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WO2007018065A1 - Near-infrared absorbing material and use thereof - Google Patents

Near-infrared absorbing material and use thereof Download PDF

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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
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WIPO (PCT)
Prior art keywords
group
infrared
general formula
infrared absorbing
substituted
Prior art date
Application number
PCT/JP2006/315136
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French (fr)
Japanese (ja)
Inventor
Harunori Narihiro
Original Assignee
Toyo Ink Mfg. Co., Ltd.
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Publication date
Application filed by Toyo Ink Mfg. Co., Ltd. filed Critical Toyo Ink Mfg. Co., Ltd.
Priority to JP2007529489A priority Critical patent/JPWO2007018065A1/en
Publication of WO2007018065A1 publication Critical patent/WO2007018065A1/en

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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
    • 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.

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Abstract

Disclosed is a near-infrared absorbing material having a repeating unit represented by the following general formula [1] or [2]. General formula [1] General formula [2] (In the formulae, M represents a metal atom; R1 and R4 independently represent a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted alkyl group; R2 and R3 independently represent a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted alkylene group; and R1 and R2 as well as R3 and R4 may combine together to form a ring; Y1-Y4 respectively represent a direct bond or a heteroatom; and A represents a direct bond or a divalent organic residue.) Also disclosed is a near-infrared absorbent composed of such a near-infrared absorbing material. Further disclosed are a near-infrared absorbing composition containing such a near-infrared absorbing material or near-infrared absorbent, and an optical filter.

Description

明 細 書  Specification
近赤外線吸収材料およびその用途  Near-infrared absorbing material and its use
技術分野  Technical field
[0001] 本発明は、新規のジチオール系近赤外線吸収材料、該近赤外線吸収材料からな る近赤外線吸収剤、並びに、前記近赤外線吸収材料または近赤外線吸収剤を含有 する近赤外線吸収組成物、近赤外線吸収フィルム、積層体および光学フィルターに 関するものである。  [0001] 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.
背景技術  Background art
[0002] 有機ニッケル系錯体は、一般に 950nm〜1200nmの近赤外部に吸収を有し、近 赤外線吸収剤として優れた性質を有している。主な用途として、近赤外線を吸収'力 ットする機能を有する半導体受光素子用の光学フィルター、省エネルギー用に熱線 を遮断する近赤外線吸収フィルムや近赤外線吸収板、太陽光の選択的な利用を目 的とする農業用近赤外線吸収フィルム、近赤外線の吸収熱を利用する記録媒体、電 子機器用近赤外線カットフィルター、写真用近赤外線フィルター、保護めがね、サン グラス、熱線遮断フィルム、光学記録用色素、光学文字読み取り記録、機密文書複 写防止用、電子写真感光体、レーザー溶着、などに用いられる。また CCDカメラ用ノ ィズカットフィルター、 CMOSイメージセンサ用フィルターとしても有用である。  [0002] 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.
[0003] プラズマディスプレイ（PDP)では、 800〜1050nmのネオンガスの輝線を発してお り、近赤外線リモコンを用いた機器の誤作動を招くという問題があり、近赤外線を吸収 し、かつ可視透過率の優れたフィルターが必要である。このフィルターに用いる色素 は高い熱安定性、高耐光性が要求されており、経時での材料劣化によるフィルター の色度変化 ·近赤外線吸収能力の低下が課題となって!、る。  [0003] Plasma display (PDP) 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!
[0004] また、カメラやビデオカメラ等の光学機器では、光信号を電気信号に変換するため に、シリコンダイオード素子、相補型金属酸化物半導体 (CMOS)や電荷結合素子（ CCD)等が使用される。これらの光—電気変換素子 (以下、光学素子という）は、 300 〜： L lOOnmという広範囲の光感応領域を有するので、人間の目の視感度 400〜70 Onmと比較すると、近赤外領域で強く感応することになる。一般に、カメラやビデオ力 メラのような光学機器では、人間の視感度領域の波長光に感応することが必要で、こ の領域力 外れた波長光はむしろ好ましくなぐ測光や色再現性に支障をきたすこと となる。したがって、この場合、可視光線を透過し、かつ、近赤外領域の光を効率よく 吸収カットする光学フィルターが必要となる。 [0004] In addition, 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. The These photoelectric conversion elements (hereinafter referred to as “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. In general, 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.
[0005] 上記 CCD、 CMOS用フィルタ一としてりん酸エステル銅化合物を榭脂に分散した もの (例えば、特許文献 1〜5参照)、ローパス機能と視感度補正機能を有する複合 光学フィルター（例えば、特許文献 6参照）ホスフィン酸ィ匕物をモノマーの一成分とし て重合させた榭脂からなるフィルター (例えば、特許文献 7参照)等があるが、耐久性 •透明性と 、う点では必ずしも満足したものではな 、。  [0005] 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.
[0006] 一方、公知のジチオール系錯体近赤外線吸収剤としては、ビス（ジチォベンジル） ニッケル錯体ィ匕合物（例えば、特許文献 8、 9参照）、ビス（1, 2 ァセナフチレンジチ ォラト)ニッケル錯体ィ匕合物（例えば、特許文献 10参照）、 4 tert—プチルー 1, 2 ベンゼンジチオールニッケル錯体 (例えば、特許文献 11参照）、アルコキシ基を有 するビス (ジチォベンジル)ニッケル錯体ィ匕合物 (例えば、特許文献 12参照）が知ら れている。また、高分子ジチオール錯体ではジチォラートニッケル高分子錯体 (例え ば、特許文献 13参照）、ビスジチオレン錯体ポリマー (例えば、特許文献 14参照)等 が知られている。ビスジチオレン錯体ポリマーは、〜800nmと比較的短波長に吸収 波長領域があり、一般的な近赤外線吸収材料用途としては不適である。また錯体骨 格部位に置換基を持たな 、ため溶解性に乏 ヽと ヽぅ欠点があった。また多核型チ オール錯体 (例えば、特許文献 15参照）ある 、は 4級ホスホ-ゥムビス (シス 1, 2— エチレンジチォラト） -ッケレート誘導体 (例えば、特許文献 16参照）、二級アルキル 基を有するジチォレート金属錯体 (例えば、特許文献 17参照)も長波長吸収材料とし て知られている力 溶媒に対する溶解性が低い、榭脂との相溶性に乏しい、あるいは 低い温度に融点を持ち耐熱性に欠けるなど、実用的ではなかった。  [0006] On the other hand, as known near-infrared absorbers of dithiol-based complexes, bis (dithiobenzyl) nickel complex compounds (see, for example, Patent Documents 8 and 9), bis (1,2 acenaphthylene dicholate) Nickel complex compound (for example, see Patent Document 10), 4 tert-Petitur 1,2 benzenedithiol nickel complex (for example, see Patent Document 11), bis (dithiobenzyl) nickel complex compound having an alkoxy group (For example, see Patent Document 12). As the polymer dithiol complex, a dithiolate nickel polymer complex (for example, see Patent Document 13), a bisdithiolene complex polymer (for example, see Patent Document 14), and the like are known. 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. In addition, since there was no substituent at the complex skeleton site, the solubility was poor and there were drawbacks. Also, there are polynuclear thiol complexes (see, for example, Patent Document 15), quaternary phospho-umbis (cis 1,2-ethylenedithiolato) -ckerlate derivatives (see, for example, Patent Document 16), secondary alkyl groups. Dithiolate metal complexes (see, for example, Patent Document 17) are also known as long-wavelength absorption materials. Low solubility in solvents, poor compatibility with rosin, or low melting point and heat resistance. It was not practical, such as lacking.
[0007] 同様に近赤外線吸収化合物としてフタロシアニン系材料が知られている。このよう なフタロシアニン系材料として、置換基を有するフタロシア-ンィ匕合物もしくはナフタ ロシア-ンィ匕合物（例えば、特許文献 18参照）、アミノ基を有するフタロシア-ンィ匕合 物（例えば、特許文献 19〜23参照）、含フッ素フタロシア-ンィ匕合物（例えば、特許 文献 24、 25参照）等が知られている。 Similarly, 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.
[0008] また、ジィモ -ゥム系色素は、長波長（950nm〜： LlOOnm)を幅広く吸収し、かつ 可視光の透明性も極めて良好な材料であり、種々のものが知られている（例えば、特 許文献 26〜、 29参照)。そしてこの色素は、高い溶解性、榭脂相溶性をも有している 。しかし、耐熱性や耐光性は、必ずしも満足できるものではない。  [0008] In addition, 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 | dye also has high solubility and a rosin compatibility. However, heat resistance and light resistance are not always satisfactory.
[0009] 上記近赤外線吸収材に用いられる近赤外線吸収色素は、一般的に、溶媒に溶解 させた後、榭脂と混合してプラスチック等の基板にコーティングするか、或いは榭脂と 加熱混練されて、フィルム状、シート状、板状或いはその他の形状に成形されて用い られる。そのため、上記近赤外線吸収色素には、溶媒に対する溶解性ゃ榭脂との相 溶性等に優れていることが求められる。さらに、上記近赤外線吸収剤は、野外で使用 される場合もあるので、近赤外線吸収色素自身にも高い耐久性、熱安定性等が要求 される。  [0009] 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. Furthermore, since 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.
[0010] 特許文献 1 :W099Z26951号公報  [0010] Patent Document 1: W099Z26951 Publication
特許文献 2 :W099Z26952号公報  Patent Document 2: W099Z26952
特許文献 3：特開 2000— 7871号公報  Patent Document 3: Japanese Patent Laid-Open No. 2000-7871
特許文献 4:W098Z55885号公報  Patent Document 4: W098Z55885 Publication
特許文献 5：特開 2000— 38396号公報  Patent Document 5: JP 2000-38396 A
特許文献 6：特開平 8 - 146216号公報  Patent Document 6: JP-A-8-146216
特許文献 7：特開 2000 -98130号公報  Patent Document 7: Japanese Patent Laid-Open No. 2000-98130
特許文献 8：特開昭 63— 227597号公報  Patent Document 8: JP-A 63-227597
特許文献 9：特開昭 64 - 61492号公報  Patent Document 9: Japanese Patent Application Laid-Open No. 64-61492
特許文献 10：特許第 2923084号公報  Patent Document 10: Japanese Patent No. 2923084
特許文献 11：特開昭 63 - 307853号公報  Patent Document 11: Japanese Patent Laid-open No. 63-307853
特許文献 12：特開平 2— 264788号公報  Patent Document 12: JP-A-2-264788
特許文献 13 :特開平 4 198304号公報  Patent Document 13: JP-A-4 198304
特許文献 14:米国特許第 5089585号明細書  Patent Document 14: US Patent No. 5089585
特許文献 15 :特開 2005— 181966号公報  Patent Document 15: Japanese Unexamined Patent Application Publication No. 2005-181966
特許文献 16：特公平 6 - 72147号公報 特許文献 17：特開 2005— 232158号公報 Patent Document 16: Japanese Patent Publication No. 6-72147 Patent Document 17: Japanese Patent Application Laid-Open No. 2005-232232
特許文献 18：特開平 10— 78509号公報  Patent Document 18: Japanese Patent Laid-Open No. 10-78509
特許文献 19 :特開 2004— 18561号公報  Patent Document 19: Japanese Patent Laid-Open No. 2004-18561
特許文献 20：特開 2001— 106689号公報  Patent Document 20: JP 2001-106689 A
特許文献 21 :特開 2000— 63691号公報  Patent Document 21: Japanese Unexamined Patent Publication No. 2000-63691
特許文献 22：特許第 2746293号公報、  Patent Document 22: Japanese Patent No. 2746293,
特許文献 23：特許第 3226504号公報  Patent Document 23: Japanese Patent No. 3226504
特許文献 24：特許第 2907624号公報、  Patent Document 24: Japanese Patent No. 2907624,
特許文献 25：特許第 3014221号公報  Patent Document 25: Japanese Patent No. 3014221
特許文献 26：特開平 05 - 247437号公報  Patent Document 26: Japanese Patent Laid-Open No. 05-247437
特許文献 27：特開 2005 - 325292号公報  Patent Document 27: Japanese Patent Laid-Open No. 2005-325292
特許文献 28：特許第 3699464号公報  Patent Document 28: Japanese Patent No. 3699464
特許文献 29：特開 2003— 096040号公報  Patent Document 29: Japanese Patent Laid-Open No. 2003-096040
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0011] 従来近赤外線吸収色素として用いられている、置換ベンゼンジチオールニッケル 錯体類、フタロシアニン類、アントラキノン類、ビスジチォベンジルニッケル錯体類等 は、近赤外線吸収剤に配合されて用いられたとき、必ずしも満足すべき効果を示して いるとはいえない。例えば、フタロシアニン類は、種々の置換基で置換されて、溶媒 への溶解性を向上させているが、その結果、耐光性、熱安定性等が劣ったものとなつ ている。また、吸収スペクトルがシャープであるため近赤外線を吸収できる波長範囲 が小さい。一方、置換ベンゼンジチオールニッケル錯体類は、製造が比較的容易で あること、耐久性が良好という等の点においては優れている力 溶媒への溶解性が小 さぐまた樹脂との相溶性に劣るという問題がある。  [0011] 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. For example, phthalocyanines are substituted with various substituents to improve solubility in a solvent, but as a result, light resistance, thermal stability, etc. are inferior. In addition, since the absorption spectrum is sharp, the wavelength range that can absorb near infrared rays is small. On the other hand, 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.
[0012] すなわち、溶媒への溶解度が小さいと、近赤外線吸収剤を溶媒に溶解させて用い るときに、基板として用いるガラス、紙又は樹脂の表面に、近赤外線を遮断するのに 十分な量の色素を含有させることが困難となる。十分な量の色素を含有させるベく膜 厚を厚くした場合、色素分子同士のスタツキングにより可視光領域に新しい吸収帯が 現れ、可視光の透過率の減少を引き起こす。また、分子間相互作用が大きくなり、結 果として近赤外線吸収特性の低下を招く。また、近赤外線吸収剤をモノマーと混合し 、このモノマーを重合硬化させて近赤外線吸収部材とするときも、モノマーへの溶解 度が小さいと、十分な量の色素を含有させることが困難となり、一方、十分な量の色 素を含有させるベく溶解度以上の色素を含有させた場合、未溶解の色素が原因とな つて、近赤外線吸収層が部分的に不透明になるという問題が生じる。さらに、上記近 赤外線吸収剤と榭脂との相溶性が悪いと均一な近赤外線吸収特性を有する層を得 ることができな!/、と!/、う問題も生じる。 That is, when the solubility in a solvent is small, when the near infrared absorber is dissolved in a solvent and used, an amount sufficient to block near infrared rays on the surface of glass, paper or resin used as a substrate. It becomes difficult to contain the dye. When the thickness of the film containing a sufficient amount of dye is increased, a new absorption band is formed in the visible light region by stacking the dye molecules. Appear and cause a decrease in the transmittance of visible light. In addition, the intermolecular interaction is increased, resulting in a decrease in near-infrared absorption characteristics. Also, 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.
[0013] したがって、本発明の目的は、製造が容易で、溶剤への溶解性、榭脂との相溶性 が良好であり、し力も近赤外吸収領域が広ぐ耐久性に優れた近赤外線吸収材料を 提供することである。 Accordingly, 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. To provide absorbent material.
また、本発明の他の目的は、上記優れた特性を有する近赤外線吸収剤を提供する ことである。  Another object of the present invention is to provide a near infrared absorber having the above-mentioned excellent characteristics.
また、本発明の更に他の目的は、上記優れた特性を有する近赤外線吸収材料ある いは近赤外線吸収剤を含有する近赤外線吸収組成物を提供することである。  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.
また、本発明の他の目的は、上記優れた特性を有する近赤外線吸収材料あるいは 近赤外線吸収剤を少なくともその一層に含有する近赤外線吸収性積層体あるいはフ イルムを提供することである。  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.
また、本発明の他の目的は、上記優れた特性を有する近赤外線吸収材料または近 赤外線吸収剤を含有する光学フィルターを提供することである。  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.
課題を解決するための手段  Means for solving the problem
[0014] すなわち、本発明は、下記の近赤外線吸収材料、該近赤外線吸収材料からなる近 赤外線吸収剤、並びに、該近赤外線吸収材料あるいは該近赤外線吸収剤を含む近 赤外線吸収組成物、近赤外線吸収積層体、近赤外線吸収フィルム、近赤外線吸収 部材、および、光学フィルターに関する。 That is, 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.
