WO2007148621A1 - Agent de protection contre la lumière - Google Patents

Agent de protection contre la lumière Download PDF

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Publication number
WO2007148621A1
WO2007148621A1 PCT/JP2007/062091 JP2007062091W WO2007148621A1 WO 2007148621 A1 WO2007148621 A1 WO 2007148621A1 JP 2007062091 W JP2007062091 W JP 2007062091W WO 2007148621 A1 WO2007148621 A1 WO 2007148621A1
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WIPO (PCT)
Prior art keywords
group
ring
light
general formula
cyanine dye
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PCT/JP2007/062091
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English (en)
Japanese (ja)
Inventor
Kentaro Yano
Hiroshi Nagaike
Junichiro Ihara
Yasushi Aizawa
Original Assignee
Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo
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Application filed by Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo filed Critical Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo
Priority to JP2008522424A priority Critical patent/JP5116673B2/ja
Publication of WO2007148621A1 publication Critical patent/WO2007148621A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/0018—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means for preventing ghost images

Definitions

  • the present invention relates to a light-shielding agent that absorbs in the near-infrared light region, has excellent near-infrared absorption performance, heat ray absorption performance, visible light transmission performance, light resistance, heat resistance, stable performance,
  • the present invention relates to an optical filter that can stably display a color tone when used in a display such as a suitsa display, an infrared absorption filter for digital cameras, and a heat ray absorption filter.
  • a plasma display is a video display device that uses gaseous plasma discharge light. It has a color purity comparable to that of a cathode ray tube, is easy to achieve full color, and has a wide viewing angle, making it compatible with high-definition television broadcasting. Development and mass production of large-sized video display devices are underway.
  • Satoshi Uchiike “The Journal of the Institute of Image Information and Television Engineers”, No. 51, No. 4, pp. 459 to 463 (1997) and Masahei Nozaki, “Monthly Display”, No. 6, Vol. 4, No.
  • the plasma display in principle, has a so-called “neon orange color” around a wavelength of 600 nm that is emitted when excited neon atoms return to the ground state. '' And unnecessary near-infrared radiation are unavoidable, and when mixed with red light emission, there is a problem that a vivid red display with good color purity cannot be obtained or the infrared remote control malfunctions. .
  • Japanese Patent Application Laid-Open No. 9-241520 discloses a near-infrared ray.
  • a front member using an organic dye compound of nickel complex type, azo type, or anthraquinone type as an absorbent is disclosed in Japanese Patent Application Laid-Open No. 10-128898.
  • a front member using a compound has been proposed.
  • Japanese Patent Application Laid-Open No. 2002-90521 proposes an optical filter using a cyanine dye.
  • cyanine dyes used as near-infrared absorbers have a maximum absorption wavelength in the vicinity of 85 Onm, and have a problem that they are slightly shorter than desired absorption wavelengths.
  • the present invention effectively blocks unnecessary artificial light, particularly near infrared rays, radiated from the image display device in the front member for image display devices, and also provides near-infrared rays of natural light. It is an object of the present invention to provide a light-shielding agent excellent in solubility in organic solvents, light resistance, and environmental resistance and its use. Another object of the present invention is to obtain a desired absorption wavelength by further increasing the absorption wavelength in a light-shielding agent comprising a cyanine dye.
  • cyanine dyes having a sulfonyl group at the meso position of the methine chain have an absorption maximum in the vicinity of a wavelength of 900 nm, such as plasma displays. It has been found that when used as a front member attached to a video display device, unnecessary light emitted from the video display device is effectively blocked. In addition, such cyanine dyes are excellent in light resistance and environmental resistance in organic solvents and in the state of thin films. It was found that it can be produced well.
  • the present invention solves the above problems by providing a light-shielding agent comprising a cyan dye having a sulfo group at the meso position represented by the general formula 1.
  • Z and Z represent a monocyclic or condensed aromatic ring or heterocyclic ring
  • R 6 represents the same or different aliphatic hydrocarbon group or aromatic hydrocarbon group, and these aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent.
  • R represents a hydrogen atom or a substituent
  • L represents an atomic group necessary for forming a cyclic structure
  • X m1 represents an m-valent counter ion, m is 1 to 3, and c is 0 or 1.
  • the present invention solves the above problems by providing an optical filter using a light-shielding agent comprising a cyanine dye represented by the general formula 1.
  • FIG. 1 shows transmission spectrum data in the thin film state of the cyanine dye chemical formula 26 of the present invention and the comparative compound chemical formula 274, respectively.
