WO1999027397A1 - Optical filter, and device, heat-ray absorbing filter, optical fiber and eye-glasses each provided with the optical filter - Google Patents

Optical filter, and device, heat-ray absorbing filter, optical fiber and eye-glasses each provided with the optical filter Download PDF

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Publication number
WO1999027397A1
WO1999027397A1 PCT/JP1998/005201 JP9805201W WO9927397A1 WO 1999027397 A1 WO1999027397 A1 WO 1999027397A1 JP 9805201 W JP9805201 W JP 9805201W WO 9927397 A1 WO9927397 A1 WO 9927397A1
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WIPO (PCT)
Prior art keywords
optical filter
monomer
filter according
optical
filter
Prior art date
Application number
PCT/JP1998/005201
Other languages
French (fr)
Japanese (ja)
Inventor
Hiroki Katono
Naoki Hayashi
Tomoyoshi Koizumi
Katsuichi Machida
Original Assignee
Kureha Kagaku Kogyo Kabushiki Kaisha
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Application filed by Kureha Kagaku Kogyo Kabushiki Kaisha filed Critical Kureha Kagaku Kogyo Kabushiki Kaisha
Publication of WO1999027397A1 publication Critical patent/WO1999027397A1/en

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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters

Definitions

  • the present invention relates to an optical filter and an application device thereof, and more particularly, to an optical filter made of a synthetic resin excellent in moisture resistance and water resistance, which efficiently cuts light in the near infrared region, and the optical filter Devices related to filters (cameras, CCD imagers, CMOS image sensors, artificial retinas, infrared communication environment maintenance devices, plasma display devices), heat ray absorption filters, optical fibers, and spectacle lenses.
  • filters cameras, CCD imagers, CMOS image sensors, artificial retinas, infrared communication environment maintenance devices, plasma display devices
  • heat ray absorption filters optical fibers
  • spectacle lenses spectacle lenses
  • a photometric filter visibility correction filter
  • a glass-made optical filter that contains copper ion in a special phosphoric acid-based glass has been used.
  • Optical filters made of glass have also been used as filters for plasma display panels (PDPs).
  • glass optical filters are heavy, for example, the weight of an optical filter for a large PDP exceeds 10 kg.
  • glass optical filters have a manufacturing problem that processing such as molding, cutting, and polishing is difficult.
  • the glass optical filter has a large hygroscopic property (water absorbency), and has a problem that a whitening / devitrification phenomenon easily occurs with time.
  • the present inventors have proposed a synthetic resin containing a resin component having a phosphate group and an ionizable metal component containing copper ions as a main component. (Refer to Japanese Patent Application Laid-Open Nos. 4-224585, 5-82527, and 8-344949). ).
  • the optical filter is light, easy to process, excellent in productivity, and low in hygroscopicity (water absorption).
  • optical filters used in high-humidity environments are required to have even better moisture resistance (low moisture absorption) and water resistance (low water absorption). Disclosure of the invention
  • the present invention has been made based on the above circumstances.
  • a first object of the present invention is to efficiently emit light in the near-infrared region (700 to 100 nm), to be lightweight, and to facilitate processing such as molding, cutting, and polishing.
  • An object of the present invention is to provide an optical filter made of a synthetic resin.
  • a second object of the present invention is to provide an optical filter made of a base resin that is more excellent in moisture resistance and water resistance than conventionally known optical filters.
  • a third object of the present invention is to provide a force meter including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for a light receiving element.
  • a fourth object of the present invention is to provide an imaging device including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a luminosity filter for a CCD. It is in.
  • a fifth object of the present invention is to provide an imaging device having an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for a CMOS image sensor.
  • a sixth object of the present invention is to provide an imaging device comprising an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for an artificial retina. It is in.
  • a seventh object of the present invention is to provide an infrared communication environment maintenance device including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a noise cut filter.
  • An eighth object of the present invention is to provide a plasma display device in which an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance is arranged on the front surface of a panel.
  • a ninth object of the present invention is to provide a heat ray absorbing filter excellent in near-infrared absorption characteristics, moisture resistance and water resistance.
  • a tenth object of the present invention is to provide an optical fiber that is excellent in near-infrared absorption characteristics, moisture resistance and water resistance.
  • a first object of the present invention is to provide a spectacle lens having excellent near-infrared absorption characteristics (effect of suppressing the onset of cataract), moisture resistance, and water resistance.
  • the optical filter of the present invention includes a monomer represented by the following general formula (hereinafter, also referred to as a “specific phosphoric acid group-containing monomer”) and a monomer copolymerizable therewith (hereinafter, referred to as “specific phosphoric acid group-containing monomer”). And a “copolymerizable monomer.”
  • a resin component obtained by copolymerizing a mixed monomer comprising: a) an ionic metal component mainly containing copper ions dissolved in the resin component; It is characterized by containing.
  • the camera of the present invention is characterized in that the above optical filter (the optical filter of the present invention) is mounted as a visibility correction filter for a light receiving element.
  • the imaging device of the present invention is characterized in that the above optical filter (: the optical filter of the present invention) is mounted as a visibility correction filter for a CCD, a CMOS image sensor, and an artificial retina. I do.
  • An infrared communication environment maintenance device according to the present invention is characterized in that the optical filter (optical filter according to the present invention) is used as a noise cut filter. Is characterized in that the above-mentioned optical filter (the optical filter of the present invention) is arranged on the front surface of the panel.
  • a heat ray absorption filter of the present invention is characterized by comprising the above optical filter (optical filter of the present invention).
  • the optical fiber of the present invention is characterized by comprising the above-mentioned optical filter (the optical filter of the present invention).
  • the optical fiber of the present invention is characterized in that the above-mentioned optical filter (the optical filter of the present invention) is provided in a lighting part.
  • a spectacle lens of the present invention is characterized by comprising the above optical filter (the optical filter of the present invention).
  • the optical filter of the present invention contains copper ion as a main component in a resin component that is a copolymer of a mixed monomer composed of a specific phosphoric acid group-containing monomer and a copolymerizable monomer.
  • the optical filter of the present invention is a synthetic resin optical filter to which an ionic metal component is added and contained.
  • the resin component constituting the optical filter is a hydrophobic high-purity resin. It is characterized by being synthesized using an acid group-containing monomer (specific phosphoric acid group-containing monomer).
  • a specific phosphoric acid group-containing monomer is used as an essential component.
  • the specific phosphoric acid group-containing monomer has a phosphoric acid group capable of binding to a copper ion described later in a molecular structure, and the obtained resin component has an ionic metal component as a component. Solubility can be imparted. Then, the copolymer holding copper ions via the phosphoric acid group has a characteristic light absorption characteristic in the near infrared region.
  • the “phosphoric acid group” means a group represented by “P 0 (OH) n —” (n is 1 or 2).
  • the carbon number ( ⁇ ) of the alkylene oxide group in the specific phosphoric acid group-containing monomer is from 3 to 18, preferably from 3 to 6.
  • the phosphoric acid group-containing monomer exhibits high hydrophobicity.
  • the resulting copolymer (and finally the obtained copolymer) Moisture resistance and water resistance of the optical filter can be improved; and when the carbon number ( ⁇ ) is as strong as 18 or less, the phosphoric acid group-containing monomer is copolymerizable.
  • the compatibility with the monomer is improved, and the obtained copolymer (and finally the obtained optical filter) has sufficient mechanical strength.
  • the number of repetitions (m) of the alkylene oxide group is an integer of 1 to 10.
  • the number (n) of hydroxyl groups may be selected from 1 or 2 depending on the molding method of the optical filter and the purpose of use.
  • n 2
  • the specific phosphoric acid group-containing monomer in which the number of radically polymerizable functional groups bonded to the phosphorus atom is 1 has a high bondability with copper ions. It becomes
  • the value of n depends on the performance of the optical filter, the molding method and the purpose of use. Although it can be selected, it is preferable to use a specific phosphoric acid group-containing monomer having a value of n of 1 and a specific phosphoric acid group-containing monomer having a value of n of 2 in combination.
  • a copper salt (optical filter) for the mixed monomer is used. This is preferable because the solubility of the salt used to introduce copper ions into the filter is improved.
  • the mixed monomer for obtaining the resin component contains a copolymerizable monomer together with the specific phosphoric acid group-containing monomer.
  • a copolymer obtained by copolymerization of a specific phosphoric acid group-containing monomer and a copolymerizable monomer has low hygroscopicity and satisfies the hardness conditions required for an optical filter. According to such a copolymer, a molded article having excellent shape retention can be obtained.
  • Such a copolymerizable monomer is (1) uniformly dissolved and mixed with a specific phosphoric acid group-containing monomer, and (2) a radical copolymerizable monomer with the specific phosphoric acid group-containing monomer. Is not particularly limited as long as it satisfies (3) that an optically transparent copolymer is obtained.
  • these copolymerizable monomers include monofunctional acrylates and monofunctional methacrylates (eg, methyl acrylate, methyl methacrylate, ethyl acrylate). Rate, ethyl acrylate, n -propyl acrylate, n-propyl acrylate, n-ethyl acrylate, 11 butyl acrylate, isobutyl acrylate Alkyl acrylates and alkyl methacrylates such as isobutyl methacrylate, 1] hexyl methacrylate, n hexyl methacrylate, n-year-old methyl acrylate, and n-year-old octyl methacrylate Rate, glycidyl acrylate, glycidyl acrylate, 2 hydroxyl acrylate, 2 hydroxyl acrylate, 2 Modified alkyl acrylates, such as hydroxypropyl acrylate, 2 hydroxypropyl acrylate
  • Polyfunctional acrylates or polyfunctional maleates eg, ethylene glycol Ruglycerate, ethylene glycol dichloride, diethylene glycol dichlorate, diethylene glycol dichlorate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol Lengglycol glycolate, polypropylene glycol glycolate, 1,3 butylene glycol glycolate, 1,3 butylene glycol glycolate, 1,4 butanediol glycolate, 1,4 butanediol glycolate 1,4 Butanediol dimethacrylate, 1,6 Hexanediol dimethacrylate, 1,6 Hexanediol dimethacrylate, Neopentyl glycol diacrylate, Neopentyl glycol dimethacrylate Crylate, 2 hydroxy 1, 3 Dimethacryloxypropane, 2,2 bis [4--(metacryloxyethoxy) phenyl] propane, 2 hydroxy 1 acryloxy 3 metaroxylprop
  • Carboxylic acids such as acrylic acid, methacrylic acid, 2-methyl chloroyloxetyl succinic acid, 2 methacryloyl oxethyl phthalic acid, styrene, a-methylstyrene, chlorostyrene
  • aromatic vinyl compounds such as dibromostyrene, methoxystyrene, divinylbenzene, vinylbenzoic acid, hydroxymethylstyrene, and trivinylbenzene.
  • These compounds may be used alone or in combination of two or more to form a copolymerizable monomer.
  • the ratio of a specific phosphoric acid group-containing monomer to a copolymerizable monomer in a mixed monomer for obtaining a resin component is determined as follows: “Specific phosphoric acid group-containing monomer: copolymerization” It is preferable that the "active monomer (weight)" is in the range of 3:97 to 80:20.
