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WO1998055885A1 - Materiau optique constitue de resine synthetique, filtre optique, et dispositif, verre de lunette, filtre d'absorption de rayons thermiques et fibre optique pourvus dudit filtre optique - Google Patents

Materiau optique constitue de resine synthetique, filtre optique, et dispositif, verre de lunette, filtre d'absorption de rayons thermiques et fibre optique pourvus dudit filtre optique Download PDF

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Publication number
WO1998055885A1
WO1998055885A1 PCT/JP1998/002250 JP9802250W WO9855885A1 WO 1998055885 A1 WO1998055885 A1 WO 1998055885A1 JP 9802250 W JP9802250 W JP 9802250W WO 9855885 A1 WO9855885 A1 WO 9855885A1
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Prior art keywords
synthetic resin
optical material
polymer
parts
optical
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PCT/JP1998/002250
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English (en)
Japanese (ja)
Inventor
Hiroki Katono
Tomoyoshi Koizumi
Yoshinobu Itoh
Katsuichi Machida
Masuhiro Shouji
Takeo Ogihara
Original Assignee
Kureha Kagaku Kogyo Kabushiki Kaisha
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.)
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Application filed by Kureha Kagaku Kogyo Kabushiki Kaisha filed Critical Kureha Kagaku Kogyo Kabushiki Kaisha
Publication of WO1998055885A1 publication Critical patent/WO1998055885A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/02—Homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus

Definitions

  • the present invention relates to an optical material made of synthetic resin and an application example thereof.
  • Optical material made of synthetic resin that has the ability to absorb rays in the linear region with high efficiency an optical filter made of this synthetic resin optical material, and a device equipped with this optical filter (plasma display device 'camera' CCD imaging device Infrared communication environment maintenance equipment), eyeglass lenses for cataract prevention, near-infrared absorption filters, and optical fibers.
  • a plasma display device since near-infrared light is emitted from the panel in addition to visible light, devices operated by a remote control device using infrared light, such as audio equipment If a plasma display device is installed near a device such as a device, an air conditioner, a television, or a VCR, the device may malfunction.
  • near-infrared rays are considered as one of the causes of cataracts and have a negative effect on human eyes. For these reasons, it is required to dispose an optical filter for absorbing near-infrared light in front of the panel of the plasma display device.
  • optical filters that absorb near-infrared rays are used as luminosity correction filters and photometric filters.
  • an optical filter that absorbs near-infrared rays a glass made of a special phosphate glass containing copper ions has been used.
  • light made of glass In the case of a scientific filter, there is a problem that it is difficult to produce a large-sized one due to a large specific gravity and difficult to form, cut, and grind, and the production cost is high.
  • an optical filter made of a synthetic resin in which copper ion is contained in a polymer obtained from an acrylic monomer containing a phosphoric acid group has been developed (for example, Japanese Patent Application Laid-open No. 6 — 11 18 228, Japanese Patent Application Laid-Open No. 6-34520).
  • Japanese Patent Application Laid-open No. 6 — 11 18 228, Japanese Patent Application Laid-Open No. 6-34520 Japanese Patent Application Laid-open No. 6 — 11 18 228, Japanese Patent Application Laid-Open No. 6-34520.
  • the above-mentioned synthetic resin optical filter is used in a high-temperature, high-humidity environment, it becomes cloudy in a short time, losing its function as an optical filter, or causing some wavelengths in visible light to be lost. It has been found that there is a problem that the transmittance in the red light wavelength range (longer wavelength region) or blue light wavelength region (shorter wavelength region) decreases. .
  • the optical filter is colored cyan or green when the transmittance of the visible light in a part of the wavelength range is reduced, so that the optical filter is used in a color image display device or a CCD. When used for a visibility correction filter, etc., the color balance of the screen or video cannot be maintained. Disclosure of the invention
  • the present invention has been made based on the above circumstances.
  • a first object of the present invention is to have a performance of absorbing near-infrared rays with high efficiency, and to produce white turbidity even when used in a high-temperature and high-humidity environment for a long period of time, and to reduce the wavelength of visible light.
  • a second object of the present invention is to have a performance of absorbing near-infrared rays with high efficiency.
  • An optical filter that suppresses a decrease in the transmittance of the optical region and changes in optical characteristics are small, and can also provide a function of selectively absorbing light in a specific wavelength region in the visible region as necessary. Is to provide.
  • a third object of the present invention is to have a performance of absorbing near-infrared rays with high efficiency, and furthermore, there is little change in optical characteristics even when used for a long time in a high-temperature and high-humidity environment, and furthermore, a visible
  • An object of the present invention is to provide a plasma display device in which an optical filter which can also be provided with a function of selectively absorbing a light beam in a specific wavelength region in a region is disposed as a front plate of a panel.
  • a fourth object of the present invention is to provide an optical filter having a performance of absorbing near-infrared rays with high efficiency and having a small change in optical characteristics even when used for a long time in a high-temperature and high-humidity environment.
  • An object of the present invention is to provide a camera provided as a visibility correction filter for an element.