  • the present invention provides a light-shielding agent comprising a cyanine dye represented by the general formula 1 and
  • the present invention relates to an optical filter using such cyanine dye.
  • Z represents a monocyclic or condensed aromatic ring or heterocyclic ring.
  • Aromatic rings in Z and Z may have a substituent.
  • Aromatic rings in Z and Z may have a substituent.
  • a benzene ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, biphenyl ring, etc. and as a heterocyclic ring, for example, an imidazoline ring, an imidazole ring, a benzimidazole ring, an ⁇ naphtho ring, etc.
  • Examples of the substituent in Z and Z include a methyl group, an ethyl group, a vinyl group, and propylene.
  • R to R represent the same or different aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
  • Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, an isopropyl group, a 1-propyl group, a 2-propyl group, and a 2-propyl group.
  • aromatic hydrocarbon groups there are phenol group, o tolyl group, m-tolyl group, p tolyl group, xylyl group. Group, mesityl group, o-tame group, m-tameyl group, p-tameryl group, biphenylyl group, benzyl group, and phenethyl group. Further, these aliphatic hydrocarbon groups or aromatic hydrocarbon groups may have a substituent. Examples of the substituent include, for example, the same substituents as those in Z and Z.
  • R and R, and R and R can be bonded to form a 3- to 8-membered ring. 3 to 8 member ring
  • a cyclohexane ring As a cyclohexane ring, a cyclopentane ring, a cyclopropane ring, a dimethylcyclohexane ring, a tetrahydran pyran ring, a piperidine ring, a tetrahydro ring, which contains carbon, oxygen, sulfur and nitrogen atoms.
  • An example is a thiopyran ring.
  • R and R further include ethyl sulfonic acid and its ion, propyl sulfone.
  • Alkyl sulfonic acid groups such as acid and its ion, butyl sulfonic acid and its ion, 1-methylpropylsulfonic acid and its ion, acetic acid and its ion, propionic acid and its ion, etc. And an alkyl carboxyl group.
  • the cationic species when it has a salt structure includes inorganic ions such as lithium, sodium and potassium and organic ions such as triethylamine, tributylamine, morpholine, piperidine, pyrrolidine and ammonia.
  • R represents a hydrogen atom or a substituent, and examples of the substituent include a methyl group, an ethyl group, a bur group, a propyl group, an isopropyl group, an isopropyl group, a 1 probe group, and a 2-probe group.
  • Base group 2-propyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2 butyr group, 1, 3 butadiene group, pentyl group, isopentyl group, neopentyl group, tert pentyl group Group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group, 2 pentene-4-yl group, hexyl group, isohexyl group, 5-methylhexyl group
  • Aromatic carbonization such as alkyl group such as syl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group, phenol group, o-tolyl group, m -tolyl group, p-tolyl group and xylyl group
  • the aryl group include a hydrogen group, a benzyl group, a phenyl group, and
  • alkyl group, aryl group, and alkylaryl group include, in addition, an arylino group, an amino group, A substituent such as an alkylamino group, a halogen group, a nitro group, an alkoxy group, a cyan group, or an alkyl group may be bonded.
  • R represents, in addition to the above-described substituents of the above-mentioned substituents, an optionally substituted alino group, amino group, halogen group, nitro group, alkoxy group, cyano group, optionally substituted alkylamino group. Examples include groups.
  • L represents an atomic group necessary for binding to the methine chain moiety and forming a cyclic structure.
  • Cyclic structures include double bonds and one or more Z or heteroatoms, such as cyclobutene ring, cyclopentene ring, cyclohexene ring, benzene ring, indonaphthene ring, dehydrodecalin ring, pyridine ring, dihydropyridine.
  • Examples thereof include monocyclic or condensed polycyclic rings such as a ring, a tetrahydropyridine ring, a furan ring, a dihydrofuran ring, a thiophene ring, a dihydrothiophene ring, and a hexahydroquinoline ring.
  • X m_ represents an m-valent counter ion that keeps the general formula 1 neutral, and m is 1 to 3, and may not be present in some cases to keep neutral (in this case, The value of c in Equation 1 represents 0).
  • the counter ion include hexafluorophosphate ion, halogen ion, phosphate ion, perchlorate ion, periodate ion, hexafluoroantimonate ion, hexafluorostannate ion, and boron hydrofluoric acid.
