JP2005107199A - Optical filter and plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical filter which can be directly pasted onto a plasma display panel, adds impact resistance to the plasma display panel and has superior transparency. <P>SOLUTION: The optical filter is to be directly pasted on the display surface of a plasma display panel module, and has an antiimpact layer which includes adhesive that is prepared by stacking viscous liquid and polymerizing and cross-linking the viscous liquid by irradiating ionization radiation, wherein the viscous liquid includes 0.1 to 20 pts.wt. cross-linking agent for 100 pts.wt. acrylic mixture consisting of 90 to 10 pts.wt. (meth)acrylic monomer and 10 to 90 pts.wt. (meth)acrylic polymer whose weight-average molecular weight of is 1,000 to 1,000,000, and has a viscosity of 1 to 500 Pa×S. The antiimpact layer has an internal haze of 0.1 to 3.0, desirably 0.1 to 1.5, and a thickness of 0.2 mm to 1.0 mm, desirably 0.2 mm to 0.5mm. Moreover, destruction energy by an impact test conducted for the plasma display panel is equal to or greater than 0.5 J when the optical filter is pasted onto the plasma display panel module. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an optical filter that can be directly attached to a plasma display panel and can impart impact resistance to the plasma display panel, and a plasma display panel having the optical filter attached thereto.

  In recent years, plasma display devices have been developed and commercialized for use in large thin televisions, thin display applications, and the like. Due to the structure of this plasma display device, near-infrared rays that cause malfunctions to other devices and affect the operation of remote control, and neon light that affects color tone are emitted from the inside of the display, thus blocking them. There is a need. Further, since electromagnetic waves are generated from the plasma display device, it is required to reduce the intensity of electromagnetic wave emission within the standard in consideration of the influence on the human body.

  In view of these requirements, various filters have already been developed for application to plasma display panel modules. For example, Japanese Patent Application Laid-Open No. 2000-59083 (Patent Document 1) discloses an electromagnetic wave shielding effect, near-infrared cut, and color. An optical filter in which correction and antireflection layers are accumulated is disclosed. Such an optical filter is basically required to have excellent transparency.

  On the other hand, the plasma display device is required to be lighter and thinner as the size of the device increases, and the impact resistance of the plasma display panel with an optical filter is increasingly required.

  However, how to increase the impact resistance of the plasma display panel and how much impact resistance is necessary should be solved in the state that the optical filter having each function is combined with the plasma display panel module. It became an issue. In addition, when a solvent-drying resin is applied to form an impact-resistant layer, fine bubbles cannot be removed from the coating film during drying, so transparency is required for plasma display panels. This optical filter cannot be used because the haze is too high. Further, the thickness of the impact resistant layer must be reduced in accordance with the demand for thinning the plasma display, but it is necessary to ensure the necessary impact resistance.

  Japanese Patent Application Laid-Open No. 2002-260539 (Patent Document 2) discloses a display panel in which an optical filter having an antireflection film is attached to the front surface of a plasma display panel module via an adhesive layer. Since the optical filter attached to the display panel module of Patent Document 2 has improved impact resistance on the pressure-sensitive adhesive layer, impact resistance and adhesiveness are required. In Example 1 of Patent Document 2, an adhesive sheet formed by melting an acrylic acid copolymer into a sheet shape is attached to an optical filter, and then attached to a plasma display panel module. In Example 2 of Patent Document 2, in order to paste a filter on the front surface of the plasma display panel module, the distance between the display panel module and the filter is kept at 1 mm, and a heat treatment is performed using transparent thermosetting silicone. It is matched. However, the method of adhering the optical filter and the plasma display panel module as in Example 2 has the problem that the productivity is poor and the yield is poor because it requires silicone pouring. Furthermore, the optical filter including the pressure-sensitive adhesive layer of Patent Document 2 does not show any degree of transparency which is a basic requirement of the optical filter itself.

Japanese Patent Laid-Open No. 2002-23649 (Patent Document 3) requires a complicated multilayer structure including a scattering prevention layer, two types of crack prevention layers, and a transparent adhesive layer in order to constitute an impact relaxation laminate. Yes.
JP 2000-59083 A JP 2002-260539 A JP 2002-23649 A

  In view of the above-mentioned problems of the prior art, the present invention constitutes an optical filter in which a specific adhesive is incorporated as an impact resistant layer, and when the optical filter is attached to a plasma display panel module, sufficient impact resistance is achieved. In addition, the present invention aims to provide a thin optical filter excellent in transparency by preventing bubbles from being contained in the impact-resistant layer, and to provide a plasma display panel having the optical filter attached thereto. To do.

  A further object of the present invention is to provide an optical filter having antireflection properties in addition to the optical filter having the above properties.

  A further object of the present invention is to provide an optical filter provided with a near-infrared absorbing resin layer in addition to the optical filter having the above properties.

  A further object of the present invention is to provide an optical filter provided with a neon light absorbing resin layer in addition to the optical filter having the above properties.

  Furthermore, an additional object of the present invention is to provide an optical filter having high transparency in addition to the optical filter having the above properties.

  A further object of the present invention is to provide an optical filter in which static electricity and / or electromagnetic wave noise is suppressed in addition to the optical filter having the above properties.

  A further object of the present invention is to provide a plasma display in which an optical filter having the above properties is attached to a display surface.

  The optical filter of the present invention for solving the above-described problems can be roughly divided into the following two types depending on the type of the impact-resistant layer imparted with tackiness.

  An optical filter according to a first aspect of the present invention is (1) an optical filter to be directly attached to a display surface of a plasma display panel module, and (2) the optical filter comprises 90 to 10 parts by weight of (meta ) 0.1 to 20 parts by weight with respect to 100 parts by weight of an acrylic monomer and an acrylic mixture comprising 10 to 90 parts by weight of a (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. A layer of a viscous fluid having a viscosity of 1 to 500 Pa · s containing a cross-linking agent, and having an impact-resistant layer containing a pressure-sensitive adhesive polymerized and crosslinked by irradiation with ionizing radiation, (3) The internal haze is 0.1 to 3.0, preferably 0.1 to 1.5, and the thickness is 0.2 mm to 1.0 mm, preferably 0.2 mm to 0.5 mm. (4) The optical filter is Plasma de Fracture energy by impact test with respect to the plasma display panel when affixed to spray panel module is characterized in that at least 0.5 J.

  In the optical filter of the first aspect of the present invention, the optical filter when the adhesive contained in the impact resistant layer is an ultraviolet curable resin, the optical filter of the first aspect of the present invention, the impact resistant layer is For 100 parts by weight of an acrylic mixture comprising 90 to 10 parts by weight of a (meth) acrylic monomer and 10 to 90 parts by weight of a (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. Then, a viscous fluid having a viscosity of 1 to 500 Pa · s containing 0.0001 to 1.0 parts by weight of a photoradical polymerization initiator and 0.1 to 20 parts by weight of a crosslinking agent is laminated and polymerized by ultraviolet irradiation. It is an impact-resistant layer containing a crosslinked adhesive.

  An optical filter according to a second aspect of the present invention is (1) an optical filter for being directly attached to a display surface of a plasma display panel module, and (2) the optical filter comprises 90 to 10 parts by weight of (meta ) 0.1 to 5 weights relative to 100 weight parts of acrylic monomer and 10 to 90 weight parts acrylic mixture composed of (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. An impact-resistant layer containing an adhesive obtained by laminating a viscous fluid having a viscosity of 1 to 500 Pa · s containing 0.1 to 20 parts by weight of a crosslinking agent, and polymerizing and crosslinking by heating. (3) The impact-resistant layer has an internal haze of 0.1 to 3.0 and a thickness of 0.2 mm to 1.0 mm. (4) The optical filter is formed into a plasma display panel module. Fracture energy by impact test with respect to the plasma display panel when adhered to, characterized in that at least 0.5 J.

  Since the plasma display panel of the present invention contains an ionizing radiation curable resin adhesive as the impact resistant layer, it is solvent-free during coating (solvent content is 3% or less, preferably 1% or less). Because the air bubble does not enter the shock-resistant layer, the impact-resistant layer should be an optical filter suitable for being attached to a plasma display panel module with an excellent impact-resistant layer having an internal haze of 0.1 to 3.0. Can do.

  The impact resistant layer in the optical filter of the present invention must have a thickness of 0.2 mm to 1.0 mm. If the thickness is less than 0.2 mm, the fracture energy is 0.5 J or more in the impact resistance test. If the thickness exceeds 1.0 mm, haze increases and transparency is lost.