  • a fifth object of the present invention is to provide an optical filter having a performance of absorbing near-infrared rays with high efficiency and having a small change in optical characteristics even when used for a long time in a high-temperature, high-humidity environment. It is an object of the present invention to provide an image pickup apparatus characterized in that the image pickup apparatus is provided as a luminosity correction filter or a filter having both luminosity correction and color purity correction.
  • a sixth object of the present invention is to provide an optical filter having a performance of absorbing near-infrared rays with high efficiency and having a small change in optical characteristics even when used in a high-temperature and high-humidity environment for a long time.
  • An object of the present invention is to provide an infrared communication environment maintenance device provided as a filter.
  • a seventh object of the present invention is to suppress the occurrence of cataract by absorbing near-infrared light with high efficiency, and to have a small change in optical characteristics even when used for a long time in a high-temperature and high-humidity environment. It is to provide a lens.
  • An eighth object of the present invention is to provide a heat ray absorbing filter which has a performance of absorbing near infrared rays with high efficiency, and has a small change in optical characteristics even when used for a long time in a high temperature and high humidity environment. Is to do.
  • a ninth object of the present invention is to provide an optical fiber having a performance of absorbing near-infrared rays with high efficiency, and having a small change in optical characteristics even when used for a long time in a high temperature and high humidity environment. It is in.
  • the synthetic resin optical material of the present invention contains a phosphoric acid group, a copper ion, And an earth metal ion.
  • the phosphoric acid group is present by being chemically bonded during the molecular structure of the polymer.
  • the polymer is a copolymer obtained by copolymerizing a phosphoric acid group-containing monomer represented by the following formula (1) and a monomer copolymerizable therewith.
  • R represents a polymerizable functional group represented by the following formula (2)
  • n 1 or 2.
  • the phosphoric acid group may be contained in the polymer as a phosphoric acid group-containing compound represented by the following formula (3).
  • R 1 is an alkyl group having 1 to 20 carbon atoms, a phenyl group,
  • R 1 is more places
  • n 1 or 2.
  • the content ratio of copper ions is at least 0.01 part by mass per 100 parts by mass of the polymer, and the content ratio of rare earth metal ions is 100 parts by mass to the polymer. It is preferable that the content is 0.01 parts by mass or more with respect to the polymer parts, and the total content of copper ions and rare earth metal ions is 25 parts by mass or less with respect to 100 parts by mass of the polymer.
  • the synthetic resin optical material of the present invention has a performance of absorbing near infrared rays with high efficiency, Moreover, even when used for a long period of time under high temperature and high humidity, opacity is not generated, and a decrease in the transmittance of a part of the visible light is suppressed, so that the change in optical characteristics is small. .
  • the synthetic resin optical material of the present invention can also have a function of selectively absorbing light in a specific wavelength range in the visible region in addition to the near-infrared absorption function, if necessary.
  • the synthetic resin optical material of the present invention can be suitably used as a filter having both a function of improving color purity and color reproducibility and a function of absorbing near-infrared rays in a color imaging device and a color image display device. Can be used.
  • An optical filter according to the present invention is characterized by comprising the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention).
  • the plasma display device of the present invention is characterized in that an optical filter made of the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention) is arranged as a front plate of a panel.
  • the camera according to the present invention is characterized in that an optical filter made of the above synthetic resin optical material (the synthetic resin optical material of the present invention) is mounted as a visibility correction filter for a light receiving element. .
  • the imaging device of the present invention comprises the above synthetic resin optical material (the synthetic resin optical material of the present invention) as a luminosity correction filter for a CCD or a filter having both luminosity correction and color purity correction. It features an optical filter.
  • the infrared communication environment maintenance device of the present invention is characterized in that an optical filter made of the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention) is mounted as a noise cut filter.
  • a spectacle lens for cataract prevention according to the present invention is characterized by comprising the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention).
  • the heat ray absorption filter of the present invention is characterized by comprising the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention).
  • An optical fiber according to the present invention is characterized by comprising the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention).
  • An optical fiber according to the present invention is characterized in that an optical filter made of the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention) is provided in a lighting part.
  • an optical filter made of the above-mentioned synthetic resin optical material (the synthetic resin optical material of the present invention) is provided in a lighting part.
  • the optical material made of a synthetic resin of the present invention contains copper ions, rare earth metal ions, and phosphoric acid groups in a polymer.
  • Copper ions can be included in the polymer in the form of a copper compound.
  • Specific examples of copper compounds used as a source of copper ion include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetate, copper pyrrolate, and copper naphthenate. And anhydrides and hydrates such as copper citrate and the like, but are not limited to these compounds.
  • Rare earth metal ions include lanthanides, i.e., lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium. .
  • metal ions of brassodidium, neodymium, erbium, holmium, and europium are preferred from the viewpoint of solubility in a mixed monomer described below.
  • rare earth metal ions can be contained in the polymer in the form of a rare earth metal compound.
  • the rare earth metal compound used as a source of rare earth metal ions includes the above rare earth metals and organic acids such as acetic acid, benzoic acid, and oxalic acid, or inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid. Examples include, but are not limited to, anhydrides or hydrates of metal salts and oxides of rare earth metals.