  • Ions inorganic acid ions such as tetrafluoroborate ion, thiocyanate, benzene sulphonate, benzene disulphonate, naphthalene sulphonate, ⁇ -toluene sulphonate , Alkyl sulfonate ions, benzene carbonate ions, benzene dicarboxylate ions, benzene tricarboxylate ions, alkyl carboxylate ions, trihaloalkyl carboxylate ions, alkyl sulfate ions, trialkyl alkyl sulfate ions, nicotinate ions, etc.
  • Ions as well as azo, bisphenyldithionole, thiocatecono Chelate, thiobis Hue methylate chelate, Bisujioru - Fei - a metal complex ion of diketone are employed.
  • counter ions containing fluorine atoms such as hexafluorophosphate ion, borohydrofluoride ion, tetrafluoroborate ion, trifluorosulfonate ion, nonafluorobutanesulfur Phosphonate, di (trifluoromethylsulfol) imido-one, di (2,2,2-trifluoroethylsulfol) imido-one, di (3, 3, 3, Trifluoropropyl sulfone) imido-one, di (4, 4, 4 trifluorobutylsulfol) imido-one, di (perfluoroethylsulfol) imido-one, di (perfluro)
  • Counter ions such as isopropylsulfonyl) imido-one and di (perfluorobutylsulfol) imido-one are soluble in the solvent
  • cyanine dyes used in the present invention include those represented by chemical formula 1 to chemical formula 257, for example. These cyanine dyes have an absorption maximum in the near-infrared region having a wavelength longer than 850 nm, preferably from 850 to lOOOnm. Furthermore, the molecular extinction coefficient at the maximum absorption wavelength (hereinafter, the molecular extinction coefficient at the maximum absorption wavelength is abbreviated as “ ⁇ ”) is usually larger than 1 X 10 5, but the visible light absorption is small.
  • cyanine dyes are highly soluble in various organic solvents, especially ketone-based, halogenated hydrocarbon-based, ether-based, and ester-based organic solvents, they can be dissolved in organic solvents. Since it is easy to apply to the transparent base material, which is the main component of the front member, it is highly resistant to ambient light such as natural light and artificial light. There is a feature that the ability is difficult to attenuate. Similarly, similar effects can be expected when used for applications that block near-infrared light in natural light. Examples of the compound include compounds represented by general formulas 11 to 121. Specific examples of compounds are shown in the corresponding table.
  • the cyanine dyes of the present invention are produced by FM Harmer, "Heterocyclic ccompine saponins" and related 'compounds, Cynine Dyes, and ⁇ Related ⁇ ompounds), Nyung Wuili ⁇ ⁇ 7 and 'Sons Clohn' Wiley '&' Sons), published in 1964, and by DM Sturmer, 'Hetero Cyclic 'Compounds 1 Special' Tsubix'in ⁇ Hair mouth cyclic ⁇ Heterocyclic ⁇ Compounds- Special ⁇ topics ⁇ i ⁇ ⁇ cyclic 'chemistry ", Chapter 18, Section 14, 482-515 Page, John Wiley & Sons, published in 1977, “Rodds 'Chemistry' of 'Carbon' Compounds ⁇ 2nd.
  • the light-shielding agent containing the cyanine dye of the present invention may contain a stabilizer.
  • the stabilizer include, for example, JP-A-60-234892 and JP-A-5- No. 43814, JP-A-6-239028, JP-A-9-309886, JP-A-10-45757, and the like.
  • dithiol metal complex salt examples include a dithiol metal complex represented by the general formula 2.
  • R 1 to R 4 in the general formula 2 are a hydrogen atom, an alkyl group, an aryl group, and a shear group, respectively.
  • R and R, and R and R are connected to each other.
  • An aromatic ring such as a benzene ring or a naphthalene ring can be formed, and these aromatic rings may have a substituent.
  • substituents include the same substituents as those bonded to the aromatic ring in the general formula 1.
  • M is a group II to group IV metal in the periodic table.
  • transition metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Mo, and Cd are preferable, and Fe, Co, Cu, Ni, and Zn are more preferable.
  • n is a cation that keeps Formula 2 neutral.
  • cations are quaternary ammonium salts or quaternary phosphonium salts.
  • the quaternary ammonia salts include tetramethyl ammonium, tetraethyl ammonium, tetraptyl ammonium, octyltrileum ammonia, trimethyl ammonium ammonia, and tributylbutyl ammonium.
