+

WO2007018065A1 - Materiau absorbant dans le proche infrarouge et son utilisation - Google Patents

Materiau absorbant dans le proche infrarouge et son utilisation Download PDF

Info

Publication number
WO2007018065A1
WO2007018065A1 PCT/JP2006/315136 JP2006315136W WO2007018065A1 WO 2007018065 A1 WO2007018065 A1 WO 2007018065A1 JP 2006315136 W JP2006315136 W JP 2006315136W WO 2007018065 A1 WO2007018065 A1 WO 2007018065A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
infrared
general formula
infrared absorbing
substituted
Prior art date
Application number
PCT/JP2006/315136
Other languages
English (en)
Japanese (ja)
Inventor
Harunori Narihiro
Original Assignee
Toyo Ink Mfg. Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink Mfg. Co., Ltd. filed Critical Toyo Ink Mfg. Co., Ltd.
Priority to JP2007529489A priority Critical patent/JPWO2007018065A1/ja
Publication of WO2007018065A1 publication Critical patent/WO2007018065A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters

Definitions

  • the present invention relates to a novel dithiol-based near-infrared absorbing material, a near-infrared absorber comprising the near-infrared absorbing material, and a near-infrared absorbing composition containing the near-infrared absorbing material or the near-infrared absorber, It relates to near-infrared absorbing films, laminates and optical filters.
  • Organonickel complexes generally have absorption in the near infrared region of 950 nm to 1200 nm, and have excellent properties as near infrared absorbers.
  • Major applications include optical filters for semiconductor light-receiving elements that have the ability to absorb and force near-infrared rays, near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, and selective use of sunlight.
  • Agricultural near-infrared absorbing film recording medium using near-infrared absorption heat, near-infrared cut filter for electronic equipment, photographic near-infrared filter, protective glasses, sunglass, heat ray-shielding film, optical recording Used for dyes, optical character reading and recording, confidential document copy prevention, electrophotographic photoreceptors, laser welding, and so on. It is also useful as a noise cut filter for CCD cameras and a filter for CMOS image sensors.
  • Plasma display emits neon gas emission lines of 800 to 1050 nm, which causes malfunction of equipment using near infrared remote control, absorbs near infrared light, and has visible transmittance.
  • An excellent filter is required.
  • the dyes used in this filter are required to have high thermal stability and high light resistance, and the chromaticity change and near-infrared absorption ability of the filter due to material deterioration over time are problems!
  • optical elements in an optical device such as a camera or a video camera, a silicon diode element, a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), or the like is used to convert an optical signal into an electric signal.
  • CMOS complementary metal oxide semiconductor
  • CCD charge coupled device
  • optical elements have a wide light sensitive region of 300 to: LlOOnm, so compared with the human eye's visual sensitivity of 400 to 70 Onm, in the near infrared region. It will be very sensitive.
  • camera and video power Optical devices such as melases need to be sensitive to light in the human visual sensitivity range, and light that falls outside this range will interfere with undesirable photometry and color reproducibility. Therefore, in this case, an optical filter that transmits visible light and efficiently absorbs and cuts near-infrared light is required.
  • a filter for the above-mentioned CCD and CMOS As a filter for the above-mentioned CCD and CMOS, a phosphoric acid ester copper compound dispersed in a resin (for example, see Patent Documents 1 to 5), a composite optical filter having a low-pass function and a visibility correction function (for example, a patent) Reference 6) There is a filter made of a resin obtained by polymerizing phosphinic acid salt as a monomer component (see, for example, Patent Document 7). However, durability and transparency are not always satisfactory. It ’s not something.
  • a dithiolate nickel polymer complex for example, see Patent Document 13
  • a bisdithiolene complex polymer for example, see Patent Document 14
  • the bisdithiolene complex polymer has an absorption wavelength region at a relatively short wavelength of ⁇ 800 nm, and is not suitable for general near infrared absorbing material applications.
  • the solubility was poor and there were drawbacks.
  • phthalocyanine-based materials are known as near-infrared absorbing compounds.
  • examples of such phthalocyanine-based materials include phthalocyanine compounds having a substituent or naphthalocyanine compounds (for example, see Patent Document 18), phthalocyanine compounds having an amino group (for example, Patent Documents). 19-23), fluorine-containing phthalocyanine compounds (for example, patents) Documents 24 and 25) are known.
  • dim-um dyes are materials that absorb a wide range of long wavelengths (950 nm to LlOOnm) and have very good transparency to visible light, and various types are known (for example, (See Patent Documents 26-29). And this pigment
  • the near-infrared absorbing dye used for the near-infrared absorbing material is generally dissolved in a solvent and then mixed with a resin and coated on a substrate such as a plastic, or heated and kneaded with a resin.
  • the film is formed into a film, sheet, plate or other shape. Therefore, the near-infrared absorbing dye is required to have excellent solubility in solvents and compatibility with rosin.
  • the near-infrared absorbing agent may be used outdoors, the near-infrared absorbing dye itself is required to have high durability, thermal stability, and the like.
  • Patent Document 1 W099Z26951 Publication
  • Patent Document 2 W099Z26952
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-7871
  • Patent Document 4 W098Z55885 Publication
  • Patent Document 5 JP 2000-38396 A
  • Patent Document 6 JP-A-8-146216
  • Patent Document 7 Japanese Patent Laid-Open No. 2000-98130
  • Patent Document 8 JP-A 63-227597
  • Patent Document 9 Japanese Patent Application Laid-Open No. 64-61492
  • Patent Document 10 Japanese Patent No. 2923084
  • Patent Document 11 Japanese Patent Laid-open No. 63-307853
  • Patent Document 12 JP-A-2-264788
  • Patent Document 13 JP-A-4 198304
  • Patent Document 14 US Patent No. 5089585
  • Patent Document 15 Japanese Unexamined Patent Application Publication No. 2005-181966
  • Patent Document 16 Japanese Patent Publication No. 6-72147
  • Patent Document 17 Japanese Patent Application Laid-Open No. 2005-232232
  • Patent Document 18 Japanese Patent Laid-Open No. 10-78509
  • Patent Document 19 Japanese Patent Laid-Open No. 2004-18561
  • Patent Document 20 JP 2001-106689 A
  • Patent Document 21 Japanese Unexamined Patent Publication No. 2000-63691
  • Patent Document 22 Japanese Patent No. 2746293,
  • Patent Document 23 Japanese Patent No. 3226504
  • Patent Document 24 Japanese Patent No. 2907624,
  • Patent Document 25 Japanese Patent No. 3014221
  • Patent Document 26 Japanese Patent Laid-Open No. 05-247437
  • Patent Document 27 Japanese Patent Laid-Open No. 2005-325292
  • Patent Document 28 Japanese Patent No. 3699464
  • Patent Document 29 Japanese Patent Laid-Open No. 2003-096040
  • Substituted benzenedithiolnickel complexes, phthalocyanines, anthraquinones, bisdithiobenzylnickel complexes, etc. which are conventionally used as near-infrared absorbing dyes, are used in combination with near-infrared absorbers.
  • the results are not necessarily satisfactory.
  • phthalocyanines are substituted with various substituents to improve solubility in a solvent, but as a result, light resistance, thermal stability, etc. are inferior.
  • the absorption spectrum is sharp, the wavelength range that can absorb near infrared rays is small.
  • substituted benzenedithiol-nickel complexes are superior in that they are relatively easy to manufacture, have good durability, etc. Solubility in solvents is low, and compatibility with resins is poor. There's a problem.
  • a near-infrared absorber when a near-infrared absorber is mixed with a monomer and this monomer is polymerized and cured to form a near-infrared absorbing member, if the solubility in the monomer is low, it becomes difficult to contain a sufficient amount of dye, On the other hand, when a dye having a sufficient solubility that contains a sufficient amount of dye is contained, there is a problem that the near-infrared absorbing layer becomes partially opaque due to the undissolved dye. Furthermore, if the compatibility between the near infrared absorber and the resin is poor, a layer having uniform near infrared absorption characteristics cannot be obtained.
  • the object of the present invention is to produce near-infrared light that is easy to manufacture, has good solubility in solvents and compatibility with rosin, and has a wide near-infrared absorption region and excellent durability.
  • Another object of the present invention is to provide a near infrared absorber having the above-mentioned excellent characteristics.
  • Still another object of the present invention is to provide a near-infrared absorbing material or a near-infrared absorbing composition containing a near-infrared absorbing agent having the above-mentioned excellent characteristics.
  • Another object of the present invention is to provide a near-infrared-absorbing laminate or film containing at least one near-infrared absorbing material or near-infrared absorber having the above-mentioned excellent characteristics.
  • Another object of the present invention is to provide an optical filter containing a near-infrared absorbing material or a near-infrared absorbing agent having the above excellent characteristics.
  • the present invention relates to the following near-infrared absorbing material, a near-infrared absorber comprising the near-infrared absorbing material, a near-infrared absorbing composition containing the near-infrared absorbing material or the near-infrared absorber,
  • the present invention relates to an infrared absorbing laminate, a near infrared absorbing film, a near infrared absorbing member, and an optical filter.
  • M represents a metal atom
  • R 1 and R 4 each independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group. Or represents a substituted or unsubstituted alkyl group
  • R 2 and R 3 each independently represents a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, or a substituted or unsubstituted group.
  • R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring ⁇ ⁇ 4 represents a direct bond or a hetero atom, and ⁇ represents a direct bond or a divalent group. Represents an organic residue.