  • the content ratio of copper ions is preferably at least 0.01 part by mass, more preferably 0.01 to 20 parts by mass, particularly preferably 0. It is 1 to 15 parts by mass.
  • the content ratio of the rare earth metal ion was 0.01 to 100 parts by mass of the polymer. It is preferably at least 0.1 part by mass, more preferably from 0.1 to 20 parts by mass, particularly preferably from 0.1 to 15 parts by mass.
  • the total content of copper ions and rare earth metal ions is preferably not more than 25 parts by mass, more preferably from 0.02 to 25 parts by mass, based on 100 parts by mass of polymer. Preferably it is 0.05 to 20 parts by mass.
  • the content ratio of copper ion is less than 0.01 parts by mass with respect to 100 parts by mass of the polymer, an optical material that absorbs near infrared rays with high efficiency may not be obtained.
  • the content ratio of the rare earth metal ion is less than 0.01 parts by mass with respect to 100 parts by mass of the polymer, the effect of including the rare earth metal ion is not sufficiently obtained. Prolonged use in a high-temperature, high-humidity environment may cause cloudiness or decrease the transmittance of visible light in some wavelength ranges. Also, the desired color purity correction function may not be obtained.
  • a phosphate group is contained in the polymer together with the copper ion and the rare earth metal ion.
  • the “phosphoric acid group” refers to a group represented by P O (OH) 1 (n is 1 or 2).
  • the above-mentioned copper ion and rare earth metal ion are coordinated to the phosphate group to be in a stable state, so that the dispersibility of these metal ions is increased.
  • a synthetic resin optical material having a performance of absorbing near-infrared rays with high efficiency can be obtained by the interaction between copper ions and phosphoric acid groups.
  • it is preferable to use a polymer in which a phosphoric acid group is chemically bonded in a molecular structure of a polymer that is, a polymer in which a phosphoric acid group is chemically bonded in a molecular structure.
  • the polymer in which the phosphate groups are chemically bonded in the molecular structure is represented by the above formula ( 1) (hereinafter referred to as “specific phosphoric acid group-containing monomer”) and a monomer copolymerizable therewith (hereinafter referred to as “copolymerizable monomer”). It is preferable to use a copolymer obtained by copolymerizing a mixed monomer composed of the above (hereinafter, also referred to as a “specific phosphate group-containing copolymer”).
  • the alkylene oxide group has 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
  • the number m of repeating alkylene oxide groups is an integer of 0 to 5. If the value of m exceeds 5, the resulting copolymer will have a significant decrease in hardness, and thus will lack practicality as an optical material.
  • the number n of the hydroxyl groups is 1 or 2, and depending on the properties of the obtained optical material, the molding method and the purpose of use, a specific phosphoric acid group-containing monomer having a value of n of 1
  • a specific phosphoric acid group-containing monomer having a value of n of 1 One or both of a monomer and a specific phosphoric acid group-containing monomer having a value of n of 2 can be used, and when both are used, the mixing ratio can be selected. .
  • a specific phosphoric acid group-containing monomer having a value of n of 1 has two radically polymerizable ethylenically unsaturated bonds bonded to a phosphorus atom and has a cross-linked polymerizable structure.
  • the specific phosphoric acid group-containing monomer having a value of n of 2 has the number of ethylenically unsaturated bonds of 1 and the number of hydroxyl groups bonded to the phosphorus atom. 2, which means that the bondability with copper ions and rare earth metal ions is large.
  • the optical material of the present invention is molded by an injection molding method or an extrusion molding method, which is a general molding method of a thermoplastic resin, a specific phosphoric acid in which the value of n is 2 It is preferable to use a group-containing monomer.
  • 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 are used, a specific phosphoric acid group-containing monomer is used.
  • a specific phosphoric acid group-containing monomer having a value of n of 1 and a specific phosphoric acid having a value of n of 2 Either or both of the group-containing monomers can be selected, but a mixed monomer having high solubility of the copper compound as the supply source of the copper ion and the rare earth metal compound as the supply source of the rare earth metal ion is used.
  • the specific phosphoric acid group-containing monomer having a value of n of 1 and the specific phosphoric acid group-containing monomer having a value of n of 2 are almost equimolar. , For example, a molar ratio of 45:55 to 55:45 is preferably used.
  • a mixed monomer of the above specific phosphoric acid group-containing monomer and a copolymerizable monomer is used.
  • the properties of the obtained optical material such as moisture absorption, refractive index, hardness, heat resistance, shape retention, and the like, can be adjusted according to the intended use.
  • Examples of such a copolymerizable monomer include (1) uniformly dissolving and mixing with the specific phosphoric acid group-containing monomer to be used, and (2) specific phosphoric acid group-containing monomer to be used. It is not particularly limited as long as it satisfies that the radical copolymerizability of and is satisfactory, and that (3) an optically transparent copolymer is obtained.
  • Such a copolymerizable monomer include methyl acrylate, methyl methyl acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, and n-propyl methacrylate.
