhesive composition for the surface-side transparent pressure-sensitive adhesive layer. Moreover, the adhesive composition for back side transparent adhesive layer formation was prepared as a composition remove | excluding various absorbers below this near-infrared absorber from this surface side transparent adhesive layer.
(2) Manufacture of Electromagnetic Wave Shielding Member Filter The surface of the intermediate member gold fine particle binder 7 produced in Production Example 1 was electrolessly treated using an electroless nickel plating solution at a bath temperature of 60 ° C. for a treatment time of 35 minutes. The plating solution was 2.8% acetic acid, 8.8% nickel sulfate hexahydrate, 7.1% sodium hypophosphite monohydrate, 9.2% complexing agent, and 72.1% ion-exchanged water. The stock solution was diluted to 250 ml / L and used. The concentration was 230 ml / L. At that time, the pH was 6.5.
The film thickness of the obtained nickel film containing 1.5% by mass of phosphorus (increase in the thickness of the conductive mesh by electroless nickel plating) was 4.1 μm.
Thereafter, chemical conversion treatment was performed using an etching (corrosion) solution at a bath temperature of 25 ° C. and a treatment time of 30 seconds. The etching solution is a mixture of 38% ferric chloride, 0.12% hydrochloric acid, 61.88% ion-exchanged water, and the stock solution is used at a 2-fold dilution (500 ml / L). In addition, a nickel columnar crystal aggregate layer 8 having an outermost surface having light diffusive fine irregularities was formed. The mesh pattern-like electromagnetic wave shielding layer 4 was constituted by the gold-metal fine particle binder 7 and the nickel columnar crystal aggregate layer 8.
The appearance color of the electromagnetic wave shielding layer 4 before etching was gray, the appearance color of the electromagnetic wave shielding layer 4 after etching was black, and the surface resistance of the electromagnetic wave shielding layer 4 after etching was 0.6Ω / □.
Thus, the electromagnetic wave shielding filter layer 20 was obtained.
(3) Manufacture of surface adjustment filter One surface of the back-side transparent base material 5 made of a long roll-wrapped PET film having a width of 1000 mm and a thickness of 100 μm that has been subjected to easy adhesion treatment on one side (the observer side of the image display device and On the opposite surface), a high refractive index layer and a low refractive index layer are sequentially formed in this order one by one to form an antireflection layer and a hard coating layer. did. The high refractive index layer is refracted at a thickness of 3 μm using a composition (trade name “KZ7973” manufactured by JSR Corporation) in which ultrafine zirconia particles are dispersed in an ultraviolet curable resin made of an acrylate-based prepolymer. It consists of a cured product layer with a rate of 1.69. On the other hand, the low refractive index resin layer is made of a cured layer having a thickness of 100 nm and a refractive index of 1.41 using a fluororesin-based ultraviolet curable resin (manufactured by JSR Corporation, trade name “TM086”). . In addition, since such an antireflection layer has a cross-linked structure and is hard, it also functions as a hard coating layer. Thus, the surface adjustment filter 10 was obtained.
(4) Manufacture of filter for image display device The adhesive composition for forming the surface-side transparent adhesive layer prepared in (1) above is dried on the electromagnetic wave shielding layer 4 side of the electromagnetic wave shielding member filter 20 produced in (2). The Meyer bar No. was adjusted so that the subsequent thickness would be 25 μm. 16 was applied. Subsequently, it heat-dried at 90 degreeC for 1 minute, and was set as the surface side transparent adhesive layer 3 containing a near-infrared absorber, a neon light absorber, a toning agent, and an ultraviolet absorber. After that, the surface adjustment filter 10 manufactured in (3) is placed so that the surface-side transparent base material 2 side faces the surface-side transparent adhesive layer 3, and is pressed with a rubber roller to shield the electromagnetic wave. On the filter 20, the surface adjustment filter 10 was laminated via the surface-side transparent adhesive layer 3.
Next, on the surface of the electromagnetic wave shielding filter 20 on the back side transparent base material 5 side, the thickness after drying the back side transparent adhesive layer forming pressure-sensitive adhesive composition prepared in (1) above becomes 20 μm. The back side transparent pressure-sensitive adhesive layer 6 was obtained by coating with a Meyer bar and heating and drying at 90 ° C. for 1 minute. Thus, the filter 100 for an image display device of the present invention was manufactured.