  • the quaternary phosphonium salts include tetramethylphosphonium, tetraethylphosphonium, tetrobinchinosephosphonium, octyltrichinenophosphonin, phenyltrimethinorephosphonium, triphenyl. -Rubutyl phosphor, triphenyl pendyl phosphor and tetraphenyl phosphor. However, it does not exist when the metal complex itself is neutral.
  • metal complex stabilizers can be used as they are by mixing with the light-shielding agent of the present invention, and those having a salt structure can be used by substituting the char-on species of the present invention.
  • dimum salt examples include a dimum salt represented by the general formula 3.
  • Rc is a substituent selected from an alkyl group, a halogenated alkyl group, a cyanoalkyl group, a aryl group, a hydroxyl group, a phenol group and a phenylalkyl group, and these are the same. Or different. Rc is not particularly limited as long as it is the above-mentioned substituent, but an alkyl group having a straight chain or a side chain having 1 to 8 carbon atoms, a halogenated alkyl group, a cyanoalkyl group, etc. are preferred. The linear alkyl group is particularly preferred.
  • particularly preferable ones include ethyl group, propyl group, butyl group, amyl group, isopropyl group, isobutyl group, isoamyl group and the like.
  • a phenylalkyl group can also be mentioned as another preferable example.
  • the alkyl group preferably has 1 to 8 carbon atoms.
  • the fur group in the phenyl alkyl group may not have a substituent, but an alkyl group, a hydroxyl group, a sulfonic acid group, an alkyl sulfonic acid group, a nitro group, an amino group, an alkoxy group,
  • the halogenated alkyl group and the group power of halogen power may have at least one substituent selected.
  • Cal phenyl group preferred tool force does not have a substituent Hue - The Ruarukiru group, a benzyl group, phenethyl group, Hue - Rupuropiru group, phenylene Lou a methylpropyl group, Hue - Lou ⁇ methylpropyl Group, a phenylbutyl group, a phenylpentyl group, a phenyloctyl group, and the like. Particularly preferred are benzyl and phenethyl groups.
  • ⁇ is a key-on for forming a salt and is a key-on species that keeps the general formula 5 neutral.
  • the anion species are an organic acid and an inorganic acid, and are not particularly limited.
  • dim-um salt examples include Chemical Formula 264 to Chemical Formula 268.
  • the above-mentioned dithiol metal complex and dimonium salt can be used in combination as a stabilizer. At that time, two or more different types can be used in combination.
  • the used member of the present invention includes at least a transparent base material as a main component of the used member and a light-shielding agent. And a cyanine dye represented by the general formula 1.
  • the “light-shielding agent” as used in the present invention is used for such a member to substantially block unnecessary light or natural light, particularly light in the near-infrared region, emitted by video display equipment.
  • a light-absorbing organic compound or a composition containing a light-absorbing organic compound is meant.
  • the amount of the above Shianin dyes respectively are generally in the range of per unit area L ⁇ 1000mgZm 2 of the optical filter, is favored properly 5: a LOOmgZm 2.
  • the transparent base material has a light transmittance of 50% or more, preferably 70% or more in the entire visible region, for example, ABS resin, polyacrylate resin, polyacrylate ester resin, Realylate resin, polyester resin, polyethersulfone resin, polyvinyl chloride resin Polyolefin resin, polycarbonate resin, polyacetic acid resin resin, polystyrene resin, polymethacrylic acid resin, polymethacrylic acid ester resin, and glass, ceramic, etc. Are used in appropriate combination. Among these, in terms of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, polyester resin, polyethersulfone resin, polyolefin resin, polycarbonate resin. Particularly preferred are fats, polymethacrylic acid coffins and polymethacrylic ester coffins.
  • the optical filter according to the present invention includes, for example, a film shape, a sheet shape, a panel, and the like, which are represented by the general formula 1, and after mixing the cyanine dye into such a transparent base material, It is expressed by general formulas 1 to 3 in close contact with one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc.
  • a light-shielding layer of cyanine dye is formed.
  • the thickness of the transparent base material depends on the material of the transparent base material and the area of the used part, from the viewpoint of strength, it is usually 0.5 mm or more, preferably 1 mm or more, while the point of mass. Is usually adjusted within a range of 10 mm or less, preferably 5 mm or less.
  • the transparent base material may not be directly attached to the use part, but the transparent base material may be bonded once to a glass plate or the like according to the shape of the use part, and the glass plate may be attached to the use part. is there.
  • the transparent substrate is formed to be relatively thin, for example, in the form of a film or a sheet, and an adhesive layer or the like for bonding the transparent substrate to a glass plate is formed on one side thereof.