  • the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [3], and the general formula [2]
  • a near-infrared ray-absorbing material, wherein the repeating unit represented by the formula is a repeating unit represented by the following general formula [4].
  • the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [5], and the general formula [2 A near-infrared ray-absorbing material, wherein the repeating unit represented by the formula is a repeating unit represented by the following general formula [6].
  • the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [7], and the general formula Represented by [2] A near-infrared absorbing material, wherein the repeating unit is a repeating unit represented by the following general formula [8].
  • (6) near-infrared-absorbing material characterized in that in the near infrared absorbing material according to any one of the above 1 to 5, wherein one at least of Ri ⁇ R 4 is a group having a substituent.
  • 1 to 3 are each independently a direct bond or NHCOO—, —OCON H, 1 O, 1 S, 1 NH, 1 COO, 1 OCO, 1 SO —, 1 CO. ,
  • a near-infrared absorber comprising the near-infrared absorbing material of any one of 1 to L0 above.
  • the near-infrared absorbing agent other than the near-infrared absorbing agent described in 11 above is a nickel complex-based dye, phthalocyanine-based dye, and di-moly dye.
  • a near-infrared absorbing composition characterized in that it is at least one near-infrared absorber selected from a group dye.
  • the near-infrared absorbing agent contained in the near-infrared ray-absorbing composition has a small difference in maximum near-infrared absorption wavelength.
  • a near-infrared absorbing composition comprising at least two kinds of near-infrared absorbers.
  • the near-infrared absorbing composition according to any one of the above items 12 to 19, wherein the near-infrared absorbing composition is a laser welding composition, a laser marking composition, or a heat ray blocking material composition. Or near-infrared absorbing composition characterized by being a composition for LED.
  • the layer containing the near-infrared absorbing material is formed of the near-infrared absorbing composition according to any one of the above 12 to 20.
  • a featured laminate is formed of the near-infrared absorbing composition according to any one of the above 12 to 20.
  • a near-infrared absorption finer comprising the near-infrared absorption material according to any one of 1 to LO above.
  • optical filter according to 25 above wherein the optical filter is an optical filter for a plasma display, a liquid crystal display, a CCD camera, or a CMOS image sensor.
  • the optical filter is an optical filter for a plasma display, a liquid crystal display, a CCD camera, or a CMOS image sensor.
  • the present invention it is possible to obtain a highly durable near-infrared absorbing material that is easy to manufacture, has good solubility in a solvent or compatibility with rosin, and has a wide near-infrared absorbing region. It can Further, according to the present invention, a near-infrared absorber having the above-mentioned excellent characteristics, a near-infrared absorbing composition containing the same, a near-infrared absorbing laminate, a near-infrared absorbing film, a near-infrared absorbing member, and an optical filter are obtained. I was able to. These optical filters can be preferably used as an optical filter for a plasma display, a liquid crystal display, a CCD camera, or a CMOS image sensor.
  • the present invention relates to a novel near-infrared absorbing material having a repeating unit represented by the above general formula [1] or [2], a near-infrared absorber using the same, a near-infrared absorbing composition,
  • the present invention relates to an infrared ray absorbing laminate, a near-infrared absorbing film, a near-infrared absorbing member, and an optical filter.
  • the repeating unit represented by the general formula [1] or [2] is preferably a repeating unit of the above general formulas [3] to [8].
  • R 4 each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group, preferably a substituted or unsubstituted phenyl group, substituted or unsubstituted An unsubstituted phenyl group or a substituted or unsubstituted alkyl group.
  • the substituted or unsubstituted aryl group is not particularly limited as long as it is a substituted or unsubstituted aryl group.
  • Examples of the substituted or unsubstituted aryl group include a phenyl group, a 2-5-dimethylphenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, a 3-trifluorophenyl group, 4 -Methylthiophenol group, 3,5-dicyanophenol group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-tameyl group, mesityl group, pental Group, indur group, naphthyl group, anthracyl group, azulyl group, heptalyl group, acenaphthyl group, fur
  • the substituted or unsubstituted heteroaryl group in R 4 is not particularly limited as long as it is a substituted or unsubstituted heteroaryl group.
  • Examples of the substituted or unsubstituted heteroaryl group include thiol group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, birazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, and isoquinolyl group.
  • Phthalajuryl group quinoxalinyl group, quinazolyl group, carbazolyl group, attalizyl group, naphthalyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazal group, funoxazinyl group, benzothiazolyl group
  • Examples include a benzoxazolyl group, a benzimidazolyl group, a 2-methylpyridyl group, and a 3-cyanopyridyl group.
  • the substituted or unsubstituted alkyl group for R 4 is not particularly limited as long as it is a substituted or unsubstituted alkyl group.
  • the alkyl group may be linear, branched or cyclized cycloalkyl group.
  • substituted or unsubstituted alkyl group examples include methyl group, ethyl group, propyl group, butyl group, sec butyl group, tert butyl group, pentyl group, hexyl group, 2-ethylhexyl group, heptyl Group, octyl group, isooctyl group, stearyl group, trifluoromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3 cyclohexagel group, 2 cyclopentene-1-yl group, 2,4 cyclopenta Gen 1 iridenyl group and the like.
  • R 2 and R 3 in the general formulas [1] to [8] are each independently a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, Alternatively, it represents a substituted or unsubstituted alkylene group, and R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring.
  • R 2 and R 3 are preferably substituted or unsubstituted phenylene group, substituted or unsubstituted chain group, substituted or unsubstituted group.
  • R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent.
  • R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent.
  • R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent.
  • R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent.
  • R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent.
  • a non-conjugated ring Is preferably formed with C2 to C6 carbon atoms.
  • olefin, benzene, and thiophene is preferable.
  • the substituted or unsubstituted arylene group in R 2 and R 3 in the general formulas [1] to [8] is not particularly limited as long as it is a substituted or unsubstituted arylene group.
  • the substituted or unsubstituted arylene group is preferably a monocyclic or condensed ring substituted or unsubstituted arylene group having 6 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, still more preferably 6 to 30 carbon atoms. Is a substituted or unsubstituted arylene group.
  • a substituted or unsubstituted arylene group include, for example, a substituted or unsubstituted phenylene group, biphenylene group, naphthalenedyl group, anthracenedyl group, phenanthryl group, pyrenedyl group, triphenyl group, and the like.
  • -Rangedyl group benzophenant lindyl group, perylene dil group, pentaferylene dil group, pentacene dil group and the like.
  • the substituted or unsubstituted heteroarylene group in R 2 and R 3 in the general formulas [1] to [8] is not particularly limited as long as it is a substituted or unsubstituted heteroarylene group.
  • it is a monocyclic or condensed ring substituted or unsubstituted aromatic heterocyclic group having 4 or 60 carbon atoms, more preferably carbon containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom.
  • substituted or unsubstituted aromatic heterocyclic groups include, for example, substituted or unsubstituted pyrrole dil, frangil, chalene, pyridin dil, pyridazine dil, pyrimidine dil, pyrazine dil, quinoline dil, isoquinoline dil Cinnoline, quinazoline, quinoxaline, phthalazine, pteridine, atalidine, phenazine, and phenantine.
  • the substituted or unsubstituted alkylene group in R 2 and R 3 in the general formulas [1] to [8] is not particularly limited as long as it is a substituted or unsubstituted alkylene group.
  • the alkylene group may be a branched one or a cyclized cycloalkylene group.
  • Specific examples of the substituted or unsubstituted alkylene group include a methylene group, an ethylene group, and a propylene group.
  • the substituent in each group in the present invention is a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a substituted or unsubstituted alkyl group, a substituted or unsubstituted group.
  • a halogen atom for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • Examples of the substituted or unsubstituted aryl group as the substituent include, for example, a phenyl group, a biphenylenyl group, a triphenylenyl group, a tetraphenylenyl group, a 3-trifluorophenyl group, a 4-methylthiophene group.
  • Examples of the substituted or unsubstituted heteroaryl group as a substituent include, for example, a thionyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, and a pyridazinyl group.
  • the mono- or di-substituted amino group as a substituent includes, for example, a methylamino group, a dimethylamino group, an ethylamino group, a jetylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, a bis (acetooxy).
  • a methylamino group a dimethylamino group, an ethylamino group, a jetylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, a bis (acetooxy).
  • Examples include methyl) amino group, bis (acetoxetyl) amino group, bis (acetooxypropyl) amino group, bis (acetooxybutyl) amino group, dibenzylamino group and the like.
  • Examples of the substituted or unsubstituted alkyl group as the substituent include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a sec butyl group, a tert butyl group, a pentyl group, a hexyl group, and 2-ethyl.
  • Examples of the substituted or unsubstituted alkoxy group as a substituent include, for example, a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, a sec butoxy group, a tert butoxy group, a pentyloxy group, a hexyloxy group, Examples include 2-ethylhexyloxy group, stearyloxy group, trifluoromethoxy group and the like.