  • Lower alkyl acrylates having 1 to 8 carbon atoms in the alkyl group such as acrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl acrylate, etc.
  • lower alkyl methacrylates
  • Acrylamide methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide N, N-methylacrylamide, N-isopropylacrylamide, N-isopropylmethylamide, N--n--propylacrylamide, N--n-propylmethacrylamide, Nt-n-butylacrylamide, N—t—butyl methacrylamide, N_sec—butyl acrylamide, N—sec butylmethyl amide, N—n butylacrylamide, N—n butylalkyl N-substituted alkyl acrylamide such as acrylamide And N-substituted alkyl methacrylamides,
  • Unsaturated carboxylic acids such as acrylic acid and methacrylic acid
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, nodogenated styrene methoxystyrene, and divinylstyrene.
  • ⁇ -substituted alkyl acrylamides ⁇ -substituted alkyl methacrylamides
  • ⁇ , ⁇ -substituted dialkyl Compounds having an amide group such as rilamides, ,, ⁇ -substituted dialkyl methacrylamides, N, N′-substituted alkylenebisacrylamides, ⁇ , N′-substituted alkylenebismethacrylamides, etc. It is preferable to use as part or all of the copolymerizable monomer.
  • amide group refers to a group represented by> NC 0—.
  • the dispersibility of rare earth metal ions can be increased.
  • the ratio of the specific phosphoric acid group-containing monomer to the copolymerizable monomer used is, by mass ratio, specific phosphoric acid group-containing monomer: copolymerizable monomer 3: 97 to 9 It is preferable that the ratio is 0:10, particularly 10:90 to 80:20.
  • the ratio of the specific phosphoric acid group-containing monomer is less than 3% by mass, copper ions and rare earth metal ions are contained in the obtained copolymer in a sufficiently dispersed state. In some cases, it is difficult to obtain the optical characteristics required for the optical material. On the other hand, when the proportion of the specific phosphoric acid group-containing monomer exceeds 90% by mass, the obtained copolymer has high flexibility, and the hardness required for the optical material is obtained. There may not be.
  • a specific phosphoric acid group-containing copolymer By subjecting a mixed monomer composed of the specific phosphoric acid group-containing monomer and the copolymerizable monomer as described above to radical polymerization, a specific phosphoric acid group-containing copolymer can be obtained.
  • the radical polymerization method of the mixed monomer is not particularly limited, and a method using a usual radical polymerization initiator, for example, a casting (cast) polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and the like. Method can be adopted.
  • a phosphoric acid group-containing compound represented by the above formula (3) is used instead of using the above-mentioned specific phosphoric acid group-containing copolymer in order to make the polymer contain a phosphoric acid group.
  • specific phosphoric acid group-containing compound may be contained in an appropriate polymer.
  • Specific examples of the specific phosphoric acid group-containing compound include monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, getyl phosphate, monopropyl phosphate, dipropyl phosphate. , Monoisopropyl phosphate, diisopropyl phosphate, mono n-butyl phosphate, di-n-butyl 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-isostearyl phosphate , Diisostearyl phosphate, Nofueniru Fosufue one preparative,-phosphate ester one Bok such diphenyl We
  • Mono (2-ethylhexyl) phosphonate esters such as 2-ethylhexylphosphonate, monomethylmethylphosphonate, monoethylethylphosphonate, monobutylbutylphosphonate and monodecyldecylphosphonate.
  • the proportion of the specific phosphoric acid group-containing compound to be used is preferably 1 to 10 mol, particularly preferably 1 to 5 mol, per 1 mol of the total of copper ions and rare earth metal ions. If the proportion of the specific phosphoric acid group-containing compound is too small, it becomes difficult to disperse copper ions and rare earth metal ions in the polymer, and the obtained optical material may be opaque. .
  • the ratio of the specific phosphoric acid group-containing compound is excessive, the mechanical properties required for the optical material such as hardness may not be obtained.
  • the polymer is not limited as long as it satisfies the optical characteristics required for the optical material. It is preferable to use Specific examples of the acryl monomer for obtaining the acryl resin include methyl acrylate, methyl methyl acrylate, ethyl acrylate, ethyl methacrylate, and n-butyl acrylate.
  • These compounds can be used alone or in combination of two or more as an acrylic monomer, and include copper ion, rare earth metal ion and specific phosphoric acid.
  • Tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate can be used to obtain an acryl-based resin having good compatibility with the group-containing compound.
  • Particularly preferred are acrylate, isobonyl acrylate and isobonyl methacrylate.
  • N-substituted alkylacrylamides and N-substituted alkylmethacrylamides are part of the acrylic monomer for obtaining the acrylic resin because the dispersibility of rare earth metal ions can be increased.
  • the acrylic resin obtained from the above monofunctional acrylates and monofunctional methacrylates has thermoplasticity and can be melt-molded. Therefore, by using such an acrylic resin, an optical material can be molded by a method applied to a general thermoplastic resin, for example, an injection molding method. Further, as a part of the acrylic monomer for obtaining the acrylic resin, polyfunctional acrylates or polyfunctional methacrylates can be used.