  • the copolymer as a resin component is obtained by radical polymerization of a mixed monomer composed of a specific phosphoric acid group-containing monomer and a copolymerizable monomer.
  • the radical polymerization method is not particularly limited, and a known radical polymerization initiator, such as a bulk (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, or a solution polymerization method, may be used. A method can be used.
  • the optical filter of the present invention comprises the above resin component and an ionic metal component containing copper ions as a main component.
  • the ionic metal component has a function of efficiently absorbing light having a wavelength in the near-infrared region due to interaction with a phosphate group contained in the resin component.
  • the ratio of copper ions to all ionic metal components is 80% by weight or more.
  • the copper salt for introducing copper ion into the optical filter various ones can be used. Examples thereof include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, and the like. Examples include anhydrides and hydrates such as copper ethyl acetate, copper pyrrolinate, copper naphthenate, and copper citrate ( ). However, the compounds are not limited to these compounds.
  • sodium, potassium, potassium, iron, manganese, cobalt, magnesium, nickel, and the like can be used as the ionizable metal component depending on the purpose of other metals.
  • the content ratio of the ionizable metal component containing copper ion as a main component is 0.1 to 25 parts by weight based on 100 parts by weight of the copolymer as the resin component. Preferably, it is 0.2 to 20 parts by weight. If this proportion is less than 0.1 part by weight, it is not possible to efficiently absorb light in the near infrared region, while if it exceeds 25 parts by weight, the metal salt (optical filter) will not be absorbed. Le evening First, a salt used to introduce an ionic metal component) is difficult to be uniformly dispersed in a mixed monomer or copolymer.
  • the content of copper ions in the optical filter of the present invention is preferably 0.1 to 20 parts by weight, more preferably 1.0 to 100 parts by weight, based on 100 parts by weight of the copolymer. To 10 parts by weight.
  • the method for incorporating the ionizable metal component containing copper ions as the main component into the copolymer is not particularly limited, but preferred methods include the following two methods. .
  • the method includes the step of including the metal salt by this method to form a monomer mixture comprising the metal salt, a specific monomer having a phosphoric acid group, and a copolymerizable monomer, and subjecting the monomer mixture to radical polymerization.
  • a copolymer (optical filter material) containing the ionic metal component is obtained.
  • This optical filter material can be used as an optical filter as it is or by being formed into a desired shape.
  • a method for adding the metal salt a method in which the copolymer is heated and melted, a method in which the copolymer is dissolved in an organic solvent, and a method in which the copolymer is added to the solution are used. it can.
  • an optical filter material containing an ionic metal component containing copper ion as a main component can be obtained.
  • the optical filter of the present invention can be manufactured by molding and polishing this optical filter material into a plate-like, column-like, lens-like, or the like shape depending on the purpose and application.
  • the optical filter of the present invention manufactured in this way can efficiently cut light in the near infrared region, and is much lighter than glass. It is. Furthermore, the optical filter of the present invention has better moisture resistance and water resistance than conventionally known optical filters, and exhibits whitening and devitrification phenomena with time even when used in a high-temperature / high-humidity environment. It is unlikely to occur.
  • the optical filter of the present invention can be suitably used as a visibility correction filter for a light receiving element (for example, a photoelectric conversion element composed of a silicon photodiode) in a photometry unit of a camera. .
  • the “visibility correction filter” composed of the optical filter of the present invention includes a visibility correction filter that is arranged alone in the optical path to the light receiving element, as well as a converging lens and the like. Shall be included
  • the light incident on the light receiving element can be substantially limited to light in the visible region.
  • an accurate photometry exposure operation
  • the optical filter of the present invention is a luminous efficiency correction for a CCD (for example, a photoelectric conversion element composed of a silicon photodiode) in an imaging device. It can be suitably used as a filter.
  • the “visibility correction filter” composed of the optical filter of the present invention includes a visibility correction filter that is independently arranged in the optical path to the CCD, as well as a lit, a lens, and a luminosity correction filter. It shall include a protection plate and the like.
  • Examples of the imaging device equipped with a CCD include a video camera, a digital camera, a board camera, a color scanner, a color facsimile, a color copier, and a color videophone device.
  • the imaging device equipped with the optical filter of the present invention human light to a CCD (silicon comfort diode) is substantially limited to light in a visible region.
  • accurate photometry exposure operation
  • the reproduction of the red component and the color balance are not hindered.
  • the imaging device include a CMOS image sensor and an artificial retina.
  • the optical filter of the present invention By mounting the optical filter of the present invention on these imaging devices, the above-described CC can be used.
  • the optical filter of the present invention can be suitably used as a noise cut filter in an environment where an infrared communication device (850-!) Is a communication device using 50 nm light as a medium.
  • a source of near-infrared rays for example, an automatic door or a remote controller
  • a “noise cut filter” comprising the optical filter of the present invention, and communication is performed by blocking infrared rays from the source. Generation of noise in the interior can be reliably prevented.
  • the optical filter of the present invention on the front surface of the panel of the plasma display device, it is possible to efficiently cut the near infrared rays emitted from the panel. As a result, a malfunction of the remote controller due to near infrared rays does not occur around the plasma display device.
  • the optical filter of the present invention can be combined with other functional filters, for example, a filter having electromagnetic wave shielding, antireflection, contamination prevention, etc., to provide a more practical plasma display.
  • a filter having electromagnetic wave shielding, antireflection, contamination prevention, etc. can be used as a filter.
  • the optical filter of the present invention is a heat ray absorbing filter, specifically, a window material of a building such as a house or a building, a window material of a car or a train, a translucent member of a greenhouse, or a lighting device. It can be suitably used as a cover or the like.
  • the optical filter of the present invention can be suitably used as a constituent material of an optical fiber. Further, the optical filter of the present invention may be provided in a lighting part of an optical fiber.
  • the optical filter of the present invention can be suitably used as a spectacle lens. According to such a spectacle lens (the spectacle lens of the present invention), it is possible to protect the eyes from heat rays and near infrared rays which cause cataracts.
  • BEST MODE FOR CARRYING OUT THE INVENTION hereinafter, examples of the present invention will be described. ⁇ The present invention is not limited to these.
  • parts means “parts by weight”.
  • Example 2 Using the monomer mixture prepared as described above, casting polymerization was carried out in the same manner as in Example 1 to obtain an optical filter (1 mm thick) comprising a cross-linked polymer containing copper ion.
  • the optical filter of the present invention was obtained.
  • the specific gravity of this optical filter was as low as 1.25, and the refractive index was 1.501.
  • a phosphate group-containing monomer represented by the following formula (ill) [hereinafter also referred to as “monomer (d)”.
  • Example 2 Using the monomer mixture prepared as described above, cast polymerization was performed in the same manner as in Example 1 to obtain an optical filter having a thickness of 1 mm consisting of a cross-linked polymer containing copper ion. A filter (optical filter for comparison) was obtained. The specific gravity of this optical filter was as low as 1.28, and the refractive index was 1.510.
  • each of the optical filters was prepared.
  • the water absorption was measured when immersed in water at 123 "C for 24 hours .
  • Table 1 shows the results of evaluation of the occurrence of whitening and devitrification after standing.
  • the water absorption (9) was obtained from the weight w, (g) before or after immersion or before immersion and the weight (g) after immersion or after immersion according to the following equation (
  • the optical filters obtained in Examples 1 and 2 have lower water absorption than the optical filters obtained in Comparative Example 1, and are excellent in water resistance and moisture resistance. It is understood that there is.
  • a spectral transmittance curve (: 250 to 100 nm) was measured using a spectrophotometer.
  • the optical filter of the present invention comprises a resin component which is a copolymer of a specific monomer containing a phosphoric acid group and a copolymerizable monomer comprising a copolymerizable monomer. Since the resin component contains an ionizable metal component containing copper ions as a main component dispersed therein, the wavelength in the near-infrared region can be efficiently applied. Further, the weight is sufficiently reduced. It is easy to process such as forming, cutting and polishing, and has excellent productivity.
  • the optical Fi le evening one aspect of the present invention is specific re phospho groups containing monomer in the Al Kirenokisai de group: - number of carbon atoms in (C ⁇ 2 ⁇ ⁇ -) is a 3 to 1 8 As a result, it has sufficient mechanical strength, excellent moisture resistance and water resistance, and is less likely to cause whitening and devitrification over time even when used in a high-temperature, high-humidity environment.
  • the light which injects into a light receiving element can be substantially limited to the light of a visible region, and accurate photometry (exposure operation) can be performed.
  • the imaging device of this invention the light which injects into CCD, CMOS image sensor, and artificial retina can be substantially limited to the light of a visible region, As a result, accurate photometry (exposure operation) can be performed. It has excellent reproducibility, redness and reproducibility.
  • ADVANTAGE OF THE INVENTION According to the infrared communication environment maintenance apparatus of this invention, the noise during communication can be prevented reliably.
  • a malfunction of the remote control due to near infrared rays does not occur around the device.
  • the temperature rise in a room etc. can be suppressed reliably.
  • the optical fiber of the present invention since heat rays (near-infrared rays) are hardly included in the light guided and emitted by the optical fiber, the temperature near the light emission site (in the apparatus-indoor) The rise can be suppressed.
  • an eye can be protected from heat rays and near-infrared rays which are a cause of cataract development.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Optical Filters (AREA)
  • Eyeglasses (AREA)
  • Light Guides In General And Applications Therefor (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Studio Devices (AREA)
  • Blocking Light For Cameras (AREA)

Abstract

An optical filter made from a synthetic resin, capable of shielding the light with a wavelength in the near-infrared region efficiently, being lightweight and easy to work by molding, machining, polishing or the like, and being more excellent than conventional optical filters in moisture and water resistances. The optical filter is characterized by comprising a resin component obtained by copolymerizing a mixture of a monomer represented by general formula (a) and a monomer copolymerizable therewith and an ionic metal component mainly containing copper ions. In said formula R represents the group (b) (wherein X represents hydrogen or methyl; p is an integer of 3 to 18; and m is an integer of 1 to 10), and n is 1 or 2.

Description

明 細 書 光学フィ ル夕一およびこれを備えた装置、 熱線吸収フィ ルター、 光ファイバ 一並びに眼鏡レンズ 技 術 分 野  Description Optical filter Yuichi and equipment equipped with it, heat ray absorption filter, optical fiber and spectacle lens technology
本発明は光学フィ ルターおよびその応用機器等に関し、 さらに詳し く は、 近赤 外領域の波長光を効率よく カツ 卜する、 耐湿性および耐水性に優れた合成樹脂製 の光学フィ ルター、 当該光学フィ ルターを備えてなる装置 (カメラ · C C D撮像 装置 ' C M O S イ メージセンサ · 人工網膜 ·赤外線通信環境整備装置 · プラズマ ディ スプレイ装置) 、 熱線吸収フィ ルター、 光ファイバ一および眼鏡レンズに関 する。 背 景 技 術  The present invention relates to an optical filter and an application device thereof, and more particularly, to an optical filter made of a synthetic resin excellent in moisture resistance and water resistance, which efficiently cuts light in the near infrared region, and the optical filter Devices related to filters (cameras, CCD imagers, CMOS image sensors, artificial retinas, infrared communication environment maintenance devices, plasma display devices), heat ray absorption filters, optical fibers, and spectacle lenses. Background technology
従来、 カ メ ラや C C D撮像装置の測光用フィ ルター (視感度補正用フィ ル夕一 ) と して、 特殊なリ ン酸系ガラスに銅ィォンが含有されたガラス製の光学フィ ル 夕一が用いられてきた,, さ らに、 プラズマディ スプレイバネル ( P D P ) 用のフ ィ ルターとしても、 ガラス製の光学フィ ルターが用いられている,.  Conventionally, as a photometric filter (visibility correction filter) for cameras and CCD imaging devices, a glass-made optical filter that contains copper ion in a special phosphoric acid-based glass has been used. Optical filters made of glass have also been used as filters for plasma display panels (PDPs).