  • Examples of the substituted or unsubstituted thioalkoxy group as a substituent include, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, A heptylthio group, an octylthio group, etc. are mentioned.
  • Examples of the substituted or unsubstituted aryloxy group as a substituent include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group.
  • Examples of the substituted or unsubstituted arylothio group as a substituent include a phenolthio group and a 3-fluorophenylthio group.
  • substituents are an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a mono- or di-substituted amino group.
  • adjacent substituents form an aliphatic, carbocyclic aromatic, heterocyclic aromatic or heterocyclic ring which may contain a 5- to 7-membered oxygen atom, nitrogen atom, sulfur atom, etc. It is also placed at any position on these rings. You may have a substituent.
  • Tables 2-1 and 2-2 below show preferred examples of the groups —Y 2 —R 2 —, —Y 3 —R 3 —, but the groups —Y 2 —R 2 —, — Y 3 — R 3 — is not limited to those exemplified in Table 2-1 and Table 2-2.
  • Y 2 — R 2 — and — Y 3 — R 3 — R 2 and R 3 are aryl, they are substituted at the ortho position relative to — Y 2 — or — Y 3 — of the aryl group. When it has a group, one having good solubility in a solvent can be obtained.
  • R 4 examples include those listed in Tables 3-1 and 3-2 below, including those listed in Tables 1-1 and 1-2.
  • R 3 examples include those listed in Table 4-1 and Table 4-2 below, including those listed in Tables 2-1 and 2-2.
  • R 2 and R 3 are preferably those containing a sulfide bond group, an arylene group, a heteroarylene group, or an alkylene group. More preferred are those having a sulfido bond group.
  • A represents a direct bond or a divalent organic residue.
  • N N—, —S— S—, substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted alkylene group, and substituted or unsubstituted amino group
  • a heteroarylene group a substituted or unsubstituted alkylene group, an ether group, a sulfide bond group, a urethane bond group, an amide bond group, a carboxyl group, an ester group or an amino group, or a combination thereof as appropriate Those are preferred.
  • the substituted or unsubstituted arylene group in A of the general formulas [1] to [8] may be any substituted or unsubstituted arylene group.
  • the arylene group is preferably a monocyclic or condensed ring arylene group having 6 to 60 carbon atoms, more preferably an arylene group having 6 to 40 carbon atoms, and further preferably 6 to 30 carbon atoms. Specific examples are Huelen and Bihue.
  • Rhen naphthalene diyl, anthracenedyl, phenanthrene lindyl, pyrene diyl, triphenylene dill diyl, benzophenanth lindyl, perylene dil, pentaphenylene dil, pentasen dil, etc., and these groups optionally have substituents. You may do it.
  • the substituted or unsubstituted heteroarylene group of A may be any substituted or unsubstituted heteroarylene group.
  • the heteroarylene group is preferably a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms, more preferably 4 to 60 carbon atoms containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom.
  • aromatic heterocyclic group examples include pyrrole diyl, frangyl diyl, chalene, pyridine diyl, pyridazine dill, pyrimidine dil, pyrazine dil, quinoline dil, isoquinoline dil, cinnoline dil, quinazoline dil, quinoxaline dil, phthalazine dil, Forces such as ataridinyl, phenazine, and phenantine ring.
  • These groups may optionally have a substituent.
  • the substituted or unsubstituted alkylene group in A may be any substituted or unsubstituted alkylene group.
  • the alkylene group include methylene, ethylene, propylene, butylene, sec-butylene, tert-butylene, pentylene, hexylene, 2-ethylhexylene, heptylene, and octylene.
  • Examples of the substituent in the above A include those described for R 1 to R 4 .
  • Tables 5-1 and 5-2 below show examples of A, but A is not limited to these [Table 5] Table 5
  • the near-infrared absorbing material having a repeating unit represented by the general formulas [1] to [8] may be a polymer mixture, a non-conjugated polymer, or a conjugated polymer.
  • the near-infrared absorbing material of the present invention may be a single polymer or copolymer having a repeating unit represented by the general formula [1] and Z or the general formula [2].
  • the copolymer may be a copolymer of two or more different repeating unit units contained in the repeating unit represented by the general formula [1] or [2], or the general formula [1] or May be a copolymer comprising a repeating unit represented by the general formula [2] and a repeating unit other than the general formula [1] or the general formula [2].
  • the copolymer may be a random, block, or graft copolymer, or may be a polymer having an intermediate structure thereof, such as a random copolymer having a block property.
  • the copolymer component other than the repeating unit represented by the general formula [1] or the general formula [2] of the present invention is a compound having a polymerizable reaction terminal, for example, a compound having at least two OH groups in the same molecule.
  • Compounds having halogen and OH groups in the same molecule, compounds having multiple halogen groups in the same molecule, compounds having multiple COOH groups in the same molecule, compounds having multiple COC1 groups in the same molecule, in the same molecule Compounds with OH and COOH groups in the same group, compounds with multiple NH groups in the same molecule, NH groups and COOH groups in the same molecule
  • the weight-average molecular weight of the near-infrared absorbing material of the present invention is not particularly limited from the viewpoints of heat resistance and light resistance, but for example, 1,000 to 10,000 in terms of polystyrene by gel permeation chromatography measurement method. , 000 is preferable.
  • M is not particularly limited as long as it is a metal atom, but nickel, cobalt, platinum, palladium or copper is more preferable.
  • R 4 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted alkyl group having 20 or less carbon atoms.
  • R 2 and R 3 are substituted or unsubstituted phenyl.
  • the compounds of general formulas B to E in the synthesis scheme are, for example, ⁇ ournal of American Chemical Society, 87: 7, April 5, 1965 or a method according to the synthesis method described in US Patent No. 5089585.
  • the compounds of general formulas F to H can be produced by the synthesis method described in JP-A-2005-232158.
  • Q corresponds to a part of A in the general formulas [1] to [8].
  • a base such as NaOH, KOH, KCO, NaCO, or triethylamine in a polar solvent such as dimethylformamide, dimethylsulfoxide, or methylethylketone
  • the near-infrared absorbing material having the repeating unit of the general formula [1] or [2] or the near-infrared absorbing agent of the present invention comprising the near-infrared absorbing material is used for applications that require absorption of near-infrared rays.
  • its use form and use form are not limited by the structure of the near-infrared absorbing material. That is, the near-infrared absorbing material or near-infrared absorbing agent of the present invention is a light-absorbing property such as a near-infrared absorbing material other than the near-infrared absorbing material containing the repeating unit structure of the general formula [1] or the general formula [2].
  • auxiliary materials such as dyes, ultraviolet absorbers, stabilizers such as antioxidants, and the near-infrared absorbing material and near-infrared absorbing agent of the present invention can be used together with these auxiliary components as a solvent. Or dissolved in a solvent or water, or if necessary, dissolved in a solvent or dispersed in a solvent or water together with a binder resin to obtain a near-infrared absorbing composition (coating agent), which is applied to a substrate or the like. If the near infrared absorption layer can be formed, and the binder resin can form a self-supporting film, the film is formed on the releasable substrate and then peeled off. Peeling off the substrate mosquitoes ⁇ Luo film, it can be used as a near infrared absorbing film. At this time, the coating composition may be oily, aqueous, solution, or pasty.
  • the near-infrared absorbing agent of the present invention is applied to other functional layers such as a pressure-sensitive adhesive or an adhesive layer, an ultraviolet absorbing layer, a hard coat layer, and a substrate. These layers may be provided with near infrared absorption characteristics.
  • a pressure-sensitive adhesive or an adhesive layer may be provided with near infrared absorption characteristics.
  • a conventionally known pressure-sensitive adhesive is used in the adhesive composition.
  • add a near-infrared absorber, and a near-infrared-absorbing pressure-sensitive adhesive is used to obtain an adhesive.
  • a near-infrared-absorbing pressure-sensitive adhesive layer or An adhesive layer may be formed, and this layer may be used as a near infrared absorption filter.
  • the other components may be included.
  • a laminate or a single film having a near-infrared absorbing layer containing the near-infrared absorbing material or near-infrared absorber of the present invention is preferably used as an optical filter.
  • the near-infrared absorbing composition of the present invention includes the near-infrared absorbing material or near-infrared absorbing agent of the present invention, and other light-absorbing dyes, stabilizers, and binders used as necessary. It is composed of fat, solvent, adhesive rosin, other auxiliary components, and components that form other functional layers if necessary.
  • Examples of the other light-absorbing dyes include cyanine, quinoline, coumarin, thiazole, oxonol, azulene, squarylium, azomethine, azo, benzylidene, xanthene , Phthalocyanine series, naphthalocyanine series, naphthoquinone series, anthroquinone series, triphenylmethane series, dimethyl series, dithiol metal complex systems other than the metal complexes represented by the above general formula [1] or general formula [2] Compounds and the like.
  • the other light-absorbing dye a nickel complex dye, a Z or phthalocyanine dye, and a Z or dimonium dye, which are near-infrared absorbers, are preferable.
  • the amount of these other light-absorbing dyes added to the near infrared absorber of the present invention is preferably 20 to 500 parts by weight, more preferably 50 to 200 parts per 100 parts by weight of the near infrared absorber of the present invention. Parts by weight.
  • the visible light transmittance when the film is 70 to 80% or more and the transmittance in the near infrared region to be 10% or less.
