WO2006070717A1 - Wavelength-selective absorption optical filter - Google Patents

Abstract

This invention provides a wavelength-selective absorption optical filter that exhibits high level and broad absorption in a near infrared region, further absorbs neon light, and exhibits high light transmittance in other visible light region. The wavelength-selective absorption optical filter is less likely to cause a change in optical properties with the elapse of time and is highly durable. The wavelength-selective absorption optical filter comprises a transparent base material and a wavelength-selective absorption layer having a single or multilayer structure stacked on the base material. The wavelength-selective absorption layer comprises a resin, an near infrared absorptive coloring matter (A) and a coloring matter (B), and the wavelength-selective absorption optical filter has maximum absorption at a wavelength of 800 to 1200 nm and a wavelength of 550 to 620 nm. The wavelength-selective absorption optical filter is characterized in that one type of the near infrared absorptive coloring matter (A) is an aromatic diimmonium coloring matter (a) of which the counter ion is bis(trifluoromethansulfonyl)imidic acid, and one type of the coloring matter (B) is a porphyrin coloring matter or azaporphyrin coloring matter (b).

Description

 Specification

 Wavelength selective absorption filter

 Technical field

 The present invention relates to an optical filter that absorbs near-infrared light and neon light. Specifically, the present invention has a wide and large absorption in the near-infrared region, further absorbs neon light, and in other visible light regions. The present invention relates to a wavelength selective absorption filter that has high light transmittance and has excellent durability with little change in optical characteristics over time even when stored at high temperature and high humidity.

 Background art

 [0002] An optical filter having near-infrared absorption ability has a property of blocking near-infrared light and allowing visible light to pass therethrough, and is used in various applications.

[0003] In recent years, the power of plasma displays attracting attention as thin large-screen displays. Near-infrared rays emitted from plasma displays have a problem that electronic devices using near-infrared remote controllers may malfunction, and are in front of plasma displays. A near-infrared absorption filter is provided.

[0004] As a near-infrared absorption filter, (1) a filter containing metal ions such as copper and iron on phosphoric acid glass, and (2) a layer having a different refractive index is laminated to interfere with transmitted light. Interference filters that transmit specific wavelengths, (3) acrylic resin filters that contain copper ions in the copolymer, and (4) filters in which a layer in which an infrared absorbing dye is dispersed or dissolved in a resin are laminated. ing.

Among these, the filter (4) has good processability and productivity, and has a relatively large degree of freedom in optical design, so various methods for producing the filter have been proposed (for example,

Patent Document:! ~ 9).

 Patent Document 1: Japanese Patent Laid-Open No. 2002-82219

 Patent Document 2: Japanese Patent Laid-Open No. 2002-214427

 Patent Document 3: Japanese Patent Laid-Open No. 2002-303720

 Patent Document 4: Japanese Patent Laid-Open No. 2002-333517

Patent Document 5: Japanese Unexamined Patent Publication No. 2003-82302 Patent Document 6: Japanese Unexamined Patent Publication No. 2003-96040

 Patent Document 7: JP-A-11 305033

 Patent Document 8: Japanese Patent Laid-Open No. 11 326629

 Patent Document 9: Japanese Patent Application Laid-Open No. 11-326631

 Patent Document 10: Japanese Unexamined Patent Publication No. 2000-227515

 Patent Document 11: Japanese Patent Laid-Open No. 2002-264278

 Patent Document 12: International Publication No. 97/38855 Pamphlet

 Patent Document 13: Japanese Unexamined Patent Publication No. 2003-114323

 Patent Document 14: Japanese Unexamined Patent Application Publication No. 2002-138203

 Disclosure of the invention

 Problems to be solved by the invention

[0006] Some of these methods have the ability to sufficiently block the near-infrared rays emitted from the plasma display, but the optical characteristics are stable over time when used for a long time under high temperature and high humidity. Was insufficient.

[0007] As a method for suppressing the temporal stability of optical properties when used for a long time under high temperature and high humidity, the glass transition temperature of the resin constituting the near infrared absorption layer is determined by the device using a near infrared absorption filter. A method of setting the temperature to be above the guaranteed use temperature (for example, see Patent Documents 7 to 10)

In addition, methods for reducing the amount of residual solvent in the near-infrared absorbing layer (see, for example, Patent Documents 10 and 11) have been proposed.

 [0008] In addition, it is known that aromatic diimonium compound dyes used as near-infrared absorbing dyes are generally vulnerable to heat (see, for example, page 17 of Patent Document 12).

 [0009] Therefore, as a technique for suppressing the deterioration of the pigment due to heat in the near-infrared absorbing layer containing the diimonium compound, the diimonium compound is purified and the endothermic peak is measured at a temperature of 220 ° C or higher in the DSC measurement. A method for containing a specific diimonium compound having a melting point in the near-infrared absorbing layer (for example, see Patent Document 13), a method for incorporating a diimonium compound having a melting point of 190 ° C or higher in the near-infrared shielding layer (for example, patents) (See Reference 14).

[0010] Furthermore, the plasma display also emits neon orange light (wavelength near 600 nm). Therefore, there is a problem that the vivid color rendering property and the clearness of the image of the display are impaired only by maintaining the temporal stability of the near infrared absorbing layer.

 An object of the present invention is to provide a selective absorption optical filter having a wide absorption in the near-infrared region and also absorbing neon light, while having a high light transmittance in other visible light regions. It is an object of the present invention to provide a wavelength selective absorption filter having excellent durability with little change in characteristics over time.

 Means for solving the problem

 [0012] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have finally completed the present invention. That is, the present invention is as follows.

[0013] The first invention is obtained by laminating a single-layer or multiple-layer wavelength selective absorption layer containing a resin, a near-infrared absorbing dye (A), and a dye (B) on a transparent substrate, and A wavelength selective absorption filter having a maximum absorption at a wavelength of 800 to 1200 ηm and a wavelength of 550 to 620 nm, wherein one of the near infrared absorbing dyes (A) has bis (trifluoromethanesulfonyl) imidic acid as a counter ion An aromatic diimonium dye (a),

 One of the dyes (B) is a porphyrin dye or azaporphyrin dye (b).

[0014] In the second invention, the multilayer wavelength selective absorption layer includes a near-infrared absorption layer containing a resin and a near-infrared absorption dye (A), and a neon cut layer containing a resin and a dye (B). The wavelength selective absorption filter according to the first aspect, wherein the wavelength selective absorption filter is formed on a transparent substrate in order.

 [0015] In a third aspect of the present invention, the wavelength-selective absorption layer has a porphyrin dye or azaporphyrin dye (b) of 5 to 100 parts by mass with respect to 100 parts by mass of the aromatic diimmonium dye (a). The wavelength selective absorption filter according to the first aspect of the invention is characterized by comprising a mass ratio).

 [0016] A fourth invention is the wavelength selective absorption filter according to the first invention, wherein the resin constituting the wavelength selective absorption layer is an acrylic resin.

[0017] According to a fifth aspect of the invention, a single wavelength selective absorption layer comprises an organic solvent, a resin, an aromatic diimonium dye (a), a porphyrin dye or an azaporphyrin color on the transparent substrate. The wavelength selective absorption filter according to the first invention, wherein the coating liquid A containing element (b) is formed by coating and drying.

 [0018] In a sixth aspect of the present invention, a multi-layer wavelength selective absorption layer is formed by coating a coating liquid B containing an organic solvent, a resin, and an aromatic diimonium dye (a) on the transparent substrate. Coating a coating solution C containing an organic solvent and a resin and a porphyrin-based dye or azaporphyrin-based dye (b) immediately above the near-infrared absorbing layer formed by drying; The wavelength selective absorption filter according to the first aspect of the invention, comprising a neon cut layer formed by drying.

 [0019] A seventh invention is the wavelength selective absorption filter according to the fifth or sixth invention, characterized in that the coating liquid A or B force, and further HLB contains a surfactant of 2 to 12:

 [0020] An eighth invention is the wavelength selective absorption filter according to the seventh invention, wherein the surfactant is a silicone-based surfactant or a fluorine-based surfactant.

 The invention's effect

 [0021] When the wavelength selective absorption filter according to the present invention is installed on the front surface of the plasma display, it absorbs unnecessary near-infrared rays emitted from the display in the same manner as the conventional wavelength selective absorption filter, thereby causing malfunction of precision equipment. Absorbing unnecessary neon light that can only be prevented, it is possible to reduce the time-dependent change in image quality of a plasma display with high image clarity and little change due to temperature and humidity. .