  The impact test is performed using the impact test apparatus shown in FIG. 5 and a steel ball 12 (mass 534 g) having a diameter of 9.6 cm to a diameter of 50.8 mm (specified in JIS B1501 ball bearing steel ball) is dropped. This was done by measuring the breaking energy at the time. As the test stand 8, a SUS base 9 and a 10 mm thick glass plate 10 bonded together were used. On the test stand 8, a high strain point glass plate (PD-200: trade name, thickness 2.8 mm) manufactured by Asahi Glass Co., Ltd. was placed as the front glass plate 11 for plasma display. PD-200 is a front glass plate 11 for plasma display that is commonly used by plasma display manufacturers. The reason why the front glass plate 11 is directly placed on the test table 8 is to eliminate the cushioning property by the casing of the plasma display.

  As described above, the optical filter of the present invention is preferably provided with an antireflection film in the layer structure, and an antireflection film is preferably provided on the outermost layer.

  The optical filter of the present invention preferably has a resin layer containing a near-infrared absorbing compound such that the transmittance in the wavelength range of 800 to 1000 nm is 20% or less in the layer configuration.

  The optical filter of the present invention has a resin layer containing a neon light absorbing compound having a maximum absorption wavelength in the wavelength range of neon light 560 to 630 nm in the layer configuration, and the transmittance of the maximum absorption wavelength in the wavelength range is 40. % Or less is desirable.

  The optical filter of the present invention desirably has an electromagnetic wave shielding layer for shielding static electricity and / or electromagnetic wave noise generated from the plasma display device in the layer structure.

  The optical filter of this invention can provide the adhesive layer for sticking to a plasma display.

  The plasma display panel of the present invention can be configured by attaching the optical filter of the above-described form to a display surface through an adhesive layer.

  The optical filter having an impact resistant layer containing the pressure-sensitive adhesive of the present invention has impact resistance and excellent transparency when attached to a plasma display panel module. In addition, the impact resistant layer in the optical filter of the present invention has a tackiness because the impact resistant layer containing an adhesive has a tackiness. Therefore, when the impact resistant layer is provided in the optical filter, the impact resistant layer is special for lamination with other layers. It is not necessary to provide a pressure-sensitive adhesive layer, and the layer structure of the optical filter can be simplified.

  FIG. 1 is a view showing an example of a laminated structure in the case where an optical filter provided with an impact-resistant layer imparted with tackiness according to the present invention is attached to the front surface of a plasma display. Reference numeral 5 denotes an electromagnetic wave shielding layer, which is a metal foil bonded to a transparent substrate with an adhesive (not shown) processed into a mesh shape by etching, and has an electromagnetic wave shielding ability. Reference numeral 4 denotes a dye-containing pressure-sensitive adhesive layer, which simultaneously flattens the mesh-like metal irregularities in the electromagnetic wave shielding layer 5, and at the same time, the dye-containing pressure-sensitive adhesive layer 4 is a fine adhesive layer remaining in the recesses of the metal mesh formed by etching. Fill in uneven steps. Reference numeral 3 denotes an adhesive impact-resistant layer, which is laminated on the transparent base material side of the electromagnetic shielding layer using the adhesiveness of the adhesive impact-resistant layer 3. Further, the antireflection layer 1 is laminated on the other surface of the adhesive impact resistant layer 3 by utilizing the adhesiveness of the adhesive impact resistant layer 3. The optical filter composed of these layers is attached to the surface of the plasma display panel module 7 using the adhesiveness of the dye-containing pressure-sensitive adhesive layer 4.

  FIG. 2 is a view showing another example of the laminated structure in the case where the optical filter provided with the impact-resistant layer imparted with the tackiness according to the present invention is attached to the front surface of the plasma display. In the embodiment of FIG. 2, an electromagnetic wave shielding layer 5 is laminated on the adhesive impact resistant layer 3 using the adhesiveness of the adhesive impact resistant layer 3, and the dye-containing adhesive layer 4 is further laminated on the electromagnetic wave shielding layer 5. Further, the antireflection layer 1 is laminated on the dye-containing pressure-sensitive adhesive layer 4 by utilizing the adhesiveness of the dye-containing pressure-sensitive adhesive layer 4. The optical filter composed of these layers is attached to the surface of the plasma display panel module 7 using the adhesiveness of the adhesive impact-resistant layer 3.

  FIG. 3 is a diagram showing an example of a laminated structure in the case where an optical filter provided with a dye-containing impact-resistant layer imparted with tackiness according to the present invention is attached to the front surface of a plasma display. In the embodiment of FIG. 3, a dye-containing tacky impact-resistant layer 31 is provided as an impact layer in order to flatten the metal irregularities on the mesh in the electromagnetic wave shielding layer 5. The step of the fine unevenness of the adhesive remaining in the concave portion of the metal mesh formed by the above is filled, and further, it has adhesiveness to other layers and has impact resistance. In the optical filter of FIG. 3, an antireflection layer 1 is further formed on the other surface of the electromagnetic wave shielding layer 5. The optical filter composed of these layers is attached to the surface of the plasma display panel module 7 by utilizing the adhesiveness of the dye-containing adhesive impact-resistant layer 31.

  FIG. 4 is a view showing another example of the laminated structure in the case where the optical filter provided with the dye-containing impact-resistant layer imparted with the tackiness according to the present invention is attached to the front surface of the plasma display. In the embodiment of FIG. 4, a dye-containing tacky impact-resistant layer 31 is provided as an impact layer in order to flatten metal irregularities on the mesh in the electromagnetic wave shielding layer 5, and at the same time, the dye-containing tacky impact-resistant layer 31 is etched. The step of the fine unevenness of the adhesive remaining in the concave portion of the metal mesh formed by the above is filled, and further, it has adhesiveness to other layers and has impact resistance. In the optical filter of FIG. 3, the antireflection layer 1 is laminated on the other surface of the dye-containing adhesive shock-resistant layer 31 using the adhesiveness of the dye-containing adhesive shock-resistant layer 31. Further, an optical filter is attached to the surface of the plasma display panel module 7 via the pressure-sensitive adhesive layer 6 on the other surface side of the electromagnetic wave shielding layer 5.

  1 and 2, the dye-containing pressure-sensitive adhesive layer 4 contains a dye such as an infrared absorbing dye and / or a neon light absorbing dye. In FIGS. 3 and 4, the infrared absorbing dye and In addition, although a dye such as a neon light absorbing dye is contained in the dye-containing tacky impact-resistant layer 31, these dyes can be further contained in any layer constituting the optical filter. .

  Hereinafter, each layer used for the layer structure of the optical filter when the optical filter of the present invention is applied to a plasma display will be described as an example.

Impact resistant layer :
The resin used for the impact resistant layer in the optical filter of the present invention includes a polymerizable low-viscosity (meth) acrylic monomer and a (meth) acrylic polymer as a high-viscosity adhesive that has already been polymerized. A solvent-free (solvent content of 3% or less, preferably 1% or less) acrylic mixture is used. As the acrylic mixture, an ionizing radiation curable resin or a thermosetting resin is used. The impact resistant layer in the optical filter of the present invention is formed of a resin composition having a viscosity of 1 to 500 Pa · s by adding a crosslinking agent to the acrylic mixture, and polymerized by ionizing radiation initiated polymerization or thermal initiated polymerization. It is a thing. Thus, since the resin used for the impact resistant layer in the present invention is a solvent-free resin containing an adhesive, it has both tackiness and elasticity and does not contain bubbles. There is a feature that an impact-resistant layer having a property can be formed. On the other hand, in the case of a general pressure-sensitive adhesive, that is, a pressure-sensitive adhesive prepared by dissolving an adhesive polymer in a solvent, since fine bubbles cannot be completely removed from the coating film when the coating film is dried, An optical filter for a plasma display panel requiring high performance has a disadvantage that the haze is too high to be used.

  The internal haze of the impact resistant layer in the optical filter of the present invention can be set to 0.1 to 3.0. Moreover, the thickness of the impact resistant layer in the optical filter of the present invention is 0.2 mm to 1.0 mm. If the thickness of the impact resistant layer is less than 0.2, it cannot be achieved that the fracture energy is 0.5 J or more in the impact resistance test, and if it exceeds 1.0 mm, the haze increases and the transparency is lost. Is called. When the thickness exceeds 1.0 mm, the adhesive sticks out to the plasma display module and adheres to other parts, and it is difficult to remove the adhesive, resulting in a significant decrease in yield.

