WO1997046897A1 - Filtre pdp et dispositif pdp - Google Patents

Filtre pdp et dispositif pdp Download PDF

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Publication number
WO1997046897A1
WO1997046897A1 PCT/JP1997/001662 JP9701662W WO9746897A1 WO 1997046897 A1 WO1997046897 A1 WO 1997046897A1 JP 9701662 W JP9701662 W JP 9701662W WO 9746897 A1 WO9746897 A1 WO 9746897A1
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WO
WIPO (PCT)
Prior art keywords
filter
infrared absorbing
pdp
infrared
monomer
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/JP1997/001662
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English (en)
Japanese (ja)
Inventor
Masuhiro Shouji
Hiroki Katono
Yoshinobu Itoh
Takeo Ogihara
Teruo Sakagami
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.)
Kureha Corp
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Kureha Corp
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 Kureha Corp filed Critical Kureha Corp
Publication of WO1997046897A1 publication Critical patent/WO1997046897A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/44—Optical arrangements or shielding arrangements, e.g. filters, black matrices, light reflecting means or electromagnetic shielding means

Definitions

  • Tn near-infrared transmittance
  • the transparent substrate is composed of a phosphoric acid group-containing monomer It must contain a copolymer obtained by copolymerizing a single-part composition composed of compatible monomers, and a metal ionizable component containing divalent copper ions as a main component. Is preferred.
  • the phosphate group-containing monomer represented by the above formula (Formula 1) has a phosphate group capable of binding to a copper ion described later in a molecular structure.
  • a copolymer holding a copper ion via a phosphate group has a characteristic light absorption characteristic in the near infrared region.
  • an acryloyloxy group or a mesyacryloyloxy group, which is a radically polymerizable functional group is bonded via an ethylene oxide group.
  • the phosphoric acid group-containing monomer is extremely copolymerizable, and can be copolymerized with various monomers.
  • R represents an acryloyloxy group (X is a hydrogen atom) to which an ethylene oxide group is bonded or a methyl acryloyloxy group.
  • (X is a methyl group).
  • the number m of repeating ethylene oxide groups is preferably an integer of 1 to 5. When the value of m exceeds 5, the hardness of the obtained copolymer tends to decrease, and the practicality as an optical filter may be reduced.
  • the molding method of the optical filter is not limited to these.
  • the monomer for obtaining the copolymer preferably contains, in addition to the phosphate group-containing monomer (Formula 1), usually another copolymerizable monomer.
  • the copolymer obtained by copolymerizing the phosphoric acid group-containing monomer (Chemical Formula 1) with the copolymerizable monomer has low hygroscopicity, satisfies the hardness conditions required for optical filters, Also excellent in shape retention. Therefore, when such a copolymer is used, the performance as an optical filter can be improved.
  • Such a copolymerizable monomer is uniformly dissolved and mixed with (1) a phosphoric acid group-containing monomer (I) and (2) a phosphoric acid group-containing monomer (Chem. 1). It is not particularly limited as long as it has good radical copolymerizability and (3) gives an optically transparent copolymer.
  • copolymerizable monomer examples include methyl acrylate, methyl methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, and n-propyl methacrylate.
  • the ratio of the phosphoric acid group-containing monomer (Formula 1) to the above-mentioned copolymerizable monomer is as follows.
  • the phosphoric acid group-containing monomer: the copolymerizable monomer (mass) is in the range of 3:97 to 90:10, and more preferably in the range of 10:90 to 80:20. Preferably, there is. If the ratio of the phosphoric acid group-containing monomer is less than 3% based on the “mass of the phosphoric acid group-containing monomer and the copolymerizable monomer”, light absorption characteristics suitable as an optical filter Expression becomes difficult. On the other hand, if this ratio exceeds 90%, the obtained copolymer tends to be flexible, and it is difficult to satisfy the hardness condition required for the filter.