[0015] (1)下記一般式 [1]または一般式 [2]で表される繰り返し単位を有する近赤外線吸 収材料。 [0015] (1) A near-infrared absorbing material having a repeating unit represented by the following general formula [1] or general formula [2].
[0016] 一般式 [1] : [化 1] [0016] General formula [1]: [Chemical 1]
Figure imgf000008_0001
Figure imgf000008_0001
[0017] 一般式 [2] [0017] General formula [2]
[化 2]  [Chemical 2]
■R2-Y! ■γ3— R3 _ 八 ■ R 2 -Y! ■ γ 3— R 3 _ 8
\ /  \ /
Μ  Μ
R1— Y Sハ Sへ Υ4— R4 R 1 — YS Ha S Υ 4 — R 4
[0018] (一般式 [1]および [2]中、 Mは金属原子を表し、 R1および R4は、それぞれ独立して 、置換もしくは未置換のァリール基、置換もしくは未置換のへテロアリール基、または 、置換もしくは未置換のアルキル基を表し、 R2および R3は、それぞれ独立して、置換 もしくは未置換のァリーレン基、置換もしくは未置換のへテロアリーレン基、または、置 換もしくは未置換のアルキレン基を表し、また R1と R2、 R3と R4は互いに結合して環を 形成してもよぐ Υ Υ4は直接結合もしくはヘテロ原子を表し、 Αは直接結合もしくは 二価の有機残基を表す。 ) (In the general formulas [1] and [2], M represents a metal atom, and 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, and 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 Υ Υ 4 represents a direct bond or a hetero atom, and Α represents a direct bond or a divalent group. Represents an organic residue.)
[0019] (2)上記 1項に記載の近赤外線吸収材料において、一般式 [1]で表される繰り返し 単位が下記一般式 [3]で表される繰り返し単位であり、また一般式 [2]で表される繰 り返し単位が下記一般式 [4]で表される繰り返し単位であることを特徴とする近赤外 線吸収材料。  [0019] (2) In the near-infrared absorbing material as described in 1 above, 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].
[0020] 一般式 [3] :  [0020] General formula [3]:
[化 3]  [Chemical 3]
Figure imgf000008_0002
[0021] 一般式 [4]
Figure imgf000008_0002
[0021] General formula [4]
[化 4]  [Chemical 4]
Figure imgf000009_0001
Figure imgf000009_0001
[0022] (一般式 [3]および [4]中、 M、
Figure imgf000009_0002
R4および Aは上記 1項で定義したものと 同一のものである。 ) [0022] (In the general formulas [3] and [4], M,
Figure imgf000009_0002
R 4 and A are the same as defined in item 1 above. )
[0023] (3)上記 1項に記載の近赤外線吸収材料において、一般式 [1]で表される繰り返し 単位が下記一般式 [5]で表される繰り返し単位であり、また一般式 [2]で表される繰 り返し単位が下記一般式 [6]で表される繰り返し単位であることを特徴とする近赤外 線吸収材料。  [0023] (3) In the near-infrared absorbing material as described in 1 above, 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].
[0024] 一般式 [5] :  [0024] General formula [5]:
[化 5]  [Chemical 5]
Figure imgf000009_0003
Figure imgf000009_0003
[0025] 下記一般式 [6] [0025] The following general formula [6]
[化 6]  [Chemical 6]
Figure imgf000009_0004
Figure imgf000009_0004
[0026] (式中、 M、
Figure imgf000009_0005
R4および Aは上記 1項で定義したものと同一のものである。 ) [0027] (4)上記 1項に記載の近赤外線吸収材料において、一般式 [1]で表される繰り返し 単位が下記一般式 [7]で表される繰り返し単位であり、また上記一般式 [2]で表され る繰り返し単位が下記一般式 [8]で表される繰り返し単位であることを特徴とする近 赤外線吸収材料。 [0026] (where M,
Figure imgf000009_0005
R 4 and A are the same as defined in item 1 above. ) [0027] (4) In the near-infrared absorbing material as described in 1 above, 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].
[0028] 一般式 [7] :  [0028] General formula [7]:
[化 7]  [Chemical 7]
Figure imgf000010_0001
Figure imgf000010_0001
[0029] 一般式 [8] [0029] General formula [8]
[化 8]  [Chemical 8]
Figure imgf000010_0002
Figure imgf000010_0002
[0030] (式中、 M、
Figure imgf000010_0003
R4および Aは上記 1項で定義したものと同一のものである。 ) [0031] (5)上記 1〜4項のいずれかに記載の近赤外線吸収材料において、 Mがニッケル、 白金、コバルト、パラジウムもしくは銅であることを特徴とする近赤外線吸収材料。 [0030] (where M,
Figure imgf000010_0003
R 4 and A are the same as defined in item 1 above. [0031] (5) The near-infrared absorbing material according to any one of items 1 to 4, wherein M is nickel, platinum, cobalt, palladium, or copper.
[0032] (6)上記 1〜5項のいずれかに記載の近赤外線吸収材料において、 Ri〜R4の少なく とも一つが置換基を有する基であることを特徴とする近赤外線吸収材料。 [0032] (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.
[0033] (7)上記 1〜6項のいずれかに記載の近赤外線吸収材料において、 R1と R2、および[0033] (7) In the near-infrared absorbing material according to any one of 1 to 6 above, R 1 and R 2 , and
/または、 R3と R4が結合して共役または非共役の環を形成して 、ることを特徴とする 近赤外線吸収材料。 Or a near-infrared absorbing material, wherein R 3 and R 4 are combined to form a conjugated or non-conjugated ring.
[0034] (8)上記 1〜7項のいずれかに記載の近赤外線吸収材料において、 A力 -NHCO 一、 一 CONH—、 一 NHCOO—、 一 OCONH—、 一 O—、 一 S—、 一 NH—、 一 C [0034] (8) In the near-infrared absorbing material according to any one of 1 to 7 above, A force -NHCO, 1 CONH—, 1 NHCOO—, 1 OCONH—, 1 O—, 1 S—, 1 NH—, I C
OO OCO SO CO C = C -N = N- S— S—、置換 もしくは未置換のァリーレン基、置換もしくは未置換のへテロアリーレン基、置換もしく は未置換のアルキレン基、および置換もしくは未置換のアミノ基力 なる群より選ばれ た基を任意に組み合わせて成る二価の有機残基であることを特徴とする近赤外線吸 収材料。 OO OCO SO CO C = C -N = N-S— S—, substituted or unsubstituted arylene group, substituted or unsubstituted heteroarylene group, substituted or unsubstituted alkylene group, and substituted or unsubstituted Selected from the group A near-infrared absorbing material, which is a divalent organic residue formed by arbitrarily combining groups.
[0035] (9)上記 8項に記載の近赤外線吸収材料において、 A力 下記一般式 [9]で表され る基であることを特徴とする近赤外線吸収材料。  [0035] (9) A near-infrared absorbing material as described in the above item 8, wherein the A force is a group represented by the following general formula [9].
[0036] 一般式 [9] : [0036] General formula [9]:
[化 9]
Figure imgf000011_0001
[Chemical 9]
Figure imgf000011_0001
[0037] (式中、 1〜：^3は、それぞれ独立して、直接結合あるいは NHCOO—、 -OCON H 、 一 O 、 一 S 、 一 NH 、 一 COO 、 一 OCO 、 一 SO —、 一 CO 、 一 C [0037] (In the formula, 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. , One C
2  2
=C一、 N=N—または— S— S を表し、 n1および n2は 0または自然数を表す。） [0038] (10)上記 1〜9項のいずれかに記載の近赤外線吸収材料において、該近赤外吸収 材料が、 2種以上の異なる繰り返し単位を有することを特徴とする近赤外線吸収材料 = C, N = N—or —S—S, n 1 and n 2 represent 0 or a natural number. [0038] (10) The near-infrared absorbing material as described in any one of 1 to 9 above, wherein the near-infrared absorbing material has two or more different repeating units.
[0039] (11)上記 1〜： L0項のいずれかの近赤外線吸収材料からなる近赤外線吸収剤。 [0039] (11) A near-infrared absorber comprising the near-infrared absorbing material of any one of 1 to L0 above.
[0040] (12)上記 11項に記載の近赤外線吸収剤の少なくとも一種を含有する近赤外線吸 収組成物。 [0040] (12) A near-infrared absorbing composition containing at least one kind of the near-infrared absorbing agent as described in 11 above.
[0041] (13)上記 12項に記載の近赤外線吸収組成物において、前記近赤外線吸収剤が 2 種以上の近赤外線吸収剤カゝらなることを特徴とする近赤外線吸収組成物。  [0041] (13) The near-infrared absorbing composition as described in the above item 12, wherein the near-infrared absorbing agent comprises two or more kinds of near-infrared absorbing agents.
[0042] (14)上記 12または 13項に記載の近赤外線吸収組成物において、上記 11項に記 載の近赤外線吸収剤以外の近赤外線吸収剤が更に含有されることを特徴とする近 赤外線吸収組成物。  [0042] (14) The near-infrared absorbing composition as described in 12 or 13 above, further comprising a near-infrared absorbing agent other than the near-infrared absorbing agent as described in 11 above, Absorbent composition.
[0043] (15)上記 14項に記載の近赤外線吸収組成物において、上記 11項に記載の近赤 外線吸収剤以外の近赤外線吸収剤が、ニッケル錯体系色素、フタロシアニン系色素 およびジィモ -ゥム系色素から選ばれた少なくとも一種の近赤外線吸収剤であること を特徴とする近赤外線吸収組成物。  [0043] (15) In the near-infrared absorbing composition described in 14 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.
[0044] (16)上記 13項または上記 14項に記載の近赤外線吸収組成物において、該近赤外 線吸収組成物に含まれる近赤外線吸収剤は、最大近赤外線吸収波長の異なる少な くとも 2種の近赤外線吸収剤からなることを特徴とする近赤外線吸収組成物。 [0044] (16) In the near-infrared absorbing composition according to item 13 or 14, 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.
[0045] (17)上記 12〜16項のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物に更にバインダー榭脂が含まれることを特徴とする近赤外線吸収組成 物。 [0045] (17) The near-infrared absorbing composition according to any one of items 12 to 16, wherein the near-infrared absorbing composition further contains a binder resin. .
[0046] (18)上記 12〜17項のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物に更に溶剤が含まれることを特徴とする近赤外線吸収組成物。  [0046] (18) The near-infrared absorbing composition as described in any one of 12 to 17 above, wherein the near-infrared absorbing composition further contains a solvent.
[0047] (19)上記 12〜18項のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が塗布用組成物であることを特徴とする近赤外線吸収組成物。 [0047] (19) The near-infrared absorbing composition as described in any one of 12 to 18 above, wherein the near-infrared absorbing composition is a coating composition.
[0048] (20)上記 12〜19項のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が粘着または接着剤組成物であることを特徴とする近赤外線吸収組 成物。 [0048] (20) The near-infrared absorbing composition according to any one of the above 12 to 19, wherein the near-infrared absorbing composition is an adhesive or adhesive composition Adult.
[0049] (21)上記項 12〜19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物がレーザー溶着用組成物、レーザーマーキング用組成物、熱線遮断 材用組成物または LED用組成物であることを特徴とする近赤外線吸収組成物。  [0049] (21) 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.
[0050] (22)基材上に、上記 1〜： LO項のいずれかに記載の近赤外線吸収材料を含む層が 形成されてなる積層体。  [0050] (22) A laminate in which a layer containing the near-infrared absorbing material according to any one of 1 to LO items above is formed on a substrate.
[0051] (23)上記 22項に記載の積層体において、前記近赤外線吸収材料を含む層が、上 記 12〜20項のいずれかに記載の近赤外線吸収組成物により形成されていることを 特徴とする積層体。  [0051] (23) In the laminate according to the above item 22, 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.
[0052] (24)上記 1〜： LO項のいずれかに記載の近赤外線吸収材料を含む近赤外線吸収フ イノレム。  [0052] (24) A near-infrared absorption finer comprising the near-infrared absorption material according to any one of 1 to LO above.
[0053] (25)上記 22または 23項に記載の積層体を含んでなる光学フィルター。  [0053] (25) An optical filter comprising the laminate as described in 22 or 23 above.
[0054] (26)上記 25項記載の光学フィルタ一にお!/、て、該光学フィルターが、プラズマディ スプレイ用、液晶ディスプレイ用、 CCDカメラ用または CMOSイメージセンサ用光学 フィルターである光学フィルター。 発明の効果  [0054] (26) The 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 invention's effect
[0055] 本発明により、製造が容易で、溶媒への溶解性もしくは榭脂との相溶性が良好であ り、また近赤外線吸収領域が広ぐ高耐久性の近赤外線吸収材料を得ることができる また、本発明により、前記優れた特性を有する近赤外線吸収剤、これを含有する近 赤外線吸収組成物、近赤外線吸収積層体、近赤外線吸収フィルム、近赤外線吸収 部材、および、光学フィルターを得ることができた。そして、これら光学フィルタ一は、 プラズマディスプレイ用、液晶ディスプレイ用、 CCDカメラ用または CMOSイメージセ ンサ用光学フィルタ一として好ましく使用することができる。 [0055] According to 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.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0056] 本発明は、上記一般式 [ 1 ]または一般式 [2]で表される繰り返し単位を有する新規 な近赤外線吸収材料、それを用いた近赤外線吸収剤、近赤外線吸収組成物、近赤 外線吸収積層体、近赤外線吸収フィルム、近赤外線吸収部材、および、光学フィル ターに関する。そして、上記一般式 [1]または [2]で表わされる繰り返し単位としては 、好ましくは、上記一般式 [3]〜 [8]の繰り返し単位が挙げられる。  [0056] 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].
[0057] 前記一般式 [1]〜 [8]の繰り返し単位を持つ新規な近赤外線吸収材料にぉ 、て、  [0057] A novel near-infrared absorbing material having a repeating unit represented by the general formulas [1] to [8],
R4は、それぞれ独立して、置換もしくは未置換のァリール基、置換もしくは未置換 のへテロァリール基、または、置換もしくは未置換のアルキル基を表わし、好ましくは 置換もしくは未置換のフエニル基、置換もしくは未置換のチェニル基、置換もしくは 未置換のアルキル基である。 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.
以下、一般式 [1] R4における各基を更に詳細に説明する。 Hereinafter, each group in the general formula [1] R 4 will be described in more detail.
[0058] 一般式 [1]〜[8]
Figure imgf000013_0001
ける置換もしくは未置換のァリール基は、置換もし くは未置換のァリール基であればよく特に限定されるものではない。置換もしくは未 置換のァリール基としては、例えば、フエ-ル基、 2— 5—ジメチルフエ-ル基、ビフエ 二レニル基、トリフエ-レニル基、テトラフヱ-レニル基、 3— -トロフエ-ル基、 4ーメ チルチオフエ-ル基、 3, 5—ジシァノフエ-ル基、 o—， m—および p—トリル基、キシ リル基、 o—， m—および p—タメ-ル基、メシチル基、ペンタレ-ル基、インデュル基 、ナフチル基、アントラセ-ル基、ァズレ-ル基、ヘプタレ-ル基、ァセナフチレ-ル 基、フヱナレニル基、フルォレニル基、アントリル基、アントラキノ-ル基、 3—メチルァ ントリル基、フエナントリル基、ピレ-ル基、クリセ-ル基、 2—ェチルー 1ークリセ-ル 基、ピセ-ル基、ペリレ-ル基、 6—クロ口ペリレ-ル基、ペンタフェ-ル基、ペンタセ -ル基、テトラフエ-レニル基、へキサフエ-ル基、へキサセ-ル基、ルビセ-ル基、 コロネ-ル基、トリナフチレ-ル基、ヘプタフェ-ル基、ヘプタセ -ル基、ピラントレ- ル基、ォバレ-ル基等が挙げられる。 [0058] General formula [1]-[8]
Figure imgf000013_0001
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, furanenyl group, fluorenyl group, anthryl group, anthraquinol group, 3-methylanthryl group, phenanthryl group , Pyraryl group, Chrysyl group, 2-Ethyl-1-Chrysal group, Picerl group, Perylene group, 6-Chromatic perylene group, Pentaphenol group, Pentase group Group, tetraphenyl group, hexaphenyl group, hexase group, rubisel group, coronal group, trinaphthyl group, heptaphenyl group, heptaceryl group, pyrantol group And an ovalyl group.