  • the transparent base material and cyanine dye are melt-kneaded and, if necessary, made into pellets, etc., and then extrusion molding, injection Molding, press molding, etc. depending on the shape of the display part in the video display device, or mixing the raw material monomer and cyanine dye of the transparent substrate and casting polymerization according to the shape of the display part
  • a cyanine dye in the latter method of providing a cyanine dye layer in close contact with a transparent substrate, for example, if necessary, a cyanine dye can be used in the presence of a binder, for example, chloroform, cyclohexanone, Ethyl methyl ketone, isopropyl methyl ketone and other ketones, halogenated hydrocarbons, ethylene glycol monopropyl ether
  • a transparent base material that is dissolved or dispersed in an appropriate organic solvent such as an ether type or an ester type and formed into, for example, a film shape, a sheet shape, or a panel shape, depending on the shape of the use part Apply the solution or dispersion prepared in the same way to the film or sheet of the same material as on the transparent substrate, and then apply the film or sheet to the shape of the part to be used. Adhere to one or both sides of the transparent substrate that has been molded accordingly.
  • Examples of the noinder include ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, cellulose acetate-based resin, vinyl acetate resin, cellulose-based resin, nylon, phenol-based resin, and phenoxy.
  • examples of these include resin, polyester resin, polyethylene methacrylate resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinylpropylene resin, and polymethylmetatalate resin. Used in combination as appropriate.
  • Such a binder is usually used in a mass ratio of 10 to 1,000 times, preferably 50 to 500 times with respect to the cyanine dye of the present invention.
  • the solid cyanine dye is dispersed as fine particles having a particle diameter of 0.1 to 10 m, preferably 0.5 to 5 m.
  • a solution or dispersion containing a cyanine dye to a transparent substrate or the like, for example, a dubbing method, a flow coating method, a spray method, a bar coating method, a gravure coating method, which is widely used in the field.
  • a roll coating method, a blade coating method, an air knife coating method, and the like are applied, and these are applied in appropriate combinations as necessary.
  • the light-shielding agent of the present invention is widely used in this field together with the cyanine dye represented by the general formula 1 within a range not departing from the object of the present invention, including the stabilizers listed above.
  • the cyanine dye represented by the general formula 1 for example, amino salt compounds, amino compounds, aminothiol nickel complex compounds, anthraquinone compounds, imumum compounds, cyanine compounds, dimonium compounds, dithiol nickel complexes Systemic compounds, triallylmethane compounds, naphthoquinone compounds, nitroso compounds and their metal salts, phthalocyanine compounds, carbon black, indium tin oxide, near infrared absorbers containing antimony tin oxide, benzotriazole compounds, benzophenone compounds, Hydroxybenzoate compound, titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate UV absorber containing such, further May contain one or more of an antioxidant, a flame retardant, a stabilizer, a lub
  • the cyanine dyes of the present invention when used in combination with near-infrared absorbers and ultraviolet absorbers as described above, markedly improve the light resistance of the organic dye compounds contained in these dyes. Effectively suppresses discoloration, denaturation, and decomposition.
  • the cyanine dye of the present invention that blocks near-infrared rays can be advantageously used as a near-infrared absorbing agent or a near-infrared blocking agent alone or in combination with other compounds that absorb near-infrared rays.
  • the optical filter of the present invention together with the cyanine dye represented by the general formula 1, is generally used in the field as necessary, for example, silver, silver-palladium alloy, indium oxide, Contains indium oxide tin oxide (ITO), electromagnetic wave shielding agent containing zinc oxide, metal oxide, metal fluoride, metal silicide, metal boride, metal carbide, metal nitride, metal sulfide, etc. Do not interfere with the use of one or more anti-reflective agents. These materials are usually capable of forming as a layer independent of the light-shielding layer by cyanine dye on the transparent substrate by a method such as vacuum deposition, sputtering, ion plating, or ion beam assist. On the film or sheet of the same material as in the transparent substrate, the UV blocking layer, electromagnetic wave blocking layer, antireflection layer, etc.
  • ITO indium oxide tin oxide
  • electromagnetic wave shielding agent containing zinc oxide, metal oxide, metal fluoride, metal silicide, metal
  • One or more are formed, and the film or sheet is bonded to a transparent substrate.
  • this optical filter is provided with a non-glare layer for suppressing glare and widening the viewing angle, a hard coat layer for protecting the surface, and an optical filter, as required. It does not interfere with the provision of one or more adhesive layers, etc. for attaching to a plate.