  • copper salts can be used as the copper salt that constitutes the metal salt described above. More specifically, examples thereof include anhydrides and hydrates such as copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetate, copper pyrophosphate, copper naphthenate, and copper citrate. However, it is not limited only to these copper salts. Further, as the “other metal” constituting the above metal salt, a metal salt containing sodium, potassium, calcium, iron, manganese, cobalt, magnesium, nickel, or the like as a metal component can be appropriately used according to the purpose. It is.
  • a method in which metal ions are added to and mixed with the mixed monomer before radical polymerization of the mixed monomer is performed. According to this method, a metal mixture containing the metal ion, a phosphate group-containing monomer (Chemical Formula 1) and a copolymerizable monomer is prepared, and the monomer mixture is subjected to radical polymerization. Polymerize.
  • the step of extracting and removing the acid component can be performed at any stage of the optical filter manufacturing process, before or after the radical polymerization.
  • a monomer mixture is prepared by mixing a mixed monomer comprising a phosphate group-containing monomer and a copolymerizable monomer with a metal salt mainly containing copper ions.
  • a stage before radical polymerization is performed, (2) a stage in which the radical polymerization of the above monomer mixture has been completed, and an optical filter material has been obtained, (3) a stage in which the optical filter material has been formed, and the like. It can be implemented at any stage.
  • the step of extracting and removing the acid component may be performed after the completion of the molding process.
  • the acid component a to be removed in the acid component extraction and removal step is preferably at least 30 (mass)%, more preferably at least 45%, based on the amount of the acid component of the metal salt used.
  • the removal amount of such an acid component can be determined, for example, by quantifying the eluted component in the solvent by an ordinary analytical method such as liquid chromatography, gas chromatography, or titration of an acid equivalent.
  • Bleed hardly occurs on the surface of the filter even when used in a high humidity atmosphere.
  • the molded article is washed with water and dried as necessary to remove the residual solvent used in the extraction, and the surface smoothness of the optical filter is reduced.
  • a step of subjecting the molded product to heat and pressure treatment may be performed in order to prevent the molded product.
  • copper ions are dispersed in a polymer using a phosphoric acid group-containing monomer having a polymerizable functional group, but copper ions are dispersed in a polymer without using such a monomer. It is also possible to disperse them inside. In the latter embodiment, from the viewpoint of dispersibility of copper ions, it is preferable to use a phosphate compound (phosphate ester, phosphonate ester) having no polymerizable functional group as shown below.
  • the phosphate ester used in such an embodiment is preferably represented by the following formula (Formula 2). (Formula 2)
  • Phosphate diisopropyl phosphate, mono-n-butyl phosphate, di-n-butyl phosphate, monobutoxetyl phosphate, dibutoxyshethyl phosphate, mono (2-ethylhexyl) phosphate, di ( 2-ethylhexyl) phosphate, mono-n-decyl phosphate, di-n-decyl phosphate, mono-isodecyl phosphate, di-isodecyl phosphate, mono-oleyl phosphate, di-oleyl phosphate, mono-iso Stearyl phosphate, diisostearyl phosphate Hue Ichito, Monofue two Rufosufue one Bok include diphenyl phosphine off We over preparative like.
  • the resin component to be used in combination with the phosphate compound is preferably an acryl-based resin.
  • the monomer constituting the acryl-based resin include n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (methyl) acrylate, and 2-ethylhexyl (meth) acrylate.
  • (Meth) acrylate, methyl (meth) acrylate, and the like may be used as long as the solubility of the copper complex is not inhibited. Further, in addition to these monomers, methoxy r-yl (meth. Acrylate), ethoxyxetil (meth- yl) acrylate, phenoxyshethyl (meth) acrylate, and the like can also be used. Since all of the above-mentioned monomers are monofunctional mono-S-isomers, the resin obtained by polymerizing the ⁇ -mer selected from these is a thermoplastic type.
  • the transparent substrate constituting the optical filter is made of a polymer containing copper ions.