[0059] また、一般式 [1]〜
Figure imgf000014_0001
R4における置換もしくは未置換のへテロアリール基 は、置換もしくは未置換のへテロアリール基であればよぐ特に限定されるものではな い。置換もしくは未置換のへテロアリール基としては、例えば、チォ-ル基、フリル基 、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ビラジニル基、ピリミジニル基 、ピリダジニル基、インドリル基、キノリル基、イソキノリル基、フタラジュル基、キノキサ リニル基、キナゾリ-ル基、カルバゾリル基、アタリジ-ル基、フ ナジ-ル基、フルフ リル基、イソチアゾリル基、イソキサゾリル基、フラザ-ル基、フ ノキサジニル基、ベン ゾチアゾリル基、ベンゾォキサゾリル基、ベンズイミダゾリル基、 2—メチルピリジル基、 3—シァノピリジル基等が挙げられる。 [0059] In addition, the general formula [1] ~
Figure imgf000014_0001
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.
[0060] さらに、一般式 [1]〜
Figure imgf000014_0002
R4における置換もしくは未置換のアルキル基は、 置換もしくは未置換のアルキル基であればよぐ特に限定されるものではない。また アルキル基は直鎖でも、分岐したものでも、環化したシクロアルキル基であってもよい[0060] Furthermore, the general formula [1] ~
Figure imgf000014_0002
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.
。置換もしくは未置換のアルキル基を具体的に示すと、メチル基、ェチル基、プロピ ル基、ブチル基、 sec ブチル基、 tert ブチル基、ペンチル基、へキシル基、 2— ェチルへキシル基、ヘプチル基、ォクチル基、イソォクチル基、ステアリル基、トリクロ ロメチル基、トリフロロメチル基、シクロプロピル基、シクロへキシル基、 1, 3 シクロへ キサジェ-ル基、 2 シクロペンテン 1ーィル基、 2, 4 シクロペンタジェン 1 イリデニル基などが挙げられる。 . Specific examples of the substituted or unsubstituted alkyl group 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.
[0061] 一方、一般式 [1]〜一般式 [8]中の R2および R3は、それぞれ独立して、置換もしく は未置換のァリーレン基、置換もしくは未置換のへテロアリーレン基、または、置換も しくは未置換のアルキレン基を表し、また R1と R2、 R3と R4は互いに結合して環を形成 してもよい。一般式 [1]〜一般式 [8]において、 R2および R3は、好ましくは、置換もし くは未置換のフエ二レン基、置換もしくは未置換のチェ-レン基、置換もしくは未置換 のアルキレン基である。さらに好ましくは R1と R2あるいは R3と R4が置換基を有してよい 共役もしくは非共役の環を形成しているものが好ましい。非共役の環を形成する場合 は C2〜C6の炭素数で形成する場合が好ま ヽ。また共役の環を形成する場合には ォレフィン、ベンゼン、チォフェン、を含むものが好ましい。 [0061] On the other hand, 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. In the general formula [1] to general formula [8], R 2 and R 3 are preferably substituted or unsubstituted phenylene group, substituted or unsubstituted chain group, substituted or unsubstituted group. An alkylene group; More preferably, R 1 and R 2 or R 3 and R 4 form a conjugated or non-conjugated ring which may have a substituent. When forming a non-conjugated ring Is preferably formed with C2 to C6 carbon atoms. Moreover, when forming a conjugated ring, what contains olefin, benzene, and thiophene is preferable.
以下、 R2および R3の基について更に詳細に説明する。 Hereinafter, the groups R 2 and R 3 will be described in more detail.
[0062] 一般式 [1]〜[8]中の R2、 R3における置換もしくは未置換ァリーレン基は、置換もし くは未置換ァリーレン基であればよく特に限定されない。置換もしくは未置換ァリーレ ン基は、好ましくは炭素数 6〜60の単環または縮合環の置換もしくは未置換ァリーレ ン基であり、より好ましくは炭素数 6〜40、更に好ましくは炭素数 6〜30の置換もしく は未置換ァリーレン基である。置換もしくは未置換ァリーレン基を具体的に示すと、例 えば、置換されたあるいは未置換のフエ-レン基、ビフエ-レン基、ナフタレンジィル 基、アントラセンジィル基、フエナント口リンジィル基、ピレンジィル基、トリフエ-レンジ ィル基、ベンゾフエナント口リンジィル基、ペリレンジィル基、ペンタフェ-レンジィル 基、ペンタセンジィル基などが挙げられる。 [0062] 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. Specific examples of 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.
[0063] また、一般式 [1]〜[8]中の R2、 R3における置換もしくは未置換へテロアリーレン基 は、置換もしくは未置換へテロアリーレン基であればよく特に限定されないが、好まし くは炭素数 4な 、し 60の単環または縮合環の置換または未置換の芳香族へテロ環 基であり、より好ましくは窒素原子、酸素原子または硫黄原子の少なくとも一つを含有 する炭素数 4ないし 60の置換または未置換の単環または縮合環の芳香族へテロ環 基であり、更に好ましくは炭素数 4ないし 30の置換または未置換 5員または 6員の芳 香族へテロ環基である。置換または未置換芳香族へテロ環基を具体的に示すと、例 えば、置換されたあるいは未置換のピロールジィル、フランジィル、チェ-レン、ピリ ジンジィル、ピリダジンジィル、ピリミジンジィル、ピラジンジィル、キノリンジィル、イソ キノリンジィル、シンノリンジィル、キナゾリンジィル、キノキサリンジィル、フタラジンジ ィル、プテリジンジィル、アタリジンジィル、フエナジンジィル、フエナント口リンジィルな どが挙げられる。 [0063] Further, 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. Preferably, 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. A substituted or unsubstituted monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms, more preferably a substituted or unsubstituted 5- or 6-membered aromatic heterocyclic group having 4 to 30 carbon atoms It is a group. Specific examples of 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.
[0064] さらに、一般式 [1]〜[8]中の R2、 R3における置換もしくは未置換アルキレン基は、 置換もしくは未置換アルキレン基であればよく特に限定されない。またアルキレン基 は直鎖以外に、分岐したものでも、環化したシクロアルキレン基であってもよい。置換 もしくは未置換アルキレン基を具体的に示すと、例えば、メチレン基、エチレン基、プ ロピレン基、ブチレン基、 sec—ブチレン基、 tert—ブチレン基、ペンチレン基、へキ シレン基、 2—ェチルへキシレン基、ヘプチレン基、オタチレン基、イソオタチレン基、 ステアリレン基、トリクロロメチレン基、シクロへキシレン基などが挙げられる。 [0064] Further, 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. In addition to the straight chain, 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. Lopylene group, butylene group, sec-butylene group, tert-butylene group, pentylene group, hexylene group, 2-ethylhexylene group, heptylene group, octylene group, isooctylene group, stearylene group, trichloromethylene group, cyclohexylene Groups and the like.
[0065] なお、本発明における各基における置換基とは、ハロゲン原子 (例えばフッ素原子 、塩素原子、臭素原子、ヨウ素原子等が挙げられる。）、置換もしくは未置換のアルキ ル基、置換もしくは未置換のアルコキシ基、置換もしくは未置換のチォアルコキシ基 、シァノ基、アミノ基、モノもしくはジ置換アミノ基、水酸基、メルカプト基、置換もしくは 未置換のァリールォキシ基、置換もしくは未置換のァリールチオ基、置換もしくは未 置換のァリール基、置換もしくは未置換のへテロアリール基を表し、また、置換基は、 隣接した置換基同士で置換もしくは未置換をもつ共役もしくは非共役の環を形成し ても良い。 [0065] 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. Substituted alkoxy group, substituted or unsubstituted thioalkoxy group, cyano group, amino group, mono- or di-substituted amino group, hydroxyl group, mercapto group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylothio group, substituted or It represents an unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and the substituent may form a conjugated or non-conjugated ring having substitution or substitution between adjacent substituents.
[0066] 置換基としての置換もしくは未置換のァリール基としては、例えば、フエ-ル基、ビ フエ-レニル基、トリフエ-レニル基、テトラフヱ-レニル基、 3— -トロフエ-ル基、 4 ーメチルチオフエ-ル基、 3, 5—ジシァノフエ-ル基、 o—， m—および p—トリル基、 キシリル基、 o—， m—および p—タメ-ル基、メシチル基、ペンタレ-ル基、インデニ ル基、ナフチル基、アントラセ-ル基、ァズレニル基、ヘプタレ-ル基、ァセナフチレ -ル基、フヱナレニル基、フルォレニル基、アントリル基、アントラキノ-ル基、 3—メチ ルアントリル基、フ ナントリル基、ピレニル基、クリセ-ル基、 2—ェチルー 1ークリセ -ル基、ピセ-ル基、ペリレ-ル基、 6—クロ口ペリレ-ル基、ペンタフェ-ル基、ペン タセ-ル基、テトラフエ-レニル基、へキサフエ-ル基、へキサセ-ル基、ルビセ-ル 基、コロネ-ル基、トリナフチレ-ル基、ヘプタフエ-ル基、ヘプタセ -ル基、ピラント レニル基、ォバレ-ル基等が挙げられる。  [0066] 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. -L group, 3,5-disyanphenol group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-tame group, mesityl group, pental group, indenyl Group, naphthyl group, anthracyl group, azulenyl group, heptalyl group, acenaphthyl group, furanenyl group, fluorenyl group, anthryl group, anthraquinol group, 3-methylanthryl group, phanthryl group, pyrenyl group, Chrysyl group, 2-ethyl 1-chrysyl group, picerl group, peryl group, 6-cylinder peryl group, pentafel group, pentacyl group, tetraphenyl group, Kisafel group, hex Cell - group, Rubise - group, Coronate - group, Torinafuchire - group, Heputafue - group, Heputase - group, Piranto Reniru group, Obare - group, and the like.
[0067] また、置換基としての置換もしくは未置換のへテロアリール基としては、例えば、チ ォニル基、フリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジ二 ル基、ピリミジニル基、ピリダジニル基、インドリル基、キノリル基、イソキノリル基、フタ ラジニル基、キノキサリニル基、キナゾリ-ル基、カルバゾリル基、アタリジニル基、フ ヱナジニル基、フルフリル基、イソチアゾリル基、イソキサゾリル基、フラザニル基、フエ ノキサジ-ル基、ベンゾチアゾリル基、ベンゾォキサゾリル基、ベンズイミダゾリル基、 2 メチルピリジル基、 3 シァノピリジル基等が挙げられる。 [0067] 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. Group, indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, quinoxalinyl group, quinazolyl group, carbazolyl group, attalidinyl group, furanazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazir group , Benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2 methylpyridyl group, 3 cyanopyridyl group and the like.
[0068] また置換基としてのモノまたはジ置換アミノ基としては、例えば、メチルァミノ基、ジメ チルァミノ基、ェチルァミノ基、ジェチルァミノ基、ジプロピルアミノ基、ジブチルァミノ 基、ジフエ-ルァミノ基、ビス（ァセトォキシメチル)アミノ基、ビス（ァセトォキシェチル） アミノ基、ビス（ァセトォキシプロピル)アミノ基、ビス（ァセトォキシブチル)アミノ基、ジ ベンジルァミノ基等が挙げられる。  [0068] 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). Examples include methyl) amino group, bis (acetoxetyl) amino group, bis (acetooxypropyl) amino group, bis (acetooxybutyl) amino group, dibenzylamino group and the like.
[0069] また置換基としての置換もしくは未置換のアルキル基としては、例えば、メチル基、 ェチル基、プロピル基、ブチル基、 sec ブチル基、 tert ブチル基、ペンチル基、 へキシル基、 2—ェチルへキシル基、ヘプチル基、ォクチル基、イソォクチル基、ステ ァリル基、トリクロロメチル基、トリフロロメチル基、シクロプロピル基、シクロへキシル基 、 1, 3 シクロへキサジェ-ル基、 2 シクロペンテン一 1—ィル基、 2, 4 シクロべ ンタジェンー 1 イリデニル基などが挙げられる。  [0069] 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. Hexyl group, heptyl group, octyl group, isooctyl group, stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1, 3 cyclohexagel group, 2 cyclopentene mono 1— Yl group, 2,4 cyclopentadiene 1 iridenyl group, and the like.
[0070] また置換基としての置換もしくは未置換のアルコキシ基としては、例えば、メトキシ基 、エトキシ基、プロポキシ基、 n—ブトキシ基、 sec ブトキシ基、 tert ブトキシ基、ぺ ンチルォキシ基、へキシルォキシ基、 2—ェチルへキシルォキシ基、ステアリルォキシ 基、トリフロロメトキシ基等が挙げられる。  [0070] 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.
[0071] また置換基としての置換もしくは未置換のチォアルコキシ基としては、例えば、メチ ルチオ基、ェチルチオ基、プロピルチオ基、ブチルチオ基、 sec ブチルチオ基、 ter tーブチルチオ基、ペンチルチオ基、へキシルチオ基、へプチルチオ基、ォクチルチ ォ基等が挙げられる。  [0071] 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.
[0072] また置換基としての置換もしくは未置換のァリールォキシ基としては、例えば、フエノ キシ基、 p— tert—ブチルフエ-キシ基、 3—フルオロフェニキシ基等が挙げられる。  [0072] 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.
[0073] また置換基としての置換もしくは未置換のァリールチオ基としては、例えば、フエ- ルチオ基、 3—フルオロフェ-ルチオ基等が挙げられる。  [0073] Examples of the substituted or unsubstituted arylothio group as a substituent include a phenolthio group and a 3-fluorophenylthio group.
[0074] これらの中で好ましい置換基は、炭素数が 1〜20のアルキル基、もしくはアルコキ シ基、もしくはモノまたはジ置換アミノ基である。また、隣接した置換基同士で 5ないし 7員環の酸素原子、窒素原子、硫黄原子等が含まれてもよい脂肪族、炭素環式芳香 族、複素環式芳香族、複素環を形成してもよぐこれらの環の任意の位置にさらに置 換基を有してもよい。 [0074] Among these, preferred substituents are an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or a mono- or di-substituted amino group. In addition, 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.
[0075] また、一般式 [1]または [2]中の 〜Y4は直接結合もしくは、酸素原子、窒素原子 、硫黄原子などのへテロ原子を表すが、硫黄原子が好ましい。前記一般式 [1]また は [2]において、 〜Y4が直接結合である場合は、一般式 [3]または [4]で表わさ れる繰り返し単位となり、
Figure imgf000018_0001
Υ4が硫黄原子、 Υ2、 Υ3が直接結合である場合は一般 式 [5]または [6]で表わされる繰り返し単位となり、 Υ -Υ4がすべて硫黄原子である 場合は、一般式 [7]または [8]で表わされる繰り返し単位となる。これらはいずれも近 赤外線吸収剤として好まし ヽ材料である。 [0075] In general formula [1] or [2] to Y 4 is a direct bond or in an oxygen atom, a nitrogen atom, represent a hetero atom such as a sulfur atom, a sulfur atom are preferred. In the general formula [1] or [2], when ˜Y 4 is a direct bond, it becomes a repeating unit represented by the general formula [3] or [4],
Figure imgf000018_0001
When Υ 4 is a sulfur atom and Υ 2 and Υ 3 are direct bonds, the repeating unit is represented by the general formula [5] or [6]. When Υ -Υ 4 is all sulfur atoms, the general formula [ It is a repeating unit represented by [7] or [8]. These are all preferred materials as near infrared absorbers.
[0076] 以下、一般式 [1]または [2]中の— Y1—!^— Y4— R4の好ましい例を表 1— 1、表 1 —2に示すが、本発明の近赤外線吸収材料における— Υ1—!^ — Y4— R4がこれら に限定されるものではない。なお、ー丫1ー1^1ぉょび7またはー丫4ー1^の1^1、 R4がァリ ール基である場合、ァリール基の— Υ1—または— Υ4—に対するオルト位に置換基を 有する場合、溶剤に対する溶解性が良好なものが得られ好ましい。 [0076] Hereinafter, preferred examples of —Y 1 —! ^ — Y 4 —R 4 in the general formula [1] or [2] are shown in Table 1-1 and Table 1-2. In the absorbent material — Υ 1 —! ^ — Y 4 — R 4 is not limited to these. In the case over丫1 - 1 ^ 1 Oyobi 7 or over丫4 - 1 ^ of 1 ^ 1, R 4 is § Li Lumpur groups, of Ariru group - Upsilon 1 - or - Upsilon 4 - against In the case of having a substituent at the ortho position, one having good solubility in a solvent is preferred.