 BEST MODE FOR CARRYING OUT THE INVENTION

 [0022] The wavelength selective absorption filter of the present invention is a resin, a near infrared absorbing dye on a transparent substrate.

 A wavelength selective absorption filter comprising a single layer or multiple layers of a wavelength selective absorption layer containing (A) and a dye (B), and having a maximum absorption at wavelengths of 800 to 1200 nm and wavelengths of 550 to 620 nm. One of the near infrared absorbing dyes (A) is an aromatic diimonium dye (a) having bis (trifluoromethanesulfonyl) imidic acid as a counter ion, and one of the dyes (B) is a porphyrin dye or It is characterized by being an azaporphyrin pigment (b).

 [0023] Hereinafter, the present invention will be described in detail.

(Transparent substrate) In the present invention, the transparent substrate is not particularly limited, but preferably has a total light transmittance of 80% or more and a haze of 5% or less. If the substrate is inferior in transparency, the sharpness of the image will be poor simply by reducing the brightness of the display.

[0024] Examples of such transparent base materials include polyester-based, acrylic-based, cellulose-based, polyethylene-based, polypropylene-based, polyolefin-based, polychlorinated bur-based, polycarbonate, phenol-based, and urethane-based plastic films. Or, a sheet, glass, and a laminate of any two or more of these may be mentioned. A polyester film having a good balance between heat resistance and flexibility is preferable, and a polyethylene terephthalate film is more preferable.

 [0025] A polyester film suitable as a transparent substrate for use in the present invention includes a dicarboxylic acid component as an aromatic dicanolevonic acid such as terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid or an ester thereof, and a glycol component as an ethylene. Polyester chips obtained by conducting esterification or transesterification using glycol, diethylene glycolol, 1,4 butanediol, neopentyl glycol, etc., and then polycondensation are dried and melted in an extruder. A finolem produced by stretching an unstretched sheet obtained by extruding into a sheet form from a T-die in at least a uniaxial direction, followed by heat setting treatment and relaxation treatment.

[0026] The film is particularly preferably a biaxially stretched film from the viewpoint of strength and the like. Examples of the stretching method include a tubular stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, and the like, but a sequential biaxial stretching method is preferable in view of flatness, dimensional stability, thickness unevenness, and the like. Sequential biaxially stretched finalem is, for example, in the longitudinal direction at a glass transition temperature (Tg) or higher (Tg + 30 ° C or lower) of the polyester in the longitudinal direction at a magnification of 2.0 to 5.0 times. And roll-drawn. Continue to preheat with a tenter, then stretch in the width direction at a temperature of 120 ° C or higher and 150 ° C or lower by a factor of 1.2 to 5.0 times. Further, this biaxially stretched film is heat-set at a temperature of 220 ° C. or higher (melting point—10 ° C. or lower). Next, by relaxing 3% to 8% in the width direction, a polyester film suitable as a transparent substrate used in the present invention can be produced. Further, in order to further improve the dimensional stability in the longitudinal direction of the film, a longitudinal relaxation treatment may be used in combination. [0027] In order to provide the film with handling properties (for example, creaseability after lamination), it is preferable to include particles to form protrusions on the film surface. The particles to be included in the film include inorganic particles such as silica, kaolinite, talc, calcium carbonate, zeolite, alumina, etc., heat resistant polymers such as acrylic, PMMA, nylon, polystyrene, polyester, benzoguanamine formalin condensate, etc. Particles. From the viewpoint of transparency, it is preferable that the content of particles in the film is small. For example, it is preferably 1 ppm or more and lOOO ppm or less. Furthermore, it is preferable to select particles having a refractive index close to that of the resin used from the viewpoint of transparency. Further, the film may contain a light resistance agent (ultraviolet ray preventing agent), a coloring matter, an antistatic agent and the like in order to impart various functions as necessary.

 [0028] The transparent substrate used in the present invention may be a single layer film or a composite film of two or more layers in which a surface layer and a center layer are laminated. In the case of a composite film, there is an advantage that the functions of the surface layer and the center layer can be designed independently. For example, by adding particles only to a thin surface layer and forming irregularities on the surface, maintaining the handleability while maintaining the handle thickness, the center layer does not substantially contain particles, so that The transparency of the film as a whole can be further improved. The method for producing the composite film is not particularly limited. However, in consideration of productivity, the raw materials for the surface layer and the central layer are extruded from different extruders, led to one die, and an unstretched sheet is obtained. It is particularly preferable to produce it by the so-called coextrusion method, which is oriented in at least one axial direction.

 [0029] The thickness of the transparent substrate varies depending on the material. When a polyester film is used, 35 µm or more is preferred, and more preferably 50 µm or more. On the other hand, the thickness is preferably 260 μm or less, more preferably 200 / m or less. If the thickness is small, not only the filming and ringing properties are deteriorated, but also when the film is heated during drying to reduce the amount of residual solvent in the wavelength selective absorption layer, the film becomes heat-sheared and flat. Is likely to be bad. On the other hand, when the thickness is thick, there is a problem in terms of cost, and when it is stored in the form of a roll, the flatness is liable to occur due to rolling.

 [0030] (Middle layer)

The wavelength selective absorption filter of the present invention has a structure in which a single layer or multiple layers of a wavelength selective absorption layer is laminated on a transparent substrate, but the adhesion between the transparent substrate and the wavelength selective absorption layer is An intermediate layer may be provided for the purpose of improving the transparency of the transparent substrate. When particles are not contained in the film, a high degree of transparency can be obtained while maintaining handling properties by simultaneously providing an intermediate layer containing particles during film production.

 [0031] Examples of the resin constituting the intermediate layer include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, and the like. For example, if the resin constituting the substrate and the wavelength selective absorption layer is an ester, it is possible to select a polyester or polyester urethane having a similar structure. preferable.

 [0032] The intermediate layer may contain a crosslinking agent to form a bridge structure for the purpose of improving adhesion and water resistance. Examples of the crosslinking agent include urea, epoxy, melamine, and isocyanate. In particular, the effect of the crosslinking agent is remarkable when the resin undergoes whitening or strength reduction under high temperature and high humidity. Instead of using a crosslinking agent, a graft copolymer resin having self-crosslinking property may be used as the resin.

 [0033] The intermediate layer may contain various kinds of particles for the purpose of forming irregularities on the surface and improving slipperiness. Examples of the particles to be included in the intermediate layer include silica, kaolinite, talc, calcium carbonate, zeolite, alumina, and other inorganic particles, acrylic, PMMA, nylon, styrene, polyester, benzoguanamine 'formalin condensate, etc. Organic particles. It is preferable to select particles having a refractive index close to that of the resin used for the point of transparency.

 [0034] Further, in order to impart various functions to the intermediate layer, a surfactant, an antistatic agent, a dye, an ultraviolet absorber, and the like may be contained.

[0035] The intermediate layer may be a single layer if it has the desired function, but may be laminated in two or more layers as required.

[0036] The thickness of the intermediate layer is not particularly limited as long as it has a desired function.

 It is preferably from 01 μm to 5 μm. When the thickness is small, the function as an intermediate layer is hardly exhibited, and conversely, when it is thick, transparency tends to be poor.

[0037] The intermediate layer is preferably provided by a coating method. Coating methods include gravure coating, kiss coating, dip coating, spray coating, curtain coating, air knife Use known coating methods such as the coating method, blade coating method, reverse roll coating method, inline coating method in which a coating layer is provided in the film manufacturing process, and offline coating method in which a coating layer is provided after film production. Can do. Among these methods, the in-line coating method is excellent in terms of cost. By adding particles to the coating layer, which eliminates the need to include particles in the transparent substrate, the transparency is highly improved. This is preferable.

 [0038] (Wavelength selective absorption layer)

 In the wavelength selective absorption filter of the present invention, a wavelength selective absorption layer composed of a single layer or multiple layers including a dye having near infrared absorption ability is laminated on a transparent substrate directly or via an intermediate layer.