  • nickel complex dye examples include those having the structure of the following general formula [10], which may further be an ionic compound with a monovalent cation.
  • Nickel complex dyes having the structure of the general formula [10] are specifically ADS845MC, ADS870MC, ADS880MC, sold by Ameri can Dye Source, Ink (Laser Dyes & Near Infrared Dyes), Examples include, but are not limited to, ADS890MC, ADS920MC, A DS990MC.
  • phthalocyanine dyes those represented by the following general formula [11] are preferable.
  • M represents a metal atom, wherein R 13 to R 28 represent a hydrogen atom or a substituent, and M is further substituted.
  • dimonium dye those having the structure of the following general formula [12] are preferable.
  • examples of the X-halogen ion include iodine ion, bromine ion, chlorine ion, and fluorine ion.
  • examples of inorganic acid ions include hexafluoroantimonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, and nitrate ions.
  • organic acid ion examples include acetate ion, trifluoroacetate ion, methanesulfonate ion, trifluoromethanesulfonate ion, benzenesulfonate ion, toluenesulfonate ion, and the like.
  • examples of commercially available products include, but are not limited to, Nippon Kayaku Co., Ltd. IRG-022, IRG-023, IRG-040, and the like.
  • Examples of the various stabilizers used for the purpose of stabilizing the near-infrared absorber of the present invention and the other light-absorbing dyes with respect to light or heat include, for example, a hydrocarbon derivative.
  • a hydrocarbon derivative U.S. Patent No. 3935016, U.S. Patent No. 3982944
  • Hyde Mouth Quinone Diether Derivative U.S. Pat. No. 4,254,216
  • Phenolic Derivative Japanese Patent Laid-Open No. Sho 54-21004
  • Spiroindane or Methylenedioxy Derivatives of benzene UK Patent Application Publication No.
  • the optical filter of the present invention may contain an aromatic-troso compound, an aminium compound, an iminum compound, a biiminium compound, a transition metal chelate compound, etc. as a quencher such as singlet oxygen.
  • Quencherons such as bisthiolate metal complexes can also be used.
  • the amount of additives such as light-absorbing pigments and various stabilizers other than the near-infrared absorber of the present invention, which is used as an auxiliary to the near-infrared absorber of the present invention, is the near-infrared absorber of the present invention.
  • the ratio is preferably such that the visible light transmittance is 70 to 80% or more and the transmittance in the near infrared region is 10% or less when used as a film.
  • the near-infrared absorber of the present invention can form a coating composition together with a binder resin if necessary.
  • coating this coating composition on a base material the layer containing a near-infrared absorber can be formed and it can be set as a laminated body with a base material.
  • This laminated body can be used as, for example, an optical filter, an optical reflecting plate, an optical diffusion plate, etc. by selecting the type of base material, as well as an agricultural near-infrared absorbing film, a heat ray shielding film, etc. It can also be used as protective glasses, sunglasses, electrophotographic photoreceptors, and the like.
  • the near-infrared absorber of the present invention includes a recording medium that utilizes near-infrared absorption heat, an optical recording dye, an optical character reading and recording material, a layer for preventing confidential document copying, and a near-infrared absorber for laser welding. It can also be used.
  • binder resin examples include aliphatic ester resin, polymethyl (meth) acrylate resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, and polycarbonate resin.
  • natural polymer materials such as gelatin, casein, starch, cellulose derivatives, alginic acid and the like can also be mentioned.
  • binder resins appropriate resins and copolymers are selected depending on whether the coating composition is oily or aqueous.
  • Organic solvents constituting the oil-based coating agent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixed solvents thereof. Can be mentioned.
  • the near-infrared absorber of the present invention is pulverized to produce fine particles of several micrometers or less. Examples thereof include a method of dispersing the fine particles in an uncolored acrylic polymer emulsion.
  • an adhesive binder may be used as a binder.
  • the adhesive binder include acrylic, urethane and rubber.
  • Monomers that can be used as acrylics are acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2— Ethyl hexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nor (meth) acrylate, decyl (meth) acrylate, undecyl (Meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth)
  • the weight average molecular weight (Mw) of an acrylic copolymer obtained by copolymerizing an acrylic monomer, an acrylic monomer having an alkylene oxide chain, and other monomers in the above-mentioned adhesive binder is 50,000 to 100. More preferred is a low molecular weight acrylic copolymer of 50,000 to 200,000.
  • the pressure-sensitive adhesive containing the pressure-sensitive adhesive binder and the near-infrared absorber of the present invention is coated on the base material by a known method to form a pressure-sensitive adhesive sheet as a laminate.
  • a known method to form a pressure-sensitive adhesive sheet as a laminate.
  • paper, metal, cloth, etc. are used as the base material used here.
  • the adhesive binder can form a sheet by itself, the adhesive sheet does not require a base material.
  • the form by which an adhesive is coated on both surfaces of a base material may be sufficient.
  • one The surface adhesive may not include the adhesive of the present invention.
  • the addition amount of the near-infrared absorber of the present invention to the binder resin containing the adhesive binder resin is 0.01 to 20 parts by weight of the near-infrared absorber with respect to 100 parts by weight of the resin. More preferably, it is 0.1 to 15 parts by weight with respect to 100 parts by weight of the resin. If this ratio is less than 0.01 parts by weight, it is not possible to efficiently absorb light in the near-infrared region, whereas if it exceeds 20 parts by weight, the dispersibility of the near-infrared absorber is not possible. May decrease and transparency (visible light transmission) may be impaired.
  • the adhesive composition in the present invention is a processed material having near-infrared absorptivity comprising the near-infrared absorber and adhesive of the present invention.
  • the adhesive composition as the near-infrared absorbing composition of the present invention can be prepared by dissolving or dispersing the near-infrared absorbing material of the present invention in an appropriate medium having adhesiveness.
  • the near-infrared absorbing material or near-infrared absorbing agent of the present invention can be preferably used as a dye constituting an optical filter.
  • the method for forming an optical filter include the near-infrared absorbing material or near-infrared absorbing material of the present invention, the other light-absorbing dyes and various stabilizers, for example, a base material or an arbitrary layer constituting the optical filter.
  • each layer such as an undercoat layer, an antireflection layer, a hard coat layer, or a lubricating layer may be provided on the base material as necessary.
  • the near-infrared absorber of the present invention can be suitably used in a method of providing a near-infrared absorbing layer by mixing it with a polymer binder, an adhesive, or a pressure-sensitive adhesive between the layers constituting the optical filter.
  • the amount used is usually 1 to: L000 mg / m 2 per unit area of the optical filter, preferably 5 ⁇ : a LOOmg / m 2. If the amount used is less than lmg / m 2 , the near-infrared absorption effect cannot be fully exerted, and if it exceeds lOOOmgZm 2 , the filter color may become too strong and the display quality may deteriorate. Further, it is not preferable because the brightness may be lowered.
  • Examples of the material of the base material include inorganic materials such as glass; and are, for example, diacetyl cellulose, triacetyl cellulose (TAC), propiole cellulose, butyrinole senorelose, acetinorepropiline ninoresenorelose, Polyester; Polyester; Polyethylene; Polyethylene; Polyethylene terephthalate; Polyethylene naphthalate; Polybutylene terephthalate; Poly 1,4-cyclohexanedimethylene terephthalate; Polyethylene 1, 2 Diphenoletane 4, Polyesters such as 4'-dicarboxylate and polybutylene terephthalate; polystyrene; polyolefins such as polyethylene, polypropylene, and polymethylpentene; acrylic resins such as polymethylmethalate; ; It includes polyoxypropylene polymeric materials such as ethylene is; polysulfones; polyethersulfones; polyetherols Honoré
  • the substrate is a transparent support.
  • the transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more.
  • the haze is preferably 2% or less, more preferably 1% or less.
  • the refractive index is preferably 1.45 to L70.
  • a light-absorbing dye, an antioxidant, a light stabilizer, an ultraviolet absorber, inorganic fine particles, and the like can be added as necessary. Can be subjected to various surface treatments.
  • Examples of the inorganic fine particles include inorganic fine particles such as silicon dioxide, titanium dioxide, barium sulfate, calcium carbonate, talc, and kaolin.
  • Examples of the various surface treatments include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Etc.
  • the undercoat layer is a base layer for improving the adhesion between the substrate, the near-infrared absorbing layer, and the like. It is a layer used between a material and a near-infrared absorption layer.
  • the undercoat layer is a layer containing a polymer having a glass transition temperature of ⁇ 60 to 60 ° C., a layer having a rough surface on the near infrared absorbing layer side, or a layer containing a polymer having affinity with the polymer of the near infrared absorbing layer. Formed as.
  • an undercoat layer is provided on the surface of the base material on which the near infrared absorption layer is not provided, It may be provided to improve the adhesive strength with the layers (eg, antireflection layer, hard coat layer) provided thereon, and the undercoat layer is an adhesive for adhering the optical filter and the image forming apparatus. May be provided to improve the affinity between the agent and the optical filter.
  • the thickness of the undercoat layer is preferably 2 nm to 20 ⁇ m, more preferably 5 nm to 5 ⁇ m, more preferably 20 nm to 2 ⁇ m, and even more preferably 50 ⁇ to 1 / ⁇ ⁇ , 80 ⁇ ! ⁇ 300nm is most preferred.