[0077] [表 1] [0077] [Table 1]
表 1 一 1 Table 1 1 1
Figure imgf000019_0002
Figure imgf000019_0002
[0078]  [0078]
表 l一 2  Table l 1 2
A- 13 A- 14
Figure imgf000019_0001
A- 13 A- 14
Figure imgf000019_0001
A-15 A- 16 f\、 A-15 A-16 f \,
^N^C2H5 ^ N ^ C 2 H 5
1  1
C2H5 ό [0079] また、以下の表 2— 1、 2— 2に、基— Y2— R2—、— Y3— R3—の好ましい例を示すが 、基— Y2— R2—、— Y3— R3—が表 2— 1、表 2— 2に例示されたものに限定されるも のではない。なお、— Y2— R2—、— Y3— R3—の R2、 R3がァリール基である場合、ァリ ール基の— Y2—または— Y3—に対するオルト位に置換基を有する場合、溶剤に対 する溶解性が良好なものが得られ好ましい。 C 2 H 5 ό [0079] Further, 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. When 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.
[0080] [表 2] 表 2— 1 [0080] [Table 2] Table 2-1
Figure imgf000020_0001
Figure imgf000020_0001
[0081] [0081]
表 2— 2  Table 2— 2
Figure imgf000021_0002
Figure imgf000021_0002
[0082] また、一般式 [5]〜 [8]においては、
Figure imgf000021_0001
R4として、上記表 1— 1、 1—2で挙げられ たものを含め、下記表 3— 1、表 3— 2に記載のものが好ましいものとして挙げられる。 [0082] In the general formulas [5] to [8],
Figure imgf000021_0001
Preferred examples of R 4 include those listed in Tables 3-1 and 3-2 below, including those listed in Tables 1-1 and 1-2.
[0083] [表 3] [0083] [Table 3]
/ O8S/-0SAV S907:/κ£ OS 9εϊε900ζ< / O8S / -0SAV S907: / κ £ OS 9εϊε900ζ <
Figure imgf000022_0001
Figure imgf000022_0001
[0084] [0084]
表 3— 2 Table 3-2
Figure imgf000023_0002
Figure imgf000023_0002
[0085] さらに、一般式 [5]〜[8]においては、
Figure imgf000023_0001
R3として、上記表 2—1、 2— 2で挙げら れたものを含め、下記表 4—1、表 4— 2に記載のものが好ましいものとして挙げられる 。 R2、 R3としては、スルフイド結合基、ァリーレン基、ヘテロァリーレン基、アルキレン基 を含むものが好ま 、。スルフイド結合基を有するものは更に好ま 、。 [0085] Further, in the general formulas [ 5 ] to [ 8 ],
Figure imgf000023_0001
Preferred examples of R 3 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.
[0086] [表 4] [0086] [Table 4]
表 4 1 Table 4 1
Figure imgf000024_0001
Figure imgf000024_0001
[0087] [0087]
表 4 _ 2  Table 4 _ 2
Figure imgf000025_0001
Figure imgf000025_0001
[0088] 一般式 [1]〜[8]において、 Aは直接結合もしくは二価の有機残基を表す。 Aの二 価の有機残基は、例えば、 NHCO—、— CONH―、— NHCOO—、— OCONH 一、 一 O 、 一 S 、 一 NH 、 一 COO 、 一 OCO 、 一 SO —、 一 CO 、 一 C = [0088] In the general formulas [1] to [8], A represents a direct bond or a divalent organic residue. The divalent organic residues of A are, for example, NHCO—, —CONH—, —NHCOO—, —OCONH mono, mono O, mono S, mono NH, mono COO, mono OCO, mono SO—, mono CO, mono C =
2  2
C一、 N = N—、—S— S—、置換もしくは未置換のァリーレン基、置換もしくは未置 換のヘテロァリーレン基、置換もしくは未置換のアルキレン基、および置換もしくは未 置換のアミノ基力 なる群より選ばれた基を任意に組み合わせて成るものであるが、 上記一般式 [9]で表される二価の有機残基を含むもの、または置換もしくは未置換 のァリーレン基、置換もしくは未置換のへテロアリーレン基、置換もしくは未置換のァ ルキレン基、エーテル基、スルフイド結合基、ウレタン結合基、アミド結合基、カルボ- ル基、エステル基またはアミノ基を含むもの、あるいは、これらを適宜組み合わせたも のが好ましい。  C, 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 group selected from any combination selected from the group consisting of a divalent organic residue represented by the general formula [9], a substituted or unsubstituted arylene group, a substituted or unsubstituted 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.
[0089] 一般式 [1]〜[8]の Aにおける置換もしくは未置換のァリーレン基は、任意の置換も しくは未置換のァリーレン基であってよい。ァリーレン基としては、好ましくは炭素数 6 〜60の単環または縮合環のァリーレン基であり、より好ましくは炭素数 6〜40、更に 好ましくは炭素数 6〜30のァリーレン基である。具体例としては、フエ-レン、ビフエ- レン、ナフタレンジィル、アントラセンジィル、フエナント口リンジィル、ピレンジィル、トリ フエ二レンジィル、ベンゾフエナント口リンジィル、ペリレンジィル、ペンタフェニレンジ ィル、ペンタセンジィルなどが挙げられ、これらの基は任意に置換基を有していても 良い。 [0089] 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.
[0090] また、 Aの置換もしくは未置換のへテロアリーレン基は、任意の置換もしくは未置換 のへテロァリーレン基であってよい。ヘテロァリーレン基としては、好ましくは炭素数 4 ないし 60の単環または縮合環の芳香族へテロ環基であり、より好ましくは窒素原子、 酸素原子または硫黄原子の少なくとも一つを含有する炭素数 4ないし 60の単環また は縮合環の芳香族へテロ環基であり、更に好ましくは炭素数 4ないし 30の 5員または 6員の芳香族へテロ環基である。芳香族へテロ環基の具体例としては、ピロールジィ ル、フランジィル、チェ-レン、ピリジンジィル、ピリダジンジィル、ピリミジンジィル、ピ ラジンジィル、キノリンジィル、イソキノリンジィル、シンノリンジィル、キナゾリンジィル、 キノキサリンジィル、フタラジンジィル、プテリジンジィル、アタリジンジィル、フエナジ ンジィル、フエナント口リンジィルなどが挙げられる力 これらの基は任意に置換基を 有していても良い。  [0090] Further, 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. A monocyclic or condensed ring aromatic heterocyclic group having 60, more preferably a 5- or 6-membered aromatic heterocyclic group having 4 to 30 carbon atoms. Specific examples of the aromatic heterocyclic group 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.
[0091] Aにおける置換もしくは未置換のアルキレン基は、任意の置換もしくは未置換のァ ルキレン基であってよい。アルキレン基としては、具体的には、メチレン基、エチレン 基、プロピレン基、ブチレン基、 sec—ブチレン基、 tert—ブチレン基、ペンチレン基、 へキシレン基、 2—ェチルへキシレン基、ヘプチレン基、オタチレン基、イソオタチレン 基、ステアリレン基、トリクロロメチレン基、シクロへキシレン基などが挙げられ、これら の基は任意に置換基を有して 、ても良 、。  [0091] The substituted or unsubstituted alkylene group in A may be any substituted or unsubstituted alkylene group. Specific examples of the alkylene group include methylene, ethylene, propylene, butylene, sec-butylene, tert-butylene, pentylene, hexylene, 2-ethylhexylene, heptylene, and octylene. Group, isooctylene group, stearylene group, trichloromethylene group, cyclohexylene group and the like, and these groups may optionally have a substituent.
なお、上記 Aにおける置換基としては、 R ~R4において説明したと同様のものが挙 げられる。 Examples of the substituent in the above A include those described for R 1 to R 4 .
[0092] 以下の表 5— 1、表 5— 2に、 Aの例を示すが、 Aがこれらに限定されるものではない [表 5] 表 5 [0092] Tables 5-1 and 5-2 below show examples of A, but A is not limited to these [Table 5] Table 5
Figure imgf000027_0001
Figure imgf000027_0001
Figure imgf000028_0001
本発明においては、一般式 [1]〜 [8]で表される繰り返し単位を持つ近赤外線吸 収材料は重合体の混合物あるいは非共役重合体であっても共役重合体であっても 良い。また本発明の近赤外線吸収材料は、一般式 [1]および Zまたは一般式 [2]で 表される繰り返し単位を有する単一重合体または共重合体であってもよ 、。共重合 体においては、一般式 [1]または一般式 [2]で表される繰り返し単位に含まれる二種 以上の異なる繰り返し単位ユニットの共重合体であっても、あるいは一般式 [1]また は一般式 [2]で表される繰り返し単位と一般式 [1]または一般式 [2]以外の繰り返し 単位とからなる共重合体であってもよい。該共重合体は、ランダム、ブロック、または グラフト共重合体であってもよいし、それらの中間的な構造を有する高分子たとえば ブロック性をもつランダム共重合体であってもよい。本発明の一般式 [1]または一般 式 [2]で表される繰り返し単位以外の共重合成分としては、重合性反応末端をもつ 化合物で、例えば同一分子内に OH基を少なくとも二つ有する化合物、同一分子 内にハロゲン基および OH基をもつ化合物、同一分子内にハロゲン基を複数もつ 化合物、同一分子内に COOH基を複数もつ化合物、同一分子内に COC1基を 複数持つ化合物、同一分子内に OH基および COOH基をもつ化合物、同一分 子内に NH基を複数持つ化合物、同一分子内に NH基および COOH基を
Figure imgf000028_0001
In the present invention, 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
2 2  twenty two
もつ化合物などが挙げられる。  And the like.
[0095] 本発明の近赤外線吸収材料は、耐熱性、耐光性の点からは重量平均分子量は特 に限定されないが、たとえばゲルパーミエイシヨンクロマトグラフィー測定法によるポリ スチレン換算で 1, 000〜10, 000程度であることが好ましい。 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.
[0096] 本発明の一般式 [1]〜 [8]における Mは金属原子であれば特に限定はないが、二 ッケル、コバルト、白金、パラジウムもしくは銅が好ましぐニッケルが更に好ましい。 [0096] In the general formulas [1] to [8] of the present invention, M is not particularly limited as long as it is a metal atom, but nickel, cobalt, platinum, palladium or copper is more preferable.
[0097] 本発明の一般式 [1]〜[8]
Figure imgf000029_0001
R4は置換または未置換のフエニル基、置換また は未置換のチェニル基、炭素数 20以下の置換または未置換のアルキル基が好まし ぐ R2、 R3は置換または未置換のフエ-ル基、スルフイド結合基を含む置換または未 置換のフエ-レン基、置換または未置換のチェ-レン基、炭素数 20以下の置換また は未置換のァノレキレン基が好まし 、。 [0097] General formulas [1] to [8] of the present invention
Figure imgf000029_0001
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. And a substituted or unsubstituted phenylene group containing a sulfido bond group, a substituted or unsubstituted chain group, and a substituted or unsubstituted arylene group having 20 or less carbon atoms.
[0098] また、上記一般式 [1]および一般式 [2]、一般式 [3]および一般式 [4]、一般式 [5 ]および一般式 [6]、一般式 [7]および [8]はそれぞれ構造異性体であり、区別せず に用いることができるので、近赤外線吸収剤として 、ずれか一方を用いてもょ 、し、 分離せずに構造異性体の混合物として用いてもよ！ヽ。また近赤外線吸収領域の異な るユニットを必要に応じて共重合しても良いし、近赤外線吸収領域の異なる重合体同 士を混合しても良 、。ポリマーに用 、られるユニットの構造例を表 6に具体的に示す 力 本発明のポリマーは以下の代表例に限定されるものではない。なお、表 6は、各 ユニットモノマーの構造を示すのみで、その重合形態を示したものではな 、。 [0098] In addition, the above general formula [1] and general formula [2], general formula [3] and general formula [4], general formula [5] and general formula [6], general formula [7] and [8] ] Are structural isomers and can be used without distinction, so either one of them can be used as a near-infrared absorber, or it can be used as a mixture of structural isomers without separation. !ヽ. In addition, units having different near-infrared absorption regions may be copolymerized as necessary, or polymers having different near-infrared absorption regions may be mixed. Examples of structures of units used in the polymer are shown in Table 6 in detail. The polymer of the present invention is not limited to the following representative examples. Table 6 shows each It only shows the structure of the unit monomer, not its polymerization form.
[表 6] [Table 6]
表 6  Table 6
Figure imgf000030_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0001
[00 TO]  [00 TO]
S908T0/.00Z OAV
Figure imgf000032_0001
S908T0 / .00Z OAV
Figure imgf000032_0001
[0102] [0102]
Figure imgf000033_0001
//:/ O 9εϊε900ί1£ S908s/-00iAV
Figure imgf000033_0001
//: / O 9εϊε900ί1 £ S908s / -00iAV
§〕ΐο
Figure imgf000034_0001
§] ΐο
Figure imgf000034_0001
0 0
Figure imgf000036_0001
Figure imgf000036_0001
[SO 10] CTSlC/900Zdf/X3d S908T0/.00Z OAV [0106] [SO 10] CTSlC / 900Zdf / X3d S908T0 / .00Z OAV [0106]
Figure imgf000037_0001
[0107]
Figure imgf000037_0001
[0107]
Figure imgf000038_0001
Figure imgf000039_0001
[0109]
Figure imgf000038_0001
Figure imgf000039_0001
[0109]
Figure imgf000040_0001
Figure imgf000040_0001
[0110] 本発明の一般式 [1]または一般式 [2]、一般式 [3]または一般式 [4]、一般式 [5] または一般式 [6]、一般式 [7]または [8]で表わされる繰り返し単位を有する近赤外 線吸収材料は、例えば次のような合成スキームに従って製造することができる。 [0110] General Formula [1] or General Formula [2], General Formula [3] or General Formula [4], General Formula [5] or General Formula [6], General Formula [7] or [8] The near-infrared ray absorbing material having a repeating unit represented by the following can be produced, for example, according to the following synthesis scheme.
[0111] なお、合成スキーム中の一般式 B〜Eの化合物は、例え ί ournal of American Chemical Society, 87 : 7, April 5, 1965もしくは米国特許第 5089585号公 報記載の合成法に従った方法で製造することができる。また、一般式 F〜Hの化合物 は、特開 2005— 232158号公報記載の合成方法により製造することができる。式中 Qは一般式 [ 1 ]〜一般式 [8]における Aの一部に相当する。 [0111] The compounds of general formulas B to E in the synthesis scheme are, for example, ί 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. In the formula, Q corresponds to a part of A in the general formulas [1] to [8].
<合成スキーム 1 >  <Synthesis Scheme 1>
[化 10]
Figure imgf000041_0001
[Chemical 10]
Figure imgf000041_0001
[0113] <合成スキーム 2 >  [0113] <Synthesis Scheme 2>
[化 11]  [Chemical 11]
R3— Br R 3 — Br
\ /  \ /
M + H0- Q ^ OH  M + H0- Q ^ OH
S,  S,
Br— R2 へ Br—to R 2
c
Figure imgf000041_0002
c
Figure imgf000041_0002
[0114] <合成スキーム 3 >  [0114] <Synthesis Scheme 3>
[化 12] R3— Br [Chemical 12] R 3 — Br
\ /  \ /
M + H7N Q — NH2 M + H 7 NQ — NH 2
Br— R 2 、へ Br—R 2
D D
Figure imgf000042_0001
Figure imgf000042_0001
[0115] <合成スキーム 4 > [0115] <Synthesis Scheme 4>
[化 13]  [Chemical 13]
Figure imgf000042_0002
Figure imgf000042_0002
[0116] <合成スキーム 5 > [0116] <Synthesis Scheme 5>
[化 14]  [Chemical 14]
Figure imgf000042_0003
Figure imgf000042_0003
[0117] <合成スキーム 6 > [0117] <Synthesis Scheme 6>
[化 15] R，一 S s s、 一 RJ— Br HO ~ I Q | ~ OH —— R2-S 5 、s' 、S— [Chemical 15] R, One S ss , One R J — Br HO ~ IQ | ~ OH —— R 2 -S 5 , s ', S—
G  G
Figure imgf000043_0001
Figure imgf000043_0001
[0118] <合成スキーム 7 > [0118] <Synthesis Scheme 7>
[化 16]  [Chemical 16]
Figure imgf000043_0002
Figure imgf000043_0002
[0119] <合成スキーム 8 > [Synthesis Scheme 8]
[化 17]  [Chemical 17]
Figure imgf000043_0003
Figure imgf000043_0003
[0120] 上記スキームにおける合成は、例えば次のようにして行われる。 [0120] The synthesis in the above scheme is performed, for example, as follows.