 [0039] The near-infrared absorbing dye is a dye having a maximum absorption in the near-infrared region having a wavelength of 800 nm or more and 1200 nm or less, and is a diimonium-based, phthalocyanine-based, dithiol metal complex-based, naphthalocyanine-based, azo-based, polymethine-based , Anthraquinone, naphthoquinone, pyrylium, thiopyrylium, squarylium, croconium, tetradehydrocholine, triphenylmethane, cyanine, azo, and amidium compounds. These compounds are used alone or in combination of two or more. In the present invention, the absorption in the near infrared region is large, the absorption region is wide, and the transmittance in the visible light region is also high. It is necessary to include a dimonium salt compound represented by

 [0040] [Chemical 1]

[0041] R ^{1 in} the general formula (I) ~! Specific examples of Γ include (1) methyl group, ethyl group, n-pro Pinole group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-amyl group, n-hexyl group, n-octyl group, 2-hydroxyethyl group, 2-cyanoethyl group Alkyl groups such as 3-hydroxypropyl group, 3-cyanopropyl group, methoxyethyl group, ethoxyethyl group, butoxycetyl group, (2) phenyl group, fluorophenyl group, chlorophenyl group, tolyl group, jetylaminophenyl, naphthyl group ( ₃ ) alkenyl groups such as butyl group, probel group, butyl group, pentenyl group, (4) benzyl group, p-fluorophenyl group, p-chlorophenyl group, phenylpropyl group, And an aralkyl group such as a naphthylethyl group.

[0042] Further, as the R ⁹ to R ^12, hydrogen, fluorine, chlorine, bromine, Jechinoreamino group, dimethylaminopyridine amino group, Shiano group, a nitro group, Mechinore group, Echiru group, a propyl group, triflate Ruo Russia methyl, methemoglobin Examples thereof include a xy group, an ethoxy group, and a propoxy group.

 [0043] In the formula (I), X- is a fluorine ion, a chlorine ion, a bromine ion, an iodine ion, a perchlorate ion, a hexafluoroantimonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, Examples thereof include bis (trifluoromethanesulfonyl) imido ion. In the present invention, since an azaporphyrin-based dye or the like is used as a neon cut dye (described later), it is necessary to include a near-infrared ray absorbing dye in which the above X- is a bis (trifluoromethanesulfonyl) imido ion. is there. This compound is commercially available, and examples thereof include CIR-1085, CIR-RL, and Nippon Kayaku IRG-068 manufactured by Nippon Carlit.

 [0044] The wavelength selective absorption filter of the present invention is not limited to the dimonium salt-based compound represented by the above formula (I), but for the purpose of expanding and adjusting the absorption region in the near infrared region. Near-infrared absorbing dyes can also be covered. Preferable ones that do not promote the deterioration of diimonium salt dyes include phthalocyanine, cyanine dyes, and dithiol metal complex systems having an absorption peak at 800 nm or more and 1200 nm or less.

[0045] In the present invention, in order to control the absorption in the near infrared region and the transmittance in the visible region of interest, the amount of the near infrared absorbing dye is arbitrary in the thickness direction of the wavelength selective absorption layer. It is preferably adjusted so that it is 0.01 g / m ² or more and 1. Og / m ² or less. When the amount of near-infrared absorbing dye is small, the absorption ability in the near-infrared region is insufficient, and conversely, when it is large, the transparency in the visible light region is insufficient and the brightness of the display decreases. There is a title.

 In the present invention, it is necessary to include a neon cut dye in the wavelength selective absorption layer. The plasma display emits so-called neon orange light centered around 600 nm, and there is a drawback that a bright red color cannot be obtained because the orange color is mixed with the red color. The above problem can be solved by including a neon strength dye.

 [0047] In the present invention, the neon cut dye is a dye having maximum absorption in a wavelength range of 550 nm or more and 620 nm or less, and specifically includes cyanine-based, squarylium-based, azomethine-based, xanthene-based, oxonol-based, azolone-based, , Phthalocyanine, quinone, azurenium, pyrylium, croconium, dithiol metal complex, pyromethene, azaponolephirin, and the like. These dyes can be used alone or in admixture of two or more. In the present invention, it is necessary to use a porphyrin dye or azaporphyrin dye.

[0048] Porphyrin dyes or azaporphyrin dyes are dyes represented by the following formulas (II) and (III). Specific examples of formula (II) and (III) in the R "to R ^M and R ¹⁵ to R ²² is hydrogen atom, a halogen atom, a nitro group, Shiano group, hydroxy group, an amino group, a carboxyl group, sul Phosphonic acid group, alkyl group having 1 to 20 carbon atoms, halogenoalkyl group, alkoxy group, alkoxyalkoxy group, aryloxy group, monoanolalkylamino group, dialkylamino group, aralkyl group, arylyl group, heteroaryl group, alkylthio group Or each of them may independently form a ring other than an aromatic ring via a linking group, M is two hydrogen atoms, a divalent metal atom, 3 Examples thereof include a monovalent metal atom, a tetravalent disubstituted metal atom, and an oxymetal atom.

[0049] [Chemical 2]

 [0051] This compound is commercially available. For example, TAP_2, TAP_5, TAP_9, TAP_10, TAP_12 manufactured by Yamada Chemical Industry, PD_319 manufactured by Mitsui Chemicals, and PD-311 strength S are listed. It is done.

[0052] The neon-cut dye content is such that the obtained wavelength selective absorption filter has sharp absorption in the wavelength region of 550 nm to 62 Onm and the transmittance power at the maximum absorption wavelength is ¾0% or less. It is preferable to adjust so that it becomes. Specifically, the Neon cut pigment is preferably present on the transparent substrate in a range of 0.001 g / m ² or more and 0.1 lg / m ² or less. In the present invention, the wavelength selective absorption layer is composed of a single layer or multiple layers. For the wavelength selective absorption layer, two types of dyes are used: an aromatic diimonium dye (a) having bis (trifluoromethanesulfonyl) imidic acid as a counter ion, and a porphyrin dye or azaporphyrin dye (b). It is preferable to have a single layer structure mixed in the same coating layer.

 [0054] In the present invention, an aromatic diimonium dye having bis (trifluoromethanesulfonyl) imidic acid as a counter ion as a near-infrared absorbing dye and a porphyrin dye as a neon cut dye in a single wavelength selective absorption layer Or, it is essential to use azaporphyrin-based dyes. By mixing these two kinds of dyes in the same coating layer, the effect of improving the durability of the wavelength selective absorption layer can be obtained. Because. Although the mechanism by which durability is improved is not clear, bis (trifluoromethanesulfonyl) imidic acid, which is a counter ion of diimonium dye, and azaporphyrin dye (or porphyrin dye) have some interaction, It is presumed that pigment deterioration due to humidity and temperature is suppressed.

 [0055] Further, in the present invention, as the wavelength selective absorption layer, a near-infrared absorption layer containing a resin and a near-infrared absorption dye (A) and a neon cut layer containing a resin and a dye (B) are transparent in this order. A wavelength selective absorption layer having a multilayer structure formed on a substrate can be used. A layer containing an aromatic diimonium dye (a) and a porphyrin dye or azaporphyrin dye (b) each containing bis (trifluoromethanesulfonyl) imidic acid as a counter ion was laminated as a wavelength selective absorption layer. Even with the multi-layer structure, the durability improvement effect can be obtained in the same manner as the single wavelength selective absorption layer. The reason for this is not clear, but the interaction between the dye (a) and the dye (b) works at the interface between the near-infrared absorbing layer and the neon cut layer. The same effect is obtained as when the pigment (a) and the pigment (b) are present in the layer.

[0056] The azaporphyrin-based dye (or porphyrin-based dye) is preferably contained in an amount of 5 parts by mass or more, more preferably 10 parts by mass or more based on 100 parts by mass of the diimonium dye. The upper limit is preferably 100 parts by mass, more preferably 50 parts by mass or less. If the ratio of the azaporphyrin dye to the aromatic diimmonium dye is not within the preferred range, the above-mentioned interaction does not work and it may be difficult to improve durability. is there.

 [0057] In the present invention, the near-infrared absorbing dye or the neon cut dye is laminated on the transparent substrate by a coating method in a state of being dispersed or dissolved in the resin. The resin is not particularly limited as long as it can dissolve or disperse the near-infrared absorbing dye or neon cut dye uniformly, but polyester-based, acrylic-based, polyamide-based, polyurethane-based, polyolefin-based, and polycarbonate-based resins are suitable. Can be used. In particular, acrylic resins that excel in transparency, heat resistance, and solvent resistance when mixing colors are preferred, especially when diimonium dyes having bis (trifluoromethanesulfonyl) imidic acid as a counter ion are used. Is preferably an acrylic resin from the viewpoint of adhesion to the substrate and affinity for the pigment.