Example 2
A filter 100 for an image display device of Example 2 was produced in the same manner as in Example 1 except that the intermediate member produced in Production Example 2 was used in (2) of Example 1.

According to the present invention, an image display that has a desired optical filter function such as a near-infrared absorption function, high transparency, and an electromagnetic wave shielding function, and that prevents whitening of the image in an external light incident environment and obtains a high-contrast image. A filter for the device can be provided.
This filter for an image display device is suitable for an image display device such as a plasma display, a cathode ray tube (CRT), and a liquid crystal display (LCD). The plasma display is particularly suitable for a plasma display, and the plasma display having the filter for an image display device of the present invention disposed on the front surface does not adversely affect peripheral electronic devices and does not exhibit a blue transmission color tone. In addition, the brightness is high, there is no reflection of external light, and the visibility is excellent.

It is a schematic diagram which shows the filter for image display apparatuses of this invention. It is a schematic diagram explaining the electromagnetic wave shielding layer in the filter for image display apparatuses of this invention. It is a schematic diagram which shows the intermediate member before electroless nickel plating of the electromagnetic wave shielding layer in the filter for image display apparatuses of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface adjustment layer 2 Front surface side transparent base material 3 Front surface side transparent adhesive layer 4 Electromagnetic wave shielding layer 5 Back surface side transparent base material 6 Back surface side transparent adhesive layer 7 Metal particle binder 7a Binder resin 7b Metal particle 8 Nickel columnar crystal the thickness B pattern portion T _a a the assembly layer 9 primer layer 10 surface conditioning filter 20 filter 100 for shielding electromagnetic image display apparatus filter 200 image display device or the image display device substrate a patterned conductor layer is formed Of portion T _B B where no conductive layer is formed

Claims (7)

On the back side transparent substrate, an electromagnetic wave shielding filter having a patterned electromagnetic wave shielding layer,
On the electromagnetic wave shielding layer of the electromagnetic wave shielding filter, the surface side transparent adhesive layer was interposed between the antireflection layer, the antiglare layer, and the hard coating layer. Laminating a surface adjustment filter having a surface adjustment layer so that the surface side transparent substrate side faces the electromagnetic wave shielding layer,
It consists of a layer structure in which a back side transparent adhesive layer is laminated on the back side transparent substrate of the electromagnetic wave shielding filter,
The electromagnetic wave shielding layer is composed of a metal fine particle binder obtained by binding metal fine particles with a binder resin, and a nickel columnar crystal aggregate layer covering the surface of the metal fine particle binder. The outermost surface has a light diffusive fine uneven surface,
In any one or two layers of the front surface side transparent adhesive layer or the back surface side transparent adhesive layer, it is selected from a near infrared absorber, a neon light absorber, a toning agent, or an ultraviolet absorber. A filter for an image display device, comprising at least one absorber.   A portion having a primer layer made of a resin formed on the back side transparent base material between the back side transparent base material and the electromagnetic wave shielding layer, wherein the electromagnetic wave shielding layer is formed in the primer layer The image display device filter according to claim 1, wherein a thickness of the image display device is larger than a thickness of a portion where the electromagnetic wave shielding layer is not formed.   The filter for an image display device according to claim 1 or 2, wherein the nickel columnar crystal aggregate layer also fills at least part of the internal voids of the metal fine particle binder.   The filter for an image display device according to claim 1, wherein the nickel columnar crystal contains phosphorus.   The image display device filter according to any one of claims 1 to 4, wherein the nickel columnar crystal aggregate layer is formed by an electroless nickel plating method.   The filter for an image display device according to claim 1, wherein the image display device is a plasma display.   The image display apparatus which stuck the filter for image display apparatuses in any one of Claims 1-6 on the front surface.

Images