  • the optical filter according to the present invention is selected from the cyanine dyes represented by the general formula 1 having an appropriate absorption range according to the wavelength of light to be blocked. It selectively blocks unwanted light in the near infrared region radiated from video display equipment that does not impair the color purity of the three primary colors of the image, especially near infrared light in plasma displays, providing excellent contrast and color reproducibility. High-quality images can be obtained, and the infrared remote control does not malfunction due to near infrared rays.
  • the optical filter of the present invention can be applied, for example, a direct-view television using a cathode ray tube
  • Examples include light-emitting panel televisions that use plasma displays and electroluminescent displays, non-light-emitting panel televisions that use liquid crystal displays, and rear projection televisions that incorporate liquid crystal projectors.
  • the optical filter according to the present invention can be applied very advantageously to a light-emitting panel television using a plasma display, an electroluminescence display, or the like that easily emits unnecessary light in principle.
  • a quencher refers to one having a function of de-exciting (taenting) an active molecule in an excited state.
  • Each of the cyanine dyes of the present invention represented by the chemical formula 114 and the chemical formula 179, the comparative compound represented by the chemical formula 269 and the chemical formula 270, respectively, and a metal complex (“EST— 5 ”(manufactured by Sumitomo Seika) was mixed at a mass ratio of 1: 1.
  • Each of the mixture of cyanine dye and EST-5 was dissolved in methylene chloride to prepare a solution containing 0.1% by mass of cyanine dye, and then added to methyl ethyl ketone (hereinafter referred to as “ME Kj”).
  • ME Kj methyl ethyl ketone
  • the absorbance at the maximum absorption wavelength ( ⁇ max) at that time was measured and stored in a brown bottle at room temperature (25 ° C) and stored in the dark.
  • the absorbance of the solution was measured, and the absorbance after 24 hours Z was calculated as a percentage of the absorbance value of the initial solution (the residual ratio of dye), which was used as a measure for the solution storage stability of cyanine dye.
  • the comparative compound shows only a stability of a dye residual ratio of 10% or less, while the present invention is 70% in a mixed solution with a metal complex quencher (“EST-5”).
  • a pigment residual ratio of% or more was shown.
  • the comparative example is the EST-5 used as Quenchia While the function could not be extracted and the solution stability was very low, the present invention was able to effectively utilize the quenching function.
  • the cyanine dye of the present invention represented by the chemical formula 4 and the chemical formula 146, the comparative compound represented by the chemical formula 271 and the chemical formula 272, respectively, and 0.1% by mass of the cyanine dye and the quencher (“IRG-023”) manufactured by Nippon Kayaku Co.) 0.6 wt 0/0, polymethyl methacrylate Tari rate (manufactured by "PMMA” Aldori Tutsi) 2.
  • IRG-023 0.6 wt 0/0
  • polymethyl methacrylate Tari rate manufactured by "PMMA” Aldori Tutsi
  • cyanine dye of the present invention represented by the chemical formula 83 and the chemical formula 126 and the comparative compound represented by the chemical formula 273, respectively, 0.1 mass% of the cyanine dye and Quentyaichi (“IRG-02 3” manufactured by Nippon Gyaku Co., Ltd.) ) 0.6 weight 0/0, polymethyl methacrylate Tari rate ( "PMMA” manufactured by Aldrich) 2. 5 wt 0/0 were dissolved in MEK solvent. A thin film of each solution was formed on a polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance at 675 nm was measured (absorbance of the initial thin film).
  • the compound of the comparative example showed a change in hue of 6% or more when heated at 90 ° C for 24 hours, whereas the cyanine dye of the present invention. Showed a small change rate of about 3%.
  • the conventional near-infrared absorbing dye used in the comparative example decomposes with the passage of time when the heat resistance is low, the absorption coefficient in the near-infrared region decreases, and further, absorption occurs in the visible light region due to the decomposition, Visible light transmittance decreased, and the color tone was lost due to yellow coloration.
  • the cyanine dye of the present invention has high heat resistance, and it is difficult for coloration in the visible light region due to decomposition of the dye with little decrease in absorption in the near infrared region. Compared with the existing cyanine dyes, the present invention has been shown to be superior in optical design, in which the hue hardly changes!
  • the cyanine dye of the present invention represented by the chemical formula 4, the chemical formula 144, the chemical formula 161, the comparative compound represented by the chemical formula 271, the chemical formula 274, and the chemical formula 275 are used.