 [0058] The glass transition temperature of the resin is preferably equal to or higher than the guaranteed use temperature of the device in which the wavelength selective absorption filter is used. If the glass transition temperature of the resin is equal to or lower than the operating temperature of the equipment using the wavelength selective absorption filter, the dyes dispersed in the resin are likely to react with each other and the resin absorbs moisture in the outside air. Deterioration of dyes and resins increases. In the present invention, the glass transition temperature of the resin is not particularly limited as long as it is equal to or higher than the operating temperature of the equipment in which the wavelength selective absorption filter is used, but it is particularly 85 ° C or higher and 160 ° C or lower. preferable.

 [0059] When the glass transition temperature of the above resin is less than 85 ° C, the interaction between the dye and the resin, the interaction between the dyes, and the like occur, and the modification of the dye occurs. If the glass transition temperature exceeds 160 ° C, the resin must be dissolved in a solvent and heated to a sufficient temperature when applied on a transparent substrate, and the substrate must be heated. Poor planarity due to wrinkles, and further deterioration of the pigment occurs. In addition, when drying at a low temperature, since drying takes a long time, the productivity is deteriorated and the productivity is deteriorated. In addition, there is a possibility that sufficient drying cannot be performed, and when a large amount of solvent remains in the coating film, the above-mentioned glass transition temperature is lower than the operating temperature of the equipment in which the wavelength selective absorption filter is used. Similarly, it causes modification of diimine salt dyes that are less durable.

[0060] When a wavelength selective absorption layer having a multilayer structure is used, the resin used for the neon cut layer is different from a diimonium salt dye, and is a porphyrin dye or azaporphyrin. Since the dye (b) itself is excellent in durability, the influence of the glass transition temperature of the resin and the drying conditions is small. However, when a highly polar resin such as ammine is used as the resin for the neon cut layer, the diimonium salt dye at the interface between the neon cut layer and the near infrared absorbing layer containing the diimmon salt dye. May worsen the durability of

[0061] As the resin used for the neon cut layer not containing a diimonium salt dye, a polyester-based, acrylic-based, polyamide-based, polyurethane-based, polyolefin-based, or polycarbonate-based resin can be suitably used. Among these resins, acrylic resins that are excellent in transparency and heat resistance when mixed with a dye are preferable. In addition, an adhesive may be used as a resin when it is bonded to an antireflection film, glass, or an electromagnetic wave prevention film.

 [0062] Examples of the adhesive include known acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl petital adhesives (PVB), ethylene vinyl acetate adhesives (EVA), polyvinyl ethers, Examples include regular polyester and melamine resin. Among these pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferable from the viewpoint of transparency.

 [0063] The acrylic pressure-sensitive adhesive is made of, for example, a resin mainly composed of acrylic acid ester or methacrylic acid ester. The pressure-sensitive adhesive, if necessary, may be used as a curing agent, for example, by mixing one or more metal chelate-based, isocyanate-based, and epoxy-based crosslinking agents together with the above-mentioned adhesive resin. it can.

 [0064] The amount of the near-infrared absorbing dye in the wavelength selective absorption layer is preferably 1% by mass or more and 10% by mass or less based on the resin. When the amount of near-infrared absorbing dye in the resin is small, it is necessary to increase the coating amount of the wavelength-selective absorbing layer in order to achieve the target near-infrared absorbing ability. It takes a high temperature and / or a long period of time to cause deterioration of the pigment and poor flatness of the substrate. Conversely, when the amount of near-infrared absorbing dye in the resin is large, the interaction between the dyes becomes strong, and even if the residual solvent is reduced, the dye is likely to be denatured over time.

[0065] In the present invention, the wavelength selective absorption layer having a single layer structure includes an organic solvent, a resin, an aromatic diimonium dye (a), a porphyrin dye, or an azaporphyrin dye. The coating liquid A containing (b) is formed by coating and drying on a transparent substrate. In addition, the wavelength selective absorption layer having a multilayer structure is formed by coating and drying a coating liquid B containing an organic solvent, a resin, and an aromatic diimonium pigment (a) on a transparent substrate. The near-infrared absorbing layer formed above, and a coating liquid C containing an organic solvent and a resin and a porphyrin-based dye or azaporphyrin-based dye (b) are applied and dried immediately above the near-infrared absorbing layer. A neon cut layer.

 [0066] At this time, it is preferable that a surfactant is contained in the coating liquid A or B. The coating liquid C can also contain a surfactant, but when a pressure-sensitive adhesive is used as the resin, the surfactant need not be contained.

 [0067] By adding a surfactant to the coating solution used for forming the wavelength selective absorption layer, the coating appearance of the wavelength selective absorption layer, in particular, dents from adhesion of foreign matter, etc. due to minute bubbles, and drying. The repellency in the process is improved. Furthermore, the surfactant in the wavelength selective absorption layer (coating layer) bleeds to the surface by heat treatment during drying of the coating layer. As a result, slipperiness can be imparted to the surface of the coating layer. In addition, the handling property is improved and it is easy to scrape into a roll shape even if the wavelength-selective absorbing layer and / or the opposite surface contains particles that cause deterioration of transparency and do not form surface irregularities. .

 In the present invention, it is important that the HLB of the surfactant is 2 or more and 12 or less. The lower limit of HLB is preferably 3, particularly preferably 4. On the other hand, the upper limit value of HLB is preferably 11, particularly preferably 10. When the HLB is low, the leveling property is insufficient due to insufficient surface activity. On the other hand, when the HLB is high, the wavelength selective absorption layer not only lacks slipperiness but also easily absorbs moisture, and the time stability of the diimonium dye becomes poor.

 [0069] HLB is a value that WC Griffin of Atlas Powder, Inc. in the US named Hydorophil Lyophile Balance and indexed the balance between hydrophilic group and lipophilic group contained in the surfactant molecule as a characteristic value. The lower the value, the higher the lipophilicity, and the higher the value, the higher the hydrophilicity.

[0070] It is important that the content of the surfactant is not less than 0.01% by mass and not more than 2% by mass with respect to the resin constituting the wavelength selective absorption layer. If the surfactant content is low In addition, the effect of improving the coating appearance and imparting slipperiness is insufficient. Conversely, when the amount is large, the wavelength-selective absorption layer easily absorbs moisture, and the deterioration of the pigment is promoted.

 [0071] As the surfactant, known cationic, anionic, and nonionic surfactants can be suitably used, but nonionic surfactants having no polar group are preferred because of problems such as deterioration with near-infrared absorbing dyes. More preferably, a silicone-based or fluorine-based surfactant having excellent surface activity is preferable.

 [0072] Examples of silicone surfactants include dimethyl silicone, aminosilane, acrylic silane, benzylbenzyl silane, benzylbenzaminosilane, glycidyl silane, mercaptosilane, dimethyl silane, polydimethylsiloxane, polyalkoxysiloxane, and hydrogen-modified. Siloxane, butyl modified siloxane, hydroxy modified siloxane, amino modified siloxane, carboxyl modified siloxane, halogenated modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, mercapto modified siloxane, fluorine modified siloxane, alkyl group modified siloxane, phenyl modified siloxane And alkylene oxide-modified siloxane.

 [0073] Fluorosurfactants include: tetrafluoroethylene, perfluoroalkyl ammonium salt, perfluoroalkyl sulfonic acid amide, perfluoroalkyl sulfonic acid sodium, perfluoroalkyl. Potassium salt, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, monofluoroalkyltrimethylammonium salt, perfluoroalkylamino Sulfonates, perfluoroalkyl phosphates, perfluoroalkylalkyl compounds

Perfluoroalkylalkylbetaines, perfluoroalkyl halides, and the like.

 [0074] In the present invention, the wavelength selective absorption layer is laminated by applying and drying a coating liquid containing a resin, a near-infrared absorbing dye, and a surfactant on a transparent substrate. From the viewpoint of coatability, it is necessary to dilute with an organic solvent.