  In the present invention, “internal haze” means the internal haze of an “impact resistant layer” alone, measured without the influence of the surface of the impact resistant layer. Therefore, when the impact-resistant layer is laminated with other layers and is not produced alone, the measurement is performed with all the layers in contact with the impact-resistant layer removed. The measuring method is a method based on JIS K7105-1981, applying oil to the test piece, eliminating the influence of the surface, and testing only the internal influence.

  The acrylic mixture used for the impact resistant layer in the present invention may be a mixture of a (meth) acrylic monomer that has not been polymerized yet and a (meth) acrylic polymer that has already been polymerized by the start of ionizing radiation polymerization or thermal polymerization. Good, or even partially polymerized by adding a small amount of ionizing radiation polymerization initiator (including ultraviolet polymerization initiator) or thermal polymerization initiator to a (meth) acrylic monomer that has not been polymerized yet Good.

  The acrylic mixture is solvent-free (solvent content is 3% or less, preferably 1% or less), and the viscosity is 1 to 500 Pa · s depending on the blending ratio of the (meth) acrylic monomer and the (meth) acrylic polymer. adjust. If the viscosity is less than 1 Pa · s, it flows down until it is cured, the film thickness cannot be controlled, and the machine is contaminated. When the (meth) acrylic monomer is less than 10 parts by weight, the viscosity of the mixed solution becomes too high, which is not suitable for coating, and when it exceeds 90 parts by weight, the viscosity becomes too low to flow down until it is cured. Cannot be done and the machine is contaminated. In addition, the polymerization rate is low, the curing time is long, and the production efficiency is lowered.

  Specific examples of resins that can be used in the impact-resistant layer that can be used in the present invention include (meth) acrylic polymers having a radical polymerizable unsaturated bond or a cationic polymerizable functional group in the molecule, and (meth) ) A composition that can be crosslinked and cured by ionizing radiation in which acrylic monomers are appropriately mixed, or a composition that can be crosslinked and cured by heating is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having energy capable of causing a crosslinking and curing reaction of the molecule, and usually ultraviolet (UV) or electronic acid (EB) is used. Here, (meth) acrylic means acrylic or methacrylic.

  The blending ratio of the (meth) acrylic monomer to the (meth) acrylic polymer is 10 to 90 parts by weight of (meth) acrylic with respect to 90 parts by weight or less and 10 parts by weight or more of the (meth) acrylic monomer. It is the ratio of the system polymer.

  Examples of the polymer or monomer include 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. These polymers and monomers are used alone or in combination. Here, for example, the (meth) acryloyl group means an acryloyl group or a methacryloyl group. Further, as the ionizing radiation curable resin, a polyene / thiol polymer based on a combination of polyene and polythiol may be used in combination.

  Examples of (meth) acrylic polymers having radically polymerizable unsaturated groups in the molecule include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, and triazine (meth). Acrylate, silicone (meth) acrylate, etc. can be used. The molecular weight is usually about 1,000 to 1,000,000.

  As the (meth) acrylic monomer that can be used in the present invention, preferably, (meth) acrylic acid alkyl esters can be suitably used. For example, alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, -2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, and the like. Can be mentioned. Examples of the alkyl methacrylates include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, -2-ethylhexyl methacrylate, octyl methacrylate, and nonyl methacrylate. , Decyl methacrylate, dodecyl methacrylate and the like. In addition, oligomers from these monomers can be used.

  In the present invention, as the monomer having a polymerizable unsaturated bond, the above-mentioned (meth) acrylic acid alkyl ester or a monomer having other polymerizable unsaturated bond as a main component is a modified monomer. And can be used in combination.

  Examples of such modifying monomers include acrylic acid aryl esters, acrylic acid alkoxyalkyl esters, acrylic acid or methacrylic acid and alkali metal salts thereof, methacrylic acid aryl esters, methacrylic acid alkoxyalkyl esters, (poly) alkylene. Diacrylates of glycol, dimethacrylates of (poly) alkylene glycol, polyvalent acrylates, halogenated vinyl compounds, methacrylic esters of alicyclic alcohols, oxazoline group-containing polymerizable compounds, Aziridine group-containing polymerizable compounds, epoxy group-containing vinyl monomers, hydroxy group-containing vinyl compounds, unsaturated carboxylic acid or its partial ester compounds and anhydrides, reactive halogen-containing vinyl monomers, amides Group included Alkenyl monomers, organic silicon group-containing vinyl compound monomers, and the like. In addition, modified oligomers of these modified monomers can be used.

  For example, examples of the acrylic acid aryl esters include phenyl acrylate and benzyl acrylate. Examples of the alkoxyalkyl acrylates include methoxyethyl acrylate, ethoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, and the like. Examples thereof include salts such as acrylic acid and alkali metal acrylate, and salts such as methacrylic acid and alkali metal methacrylate. Examples of the methacrylic acid aryl esters include phenyl methacrylate and benzyl methacrylate. Examples of the alkoxyalkyl methacrylates include methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, ethoxypropyl methacrylate, and the like.

  (Poly) alkylene glycol diacrylates include: ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, Examples include propylene glycol diacrylate. (Di) alkylene glycol dimethacrylates include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate. Examples thereof include methacrylic acid esters, dipropylene glycol dimethacrylate, and tripropylene glycol dimethacrylate.

  Examples of the polyvalent acrylates include trimethylolpropane triacrylate. Examples of the polyvalent methacrylate include trimethylolpropane trimethacrylate. Examples of nitriles include acrylonitrile and methacrylonitrile. Examples of vinyl compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, pt- Examples thereof include vinyl butylbenzoate, vinyl salicylate, vinylidene chloride, vinyl chlorohexanecarboxylate, 2-chloroethyl acrylate, and 2-chloroethyl methacrylate. Examples thereof include acrylic esters of alicyclic alcohols such as cyclohexyl acrylate, and methacrylic esters of alicyclic alcohols such as cyclohexyl methacrylate.

  Examples of the oxazoline group-containing polymerizable compounds include 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropynyl-2-oxazoline and the like. Examples of the aziridine group-containing polymerizable compounds include acryloylaziridine, methacryloylaziridine, acrylic acid-2-aziridinylethyl, and methacrylate-2-aziridinylethyl.

  Epoxy group-containing polymerizable compounds include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, acrylate-2-ethyl glycidyl ether, methacrylic acid-2-ethyl glycidyl ether, 2-methylallyl glycidyl ether, styrene. -P-glycidyl ether, glycidyl acrylate, glycidyl methacrylate, mono and diglycidyl esters of maleic acid, mono and diglycidyl esters of fumaric acid, mono and diglycidyl esters of crotonic acid, mono and diglycidyl esters of tetrahydrophthalic acid, itacon Mono- and glycidyl esters of acid, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, allylco Mono- and alkyl glycidyl esters of dicarboxylic acids such as mono- and glycidyl esters of succinic acid, alkyl glycidyl esters of p-styrene carboxylic acid, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, and the like.

  Examples of the hydroxy group-containing polymerizable compounds include acrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxyethyl, acrylic acid-2-hydroxypropyl, monoester of acrylic acid or methacrylic acid and polypropylene glycol or polyethylene glycol, Examples include adducts of lactones and (meth) acrylic acid-2-hydroxyethyl. Fluorine vinyl monomers include fluorine-substituted methacrylic acid alkyl ester, fluorine-substituted acrylic acid alkyl ester, and the like.

  Examples of unsaturated carboxylic acids, salts thereof, and (partial) ester compounds and acid anhydrides thereof include itaconic acid, crotonic acid, maleic acid, and fumaric acid, excluding (meth) acrylic acid. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5,6 -Dicarboxylic acid and the like, and these derivatives include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6- Examples thereof include dicarboxylic acid anhydrides, acid halides, aminoethyl methacrylate and aminopropyl methacrylate, and maleylimide.

  Examples of the amide group-containing vinyl monomers include methacrylamide, N-methylol methacrylamide, N-methoxyethyl methacrylamide, N-butoxymethyl methacrylamide and the like. Examples of amino group-containing ethylenically unsaturated compounds include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, phenylaminoethyl methacrylate, Alkyl ester derivatives of acrylic acid or methacrylic acid such as cyclohexylaminoethyl methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine, methacrylamine, N-methylacrylamine, N, N -Allylamine derivatives such as dimethylacrylamide and N, N-dimethylaminopropylacrylamide, acrylamide derivatives such as acrylamide and N-methylacrylamide, and amino acids such as p-aminostyrene Styrenes, 6-aminohexyl succinimide and 2-aminoethyl succinimide and the like.