(合成条件例）  (Example of synthesis conditions)
窒素雰囲気下、ジメチルフオルムアミド、ジメチルスルホキシド、メチルェチルケトン などの極性溶剤中 NaOH、 KOH、 K CO 、 Na CO、トリェチルァミンなどの塩基を  Under a nitrogen atmosphere, a base such as NaOH, KOH, KCO, NaCO, or triethylamine in a polar solvent such as dimethylformamide, dimethylsulfoxide, or methylethylketone
2 3 2 3  2 3 2 3
B〜Hに対して 2当量〜 50当量、好ましくは 8当量〜 20当量使用して Qを含むジォ ール、ジァミン、ジ酸塩化物、ジブロマイドと共に 40°C〜150°C、好ましくは 50°C〜1 00°Cにおいて加熱撹拌するとスキーム中、括弧内の繰り返し単位をもつ化合物を合 成することができる。取り出しは不溶物をろ過後、メタノール、エタノールなどのアルコ 一ルに再沈殿することにより行う。 Use 2 to 50 equivalents, preferably 8 to 20 equivalents of B to H , Diamide, diacid chloride, and dibromide to form a compound having repeating units in parentheses in the scheme when heated and stirred at 40 ° C to 150 ° C, preferably 50 ° C to 100 ° C. be able to. Remove the insoluble material by filtering and reprecipitating it in alcohol such as methanol or ethanol.
[0121] 前記一般式 [1]または [2]の繰り返し単位を有する近赤外線吸収材料あるいはこの 近赤外線吸収材料からなる本発明の近赤外線吸収剤は、近赤外線の吸収が必要と される用途であればどのような用途においても用いることができ、またその使用態様、 使用形態も近赤外線吸収材料の構造により制限を受けることはない。すなわち、本 発明の近赤外線吸収材料あるいは近赤外線吸収剤は、一般式 [1]または一般式 [2 ]の繰り返し単位構造を含む近赤外線吸収材料以外の他の近赤外線吸収剤等の光 吸収性色素や紫外線吸収剤、酸化防止剤などの安定剤等の補助的材料とともに用 いることができるし、また、本発明の近赤外線吸収材料および近赤外線吸収剤は、こ れら補助的成分と共に溶剤に溶解または溶剤または水に分散させる、あるいは必要 であればバインダー榭脂等とともに溶剤に溶解または溶剤または水に分散して近赤 外線吸収組成物（塗布剤）とし、これを基材等に塗布して近赤外線吸収層を形成す ることができるし、バインダー榭脂が自己支持性フィルムを形成することができるもの であれば、剥離性基材上に塗布してフィルムを形成した後、剥離性基材カゝらフィルム を剥離し、近赤外線吸収フィルムとして利用することもできる。このとき塗布用組成物 は油性であっても、水性であってもよぐ溶液であっても、ペースト状であってもよい。  [0121] 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. As long as it can be used for any purpose, 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]. It can be used together with 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 ゝ 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.
[0122] また、前記のように近赤外線吸収層を形成することに代え、粘着剤あるいは接着剤 層、紫外線吸収層、ハードコート層、基材など他の機能層に本発明の近赤外線吸収 剤を含有させ、これら層に近赤外線吸収特性を付与してもよい。例えば、粘着剤層あ るいは接着剤層に本発明の近赤外線吸収材料または近赤外線吸収剤を含有させる には、従来公知の粘着剤ある ヽは接着剤組成物に本発明の近赤外線吸収材料ある いは近赤外線吸収剤を添加し、近赤外線吸収性の粘着剤ある ヽは接着剤を得ること 、この近赤外線吸収性の粘着剤あるいは接着剤を用いて、近赤外線吸収性の粘着 層あるいは接着層を形成し、この層を近赤外線吸収フィルタ一層として利用すればよ い。このとき、必要であれば、前記他の成分を含ませてもよい。また必要であれば、成 形榭脂中に含有させ、近赤外線吸収フィルムあるいは成形物を形成することもできる 。前記本発明の近赤外線吸収材料あるいは近赤外線吸収剤を含む近赤外線吸収 層を有する積層体あるいは単体フィルムは光学フィルタ一として好ましく用いられる。 [0122] Further, instead of forming the near-infrared absorbing layer as described above, 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. For example, in order to make the pressure-sensitive adhesive layer or the adhesive layer contain the near-infrared absorbing material or near-infrared absorbing material of the present invention, a conventionally known pressure-sensitive adhesive is used in the adhesive composition. Or add a near-infrared absorber, and a near-infrared-absorbing pressure-sensitive adhesive is used to obtain an adhesive. Using this near-infrared-absorbing pressure-sensitive adhesive or 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. At this time, if necessary, the other components may be included. If necessary, It is possible to form a near-infrared absorbing film or a molded article by containing it in the shaped resin. 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.
[0123] 前記のとおり、本発明の近赤外線吸収組成物は、本発明の近赤外線吸収材料また は近赤外線吸収剤と、必要に応じ用いられる他の光吸収性色素、安定剤、バインダ ー榭脂、溶剤、粘着性榭脂、他の補助成分、必要であれば他の機能層を形成する 成分などにより構成される。  [0123] As described above, 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.
[0124] 前記他の光吸収性色素としては、例えば、シァニン系、キノリン系、クマリン系、チア ゾール系、ォキソノール系、ァズレン系、スクァリリウム系、ァゾメチン系、ァゾ系、ベン ジリデン系、キサンテン系、フタロシアニン系、ナフタロシアニン系、ナフトキノン系、ァ ントロキノン系、トリフエ-ルメタン系、ジィモ -ゥム系、前記一般式 [1]または一般式 [ 2]で表される金属錯体以外のジチオール金属錯体系化合物等が挙げられる。  [0124] 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.
[0125] 上記他の光吸収性色素としては、近赤外線吸収剤であるニッケル錯体系色素およ び Zまたはフタロシアニン系色素および Zまたはジィモ -ゥム系色素が好ましいもの である。本発明の近赤外線吸収剤に対するこれら他の光吸収性色素の添加量は、 本発明の近赤外線吸収剤 100重量部に対して、好ましくは 20〜500重量部、より好 ましくは 50〜200重量部である。吸収スペクトルとの兼ね合 、でフィルムとしたときの 可視光透過率が 70〜80%以上、近赤外領域の透過率は 10%以下となる比率が好 ましい。  [0125] As 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. In view of the absorption spectrum, it is preferable that 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.
[0126] 上記ニッケル錯体系色素としては、下記一般式 [10]の構造を有するものが挙げら れ、これはさらに一価のカチオンとのイオンィ匕化合物となって 、ても良!、。  [0126] Examples of the nickel complex dye include those having the structure of the following general formula [10], which may further be an ionic compound with a monovalent cation.
[0127] 一般式 [10] :  [0127] General formula [10]:
[化 18]  [Chemical 18]
Figure imgf000045_0001
Figure imgf000045_0001
[0128] [式中 R9〜R12は Oまたは Sまたは Nを表す。 ] [0129] 上記一般式 [10]の構造を有するニッケル錯体系色素としては、具体的には Ameri can Dye Source, Ink (Laser Dyes & Near Infrared Dyes)力ら巿販 れ る ADS845MC、 ADS870MC、 ADS880MC、 ADS890MC、 ADS920MC、 A DS990MC等が挙げられるがこれらに限定したものではない。 [Wherein R 9 to R 12 represent O, S, or N.] ] [0129] 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.
[0130] 一方、フタロシアニン系色素としては、下記一般式 [11]で挙げられるものが好まし いものである。  [0130] On the other hand, as the phthalocyanine dyes, those represented by the following general formula [11] are preferable.
[0131] 一般式 [11] :  [0131] General formula [11]:
[化 19]  [Chemical 19]
Figure imgf000046_0001
Figure imgf000046_0001
[0132] (Mは金属原子、式中 R13〜R28は水素原子もしくは置換基を表し、 Mにはさらに置 [0132] (M represents a metal atom, wherein R 13 to R 28 represent a hydrogen atom or a substituent, and M is further substituted.
1 1  1 1
換基を有しても良い。）  You may have a substituent. )
[0133] 具体的には株式会社日本触媒製ィーエタスカラー IR— 10、 IR— 12、 IR— 14等が あるが、フタロシアニン系色素がこれらに限定されるものではない。  [0133] Specific examples include IETAS Color IR-10, IR-12, IR-14 manufactured by Nippon Shokubai Co., Ltd., but phthalocyanine dyes are not limited to these.
[0134] さらにジィモ -ゥム系色素としては、下記一般式 [12]の構造を含むものが好ましい ものである。  [0134] Further, as the dimonium dye, those having the structure of the following general formula [12] are preferable.
[0135] 一般式 [12] :  [0135] General formula [12]:
[化 20]
Figure imgf000046_0002
[0136] (式中、 ΧΊまハロゲンイオン、無機酸イオンまたは有機酸イオンを表す。 ) [Chemical 20]
Figure imgf000046_0002
[In the formula, it represents a halogen ion, an inorganic acid ion or an organic acid ion.]
[0137] 上記一般式 [12]において X—のハロゲンイオンとしては、例えばヨウ素イオン、臭素 イオン、塩素イオン、フッ素イオン等が挙げられる。また、無機酸イオンとしては、例え ば、へキサフルォロアンチモン酸イオン、過塩素酸イオン、テトラフルォロホウ酸ィォ ン、へキサフルォロリン酸イオン、硝酸イオン等が挙げられる。有機酸イオンとしては、 例えば、酢酸イオン、トリフルォロ酢酸イオン、メタンスルホン酸イオン、トリフルォロメ タンスルホン酸イオン、ベンゼンスルホン酸イオン、トルエンスルホン酸イオン等が挙 げられる。市販品としては、例えば日本化薬 (株)製 IRG— 022、 IRG— 023、 IRG— 040等が挙げられるがこれらに限定されるものではない。 [0137] In the above general formula [12], 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. Examples of the organic acid ion 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.
[0138] また、本発明の近赤外線吸収剤や上記他の光吸収性色素の、光あるいは熱に対 する安定化を図る目的で使用される上記各種安定化剤としては、例えば、ハイドロキ ノン誘導体 (米国特許 3935016号明細書、米国特許 3982944号明細書）、ハイド口 キノンジエーテル誘導体 (米国特許 4254216号明細書）、フエノール誘導体 (特開 昭 54— 21004号公報）、スピロインダン又はメチレンジォキシベンゼンの誘導体（英 国特許出願公開 2077455号明細書、英国特許 2062888号明細書）、クロマン、ス ピロクロマン又はクマランの誘導体（米国特許 3432300号明細書、米国特許 35730 50号明細書、米国特許 3574627号明細書、米国特許 3764337号明細書、特開昭 52— 152225号公報、特開昭 53— 20327号公報、特開昭 53— 17729号公報、特 開昭 61— 90156号公報）、ハイドロキノンモノエーテル又はパラアミノフエノールの誘 導体 (英国特許 1347556号明細書、英国特許 2066975号明細書、特公昭 54—1 2337号公報、特開昭 55— 6321号公報）、ビスフ ノール誘導体 (米国特許 37004 55号明細書、特公昭 48— 31625号公報）、金属錯体 (米国特許 4245018号明細 書、特開昭 60— 97353号公報）、 -トロソ化合物（特開平 2— 300288号公報）、ジィ ンモニゥム化合物（米国特許 465612号明細書）、ニッケル錯体（特開平 4 14618 9号公報)、酸ィ匕防止剤 (欧州特許 820057号明細書)が挙げられる。また、本発明 の光学フィルタ一は、一重項酸素等のクェンチヤ一として、芳香族-トロソ化合物、ァ ミニゥム化合物、イミニゥム化合物、ビスイミニゥム化合物、遷移金属キレート化合物 等を含有してもよぐ本発明の近赤外線吸収剤の効果を阻害しない範囲において、 ビスチォラート金属錯体ァ二オン等のクェンチヤーァ-オンを用いてもよ 、。 [0138] 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. (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. 2077455, British Patent 2062888), Chromans, Spirochromans or Coumaran Derivatives (US Pat. No. 3,432,300, US Pat. No. 3573050, US Pat. No. 3,574,627) Specification, US Pat. No. 3764337, JP-A-52-152225, JP-A-53-20327, JP-A-53-17729, JP-A-61-90156), hydroquinone Monoether or paraaminophenol derivatives (British Patent 1347556, British Patent 2066975, Japanese Patent Publication No. 54-1 2337, Japanese Patent Laid-Open No. 55-6321), Bisphenol derivatives (US Patent 37004 55) No., JP-B-48-31625), metal complexes (US Pat. No. 4245018, JP-A-60-97353), -troso compounds (JP-A-2-300288), dimonium compounds ( U.S. Pat. No. 465612), nickel complex (Japanese Patent Laid-open No. 4 14618 9), and acid-fouling inhibitor (European Patent 820057). Further, 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. In a range that does not hinder the effect of the near infrared absorber, Quencherons such as bisthiolate metal complexes can also be used.
[0139] 本発明の近赤外線吸収剤に対し補助的に用いられる、本発明の近赤外線吸収剤 以外の光吸収性色素や各種安定剤等の添加剤の量は、本発明の近赤外線吸収剤 100重量部に対し、好ましくは 20〜200重量部、更に好ましくは 50〜150重量部で ある。吸収スペクトルとの兼ね合 、でフィルムとしたときの可視光透過率が 70〜80% 以上、近赤外領域の透過率は 10%以下となる比率が好ましい。  [0139] 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. Preferably it is 20-200 weight part with respect to 100 weight part, More preferably, it is 50-150 weight part. In view of the absorption spectrum, 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.
[0140] 前記したとおり、本発明の近赤外線吸収剤は、必要に応じてバインダー榭脂と共に 塗布組成物を形成することができる。この塗布組成物を基材上に塗布することにより 、近赤外線吸収剤を含む層を形成して、基材との積層体とすることができる。この積 層体は、基材の種類を選択することにより、例えば、光学フィルター、光学反射板、光 学拡散板などとして用いることができるし、その他、農業用近赤外線吸収フィルム、熱 線遮断フィルム、保護めがね、サングラス、電子写真感光体などとしても利用できる。 また本発明の近赤外線吸収剤は、近赤外線の吸収熱を利用する記録媒体、光学記 録用色素、光学文字読み取り記録用材料、機密文書複写防止用層、レーザー溶着 のための近赤外線吸収剤などしても利用できる。  [0140] As described above, the near-infrared absorber of the present invention can form a coating composition together with a binder resin if necessary. By apply | 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. Further, 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.
[0141] 前記バインダー榭脂としては、例えば、脂肪族エステル系榭脂、ポリメチル (メタ)ァ タリレート系榭脂、アクリル系榭脂、メラミン榭脂、ウレタン榭脂、芳香族エステル榭脂 、ポリカーボネート榭脂、脂肪族ポリオレフイン榭脂、芳香族ポリオレフイン榭脂、ポリ ビュル系榭脂、ポリビュルアルコール榭脂、ポリビュル系変性榭脂、ポリ塩ィ匕ビュル 榭脂、スチレン ブタジエンコポリマー、ポリスチレン榭脂、ポリアミド榭脂およびそれ らの共重合榭脂を挙げることができるがこれらに限定されるものではない。また、ゼラ チン、カゼイン、澱粉、セルロース誘導体、アルギン酸等の天然高分子材料も挙げら れる。これらバインダー榭脂は、塗布組成物が油性であるか水性であるかにより、適 宜の榭脂、共重合体が選択される。  [0141] Examples of the binder resin include aliphatic ester resin, polymethyl (meth) acrylate resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, and polycarbonate resin. Fatty, Aliphatic polyolefin resin, Aromatic polyolefin resin, Polybule resin, Polybulol alcohol resin, Polybule modified resin, Polysalt resin resin, Styrene butadiene copolymer, Polystyrene resin, Polyamide resin Examples thereof include but are not limited to fats and copolymerized rosins thereof. Further, natural polymer materials such as gelatin, casein, starch, cellulose derivatives, alginic acid and the like can also be mentioned. As these binder resins, appropriate resins and copolymers are selected depending on whether the coating composition is oily or aqueous.
[0142] 油性の塗布剤を構成する有機溶媒としては、ハロゲン系、アルコール系、ケトン系、 エステル系、脂肪族炭化水素系、芳香族炭化水素系、エーテル系溶媒、およびそれ らの混合溶媒を挙げることができる。一方、水性の塗布剤の調製方法としては、例え ば、本発明の近赤外線吸収剤を微粉化処理して数マイクロメーター以下の微粒子を 得、当該微粒子を、未着色のアクリル系のポリマーエマルジョン中に分散させる方法 を挙げることができる。 [0142] 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. On the other hand, as a method for preparing an aqueous coating agent, for example, 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.