しかし、 これらのガラス製の光学フィ ル夕一は、 重く、 例えば、 大型の P D P 用の光学フィ ルターの重量は 1 0 k gを超えてしまう。 また、 ガラス製の光学フ ィ ルターは、 成形 ·切削 ·研磨等の加工が難しいという製造上の問題があった。 さらに、 ガラス製の光学フィ ルタ一は、 吸湿性 (吸水性) が大きく 、 経時的に 白化 ·失透現象を生じやすいという問題もあった。  However, these glass optical filters are heavy, for example, the weight of an optical filter for a large PDP exceeds 10 kg. In addition, glass optical filters have a manufacturing problem that processing such as molding, cutting, and polishing is difficult. Further, the glass optical filter has a large hygroscopic property (water absorbency), and has a problem that a whitening / devitrification phenomenon easily occurs with time.
上記のような問題を解決するための手段と して、 本発明者らは、 リ ン酸基を含 有する樹脂成分と、 銅イオンを主成分とするィォン性金属成分とを含有する合成 樹脂製の光学フィ ルターを提案している (特開願 4 - 2 4 2 5 8 5号明細書, 同 5 - 8 2 5 2 7号明細書, 同 8 — 3 4 7 4 4 9号明細書参照) 。  As means for solving the above-mentioned problems, the present inventors have proposed a synthetic resin containing a resin component having a phosphate group and an ionizable metal component containing copper ions as a main component. (Refer to Japanese Patent Application Laid-Open Nos. 4-224585, 5-82527, and 8-344949). ).
かかる合成榭脂製の光学フィ ルターによれば、 近赤外線領域の波長光を効率よ く 力ッ 卜することができ、 しかも、 当該光学フィ ルターは、 軽く 、 加工が容易で 生産性に優れ、 吸湿性 (吸水性) が小さいものである。 According to such synthetic resin optical filters, wavelength light in the near-infrared region can be efficiently emitted. The optical filter is light, easy to process, excellent in productivity, and low in hygroscopicity (water absorption).
しかしながら、 高湿度環境などで使用される光学フィ ルターに対しては、 さら に優れた耐湿性 (吸湿性が小さいこと) および耐水性 (吸水性が小さいこと) が 要求されつつある。 発 明 の 開 示  However, optical filters used in high-humidity environments are required to have even better moisture resistance (low moisture absorption) and water resistance (low water absorption). Disclosure of the invention
本発明は、 以上のような事情に基いてなされたものである。  The present invention has been made based on the above circumstances.
本発明の第 1の目的は、 近赤外領域の波長光 ( 7 0 0〜 1 0 0 O n m ) を効率 よく に力 ッ ト し、 軽量で、 成形 · 切削 ·研磨等の加工が容易な合成樹脂製の光学 フィ ルターを提供することにある。  A first object of the present invention is to efficiently emit light in the near-infrared region (700 to 100 nm), to be lightweight, and to facilitate processing such as molding, cutting, and polishing. An object of the present invention is to provide an optical filter made of a synthetic resin.
本発明の第 2の目的は、 従来公知の光学フィ ル夕一より も、 耐湿性および耐水 性に優れた台成樹脂製の光学フィ ルターを提供することにある。  A second object of the present invention is to provide an optical filter made of a base resin that is more excellent in moisture resistance and water resistance than conventionally known optical filters.
本発明の第 3の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ルターを受光素子のための視感度補正フィ ルターと して備えてなる力メ ラ を提供することにある A third object of the present invention is to provide a force meter including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for a light receiving element. Is in
本発明の第 4の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ルターを C C Dのための視感度浦正フ ィ ルターと して備えてなる撮像装置 を提供することにある。  A fourth object of the present invention is to provide an imaging device including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a luminosity filter for a CCD. It is in.
本発明の第 5の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ル夕一を C M O Sィ メ一ジセンサのための視感度補正フィ ル夕一として備 えてなる撮像装置を提供することにある,  A fifth object of the present invention is to provide an imaging device having an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for a CMOS image sensor. In providing equipment,
本発明の第 6の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ルターを人工網膜のための視感度補正フィ ルターと して備えてなる撮像装 置を提供することにある。  A sixth object of the present invention is to provide an imaging device comprising an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a visibility correction filter for an artificial retina. It is in.
本発明の第 7の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ルターをノィズカッ 卜フィ ルターとして備えてなる赤外線通信環境整備装 置を提供することにある。 本発明の第 8の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた光 学フィ ルターをパネル前面に配置してなるプラズマディ スプレイ装置を提供する ことにある。 A seventh object of the present invention is to provide an infrared communication environment maintenance device including an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance as a noise cut filter. An eighth object of the present invention is to provide a plasma display device in which an optical filter having excellent near-infrared absorption characteristics, moisture resistance and water resistance is arranged on the front surface of a panel.
本発明の第 9の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた熱 線吸収フィ ル夕一を提供することにある。  A ninth object of the present invention is to provide a heat ray absorbing filter excellent in near-infrared absorption characteristics, moisture resistance and water resistance.
本発明の第 1 0の目的は、 近赤外線の吸収特性、 耐湿性および耐水性に優れた 光学フアイパ'一を提供することにある。  A tenth object of the present invention is to provide an optical fiber that is excellent in near-infrared absorption characteristics, moisture resistance and water resistance.
本発明の第 1 1 の目的は、 近赤外線の吸収特性 (白内障発症の抑制効果) 、 耐 湿性および耐水性に優れた眼鏡レンズを提供することにある。  A first object of the present invention is to provide a spectacle lens having excellent near-infrared absorption characteristics (effect of suppressing the onset of cataract), moisture resistance, and water resistance.
本発明の光学フィ ルタ一は、 下記一般式で表される単量体 (以下、 「特定のリ ン酸基含有単量体」 ともいう。 ) およびこれと共重合可能な単量体 (以下、 「共 重合性単量体」 ともいう。 ) よりなる混合単量体を共重合して得られる樹脂成分 と、 この樹脂成分に溶解された、 銅イオンを主成分とするイオン性金属成分とを 含有してなることを特徴とする。  The optical filter of the present invention includes a monomer represented by the following general formula (hereinafter, also referred to as a “specific phosphoric acid group-containing monomer”) and a monomer copolymerizable therewith (hereinafter, referred to as “specific phosphoric acid group-containing monomer”). And a “copolymerizable monomer.” A resin component obtained by copolymerizing a mixed monomer comprising: a) an ionic metal component mainly containing copper ions dissolved in the resin component; It is characterized by containing.
P O ( O H) n R 3-n PO (OH) n R 3 - n
〔但し、 Rは
Figure imgf000005_0001
[However, R is
Figure imgf000005_0001
(Xは水素原子またはメチル基を示し、 Pは 3〜1 8の整数であり、 mは!〜 1 0の整数である。) を示し、 nは 1または 2である。 〕 本発明のカメラは、 受光素子のための視感度補正フィ ルターと して、 上記の光 学フィ ルター (本発明の光学フィ ルター) が搭載されていることを特徴とする。 本発明の撮像装置は、 C C D、 C M O Sイメージセンサ、 人工網膜のための視 感度補正フィ ルターと して、 上記の光学フィ ルター (:本発明の光学フィ ルター) が搭載されていることを特徵とする。 本発明の赤外線通信環境整備装置は、 ノイズカ ツ トフィ ル夕一と して、 上記の 光学フィ ルター (本発明の光学フィ ルター) が使用されていることを特徴とする 本発明のプラズマディ スプレイ装置は、 上記の光学フィ ルター (本発明の光学 フィ ルター) がパネル前面に配置されてなることを特徴とする。 (X represents a hydrogen atom or a methyl group, P is an integer of 3 to 18, m is an integer of! To 10), and n is 1 or 2. The camera of the present invention is characterized in that the above optical filter (the optical filter of the present invention) is mounted as a visibility correction filter for a light receiving element. The imaging device of the present invention is characterized in that the above optical filter (: the optical filter of the present invention) is mounted as a visibility correction filter for a CCD, a CMOS image sensor, and an artificial retina. I do. An infrared communication environment maintenance device according to the present invention is characterized in that the optical filter (optical filter according to the present invention) is used as a noise cut filter. Is characterized in that the above-mentioned optical filter (the optical filter of the present invention) is arranged on the front surface of the panel.
本発明の熱線吸収フィ ルタ一は、 上記の光学フ ィ ルター (本発明の光学フィ ル 夕一) からなることを特徴とする。  A heat ray absorption filter of the present invention is characterized by comprising the above optical filter (optical filter of the present invention).
本発明の光ファィバーは、 上記の光学フィ ルター (本発明の光学フィ ル夕一) からなることを特徴とする。  The optical fiber of the present invention is characterized by comprising the above-mentioned optical filter (the optical filter of the present invention).
本発明の光ファイバ一は、 上記の光学フィ ルター (本発明の光学フィ ルター) が採光部に設けられていることを特徴とする。  The optical fiber of the present invention is characterized in that the above-mentioned optical filter (the optical filter of the present invention) is provided in a lighting part.
本発明の眼鏡レンズは、 上記の光学フィ ルター (本発明の光学フィ ルター) か らなることを特徴とする。  A spectacle lens of the present invention is characterized by comprising the above optical filter (the optical filter of the present invention).
以下、 本発明について詳細に説明する。  Hereinafter, the present invention will be described in detail.
本発明の光学フィ ルターは、 特定のリ ン酸基含有単量体および共重合性単量体 よりなる混台単量体の共重台体である榭脂成分中に、 銅ィォンを主成分とするィ オン性金属成分が添加含有されてなる合成樹脂製の光学フィ ルターである. そして、 本発明の光学フ ィ ルタ一は、 これを構成する樹脂成分が、 疎水性の高 ぃリ ン酸基含有単量体 (特定のリ ン酸基含有単量体) を使用して合成される点に 特徴を有するものである。  The optical filter of the present invention contains copper ion as a main component in a resin component that is a copolymer of a mixed monomer composed of a specific phosphoric acid group-containing monomer and a copolymerizable monomer. The optical filter of the present invention is a synthetic resin optical filter to which an ionic metal component is added and contained. The resin component constituting the optical filter is a hydrophobic high-purity resin. It is characterized by being synthesized using an acid group-containing monomer (specific phosphoric acid group-containing monomer).