  • polyfunctional acrylates or polyfunctional methacrylates can be used as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol-dimethacrylate, 1,4-butanediol dimethacrylate, 2,2—bis (4 oxymethyloxoxy) Proha. , Trimethylolpropanthate rerate, pentaerythrite trimethacrylate, pen pen erythrite tritraterate, and the like.
  • the resulting acryl-based resin has a crosslinked structure, which makes melt molding difficult.
  • the material has high mechanical properties suitable as an optical material.
  • the method for producing the synthetic resin optical material of the present invention is not particularly limited. However, preferred methods include the following two methods (1) and (2).
  • the method further includes (1) a method in which a copper compound and a rare earth metal compound are added to a melted polymer and kneading, and (2) a polymer is dissolved in an appropriate organic solvent, and the copper compound and the rare earth metal compound are added to this solution. Then, the organic solvent is removed from the solution.
  • a monomer composition can be prepared by adding a copper compound and a rare earth metal compound to the mixed monomer and mixing them.
  • a monomer composition can be prepared by adding and mixing a compound, a rare earth metal compound and a specific phosphoric acid group-containing compound.
  • the specific method of the radical polymerization treatment of the monomer composition is not particularly limited, and may be a radical polymerization method using a usual radical polymerization initiator, that is, a radical polymerization method using a monomer composition.
  • a method in which an initiator is added and a monomer is polymerized under appropriate conditions can be used.However, when the obtained polymer has a crosslinked structure, it is difficult to melt-mold the polymer. For this reason, it is preferable to adopt a cast polymerization method that can directly obtain the shape of the desired optical product.
  • radical polymerization initiator various organic peroxide-based polymerization initiators can be used.However, in order to obtain a polymer with little coloring, tert-butyl peroxy-noate and tert-butyl peroxy-neodecane Tert-Butyl-oxypivalate, tert-Butylperoxy-2-ethylhexanoate. Non-homologous peroxyesters such as tert-butylperoxylaurate It is preferable to use disilver oxide such as lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and the like.
  • radical polymerization reaction of the monomer can be carried out at the same reaction temperature and reaction time as in a normal radical polymerization reaction.
  • the result of the reaction between the copper compound and the rare earth metal compound and the phosphoric acid group in the specific phosphoric acid group-containing monomer or the phosphoric acid group-containing compound when preparing the monomer composition The acid component in the metal compound is released. Since this acid component may cause a decrease in the moisture resistance of the obtained synthetic resin optical material, it is preferable to remove the acid component as necessary.
  • Means for removing such an acid component include (a) means for washing the monomer composition with a solvent before the polymerization treatment of the monomer composition, and (b) means for washing the monomer composition. After the radical polymerization treatment, the obtained synthetic resin is immersed in a solvent, so that a means for extracting an acid component from the synthetic resin and other means can be used.
  • the solvent used for the acid component removal treatment is capable of dissolving the released acid component and has an appropriate affinity for the polymer (does not dissolve the polymer, but has a degree of permeation into the polymer) (Affinity) is not particularly limited.
  • Such a solvent include water, lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. , Ethers such as ethyl ether and petroleum ether, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, chloroform, methylene chloride, carbon tetrachloride, and their halides And aromatic hydrocarbons such as benzene, toluene and xylene. These solvents may be used alone or in combination of two or more. Can be used.
  • water, methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methylene chloride, and the like are particularly preferable because they do not easily remain in the polymer after the acid component removal treatment is completed.
  • the amount of the acid component removed from the monomer composition or the synthetic resin is preferably at least 30% by mass, more preferably at least 40% by mass of the acid component of the metal salt used.
  • the amount of the removed acid component can be measured, for example, by quantifying the extracted component in the solvent used by an analytical means such as liquid chromatography, gas chromatography or titration.
  • the monomer composition or the synthetic resin is washed with water and dried to remove the solvent used in the acid component removal treatment from the monomer composition or the synthetic resin. Removal is preferred.
  • the specific phosphoric acid group-containing compound is added to the polymer together with the copper compound and the rare earth metal compound.
  • optical material thus obtained can be applied to various applications as shown below, either as it is or by shaping and polishing into plate, column, lens, fiber and other shapes. can do.
  • the synthetic resin optical material of the present invention can be suitably used as an optical filter.
  • the optical filter which consists of a synthetic resin optical material of this invention, the performance which absorbs near infrared rays with high efficiency is acquired.
  • the optical filter is not opaque even when used for a long time in a high-temperature and high-humidity environment, In this case, a decrease in transmittance in the wavelength range of the portion is suppressed and a change in optical characteristics is small.
  • the optical filter made of the synthetic resin optical material of the present invention has a performance of absorbing light in a specific wavelength range in the visible range by rare-earth metal ions, if necessary, in addition to the near-infrared absorption function. Thus, a color purity correction function can be provided.
  • the wavelength distribution of each color can be further improved by cutting light in the intermediate wavelength range between the colors. Independently, the purity of each color can be improved. From such a viewpoint, neodymium ion is preferable as the rare earth metal ion.