[0075] Examples of the organic solvent include: (1) methyl alcohol, ethyl alcohol, n-propyl alcohol monole, isopropylino alcoholo, n-butino alcoholo, tridecino vinylo, cyclohexyl alcohol Alcohols such as 2-methylcyclohexyl alcohol, (2) Glycols such as tylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, etc., (3) ethylene glycol monomethyl ether, ethylene glycol monoethylene ether, ethylene glycol monobutino reetenole, Diethylene glycol monomethinoreateolate, diethyleneglycolenomethinoleatenore, diethyleneglycolenolebutinoreatenore, ethylene glycolenoremonomethinoreatenoacetate, ethyleneglycolenomonoethylenoate acetate, ethyleneglycol Nolemonobutinoreacetate, diethyleneglycolenomonomethinorea cetate, diethyleneglycolenomonoethylenocetate, diety Glycol ethers such as lenglycol-no-monobutyl acetate, (4) esters such as ethyl acetate, isopropylene acetate, n-butyl acetate, (5) acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Examples thereof include ketones such as cyclopentanone, isophorone and diacetone alcohol, and these can be used alone or in admixture of two or more.

[0076] Preferably, ketones having excellent dye solubility are contained in an amount of 30% by mass or more and 80% by mass or less with respect to the total organic solvent used in the coating solution, and the other organic solvent contains a leveling property, It is preferable to select in consideration of dryness. The boiling point of the organic solvent is preferably 60 ° C or higher and 180 ° C or lower. When the boiling point is low, the solid concentration of the coating solution changes during coating, and the coating thickness is difficult to stabilize. On the other hand, when the boiling point is high, the amount of organic solvent remaining in the coating film increases, resulting in poor temporal stability.

[0077] Examples of the method for dissolving or dispersing the near-infrared absorbing dye and the resin in an organic solvent include stirring, dispersion and pulverization methods under heating. By heating, the solubility of the dye and the resin can be improved, and the poor appearance of the coating due to undissolved substances is prevented. Further, by dispersing and pulverizing, the resin and the pigment are dispersed in the coating solution in a fine particle state of 0.3 zm or less, whereby a layer having excellent transparency can be formed. As the disperser and pulverizer, known ones can be used. Specifically, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a colloid mill, an ultrasonic homogenizer, a homomixer, a pearl mill, a wet jet mill, Paint shaker, butterfly mixer, planetary mixer, Henschel mixer, etc. [0078] If contamination or undissolved material of 1 μm or more is present in the coating solution, the appearance after coating becomes unsatisfactory, so it is necessary to remove it with a filter or the like before coating. As the filter, it is preferable to use a filter that removes 99% or more of a force having a magnitude of 1 μΐη that can be suitably used. : When a coating solution containing 1 zm or more of contamination or undissolved material is applied and dried, a dent or the like is generated in the surrounding area, which may be a disadvantage of a size of lOO xm or more and lOOO xm or less.

 [0079] The solid content concentration of the resin, pigment, and the like contained in the coating solution is preferably 10% by mass or more and 30% by mass or less. When the solid content concentration is low, it takes time to dry after coating, and not only productivity is inferior, but also the amount of the solvent remaining in the coating film is increased, resulting in poor temporal stability. On the other hand, when the solid content concentration is high, the viscosity of the coating solution becomes high and the leveling property becomes insufficient, resulting in a poor coating appearance. Ability to adjust the viscosity of the coating solution to lOcps or more and 300 cps or less It is preferable to adjust the solid content concentration, the organic solvent, etc. so as to be within this range which is preferable in terms of coating appearance.

 [0080] In the present invention, as a method for applying the wavelength selective absorption layer on the transparent substrate, gravure coating method, kiss coating method, dip method, spray coating method, curtain coating method, air knife coating method, blade coating method, Conventional methods such as reverse roll coating, bar coating, and lip coating can be applied. Among these, a gravure coating method that can be applied uniformly, particularly a reverse gravure method is preferable. The diameter of the gravure is preferably 80 mm or less. When the diameter is large, the frequency of ridges in the flow direction increases.

[0081] The coating amount of the wavelength selective absorption layer after drying is not particularly limited, but the lower limit is preferably lg / m ² , more preferably 3 g / m ² , and the upper limit is preferably 50 g / m ^2. More preferably, it is 30 g / m ² . If the coating amount after drying is small, the near-infrared absorbing power tends to be insufficient. Therefore, if the amount of the near-infrared absorbing dye in the resin is increased, the amount of the dye present at the surface and the interface between the anchor layers increases, and the resin is easily influenced by the outside air and the anchor layer resin. As a result, the deterioration of the dye is likely to occur, and the temporal stability becomes poor. On the other hand, when the coating amount after drying is large, the near-infrared absorbing ability is sufficient, but the transparency in the visible light region is lowered and the brightness of the display is lowered. For that reason, Reducing the amount of infrared absorbing dye can adjust the optical properties, but tends to cause insufficient drying. As a result, the temporal stability of the dye becomes poor due to the residual solvent in the coating film. On the other hand, when the drying is sufficient, the flatness of the substrate becomes poor.

 [0082] Examples of the method of applying the coating liquid on the transparent substrate and drying include known hot air drying, infrared heaters, etc., but the drying speed is fast and hot air drying is preferred.

 [0083] In the initial constant rate drying stage after coating, drying is preferably performed at 20 ° C or higher and 80 ° C or lower using hot air of 2mZ seconds to 30m / second. When initial drying is carried out strongly (hot air temperature is high, hot air volume is large), fine defects of the coating such as fine foam removal, fine repellency and cracks are likely to occur. On the other hand, when initial drying is weak (hot air temperature is low, hot air volume is small), the appearance will be good, but it takes time to dry, and there is a problem in terms of cost. When a surfactant is not added to the coating solution, the above-mentioned minute defects occur and it is necessary to weaken the initial drying considerably.

[0084] In the reduction drying process, it is necessary to set the temperature higher than the initial drying and reduce the solvent in the coating film, and the preferable temperature is 120 ° C or higher and 180 ° C or lower. Particularly preferably, the lower limit is 140 ° C and the upper limit is 170 ° C. When the temperature is low, the solvent in the coating film decreases and becomes a residual solvent, resulting in insufficient stability of the dye over time. On the other hand, in the case of high temperature, the near-infrared-absorbing dye is deteriorated by heat, as well as the flatness of the base material is deteriorated due to heat. The transit time is preferably 5 seconds or more and 180 seconds or less. When the time is short, the amount of solvent remaining in the coating film increases, resulting in poor stability over time. On the other hand, when the time is long, heat loss occurs on the substrate as well as poor productivity. Therefore, the flatness becomes poor. The upper limit of the passage time is particularly preferably 30 seconds from the viewpoint of productivity and flatness.

 [0085] In the final stage of drying, it is preferable to set the hot air temperature to be equal to or lower than the glass transition temperature of the resin and to set the actual temperature of the substrate to be equal to or lower than the glass transition temperature of the resin in a flat state. When leaving the drying furnace at a high temperature, slipping may be poor when the coated surface comes into contact with the roll surface, and there may be a case where a curl or the like is generated just by causing scratches.

 [0086] (Wavelength selective absorption filter)

In the present invention, the wavelength selective absorption filter means a wavelength of 800 to 1200 nm and a wavelength of 550. It is an optical filter having a maximum absorption at ˜620 nm. This wavelength selective absorption filter is preferred as the transmittance in the near-infrared region of wavelengths from 800 nm to 1200 nm is lower. Specifically, the transmittance in the near infrared region is preferably 20% or less, and particularly preferably 10% or less. When the transmittance is high, the absorption of near-infrared light emitted from the plasma display is insufficient, and malfunction of electronic devices using the near-infrared remote control cannot be prevented.

 [0087] The average transmittance in the visible region is higher than the average transmittance in the near-infrared region, and has a sharp absorption at a wavelength of 55 Onm or more and 620 nm or less, and further at a wavelength of 570 nm to 600 nm. preferable. Specifically, the transmittance at the maximum absorption wavelength within the above wavelength range is preferably 40% or less, particularly preferably 30% or less. When the transmittance in this region is high, it is difficult to obtain the effect of absorbing the neon light emitted from the plasma display and improving the red color. In addition, when the absorption in this region is wide, the overall transmittance in the visible light region is lowered, and the brightness of the display tends to be lowered. The transmittance in the visible light region excluding wavelengths of 550 nm to 620 nm is preferably as high as possible, preferably 50% or more, particularly preferably 60% or more. When the transmittance is low, the color of the display is hindered and the image is low in brightness.

 [0088] The adjustment of the transmittance can be changed according to the coating amount of the wavelength selective absorption layer and the abundance of the near-infrared absorbing pixel per unit area.