  In the present invention, these acrylic monomers or the above-mentioned oligomers are not particularly limited even if they are gases, liquids or solids, depending on the reaction conditions, but are preferably liquid at room temperature because of their handling properties. Is preferred. In addition, as described above, in the present invention, the (meth) acrylic acid alkyl ester or the above-described main component is used as the main component. As monomers or modified monomers having a polymerizable unsaturated bond, they can be used suitably and suitably, alone or in combination.

  Examples of the crosslinking agent added to the resin of the impact-resistant layer in the optical filter of the present invention include generally referred crosslinking agents (for example, isocyanate-based and epoxy-based crosslinking agents) and polyfunctional monomers.

  The crosslinking agent used in the present invention will be described more specifically. Crosslinking agents such as isocyanate crosslinking agents and epoxy crosslinking agents may be used alone or in combination of two or more. Examples of isocyanate compounds include isocyanate monomers such as tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like. Isocyanate compounds obtained by adding these isocyanate monomers with trimethylolpropane, isocyanurates, burette type compounds, and urethanes subjected to addition reaction such as known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Examples include prepolymer type isocyanate.

  Examples of the epoxy compound include ethylene glycol glycidyl ether, polyethylene glycol glycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′. , N′-tetraglycidyl-m-xylylenediamine, N, N, N ′, N′-tetraglycidylaminophenylmethane, triglycidyl isocyanurate, m-N, N-diglycidylaminophenylglycidyl ether, N, N -Diglycidyl toluidine, N, N-diglycidyl aniline, etc. can be mentioned.

Examples of the aziridine-based crosslinking agent include trimethylolpropane tri-β-aziridinylpropionate, trimethylolpropane tri-β- (2-methylaziridine) propionate, tetramethylolmethane tri-β-aziridinylpropionate, etc. Can be mentioned. Examples of the metal chelate-based crosslinking agent include aluminum isopropylate, diisopropoxybisacetylacetone titanate, and aluminum triethylacetoacetate. Examples of the melamine resin-based crosslinking agent include methylated melamine resin, butylated melamine resin, and benzoguanamine resin. Examples of silane coupling agents include glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, and chloropropyltrimethoxysilane. They are added to the (meth) acrylic mixture used for the formation of impact-resistant layers. As the polymerization initiator, commonly used ionizing radiation polymerization initiators and thermal polymerization initiators are used.

(Formation of impact resistant layer)
1) When using an ionizing radiation curable resin An impact resistant layer is formed by applying an ionizing radiation curable resin adhesive on a transparent substrate sheet and irradiating it. Various known methods can be applied to the coating means, and for example, methods such as knife coating, roll coating, curtain flow coating, and T-die coating can be used. In particular, in the case of plate cylinder coating, a rotating plate cylinder can be immersed in a liquid composition in an ink pan (so-called soaking).

  Here, the ionizing radiation means an electromagnetic wave or charged particle beam having energy capable of polymerizing and crosslinking molecules, and includes ultraviolet rays, visible rays, X-rays, electron beams, α rays, etc. Ultraviolet rays or electron beams are used. As the ultraviolet ray source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light lamp, a metal halide lamp is used. As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. are used, preferably 100 to 1000 keV, preferably That irradiates electrons having energy of 100 to 300 keV is used.

2) When thermosetting resin is used 1) Coating or laminate molding is performed in the same manner as in the case of using ionizing radiation curable resin. The thermosetting resin is cured by heating.

  FIG. 6 is an example of a coextrusion laminating machine for forming a preferred impact resistant layer in the optical filter of the present invention. In order to form the impact resistant layer in the optical filter of the present invention, the impact resistant layer is formed by using a coextrusion laminating machine shown in FIG. 6 and pouring a molten resin film serving as the impact resistant layer between the films. In FIG. 6, 35 is a 1st film supply part, and the antireflection layer 1 is wound up in the film form. The antireflection layer 1 is supplied from the first film supply unit 35. On the other hand, a laminated sheet composed of a release film (not shown) / dye-containing pressure-sensitive adhesive layer 4 / electromagnetic wave shielding layer 5 is wound on the second film supply unit 39, and the second film supply unit 39 A die 42 of a coextrusion laminating machine is interposed between the antireflection layer 1 supplied from the first film supply unit 35 and the laminated film from the second film supply unit 39 when the film is superposed on the laminated film. A resin for forming the adhesive impact resistant layer 3 melt extruded is sandwiched between the cooling roll 37 and the nip roll 38 to form a laminated sheet. Next, the obtained laminated sheet is discharged from the paper discharge unit 41, and an optical filter with release paper is obtained.

Electromagnetic wave shielding layer :
The electromagnetic wave shielding layer 5 has a laminated structure in which a transparent substrate, an adhesive layer (not shown), and a metal mesh layer are laminated in this order.

(Metal mesh layer)
The metal mesh layer is a partial layer constituting the electromagnetic wave shielding layer 5 having a laminated structure. The metal mesh layer used in the present invention has a function of shielding electromagnetic waves generated from PDP or the like. Such a metal mesh layer is formed by laminating a metal foil on a transparent substrate, which will be described later, with an adhesive layer and etching the metal foil into a mesh shape. In the present invention, the metal mesh layer is not particularly limited as long as the metal mesh layer has electromagnetic wave shielding properties. For example, copper, iron, nickel, chromium, aluminum, gold, silver, Stainless steel, tungsten, titanium, or the like can be used. In the present invention, among the above, copper is preferable from the viewpoints of electromagnetic shielding properties, etching processing suitability, and handling properties. Moreover, as a kind of copper foil used, although rolled copper foil, electrolytic copper foil, etc. are mentioned, it is especially preferable that it is electrolytic copper foil. As a result, a uniform metal mesh layer having a thickness of 10 μm or less can be obtained, and when the surface of the metal mesh layer is blackened, the adhesion with chromium oxide or the like is good. Because it can be.

  Here, in the present invention, it is preferable that one side or both sides of the metal foil is blackened. The blackening process is a process of blackening the surface of the metal mesh layer with chromium oxide or the like. In the optical filter, the oxidation-treated surface is arranged to be a surface on the viewer side. The external light on the surface of the optical filter is absorbed by chromium oxide or the like formed on the surface of the metal mesh layer by this blackening treatment, so that it is possible to prevent light from being scattered on the surface of the optical filter and to achieve good transmission. Therefore, the optical filter can be obtained. Such a blackening treatment can be performed by applying a blackening treatment liquid to the metal foil.

As a blackening treatment method, different oxycarboxylic acid compounds such as tartaric acid, malonic acid, citric acid, and lactic acid are added to a CrO ₂ aqueous solution or a chromic anhydride aqueous solution to convert a part of hexavalent chromium into trivalent chromium. The reduced solution or the like can be applied by a roll coating method, an air curtain method, an electrostatic atomization method, a squeeze roll coating method, a dipping method or the like and dried. In addition, this blackening process may be performed after a metal foil is bonded to a transparent substrate with an adhesive layer or an adhesive layer and etched into a mesh shape.

  The black density on the surface of the blackened metal foil is preferably 0.6 or more. This is because the non-visibility can be further improved. Here, the black density is set to an observation viewing angle of 10 °, an observation light source D50, and a density standard ANSI T as an illumination type using GRETAG SPM100-11 (manufactured by KIMOTO) of COLOR CONTROL SYSTEM. It is a value measured later.

  The film thickness of the metal foil is preferably in the range of 1 μm to 100 μm, more preferably in the range of 5 μm to 20 μm. If the film thickness is thicker than the above range, it is difficult to make the pattern line width fine and fine by etching, and if the film thickness is thinner than the above range, sufficient electromagnetic shielding properties cannot be obtained.

  Furthermore, it is preferable that the said metal foil has the 10-point average roughness based on JISB0601 in the range of 0.5 micrometer-10 micrometers. When it is smaller than the above range, even when the blackening treatment is performed, the external light on the surface of the optical filter is specularly reflected, so that the visibility is deteriorated. This is because it becomes difficult to apply the resist or the resist.

  Here, the etching of the metal foil is performed after the metal foil is bonded to the transparent substrate described later via an adhesive layer or an adhesive layer. This etching can be performed by an ordinary photolithography method. For example, the resist can be applied to the surface of the metal foil, dried, and then exposed to light with a pattern plate and developed.