  • an optical filter made of the synthetic resin optical material of the present invention as a front panel of a panel in a plasma display device, it is possible to absorb near infrared rays emitted from the panel with high efficiency. As a result, it is possible to prevent the remote control from malfunctioning due to near infrared rays around the plasma display device.
  • the optical filter used as the front panel of the panel may become cloudy or the transmittance of visible light in a certain wavelength range may be reduced. Since the decrease is suppressed and the change in the optical characteristics is small, a good color balance can be maintained.
  • the optical filter made of the synthetic resin optical material of the present invention can be suitably used as a visibility correction filter for a light receiving element (for example, a photoelectric conversion element made of a silicon photodiode) in a photometry unit of a camera.
  • a light receiving element for example, a photoelectric conversion element made of a silicon photodiode
  • the "visibility correction filter 1" made of the synthetic resin optical material of the present invention includes a converging lens and the like, in addition to the visibility correction filter which is independently disposed in the optical path to the light receiving element. Shall be taken.
  • the light incident on the light receiving element is substantially limited to light in a visible region. Even when used for long periods in a high-temperature, high-humidity environment, changes in optical characteristics are small, resulting in accurate photometry (exposure operation). be able to.
  • the optical filter made of the synthetic resin optical material of the present invention can be suitably used as a visibility correction filter for CCD (for example, a photoelectric conversion element made of a silicon photodiode) in an imaging device.
  • the “visibility correction filter” made of the synthetic resin optical material of the present invention includes a sight, a lens, a protection plate, and the like, in addition to a visibility correction filter that is independently arranged in an optical path to a CCD. Shall be included.
  • the visibility correction filter may be provided with a color purity correction function according to the purpose.
  • Examples of the imaging device on which the CCD is mounted include a video camera, a digital camera, a board camera, a color scanner, a color fax machine, a color copier, and a color videophone device.
  • incident light to a CCD for example, a silicon photodiode
  • Photometry exposure operation
  • color purity can be corrected according to the purpose.
  • the optical characteristics change little. Good power balance can be maintained.
  • the optical filter made of the synthetic resin optical material of the present invention is used as a noise cut filter in an environment where an infrared communication device (a communication device using light having a wavelength of 850 to 950 nm as a medium) is used. It can be suitably used.
  • the “noise cut filter” made of the synthetic resin optical material of the present invention blocks infrared rays from sources of near-infrared rays (for example, automatic doors and remote controllers) to reduce noise during communication. Occurrence can be reliably prevented.
  • the synthetic resin optical material of the present invention can be suitably used as a constituent material of a spectacle lens for cataract prevention.
  • the eyes can be reliably protected from heat rays and near infrared rays that cause cataracts. Moreover, this spectacle lens becomes cloudy even if it is used for a long time in a high temperature and high humidity environment. And the change in optical properties is small due to the suppression of coloring or coloring.
  • the synthetic resin optical material of the present invention is used as a heat ray absorption filter, specifically, for window materials in buildings such as houses and buildings, window materials for vehicles such as automobiles and trains, and transparent materials for greenhouses for agricultural use and the like. It can be suitably used as a light member, a lighting cover, and the like.
  • the heat ray absorption filter which consists of a synthetic resin optical material of this invention, the performance which absorbs near infrared rays with high efficiency is acquired.
  • the heat ray absorbing filter has a small change in optical characteristics even when used in a high temperature and high humidity environment for a long period of time, while suppressing cloudiness and coloring.
  • the synthetic resin optical material of the present invention can be suitably used as a constituent material of an optical fiber.
  • an optical filter made of the synthetic resin optical material of the present invention may be provided in the lighting part of the optical fiber.
  • parts means “parts by mass”.
  • Cast polymerization was performed using this monomer composition in the same manner as in Example 1 to produce a plate-shaped synthetic resin optical material having a thickness of 2 mm.
  • Cast polymerization was performed using this monomer composition in the same manner as in Example 1 to produce a plate-shaped synthetic resin optical material having a thickness of 2 mm.
  • Example 4 Instead of praseodymium acetate dihydrate, 2.0 parts of erbium acetate tetrahydrate (0.8 parts of erbium ion based on 100 parts of mixed monomer) was used. Except for the above, a monomer composition was prepared in the same manner as in Example 4, and casting polymerization was performed using this monomer composition in the same manner as in Example 1 to obtain a plate having a thickness of 2 mm. An optical material made of resin was manufactured.
  • a monomer composition was prepared in the same manner as in Example 4, and cast polymerization was carried out using this monomer composition in the same manner as in Example 1 to obtain a plate-like synthetic resin having a thickness of 2 mm. Optical materials were manufactured.
  • a monomer composition was prepared in the same manner as in Example 4, and cast polymerization was performed using this monomer composition in the same manner as in Example 1 to obtain a plate-shaped synthetic resin having a thickness of 2 mm. Optical materials were manufactured.
  • Cast polymerization was carried out using this monomer composition in the same manner as in Example 1 to produce a plate-shaped synthetic resin optical material having a thickness of 2 mm.