[0143] 本発明の近赤外線吸収組成物が粘着剤として用いられる場合、バインダーとして 粘着性バインダーを使用しても良い。粘着性バインダーとしては、アクリル系、ウレタ ン系、ゴム系などが挙げられる。アクリル系として用いることのできるモノマーとしては アクリルモノマー、メチル (メタ）アタリレート、ェチル (メタ）アタリレート、プロピル (メタ） アタリレート、ブチル (メタ）アタリレート、ペンチル (メタ）アタリレート、 2—ェチルへキシ ル (メタ）アタリレート、ヘプチル (メタ）アタリレート、へキシル (メタ）アタリレート、ォクチ ル (メタ）アタリレート、ノ-ル (メタ）アタリレート、デシル (メタ）アタリレート、ゥンデシル（ メタ)アタリレート、ドデシル (メタ）アタリレート、トリデシル (メタ)アタリレート、テトラデシ ル (メタ）アタリレート、ペンタデシル (メタ）アタリレート、へキサデシル (メタ）アタリレート 、ヘプタデシル (メタ）アタリレート、ォクタデシル (メタ）アタリレート、ノナデシル (メタ） アタリレート、ィコシル (メタ）アタリレート、ヘンィコシル (メタ）アタリレート、ドコシル (メ タ）アタリレート、（メタ)アクリル酸等を挙げることができる。これらは、粘着剤としての 望ましい物性を得る目的のため、適宜選択して単独で、あるいは 2種類以上を組み 合わせて使用することができる。本発明においては、粘着物性を確保するという点で 、炭素数力 〜12のアクリル系モノマーを共重合成分として用いることが好ましぐさ らに好ましくは、ブチル (メタ）アタリレート、 2—ェチルへキシル (メタ）アタリレートを共 重合成分として用いることである。  [0143] When the near-infrared absorbing composition of the present invention is used as an adhesive, an adhesive binder may be used as a binder. Examples of 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) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate Octadecyl (meth) ate, nonadecyl (meta Atari rate, Ikoshiru (meth) Atari rate, Henikoshiru (meth) Atari rate, docosyl (meth) Atari rate, and (meth) acrylic acid. These can be selected as appropriate for the purpose of obtaining desirable physical properties as an adhesive, and can be used alone or in combination of two or more. In the present invention, it is preferable to use an acrylic monomer having a carbon number of ˜12 as a copolymerization component from the viewpoint of securing adhesive properties, and it is more preferable to use butyl (meth) acrylate or 2-ethyl. Xyl (meth) acrylate is used as a copolymerization component.
[0144] 上述粘着性バインダーにおいてアクリル系モノマー、アルキレンオキサイド鎖を有 するアクリル系モノマー、及びその他のモノマー等を共重合してなるアクリル系共重 合体の重量平均分子量（Mw)は 5万〜 100万であることが好ましぐ 5万〜 20万の低 分子量アクリル系共重合体であることがより好ま 、。  [0144] 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.
[0145] さらに、粘着性バインダーと本発明の近赤外線吸収剤とを含んでなる粘着剤は、基 材上に公知の方法で塗工されて、積層体である粘着剤シートとなる。ここで用いられ る基材は、後に記載する基材のほか、紙、金属、布なども用いられる。また、粘着性 ノ インダ一が、単独でシートを構成できる場合は、基材を必要としない粘着剤シート となる。また、基材の両面に粘着剤が塗工される形態であってもよい。ただし、一方の 面の粘着剤が、本発明の粘着剤を含まな 、場合であってもよ 、。 [0145] Further, 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. In addition to the base material described later, paper, metal, cloth, etc. are used as the base material used here. In addition, when the adhesive binder can form a sheet by itself, the adhesive sheet does not require a base material. Moreover, the form by which an adhesive is coated on both surfaces of a base material may be sufficient. However, one The surface adhesive may not include the adhesive of the present invention.
[0146] 粘着性バインダー榭脂を含むバインダー榭脂に対する本発明の近赤外線吸収剤 の添加量は、該榭脂 100重量部に対して近赤外線吸収剤 0. 01〜20重量部である ことが好ましぐ更に好ましくは該榭脂 100重量部に対して 0. 1〜15重量部である。 この割合が 0. 01重量部未満である場合には、近赤外線領域の波長光を効率よく吸 収することができず、一方、 20重量部を超える場合には、近赤外線吸収剤の分散性 が低下して透明性 (可視光線透過性)が損なわれることがある。  [0146] 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.
[0147] 本発明における接着剤組成物は本発明の近赤外線吸収剤および接着剤からなる 近赤外線吸収性を有する加工材料である。本発明の近赤外線吸収組成物としての 接着剤組成物は、本発明の近赤外線吸収材料を、接着性を有する適宜の媒体に溶 解または分散させること〖こより調製することができる。  [0147] 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.
[0148] 本発明の近赤外線吸収材料または近赤外線吸収剤は、光学フィルターを構成する 色素として好ましく利用することができる。光学フィルターを形成する方法としては、本 発明の近赤外線吸収材料または近赤外線吸収剤、上記の他の光吸収性色素や各 種安定剤を、例えば、光学フィルターを構成する基材又は任意の層に含有させる方 法、基材又は任意の層上にコーティングする方法、各層間のポリマーバインダーや 接着剤、粘着材に混入させる方法、本発明の近赤外線吸収剤等を含有する近赤外 線吸収層を上記の各層とは別に設ける方法等が挙げられる。基材上に近赤外線吸 収層を形成する場合、基材に、必要に応じて、下塗り層、反射防止層、ハードコート 層、潤滑層等の各層が設けられてもよい。本発明の近赤外線吸収剤は、光学フィル ターを構成する層間にポリマーバインダーや接着剤、粘着剤に混入させて近赤外線 吸収層を設ける方法に好適に用いることができる。  [0148] 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. Examples of 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. Near infrared absorption containing the near infrared absorber of the present invention, the method of coating on a base material or an arbitrary layer, the method of mixing with a polymer binder or adhesive between each layer, the method of mixing in an adhesive material, etc. The method of providing a layer separately from said each layer etc. are mentioned. When forming a near-infrared absorbing layer on a base material, 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.
[0149] 本発明の近赤外線吸収材料または近赤外線吸収剤が光学フィルターで用いられ る場合、その使用量は、光学フィルターの単位面積当たり、通常 1〜： L000mg/m2 であり、好ましくは 5〜： LOOmg/m2である。 lmg/m2未満の使用量では、近赤外線 吸収効果を十分に発揮することができず、 lOOOmgZm2を超えて使用した場合には 、フィルターの色目が強くなりすぎて表示品質等を低下させるおそれがあり、さらには 、明度が低下するおそれもあるため好ましくない。 [0150] 上記基材の材料としては、例えば、ガラス等の無機材料；ある 、は、例えば、ジァセ チルセルロース、トリァセチルセルロース（TAC)、プロピオ-ルセルロース、ブチリノレ セノレロース、ァセチノレプロピ才ニノレセノレロース、ニトロセノレロース等のセノレロースエス テル；ポリアミド；ポリカーボネート；ポリエチレンテレフタレート、ポリエチレンナフタレ ート、ポリブチレンテレフタレート、ポリ 1, 4ーシクロへキサンジメチレンテレフタレー ト、ポリエチレン 1, 2 ジフエノキシェタン 4, 4'ージカルボキシレート、ポリブチ レンテレフタレート等のポリエステル；ポリスチレン；ポリエチレン、ポリプロピレン、ポリ メチルペンテン等のポリオレフイン；ポリメチルメタタリレート等のアクリル系榭脂；ポリ力 ーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテノレケトン；ポリエーテルイミ ド;ポリオキシエチレン等の高分子材料が挙げられる。光学フィルター用途であれば、 基材は透明支持体であることが好ましぐ透明支持体の透過率は 80%以上であるこ と力 子ましく、 86%以上であることがさらに好ましい。ヘイズは、 2%以下であることが 好ましぐ 1%以下であることがさらに好ましい。屈折率は、 1. 45〜： L 70であることが 好ましい。 [0149] When the near-infrared absorbing material or near-infrared absorbing agent of the present invention is used in an 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. [0150] 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 ketone; polyether imide. For optical filter applications, it is preferable that 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.
[0151] これらの基材中には、必要に応じ、光吸収性色素、酸化防止剤、光安定剤、紫外 線吸収剤、無機微粒子等を添加することができ、また、これらの基材には各種の表面 処理を施すことができる。  [0151] In these base materials, 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.
[0152] 上記無機微粒子としては、例えば、二酸化珪素、二酸化チタン、硫酸バリウム、炭 酸カルシウム、タルク、カオリン等の無機微粒子が挙げられる。また、上記各種表面 処理としては、例えば、薬品処理、機械的処理、コロナ放電処理、火焰処理、紫外線 照射処理、高周波処理、グロ一放電処理、活性プラズマ処理、レーザー処理、混酸 処理、オゾン酸化処理等が挙げられる。  [0152] 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.
[0153] 上記下塗り層は、本発明の近赤外線吸収材料または近赤外線吸収剤を含有する 近赤外線吸収層を設ける場合に、基材と近赤外線吸収層と接着性などを改善するた めに基材と近赤外線吸収層との間に用いる層である。上記下塗り層は、ガラス転移 温度が— 60〜60°Cのポリマーを含む層、近赤外線吸収層側の表面が粗面である層 又は近赤外線吸収層のポリマーと親和性を有するポリマーを含む層として形成される 。なお、近赤外線吸収層が設けられていない基材の面に下塗り層を設けて、基材と その上に設けられる層（例えば、反射防止層、ハードコート層）との接着力を改善する ために設けてもよぐまた、下塗り層は、光学フィルターと画像形成装置とを接着する ための接着剤と光学フィルターとの親和性を改善するために設けてもょ 、。下塗り層 の厚みは、 2nm〜20 μ mが好ましぐ 5nm〜5 μ mがより好ましぐ 20nm〜2 μ mが さらに好ましぐ 50ηπι〜1 /ζ πιがさらにまた好ましぐ 80ηπ！〜 300nmが最も好まし い。ガラス転移温度が 60〜60°Cのポリマーを含む下塗り層は、ポリマーの粘着性 で、基材と近赤外線吸収層とを接着する。ガラス転移温度が— 60〜60°Cのポリマー は、例えば、塩化ビニル、塩化ビ-リデン、酢酸ビュル、ブタジエン、ネオプレン、スチ レン、クロ口プレン、アクリル酸エステル、メタクリル酸エステル、アクリロニトリル又はメ チルビ-ルエーテルの重合又はこれらの共重合により得ることができる。上記ガラス 転移温度は、 50°C以下であることが好ましぐ 40°C以下であることがより好ましぐ 30 °C以下であることがさらに好ましぐ 25°C以下であることがさらにまた好ましぐ 20°C 以下であることが最も好ましい。下塗り層の 25°Cにおける弾性率は、 1〜： LOOOMPa であることが好ましぐ 5〜800MPaであることがさらに好ましぐ 10〜500MPaである ことが最も好ましい。表面が粗面である下塗り層は、粗面の上に近赤外線吸収層を 形成することで、基材と近赤外線吸収層とを接着する。表面が粗面である下塗り層は 、ポリマーラテックスの塗布により容易に形成することができる。ラテックスの平均粒径 は、 20ηπ！〜 3 μ mであることが好ましぐ 50ηπ！〜 1 μ mであることがさらに好ましい。 近赤外線吸収層のバインダーポリマーと親和性を有するポリマーとしては、アクリル 榭脂、セルロース誘導体、ゼラチン、カゼイン、でんぷん、ポリビュルアルコール、可 溶性ナイロン、高分子ラテックス等が挙げられる。また、本発明の光学フィルタ一にお いては、二以上の下塗り層を設けてもよい。下塗り層には、基材を膨潤させる溶剤、 マット剤、界面活性剤、帯電防止剤、塗布助剤や硬膜剤等を添加してもよい。 [0153] When the near-infrared absorbing layer containing the near-infrared absorbing material or near-infrared absorbing agent of the present invention is provided, 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. In addition, 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 μm, more preferably 5 nm to 5 μm, more preferably 20 nm to 2 μm, and even more preferably 50ηπι to 1 / ζ πι, 80ηπ! ~ 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 20ηπ! It is preferable to be ~ 3 μm 50ηπ! More preferably, it is ˜1 μm. Examples of 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. In the optical filter of the present invention, two or more undercoat layers may be provided. In the undercoat layer, 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.
また、上記反射防止層中においては、低屈折率層が必須である。低屈折率層の屈 折率は、上記透明支持体の屈折率よりも低い。低屈折率層の屈折率は、 1. 20〜： L 55であることが好ましぐ 1. 30〜： L 50であることがさらに好ましい。低屈折率層の厚 さは、 50〜400nmであることが好ましぐ 50〜200nmであることがさらに好ましい。 低屈折率層は、屈折率の低い含フッ素ポリマーからなる層（特開昭 57— 34526号、 特開平 3— 130103号、同 6— 115023号、同 8— 313702号、同 7— 168004号の 各公報記載）、ゾルゲル法により得られる層（特開平 5— 208811号、同 6— 299091 号、同 7— 168003号の各公報記載）、あるいは微粒子を含む層（特公昭 60— 5925 0号、特開平 5— 13021号、同 6— 56478号、同 7— 92306号、同 9— 288201号の 各公報に記載）として形成することができる。微粒子を含む層では、微粒子間又は微 粒子内のミクロボイドとして、低屈折率層に空隙を形成することができる。微粒子を含 む層は、 3〜50体積％の空隙率を有することが好ましぐ 5〜35体積％の空隙率を 有することがさらに好ましい。 In the antireflection layer, 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. 57-34526, 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 (Japanese Patent Publication Nos. 60-59250, JP-A-5-13021, JP-A-6-56478, JP-A-7-92306, JP-A-9-288201) (Described in each publication). In the 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.
[0155] 広い波長領域の反射を防止するためには、上記反射防止層において、低屈折率 層に加えて、屈折率の高い層（中'高屈折率層）を積層することが好ましい。高屈折 率層の屈折率は、 1. 65-2. 40であることが好ましぐ 1. 70-2. 20であることがさ らに好ましい。中屈折率層の屈折率は、低屈折率層の屈折率と高屈折率層の屈折 率との中間の値となるように調整する。中屈折率層の屈折率は、 1. 50〜： L 90であ ることが好ましぐ 1. 55〜： L 70であることがさらに好ましい。中'高屈折率層の厚さ は、 5ηπι〜100 /ζ πιであることが好ましぐ 10ηπι〜10 /ζ mであることがさらに好まし く、 30ηπι〜1 /ζ πιであることが最も好ましい。中'高屈折率層のヘイズは、 5%以下で あることが好ましぐ 3%以下であることがさらに好ましぐ 1%以下であることが最も好 ましい。中'高屈折率層は、比較的高い屈折率を有するポリマーバインダーを用いて 形成することができる。屈折率が高いポリマーとしては、ポリスチレン、スチレン共重合 体、ポリカーボネート、メラミン榭脂、フエノール榭脂、エポキシ榭脂、環状 (脂環式又 は芳香族)イソシァネートとポリオールとの反応で得られるポリウレタン等が挙げられる 。その他の環状 (芳香族、複素環式、脂環式)基を有するポリマーや、フッ素以外の ノ、ロゲン原子を置換基として有するポリマーも、屈折率が高い。二重結合を導入して ラジカル硬化を可能にしたモノマーの重合反応により形成されたポリマーを用いるこ とちでさる。 [0155] In order to prevent reflection in a wide wavelength region, in the antireflection layer, in addition to the low refractive index layer, 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 5ηπι to 100 / ζ πι, more preferably 10ηπι to 10 / ζ m, and most preferably 30ηπι to 1 / ζ πι. 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. Examples of the polymer having a high refractive index 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. The use of a polymer formed by the polymerization reaction of a monomer that allows radical curing by introducing a double bond.