本発明の光学フィ ルターを構成する樹脂成分を得るための混合単量体には、 必 須成分と して特定のリ ン酸基含有単量体が用いられる。  In the mixed monomer for obtaining the resin component constituting the optical filter of the present invention, a specific phosphoric acid group-containing monomer is used as an essential component.
上記一般式で表すように、 特定のリ ン酸基含有単量体は、 後述する銅イオンと 結合可能なリ ン酸基を分子構造中に有しおり、 得られる樹脂成分にイオン性金属 成分の溶解性を付与することができる。 そして、 リ ン酸基を介して銅イオンを保 持してなる共重合体は、 近赤外領域に特徴ある光吸収特性を示すものとなる。 な お、 本発明において、 「リ ン酸基」 とは、 「P 0 ( O H ) n ―」 ( nは 1 または 2である。 ) で表される基を意味するものとする。 更に、 特定のリ ン酸基含有単量体の分子構造中において、 アルキレンォキサイ ド基 (— C H 2 μ Ο— : ρ = 3〜 1 8 ) を介して、 ラジカル重合性の官能基であ るァク リ ロイルォキシ基またはメ 夕ク リ ロイルォキシ基が結合されているため、 当該特定のリ ン酸基含有単量体は極めて共重合性にとみ、 種々の単量体との共重 合を行うことが可能となる。 As represented by the above general formula, the specific phosphoric acid group-containing monomer has a phosphoric acid group capable of binding to a copper ion described later in a molecular structure, and the obtained resin component has an ionic metal component as a component. Solubility can be imparted. Then, the copolymer holding copper ions via the phosphoric acid group has a characteristic light absorption characteristic in the near infrared region. In the present invention, the “phosphoric acid group” means a group represented by “P 0 (OH) n —” (n is 1 or 2). Furthermore, in the molecular structure of a specific phosphoric acid group-containing monomer, a radical polymerizable functional group is formed via an alkylene oxide group (—CH 2 μ Ο—: ρ = 3 to 18). Since the specific carboxylic acid group or the methacryloyloxy group is bonded, the specific phosphoric acid group-containing monomer is considered to be extremely copolymerizable, and the copolymerization with various monomers is considered. It is possible to do.
ここで、 特定のリ ン酸基含有単量体におけるアルキレンォキサイ ド基の炭素数 ( ρ ) は、 3〜 1 8 とされ、 好ま し く は 3〜 6 とされる。  Here, the carbon number (ρ) of the alkylene oxide group in the specific phosphoric acid group-containing monomer is from 3 to 18, preferably from 3 to 6.
この炭素数 (: ρ ) が 3以上であることによって、 当該リ ン酸基含有単量体は、 高い疎水性を示すようになり、 この結果、 得られる共重合体 (更に最終的に得ら れる光学フィ ルター) における耐湿性および耐水性を向上させることができる; また、 この炭素数 ( ρ ) 力く 1 8以下であることによって、 当該リ ン酸基含有単 量体は、 共重合性単量体との相溶性が向上し、 得られる共重合体 (更に最終的に 得られる光学フィ ルター) は、 十分な機械的強度を有するものとなる,,  When the number of carbon atoms (: ρ) is 3 or more, the phosphoric acid group-containing monomer exhibits high hydrophobicity. As a result, the resulting copolymer (and finally the obtained copolymer) Moisture resistance and water resistance of the optical filter can be improved; and when the carbon number (ρ) is as strong as 18 or less, the phosphoric acid group-containing monomer is copolymerizable. The compatibility with the monomer is improved, and the obtained copolymer (and finally the obtained optical filter) has sufficient mechanical strength.
また、 アルキレンォキサイ ド基の繰り返し数 ( m ) は 1〜 1 0の整数とされる , この mの値が 1 0を超える場合には、 得られる共重合体の硬度が大幅に低下し 、 光学フィ ル夕一としての実用性に欠けたものとなる。  Further, the number of repetitions (m) of the alkylene oxide group is an integer of 1 to 10. When the value of m exceeds 10, the hardness of the obtained copolymer is significantly reduced, It lacks practicality as an optical filter.
また、 水酸基の数 ( n ) は、 光学フィ ルターの成形法や使用目的に応じて 1 ま たは 2のいずれかの値を選択すればよい  The number (n) of hydroxyl groups may be selected from 1 or 2 depending on the molding method of the optical filter and the purpose of use.
nの値が 2であるとき、 すなわち、 リ ン原子に結合したラジカル重合性の官能 基の数が 1である特定のリ ン酸基含有単量体は、 銅イオンとの結合性が大きいも のとなる。  When the value of n is 2, that is, the specific phosphoric acid group-containing monomer in which the number of radically polymerizable functional groups bonded to the phosphorus atom is 1 has a high bondability with copper ions. It becomes
一方、 nの値が 1である特定のリ ン酸基含有単量体、 すなわち、 前記官能基の 数が 2である特定のリ ン酸基含有単量体は架橋重合性を有するものとなる。 従って、 本発明の光学フィ ルターを、 熱可塑性樹脂の一般的な成形加工法であ る射出成形法或いは押出成形法により製造する場合には、 nの値が 2である特定 のリ ン酸基含有単量体を用いることが好ましい。 ただし、 光学フィ ルターの成形 法はこれらに限定されるものではない。  On the other hand, the specific phosphoric acid group-containing monomer in which the value of n is 1, that is, the specific phosphoric acid group-containing monomer in which the number of the functional groups is 2, becomes crosslinkable. . Therefore, when the optical filter of the present invention is manufactured by an injection molding method or an extrusion molding method, which is a general molding method of a thermoplastic resin, a specific phosphoric acid group in which the value of n is 2 It is preferable to use a contained monomer. However, the molding method of the optical filter is not limited to these.
このように、 光学フィ ルターの性能、 成形法および使用目的に応じて nの値を 選択することができるが、 nの値が 1である特定のリ ン酸基含有単量体と、 nの 値が 2である特定のリ ン酸基含有単量体とを併用することが好ま しく、 特に、 こ れら 2種類の特定のリ ン酸基含有単量体を、 それぞれがほぼ等量となる割台で用 いる場合には、 当該混合単量体への銅塩 (光学フィ ルターに銅イオンを導入する ために用いる塩) の溶解性が向上するので好ま しい。 Thus, the value of n depends on the performance of the optical filter, the molding method and the purpose of use. Although it can be selected, it is preferable to use a specific phosphoric acid group-containing monomer having a value of n of 1 and a specific phosphoric acid group-containing monomer having a value of n of 2 in combination. In particular, when these two types of specific phosphoric acid group-containing monomers are used on a slab having almost the same amount, a copper salt (optical filter) for the mixed monomer is used. This is preferable because the solubility of the salt used to introduce copper ions into the filter is improved.
樹脂成分を得るための混合単量体には、 前記特定のリ ン酸基含有単量体ととも に、 共重合体性単量体が含有されている。  The mixed monomer for obtaining the resin component contains a copolymerizable monomer together with the specific phosphoric acid group-containing monomer.
特定のリ ン酸基含有単量体と共重合性単量体との共重合によつて得られる共重 合体は、 吸湿性が小さく 、 光学フ ィ ルターに要求される硬度条件を満足するもの となり、 このような共重合体によれば、 形状保持性に優れた成形物を得ることが できる。  A copolymer obtained by copolymerization of a specific phosphoric acid group-containing monomer and a copolymerizable monomer has low hygroscopicity and satisfies the hardness conditions required for an optical filter. According to such a copolymer, a molded article having excellent shape retention can be obtained.
斯かる共重合性単量体は、 ( 1 ) 特定のリ ン酸基含有単量体と均一に溶解混合 すること、 ( 2 ) 特定のリ ン酸基含有単量体とのラジカル共重合性が良好である こと、 ( 3 ) 光学的に透明な共重合体が得られること、 を満足するものであれば 特に限定されるものではない。  Such a copolymerizable monomer is (1) uniformly dissolved and mixed with a specific phosphoric acid group-containing monomer, and (2) a radical copolymerizable monomer with the specific phosphoric acid group-containing monomer. Is not particularly limited as long as it satisfies (3) that an optically transparent copolymer is obtained.