The above-described metal mesh layer used in the present invention preferably has a surface resistance in the range of 10 ⁻⁶ Ω / □ to 5 Ω / □, and more preferably in the range of 10 ⁻⁴ Ω / □ to 3Ω / □. . In general, the electromagnetic wave shielding property can be measured by surface resistance. It can be said that the lower the surface resistance, the better the electromagnetic wave shielding property. Here, the value of the surface resistance is measured by the method described in JIS K7194 “Resistivity test method using 4-probe method of conductive plastic” by a surface resistance measuring device Lorester GP, manufactured by Dia Instruments Co., Ltd. Value.

  The metal mesh layer after the etching treatment is preferably in the range of 50 μm □ to 500 μm □, more preferably in the range of 100 μm □ to 400 μm □, and particularly preferably in the range of 200 μm □ to 300 μm □. Is preferably in the range of 5 μm to 20 μm. When the mesh line width is finer than the above range, disconnection may occur, which is not preferable from the aspect of electromagnetic shielding properties, and when the mesh line width is thicker than the above range, the visible light transmittance is low, for example, This is because the brightness of the plasma display is not preferable.

Transparent substrate:
The transparent substrate is a part of the layers constituting the electromagnetic wave shielding layer 5 having a laminated structure. The transparent substrate used in the present invention is not particularly limited as long as it has transparency and an adhesive layer can be formed. For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN) ), Etc., polyolefins such as cyclic polyolefin, polyethylene, polypropylene, polystyrene, etc., vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polycarbonate, acrylic resin, triacetyl cellulose (TAC), polyethersulfone, poly A film made of ether ketone and having a light transmittance of 80% or more in the visible region can be mentioned.

  These films may be colored as long as they do not interfere with the object of the present invention, and can be used as a single layer, but may be used as a multilayer film in which two or more layers are combined. Among these, PET is most preferable from the viewpoints of transparency, heat resistance, cost, and handleability. It is desirable that the light transmittance in the visible region is as high as possible. However, since the light transmittance of 50% or more is required for the final product, even when at least two sheets are laminated, the transparent substrate has 80%. This is because it suits the purpose. Since the higher the transmittance, the more transparent substrates can be laminated, the light transmittance is preferably 85% or more, and most preferably 90% or more. Therefore, it is also an effective means to reduce the thickness. It is. The thickness of the transparent substrate is not particularly limited as long as the transparency is satisfied, but is preferably in the range of 12 μm to 300 μm from the viewpoint of workability. If the thickness is less than 12 μm, the film is too flexible, and the metal mesh layer, which is a conductive layer, is easily stretched and wrinkled due to the tension during film formation and processing. . If it exceeds 300 μm, the flexibility of the film decreases, and continuous winding in each step is difficult and unsuitable. Furthermore, when laminating a plurality of sheets, there is a problem that workability is greatly deteriorated.

Adhesive layer:
Although not shown in FIGS. 1 and 2, the adhesive layer is a layer used for bonding the transparent substrate and the metal foil. The type of the adhesive layer is not particularly limited as long as the adhesive layer is a layer capable of bonding the metal mesh layer and the transparent base material. In the present invention, the metal mesh layer is configured. Since the metal foil and the transparent base material are bonded together via the adhesive layer, and then the metal foil is meshed by etching, the adhesive layer preferably has etching resistance. Specifically, acrylic resin, polyester resin, polyurethane resin, polyvinyl alcohol alone or partially saponified product thereof, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyimide resin, epoxy resin, polyurethane ester resin Etc. The adhesive layer used in the present invention may be an ultraviolet curable type or a thermosetting type. In particular, an acrylic resin or a polyester resin is preferable from the viewpoints of adhesion to a transparent substrate, compatibility with near-infrared absorbing dyes and / or neon light absorbing dyes, dispersibility, and the like.

  Further, the adhesive layer may contain one or more near infrared absorbing dyes and / or neon light absorbing dyes. In that case, the light transmittance in the near infrared region is 20% or less, especially 10% or less, and the light transmittance at 560-630 nm is 40% or less, preferably 30% or less, particularly 25% or less. . Furthermore, the hydroxyl value and acid value of the resin must each be 10 or less. Thereby, it is possible to prevent the near-infrared absorbing dye and / or the neon light-absorbing dye from reacting with the reactive group in the resin due to the hydroxyl group and acid contained in the resin, stably absorbing near-infrared light, and / or Alternatively, the neon light absorbing function can be exhibited.

  The transparent substrate and the metal foil for forming the metal mesh layer can be bonded via the adhesive layer by a dry lamination method or the like. Moreover, it is preferable that the film thickness of this adhesive bond layer is in the range of 0.5 μm to 50 μm, especially 1 μm to 20 μm. Thereby, a transparent base material and a metal mesh layer can be firmly bonded, and the transparent base material is prevented from being affected by an etching solution such as iron oxide during etching to form the metal mesh layer. Because it can.

Dye-containing adhesive layer :
As shown in FIGS. 1 and 2, the dye-containing pressure-sensitive adhesive layer 4 used in the optical filter of the present invention is a layer for flattening the unevenness of the metal mesh layer having the electromagnetic wave shielding properties described above. It has a function of preventing the transparency of the optical filter from being lowered due to the unevenness of the layer. In addition, the etching performed when forming the metal mesh layer can improve the transparency that is deteriorated due to deterioration of the surface of the adhesive layer, and also prevent irregular reflection of the cross section when the metal mesh layer is viewed obliquely. Is possible. The type of the dye-containing pressure-sensitive adhesive layer 4 used in the present invention is not particularly limited as long as it can flatten the unevenness of the metal mesh layer, but in the present invention, the dye-containing pressure-sensitive adhesive layer 4 is not limited. The glass transition temperature (Tg) of the resin used for the agent layer 4 is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 40 ° C to 120 ° C. Accordingly, when the resin is dissolved in a solvent and applied onto the metal mesh layer, and the solvent is volatilized and dried, the unevenness formed by the unevenness of the metal mesh layer on the surface is equal to or greater than the Tg of the transparent substrate. This is because, for example, it can be flattened by applying pressure using a mirror roll or the like, and a high-quality optical filter with high transparency can be obtained. The temperature and pressure in the step of flattening the dye-containing pressure-sensitive adhesive layer 4 are appropriately selected depending on the type of the transparent resin, but are usually in the range of 50 ° C. to 170 ° C., and the pressure is linear pressure. it is preferably in the range of ^{0.1kg / cm 2 ~10kg / cm 2} .

  Specific examples of the resin having the above-described properties include acrylic resins, ester resins, polycarbonate resins, urethane resins, cyclic polyolefin resins, polystyrene resins, polyimide resins, or polytetrafluoroethylene. (PTFE), perfluoroalkoxy resin (PFA) made of a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, tetrafluoroethylene and hexafluoropropylene copolymer (FEP), tetrafluoroethylene and perfluoroalkyl vinyl ether and hexafluoropropylene copolymer ( EPE), copolymers of tetrafluoroethylene and ethylene or propylene (ETFE), polychlorotrifluoroethylene resin (PCTFE), ethylene and chlorine Fluoropolymers such as copolymer with trifluoroethylene (ECTFE), vinylidene fluoride resin (PVDF), and vinyl fluoride resin (PVF) can be mentioned. Among them, acrylic resins and ester resins are preferred from the viewpoint of transparency. A resin or a polycarbonate-based resin is preferable. The average molecular weight of the resin is preferably in the range of 500 to 600,000, particularly 10,000 to 400,000. This is because a transparent resin having the above properties can be obtained.

  In this invention, it is preferable that the film thickness of such a pigment | dye containing adhesive layer 4 has the film thickness of the part in which the metal mesh layer is not formed in the range of 10 micrometers-50 micrometers. This is because the unevenness of the metal mesh layer can be flattened. One or more near-infrared absorbing dyes and / or neon light absorbing dyes in the dye-containing pressure-sensitive adhesive layer 4 of the optical filter of the present invention may be contained. In that case, the light transmittance in the near infrared region is 20% or less, particularly 10% or less, and the light transmittance at 560-630 nm is 40% or less, preferably 30% or less, particularly 25% or less. . Furthermore, the hydroxyl value and / or acid value of the resin must be 10 or less, respectively. As a result, it is possible to prevent the near-infrared absorbing dye and / or neon light-absorbing dye from reacting with the hydroxyl group and acid group contained in the resin, and stably absorb near-infrared and / or neon light absorption. The function can be exhibited.