 [0089] As the color tone of the wavelength selective absorption filter, when expressed in the Lab color system, the a value is preferably 10.0 to +10.0 and the b value is preferably 10 · 0 to +10.0. ,. Within this range, a natural color is preferable even when installed in front of a plasma display.

 [0090] The method of adjusting the color tone can be achieved by applying the wavelength selective absorption layer, the amount of the near-infrared absorbing dye per unit area, mixing other dyes, or optimizing the drying conditions. . If there is a colored adhesive layer or other optical filter on the front or back surface of the wavelength selective absorption filter described later, it is preferable to adjust the color tone of the wavelength selective absorption filter to include the natural color. .

[0091] As a coating appearance of the wavelength selective absorption layer, there should be no defect of a size having a maximum diameter of 300 μm or more, more preferably 100 μm. Disadvantages over 300 μm If it is installed on the front of the plasma display, it becomes like a bright spot and the defects become noticeable. Also, streaks, unevenness, etc. with a thin coating layer become prominent on the front surface of the display and become a problem.

 [0092] It is preferable that the wavelength selective absorption filter 1 does not change the transmittance of near-infrared rays and the transmittance of visible light even when left for a long period of time under high temperature and high humidity. If the temporal stability under high temperature and high humidity is poor, not only the color tone of the display image will change, but the effect of the present invention for preventing malfunction of electronic equipment using the near infrared remote control may be lost. .

 [0093] Stability over time is improved by mixing an aromatic diimonium dye (a) with a bis (trifluoromethanesulfonyl) imide acid as a counter ion and a porphyrin dye or azaporphyrin dye (b). However, it is also possible to reduce the amount of residual solvent in the wavelength selective absorption layer by controlling the type of organic solvent used in the coating solution, the thickness of the coating layer, the drying conditions, etc. It can be made even better by adjusting the content.

 [0094] Further, as described above, a near-infrared absorbing layer containing an aromatic diimonium dye (a) having a resin and bis (trifluoromethanesulfonyl) imidic acid as a counter ion, and a resin and a porphyrin dye or From the viewpoint of stability over time, it is also preferable to use a wavelength selective absorption layer having a multilayer structure in which a neon cut layer containing an azaporphyrin-based dye (b) is formed on a transparent substrate in this order. It is.

 [0095] The amount of residual solvent in the wavelength selective absorption layer is preferably as small as possible, but is preferably 3% by mass or less. If the amount is 3% by mass or less, there is substantially no difference in stability over time. However, in order to further reduce the amount of residual solvent, for example, if drying is performed under severe conditions, problems such as poor flatness of the filter may occur, and productivity such as drying under reduced pressure may be lost. descend.

[0096] In the present invention, for the purpose of blocking harmful electromagnetic waves emitted from the display, a conductive layer may be provided directly or via an adhesive on the same surface as the infrared absorption layer or on the opposite surface. . In the case where a metal mesh that can use either a metal mesh or a conductive thin film is used, the conductive layer needs to have a metal mesh conductive layer having an aperture ratio of 50% or more. If the aperture ratio of the metal mesh is low, the electromagnetic wave shielding property is good, but there is a problem that the light transmittance is lowered. For this reason, an aperture ratio of 50% or more is necessary to obtain good light transmittance. It becomes important. As the metal mesh used in the present invention, a metal foil having high electrical conductivity is subjected to etching treatment to form a mesh, a woven mesh using metal fibers, or a metal fiber on the surface of polymer fibers. Fibers attached using a method such as Metsu may be used. The metal used for the electromagnetic wave absorbing layer may be a metal having high electrical conductivity and good stability, and is not particularly limited. However, from the viewpoint of workability and cost, copper, Nickel, tungsten, etc. are preferable.

 [0097] When a conductive thin film is used, the transparent conductive layer may be any conductive film, but is preferably a metal oxide. This makes it possible to obtain higher visible light transmittance. In the present invention, when it is desired to improve the conductivity of the transparent conductive layer, it is preferably a repeating structure of three or more layers of metal oxide / metal / metal oxide. Conductivity can be obtained while maintaining a high visible light transmittance by multilayering the metal. Used in the present invention. The metal oxide may be any metal oxide as long as it has electrical conductivity and visible light transmittance. Examples include tin oxide, indium oxide, indium tin oxide, zinc oxide, titanium oxide, and bismuth oxide. The above is an example and is not particularly limited. Further, the metal layer used in the present invention is preferably gold, silver or a compound containing them from the viewpoint of conductivity.

 [0098] Further, when the conductive layer is multi-layered, for example, when the number of repeated layers is 3, the thickness of the silver layer is preferably 50A to 200A, more preferably 50A to 100A. When the film thickness is thicker than this, the light transmittance decreases, and when it is thin, the resistance value increases. Further, the thickness of the metal oxide layer is preferably 100 mm to 100θ mm, more preferably 100 mm to 500 mm. If it is thicker than this, it will be colored and the tone will change, and if it is thinner, the resistance will increase. In addition, when three or more layers are formed, for example, when five layers are formed such as metal oxide / silver / metal oxide / silver / metal oxide, the thickness of the central metal oxide is the other metal. It is preferable that it is thicker than the thickness of the oxide layer. By doing so, the light transmittance of the entire multilayer film is improved.

[0099] In the present invention, an antireflection layer or an anti-flicker layer may be provided directly or via an adhesive on the same surface as the wavelength selective absorption layer of the wavelength selective absorption filter or on the opposite surface. In addition, in the wavelength selective absorption layer composed of a plurality of layers, the neon cut layer has an adhesive resin. , The function of the adhesive layer can be imparted to the neon cut layer and bonded to a glass plate or a resin sheet, or directly to a display. Further, an adhesive layer may be formed on the surface of the single wavelength selective absorption layer.

 [0100] In the wavelength selective absorption filter of the present invention, a layer having an ultraviolet absorbing ability may be provided for the purpose of improving light resistance. In order to impart ultraviolet absorbing ability, an ultraviolet absorber may be added to any of the wavelength selective absorption layer, transparent substrate, pressure-sensitive adhesive layer, antireflection layer, and glare prevention layer. As the UV absorber, known ones such as organic UV inhibitors and inorganic UV inhibitors can be used.

 Example

 [0101] Examples of the present invention and comparative examples are shown below. The characteristic value measurement method and effect evaluation method used in the present invention are as follows.

 [0102] <Viscosity of coating solution>

 The coating solution was adjusted to 20 ° C. and measured using a B-type viscometer (BL) manufactured by Tokyo Keiki Co., Ltd. at a rotor rotation speed of 60 rpm.

[0103] <Total light transmittance, haze>

 The total light transmittance and haze were measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).

[0104] <Light transmittance>

 Using a spectrophotometer (U-3500, manufactured by Hitachi, Ltd.), irradiating the wavelength selective absorption layer with light in the wavelength range of 1100 nm to 200 nm, and using the indoor air as a reference for transmittance. And measured.

[0105] <Color tone>

 Using a color difference meter (Nippon Denshoku Industries Co., Ltd., ZE-2000), irradiating the wavelength selective absorption layer with light, and using the Lab color system a and b values as standard light, C light source Measured at 2 degree viewing angle

[0106] <Stability over time>

After being left for 48 hours in an atmosphere of temperature 80 ° C and humidity 95%, the above transmittance and color tone were measured. As the amount of change in color tone, ΔΕ was obtained from Equation 1 below. Note that the smaller the value of Δ Ε, the color tone This means that there is little change.

[0107] Δ Ε = ^ ((a value before treatment, a value after treatment) ² + (HI before treatment b value after treatment 1) ² )

 ••• (1)

 [0108] Next, the amount of change Δ の before and after the temporal treatment of the transmittance was obtained from the following equation 2. ΔΤ indicates that the smaller the value, the smaller the amount of change.

[0109] Change amount (%) = (I transmittance after treatment—transmittance before treatment I / transmittance before treatment) X 10

0

 ••• (2)

 [0110] Appearance of Gu coating>

 (1) Minute defects

The filter after the formation of the wavelength selective absorption layer was placed on a white film, visually observed under a three-wavelength fluorescent lamp, and the following evaluation was performed. For micro defects, measure the number of defects with a size of 300 β m or more per 100 m ^{2 and} rank them according to the following criteria.