  • near-infrared absorption is performed instead of or together with copper ions.
  • a dye may be contained in the transparent substrate.
  • These dyes or compounds have a thickness of about 0.01% to 10% when the thickness of the filler is 0.005 to 0.1 mm and the thickness of the filler is based on the weight of the resin component. When the thickness exceeds 0.1 mm and is equal to or less than 20 mm, it is preferable to use a ratio of about 0.001 to 0.1%.
  • an infrared absorbing agent comprising a phenylenediamine derivative represented by the following formula (Formula 4) can be particularly preferably used.
  • Such infrared absorbers exhibit good infrared absorption properties in the wavelength range from about 900 to 1000 nm. (Formula 4)
  • phenylenediamine derivative (I-Dani 4) include N, N, N ', N'-tetrakis (p-di-n-butylaminophenyl) -p-benzoquinone-bis
  • the above-mentioned metal oxide is preferably composed mainly of indium oxide and / or tin oxide from the viewpoint of non-transmission of infrared rays.
  • the use of such a metal oxide is particularly effective in increasing the cutting effect in the infrared region of 1200 nm or more.
  • the gold oxide contains indium oxide as a main component, the-part of the indium atom in the indium oxide is replaced with a tin atom, and further, oxygen vacancies are introduced to increase the carrier electron density in the indium oxide.
  • It is preferably a composite oxide of indium oxide and tin oxide (IT ⁇ , Indium Tin Oxide).
  • the gold oxide is mainly composed of tin oxide, some of the tin atoms in the tin oxide are replaced by antimony atoms, and oxygen defects are introduced to increase the carrier electron density in the tin oxide. Further, it is preferably a composite oxide of tin oxide and antimony oxide (AT 0, Antimony Tin Oxide).
  • the binder in the dispersion type film is not particularly limited as long as it is a synthetic resin having a large light transmittance in a visible light region, that is, an excellent transparency. More specifically, for example, acrylic resin, vinyl chloride resin, styrene resin, polyurethane resin, melamine resin, epoxy resin, polyester resin, polyamide resin, fluororesin, silicone resin, cellulose resin, polyvinyl resin A thermoplastic resin such as an alcohol-based resin, or a thermosetting resin or a photocurable resin can be used.
  • the metal oxide When the metal oxide is contained in the transparent substrate, its content is preferably 0.1 to 98%, more preferably 1 to 98%.
  • the amount of the metal oxide is as large as possible as long as the adhesion of the dispersion-type film to the transparent substrate, the transparency and mechanical properties of the dispersion-type film itself are not substantially impaired. More preferably, it is preferably 30 to 98%, more preferably 50 to 95% by mass in the dispersion type membrane.
  • the above-mentioned deposition type film deposits the above metal oxide directly on the surface of the transparent substrate.
  • the thickness of this deposition type film is 0.01 to 10 m, and further 0.05 to 1 / m. It is preferred that
  • this discharge cell 10 is composed of a pair of opposing electrodes (a cathode 1 la serving as a transparent electrode and an anode 1). lb) is inserted therein, and gas (not shown) is sealed between the pair of electrodes 1 la and 1 lb.
  • the phosphor 12 in the case of a color PDP
  • the cathodes 1 la and 11 b are exposed to the discharge space.
  • the cathode electrode 11 a is disposed on a front (visible light transmitting side) glass 13, while the electrode 11 b is disposed on a rear glass 14.
  • the optical filter of the present invention that is, at least a transparent substrate made of a polymer containing divalent copper ions and / or a near-infrared absorbing dye is included, and the visible light transmittance ( A filter (not shown) having a ratio ( ⁇ / ⁇ ) between Tv) and 800-: near infrared transmittance (Tn) of L 000 nm is 3 or more is arranged on the surface glass 13.
  • the gas to be filled in the PD ⁇ discharge cell can be appropriately selected from publicly known PD ⁇ ⁇ ⁇ ⁇ gas (combination of two or more if necessary), but from the viewpoint of stability during discharge.
  • Noble gases He, Ne, Ar, Kr, Xe, etc.
  • Two or more types can be used in combination.
  • Ne, Ne—Ar, Ne-Xe for monochromatic PDPs
  • Ne-Xe for i-color PDPs
  • He— for multicolor or full-color PDPs X e can be suitably used.