Dye-containing adhesive impact-resistant layer :
As shown in FIGS. 3 and 4, the dye-containing adhesive impact-resistant layer 31 used in the optical filter of the present invention has the function of the dye-containing adhesive layer described above, that is, a metal mesh having electromagnetic wave shielding properties. It is a layer for flattening the unevenness of the layer, and has a function of preventing the transparency of the optical filter from being lowered by the unevenness of the metal mesh layer. The dye-containing tacky impact-resistant layer 31 in the optical filter of the present invention uses the (meth) acrylic mixture used in the above-mentioned tacky impact-resistant layer, and the crosslinking agent described above, and if necessary, ionizing radiation polymerization starts. An adhesive (including an ultraviolet polymerization initiator) or a thermal polymerization initiator and a composition containing an infrared absorbing dye or a neon light absorbing dye are used in the same manner as the above-described adhesive impact resistant layer.

Antireflection layer :
As for the antireflection layer, it is possible to adopt a bocus method by scattering or diffusing light like polished glass. That is, in order to scatter or diffuse light, it is fundamental to roughen the light incident surface. For this roughening treatment, the surface of the substrate is directly roughened by a sandblasting method or an embossing method. A method of providing a roughened layer containing an inorganic filler such as silica or an organic filler such as resin particles in a resin that is cured by radiation, heat, or a combination on the substrate surface; and a sea-island structure on the substrate surface A method of forming a porous film by the above can be mentioned.

As another method for forming the antireflection layer, the surface reflection is suppressed by alternately laminating a material with a high refractive index and a material with a low refractive index, and forming a multilayer (multi-coating). Can be obtained. Usually, the antireflection layer is formed by a vapor phase method or the like in which a low refractive index material typified by SiO ₂ and a high refractive index material such as TiO ₂ or ZrO ₂ are alternately formed by vapor deposition.

In order to improve the antireflection effect, the refractive index of the low refractive index layer is preferably 1.45 or less. Examples of the material having these characteristics include LiF (refractive index n = 1.4), MgF ₂ (refractive index n = 1.4), 3NaF · AlF ₃ (refractive index n = 1.4), AlF ₃ ( Inorganic materials such as refractive index n = 1.4), Na ₃ AlF ₆ (refractive index n = 1.33), SiO ₂ (refractive index n = 1.45) are made into fine particles, and acrylic resin, epoxy resin, etc. Inorganic low-reflective materials, fluorine-based / silicone-based organic compounds, thermoplastic resins, thermosetting resins, radiation-curable resins, and the like can be used.

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% strength by weight 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. As the film forming agent, alkoxysilane, metal alkoxide, hydrolyzate of metal salt, or fluorine-modified polysiloxane can be used.

  The low refractive index layer is obtained by diluting the above-described material into a solvent, for example, a wet coating method such as spin coating, roll coating or printing, or a vapor phase method such as vacuum deposition, sputtering, plasma CVD, or ion plating. After being provided on the high refractive index layer and dried, it can be obtained by curing with heat or radiation (in the case of ultraviolet rays, the above-mentioned photopolymerization initiator is used).

  The high refractive index layer is formed by using a binder resin having a high refractive index in order to increase the refractive index, adding ultrafine particles having a high refractive index to the binder resin, or using these in combination. To do. The refractive index of the high refractive index layer is preferably in the range of 1.55 to 2.70.

  As the resin used for the high refractive index layer, any resin can be used as long as it is transparent, and a thermosetting resin, a thermoplastic resin, a radiation (including ultraviolet) curable resin, or the like can be used. Thermosetting resins include phenolic resin, melamine resin, polyurethane resin, urea resin, diallyl phthalate resin, guanamine resin, unsaturated polyester resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polysiloxane resin, etc. A curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like can be added to these resins as necessary.

As ultrafine particles having a high refractive index, for example, ZnO (refractive index n = 1.9), TiO ₂ (refractive index n = 2.3 to 2.7), which can also have an ultraviolet shielding effect, Fine particles of CeO ₂ (refractive index n = 1.95), antimony-doped SnO ₂ (refractive index n = 1.95) or antistatic effect, which can prevent dust adhesion. Examples thereof include fine particles of ITO (refractive index n = 1.95). Other fine particles include Al ₂ O ₃ (refractive index n = 1.63), La ₂ O ₃ (refractive index n = 1.95), ZrO ₂ (refractive index n = 2.05), Y ₂ O _3. (Refractive index n = 1.87). These fine particles are used alone or in combination, and those in the form of a colloid dispersed in an organic solvent or water are good in terms of dispersibility. The particle diameter is 1 to 100 nm, the transparency of the coating film To preferably 5 to 20 nm.

  In order to provide the high refractive index layer, the material described above is diluted with a solvent, for example, provided on a substrate by a method such as spin coating, roll coating, or printing, dried, and then heated or irradiated (in the case of ultraviolet rays, the above-mentioned The photopolymerization initiator may be used for curing.

  Further, the antireflection layer may contain one or more near infrared absorbing dyes and / or neon light absorbing dyes. In that case, the light transmittance in the near infrared region is 20% or less, in particular, 10% or less, and the light transmittance at 560-630 nm is 40% or less, preferably 30% or less, particularly 25% or less. Further, the resin must have a hydroxyl value and an acid value that are not more than predetermined values. As a result, it is possible to prevent the near-infrared absorbing dye and / or neon light-absorbing dye from reacting due to the hydroxyl group and acid value contained in the resin, and the near-infrared absorbing ability and / or neon light can be stably stabilized. An absorption function can be exhibited.

Adhesive layer :
The pressure-sensitive adhesive layer 6 in FIG. 4 is a layer for adhering the optical filter to the plasma display panel module 7. For example, a commercially available double-sided adhesive tape (for example, CS-9611: trade name, manufactured by Nitto Denko Corporation) Can be used.

  To a mixture of 92 parts by weight (15.6 kg) of acrylic acid-2-ethylhexyl acrylate and 8 parts by weight (1.4 kg) of acrylic acid, a photoinitiator (Irgacure 369: trade name, manufactured by Ciba Geigy Co., Ltd.) 003 parts by weight were added uniformly.

  The obtained mixture is put into a transparent polymerization tank having a cooling pipe, a nitrogen inlet, a stirring blade, a heating jacket, and a thermometer, nitrogen gas is sealed in the container for 20 minutes, and the air in the container is replaced with nitrogen gas. After that, the temperature of the mixture was raised to 80 ° C. in a nitrogen stream, and while maintaining this temperature constant, the water-cooled high-pressure mercury lamp installed outside the apparatus was irradiated with UV light intermittently until the UV irradiation amount became 1000 mJ. Irradiation was repeated. The obtained partial polymer of the acrylic copolymer had a weight average molecular weight of 750,000 and a number average molecular weight of 230,000.

  A crosslinking agent (Light acrylate 1.6HX-A: trade name, manufactured by Kyoeisha Hokugaku) 0.05 part by weight was blended with the above mixture to prepare a solvent-free coating solution.

  This solventless coating liquid did not contain a substantial solvent (solvent content of 1 wt% or less), and its viscosity was 150 Pa · s. The solvent-free coating solution was defoamed by placing it under reduced pressure at room temperature.

  Realic 8200 UV (trade name, manufactured by NOF Corporation, 80 μm thick triacetylcellulose film / 5 μm thick AR layer / laminated film comprising 40 μm thick protective film) was prepared as an antireflection film. The solvent-free coating liquid after the defoaming treatment obtained in the above step was applied on the antireflection film by a knife coating method so as to have a coating thickness of 300 to 500 μm. A separator made of a PET film having a thickness of 100 μm which had been peeled off was attached to the surface of the solvent-free coating solution thus coated, and the coating solution was sealed in a sandwich shape. In the coating film produced using the coating solution subjected to the defoaming treatment, bubbles were not contained, and an impact resistant layer having no defects was obtained.