 ◎: Less than 1 minute defect

 ○: 1 to less than 5 minor defects

 Δ: 5 or more and less than 10 minor defects

 X: 10 or more micro defects

 [0111] (2) Coating failure

 For coating defects such as coating spots and streaks, place the wavelength selective absorption filter on a white film, visually observe the wavelength selective absorption layer surface under a three-wavelength fluorescent lamp, and rank according to the following criteria. Went.

 ◎: Even if the wavelength selective absorption filter is observed, no coating failure is observed. ○: When the wavelength selective absorption filter is observed, the coating failure is slightly understood. △: When the wavelength selective absorption filter is observed. Can understand coating defects X: Even when the wavelength selective absorption filter is in a stationary state, coating defects can be identified

 [0112] <Adhesion>

The adhesion was measured by a test method in accordance with JIS K 5400 8.5.1. Specifically Attach 100 cell-shaped scratches from the side where the wavelength selective absorption layer is laminated using a cutter guide with a gap interval of 2 mm, and attach cellophane adhesive tape (Nichiban "405", 24 mm width) Affixed to the checkered scratched surface, rubbed with an acrylic board (“Sumipex” manufactured by Sumitomo Chemical Co., Ltd.) and completely adhered, and then observed by visually observing the situation when peeled off vertically.

 ◯: No peeling

 Δ: There are peeled cells, but the peeled cells are less than 10 cells.

 X: 10th eye or more peeled

[0113] Example 1

 (Preparation of base material)

 Polyethylene terephthalate resin with an intrinsic viscosity of 0.62 dlZg was put into a twin-screw extruder, melt-extruded from a T-die at 290 ° C, solidified while applying electrostatic force on a cooled rotating metal roll, An unstretched sheet was obtained.

[0114] Next, the unstretched sheet was heated to 90 ° C with a roll stretching machine and longitudinally stretched 3.5 times, and then the coating amount after drying the following coating solution A on the longitudinally stretched film was It was applied to both sides of the longitudinally stretched film so as to be 0.5 g / m ^2, and allowed to pass under hot air at a wind speed of 10 m / second and 120 ° C. for 20 seconds to form an intermediate coating layer. Furthermore, it was heated to 140 ° C with a tenter and stretched 3.7 times, and then heat-treated at 235 ° C while relaxing 5% in the width (transverse) direction, and biaxially stretched with an intermediate coating layer on both sides. A polyethylene terephthalate film was obtained. The obtained film had a thickness of 100 / im, a total light transmittance of 90.2%, and a haze of 0.5%.

[0115] (Composition of coating liquid A for intermediate coating layer)

 • Ion-exchanged water 50.0% by mass

 • Isopropyl alcohol 28.9% by mass

'Acrylic one melamine resin 10.0 mass ^_0/0

 (Nippon Carbide Industries, A_08, solid content: 46% by mass)

'Polyester resin 10.0 mass ^_0/0

(Toyobo, Vironal MD-1250, solid content: 30% by mass) -Polymethyl methacrylate cross-linked particles 1.0% by mass (Nippon Shokubai, poster MA1001)

 • Silicon surfactant 0.1% by mass

 (Dow Corning, Paintad 32)

[0116] (Adjustment of coating solution B for wavelength selective absorption layer)

 Toluene, methyl ethyl ketone and resin were mixed at the following mass ratio and stirred under heating to dissolve the resin. Then, a dye and a surfactant were added and stirred for 30 minutes or more. Next, the undissolved material was removed with a filter having a nominal filtration accuracy of 1 β m to prepare a coating solution.

'Toluene 39.995 mass ^_0/0

'Methylate Norre ethyl Roh reggaeton 40.000 mass ^_0/0

 • Acrylic resin 18. 776% by mass

 (Mitsubishi Rayon, BR_80, Tg = 105 ° C)

'Aromatic Jiinmoniumu based dyes 0.695 mass ^_0/0

(Nippon Carlit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imidic acid)

'Phthalocyanine dyes 0.357 mass ^_0/0

 (Nippon Shokubai, IR-10A)

. § The porphyrin dyes 0.118 mass ^_0/0

 (Yamada Kasei, TAP— 2)

 • Silicone-based surfactant 0.059% by mass

 (Dow Corning, Paintad 57, HLB = 6.7)

[0117] (Production of wavelength selective absorption filter)

The coating liquid B (solid content concentration: 20 mass%, viscosity: 40 cps) is applied to one of the intermediate coating layers, and the transmittance at 950 nm after drying is 4.3% (the coating amount after drying is 8. OgZm ² ) was applied using a reverse gravure with a diameter of 60 cm, and heated for 20 seconds at 40 ° C with hot air of 5 m / second, hot air of 20 m / second at 150 ° C for 20 seconds, and 90 The filter was dried by passing it through hot air of 20 mZ seconds at ° C for 10 seconds to obtain a wavelength selective absorption filter. The mass ratio of the aromatic diimonium dye (a) to the azaporphyrin dye (b) in the wavelength selective absorption layer was (a) Z (b) = 100 Zl 7. [0118] The obtained wavelength selective absorption filter 1 had a strong absorption in the near infrared region, a high transmittance in the visible light region, and a sharp absorption near 590 nm. Furthermore, the stability over time and the coating appearance were also good.

 Table 1 shows the types of dyes used in the wavelength selective absorption layer, and Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.

 [0119] Example 2

 A wavelength selective absorption filter 1 was obtained in the same manner as in Example 1 except that the following coating solution C was used. In the wavelength selective absorption layer, the mass ratio of the aromatic diimonium dye (a) to the azaporphyrin dye (b) was (a) / (b) = 100Z17.

[0120] (Adjustment of coating solution C for wavelength selective absorption layer)

 Toluene, cyclopentanone, and a resin were mixed at the following mass ratio, stirred under heating to dissolve the resin, added with a dye and a surfactant, and stirred for 30 minutes or more. Subsequently, undissolved material was removed with a filter having a nominal filtration accuracy of 1 β m to prepare a coating solution C.

'Toluene 40.088 mass ^_0/0

'Cyclopentanone 40.088 mass ^_0/0

 'Copolyester resin with fluorene skeleton 18. 776% by mass

(Kanebo, ○ 1 PET, Tg = 150 ° C)

 'Aromatic diimonium dyes 0. 695% by mass

 (Nippon Carlit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imidic acid)

'Phthalocyanine dyes 0.176 mass ^_0/0

 (Nippon Shokubai, IR-12)

 -Azaporphyrin pigment 0.18% by mass

 (Yamada Kasei, TAP— 2)

 -Silicone-based surfactant 0.05% by mass

 (Dowcoung, Paintad 57, HLB = 6.7)

[0121] As in Example 1, the obtained wavelength selective absorption filter 1 has strong absorption in the near infrared region, high transmittance in the visible light region, and sharp absorption in the vicinity of 590 nm. It was. Furthermore, stability over time and coating appearance were also good. However, the adhesion to the substrate was slightly poor.

 Table 1 shows the types of dyes used in the wavelength selective absorption layer, and Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.

[0122] Comparative Example 1

 A wavelength selective absorption filter 1 was obtained in the same manner as in Example 1 except that the following coating solution D was used.

 (Adjustment of coating solution D for wavelength selective absorption layer)

 Toluene, methyl ethyl ketone and resin were mixed at the following mass ratio and stirred under heating to dissolve the resin. Then, a dye and a surfactant were added and stirred for 30 minutes or more. Subsequently, undissolved material was removed with a filter having a nominal filtration accuracy of 1 μm to prepare a coating solution D.

'Toluene 39.998 mass ^_0/0

'Methylate Norre ethyl Roh reggaeton 39.998 mass ^_0/0

 • Acrylic resin 18.825% by mass

 (Mitsubishi Rayon, BR-80)

 'Aromatic diimonium dyes 0.697% by mass

 (Nippon Carlit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imidic acid)

'Phthalocyanine dyes 0.358 mass ^_0/0

 (Nippon Shokubai, IR-10A)

 'Squarium dyes 0.065% by mass

 (Kyowa Hakko, SD184)

 -Silicone-based surfactant 0.05% by mass

 (Dowcoung, Paintad 57, HLB = 6.7)

The obtained wavelength selective absorption filter 1 has a strong absorption in the near-infrared region, a high transmittance in the visible light region, and a sharp absorption near 590 nm, as in Example 1. It was. However, the stability over time was poor.