  • the undercoat layer containing a polymer having a glass transition temperature of 60 to 60 ° C. adheres the substrate and the near-infrared absorbing layer due to the tackiness of the polymer.
  • Polymers having a glass transition temperature of -60 to 60 ° C are, for example, vinyl chloride, vinylidene chloride, butyl acetate, butadiene, neoprene, styrene, black mouth plain, acrylic acid ester, methacrylic acid ester, acrylonitrile or methyl vinyl. It can be obtained by polymerization of ether or copolymer thereof.
  • the glass transition temperature is preferably 50 ° C or lower, more preferably 40 ° C or lower, more preferably 30 ° C or lower, and further preferably 25 ° C or lower. Further, it is most preferable that the temperature is 20 ° C or less.
  • the elastic modulus at 25 ° C of the undercoat layer is most preferably 1 to: 5 to 800 MPa, more preferably 10 to 500 MPa, more preferably LOOOMPa.
  • the undercoat layer having a rough surface forms a near-infrared absorbing layer on the rough surface, thereby bonding the substrate and the near-infrared absorbing layer.
  • the undercoat layer having a rough surface can be easily formed by applying a polymer latex.
  • the average particle size of latex is 20 ⁇ !
  • the polymer having an affinity for the binder polymer of the near-infrared absorbing layer include acrylic resin, cellulose derivatives, gelatin, casein, starch, polybutyl alcohol, soluble nylon, and polymer latex.
  • two or more undercoat layers may be provided.
  • a solvent that swells the base material, a matting agent, a surfactant, an antistatic agent, a coating aid, a hardening agent, and the like may be added.
  • a low refractive index layer is essential.
  • the refractive index of the low refractive index layer is lower than the refractive index of the transparent support.
  • the refractive index of the low refractive index layer is preferably 1.20 to L55, more preferably 1.30 to L50.
  • the thickness of the low refractive index layer is preferably 50 to 400 nm, and more preferably 50 to 200 nm.
  • the low refractive index layer is a layer made of a fluorine-containing polymer having a low refractive index (Japanese Patent Laid-Open No.
  • JP-A-3-130103 JP-A-6-115023, JP-A-8-313702, JP-A-7-168004
  • layers obtained by the sol-gel method JP-A-5-208811, JP-A-6-299091, No. 7-168003 or a layer containing fine particles
  • voids can be formed in the low refractive index layer as microvoids between the fine particles or within the fine particles.
  • the layer containing fine particles preferably has a porosity of 3 to 50% by volume, more preferably 5 to 35% by volume.
  • a layer having a high refractive index (medium'high refractive index layer) is preferably laminated.
  • the refractive index of the high refractive index layer is preferably 1.65-2.40, more preferably 1.70-2.20.
  • the refractive index of the middle refractive index layer is adjusted to be an intermediate value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer.
  • the refractive index of the middle refractive index layer is preferably 1.50 to L90, more preferably 1.55 to L70.
  • the thickness of the medium / high refractive index layer is preferably 5 ⁇ to 100 / ⁇ ⁇ , more preferably 10 ⁇ to 10 / ⁇ m, and most preferably 30 ⁇ to 1 / ⁇ ⁇ . preferable.
  • the haze of the medium / high refractive index layer is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less.
  • the middle / high refractive index layer can be formed using a polymer binder having a relatively high refractive index.
  • polystyrene examples include polystyrene, styrene copolymer, polycarbonate, melamine resin, phenol resin, epoxy resin, polyurethane obtained by reaction of cyclic (alicyclic or aromatic) isocyanate and polyol, etc. Can be mentioned.
  • Polymers having other cyclic (aromatic, heterocyclic, and alicyclic) groups and polymers having a non-fluorine atom or a rogen atom as a substituent also have a high refractive index.
  • inorganic fine particles may be dispersed in the polymer binder.
  • the refractive index of the inorganic fine particles is preferably 1.80 to 2.80.
  • the inorganic fine particles are preferably formed from metal oxides or sulfides. With metal oxides or sulfides Examples thereof include acid titanium (for example, rutile, a mixed crystal of rutile z anatase, anatase, amorphous structure), tin oxide, indium oxide, zinc oxide, acid zirconium, zinc sulfide and the like. Of these, titanium oxide, acid tin oxide and indium oxide are particularly preferred.
  • the inorganic fine particles can contain oxides or sulfides of these metals as main components and further contain other elements.
  • the main component means a component having the highest content (% by weight) among the components constituting the inorganic fine particles.
  • other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S.
  • it is a film-forming inorganic material that can be dispersed in a solvent or is itself a liquid, such as alkoxides of various elements, salts of organic acids, and coordination compounds combined with coordination compounds.
  • a medium (high refractive index layer) can also be formed using a compound (for example, a chelate compound), an active inorganic polymer, or the like.
  • the antireflection layer surface can be provided with an antiglare function (a function of scattering incident light on the surface and preventing the scenery around the film from moving to the film surface).
  • an antiglare function a function of scattering incident light on the surface and preventing the scenery around the film from moving to the film surface.
  • the anti-glare function can be achieved by forming fine irregularities on the surface of a transparent film and forming an antireflection layer on the surface, or by forming irregularities on the surface with an embossing roll after forming the antireflection layer. It is possible to obtain an antireflection layer having An antireflection layer having an antiglare function generally has a haze of 3 to 30%.
  • the hard coat layer has a hardness higher than that of the transparent support.
  • the hard coat layer preferably contains a crosslinked polymer.
  • the hard coat layer can be formed using an acrylic, urethane, or epoxy polymer, oligomer, or monomer (for example, an ultraviolet curable resin).
  • the silica-based material strength can be achieved by forming a hard coat layer.
  • a lubricating layer may be formed on the surface of the antireflection layer (low refractive index layer).
  • the lubricating layer has a function of imparting slipperiness to the surface of the low refractive index layer and improving scratch resistance.
  • the lubricating layer can be formed using polyorganosiloxane (for example, silicon oil), natural wax, petroleum wax, higher fatty acid metal salt, fluorine-based lubricant or derivative thereof.
  • the thickness of the lubricating layer is preferably 2 to 20 nm.
  • the near-infrared absorbing layer, undercoat layer, antireflection layer, hard coat layer, lubricating layer and the like can be formed by a general coating method.
  • Application methods include dip coating, Examples thereof include an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and an etha trusion coating method using a hopper (see US Pat. No. 2,681,294).
  • Two or more layers may be formed by simultaneous application. Simultaneous coating method [Described by Kotsu Tetsuma, U.S. Patent Nos. 2761791, 2941898, 3508947, 3526528 and Yuji Harasaki "Coating Engineering", page 253 (published by Asakura Shoten in 1973) There is.
  • the near-infrared absorbing material of the present invention is used for welding a resin material, the color difference between the resin materials can be reduced by laser irradiation, and the contact surfaces can be reliably welded together. Adhesive strength can be obtained by wearing. That is, in recent years, resin molded products are frequently used as parts in various fields such as automobile parts from the viewpoint of light weight and cost reduction. In addition, from the viewpoint of increasing the productivity of a resin molded product, a method is often employed in which the resin molded product is divided into a plurality of pieces in advance and these divided molded products are joined to each other.
  • the resin materials can be joined together by superimposing a transparent resin material that is permeable to laser and an absorbent resin material that is absorbent to the laser, and then transmitting the permeable material. It is performed by a laser welding method that heats and melts the contact surfaces of the permeable and absorbent resin materials by irradiating the laser from the side of the resin material, thereby joining them together.
  • the resin members to be bonded are of two types, those having absorption with respect to the laser and those having no absorption. For this reason, there is a difference in the color tone, and there is a limit to the use of the bonded resin member.
  • the non-absorbable resin material for laser is white or transparent laser transmission color
  • the absorptive member is black laser absorption color such as carbon black. It seemed to cause a sense of incongruity. In other words, when these different colored resin materials are joined, the apparent joining force is felt weak and the joint is conspicuous.
  • the laser that has passed through the permeable resin material reaches the contact surface of the absorbent resin material and is absorbed, and the laser beam absorbed by this contact surface is used as energy. Accumulated.
  • the contact surface of the absorbent resin material is heated and melted, and the heat transfer of the contact surface force of the absorbent resin material heats and melts the contact surface of the permeable resin material. .
  • the contact surfaces of the permeable resin material and the absorbent resin material are pressure-bonded, the two can be integrally bonded.
  • this material Since this material has a good transmittance for visible light, it can reduce the color difference from the laser-transmissible resin material, and has a large molar extinction coefficient in absorption in the near infrared region.
  • the resin composition having sufficient bonding strength can be provided by reliably welding the contact surfaces of the permeable resin material and the absorbent resin material.
  • the optical filter according to the present invention can be suitably used as a visibility correction filter for a CCD (for example, a photoelectric conversion element made of a silicon photodiode) in an imaging device (image input device).
  • a visibility correction filter for CCD includes a lid, a lens, a protective plate, etc., in addition to a visibility correction filter arranged alone in the optical path to the CCD.
  • imaging devices equipped with CCDs include video cameras, digital cameras, board cameras, color scanners, color fax machines, color copiers, and color videophones.