  This laminate was polymerized by irradiating an electron beam with an acceleration voltage of 250 hV and an irradiation dose of 5 Mrad from the PET separator side. Next, after peeling the PET separator, the adhesive impact-resistant layer side of the laminate was bonded to the support side of the electromagnetic wave shielding layer on which a separately prepared dye-containing pressure-sensitive adhesive layer was laminated. A filter was obtained. The dye-containing pressure-sensitive adhesive layer is formed by copolymerizing 78.4% by weight of n-butyl acrylate, 19.6% by weight of 2-ethylhexyl acrylate and 2.0% by weight of acrylic acid on the metal mesh side of the electromagnetic wave shielding layer. After the melted acrylic ester copolymer was melted and stirred, 0.03 part of a near-infrared absorber (“EXEX” TX-EX-805K: trade name, manufactured by Nippon Shokubai Co., Ltd.) Dye (Mitsui Chemicals, Inc.) “PS Blue BN” (trade name) manufactured by 0.0001 parts by weight, and a mixture made by adding 0.0013 parts by weight of neon absorbing compound (TY-102: trade name by Asahi Denka Co., Ltd.) was applied. The metal mesh was coated and formed so as to flatten the unevenness of the metal mesh.

Manufacture of plasma display panel Next, the optical filter with the antireflection film obtained in the above process was attached to the front surface of the plasma display panel module to obtain three types of plasma display panels.

  The obtained plasma display panel was subjected to an impact test using the impact test apparatus shown in FIG. 3, and a steel ball 12 having a height of 9.6 cm to a diameter of 50.8 mm (mass 534 g) (JIS B1501 steel ball for ball bearings) When the thickness of the impact-resistant layer was 300 μm, the plasma display panel was not cracked at 0.5 J and cracked at 0.6 J. In the case of the impact-resistant layer having a thickness of 400 μm, the plasma display panel was not cracked at 0.6 J, but was cracked at 0.7 J. When the thickness of the impact resistant layer was 500 μm, the plasma display panel was not cracked at 0.8 J, but was cracked at 0.9 J. When the thickness of the impact resistant layer was 300 μm, 400 μm, and 500 μm, the internal haze of the impact resistant layer was 0.2, 0.5, and 0.7, respectively. The results are shown in Table 1 below.

  The antireflection performance of the optical filter with an antireflection film obtained in Example 1 was 0.5%. In addition, the plasma display panel obtained in Example 1 did not generate bubbles or peel off the filter. The near-infrared shielding performance of the optical filter with an antireflection film of Example 1 was 85% or more at a wavelength of 800 to 1200 nm, and the neon light shielding performance was 40% or less at a wavelength of 587 nm.

  To a mixture of 92 parts by weight (15.6 kg) of acrylic acid-2-ethylhexyl acrylate and 6 parts by weight (1.4 kg) of acrylic acid, 0.003 part of photoinitiator (Irgacure 369: trade name, manufactured by Ciba Geigy Co., Ltd.) Part by weight was added uniformly.

  The obtained mixture is charged into a transparent polymerization tank having a cooling pipe, a nitrogen inlet, a stirring blade, a heating jacket and a thermometer, and nitrogen gas is sealed in the container for 20 minutes, and the air in the container is replaced with nitrogen gas. After that, the temperature of the mixture was raised to 80 ° C. in a nitrogen stream, and while maintaining this temperature constant, the water-cooled high-pressure mercury lamp installed outside the apparatus was irradiated with UV light intermittently until the UV irradiation amount became 1000 mJ. Irradiation was repeated. The obtained partial polymer of the acrylic copolymer had a weight average molecular weight of 750,000 and a number average molecular weight of 230,000.

  As a photoinitiator in the above mixture, 0.3 part by weight of 2-hydroxy-2-dimethoxy-1-phenylpropan-1-one (manufactured by Ciba Geigy Co., Ltd.), a crosslinking agent (trade name: Light Acrylate 1.6HX-A , Manufactured by Kyoeisha Chemical Co., Ltd.) 0.05 parts by weight was mixed and mixed, and then defoamed (placed under reduced pressure at room temperature) to prepare a solventless coating solution. The obtained solvent-free coating solution did not contain a substantial solvent (solvent content of 1 wt% or less), and its viscosity was 150 Pa · s.

  Realic 8200 UV (trade name, manufactured by NOF Corporation, 80 μm thick triacetylcellulose film / 5 μm thick AR layer / laminated film comprising 40 μm thick protective film) was prepared as an antireflection film. The solventless coating solution obtained in the above step was applied on the antireflection film by a knife coating method so as to have a coating thickness of 300 to 500 μm. A separator made of a PET film having a thickness of 100 μm which had been peeled off was attached to the surface of the solvent-free coating solution thus coated, and the coating solution was sealed in a sandwich shape.

The resulting laminate 360 seconds from the PET separator made side by black light fluorescent lamp 3 mW / cm ^2, was then irradiated with 10 seconds of ultraviolet high-pressure mercury lamp 500mW / cm ² (UV) polymerization. Next, after peeling off the PET separator, the optical filter of Example 2 was obtained by pasting together with the support side of the electromagnetic wave shielding layer on which the dye-containing pressure-sensitive adhesive layer was separately laminated. The dye-containing pressure-sensitive adhesive layer was formed in the same manner as in Example 1. Further, in the same manner as in Example 1, a plasma display panel of Example 2 was obtained.

  The obtained plasma display panel was subjected to an impact resistance test in the same manner as in Example 1. As a result, when the thickness of the impact resistant layer was 300 μm, the plasma display panel did not crack at 0.6 J, and at 0.7 J cracked. When the thickness of the impact resistant layer was 400 μm, the plasma display panel was not cracked at 0.7 J, but was cracked at 0.8 J. When the thickness of the impact resistant layer was 500 μm, the plasma display panel was not cracked at 1.2 J, but was cracked at 1.3 J. When the thickness of the impact resistant layer was 300 μm, 400 μm, and 500 μm, the internal haze of the impact resistant layer was 0.2, 0.5, and 0.8, respectively. The results are shown in Table 1 below.

  The antireflection performance of the optical filter with an antireflection film obtained in Example 2 was 0.5%. The plasma display panel obtained in Example 2 did not generate bubbles or peel off the filter. The near-infrared shielding performance of the optical filter with an antireflection film of Example 2 was 85% or more at a wavelength of 800 to 1200 nm, and the neon light shielding performance was 40% or less at a wavelength of 587 nm.

  To a mixture of 92 parts by weight (15.6 kg) of acrylic acid-2-ethylhexyl acrylate and 8 parts by weight (1.4 kg) of acrylic acid, 0.003 part of photoinitiator (Irgacure 369: trade name, manufactured by Ciba Geigy Co., Ltd.) Part by weight was added uniformly.

  The obtained mixture is charged into a transparent polymerization tank having a cooling pipe, a nitrogen inlet, a stirring blade, a heating jacket and a thermometer, and nitrogen gas is sealed in the container for 20 minutes, and the air in the container is replaced with nitrogen gas. After that, the temperature of the mixture was raised to 80 ° C. in a nitrogen stream, and while maintaining this temperature constant, the water-cooled high-pressure mercury lamp installed outside the apparatus was irradiated with UV light intermittently until the UV irradiation amount became 1000 mJ. Irradiation was repeated. The obtained partial polymer of the acrylic copolymer had a weight average molecular weight of 750,000 and a number average molecular weight of 230,000.

  0.5 parts by weight of t-butyl peroxyneodecate (perbutyl ND: trade name, manufactured by NOF Corporation), benzoyl peroxide (NIPA BO: trade name, manufactured by NOF Corporation) 5 parts by weight and 0.005 part by weight of a crosslinking agent (Light acrylate 1.6HX-A: trade name, manufactured by Kyoeisha Chemical Co., Ltd.) are mixed and mixed, and then the mixture is put under reduced pressure at room temperature to remove bubbles. The solventless coating liquid was prepared by processing. The obtained solvent-free coating solution did not contain a substantial solvent (solvent content of 1 wt% or less), and its viscosity was 150 Pa · s.

  Realic 8200 UV (trade name, manufactured by NOF Corporation, 80 μm thick triacetylcellulose film / 5 μm thick AR layer / laminated film comprising 40 μm thick protective film) was prepared as an antireflection film. The solventless coating liquid obtained in the above step was coated on the antireflection layer by a knife coating method so as to have a coating thickness of 300 to 500 μm. A separator made of a PET film having a thickness of 100 μm which had been peeled off was attached to the surface of the coated solventless coating liquid, and the coating liquid was sealed in a sandwich shape.

  This laminate was cured at 80 ° C. for 15 minutes and subjected to thermal polymerization. Next, after separating the PET separator, the optical filter of Example 3 was obtained by pasting it together with the support side of the electromagnetic wave shielding layer on which the dye-containing pressure-sensitive adhesive layer was separately laminated. The dye-containing pressure-sensitive adhesive layer was formed in the same manner as in Example 1. Further, in the same manner as in Example 1, a plasma display panel of Example 3 was obtained.