Table 1 shows the types of dyes used in the wavelength selective absorption layer. The physical properties are shown in Table 2 and Table 3.

[0124] Comparative Example 2

 A wavelength selective absorption filter 1 was obtained in the same manner as in Example 1 except that the following coating solution E was used. In the wavelength selective absorption layer, the mass ratio of the aromatic diimonium dye (a) to the azaporphyrin dye (b) was (a) / (b) = 100Z19.

[0125] (Adjustment of coating solution E for wavelength selective absorption layer)

 Toluene, methyl ethyl ketone and resin were mixed at the following mass ratio and stirred under heating to dissolve the resin. Then, a dye and a surfactant were added and stirred for 30 minutes or more. Next, an undissolved material was removed with a filter having a nominal filtration accuracy of 1 μm to prepare a coating liquid tank.

Toluene 40.002 mass ^_0/0

40.002 mass ^_0/0

• acrylic resin 18.839 mass ^_0/0

 (Mitsubishi Rayon, BR-80)

• aromatic Jiinmoniumu-based dye 0.622 mass ⁰

 (Nippon Shokubai Co., Ltd., IRG022, counter ion: xafluoroantimonic acid)

'Phthalocyanine dyes 0.358 mass ^_0/0

 (Nippon Shokubai, IR-10A)

 'Azaporphyrin pigment 0.18% by mass

 (Yamada Kasei, TAP— 2)

 • Silicone-based surfactant 0.059% by mass

 (Dow Corning, Paintad 57, HLB = 6.7)

 The obtained wavelength selective absorption filter 1 has a strong absorption in the near-infrared region, a high transmittance in the visible light region, and a sharp absorption in the vicinity of 590 nm, as in Example 1. It was. However, the stability over time was poor.

 Table 1 shows the types of dyes used in the wavelength selective absorption layer, and Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.

 [0127] Example 3

(Adjustment of coating solution F for near-infrared absorbing layer in wavelength selective absorbing layer) Toluene, methyl ethyl ketone and resin were mixed at the following mass ratio and stirred under heating to dissolve the resin. Then, a dye and a surfactant were added and stirred for 30 minutes or more. Next, the coating solution F was prepared by removing undissolved material with a filter having a nominal filtration accuracy of 1 β m.

'Toluene 40.056 mass ^_0/0

. Methylate Norre ethyl Roh reggaeton 40.057 mass ^_0/0

 • Acrylic resin 18. 776% by mass

 (Mitsubishi Rayon, BR_80, Tg = 105 ° C)

'Aromatic Jiinmoniumu based dyes 0.695 mass ^_0/0

(Nippon Carlit, CIR1085, counter ion: bis (trifluoromethanesulfonyl) imidic acid)

 • Phthalocyanine pigments 0.357% by mass

 (Nippon Shokubai, IR-10A)

 • Silicone-based surfactant 0.059% by mass

 (Dow Corning, Paintad 57, HLB = 6.7)

[0128] (Adjustment of coating liquid G for neon cut layer in wavelength selective absorption layer)

 After mixing at the following mass ratio, the mixture was stirred for 30 minutes or more. Next, the coating solution G was prepared by removing undissolved substances with a filter having a nominal filtration accuracy of 1 μηι.

'Methylcarbamoyl Norre ethyl Honoré ketone 49.808 mass ^_0/0

 • Acrylic adhesive 49. 847% by mass

 (Manufactured by Soken Chemical, SK Dyne 1435, solid content 30% by weight)

'§ The porphyrin dyes 0.045 mass ^_0/0

 (Yamada Kasei, TAP— 2)

 -Curing agent 0.150% by mass

 (Soken Chemicals, L-45)

 -Curing agent 0.150% by mass

 (Soken Chemicals, TD-75)

[0129] (Production of wavelength selective absorption filter)

On the intermediate coating layer forming surface obtained in the same manner as in Example 1, the coating liquid F was dried at 950 nm. In order to achieve a transmittance of 4.3% (applying amount after drying: 8. Og / m ² ), reverse coating was performed using a diagonal gravure with a diameter of 60 cm, and hot air of 5 m / sec at 40 ° C. It was dried by passing for 20 seconds with hot air of 20 m / second at 150 ° C. for 20 seconds and further with hot air of 20 m / second at 90 ° C. for 10 seconds to form a near-infrared absorbing layer. Next, the coating solution G was applied onto the near infrared absorbing layer using a lip coater so that the coating amount after drying was 16 g / m ² , and heated at 40 ° C with hot air of 5 mZ seconds for 20 seconds. A neon cut layer was formed by passing it through hot air at 150 ° C. for 20 seconds with hot air of 20 mZ seconds and further passing it with hot air of 20 m / second at 90 ° C. for 10 seconds. In other words, a wavelength selective absorption filter having a wavelength selective absorption layer composed of two layers of a near infrared absorption layer and a neon cut layer was obtained. The mass ratio of the aromatic diimine dye (a) to the azaporphyrin dye (b) in the wavelength selective absorption layer was (a) / (b) = 100/17.

 [0130] The obtained wavelength selective absorption filter 1 had a strong absorption in the near-infrared region, a high transmittance in the visible light region, and a sharp absorption in the vicinity of 590 nm. Furthermore, the stability over time and the coating appearance were also good.

 Table 1 shows the types of dyes used in the wavelength selective absorption layer, and Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.

 [0131] [Table 1]

[0132] [Table 2]

 [0133] [Table 3] Banquet 1 Steel 1 2 Steel 1 Organ steel 2 Banquet 3 Color 18

 厶 E I -2 0.9 4.9 2.8 1.4 Transmissivity © 950η »I I, 2 10.9 30.8 15.0 1 1, 8

I 靈 ft <<<< 850ηιι 6.1 5.9 7.2 6.3 6.1 Industrial applicability

 The wavelength selective absorption filter of the present invention has excellent durability with low transmittance in the near infrared region and neon light region, high transmittance in the visible light region, and little change in optical characteristics over time. Therefore, it is possible to stably display a good image by installing it in front of the plasma display, and it is possible to prevent malfunction of precision equipment using a near-infrared remote controller, which can greatly contribute to the industry.

Claims

The scope of the claims  [1] A single-layer or multi-layer wavelength selective absorption layer containing a resin, a near-infrared absorbing dye (A), and a dye (B) is laminated on a transparent substrate, and the wavelength is 800 to 1200 nm. And a wavelength selective absorption filter having a maximum absorption at a wavelength of 550 to 620 nm,  One of the near infrared absorbing dyes (A) is an aromatic diimonium dye (a) having bis (trifluoromethanesulfonyl) imidic acid as a counter ion,  One of the pigments (B) is a porphyrin pigment or azaporphyrin pigment (b).  [2] The multi-layer wavelength selective absorption layer comprises a near-infrared absorption layer containing a resin and a near-infrared absorption dye (A), and a neon cut layer containing a resin and a dye (B) in this order on the transparent substrate. 2. The wavelength selective absorption filter according to claim 1, wherein the wavelength selective absorption filter is formed.  [3] The wavelength selective absorption layer contains 100 parts by mass of the aromatic diimonium dye (a) and the porphyrin dye or azaporphyrin dye (b) 5 to 100 parts by mass (mass ratio). The wavelength selective absorption filter according to claim 1, wherein:  4. The wavelength selective absorption filter according to claim 1, wherein the resin constituting the wavelength selective absorption layer is an acrylic resin. [5] The single wavelength selective absorption layer contains an organic solvent, a resin, an aromatic diimonium dye ( _a ), a porphyrin dye or an azaporphyrin dye ( _b ) on the transparent substrate. 2. The wavelength selective absorption filter according to claim 1, wherein the coating liquid A is applied and dried.  [6] A multilayer wavelength selective absorption layer was formed on the transparent substrate by applying and drying a coating liquid B containing an organic solvent, a resin, and an aromatic diimonium dye (a). A coating solution C containing an organic solvent and a resin and a porphyrin-based dye or azaporphyrin-based dye (b) was formed by coating and drying immediately above the near-infrared absorbing layer and the near-infrared absorbing layer. 2. The wavelength selective absorption infinole according to claim 1, further comprising a neon cut layer. [7] The wavelength selective absorption filter according to claim 5 or 6, wherein the coating liquid A or B force further contains HLB of 2 to 12 surfactant. 8. The wavelength selective absorption filter according to claim 7, wherein the surfactant is a silicone-based surfactant or a fluorine-based surfactant.