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WO2006070717A1 - Filtre optique a absorption en selection de longueurs d'onde - Google Patents

Filtre optique a absorption en selection de longueurs d'onde Download PDF

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Publication number
WO2006070717A1
WO2006070717A1 PCT/JP2005/023728 JP2005023728W WO2006070717A1 WO 2006070717 A1 WO2006070717 A1 WO 2006070717A1 JP 2005023728 W JP2005023728 W JP 2005023728W WO 2006070717 A1 WO2006070717 A1 WO 2006070717A1
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WO
WIPO (PCT)
Prior art keywords
selective absorption
wavelength selective
dye
layer
wavelength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2005/023728
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English (en)
Japanese (ja)
Inventor
Kenichi Mori
Akira Yoshimi
Shinya Onomichi
Shinji Sawasaki
Chikao Morishige
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Publication of WO2006070717A1 publication Critical patent/WO2006070717A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B53/00—Quinone imides
    • C09B53/02—Indamines; Indophenols
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • 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.
  • 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.
  • 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.
  • 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 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
  • 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.
  • 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.
  • aromatic diimonium compound dyes used as near-infrared absorbing dyes are generally vulnerable to heat (see, for example, page 17 of Patent Document 12).
  • 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
  • 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.
  • the present invention is as follows.
  • 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 ⁇ m 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).
  • 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 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).
  • 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.
  • 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.
  • 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.
  • 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:
  • 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 wavelength selective absorption filter according to the present invention 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. .
  • 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
  • one of the dyes (B) is a porphyrin dye or It is characterized by being an azaporphyrin pigment (b).
  • 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.
  • 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.
  • 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.
  • the film is particularly preferably a biaxially stretched film from the viewpoint of strength and the like.
  • 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.
  • 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.
  • a light resistance agent ultraviolet ray preventing agent
  • 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.
  • 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.
  • the thickness of the transparent substrate varies depending on the material.
  • a polyester film is used, 35 ⁇ m or more is preferred, and more preferably 50 ⁇ m or more.
  • the thickness is preferably 260 ⁇ m 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.
  • 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.
  • 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.
  • An intermediate layer may be provided for the purpose of improving the transparency of the transparent substrate.
  • Examples of the resin constituting the intermediate layer include polyester resins, polyurethane resins, polyester urethane resins, acrylic resins, melamine resins, and the like.
  • 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.
  • the intermediate layer may contain a crosslinking agent to form a bridge structure for the purpose of improving adhesion and water resistance.
  • a crosslinking agent examples include urea, epoxy, melamine, and isocyanate.
  • the effect of the crosslinking agent is remarkable when the resin undergoes whitening or strength reduction under high temperature and high humidity.
  • a graft copolymer resin having self-crosslinking property may be used as the resin.
  • the intermediate layer may contain various kinds of particles for the purpose of forming irregularities on the surface and improving slipperiness.
  • 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.
  • a surfactant 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.
  • 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.
  • the thickness of the intermediate layer is not particularly limited as long as it has a desired function.
  • It is preferably from 01 ⁇ m to 5 ⁇ m.
  • the thickness is small, the function as an intermediate layer is hardly exhibited, and conversely, when it is thick, transparency tends to be poor.
  • 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.
  • 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.
  • 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.
  • 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
  • ⁇ 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-fluoropheny
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 disubstit
  • 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.
  • 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 3 ⁇ 40% or less. It is preferable to adjust so that it becomes.
  • 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.
  • the wavelength selective absorption layer is composed of a single layer or multiple layers.
  • an aromatic diimonium dye (a) having bis (trifluoromethanesulfonyl) imidic acid as a counter ion
  • a porphyrin dye or azaporphyrin dye (b). It is preferable to have a single layer structure mixed in the same coating layer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • acrylic resins that are excellent in transparency and heat resistance when mixed with a dye are preferable.
  • an adhesive may be used as a resin when it is bonded to an antireflection film, glass, or an electromagnetic wave prevention film.
  • 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.
  • acrylic pressure-sensitive adhesives are preferable from the viewpoint of transparency.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 is applied and dried immediately above the near-infrared absorbing layer.
  • 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.
  • 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.
  • the surfactant in the wavelength selective absorption layer (coating layer) bleeds to the surface by heat treatment during drying of the coating layer.
  • slipperiness can be imparted to the surface of the coating layer.
  • 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. .
  • the HLB of the surfactant is 2 or more and 12 or less.
  • the lower limit of HLB is preferably 3, particularly preferably 4.
  • the upper limit value of HLB is preferably 11, particularly preferably 10.
  • the HLB is low, the leveling property is insufficient due to insufficient surface activity.
  • the wavelength selective absorption layer not only lacks slipperiness but also easily absorbs moisture, and the time stability of the diimonium dye becomes poor.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 Nole
  • 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.
  • 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.
  • the disperser and pulverizer known ones can be used.
  • a filter it is preferable to use a filter that removes 99% or more of a force having a magnitude of 1 ⁇ that can be suitably used.
  • 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.
  • 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.
  • 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.
  • gravure coating method 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • drying is preferably performed at 20 ° C or higher and 80 ° C or lower using hot air of 2mZ seconds to 30m / second.
  • hot air 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.
  • initial drying 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.
  • 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.
  • the preferable temperature is 120 ° C or higher and 180 ° C or lower.
  • the lower limit is 140 ° C and the upper limit is 170 ° C.
  • the transit time is preferably 5 seconds or more and 180 seconds or less.
  • the upper limit of the passage time is particularly preferably 30 seconds from the viewpoint of productivity and flatness.
  • the hot air temperature is set 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.
  • 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.
  • 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.
  • the transmittance in the near infrared region is preferably 20% or less, and particularly preferably 10% or less.
  • 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.
  • the transmittance at the maximum absorption wavelength within the above wavelength range is preferably 40% or less, particularly preferably 30% or less.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • the wavelength selective absorption layer As a coating appearance of the wavelength selective absorption layer, there should be no defect of a size having a maximum diameter of 300 ⁇ m or more, more preferably 100 ⁇ m. Disadvantages over 300 ⁇ m 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.
  • 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. .
  • 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).
  • a aromatic diimonium dye
  • b porphyrin dye or azaporphyrin dye
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the transparent conductive layer 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.
  • 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.
  • the metal layer used in the present invention is preferably gold, silver or a compound containing them from the viewpoint of conductivity.
  • the thickness of the silver layer is preferably 50A to 200A, more preferably 50A to 100A.
  • the thickness of the metal oxide layer is preferably 100 mm to 100 ⁇ 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.
  • 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.
  • 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.
  • 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.
  • an adhesive layer may be formed on the surface of the single wavelength selective absorption layer.
  • a layer having an ultraviolet absorbing ability may be provided for the purpose of improving light resistance.
  • 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.
  • the UV absorber known ones such as organic UV inhibitors and inorganic UV inhibitors can be used.
  • 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.
  • BL B-type viscometer
  • the total light transmittance and haze were measured using a haze meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.).
  • 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.
  • ⁇ ⁇ ⁇ ((a value before treatment, a value after treatment) 2 + (HI before treatment b value after treatment 1) 2 )
  • 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.
  • micro defects measure the number of defects with a size of 300 ⁇ m or more per 100 m 2 and rank them according to the following criteria.
  • wavelength selective absorption filter 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
  • 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.
  • ⁇ There are peeled cells, but the peeled cells are less than 10 cells.
  • 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.
  • 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%.
  • 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 ⁇ m to prepare a coating solution.
  • 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 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
  • Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.
  • 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.
  • 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 ⁇ m to prepare a coating solution C.
  • 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
  • Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.
  • 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.
  • a coating solution D 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 ⁇ m to prepare a coating solution D.
  • 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.
  • 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.
  • 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 ⁇ m to prepare a coating liquid tank.
  • 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
  • Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.
  • the coating solution G was prepared by removing undissolved substances with a filter having a nominal filtration accuracy of 1 ⁇ .
  • the coating liquid F was dried at 950 nm.
  • 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.
  • 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.
  • 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 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
  • Tables 2 and 3 show the physical properties of the obtained wavelength selective absorption filter.
  • 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.