これらの共重合性単量体の具体例としては、 単官能ァク リ レー 卜または単官能 メ 夕 ク リ レー 卜類 (例えばメチルァク リ レー 卜、 メ チルメ 夕 ク リ レー 卜、 ェチル ァク リ レー ト、 ェチルメ 夕 ク リ レー 卜、 n プロ ピルァク リ レー 卜、 n ―プ口 ピ ルメ タ ク リ レー 卜、 n—プチルァク リ レー 卜、 11 プチルメ 夕ク リ レー ト、 イ ソ ブチルァク リ レー ト、 ィ ソブチルメ タク リ レー ト、 1] 一へキシルァク リ レー 卜、 n へキシルメ タ ク リ レー ト、 n 才クチルァク リ レー 卜、 n 才クチルメ タク リ レー 卜等のアルキルァク リ レー トやアルキルメ タク リ レー ト、 グリ シジルァク リ レー 卜、 グリ シジルメ 夕 ク リ レー ト、 2 ヒ ドロキシェチルァク リ レ一 卜、 2 ヒ ドロキシェチルメ 夕 ク リ レー ト、 2 ヒ ドロキシプロ ピルァク リ レー 卜、 2 ヒ ドロ キシプロ ピルメ タク リ レー ト、 2 ヒ ドロキンブチルァク リ レー ト、 2 ヒ ドロキシ プチルメ タク リ レー 卜等の変性アルキルァク リ レー トゃ変性ァルキルメ 夕ク リ レ ― 卜等) 、 Specific examples of these copolymerizable monomers include monofunctional acrylates and monofunctional methacrylates (eg, methyl acrylate, methyl methacrylate, ethyl acrylate). Rate, ethyl acrylate, n -propyl acrylate, n-propyl acrylate, n-ethyl acrylate, 11 butyl acrylate, isobutyl acrylate Alkyl acrylates and alkyl methacrylates such as isobutyl methacrylate, 1] hexyl methacrylate, n hexyl methacrylate, n-year-old methyl acrylate, and n-year-old octyl methacrylate Rate, glycidyl acrylate, glycidyl acrylate, 2 hydroxyl acrylate, 2 hydroxyl acrylate, 2 Modified alkyl acrylates, such as hydroxypropyl acrylate, 2 hydroxypropyl acrylate, 2 hydroxybutyl acrylate, 2 hydroxybutyl acrylate, etc. -Utara),
多官能ァク リ レー トまたは多官能メ 夕ク リ レー ト類 (例えばエチレングリ コー ルジァク リ レー ト、 エチレングリ コールジメ 夕ク リ レー ト、 ジエチレングリ コー ルジァク リ レー ト、 ジエチレングリ コールジメ タ ク リ レー 卜、 ポリエチレングリ コールジァク リ レー 卜、 ポリエチレングリ コールジメ 夕 ク リ レー ト、 ポリ プロ ピ レングリ コ一ルジァク リ レー 卜、 ポリ プロピレングリ コールジメ 夕ク リ レー ト、 1 , 3 ブチレングリ コールジァク リ レー 卜、 1 , 3 ブチレングリ コールジメ タ ク リ レー 卜、 1, 4 ブタンジオールジァク リ レー ト、 1 , 4 ブタ ンジオールジメ 夕 ク リ レー 卜、 1 , 6へキサンジオールジァク リ レー 卜、 1 , 6へキサンジオール ジメ 夕 ク リ レー ト、 ネオペンチルグリ コールジァク リ レー 卜、 ネオペンチルグリ コールジメ 夕 ク リ レー ト、 2 ヒ ドロキシ 1 , 3 ジメ タ ク リ ロキシプロバン、 2 , 2 ビス 〔 4 - - (メ タ ク リ ロキシエ トキシ) フエニル〕 プロパン、 2 ヒ ドロキシ 1 ァク リ ロキシ 3 メ タク リ ロキシプロバン、 卜 リ メ チロールプロパン 卜 リ メ タク リ レー ト、 卜 リ メチロ一ルプロハ。ン 卜 リ アク リ レー ト、 ペン夕エリ 卜 リ ツ 卜 卜 リ ア ク リ レー 卜、 ペンタエリ ト リ ッ ト ト リ メ タク リ レー ト、 ペン夕エリ ト リ ッ トテ ト ラァク リ レー 卜、 ペンタエリ ト リ ッ トテ トラメ 夕 ク リ レー ト等) 、 Polyfunctional acrylates or polyfunctional maleates (eg, ethylene glycol Ruglycerate, ethylene glycol dichloride, diethylene glycol dichlorate, diethylene glycol dichlorate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol Lengglycol glycolate, polypropylene glycol glycolate, 1,3 butylene glycol glycolate, 1,3 butylene glycol glycolate, 1,4 butanediol glycolate, 1,4 butanediol glycolate 1,4 Butanediol dimethacrylate, 1,6 Hexanediol dimethacrylate, 1,6 Hexanediol dimethacrylate, Neopentyl glycol diacrylate, Neopentyl glycol dimethacrylate Crylate, 2 hydroxy 1, 3 Dimethacryloxypropane, 2,2 bis [4--(metacryloxyethoxy) phenyl] propane, 2 hydroxy 1 acryloxy 3 metaroxylpropane, trimethylolpropane trimetak Relay, tri-methyl pro-ha. Retrieval rate, Pentauri retriate, Pentaeli retriate, Pentaelitrit trimethacrylate, Pentaeli retritrate triclearrate, Pentaeri Tritte, evening creation, etc.),
アク リ ル酸、 メ 夕ク リ ル酸、 2 メ 夕 ク リ ロイルォキシェチルコハク酸、 2 メ タ ク リ ロイルォキシェチルフタル酸等のカルボン酸、 スチレン、 a メチルスチレン 、 クロルスチレン、 ジブロムスチレン、 メ トキシスチレン、 ジビニルベンゼン、 ビニル安息香酸、 ヒ ドロキシメチルスチレン、 ト リ ビニルベンゼン等の芳香族ビ ニル化合物を挙げることができる。  Carboxylic acids such as acrylic acid, methacrylic acid, 2-methyl chloroyloxetyl succinic acid, 2 methacryloyl oxethyl phthalic acid, styrene, a-methylstyrene, chlorostyrene And aromatic vinyl compounds such as dibromostyrene, methoxystyrene, divinylbenzene, vinylbenzoic acid, hydroxymethylstyrene, and trivinylbenzene.
これらの化合物は、 単独で、 或いは 2種以上混合して共重合性単量体を構成し てもよい。  These compounds may be used alone or in combination of two or more to form a copolymerizable monomer.
樹脂成分を得るための混合単量体中において、 特定のリ ン酸基含有単量体と共 重合性単量体との使用割合は、 「特定のリ ン酸基含有単量体 : 共重合性単量体 ( 重量) 」 が 3 : 9 7〜 8 0 : 2 0の範囲にあることが好ま しい。  The ratio of a specific phosphoric acid group-containing monomer to a copolymerizable monomer in a mixed monomer for obtaining a resin component is determined as follows: “Specific phosphoric acid group-containing monomer: copolymerization” It is preferable that the "active monomer (weight)" is in the range of 3:97 to 80:20.
特定のリ ン酸基含有単量体の割合が 3重量 未満である場合には、 光フィ ル夕 一と して好適な光吸収特性が発現されにく い。 一方、 この割合が 8 0重量 °。を超 える場合には、 得られる共重合体が、 要求される硬度条件を満足できない柔軟な ものとなりやすい。 樹脂成分である共重合体は、 特定のリ ン酸基含有単量体と、 共重合性単量体と よりなる混合単量体をラジカル重合させて得られる。 When the ratio of the specific phosphoric acid group-containing monomer is less than 3% by weight, it is difficult to exhibit light absorption characteristics suitable as an optical filter. On the other hand, this ratio is 80 weight °. If the hardness exceeds the above range, the obtained copolymer tends to be flexible which cannot satisfy the required hardness conditions. The copolymer as a resin component is obtained by radical polymerization of a mixed monomer composed of a specific phosphoric acid group-containing monomer and a copolymerizable monomer.
ラジカル重台方法と しては特に限定されるものではなく 、 通常のラジカル重台 開始剤を用いる、 塊状 (キャス ト ) 重合法、 懸濁重合法、 乳化重合法、 溶液重合 法等の公知の方法を使用することができる。  The radical polymerization method is not particularly limited, and a known radical polymerization initiator, such as a bulk (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, or a solution polymerization method, may be used. A method can be used.
本発明の光学フ ィ ルタ一は、 上記の樹脂成分と、 銅イオンを主成分とするィォ ン性金属成分とを含有してなるものである。  The optical filter of the present invention comprises the above resin component and an ionic metal component containing copper ions as a main component.
このイオン性金属成分は、 前記樹脂成分中に含有されたリ ン酸基との相互作用 により近赤外領域の波長光を効率よく吸収する作用を有するものである。  The ionic metal component has a function of efficiently absorbing light having a wavelength in the near-infrared region due to interaction with a phosphate group contained in the resin component.
ここで、 「銅イオンを主成分とする」 とは、 全てのイオン性金属成分に対して 銅イオンの占める割合が 8 0重量%以上であることを意味する。 具体的には、 2 価の銅イオンと、 他の金属イオンと力';、 前記割合を満足する条件で含有されてな るイオン性金属成分である. 銅イオンの割合が 8 0重量 ('0未満である場合には、 得られる光学フィ ルターが近赤外領域の波長光を効率よく吸収するものとならな い。 Here, “having copper ions as a main component” means that the ratio of copper ions to all ionic metal components is 80% by weight or more. Specifically, the divalent copper ions, other metal ions and force ';., The ratio is an ionic metal component ing is contained in satisfying conditions the ratio of copper ions 8 0 Weight (' If it is less than 0 , the obtained optical filter does not efficiently absorb light in the near infrared region.
光学フィ ルターに銅ィォンを導入するための銅塩としては、 種々のものを用い ることができ、 その一例を示せば、 酢酸銅、 塩化銅、 ギ酸銅、 ステアリ ン酸銅、 安息香酸銅、 ェチルァセ ト酢酸銅、 ピロリ ン酸銅、 ナフテン酸銅、 クェン酸銅等 の無水物や水和物を挙げることができる () なお、 これらの化合物のみに限定され るものではない。 As the copper salt for introducing copper ion into the optical filter, various ones can be used. Examples thereof include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, and the like. Examples include anhydrides and hydrates such as copper ethyl acetate, copper pyrrolinate, copper naphthenate, and copper citrate ( ). However, the compounds are not limited to these compounds.
また、 他の金属によりィォン性金属成分としては、 ナ ト リ ウム、 カ リ ウム、 力 ルシゥ厶、 鉄、 マンガン、 コバル ト、 マグネシウム、 ニッケル等を目的に応じて 用いることができる。  In addition, sodium, potassium, potassium, iron, manganese, cobalt, magnesium, nickel, and the like can be used as the ionizable metal component depending on the purpose of other metals.
本発明の光学フィ ルターにおいて、 銅ィォンを主成分とするィォン性金属成分 の含有割合としては、 榭脂成分である共重合体 1 0 0重量部に対して 0 . 1〜 2 5重量部であることが好まし く、 更に好ま し く は 0 . 2〜 2 0重量部である。 こ の割合が 0 . 1重量部未満である場合には、 近赤外領域の波長光を効率よく吸収 することができず、 一方、 2 5重量部を超える場合には、 金属塩 (光学フィ ル夕 一にイオン性金属成分を導入するために用いる塩) 力^ 混合単量体や共重合体中 に均一に分散されにく くなる。 In the optical filter of the present invention, the content ratio of the ionizable metal component containing copper ion as a main component is 0.1 to 25 parts by weight based on 100 parts by weight of the copolymer as the resin component. Preferably, it is 0.2 to 20 parts by weight. If this proportion is less than 0.1 part by weight, it is not possible to efficiently absorb light in the near infrared region, while if it exceeds 25 parts by weight, the metal salt (optical filter) will not be absorbed. Le evening First, a salt used to introduce an ionic metal component) is difficult to be uniformly dispersed in a mixed monomer or copolymer.
また、 本発明の光学フィ ルターにおける銅イオンの含有量は、 共重合体 1 0 0 重量部に対して 0 . 1〜 2 0重量部であることが好ま し く、 更に好ま しく は 1 . 0〜 1 0重量部とされる。  Further, the content of copper ions in the optical filter of the present invention is preferably 0.1 to 20 parts by weight, more preferably 1.0 to 100 parts by weight, based on 100 parts by weight of the copolymer. To 10 parts by weight.
銅イオンを主成分とするィォン性金属成分を前記共重合体に含有させる方法と しては特に限定されるものではないが、 好ま しい方法として、 以下の 2通りの方 法を挙げることができる。  The method for incorporating the ionizable metal component containing copper ions as the main component into the copolymer is not particularly limited, but preferred methods include the following two methods. .
( 1 ) 混合単量体のラジカル重合を行う前に、 当該混合単量体中に、 前記金属塩 を添加して溶解含有させる方法。  (1) A method in which the metal salt is added to and dissolved in the mixed monomer before radical polymerization of the mixed monomer is performed.
この方法によって前記金属塩を含有させ、 当該金属塩、 特定のリ ン酸基含有単 量体および共重合性単量体よりなる単量体混合物とし、 この単量体混合物をラジ カル重合させることにより、 前記イオン性金属成分が含有された共重合体 (光学 フィ ルター材料) が得られる。 この光学フ ィ ルター材料は、 そのままで、 或いは 、 目的とする形状に成形加工することにより、 光学フィ ルクーと して用いること ができる。  The method includes the step of including the metal salt by this method to form a monomer mixture comprising the metal salt, a specific monomer having a phosphoric acid group, and a copolymerizable monomer, and subjecting the monomer mixture to radical polymerization. Thus, a copolymer (optical filter material) containing the ionic metal component is obtained. This optical filter material can be used as an optical filter as it is or by being formed into a desired shape.