  • the light stability was examined. Cyanine dye 0.1% by mass and polymethyl Metatalitate (“PMMA” manufactured by Aldrich) was dissolved in MEK solvent. Each solution was formed into a thin film by spin coating on a polycarbonate substrate. The absorption of the thin film at that time was measured, and the absorption rate of the dye at ⁇ max was determined and taken as 100%.
  • PMMA polymethyl Metatalitate
  • the compound of the comparative example had a dye residual ratio of 40% or less, and the cyanine dye of the present invention had a high value of 60% or more.
  • the dye residual ratio was shown.
  • the present invention showed high light resistance even with the dye alone.
  • a thin film of the cyanine dye of the present invention and chemical formula 26 alone was prepared in the same manner as in Example 4, and the transmission spectrum was measured. The obtained transmission spectrum data is shown in Fig. 1.
  • the cyanine dye of the present invention has a maximum absorption wavelength on the longer wavelength side than the conventional cyanine dye, so that while cutting the desired near-infrared wavelength region, At the same time, it has high characteristics as an optical filter with little visible absorption, 850 ⁇ ! ⁇ 1 Optical filters can be created without impairing the purity of the three primary colors by efficiently cutting light in the near-infrared region of OOOnm.
  • a wavelength longer than lOOnm was achieved compared to the conventional near-infrared absorbing dye used in the comparative example. From this, it is possible to propose that the dye of the present invention efficiently cuts light having a desired wavelength in the vicinity of 850 to lOOOnm, and it has been shown that it has high characteristics.
  • All of the optical filters in this example that effectively block the unnecessary light emitted from the video display device that does not impair the color purity of the three primary colors of the video can be used for video display devices such as plasma displays. It can be advantageously applied.
  • An indium tin oxide alloy was laminated on the side of the optical filter produced by the method of Example 6 on the side where the light-shielding layer of cyanine dye was formed in an argon-Z oxygen mixed gas stream.
  • a non-glare layer of a commercially available poly (methyl methacrylate) resin panel (trade name “MR-NG”, manufactured by Mitsubishi Rayon Co., Ltd.) having a non-glare layer is formed on the surface opposite to the front member. The surfaces were bonded together to obtain two types of front members for video display equipment.
  • the front members of this example that effectively block unwanted light radiated from video display equipment that does not cause glare and impair the color purity of the three primary colors of the video are all plasma display. It can be advantageously applied to video display devices such as the first.
  • the cyanine dye used in the present invention has an absorption maximum in the near-infrared region, and does not impair the color purity of the three primary colors of an image for a video display device such as a plasma display. Since the unnecessary light emitted from the image display device is effectively blocked, a high-quality image with excellent contrast and color reproducibility can be obtained. It is extremely useful as an optical filter that can be attached to video display equipment such as a plasma display as a light-shielding agent without fear of malfunction.
  • the cyanine dye used in the present invention is excellent in light resistance and environmental resistance in an organic solvent, it is possible to produce an optical filter having a low light-blocking ability with good work efficiency even when used for a long period of time. It will be.
  • the cyanine dye used in the present invention has the property that the maximum absorption wavelength reaches around lOOOnm depending on the structural design, so when it is used in combination with other organic dye compounds to form a light shielding layer in an optical filter, This has the advantage that the amount of the organic dye compound is small.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Toxicology (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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Abstract

Un but de l'invention consiste à fournir un agent de protection contre la lumière qui peut intercepter avec efficacité une lumière artificielle indésirable (en particulier, un rayon proche des infrarouges) émise à partir d'un dispositif d'affichage d'images dans un élément frontal du dispositif d'affichage d'images, qui peut également intercepter avec efficacité un rayon proche des infrarouges dans une lumière naturelle, et qui est excellent en terme de solubilité dans un solvant organique, résistant à la lumière et résistant à l'environnement, et à fournir également une utilisation de l'agent de protection contre la lumière. Un autre but de l'invention consiste à étirer la longueur d'onde d'absorption d'un colorant à la cyanine et d'obtenir une longueur d'onde d'absorption souhaitable dans le colorant à la cyanine. Par conséquent, l'invention concerne un agent de protection contre la lumière comprenant un colorant à la cyanine qui comporte un groupe sulfonyle en position méso représenté par la formule générale 1. [General formula 1] où Z1 et Z2 représentent indépendamment un noyau hétérocyclique ou cyclique aromatique fusionné qui peut comporter un substituant ; R1 à R6 représentent indépendamment un groupe hydrocarboné aliphatique ou un groupe hydrocarboné aromatique qui peut comporter un substituant, à condition que R3 et R4 ou R5 et R6 puissent former ensemble un noyau de 3 à 8 chaînons ; R7 représente un atome d'hydrogène ou un substituant ; L représente un groupe d'atomes requis en vue de la formation d'une structure cyclique ; Xm- représente un contre-ion qui a une valence de m ; m représente un nombre entier allant de 1 à 3 ; et c vaut 0 ou 1.