  • a mixed gas containing xenon such as He—Xe or Ne—Xe can be particularly preferably used from the viewpoint of matching with the permeability of the filter.
  • Fig. 5 shows an example of the emission characteristics of Xe gas (xenon 'in a short arc lamp). As shown in Figure 5, xenon gives emission spectra at 500 nm, 840 nm, 920 nm, and 930 nm.
  • the filling gas pressure is not particularly limited.
  • the gas pressure may vary slightly depending on the electrode spacing of the panel, but usually about 200 to 600 torr (more about 200 to 300 torr) for AC type PDP, and about 100 to 600 torr for DC type PDP (more Is about 200 to 300 torr), and a pressure of about several orr is suitably used in the plasma cathode.
  • a monolithic composition comprising
  • H2C C-CH 3 O
  • the spectral transmittance of the film substrate obtained above was measured using a spectrophotometer (trade name: U-4000, manufactured by Hitachi, Ltd.). Based on this measurement data, the visible light transmittance Tv (Equation 1) and the near-infrared light transmittance ( ⁇ ) were calculated by the above-described definitions, and the ⁇ / ⁇ ratio was obtained. The results obtained by the calculation are shown below (Table 2).
  • the Tv / Tn ratio of the film substrate obtained above was determined in the same manner as in Example 1. The results obtained are summarized in the above (Table 2).
  • t-BuMMA chilume acrylate
  • MMA methyl methacrylate
  • DEHAP methyl methacrylate
  • CA anhydrous copper acetate
  • IE combined thickness of 7 A filter-substrate was obtained in the same manner as in Example 7, except that mm was used.
  • the polymer thus obtained was thermoplastic.
  • MONO 2-ethylhexyl 2-ethylhexylphosphonate (trade name: PC-88A, manufactured by Daihachi Chemical Co., Ltd.) 612 parts, 181 parts of anhydrous copper acetate, and 100 parts of toluene are sufficiently mixed and stirred at 80 ° C. Then, anhydrous copper acetate was completely dissolved in PC88A.
  • a monomer composition (t-butyl methacrylate) was prepared using 55 parts of t-butyl methyl acrylate (t-BuMMA), 45 parts of methyl methacrylate (MMA), and 5 parts of PC88A-Cu used in Example 7.
  • a filter substrate was obtained in the same manner as in Example 7 except that 2.0 parts of butyl peroxyvivalate was added; the same as in Example 7), and the thickness of the polymer was changed to 3 mm. .
  • the obtained polymer was thermoplastic.
  • the Tv / Tn value of the filter base obtained as described above was determined in the same manner as in Example 1. The results obtained are summarized below (Table 3).
  • Tv / Tn value of the film substrate obtained above was determined in the same manner as in Example 1. The results obtained are summarized below (3 ⁇ 44).
  • the mixture obtained above was used to obtain a filter-substrate having a thickness of 2 mm using a hot press having a surface temperature of 200 ° C.
  • a metal complex-based near-infrared absorbing dye MIR (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.) was added, followed by stirring and mixing to obtain a divalent compound.
  • a solution was obtained in which copper ions and a near-infrared absorbing dye were dissolved and dispersed in the mixed monomer.
  • the solution thus obtained was polymerized in the same manner as in Example 7 to obtain a plate polymer having a thickness of 3 mm.
  • a filter including at least a transparent substrate made of a polymer containing a near-infrared absorbing component, wherein the near-infrared absorbing component is a divalent copper ion and / or a near-infrared ray.
  • An optical device for a plasma display comprising an absorbing dye, wherein the ratio ( ⁇ / ⁇ ) of the visible light transmittance ( ⁇ ) as a filter to the near infrared transmittance ( ⁇ ) of 800 to 1000 nm is 3 or more. Phil Yuichi is offered.
  • At least one discharge cell having a pair of electrodes facing each other therein, and filling a gas between the pair of electrodes
  • An optical filter disposed on the visible light transmitting side of the discharge cell; and the optical filter contains divalent copper ions and / or a near-infrared absorbing dye.
  • At least one transparent substrate consisting of a transparent polymer; the ratio ( ⁇ / ⁇ ) between the visible light transmittance (Tv) as the filter and the near-infrared transmittance (800 ⁇ ) from 800 to 1000 nm
  • a plasma display device having three or more is provided.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Optical Filters (AREA)