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Abstract

La présente invention a trait à un filtre optique à absorption en sélection de longueurs d'onde présentant une large absorption de niveau élevé dans la région de proche infrarouge, également d'absorption de néon, et présentant un facteur de transmission élevé dans l'autre région de la lumière visible. Le filtre optique à absorption en sélection de longueurs d'onde est moins susceptible d'entraîner une modification dans les propriétés optiques avec l'écoulement du temps et est extrêmement durable. Le filtre optique à absorption en sélection de longueurs d'onde comporte un matériau de base transparent et une couche d'absorption en sélection de longueurs d'onde présentant une structure monocouche ou multicouche superposée au matériau de base. Le couche d'absorption en sélection de longueurs d'onde comporte une résine, une substance colorante d'absorption de proche infrarouge (A) et un matière colorante (B), et le filtre optique à absorption en sélection de longueurs d'onde présente une absorption maximale à une longueur d'onde de 800 à 1200 nm et une longueur d'onde de 550 à 620 nm. Le filtre optique à absorption en sélection de longueurs d'onde se caractérise en ce qu'un type de la matière colorante d'absorption de proche infrarouge (A) est une matière colorante à base de diimmonium aromatique (a) dont le contre-ion est l'acide bis(trifluorométhansulphonyl) imidique, et un type de la matière colorante (B) est une matière colorante à base de porphyrine ou une matière colorant à base d'azaporphyrine (b).
PCT/JP2005/023728 2004-12-28 2005-12-26 Filtre optique a absorption en selection de longueurs d'onde Ceased WO2006070717A1 (fr)

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WO2014168190A1 (fr) * 2013-04-10 2014-10-16 旭硝子株式会社 Filtre de balayage infrarouge, élément d'imagerie à semi-conducteur, et dispositif d'imagerie/affichage
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CN103858028A (zh) * 2011-10-14 2014-06-11 Jsr株式会社 滤光器及使用该滤光器的固体摄影装置及照相机模块
JPWO2013054864A1 (ja) * 2011-10-14 2015-03-30 Jsr株式会社 光学フィルターならびに該光学フィルターを用いた固体撮像装置およびカメラモジュール
CN103858028B (zh) * 2011-10-14 2016-12-28 Jsr株式会社 固体摄影装置用滤光器及使用该滤光器的固体摄影装置及照相机模块
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CN100495082C (zh) 2009-06-03
TWI296650B (en) 2008-05-11
TW200630470A (en) 2006-09-01
KR100761646B1 (ko) 2007-09-27
CN101076746A (zh) 2007-11-21

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