  • Visible light at wavelengths of 400 nm, 500 nm and 600 nm, and near-infrared light transmission at 900 nm at an environment of 23 ° C and 50% relative humidity was measured.
  • the wavelength region where the transmittance of the line was 50% or more (hereinafter, referred to as “visible light transmission region”) was measured.
  • Cast polymerization was performed using this monomer composition in the same manner as in Example 1 to produce a plate-shaped synthetic resin optical material having a thickness of 2 mm.
  • a monomer composition was prepared in the same manner as in Example 10 except that neodymium shaunate monohydrate was not used, and cast polymerization was performed in the same manner as in Example 1 using this monomer composition.
  • a plate-shaped synthetic resin optical material having a thickness of 2 mm was manufactured.
  • the visibility correction filter was removed from the CCD camera for a computer, and a plate-shaped optical material made of synthetic resin cut into a predetermined size was attached to the front of the CCD camera.
  • the CCD camera was connected to a computer, and the red, green, and blue samples were photographed from the position where the separation distance was 20 cm by the CCD camera, and the images were displayed on the display screen.
  • the displayed image is subjected to color measurement using an XYZ display system using a color analyzer.
  • the chromaticity coordinates x and y were measured. The results are shown in Table 2.
  • the equipment used is as follows.
  • the rare earth metal ion since it contains a rare earth metal ion with a copper ion, it has the performance which absorbs near-infrared rays with high efficiency, and is used under high temperature and high humidity environment.
  • a synthetic resin optical material in which the generation of white turbidity and a decrease in the transmittance of visible light in a part of the wavelength range are suppressed, and the change in optical characteristics is small.
  • the synthetic resin optical material of the present invention since the rare earth metal ion is contained, the optical property according to the rare earth metal ion, that is, the specific wavelength range in the visible region by the rare earth metal ion is obtained. A color purity correction characteristic that absorbs light is obtained.
  • the optical filter of this invention the performance which absorbs a near-infrared ray with high efficiency is acquired, Moreover, even if it uses under a high-temperature and high-humidity environment, it produces white turbidity and some wavelengths in visible light. A decrease in the transmittance of the region can be suppressed. Further, according to the purpose, the optical filter of the present invention may be provided with a color purity correcting function.
  • the plasma display device of the present invention it is possible to prevent the remote controller from malfunctioning due to near-infrared rays around the device.
  • a good color balance can be maintained even when used for a long time 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, Moreover, the change of an optical characteristic is small even if it uses for a long time under high temperature and high humidity environment. As a result, accurate photometry (exposure operation) can be performed.
  • ADVANTAGE OF THE INVENTION According to the imaging device of this invention, the light which injects into a light receiving element can be substantially limited to the light of a visible region, As a result, accurate photometry (exposure operation) can be performed. Good color balance can be maintained even when used for a long time in a high temperature and high humidity environment.
  • the noise during communication can be prevented reliably.
  • the spectacle lens for cataract prevention of this invention an eye can be reliably protected from heat rays and near-infrared rays which are the cause of cataract onset.
  • the spectacle lens suppresses clouding and coloring even when used for a long time in a high-temperature, high-humidity environment, and has a small change in optical characteristics.
  • ADVANTAGE OF THE INVENTION According to the heat ray absorption filter of this invention, since it has the performance which absorbs near-infrared rays with high efficiency, the temperature rise in a room etc. can be suppressed reliably.
  • the heat ray absorbing filter has a small change in optical characteristics even when used for a long time in a high temperature and high humidity environment.
  • the optical fiber of the present invention since the heat ray (near infrared ray) hardly is included in the light guided and radiated by the optical fiber, the temperature rise near the light radiating portion (in the apparatus-indoor). Can be suppressed.
  • the optical fiber has a small decrease in light transmittance in the visible region even when used in a high-temperature and high-humidity environment for a long time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne: un matériau optique qui est constitué d'une résine synthétique, qui peut absorber efficacement les rayons dans l'infrarouge proche et qui, même lorsqu'il est utilisé pendant longtemps dans une atmosphère à température élevée et à forte humidité, ne peut pas souffrir de la formation d'un voile ou d'une diminution de la transmittance dans une partie de la plage de lumière visible; un filtre optique constitué de ce matériau optique; et un dispositif, un verre de lunette, un filtre d'absorption de rayons thermiques et une fibre optique pourvus dudit filtre optique. Le matériau optique constitué de résine synthétique se caractérise en ce qu'il comprend un polymère et des groupes phosphate, des ions cuivre et des ions de métaux des terres rares. De préférence, les groupes phosphates ont été chimiquement liés à la structure moléculaire du polymère. Le polymère est de préférence un copolymère obtenu par copolymérisation d'un monomère contenant un groupe phosphate et représenté par la formule générale (1) PO(OH)nR3-n avec un monomère pouvant être copolymérisé avec le monomère susmentionné. Dans ladite formule (1), R représente un groupe fonctionnel polymérisable correspondant à la formule générale (2) CH2=CXCOO(CpH2pO)m- où X représente hydrogène ou méthyle, p représente un nombre entier pouvant aller de 2 à 6 et m représente un nombre entier pouvant aller de 0 à 5, n pouvant valoir 1 ou 2.