Abstract

Cette invention se rapporte à un filtre PDP et à un dispositif PDP, dont la sécurité concernant la fuite d'ondes électromagnétiques de diverses longueurs d'ondes est encore accrue, tandis que les caractéristiques d'un écran d'affichage au plasma (écran PDP) ne sont pas détériorées. Le filtre optique de l'écran d'affichage à plasma PDP, qui est conçu de sorte que le rapport (Tv/Tn) entre la transmissivité de la lumière visible (Tv) et la transmissivité (Tn) d'un rayonnement dans l'infrarouge proche à des longueurs d'ondes comprises entre 800 et 1000 nm ne soit pas inférieur à 3, est constitué par un substrat transparent (3) fabriqué à base d'un polymère contenant un constituant absorbant l'infrarouge proche composé d'ions de cuivre divalent (1) et un pigment absorbant l'infrarouge proche (2).
PCT/JP1997/001662 1996-06-03 1997-05-16 Filtre pdp et dispositif pdp Ceased WO1997046897A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP14055296 1996-06-03
JP8/140552 1996-06-03

Publications (1)

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WO1997046897A1 true WO1997046897A1 (fr) 1997-12-11

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303634C (zh) * 2002-09-10 2007-03-07 富士通日立等离子显示器股份有限公司 气体放电显示设备
WO2017054779A1 (fr) * 2015-09-30 2017-04-06 Hong Kong Baptist University Dispositif de décalage spectral électromagnétique à base d'un bimatériau nanométrique

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5770146A (en) * 1980-10-17 1982-04-30 Mitsubishi Rayon Co Ltd Methacrylate resin material for optical filter and production thereof
JPH04174402A (ja) * 1990-11-07 1992-06-22 Nippon Hikyumen Lens Kk 赤外線吸収フィルターおよびその製造方法
JPH0542622A (ja) * 1991-08-15 1993-02-23 Japan Carlit Co Ltd:The 光線選択透過性フイルム
JPH05205643A (ja) * 1992-01-24 1993-08-13 Fujitsu Ltd プラズマディスプレイパネル
JPH069818A (ja) * 1992-06-22 1994-01-18 Tokyo Seihin Kaihatsu Kenkyusho:Kk 有機光学材料
JPH06118228A (ja) * 1992-08-20 1994-04-28 Kureha Chem Ind Co Ltd 光学フィルターおよびその製造法
JPH06166708A (ja) * 1992-11-30 1994-06-14 Kuraray Co Ltd 赤外線吸収板およびその製造方法
JPH06194517A (ja) * 1992-12-25 1994-07-15 Mitsui Toatsu Chem Inc 熱線遮断シート
JPH06214113A (ja) * 1993-01-20 1994-08-05 Mitsui Toatsu Chem Inc 近赤外線吸収フィルム及びそれを用いた熱線遮断シート
JPH06222211A (ja) * 1993-01-26 1994-08-12 Kuraray Co Ltd フイルタ−材
JPH0862418A (ja) * 1994-06-16 1996-03-08 Kureha Chem Ind Co Ltd 赤外線非透過性光学フィルター

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5770146A (en) * 1980-10-17 1982-04-30 Mitsubishi Rayon Co Ltd Methacrylate resin material for optical filter and production thereof
JPH04174402A (ja) * 1990-11-07 1992-06-22 Nippon Hikyumen Lens Kk 赤外線吸収フィルターおよびその製造方法
JPH0542622A (ja) * 1991-08-15 1993-02-23 Japan Carlit Co Ltd:The 光線選択透過性フイルム
JPH05205643A (ja) * 1992-01-24 1993-08-13 Fujitsu Ltd プラズマディスプレイパネル
JPH069818A (ja) * 1992-06-22 1994-01-18 Tokyo Seihin Kaihatsu Kenkyusho:Kk 有機光学材料
JPH06118228A (ja) * 1992-08-20 1994-04-28 Kureha Chem Ind Co Ltd 光学フィルターおよびその製造法
JPH06166708A (ja) * 1992-11-30 1994-06-14 Kuraray Co Ltd 赤外線吸収板およびその製造方法
JPH06194517A (ja) * 1992-12-25 1994-07-15 Mitsui Toatsu Chem Inc 熱線遮断シート
JPH06214113A (ja) * 1993-01-20 1994-08-05 Mitsui Toatsu Chem Inc 近赤外線吸収フィルム及びそれを用いた熱線遮断シート
JPH06222211A (ja) * 1993-01-26 1994-08-12 Kuraray Co Ltd フイルタ−材
JPH0862418A (ja) * 1994-06-16 1996-03-08 Kureha Chem Ind Co Ltd 赤外線非透過性光学フィルター

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303634C (zh) * 2002-09-10 2007-03-07 富士通日立等离子显示器股份有限公司 气体放电显示设备
WO2017054779A1 (fr) * 2015-09-30 2017-04-06 Hong Kong Baptist University Dispositif de décalage spectral électromagnétique à base d'un bimatériau nanométrique

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