  • the incident light to the CCD (silicon photodiode) can be substantially limited to light in the visible region. As a result, accurate photometry ( (Exposure operation) can be performed, and there is no trouble in reproducing the red component.
  • the optical filter according to the present invention can be suitably used as a visibility correction filter for an imaging device (image input device) equipped with a CMOS image sensor or an artificial retina.
  • an imaging device image input device
  • CMOS image sensor and artificial retina provided with the optical filter of the present invention, and an imaging device equipped with these, the same effects as those of the above-described CCD can be obtained.
  • the optical filter of the present invention can be suitably used as a noise cut filter in an environment where an infrared communication device (communication device using light of 850 to 950 nm as a medium) is used.
  • the powerful noise-cut filter covers near-infrared sources (for example, machines that use near-infrared, such as automatic doors and remote controls), and blocks infrared rays from the source. By disconnecting, the generation of noise during communication can be reliably prevented.
  • the optical filter of the present invention on the front surface of the panel of the plasma display device or the liquid crystal panel display device, the near infrared rays emitted from the panel can be efficiently cut. As a result, the remote control will not malfunction due to near-infrared light around the display device.
  • the optical filter of the present invention is preferably arranged as a display filter or a filter for CCD or CMOS image sensor, and the arrangement method is not limited at all.
  • LEDs are currently used in various fields with three colors of RGB with high efficiency and high luminance.
  • it since it generates a relatively large amount of energy, it becomes a heat source, and the diode equipment is always exposed to high temperatures.
  • the cause of heat generation is due to the radiant heat of the diode and the generation of infrared rays.
  • the near-infrared absorbing material and near-infrared absorbing material of the present invention have excellent near-infrared absorbing ability and high visible light transparency, so that infrared rays can be cut without changing the LED emission color. . It also has high heat resistance and high light resistance!
  • the LED composition using the near-infrared absorbing material and the near-infrared ray absorbing agent of the present invention can suppress heat generation due to light emission of the LED light-emitting diode.
  • marking by laser light irradiation is actively performed.
  • This marking method by laser light irradiation is such that characters and illustrations can be identified by scattering of light when the portion irradiated with laser light in the form of letters or illustrations changes color due to thermal energy.
  • JP-A-11-92632 discloses a laser on the surface of a resin molded product by irradiating an epoxy resin containing a copper compound and a nickel compound as a color former with laser light. The ability to disclose a single marking technique In this case, it is limited to black marking.
  • 8-120133 discloses a rosin composition capable of chromatic laser marking in which a compound such as titanium black is blended with a rubber-reinforced rubber-based rosin. It is limited to rubber-reinforced vinyl resin, and its application development is limited.
  • the material of the present invention has high visible light transmittance and high near infrared absorption ability, it can provide a highly transparent marking composition that can be marked with a low-power active energy ray. In addition, clear, high-speed, high-precision characters and illustrations can be easily and quickly marked.
  • FIG. 1 shows an absorption spectrum of P-1.
  • FIG. 2 shows an absorption spectrum of the P-1 laminate.
  • FIG. 3 shows an absorption spectrum of the P-23 laminate.
  • FIG. 4 shows an absorption spectrum of a laminate of P-43.
  • FIG. 5 shows an absorption spectrum of the laminate using P-23 in Example 3.
  • FIG. 6 shows an absorption spectrum of a laminate using P-43 in Example 8.
  • Figure 1 shows the absorption spectrum of P-1 in the black mouth form.
  • Figure 1 shows that P-1 has a large absorption in the near-infrared region where there is little absorption in visible light.
  • the Haze value was measured with a Haze Mater NDH2000 manufactured by NIPPON DENSHOKU.
  • Dimo-um dye IRG-022 manufactured by Nippon Kayaku Co., Ltd.
  • Example 2 The results are shown in Table 9.
  • Example 4 Compound 5, Compound 6,? -1 Oyobi 1 3 - 23, respectively 25% solids acrylic adhesive (monomer composition: butyl acrylate 60%, isobutyl acrylate 30%, 3% acrylic acid, hexyl 7% to acrylic acid 2 Echiru Solvent composition: Ethyl acetate 80%, Toluene 20%) About 2.0% of solid content was mixed and applied to PET film. The Haze value of this film was measured in the same manner as in Example 2. The results are shown in Table 10.
  • the color (y) value was measured with a color difference meter CR-300 manufactured by MINOLTA.
  • the obtained polymer was cut into a plate shape having a thickness of 1 mm, and the surface was polished to produce an optical filter (see Japanese Patent Application Laid-Open No. 2000-98130).
  • This filter was subjected to a heat and humidity resistance test for 48 hours at a humidity of 90% and a temperature of 100 ° C.
  • the Haze value and color change value (Ay value) of each film before and after the test were measured. Was measured or calculated. The results are shown in Table 11.
  • the Haze value of the filter using P-11 and P-23 is smaller than the Haze value of the filter of Comparative Example 1, and the filter Haze of P-1 and P-23 is used. Although the values hardly change before and after the test, the Haze value of the comparative example has increased greatly after the test, and it is clear that the change in Haze value of P-1 and P-23 is smaller than that of the comparative example. Karu. Table 11 also shows that the color change Ay values are smaller for P-1 and P-23.
  • the filter of Comparative Example 1 is known as a conventional CCD and CMOS filter. From the above results, the filter of the present invention has a smaller Haze value than the conventional CCD and CMOS filter. In addition, it is excellent in durability.
  • Compound 10, Compound 11, Compound 12, and ⁇ -43 were each converted into an acrylic adhesive with a solid content of 25% (monomer composition: 60% butyl acrylate, 30% isobutyl acrylate, 3% acrylic acid, 2 ethyl acrylate) About 2.0% of the solid content was mixed with xyl 7%, solvent composition: ethyl acetate 80%, toluene 20%) and applied to a PET film. These films were subjected to a heat resistance test for 24 hours and 48 hours under conditions of a temperature of 80 ° C and a humidity of 80%, and the transmittance of the maximum absorption wavelength of the compound before and after the test was measured. ⁇ ) was calculated (%). The results are shown in Table 13.
  • P-43 of the present invention is superior in heat resistance to Compound 10, Compound 11, and Compound 12 even when two types of dyes are mixed.
  • the Haze value of the P-23 and P-43 filters is very small compared to the Haze value of the filter of Comparative Example 2, and the Haze values of the P-23 and P-43 filters are tested.
  • the Haze value in Comparative Example 2 increased after the test compared to P-23 and P-43, while P23 and P-43 changed the Haze value compared to the comparative example. It can be seen that is small.
  • Table 15 also shows that the color change Ay values are smaller for P-23 and P-43 than for Comparative Example 2. This is due to the low compatibility of the succinic acid of Compound 13 and the low durability of the molecular skeleton, which means that the filter of the present invention is more durable.
  • the near-infrared absorber of the present invention is a material excellent in solubility in solvents, compatibility with rosin and durability.
  • P-51 was synthesized in Production Examples 11 to 13 according to the following synthesis scheme.
  • the compound 15 was obtained in the same manner as in Production Example 2 except that Compound 14 obtained in Production Example 11 was used in place of Compound 1. Yield 22%.
  • P-54 was obtained in the same manner as in Production Example 3, except that Compound 23 obtained in Production Example 21 was used instead of Compound 2. Yield 78%.
  • the molecular weight Mw Mn and the near infrared maximum absorption wavelength are shown below for some of the polymers of the present invention.
  • the molecular weight was measured using a high-speed GPC manufactured by Tosoh Corporation; HLC8120GPC with a solvent THF and UV detection at 254 nm. (Polystyrene conversion)
  • the near-infrared absorbing material of the present invention is useful as a near-infrared absorbing agent, and the near-infrared absorbing material of the present invention is much more soluble than conventional similar infrared absorbing agents.
  • various applications such as optical filter compositions, laser welding compositions, laser marking compositions, heat ray blocking material compositions, and near infrared absorbers such as LED compositions. It became possible to use it.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Optical Filters (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un matériau absorbant proche de l'infrarouge doté d'une unité récurrente représentée par la formule générale suivante [1] ou [2]. Formule générale [1] Formule générale [2] (dans les formules, M représente un atome de métal ; R1 et R4 représentent indépendamment un groupe aryle substitué ou non substitué, un groupe hétéroaryle substitué ou non substitué ou un groupe alkyle substitué ou non substitué ; R2 et R3 représentent indépendamment un groupe arylène substitué ou non substitué, un groupe hétéroarylène substitué ou non substitué ou un groupe alkylène substitué ou non substitué ; et R1 et R2 ainsi que R3 et R4 peuvent se combiner pour former un anneau ; Y1-Y4 représentent respectivement une liaison directe ou un hétéroatome ; et A représente une liaison directe ou un résidu organique divalent). La présente invention concerne également un absorbant proche de l'infrarouge composé d'un tel matériau. La présente invention concerne enfin une composition absorbante proche de l'infrarouge contenant un tel matériau ou absorbant, et un filtre optique.
PCT/JP2006/315136 2005-08-10 2006-07-31 Materiau absorbant dans le proche infrarouge et son utilisation WO2007018065A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007529489A JPWO2007018065A1 (ja) 2005-08-10 2006-07-31 近赤外線吸収材料およびその用途