PCT/JP1998/002250 1997-06-03 1998-05-22 Materiau optique constitue de resine synthetique, filtre optique, et dispositif, verre de lunette, filtre d'absorption de rayons thermiques et fibre optique pourvus dudit filtre optique WO1998055885A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/145165 1997-06-03
JP14516597 1997-06-03

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WO1998055885A1 true WO1998055885A1 (fr) 1998-12-10

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Cited By (9)

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JP2002006101A (ja) * 2000-06-27 2002-01-09 Kureha Chem Ind Co Ltd 光学材料
WO2006004187A1 (fr) * 2004-07-05 2006-01-12 Kri, Inc. Composite organique/inorganique
US7067074B2 (en) 2000-04-10 2006-06-27 Kureha Corporation Near-infrared-absorbing composition and optical material
JP2007063490A (ja) * 2005-09-02 2007-03-15 Denki Kagaku Kogyo Kk スチレン系樹脂組成物および成形体
JP2011063814A (ja) * 2010-12-02 2011-03-31 Kureha Corp 光学材料
CN102933624A (zh) * 2010-06-08 2013-02-13 Lg化学株式会社 具有高耐热性和高强度的丙烯酸类共聚物以及包含该丙烯酸类共聚物的光学膜
WO2014157304A1 (fr) * 2013-03-27 2014-10-02 富士フイルム株式会社 Composition absorbant les infrarouges, filtre arrêtant les infrarouges, module de caméra et procédé de fabrication d'un module de caméra
JP2017111185A (ja) * 2015-12-14 2017-06-22 川本光学工業株式会社 近赤外線カット用眼鏡
KR102779730B1 (ko) * 2024-05-03 2025-03-10 경북대학교 산학협력단 근적외선 방출 고분자 복합체 및 이를 포함하는 근적외선 방출 물품

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JPH069846A (ja) * 1983-05-25 1994-01-18 Kuraray Co Ltd ネオジム含有透明樹脂およびその製造方法
JPH0413654A (ja) * 1990-04-27 1992-01-17 Sumitomo Chem Co Ltd アントラキノン系化合物とそれを用いた近赤外線吸収用フィルター
JPH04106150A (ja) * 1990-08-24 1992-04-08 Seiko Epson Corp プラスチック組成物
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
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7067074B2 (en) 2000-04-10 2006-06-27 Kureha Corporation Near-infrared-absorbing composition and optical material
JP2002006101A (ja) * 2000-06-27 2002-01-09 Kureha Chem Ind Co Ltd 光学材料
JP4684393B2 (ja) * 2000-06-27 2011-05-18 株式会社クレハ 光学材料
US8153026B2 (en) 2004-07-05 2012-04-10 Kri Inc. Organic/inorganic composite
WO2006004187A1 (fr) * 2004-07-05 2006-01-12 Kri, Inc. Composite organique/inorganique
US7695641B2 (en) 2004-07-05 2010-04-13 Kri, Inc. Organic/inorganic composite
JP2007063490A (ja) * 2005-09-02 2007-03-15 Denki Kagaku Kogyo Kk スチレン系樹脂組成物および成形体
CN102933624A (zh) * 2010-06-08 2013-02-13 Lg化学株式会社 具有高耐热性和高强度的丙烯酸类共聚物以及包含该丙烯酸类共聚物的光学膜
JP2013534942A (ja) * 2010-06-08 2013-09-09 エルジー・ケム・リミテッド 耐熱性・高強度のアクリル系共重合体及びそれを含む光学フィルム
US8765896B2 (en) 2010-06-08 2014-07-01 Lg Chem, Ltd. Acrylic copolymer with high heat resistance and high strength, and optical film comprising the same
CN102933624B (zh) * 2010-06-08 2015-11-25 Lg化学株式会社 具有高耐热性和高强度的丙烯酸类共聚物以及包含该丙烯酸类共聚物的光学膜
JP2011063814A (ja) * 2010-12-02 2011-03-31 Kureha Corp 光学材料
WO2014157304A1 (fr) * 2013-03-27 2014-10-02 富士フイルム株式会社 Composition absorbant les infrarouges, filtre arrêtant les infrarouges, module de caméra et procédé de fabrication d'un module de caméra
JP2014191190A (ja) * 2013-03-27 2014-10-06 Fujifilm Corp 赤外線吸収性組成物、赤外線カットフィルタ、カメラモジュール及びカメラモジュールの製造方法
CN105051576A (zh) * 2013-03-27 2015-11-11 富士胶片株式会社 红外线吸收性组合物、红外线截止滤波器、照相机模块及照相机模块的制造方法
JP2017111185A (ja) * 2015-12-14 2017-06-22 川本光学工業株式会社 近赤外線カット用眼鏡
KR102779730B1 (ko) * 2024-05-03 2025-03-10 경북대학교 산학협력단 근적외선 방출 고분자 복합체 및 이를 포함하는 근적외선 방출 물품

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