[0156] さらに高い屈折率を得るため、ポリマーバインダー中に無機微粒子を分散してもよ い。無機微粒子の屈折率は、 1. 80〜2. 80であることが好ましい。無機微粒子は、 金属の酸化物又は硫化物から形成することが好ま ヽ。金属の酸化物又は硫化物と しては、酸ィ匕チタン (例えば、ルチル、ルチル zアナターゼの混晶、アナターゼ、ァモ ルファス構造）、酸化錫、酸化インジウム、酸化亜鉛、酸ィ匕ジルコニウム、硫化亜鉛等 が挙げられる。これらの中でも、酸化チタン、酸ィ匕錫及び酸化インジウムが特に好まし い。無機微粒子は、これらの金属の酸化物又は硫化物を主成分とし、さらに他の元 素を含むことができる。ここで、主成分とは、無機微粒子を構成する成分の中で最も 含有量 (重量％)が多い成分を意味する。他の元素としては、 Ti、 Zr、 Sn、 Sb、 Cu、 Fe、 Mn、 Pb、 Cd、 As、 Cr、 Hg、 Zn、 Al、 Mg、 Si、 P、 S等力挙げ、られる。また、被 膜形成性で溶剤に分散し得るか、それ自身が液状である無機材料、例えば、各種元 素のアルコキシド、有機酸の塩、配位性ィ匕合物と結合した配位ィ匕合物（例えばキレー ト化合物）、活性無機ポリマー等を用いて、中'高屈折率層を形成することもできる。 [0156] In order to obtain a higher 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. Here, the main component means a component having the highest content (% by weight) among the components constituting the inorganic fine particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S. In addition, 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.
[0157] 上記反射防止層の表面には、アンチグレア機能 (入射光を表面で散乱させて、膜 周囲の景色が膜表面に移るのを防止する機能)を付与することができる。例えば、透 明フィルムの表面に微細な凹凸を形成し、そしてその表面に反射防止層を形成する 力 あるいは、反射防止層を形成後、エンボスロールにより表面に凹凸を形成するこ とにより、アンチグレア機能を有する反射防止層を得ることができる。アンチグレア機 能を有する反射防止層は、一般に 3〜30%のヘイズを有する。 [0157] 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). For example, 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%.
[0158] 上記ハードコート層は、透明支持体の硬度よりも高い硬度を有する。ハードコート層 は、架橋しているポリマーを含むことが好ましい。ハードコート層は、アクリル系、ウレ タン系、エポキシ系のポリマー、オリゴマー又はモノマー（例えば紫外線硬化型榭脂） を用いて形成することができる。また、シリカ系材料力もハードコート層を形成すること ちでさる。 [0158] 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). In addition, the silica-based material strength can be achieved by forming a hard coat layer.
[0159] 上記反射防止層（低屈折率層）の表面には潤滑層を形成してもよい。潤滑層は、低 屈折率層表面に滑り性を付与し、耐傷性を改善する機能を有する。潤滑層は、ポリオ ルガノシロキサン (例えばシリコンオイル）、天然ワックス、石油ワックス、高級脂肪酸金 属塩、フッ素系潤滑剤又はその誘導体を用いて形成することができる。潤滑層の厚さ は、 2〜20nmであることが好ましい。  [0159] 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.
[0160] 上記の近赤外線吸収層、下塗り層、反射防止層、ハードコート層、潤滑層等は、一 般的な塗布方法により形成することができる。塗布方法としては、ディップコート法、 エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、 グラビアコート法、ホッパーを使用するエタストルージョンコート法（米国特許 268129 4号明細書参照)等が挙げられる。二以上の層を同時塗布により形成してもよい。同 時塗布法【こつ ヽて ίま、米国特許 2761791号、同 2941898号、同 3508947号、同 3526528号の各明細書及び原崎勇次著「コーティング工学」 253頁（1973年朝倉 書店発行）に記載がある。 [0160] 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.
[0161] 本発明の近赤外線吸収材料を榭脂材の溶着に用いれば、レーザーを照射すること により榭脂材同士の色調差を小さく接合することができ、また当接面同士を確実に溶 着させて十分な接合強度を得ることができる。すなわち、近年、軽量ィ匕及び低コスト 化等の観点より、自動車部品等、各種分野の部品として榭脂成形物が頻繁に用いら れている。また、榭脂成形物の高生産性化等の観点より、榭脂成形物を予め複数に 分割して成形し、これらの分割成形物を互いに接合する手段が採られることが多い。 榭脂材同士の接合は、従来、レーザーに対して透過性のある透過性榭脂材と、レー ザ一に対して吸収性のある吸収性榭脂材とを重ね合わせた後、前記透過性榭脂材 側からレーザーを照射することにより、透過性榭脂材と吸収性榭脂材との当接面同 士を加熱溶融させて両者を一体的に接合するレーザー溶着方法により行われている 。さらに、従来のレーザー溶着方法では、同種あるいは異なる種類の榭脂部材の接 合において、接合される榭脂部材がレーザーに対して吸収性を有するものと吸収性 を有さないものの 2種類となるため、その色調に差が生じ、接合された榭脂部材の使 用用途に限界があった。具体的には、レーザーに対して非吸収性の榭脂材料は白 色あるいは透明のレーザー透過色であり、吸収性の部材はカーボンブラック等の黒 色系のレーザー吸収色であるため、見た目の違和感を生じるようになつていた。すな わち、このような異なる色の榭脂材料を接合すると、見た目の接合力が弱く感じられる とともに、接合部が目立つという問題を有していた。  [0161] If 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. Conventionally, 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. . Further, in the conventional laser welding method, when the same or different types of resin members are bonded, 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. Specifically, the non-absorbable resin material for laser is white or transparent laser transmission color, and 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.
[0162] 本発明の材料を用いれば、透過性榭脂材内を透過したレーザーが吸収性榭脂材 の当接面に到達して吸収され、この当接面に吸収されたレーザーがエネルギーとし て蓄積される。その結果、吸収性榭脂材の当接面が加熱溶融されると共に、この吸 収性榭脂材の当接面力 の熱伝達により透過性榭脂材の当接面が加熱溶融される 。この状態で、透過性榭脂材及び吸収性榭脂材の当接面同士を圧着させれば、両 者を一体的に接合することができる。本材料は可視光線の透過率が良好であること から、レーザー透過性榭脂材との色調差を小さくすることができ、また近赤外線領域 の吸収において大きなモル吸光係数を有しているためレーザーの照射により透過性 榭脂材及び吸収性榭脂材の当接面同士を確実に溶着させて十分な接合強度をもつ 榭脂組成物を提供できる。 [0162] If the material of the present invention is used, 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. As a result, 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. . In this state, if the contact surfaces of the permeable resin material and the absorbent resin material are pressure-bonded, the two can be integrally bonded. 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.
[0163] 本発明の光学フィルターを用いれば太陽光の可視光線を有効に透過させ、かつ熱 線を確実にカットできる。また耐久性に優れているため長期にわたって太陽光に暴露 しても熱線遮断能力が損なわれることはない。  [0163] By using the optical filter of the present invention, visible rays of sunlight can be effectively transmitted and heat rays can be cut reliably. In addition, because of its excellent durability, the ability to block heat rays is not impaired even when exposed to sunlight for a long time.
[0164] 本発明の光学フィルタ一は、撮像装置 (画像入力装置）における CCD (例えばシリ コンフォトダイオードからなる光電変換素子）のための視感度補正フィルタ一として好 適に用いることができる。ここに、「CCDのための視感度補正フィルター」には、 CCD に至る光路中に単独で配置される視感度補正フィルターのほか、リツド、レンズおよ び保護板などが含まれるものとする。また、 CCDを搭載する撮像装置としては、例え ばビデオカメラ、デジタルカメラ、ボードカメラ、カラースキャナ、カラーファックス、カラ 一複写機、カラーテレビ電話装置などを挙げることができる。本発明の光学フィルタ 一を搭載してなる撮像装置によれば、 CCD (シリコンフォトダイオード)への入射光を 、実質的に可視領域の光に限定することができ、この結果、正確な測光 (露出操作） を行うことができ、し力も、赤色成分の再現にも支障を来すことはない。  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). Here, “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. Examples of imaging devices equipped with CCDs include video cameras, digital cameras, board cameras, color scanners, color fax machines, color copiers, and color videophones. According to the imaging apparatus equipped with the optical filter of the present invention, 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.
[0165] 本発明の光学フィルタ一は、 CMOSイメージセンサまたは人工網膜が搭載された 撮像装置 (画像入力装置)のための視感度補正フィルタ一として好適に用いることが できる。本発明の光学フィルターを備えた CMOSイメージセンサおよび人工網膜、並 びにこれらを搭載してなる撮像装置によれば、上述した CCDにおける効果と同様の 効果を奏することができる。  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. According to the 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.
[0166] また本発明の光学フィルタ一は、赤外線通信装置（850〜950nmの光を媒体とす る通信装置）が使用される環境におけるノイズカットフィルタ一として好適に用いること ができる。力かるノイズカットフィルターによれば、近赤外線の発生源 (例えば自動ド ァ、リモコンなど近赤外線を用いた機械)をカバーし、当該発生源からの赤外線を遮 断することにより、通信中におけるノイズの発生を確実に防止することができる。 [0166] 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.
[0167] また、本発明の光学フィルターを、プラズマディスプレイ装置もしくは液晶パネルデ イスプレイ装置のパネルの前面に配置することによって、当該パネルから照射される 近赤外線を効率よくカットすることができる。この結果、当該ディスプレイ装置の周囲 にお 、て、近赤外線に起因するリモコンの誤動作などを生じさせることはな 、。  [0167] Further, by arranging 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.
[0168] 本発明の光学フィルタ一は好ましくは、ディスプレイ用フィルターまたは CCD、 CM OSイメージセンサ用フィルタ一として配置されその配置方法は何ら制限を受けるもの ではない。  [0168] 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.
[0169] さらに、 LEDは高効率かつ高輝度発光で RGB三色にて現在様々な分野で利用さ れている。し力しながら、比較的大きなエネルギーを発生させるため発熱源となり、ダ ィオード使用機器は常に高温にさらされるという問題を有している。発熱の原因は、 ダイオードの輻射熱'赤外線発生によるものである。本発明の近赤外線吸収材料お よび近赤外線吸収剤は、近赤外線の吸収能に優れており、かつ高い可視光透明性 を有しているため、 LEDの発光色を変えることなく赤外線をカットできる。また、高耐 熱性および高耐光性を有して！/ヽるため、長時間本材料を LEDに用いても近赤外線 吸収能が衰えることは無い。このように、本発明の近赤外線吸収材料および近赤外 線吸収剤を用いた LED用組成物により、 LED発光ダイオードの発光による発熱を抑 ff¾することができる。  [0169] Furthermore, LEDs are currently used in various fields with three colors of RGB with high efficiency and high luminance. However, 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! Therefore, even if this material is used for LED for a long time, the near-infrared absorption capacity will not decline. As described above, 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.
[0170] また、最近では、簡便かつ効率的にマーキングを行う方法として、レーザー光の照 射によるマーキングが盛んに行われている。このレーザー光の照射によるマーキング 方法は、文字やイラスト状にレーザー光を照射した部分が熱エネルギーにより変色し 、光の散乱によって文字やイラストが識別できると 、うものである。  [0170] Further, recently, as a method of performing marking easily and efficiently, 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.
[0171] 例えば、特開平 9— 302236号公報には、ロイコ色素、発色補助成分及び熱可塑 性榭脂からなる榭脂組成物を、成形後、レーザー光を照射することにより、レーザー マーキングが可能であることが開示されている。し力しながら、混練時の熱により発色 成分の反応が起こるため、発色成分が限定され、発色の自由度が制約される。また、 特開平 11— 92632号公報には、発色剤として銅系化合物及びニッケル系化合物を 含むエポキシ榭脂にレーザー光を照射することにより、榭脂成形品の表面にレーザ 一マーキングする技術が開示されている力 この場合は黒色のマーキングに限られ ている。特開平 8— 120133号公報には、ゴム強化ビュル系榭脂にチタンブラック等 の化合物を配合した有彩色のレーザーマーキングが可能な榭脂組成物が開示され ているが、この場は榭脂が、ゴム強化ビニル系榭脂に限られており、その応用展開に 制約がある。 [0171] For example, in Japanese Patent Laid-Open No. 9-302236, laser marking is possible by irradiating a resin composition comprising a leuco dye, a coloring aid component and a thermoplastic resin with a laser beam after molding. It is disclosed that. However, since the reaction of the coloring component occurs due to heat during kneading, the coloring component is limited, and the degree of freedom in coloring is limited. 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. Japanese Laid-Open Patent Publication No. 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.
[0172] 本発明の材料は高 ヽ可視光線透過率および高!ヽ近赤外線吸収能を持っため低 出力の活性エネルギー線でマーキング可能な、透明性の高!、マーキング用組成物 を提供できる。また鮮明で高速且つ高精度の文字やイラスト等の模様を、簡単に素 早くマーキングすることができる。  [0172] Since 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.
図面の簡単な説明  Brief Description of Drawings
[0173] [図 1]図 1は、 P— 1の吸収スペクトルを示す。 [0173] [FIG. 1] FIG. 1 shows an absorption spectrum of P-1.
[図 2]図 2は、 P— 1の積層体における吸収スペクトルを示す。  FIG. 2 shows an absorption spectrum of the P-1 laminate.
[図 3]図 3は、 P— 23の積層体における吸収スペクトルを示す。  FIG. 3 shows an absorption spectrum of the P-23 laminate.
[図 4]図 4は、 P— 43の積層体における吸収スペクトルを示す。  FIG. 4 shows an absorption spectrum of a laminate of P-43.
[図 5]図 5は、実施例 3における P— 23使用の積層体における吸収スペクトルを示す。  FIG. 5 shows an absorption spectrum of the laminate using P-23 in Example 3.
[図 6]図 6は、実施例 8における P— 43使用の積層体における吸収スペクトルを示す。 実施例  FIG. 6 shows an absorption spectrum of a laminate using P-43 in Example 8. Example
[0174] 以下、製造例および実施例にて本発明を詳細に説明する。しかし本発明は以下の 実施例等によって何ら制限を受けるものではない。  [0174] Hereinafter, the present invention will be described in detail with reference to production examples and examples. However, the present invention is not limited by the following examples.
[0175] [製造例 1]化合物 1の合成 [0175] [Production Example 1] Synthesis of Compound 1
[化 21]  [Chemical 21]
Figure imgf000058_0001
窒素気流下、四つ口フラスコにフエ-ルグリオキサール一水和物（4. 56g、 30mm ol)、ブロモェチルベンゼン（11. lg、 60mmol)、ジクロロェタン 60mlを仕込み、こ れに四塩化チタン（8. 54g、 45mmol)をゆっくり滴下し、室温において 3時間撹拌を 行った。反応終了後水をカ卩えて抽出を行ったのちエバポレーシヨンを行い、へキサン で再結晶を行い、上記化合物 1を得た。収率 46%。
Figure imgf000058_0001
In a nitrogen stream, charge 4-glyoxal monohydrate (4.56 g, 30 mmol), bromoethylbenzene (11.lg, 60 mmol), and 60 ml of dichloroethane into a 4-neck flask. Titanium tetrachloride (8.54 g, 45 mmol) was slowly added dropwise thereto, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water was added for extraction, evaporation was performed, and recrystallization was performed with hexane to obtain Compound 1 above. Yield 46%.
[0177] [製造例 2]化合物 2の合成 [0177] [Production Example 2] Synthesis of Compound 2
[化 22]  [Chemical 22]
Figure imgf000059_0001
Figure imgf000059_0001
[0178] 製造例 1で合成したベンゾイン誘導体化合物 1 (3. Og、 9. 4mmol)、五硫化二りん [0178] Benzoin derivative compound 1 (3. Og, 9.4 mmol) synthesized in Production Example 1 and diphosphorus pentasulfide
(12. 53g、 28. 2mmol)、ジォキサン 50mlを四つ口フラスコに加え、窒素雰囲気下 、 2時間リフラックスした。反応後ろ過を行い、ろ液に NiCl · 6Η Ο (1. 12g、 4. 7mm  (12.53 g, 28.2 mmol) and 50 ml of dioxane were added to a four-necked flask and refluxed for 2 hours under a nitrogen atmosphere. After the reaction, it was filtered, and the filtrate was NiCl 6 · (1.12g, 4.7mm
2 2  twenty two
ol)水溶液を加え、再びリフラックスを 2時間行った。反応終了後、水、メタノールをカロ えしばらく撹拌した後、ろ過を行い上記化合物 2を回収した。収率 45%。  ol) Aqueous solution was added and refluxing was performed again for 2 hours. After completion of the reaction, water and methanol were added and stirred for a while, followed by filtration to recover the compound 2. Yield 45%.
[0179] [製造例 3]P— 1の合成 [0179] [Production Example 3] Synthesis of P-1
[化 23] [Chemical 23]
Figure imgf000060_0001
Figure imgf000060_0001
[0180] 製造例 2で合成した化合物 2 (0. 8g、 1. 06mmol)とビスフエノール A(0. 24g、 1. [0180] Compound 2 (0.8 g, 1.06 mmol) synthesized in Production Example 2 and bisphenol A (0.24 g, 1.