  The obtained plasma display panel was subjected to an impact resistance test in the same manner as in Example 1. As a result, when the thickness of the impact resistant layer was 300 μm, the plasma display panel did not crack at 0.6 J, and at 0.7 J cracked. When the thickness of the impact resistant layer was 400 μm, the plasma display panel was not cracked at 0.8 J, but was cracked at 0.9 J. When the thickness of the impact-resistant layer was 500 μm, the plasma display panel was not cracked at 1.3 J, but was cracked at 1.4 J. When the thickness of the impact resistant layer was 300 μm, 400 μm, and 500 μm, the internal haze of the impact resistant layer was 0.2, 0.6, and 0.9, respectively. The results are shown in Table 1 below.

The antireflection performance of the optical filter with an antireflection film obtained in Example 3 was 0.5%. In addition, the plasma display panel obtained in Example 3 did not generate bubbles or peel off the filter. The near-infrared shielding performance of the optical filter with an antireflection film of Example 3 was 85% or more at a wavelength of 800 to 1200 nm, and the neon light shielding performance was 40% or less at a wavelength of 587 nm.
[Comparative Example 1]
Example of producing optical filter using solvent-diluted adhesive N-butyl acrylate 15.2 kg (82 mol), acrylic acid 2 kg (27 mol) on a patch having a cooling tube, nitrogen inlet, stirring blade and heating jacket 0.8 mol) and 90 kg of ethyl acetate, 100 g of 2.2-azobisisobutyronitrile was added, and the reaction system was controlled at 65 ° C. and heated for 5 hours for polymerization. Finally, the pressure-sensitive adhesive composition was obtained by adjusting the ethyl acetate content and setting the solvent ratio to about 40%. This was coated by knife coating so that the film thickness after drying was 300, 400, or 500 μm. Drying was performed at 120 ° C. for 5 minutes after coating. After drying, the optical filter of Comparative Example 1 was obtained by pasting together with the support side of the electromagnetic wave shielding layer separately laminated with the dye-containing pressure-sensitive adhesive. Further, a plasma display panel of Comparative Example 1 was obtained in the same manner as in Example 1.

  The obtained plasma display panel was subjected to an impact resistance test in the same manner as in Example 1. As a result, when the thickness of the impact resistant layer was 300 μm, the plasma display panel did not crack at 0.6 J, and at 0.7 J cracked. When the thickness of the impact-resistant layer was 400 μm, the plasma display panel was not cracked at 0.9 J, and cracked at 1.0 J. When the thickness of the impact resistant layer was 500 μm, the plasma display panel was not cracked at 1.4 J, but was cracked at 1.5 J. When the thickness of the impact resistant layer was 300 μm, 400 μm, and 500 μm, the internal haze of the impact resistant layer was 0.6, 1.1, and 3.1, respectively. The results are shown in Table 1 below.

  In Table 1, OO indicates that the PDP panel is not cracked twice in the two impact resistance tests, and ●● indicates that the PDP panel is cracked twice in the two impact resistance tests. Show. In the presence / absence of bubbles, ○ indicates that no bubbles were visually observed, and × indicates that bubbles were visually observed in some places.

  The optical filter of the present invention can impart impact resistance to the plasma display panel when pasted on the front surface of the plasma display, and can simplify the layer structure of the optical filter.

It is a figure which shows an example of the laminated structure at the time of arrange | positioning the optical filter which provided the impact-resistant layer which has the adhesiveness of this invention in the front surface of a plasma display panel module. It is a figure which shows an example of another laminated structure at the time of arrange | positioning the optical filter which provided the impact-resistant layer which has the adhesiveness of this invention in the front surface of a plasma display panel module. It is a figure which shows an example of the laminated structure at the time of sticking the optical filter which provided the pigment | dye containing impact-resistant layer which provided the adhesiveness of this invention on the front surface of a plasma display. It is a figure which shows an example of another laminated structure at the time of sticking the optical filter which provided the pigment | dye containing impact-resistant layer which provided the adhesiveness of this invention to the front surface of a plasma display. It is a figure which shows an impact test apparatus. It is a figure which shows one example of the coextrusion laminating machine for forming the preferable impact-resistant layer in the optical filter of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection layer 3 Adhesive impact resistant layer 31 Dye containing adhesive impact resistant layer 4 Dye containing adhesive impact layer 4 Dye containing adhesive layer 5 Electromagnetic wave shielding layer 6 Adhesive layer 7 Plasma display panel module 8 Test stand 9 Base 10 Glass plate 11 Front glass plate 12 Steel ball 35 First film supply unit 37 Cooling roll 38 Nip roll 39 Second film supply unit 41 Paper discharge unit 42 Dice

Claims (11)

(1) An optical filter for being directly attached to a display surface of a plasma display panel module,
(2) The optical filter is composed of 90 to 10 parts by weight of a (meth) acrylic monomer and 10 to 90 parts by weight of a (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. Laminating a viscous fluid containing 0.1 to 20 parts by weight of a crosslinking agent with respect to 100 parts by weight of the acrylic mixture, and having an impact-resistant layer containing an adhesive that has been polymerized and crosslinked by irradiation with ionizing radiation,
(3) The impact resistant layer has an internal haze of 0.1 to 3.0 and a thickness of 0.2 mm to 1.0 mm. (4) Plasma when the optical filter is attached to a plasma display panel module. An optical filter having a breaking energy of 0.5 J or more by an impact test on a display panel. (1) An optical filter for being directly attached to a display surface of a plasma display panel module,
(2) The optical filter is composed of 90 to 10 parts by weight of a (meth) acrylic monomer and 10 to 90 parts by weight of a (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. A viscous fluid containing 0.0001 to 1.0 part by weight of a photoradical polymerization initiator and 0.1 to 20 parts by weight of a crosslinking agent is laminated on 100 parts by weight of an acrylic mixture, and polymerized and crosslinked by ultraviolet irradiation. Having an impact-resistant layer containing a tacky adhesive,
(3) The impact resistant layer has an internal haze of 0.1 to 3.0 and a thickness of 0.2 mm to 1.0 mm. (4) Plasma when the optical filter is attached to a plasma display panel module. An optical filter having a breaking energy of 0.5 J or more by an impact test on a display panel. (1) An optical filter for being directly attached to a display surface of a plasma display panel module,
(2) The optical filter is composed of 90 to 10 parts by weight of a (meth) acrylic monomer and 10 to 90 parts by weight of a (meth) acrylic polymer having a weight average molecular weight of 1,000 to 1,000,000. An adhesive obtained by laminating a viscous fluid containing 0.1 to 5 parts by weight of a thermal radical polymerization initiator and 0.1 to 20 parts by weight of a crosslinking agent with respect to 100 parts by weight of an acrylic mixture, and polymerizing and crosslinking by heating. Having an impact-resistant layer containing an agent,
(3) The impact resistant layer has an internal haze of 0.1 to 3.0 and a thickness of 0.2 mm to 1.0 mm. (4) Plasma when the optical filter is attached to a plasma display panel module. An optical filter having a breaking energy of 0.5 J or more by an impact test on a display panel.   The optical filter according to any one of claims 1 to 3, comprising a resin layer containing a near-infrared absorbing compound and having a transmittance in the wavelength range of 800 to 1000 nm of 20% or less.   The optical filter according to any one of claims 1 to 4, wherein the impact-resistant layer contains a near-infrared absorbing compound and has a transmittance in the wavelength range of 800 to 1000 nm of 20% or less.   5. The resin layer comprising a neon light absorbing compound having a maximum absorption wavelength in a wavelength range of neon light of 560 to 630 nm, wherein the transmittance of the maximum absorption wavelength in the wavelength range is 40% or less. 1. An optical filter according to item 1.   7. The impact-resistant layer contains a neon light absorbing compound having a maximum absorption wavelength in a wavelength range of neon light of 560 to 630 nm, and the transmittance of the maximum absorption wavelength in the wavelength range is 40% or less. The optical filter of any one of Claims.   The optical filter according to any one of claims 1 to 7, wherein transmittance in a wavelength range of visible light of 380 to 780 nm is 40% or more.   The optical filter according to claim 1, further comprising an electromagnetic wave shielding layer that shields static electricity and / or electromagnetic noise generated from the plasma display device.   The optical filter according to any one of claims 1 to 9, further comprising an adhesive layer for adhering to the plasma display panel module.   A plasma display panel comprising the optical filter according to claim 1 attached to a display surface through an adhesive layer.