( 2 ) 混合単量体のラジカル重合を行って得られた共重合体中に、 前記金属塩を 添加して混合する方法。  (2) A method in which the metal salt is added to a copolymer obtained by performing radical polymerization of a mixed monomer and mixed.
この場合において、 前記金属塩の添加方法と しては、 共重合体を加熱溶融 させて添加する方法、 共重合体を有機溶剤に溶解させ、 この溶液中に添加す る方法等を用いることができる。  In this case, as a method for adding the metal salt, a method in which the copolymer is heated and melted, a method in which the copolymer is dissolved in an organic solvent, and a method in which the copolymer is added to the solution are used. it can.
上記 ( 1 ) および ( 2 ) のような方法により、 銅ィォンを主成分とするイオン 性金属成分が含有された光学フィ ルター材料を得ることができる。  By the methods as described in (1) and (2) above, an optical filter material containing an ionic metal component containing copper ion as a main component can be obtained.
この光学フィ ルター材料を、 目的、 用途に応じて、 板状、 円柱状、 レンズ状等 の形状に成形、 研磨することにより本発明の光学フィ ルターを製造することがで きる。  The optical filter of the present invention can be manufactured by molding and polishing this optical filter material into a plate-like, column-like, lens-like, or the like shape depending on the purpose and application.
このようにして製造される本発明の光学フィ ルタ一は、 近赤外領域の波長光を 効率よく にカツ 卜することができ、 しかも、 ガラス製のものと比べて格段に軽量 である。 さ らに、 本発明の光学フィ ルターは、 従来公知の光学フィ ルターより も 、 耐湿性および耐水性に優れ、 高温 · 高湿環境などで使用しても、 経時的な白化 •失透現象が発生しにく い。 The optical filter of the present invention manufactured in this way can efficiently cut light in the near infrared region, and is much lighter than glass. It is. Furthermore, the optical filter of the present invention has better moisture resistance and water resistance than conventionally known optical filters, and exhibits whitening and devitrification phenomena with time even when used in a high-temperature / high-humidity environment. It is unlikely to occur.
本発明の光学フィ ル夕一は、 カメ ラの測光部における受光素子 (例えばシリ コ ンフォ トダイォー ドからなる光電変換素子.) のための視感度補正フィ ル夕一とし て好適に用いることができる。  The optical filter of the present invention can be suitably used as a visibility correction filter for a light receiving element (for example, a photoelectric conversion element composed of a silicon photodiode) in a photometry unit of a camera. .
ここに、 本発明の光学フィ ル夕一からなる 『視感度補正フィ ルター』 には、 受 光素子に至る光路中に単独で配置される視感度補正フィ ルターのほか、 集光レン ズなどが含まれるものとする  Here, the “visibility correction filter” composed of the optical filter of the present invention includes a visibility correction filter that is arranged alone in the optical path to the light receiving element, as well as a converging lens and the like. Shall be included
本発明の光学フィ ルターを搭載してなるカメラ (本発明のカメラ) によれば、 受光素子 ( シリ コンフ ォ トダイォー ド) への入射光を、 実質的に可視領域の光に 限定することができ、 この結果、 正確な測光 (露出操作) を行なうことができる 本発明の光学フィ ルタ一は、 撮像装置における C C D (例えばシ リ コ ンフォ ト ダイォー ドからなる光電変換素子) のための視感度補正フ ィ ルターとして好適に 用いることができる。  According to the camera equipped with the optical filter of the present invention (camera of the present invention), the light incident on the light receiving element (silicon photodiode) can be substantially limited to light in the visible region. As a result, an accurate photometry (exposure operation) can be performed. The optical filter of the present invention is a luminous efficiency correction for a CCD (for example, a photoelectric conversion element composed of a silicon photodiode) in an imaging device. It can be suitably used as a filter.
ここに、 本発明の光学フィ ル夕一からなる 『視感度補正フィ ルター』 には、 C C Dに至る光路中に単独で配置される視感度補正フ ィ ルターのほか、 リ ツ ド、 レ ンズおよび保護板などが含まれるものとする。  Here, the “visibility correction filter” composed of the optical filter of the present invention includes a visibility correction filter that is independently arranged in the optical path to the CCD, as well as a lit, a lens, and a luminosity correction filter. It shall include a protection plate and the like.
また、 C C Dを搭載する撮像装置としては、 例えばビデオカメラ、 デジ夕ルカ メ ラ、 ボー ドカメ ラ、 カラースキャナ、 カラーフ ァ ッ クス、 カラー複写機、 カラ ーテレビ電話装置などを挙げることができる„  Examples of the imaging device equipped with a CCD include a video camera, a digital camera, a board camera, a color scanner, a color facsimile, a color copier, and a color videophone device.
本発明の光学フ ィ ルターを搭載してなる撮像装置 (本発明の撮像装置) によれ ば、 C C D (シ リ コンフォ トダイォー ド) への人射光を、 実質的に可視領域の光 に限定することができ、 この結果、 正確な測光 (露出操作) を行なうことができ 、 しかも、 赤色成分の再現およびカラーパ'ランスにも支障を来すことはない。 撮像装置としては、 C M O Sイメージセンサ、 人工網膜も挙げることができ、 これら撮像装置に本発明の光学フィ ルターを搭載することにより、 上述した C C Dに対してと同様の効果が得られる 本発明の光学フィ ルターを搭載した撮像装 置を用いた P Cカメラ、 デジタルカメ ラ、 ビデオカメラ、 ボー ドカメラ、 テレビ 電話装置等は、 良好な側光とカラーバランスが得られる。 According to the imaging device equipped with the optical filter of the present invention (the imaging device of the present invention), human light to a CCD (silicon comfort diode) is substantially limited to light in a visible region. As a result, accurate photometry (exposure operation) can be performed, and the reproduction of the red component and the color balance are not hindered. Examples of the imaging device include a CMOS image sensor and an artificial retina. By mounting the optical filter of the present invention on these imaging devices, the above-described CC can be used. A PC camera, a digital camera, a video camera, a board camera, a videophone device, and the like using an imaging device equipped with the optical filter of the present invention, which can obtain the same effect as that of D, have good side light and Color balance is obtained.
本発明の光学フィ ルターは、 赤外線通信装置 ( 8 5 0〜!) 5 0 n mの光を媒体 とする通信装置) が使用される環境におけるノイズカツ トフィ ルタ一と して好適 に用いることができる。 ここに、 本発明の光学フィ ル夕一からなる 『ノイズカツ 卜フィ ルター』 によって近赤外線の発生源 (例えば自動ドア、 リモコン) をカバ 一し、 当該発生源からの赤外線を遮断することにより、 通信中におけるノイズの 発生を確実に防止することができる。  INDUSTRIAL APPLICABILITY The optical filter of the present invention can be suitably used as a noise cut filter in an environment where an infrared communication device (850-!) Is a communication device using 50 nm light as a medium. Here, a source of near-infrared rays (for example, an automatic door or a remote controller) is covered by a “noise cut filter” comprising the optical filter of the present invention, and communication is performed by blocking infrared rays from the source. Generation of noise in the interior can be reliably prevented.
また、 本発明の光学フィ ルターを、 プラズマディ スプレイ装置のバネルの前面 に配置することにより、 当該バネルから照射される近赤外線を効率よく カツ 卜す ることができる。 この結果、 当該プラズマディ スプレイ装置の周囲において、 近 赤外線に起因する リモコンの誤動作などを生じさせることはない。  Further, by disposing the optical filter of the present invention on the front surface of the panel of the plasma display device, it is possible to efficiently cut the near infrared rays emitted from the panel. As a result, a malfunction of the remote controller due to near infrared rays does not occur around the plasma display device.
また、 本発明の光学フィ ル夕一は、 他の機能フィ ルター、 例えば電磁波シール ド、 反射防止、 汚染防止等の機能を有するフィ ル夕一と組み合わせることにより 、 さらに実用性の高いプラズマディ スプレイ用のフィ ルターと して使用すること ができる。  The optical filter of the present invention can be combined with other functional filters, for example, a filter having electromagnetic wave shielding, antireflection, contamination prevention, etc., to provide a more practical plasma display. Can be used as a filter.
本発明の光学フィ ルターは、 熱線吸収フィ ルターと して、 具体的には、 家屋、 ビル等の建築物における窓材、 自動車、 電車の車輛等の窓材、 温室の透光部材、 照明用カバーなどとして好適に用いることができる。  The optical filter of the present invention is a heat ray absorbing filter, specifically, a window material of a building such as a house or a building, a window material of a car or a train, a translucent member of a greenhouse, or a lighting device. It can be suitably used as a cover or the like.
本発明の光学フィ ルターは、 光フアイバーの構成材料と して好適に用いること ができる。 また、 本発明の光学フィ ルターを光フアイバーの採光部に設けてもよ い。  The optical filter of the present invention can be suitably used as a constituent material of an optical fiber. Further, the optical filter of the present invention may be provided in a lighting part of an optical fiber.
本発明の光学フィ ル夕一は、 眼鏡レンズと して好適に用いることができる。 か かる眼鏡レンズ (本発明の眼鏡レンズ) によれば、 白内障発症の原因である熱線 や近赤外線から眼を保護することができる。 発明を実施するための最良の形態 以下、 本発明の実施例を説明するカ^ 本発明がこれらによって限定されるもの ではな ^ , The optical filter of the present invention can be suitably used as a spectacle lens. According to such a spectacle lens (the spectacle lens of the present invention), it is possible to protect the eyes from heat rays and near infrared rays which cause cataracts. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples of the present invention will be described. ^ The present invention is not limited to these.
なお、 以下において、 「部」 は 「重量部」 を意味する。  In the following, “parts” means “parts by weight”.
〔実施例 1〕  (Example 1)
表 1 に示す処方に従って、 下記式 ( ί ) で表される特定のリ ン酸基含有単量体 〔上記一般式中、 ρ = 3 , m= 5 , n = 1 : 以下 「単量体 ( D) 」 ともいう。 〕 4 9部と、 下記式 ( ii ) で表される特定のリ ン酸基含有単量体 〔上記一般式中、 p = 3. m= 5. n = 2 :以下 「単量体 (M) 」 ともいう。 2 1部と、 メチル メ 夕 ク リ レー ト 1 0部と、 1 , 6 へキサンジォ一ルジメ ク ク リ レー 卜 2 0部と を良く混合して混合単量体を調製した。 この混合単量体に、 無水安息香酸銅 2 4 部 (混合単量体 1 ϋ 0部に対する銅の含有量が 5. 0部) を添加し、 6 (TCで攪 拌混合することによって十分に溶解させ、 無水安息香酸銅が混合単量体中に溶解 されてなる単量体混合物を得た。  According to the formulation shown in Table 1, a specific phosphoric acid group-containing monomer represented by the following formula (() [wherein ρ = 3, m = 5, n = 1: D) ". ] 49 parts and a specific phosphoric acid group-containing monomer represented by the following formula (ii) [in the above general formula, p = 3. m = 5. n = 2: ) ". 21 parts, 10 parts of methyl methyl acrylate, and 20 parts of 1,6 hexanediol dimethacrylate were mixed well to prepare a mixed monomer. To this mixed monomer was added 24 parts of copper benzoate anhydride (a copper content of 5.0 parts relative to 100 parts of the mixed monomer), and 6 (sufficiently mixed by stirring with TC). The mixture was dissolved to obtain a monomer mixture in which copper benzoate anhydride was dissolved in the mixed monomer.