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2005231742 2005-08-10
JP2005-231742 2005-08-10
JP2005-346504 2005-11-30
JP2005346504 2005-11-30
JP2006-146636 2006-05-26
JP2006146636 2006-05-26

Publications (1)

Publication Number Publication Date
WO2007018065A1 true WO2007018065A1 (fr) 2007-02-15

Family

ID=37727253

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/315136 WO2007018065A1 (fr) 2005-08-10 2006-07-31 Materiau absorbant dans le proche infrarouge et son utilisation

Country Status (4)

Country Link
JP (1) JPWO2007018065A1 (fr)
KR (1) KR20080042834A (fr)
TW (1) TW200714674A (fr)
WO (1) WO2007018065A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008029594A1 (fr) * 2006-09-08 2008-03-13 Toyo Ink Mfg. Co., Ltd. Matière pouvant absorber des rayons du proche infrarouge, composition pouvant absorber des rayons du proche infrarouge comprenant la matière et utilisation de celles-ci
JP2009012276A (ja) * 2007-07-04 2009-01-22 Nippon Kararingu Kk レーザーマーキング用多層シートとレーザーマーキング方法
JP2009023915A (ja) * 2007-07-17 2009-02-05 Api Corporation ジチアシクロペンテン誘導体またはジセレナシクロペンテン誘導体の製造方法
JP2012007038A (ja) * 2010-06-23 2012-01-12 Api Corporation 近赤外線吸収色素及び近赤外線吸収色素含有粘着剤
US8119037B2 (en) 2008-10-16 2012-02-21 Novaled Ag Square planar transition metal complexes and organic semiconductive materials using them as well as electronic or optoelectric components
US8713398B2 (en) 2011-03-22 2014-04-29 Nec Corporation Error correct coding device, error correct coding method, and error correct coding program
US20180118865A1 (en) * 2015-05-29 2018-05-03 Fujifilm Corporation Near infrared absorbing colorant polymer, composition, film, optical filter, pattern forming method, and device
CN109844620A (zh) * 2016-11-04 2019-06-04 依视路国际公司 具有低残余颜色的近红外光截止光学制品
CN111650674A (zh) * 2020-06-08 2020-09-11 苏州奥浦迪克光电技术有限公司 近红外、可见光双波段深色透光膜片及其制备方法、透光模组
JP2022525044A (ja) * 2019-03-25 2022-05-11 エシロール アンテルナショナル より広範なｎｉｒカット及びより良好な美的価値のためのｎｉｒ染料の混合物
DE102008051737B4 (de) 2007-10-24 2022-10-06 Novaled Gmbh Quadratisch planare Übergangsmetallkomplexe, organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente, die diese umfassen und Verwendung derselben