PCT/JP2007/062091 2006-06-20 2007-06-15 Agent de protection contre la lumière WO2007148621A1 (fr)

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JP2011225761A (ja) * 2010-04-22 2011-11-10 Shin-Etsu Chemical Co Ltd 近赤外光吸収膜形成材料及び積層膜
US20110287364A1 (en) * 2008-12-18 2011-11-24 Agfa Graphics Nv Lithographic printing plate precursor
US8685622B2 (en) 2009-04-24 2014-04-01 Agfa Graphics Nv Method for preparing a lithographic printing plate
US20150261080A1 (en) * 2012-10-11 2015-09-17 Agfa-Gevaert Infrared dyes for laser marking
WO2017094858A1 (fr) * 2015-12-01 2017-06-08 旭硝子株式会社 Filtre optique et dispositif d'imagerie
CN107108987A (zh) * 2014-12-01 2017-08-29 陶氏环球技术有限责任公司 聚合物组合物、收缩膜以及其制得方法

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JP2000025350A (ja) * 1998-06-24 2000-01-25 Eastman Kodak Co レ―ザ着色剤転写用の赤外吸収シアニン着色剤
JP2002090521A (ja) * 2000-07-06 2002-03-27 Fuji Photo Film Co Ltd 光学フィルター
JP2004190000A (ja) * 2002-12-06 2004-07-08 Kodak Polychrome Graphics Gmbh メソ置換シアニン染料の製造方法

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JPH09120115A (ja) * 1995-06-29 1997-05-06 Eastman Kodak Co シアニン色素含有写真要素
JP2000025350A (ja) * 1998-06-24 2000-01-25 Eastman Kodak Co レ―ザ着色剤転写用の赤外吸収シアニン着色剤
JP2002090521A (ja) * 2000-07-06 2002-03-27 Fuji Photo Film Co Ltd 光学フィルター
JP2004190000A (ja) * 2002-12-06 2004-07-08 Kodak Polychrome Graphics Gmbh メソ置換シアニン染料の製造方法

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110287364A1 (en) * 2008-12-18 2011-11-24 Agfa Graphics Nv Lithographic printing plate precursor
US8778590B2 (en) * 2008-12-18 2014-07-15 Agfa Graphics Nv Lithographic printing plate precursor
US8685622B2 (en) 2009-04-24 2014-04-01 Agfa Graphics Nv Method for preparing a lithographic printing plate
US9069245B2 (en) 2010-04-22 2015-06-30 Shin-Etsu Chemical Co., Ltd. Near-infrared absorptive layer-forming composition and multilayer film
JP2011225761A (ja) * 2010-04-22 2011-11-10 Shin-Etsu Chemical Co Ltd 近赤外光吸収膜形成材料及び積層膜
KR101755595B1 (ko) * 2010-04-22 2017-07-07 신에쓰 가가꾸 고교 가부시끼가이샤 근적외광 흡수층 형성재료 및 적층막
US20150261080A1 (en) * 2012-10-11 2015-09-17 Agfa-Gevaert Infrared dyes for laser marking
CN107108987A (zh) * 2014-12-01 2017-08-29 陶氏环球技术有限责任公司 聚合物组合物、收缩膜以及其制得方法
WO2017094858A1 (fr) * 2015-12-01 2017-06-08 旭硝子株式会社 Filtre optique et dispositif d'imagerie
JP6202230B1 (ja) * 2015-12-01 2017-09-27 旭硝子株式会社 光学フィルタおよび撮像装置
CN107430225A (zh) * 2015-12-01 2017-12-01 旭硝子株式会社 光学滤波器和摄像装置
CN107430225B (zh) * 2015-12-01 2019-11-08 Ａｇｃ株式会社 光学滤波器和摄像装置
US10598834B2 (en) 2015-12-01 2020-03-24 AGC Inc. Near-infrared light blocking optical filter having high visible light transmission and an imaging device using the optical filter

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