式 ( i ) Equation (i)
!"!2し二し一 C ti 3 〇 n 3 し一し =し H 2 ! "! 2 2 C ti 3 〇 n 3 1 = H 2
II  II
C—〇4C3H6-〇 C3 H6K3— C C—〇4C 3 H 6 -〇 C 3 H 6 K3— C
II II  II II
0 OH 0 式 ( ii )  0 OH 0 formula (ii)
Figure imgf000014_0001
以上のようにして調製された単量体混合物に、 t ブチルバーオキシピバレー ト 2. 0部を添加し、 この単量体混合物をガラスモールド中に注入し、 4 5 "Cで 1 6時間、 6 0 °Cで 8時間、 9 0 !>Cで 3時間と順次異なる温度で加熱して注型重 合を行うことにより、 銅ィォンが含有された架橋重合体よりなる厚さ 1 mmの光 学フィ ルター (本発明の光学フィ ルター) を得た。 この光学フィ ルターの比重は 1 . 2 9 と小さ く 、 屈折率は 1 . 5 1 1であった。
Figure imgf000014_0001
To the monomer mixture prepared as described above, 2.0 parts of t-butyl baroxypivalate was added, and the monomer mixture was poured into a glass mold, and the mixture was heated at 45 "C for 16 hours. By heating at 60 ° C for 8 hours and 90 !> C for 3 hours at different temperatures and performing casting polymerization, a 1 mm thick cross-linked polymer containing copper ion was obtained. light The optical filter (the optical filter of the present invention) was obtained. The specific gravity of this optical filter was as small as 1.29, and the refractive index was 1.511.
〔実施例 2〕  (Example 2)
表 1 に示す処方に従って、 単量体 ( D ) 7部と、 単量体 (M ) 3部と、 メチル メ タク リ レー 卜 6 0部と、 1 , 6 —へキサンジオールジメ 夕ク リ レ一 卜 2 0部と 、 フユノキシェチルメ タク リ レー ト 1 0部とを良く混合して混合単量体を調製し た。 この混合単量体に、 無水安息香酸銅 5部 (混合単量体 1 0 0部に対する銅の 含有量が 1 . 0部) とを添加し、 6 0 °Cで攪拌混合することによって十分に溶解 させ、 安息香酸銅が混合単量体中に溶解されてなる単量体混合物を得た。  According to the recipe shown in Table 1, 7 parts of monomer (D), 3 parts of monomer (M), 60 parts of methyl methacrylate, and 1,6-hexanediol dimethyl A mixed monomer was prepared by thoroughly mixing 20 parts of the mixture and 10 parts of funonokishetyl methacrylate. To this mixed monomer, 5 parts of copper benzoate anhydride (the copper content relative to 100 parts of the mixed monomer is 1.0 part) is added, and the mixture is sufficiently stirred and mixed at 60 ° C. The mixture was dissolved to obtain a monomer mixture in which copper benzoate was dissolved in the mixed monomer.
以上のようにして調製された単量体混合物を用い、 実施例 1 と同様にして注型 重合を行うことにより、 銅ィォンが含有された架橋重合体よりなる厚さ 1 m mの 光学フィ ルター (本発明の光学フィ ルター) を得た。 この光学フィ ルターの比重 は 1 . 2 5 と小さ く 、 屈折率は 1 . 5 0 1であつた,  Using the monomer mixture prepared as described above, casting polymerization was carried out in the same manner as in Example 1 to obtain an optical filter (1 mm thick) comprising a cross-linked polymer containing copper ion. The optical filter of the present invention) was obtained. The specific gravity of this optical filter was as low as 1.25, and the refractive index was 1.501.
〔比較例 1〕  (Comparative Example 1)
表 1 に示す処方に従って、 下記式 ( ill ) で表される比較用のリ ン酸基含有単量 体 〔以下 「単量体 ( d ) 」 ともいう。 〕 3 】 . 2 5部と、 下記式 ( iv ) で表され る比較用のリ ン酸基含有単量体 〔以下 「単量体 (m ) 」 ともいう。 〕 1 8 . 7 5 部と、 メ チルメ 夕 ク リ レー 卜 2 0部と、 1 , 6 —へキサンジオールジメ 夕 ク リ レ ー ト 2 0部と、 フヱノキシェチルメ 夕ク リ レー ト 1 0部とを良く混台して混合単 量体を調製した。 この混台単量体に、 無水安息香酸銅 2 4部 (混合単量体 1 0 0 部に対する銅の含有量が 5 . 0部) を添加し、 6 0 °Cで攪拌混合することによつ て十分に溶解させ、 無水安息香酸銅が混合単量体中に溶解されてなる単量体混合 物を得た。  In accordance with the formulation shown in Table 1, a phosphate group-containing monomer represented by the following formula (ill) [hereinafter also referred to as “monomer (d)”. 3] .25 parts and a phosphoric acid group-containing monomer for comparison represented by the following formula (iv) [hereinafter also referred to as “monomer (m)”. 18.7 5 parts, methyl dimethyl acrylate 20 parts, 1,6-hexanediol dimethyl creat 20 parts, and phenolic dimethyl acrylate And 10 parts were mixed well to prepare a mixed monomer. To this mixed monomer was added 24 parts of copper benzoate anhydride (a copper content of 5.0 parts based on 100 parts of the mixed monomer), and the mixture was stirred and mixed at 60 ° C. The resulting mixture was sufficiently dissolved to obtain a monomer mixture obtained by dissolving copper benzoate anhydride in the mixed monomer.
式 ( iM ) Formula (iM)
H2 C C H :
Figure imgf000015_0001
式 (iv )
H 2 CCH :
Figure imgf000015_0001
Equation (iv)
H2 C = C一 CH: 〇 H 2 C = C-CH: 〇
II  II
C-0-C2 H4 O-P-OH C-0-C 2 H 4 OP-OH
II I  II I
〇 OH 以上のようにして調製された単量体混合物を用い、 実施例 1 と同様にして注型 重合を行うことにより、 銅ィォンが含有された架橋重合体よりなる厚さ 1 mmの 光学フィ ルター (比較用の光学フィ ルター) を得た。 この光学フィ ルターの比重 は 1. 2 8 と小さ く、 屈折率は 1. 5 1 0であつた。  〇 OH Using the monomer mixture prepared as described above, cast polymerization was performed in the same manner as in Example 1 to obtain an optical filter having a thickness of 1 mm consisting of a cross-linked polymer containing copper ion. A filter (optical filter for comparison) was obtained. The specific gravity of this optical filter was as low as 1.28, and the refractive index was 1.510.
く'光学フィ ルターの性能評価 ..、 Evaluation of optical filter performance
( 1 ) 耐湿性および耐水性 :  (1) Moisture and water resistance:
実施例 1〜 2および比較例 1 で得られた光学フ ィ ルター (各例あたり 3つを用 意した, ) を 8 0 Cで 5時間乾燥した後、 当該光学フ ィ ル夕一の各々について、 1 2 3 "Cの水中に 2 4時間浸漬したときの吸水率を測定し、 1 温度 5 0 "C , 相対湿度 ί) 5 ΰ。に設定された恒温恒湿槽内に 1 4時間放置したときの吸水率を測 定し、 温度 5 0 °C. 相対湿度 9 0 Q 0に設定された恒温恒湿槽内に 1 ϋ 0時間 放置した後における白化 · 失透現象の発生の有無を評価した 結果を下記表 1 に 示す After drying the optical filters (three prepared for each example) obtained in Examples 1 and 2 and Comparative Example 1 at 80 ° C. for 5 hours, each of the optical filters was prepared. The water absorption was measured when immersed in water at 123 "C for 24 hours . 1 Temperature 50" C, relative humidity ί) . Measure the water absorption when left for 14 hours in a thermo-hygrostat set at a temperature of 50 ° C. Relative humidity 1 Q 0 h in a thermo-hygrostat set at 90 Q 0 Table 1 shows the results of evaluation of the occurrence of whitening and devitrification after standing.
なお、 吸水率 (9 ) は、 浸漬前もしく は放置前における重量 w , ( g ) および 浸漬後もしくは放置後における重量 ( g ) から、 次式により求めた ( The water absorption (9) was obtained from the weight w, (g) before or after immersion or before immersion and the weight (g) after immersion or after immersion according to the following equation (
式) : W= ( wL, — .) , w , - 1 0 0 ( ) 〔表 1〕 Formula): W = (w L , —.), W,-1 0 0 () 〔table 1〕
5 Five
Figure imgf000017_0001
表 1 に示す結果から明らかなように、 実施例 1〜 2で得られた光学フィ ルター は、 比較例 1で得られた光学フィ ルターより も吸水率が低く、 耐水性および耐湿 性に優れていることが理解される。
Figure imgf000017_0001
As is evident from the results shown in Table 1, the optical filters obtained in Examples 1 and 2 have lower water absorption than the optical filters obtained in Comparative Example 1, and are excellent in water resistance and moisture resistance. It is understood that there is.
( 2 ) 光吸収特性 :  (2) Light absorption characteristics:
実施例 1〜 3および比較例 1で得られた光学フィ ルターの各々について、 分光 光度計を用いて分光透過率曲線 (: 2 5 0〜 1 0 0 0 n m ) を測定した。  For each of the optical filters obtained in Examples 1 to 3 and Comparative Example 1, a spectral transmittance curve (: 250 to 100 nm) was measured using a spectrophotometer.
結果を下記表 2に示す。 〔表 2〕 The results are shown in Table 2 below. (Table 2)
透 過 率 (¾ ) Transmission rate (¾)
Figure imgf000018_0001
表 2に示す結果から明らかなように、 実施例 1 〜 2および比較例 1で得られた 光学フィ ル夕—は、 近赤外領域 ( 7 0 0 〜 1 0 () 0 n m ) の波長光を効率よく吸 収していることが理解される。 発 明 の 効 果
Figure imgf000018_0001
As is clear from the results shown in Table 2, the optical filters obtained in Examples 1 and 2 and Comparative Example 1 have wavelengths in the near-infrared region (700 to 10 () 0 nm). It is understood that the water is efficiently absorbed. The invention's effect
以上のように、 本発明の光学フィ ルタ一は、 特定のリ ン酸基含有単量体と、 共 重合性単量体とよりなる混台単量体の共重合体である樹脂成分と、 この樹脂成分 中に分散された銅イオンを主成分とするィォン性金属成分とを含有してなるので 、 近赤外領域の波長を効率よく に力ッ 卜することができる 更に、 十分に軽量化 が図られ、 成形 · 切削 ·研磨等の加工が容易で生産性に優れたものである。  As described above, the optical filter of the present invention comprises a resin component which is a copolymer of a specific monomer containing a phosphoric acid group and a copolymerizable monomer comprising a copolymerizable monomer. Since the resin component contains an ionizable metal component containing copper ions as a main component dispersed therein, the wavelength in the near-infrared region can be efficiently applied. Further, the weight is sufficiently reduced. It is easy to process such as forming, cutting and polishing, and has excellent productivity.