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101497112B1 (ko) * 2013-07-18 2015-03-03 이태훈 열선 차폐 필름용 조성물, 이를 이용하여 제조된 열선 차폐 필름 및 열선 차폐 필름의 제조 방법
TW201518763A (zh) * 2013-11-07 2015-05-16 Morrison Opto Electronics Ltd 複合型濾光元件

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01166988A (ja) * 1987-12-23 1989-06-30 Dainippon Printing Co Ltd 情報記録媒体
JPH02232290A (ja) * 1989-03-06 1990-09-14 Fuji Photo Film Co Ltd 赤外線吸収剤とその調製方法
JPH0641168A (ja) * 1992-04-02 1994-02-15 Nippon Paper Ind Co Ltd 新規なビスジチオベンジルニッケル錯体およびベンゾイン誘導体
JP2000007929A (ja) * 1998-06-22 2000-01-11 Mitsubishi Chemicals Corp 赤外線吸収剤
JP2001288380A (ja) * 2000-04-04 2001-10-16 Sumitomo Seika Chem Co Ltd 近赤外線吸収色素及びこれを用いた近赤外線吸収材
US6489399B1 (en) * 2000-07-31 2002-12-03 Molecular Optoelectronics Corp. Dye-appended polymers for broadband fiber optic devices
JP2004069952A (ja) * 2002-08-06 2004-03-04 Asahi Denka Kogyo Kk 光学フィルター用近赤外線吸収剤及び光学フィルター

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01166988A (ja) * 1987-12-23 1989-06-30 Dainippon Printing Co Ltd 情報記録媒体
JPH02232290A (ja) * 1989-03-06 1990-09-14 Fuji Photo Film Co Ltd 赤外線吸収剤とその調製方法
JPH0641168A (ja) * 1992-04-02 1994-02-15 Nippon Paper Ind Co Ltd 新規なビスジチオベンジルニッケル錯体およびベンゾイン誘導体
JP2000007929A (ja) * 1998-06-22 2000-01-11 Mitsubishi Chemicals Corp 赤外線吸収剤
JP2001288380A (ja) * 2000-04-04 2001-10-16 Sumitomo Seika Chem Co Ltd 近赤外線吸収色素及びこれを用いた近赤外線吸収材
US6489399B1 (en) * 2000-07-31 2002-12-03 Molecular Optoelectronics Corp. Dye-appended polymers for broadband fiber optic devices
JP2004069952A (ja) * 2002-08-06 2004-03-04 Asahi Denka Kogyo Kk 光学フィルター用近赤外線吸収剤及び光学フィルター

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG F. ET AL.: "Elctroactive, near-infrared-absorbing, nickel bis(dithiolene) complex polycarbonates and polyurethanes", MACROMOLECULES, vol. 24, no. 16, 1991, pages 4567 - 4574, XP000243808 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008029594A1 (fr) * 2006-09-08 2008-03-13 Toyo Ink Mfg. Co., Ltd. Matière pouvant absorber des rayons du proche infrarouge, composition pouvant absorber des rayons du proche infrarouge comprenant la matière et utilisation de celles-ci
JP2009012276A (ja) * 2007-07-04 2009-01-22 Nippon Kararingu Kk レーザーマーキング用多層シートとレーザーマーキング方法
JP2009023915A (ja) * 2007-07-17 2009-02-05 Api Corporation ジチアシクロペンテン誘導体またはジセレナシクロペンテン誘導体の製造方法
DE102008051737B4 (de) 2007-10-24 2022-10-06 Novaled Gmbh Quadratisch planare Übergangsmetallkomplexe, organische halbleitende Materialien sowie elektronische oder optoelektronische Bauelemente, die diese umfassen und Verwendung derselben
US8119037B2 (en) 2008-10-16 2012-02-21 Novaled Ag Square planar transition metal complexes and organic semiconductive materials using them as well as electronic or optoelectric components
JP2012007038A (ja) * 2010-06-23 2012-01-12 Api Corporation 近赤外線吸収色素及び近赤外線吸収色素含有粘着剤
US8713398B2 (en) 2011-03-22 2014-04-29 Nec Corporation Error correct coding device, error correct coding method, and error correct coding program
US20180118865A1 (en) * 2015-05-29 2018-05-03 Fujifilm Corporation Near infrared absorbing colorant polymer, composition, film, optical filter, pattern forming method, and device
US10711082B2 (en) * 2015-05-29 2020-07-14 Fujifilm Corporation Near infrared absorbing colorant polymer, composition, film, optical filter, pattern forming method, and device
US11124599B2 (en) 2016-11-04 2021-09-21 Essilor International Near infrared light-cutting optical articles with low residual color
CN109844620B (zh) * 2016-11-04 2021-11-30 依视路国际公司 具有低残余颜色的近红外光截止光学制品
CN109844620A (zh) * 2016-11-04 2019-06-04 依视路国际公司 具有低残余颜色的近红外光截止光学制品
JP2022525044A (ja) * 2019-03-25 2022-05-11 エシロール アンテルナショナル より広範なｎｉｒカット及びより良好な美的価値のためのｎｉｒ染料の混合物
CN111650674A (zh) * 2020-06-08 2020-09-11 苏州奥浦迪克光电技术有限公司 近红外、可见光双波段深色透光膜片及其制备方法、透光模组

Also Published As

Publication number Publication date
JPWO2007018065A1 (ja) 2009-02-19
TW200714674A (en) 2007-04-16
KR20080042834A (ko) 2008-05-15

Similar Documents

Publication Publication Date Title
WO2007018065A1 (fr) Materiau absorbant dans le proche infrarouge et son utilisation
CN101233208A (zh) 近红外线吸收材料及其用途
CN104350108B (zh) 黑色着色剂混合物
TW457383B (en) Color filter grade photosensitive resin coloring composition, color filter using the same novel anthraquinone compound and method for production thereof
KR101921752B1 (ko) 착색 조성물, 컬러 필터 및 표시 소자
CN105074570B (zh) 着色感放射线性组合物与其用途
JP5446423B2 (ja) 着色組成物、カラーフィルタおよびカラー液晶表示素子
CN107835843A (zh) 含有有机着色颜料与红外吸收染料的颜料分散液、着色树脂组合物及光学滤波器
TW201136903A (en) Color tone-correcting agent, squarylium compound, and optical filter
TW201321438A (zh) 光學濾器及使用該光學濾器的固體攝影裝置及照相機模組
KR20120035908A (ko) 쉬프 베이스형 화합물 및 상기 화합물을 함유하는 색소 재료
KR100930013B1 (ko) 근적외선 흡수 필름
TW200804873A (en) Optical filter
CN101008688B (zh) 滤光器
JP2023100619A (ja) 色材、及び造塩化合物
JPWO2019049626A1 (ja) 組成物及びその製造方法、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置、並びに、赤外線センサ
JP4055824B1 (ja) 近赤外線吸収材料、これを含む近赤外線吸収組成物およびその用途
JPWO2019039159A1 (ja) 硬化性組成物、膜、近赤外線カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ
JP5697894B2 (ja) 赤外線吸収性組成物、赤外線吸収性インキ、記録物、画像記録方法、及び画像検出方法
JP2008184484A (ja) 近赤外線吸収材料およびそれを用いたフィルター
JP2007211174A (ja) 近赤外線吸収剤およびその用途
JPWO2020129909A1 (ja) 光学フィルタ、撮像装置および光学センサー
JP2009127016A (ja) 近赤外線吸収材料、およびこれを含む積層体
JP2008208214A (ja) 近赤外線吸収材料およびそれを用いたフィルター
JP2008088398A (ja) 近赤外線吸収材料及びそれを用いた組成物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680028180.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007529489

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: KR

122 Ep: pct application non-entry in european phase

Ref document number: 06782014

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载