し力、も、 本発明の光学フィ ル夕一は、 特定のリ ン酸基含有単量体におけるアル キレンォキサイ ド基 (:— C Η 2 μ Ο— ) の炭素数が 3 〜 1 8であることにより、 十分な機械的強度を有するとともに、 耐湿性および耐水性に優れ、 高温 · 高湿環 境などで使用しても、 経時的な白化 ·失透現象が発生しにく い。 And power, also, the optical Fi le evening one aspect of the present invention is specific re phospho groups containing monomer in the Al Kirenokisai de group: - number of carbon atoms in (C Η 2 μ Ο-) is a 3 to 1 8 As a result, it has sufficient mechanical strength, excellent moisture resistance and water resistance, and is less likely to cause whitening and devitrification over time even when used in a high-temperature, high-humidity environment.
本発明の力メラによれば、 受光素子への入射光を実質的に可視領域の光に限定 することができ、 正確な測光 (露出操作) を行なうことができる。  ADVANTAGE OF THE INVENTION According to the power lens of this invention, the light which injects into a light receiving element can be substantially limited to the light of a visible region, and accurate photometry (exposure operation) can be performed.
本発明の撮像装置によれば、 C C D 、 C M O S イメージセンサ、 人工網膜への 入射光を実質的に可視領域の光に限定することができ、 この結果、 正確な測光 ( 露出操作) を行なうことができ、 し力、も、 赤色成分の再現性にも優れている。 本発明の赤外線通信環境整備装置によれば、 通信中におけるノィズを確実に防 止することができる。 ADVANTAGE OF THE INVENTION According to the imaging device of this invention, the light which injects into CCD, CMOS image sensor, and artificial retina can be substantially limited to the light of a visible region, As a result, accurate photometry (exposure operation) can be performed. It has excellent reproducibility, redness and reproducibility. ADVANTAGE OF THE INVENTION According to the infrared communication environment maintenance apparatus of this invention, the noise during communication can be prevented reliably.
本発明のプラズマディ スプレイ装置によれば、 その周囲において、 近赤外線に 起因するリモコ ンの誤動作などを生じさせることはない。  According to the plasma display device of the present invention, a malfunction of the remote control due to near infrared rays does not occur around the device.
本発明の熱線吸収フィ ルターによれば、 室内等における温度上昇を確実に抑制 することができる。  ADVANTAGE OF THE INVENTION According to the heat ray absorption filter of this invention, the temperature rise in a room etc. can be suppressed reliably.
本発明の光ファィバーによれば、 当該光ファィパ'一により導かれて放射される 光の中に熱線 (近赤外線) が殆ど含まれないので、 光の放射部位付近 (装置内 - 室内) における温度上昇を抑制することができる。  According to the optical fiber of the present invention, since heat rays (near-infrared rays) are hardly included in the light guided and emitted by the optical fiber, the temperature near the light emission site (in the apparatus-indoor) The rise can be suppressed.
本発明の眼鏡レンズによれば、 白内障発症の原因である熱線、 近赤外線から眼 を保護することができる。  ADVANTAGE OF THE INVENTION According to the spectacle lens of this invention, an eye can be protected from heat rays and near-infrared rays which are a cause of cataract development.

Claims

δ 求 の δ
( 1〕 下記一般式で表される単量体およびこれと共重合可能な単量体よりなる混 合単量体を共重台して得られる樹脂成分と、  (1) a resin component obtained by copolymerizing a monomer represented by the following general formula and a mixed monomer comprising a monomer copolymerizable therewith,
この樹脂成分に溶解された、 銅イオンを主成分とするィォン性金属成分と を含有してなることを特徴とする光学フィ ルター。  An optical filter comprising: a resin component; and an ionizable metal component containing copper ions as a main component.
Ρ 0 (0 H)„ R 3-„ Ρ 0 (0 H) „R 3-
〔但し、 Rは  [However, R is
X X
C H 2 = C— C一 C C P H2 PCH 2 = C— C-CC P H 2 P
II  II
0  0
(Xは水素原子またはメチル基を示し、 Pは 3 1 8の整数であり、 mは 1〜 0の整数である。) を示し、 nは 1または 2である。 〕  (X represents a hydrogen atom or a methyl group, P is an integer of 318, m is an integer of 1 to 0), and n is 1 or 2. ]
〔 2〕 請求項 1 に記載の光学フィ ル夕一において、 上記一般式で表される単量体 におけるアルキレンォキサイ ド基の炭素数 ( r〕) が 3 6であることを特徵とす る光学フィ ルター [2] The optical filter according to claim 1, wherein the carbon number (r) of the alkylene oxide group in the monomer represented by the general formula is 36. Optical filter
〔 3〕 請求項 1 に記載の光学フィ ル夕一において、 樹脂成分を得るための混台単 量体中に、 上記一般式における nの値が 1である単量体と、 nの値が 2である単 量体とが含有されていることを特徴とする光学フィ ルター。  [3] In the optical filter according to claim 1, in the mixed monomer for obtaining the resin component, a monomer in which the value of n in the above general formula is 1 and a value of n are 2. An optical filter, comprising: a monomer of 2.
〔 4〕 請求項 1 に記載の光学フィ ルターにおいて、 樹脂成分を得るための混合単 量体中に、 上記一般式における nの値が 1である単量体と、 nの値が 2である単 量体とが、 ほぼ等量となる割合で含有されていることを特徴とする光学フィ ル夕  (4) The optical filter according to claim 1, wherein in the mixed monomer for obtaining the resin component, the monomer having the value of n in the above general formula is 1 and the value of n is 2 The optical filter is characterized in that the monomer and the monomer are contained in a proportion that is almost equal.
〔 5〕 請求項 1 に記載の光学フィ ルターにおいて、 樹脂成分を得るための混合単 量体中における上記一般式で表される単量体の含有割合が 3 8 0重量%である ことを特徴とする光学フィ ルター。 [5] The optical filter according to claim 1, wherein the content of the monomer represented by the above general formula in the mixed monomer for obtaining the resin component is 380% by weight. Optical filter.
〔 6〕 請求項 1 に記載の光学フィ ルターにおいて、 樹脂成分である共重合体 1 0 0重量部に対して、 銅イオンを主成分とするイオン性金属成分が 0 . 1〜 2 5重 量部含有されていることを特徴とする光学フィ ル夕一。 [6] The optical filter according to claim 1, wherein the copolymer 10 is a resin component. An optical filter characterized by comprising 0.1 to 25 parts by weight of an ionic metal component mainly composed of copper ions with respect to 0 parts by weight.
〔 7〕 請求項 1 に記載の光学フィ ルターにおいて、 樹脂成分である共重合体 1 0 0重量部に対して、 銅イオンを主成分とするイオン性金属成分が 0 . 2〜 2 0重 量部含有されていることを特徴とする光学フィ ルター。  [7] The optical filter according to claim 1, wherein the ionic metal component containing copper ion as a main component is 0.2 to 20 weight per 100 parts by weight of the copolymer as a resin component. An optical filter characterized in that the optical filter is partially contained.
[ 8 ] 受光素子のための視感度補正フィ ルタ一と して、 請求項 1 に記載の光学フ ィ ルターが搭載されていることを特徴とする力メラ。  [8] A force lens comprising the optical filter according to claim 1 as a visibility correction filter for a light receiving element.
〔 9〕 C C Dのための視感度補正フィ ルターと して、 請求項 1 に記載の光学フィ ル夕一が搭載されていることを特徴とする撮像装置。  [9] An imaging device, comprising the optical filter according to claim 1 as a visibility correction filter for CCD.
〔10〕 C M O S ィ メージセンサのための視感度補正フィ ルターと して、 請求項 1 に記載の光学フィ ルターが搭載されていることを特徴とする撮像装置。  [10] An imaging device, comprising the optical filter according to claim 1 as a visibility correction filter for a CMOS image sensor.
〔1 1〕 人工網膜のための視感度補正フィ ルタ一と して、 請求項 1 に記載の光学フ ィ ルターが搭載されていることを特徴とする撮像装置。  [11] An imaging device comprising the optical filter according to claim 1 as a visibility correction filter for an artificial retina.
〔12〕 ノィズカッ 卜フィ ル夕一と して、 請求項 1 に記載の光学フィ ルターを有し てなることを特徴とする赤外線通信環境整備装置。  [12] An infrared communication environment maintenance device comprising the optical filter according to claim 1 as a noise cut filter.
〔13〕 請求項 1 に記載の光学フィ ルターがパネル前面に配置されてなることを特 徴とするブラズマデイ スプレィ装置。  [13] A plasma display device characterized in that the optical filter according to claim 1 is arranged on a front surface of the panel.
〔 14〕 請求項 1 に記載の光学フィ ル夕一からなることを特徴とする熱線吸収フィ ルター。  [14] A heat ray absorbing filter comprising the optical filter according to [1].
( 15] 請求項 1 に記載の光学フィ ルターからなることを特徴とする光ファイバ一  (15) An optical fiber comprising the optical filter according to claim 1.
〔16〕 請求項 1 に記載の光学フィ ルターが採光部に設けられていることを特徴と する光ファィバー。 [16] An optical fiber, wherein the optical filter according to claim 1 is provided in a lighting part.
〔17〕 請求項 1 に記載の光学フィ ルターからなることを特徴とする眼鏡レンズ。  [17] A spectacle lens comprising the optical filter according to claim 1.
PCT/JP1998/005201 1997-11-21 1998-11-19 Optical filter, and device, heat-ray absorbing filter, optical fiber and eye-glasses each provided with the optical filter WO1999027397A1 (en)

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JPH10152598A (en) * 1996-11-22 1998-06-09 Sumitomo Chem Co Ltd Near-infrared absorption resin composition and material
JPH10221523A (en) * 1996-12-06 1998-08-21 Kureha Chem Ind Co Ltd Optical filter, device with it, spectacle lens, heat ray absorbing filter, and optical fiber

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008046933A1 (en) 2006-10-16 2008-04-24 Universidad Complutense De Madrid Lighting device with prophylactic and therapeutic filter for healthy eyes, pseudoaphakic eyes and/or eyes suffering neurodegeneration
US7832903B2 (en) 2006-11-07 2010-11-16 Universidad Complutense De Madrid Illumination system fitted with a therapeutic/prophylactic filter for healthy eyes, pseudoaphakic eyes or eyes suffering neurodegeneration
US7914177B2 (en) 2006-11-07 2011-03-29 Universidad Complutense De Madrid Prophylaxic/therapeutic vehicle filter component for healthy eyes, pseudoaphakic eyes or eyes suffering neurodegeneration
EP2128684A1 (en) * 2008-05-30 2009-12-02 Yamamoto Kogaku Co., Ltd. Synthetic resin lens and eye lens article thereof
US7922324B2 (en) 2008-05-30 2011-04-12 Yamamoto Kogaku Co., Ltd. Synthetic resin lens and eye lens article thereof

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