06g)および K CO (1. 16g、8. 44mmol)および DMF40mlを四つ口フラスコに加  06 g) and K CO (1.16 g, 8.44 mmol) and 40 ml DMF are added to a four-necked flask.
2 3  twenty three
え、窒素雰囲気下 80°Cで 8時間撹拌した。反応終了後ろ過、エバポレーシヨンを行 い、水 Zメタノール = 1Z2の溶液に滴下、さらに少量の HC1水溶液をカ卩え、洗浄を 行った。ろ過して目的物である P—1を回収した。収率 50%。  The mixture was stirred at 80 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, filtration and evaporation were performed, and the resulting solution was added dropwise to a solution of water Z methanol = 1Z2, and a small amount of HC1 aqueous solution was collected and washed. The target product P-1 was recovered by filtration. Yield 50%.
図 1に P—1のクロ口ホルム中での吸収スペクトルを示す。図 1から、 P—1は、可視 光に吸収が少なぐ近赤外領域で大きな吸収を持つことが分力る。  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.
[0181] [製造例 4]化合物 3の合成 [0181] [Production Example 4] Synthesis of Compound 3
[化 24]  [Chemical 24]
Figure imgf000060_0002
Figure imgf000060_0002
[0182] 窒素気流下、四つ口フラスコにジメチルフエ-ルグリオキサール（70g、 388mmol) 、ブロモェチルベンゼン（72g、 388mmol)、ジクロロェタン 500mlを仕込み、これに 四塩化チタン（110g、 583mmol)をゆっくり滴下し、室温において 3時間撹拌を行つ た。反応終了後水をカ卩えて抽出を行ったのちエバポレーシヨンを行い、へキサンで再 結晶を行い、上記化合物 3を得た。収率 60%。 [製造例 5]化合物 4の合成 [0182] Under a nitrogen stream, dimethylphenol glyoxal (70 g, 388 mmol), bromoethylbenzene (72 g, 388 mmol), and dichloroethane 500 ml were charged into a four-necked flask, and titanium tetrachloride (110 g, 583 mmol) was slowly added dropwise thereto. The mixture was stirred at room temperature for 3 hours. After completion of the reaction, water was added for extraction, evaporation was performed, and recrystallization was performed with hexane to obtain Compound 3 above. Yield 60%. [Production Example 5] Synthesis of Compound 4
[化 25]  [Chemical 25]
Figure imgf000061_0001
Figure imgf000061_0001
[0184] 製造例 4で得たベンゾイン誘導体化合物 3 (50g、 94mmol)、五硫化二りん（12. 5 g、 56mmol)、ジォキサン 200mlを四つ口フラスコに加え、窒素雰囲気下、 2時間リ フラックスした。反応後ろ過を行ない、ろ液に NiCl · 6Η 0 (11. 2g、 47mmol)水溶 [0184] The benzoin derivative compound 3 (50 g, 94 mmol), diphosphorus pentasulfide (12.5 g, 56 mmol) obtained in Production Example 4 and 200 ml of dioxane were added to a four-necked flask and refluxed for 2 hours in a nitrogen atmosphere. did. After the reaction, filtration was performed, and the filtrate was NiCl 6 · 0 (11.2 g, 47 mmol) in water.
2 2  twenty two
液を加え、再びリフラックスを 2時間行った。反応終了後、水、メタノールをカ卩えしばら く撹拌した後、ろ過を行い、上記化合物 4を回収した。収率 45%。  The solution was added and refluxed again for 2 hours. After completion of the reaction, water and methanol were stirred for a while and then filtered to recover the above compound 4. Yield 45%.
[0185] [製造例 6] P— 23の合成 [0185] [Production Example 6] Synthesis of P-23
[化 26]  [Chemical 26]
Figure imgf000061_0002
Figure imgf000061_0002
[0186] 製造例 5で合成した化合物 4 (1. 5g、 1. 8mmol)とデカンジオール（0. 32g、 1. 8 mmol)および K CO (1. 16g、 8. 44mmol)および DMF (ジメチルホルムアミド） 40 mlを四つ口フラスコに加え、窒素雰囲気下 80°Cで 8時間撹拌した。反応終了後ろ過 、エバポレーシヨンを行い、水 Zメタノール = 1Z2の溶液に滴下、さらに少量の HC1 水溶液を加え、洗浄を行った。ろ過して目的物である上記 P— 23を回収した。収率 5 0%。 [0186] Compound 4 (1.5 g, 1.8 mmol) synthesized in Preparation Example 5, decanediol (0.32 g, 1.8 mmol), K 2 CO 3 (1.16 g, 8.44 mmol) and DMF (dimethylformamide) 40 ml was added to a four-necked flask and stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. After completion of the reaction, filtration and evaporation were performed, and the resulting solution was added dropwise to a solution of water Z methanol = 1Z2, and further a small amount of HC1 aqueous solution was added for washing. The target P-23 was recovered by filtration. Yield 50%.
[0187] [実施例 1]  [0187] [Example 1]
下記化合物 5、化合物 6 (特開平 2— 264788号公報参照）および製造例 3で得ら れた P— 1、製造例 6で得られた P— 23のトルエンに対する溶解度を測定した。結果 を表 3示す。  The solubility of toluene in the following compounds 5, 6 (see JP-A-2-264788), P-1 obtained in Production Example 3 and P-23 obtained in Production Example 6 was measured. Table 3 shows the results.
[0188] [化 27]  [0188] [Chemical 27]
Figure imgf000062_0001
Figure imgf000062_0001
化合物 5 化合物 6  Compound 5 Compound 6
[0189] [表 7] 表 7 [0189] [Table 7] Table 7
材 料 トルエンに対する溶解度 （wt%)  Material Solubility in toluene (wt%)
化合物 5 0 . 8  Compound 5 0.8
化合物 6 2 . 0  Compound 6 2.0
P— 1 5 . 0  P— 1 5. 0
P - 2 3 6 . 0  P-2 3 6. 0
[0190] 表 7から、化合物 5、化合物 6に比べて本発明の P—1および P— 23の方が溶解性 に優れていることが分かる。 [0190] From Table 7, it can be seen that P-1 and P-23 of the present invention are superior in solubility compared to Compound 5 and Compound 6.
[0191] [実施例 2] [0191] [Example 2]
化合物 5、化合物 6、 P— 1および P— 23を、各々固形分 25%のポリスチレン（Mw = 100000)溶液 (溶剤トルエン）に、固形分に対して約 2%混合し、 PETフィルムに 塗工した。これらのフィルムについて下記 <Haze値の測定 >により Haze値を測定し た。結果を表 4に示す。 [0192] < Haze値の測定 > Compound 5, Compound 6, P-1 and P-23 are each mixed in a polystyrene (Mw = 100000) solution (solvent toluene) with a solid content of 25%, approximately 2% of the solid content, and applied to PET film. did. For these films, the Haze value was measured by the following <Measurement of Haze Value>. The results are shown in Table 4. [0192] <Measure Haze value>
Haze値の測定は、 NIPPON DENSHOKU製 Haze Mater NDH2000に て行った。  The Haze value was measured with a Haze Mater NDH2000 manufactured by NIPPON DENSHOKU.
[0193] [表 8] 表 8 [0193] [Table 8] Table 8
Figure imgf000063_0001
Figure imgf000063_0001
[0194] 上記表 8より、化合物 5、化合物 6に比べて P— 1および P— 23が比較的低 Haze値 を有していることが分かる。このことは榭脂に対する相溶性、溶解性が他に比べて優 れて 、ると!/、うことを意味して 、ると考えられる。 From Table 8 above, it can be seen that P-1 and P-23 have relatively low Haze values compared to Compound 5 and Compound 6. This is considered to mean that the compatibility and solubility with respect to rosin are better than others!
[0195] [実施例 3]  [0195] [Example 3]
化合物 5、化合物 6、 P— 1および P— 23を、各々固形分 25%のポリスチレン（Mw = 100, 000)溶液 (溶剤トルエン）に、固形分に対して約 1. 0%、またそれぞれにジ ィモ -ゥム色素（日本化薬株式会社製 IRG— 022) 2%を混合し、 PETフィルムに塗 ェした。これらフィルムについて、実施例 2と同様にして Haze値を測定した。結果を 表 9に示す。  Compound 5, Compound 6, P-1 and P-23 are each added to a polystyrene (Mw = 100,000) solution (solvent toluene) having a solid content of 25%, and about 1.0% to the solid content. Dimo-um dye (IRG-022 manufactured by Nippon Kayaku Co., Ltd.) 2% was mixed and applied to PET film. For these films, the Haze value was measured in the same manner as in Example 2. The results are shown in Table 9.
[0196] [表 9] [0196] [Table 9]
表 9  Table 9
Figure imgf000063_0002
Figure imgf000063_0002
[0197] 上記表 9より、化合物 5、化合物 6に比べて P— 1および P— 23が低 Haze値を有し ていることが分かる。 [0197] From Table 9 above, it can be seen that P-1 and P-23 have lower Haze values than Compound 5 and Compound 6.
[0198] [実施例 4] 化合物 5、化合物 6、？ー1ぉょび13— 23を、各々固形分 25%のアクリル系粘着材( モノマー組成：アクリル酸ブチル 60%、アクリル酸イソブチル 30%、アクリル酸 3%、 アクリル酸 2 ェチルへキシル 7%、溶剤組成：酢酸ェチル 80%、トルエン 20%) に、固形分に対し約 2. 0%混合し、 PETフィルムに塗工した。このフィルムについて 実施例 2と同様にして Haze値を測定した。結果を表 10に示す。 [0198] [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.
[表 10] 表 1 0  [Table 10] Table 1 0
Figure imgf000064_0001
Figure imgf000064_0001
[0200] 上記表 10より、化合物 5、化合物 6に比べて P— 1および P— 23が低 Haze値を有し ていることが分かる。 [0200] From Table 10 above, it can be seen that P-1 and P-23 have lower Haze values than Compound 5 and Compound 6.
[0201] [実施例 5] [0201] [Example 5]
P— 1および P— 23を固形分 25%のポリメチルメタタリレート（Mw= 100, 000)溶 液 (溶剤トルエン）に、固形分に対し約 2%混合し、 PETフィルムに塗工し、 80°C、 3 分乾燥した。これらのフィルムについて、湿度 90%、温度 100°Cの条件で 48時間の 耐湿熱試験を行い、試験前後における各フィルムの Haze値、色味 (y値)を測定した 。そして色味については試験前後の変化値（A y値)を算出した。結果を表 11に示す 。なお、 Haze値の測定は実施例 2と同様の方法で、また色味 (y値)の測定は下記方 法により行った。  P-1 and P-23 were mixed in a 25% solids polymethylmetatalate (Mw = 100,000) solution (solvent toluene), approximately 2% of the solids, and applied to a PET film. Dry at 80 ° C for 3 minutes. These films were subjected to a moisture and heat resistance test for 48 hours under the conditions of a humidity of 90% and a temperature of 100 ° C., and the Haze value and color (y value) of each film before and after the test were measured. And about the color, the change value (Ay value) before and behind a test was computed. The results are shown in Table 11. The Haze value was measured by the same method as in Example 2, and the color (y value) was measured by the following method.
[0202] <色味 (y値)の測定 >  [0202] <Measurement of color (y value)>
色味 (y)値の測定は、 MINOLTA製 色彩色差計 CR— 300にて行った。  The color (y) value was measured with a color difference meter CR-300 manufactured by MINOLTA.
[0203] (比較例 1)  [0203] (Comparative Example 1)
ビス（3—メタクリロイルォキシプロピル）ホスフィン酸 19g、メチルメタタリレート 50g、 ジエチレングリコールジメタタリレート 30g、 aーメチルスチレン 2. Ogをよく混合し、こ の混合単量体に無水安息香酸銅 5. Ogを添加して、 60°Cで撹拌混合することにより 、均一な青色混合溶液を得た。この混合溶液に、ラジカル開始剤 tert ブチルパー ォキシ 2 ェチルへキサネート 3. 4部を添加し、グラスフィルターでろ過した。 50°C で 15時間、 70°Cで 8時間、 100°Cで 2時間と昇温加熱して、キャスト重合させた。得ら れた重合体を厚さ lmmの板状に切削し、表面を研磨して光学フィルター（特開 200 0— 98130号公報参照）を製作した。このフィルターに対して湿度 90%、温度 100°C の条件で 48時間の耐湿熱試験を行 、、実施例 5と同様にして試験前後における各 フィルムの Haze値、色味変化値（Ay値)を測定または算出した。結果を表 11に示す Bis (3-methacryloyloxypropyl) phosphinic acid 19g, Methyl methacrylate 50g, Diethylene glycol dimethacrylate 20g, a-methylstyrene 2. Og is mixed well, and copper benzoic anhydride 5. Og is added to this mixed monomer. By adding and stirring at 60 ° C A uniform blue mixed solution was obtained. To this mixed solution, 3.4 parts of a radical initiator tert-butyl peroxy-2-ethylhexanate was added and filtered through a glass filter. Cast polymerization was carried out by heating at 50 ° C for 15 hours, 70 ° C for 8 hours, and 100 ° C for 2 hours. 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. In the same manner as in Example 5, 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.
[0204] [表 11] 表 1 1
Figure imgf000065_0001
[0204] [Table 11] Table 1 1
Figure imgf000065_0001
[0205] 表 11力ら、 P—1および P— 23を用いたフィルターの Haze値は比較例 1のフィルタ 一の Haze値に比べ小さぐさらに P—1および P— 23を用いたフィルターの Haze値 は試験前後において殆ど変わらないのに対し、比較例の Haze値は試験後大きく増 大しており、 P— 1および P— 23の方が比較例と比べて Haze値変ィ匕も小さい事が分 かる。また、表 11から、色味変化 Ay値も P—1および P— 23のほうが小さいことが分 力る。なお、比較例 1のフィルタ一は、従来 CCD、 CMOS用フィルタ一として知られ ているものであり、前記結果から、従来の CCD、 CMOS用フィルターに比べ本発明 のフィルターのほうが Haze値も小さぐ且つ、耐久性にも優れていることが分力る。 [0205] 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.
[0206] [製造例 7]化合物 7の合成  [Production Example 7] Synthesis of Compound 7
[化 28]
Figure imgf000066_0001
化合物 7 [Chemical 28]
Figure imgf000066_0001
Compound 7
[0207] 窒素雰囲気下、ポタッシゥムイソイソプロピルキサンテート（25g、 143mmol)、ァセ トン 80ml〖こ対し、ジクロロアセテート（10. 2g、 71. 5mmol)を加え、 5時間リフラック ス撹拌を行った。反応終了後室温まで戻し、ろ過、脱溶剤を行い、得られたペースト を 1. 5L濃硫酸に 0°C〜5°Cにおいて滴下した。その後室温まで戻し、 4Lの氷水に ゆっくりと注いだ。固体をろ過して得られたペーストをメタノール力 再結晶し、上記化 合物 7を得た。収率 75%。 [0207] Under a nitrogen atmosphere, potassium isoisopropylxanthate (25 g, 143 mmol) and 80 ml of acetone were added, and dichloroacetate (10.2 g, 71.5 mmol) was added, followed by relux stirring for 5 hours. . After completion of the reaction, the temperature was returned to room temperature, filtration and solvent removal were performed, and the obtained paste was added dropwise to 1.5 L concentrated sulfuric acid at 0 ° C to 5 ° C. After that, it was returned to room temperature and poured slowly into 4 L of ice water. The paste obtained by filtering the solid was recrystallized with methanol to obtain Compound 7 above. Yield 75%.
[0208] [製造例 8]化合物 8の合成  [Production Example 8] Synthesis of Compound 8
[化 29]  [Chemical 29]
Figure imgf000066_0002
Figure imgf000066_0002
[0209] 化合物 7 (5g、 24mmol)に対し、 1Mの NaOCH /CH OH (48mL、 48mmol) [0209] 1M NaOCH 3 / CH 2 OH (48 mL, 48 mmol) for compound 7 (5 g, 24 mmol)
3 3  3 3
を窒素雰囲気下 20°C以下で加え、 10分撹拌を行った。これにジブロモプロパノール (5. 2g、 24mmol)をカ卩え、室温にて 3時間撹拌を行った後、水 300mLに注ぎ、クロ 口ホルムにて抽出を行った。抽出液の脱溶剤を行い、メタノールで再結晶を行って、 化合物 8を得た。収率 80%。  Was added at 20 ° C. or lower under a nitrogen atmosphere and stirred for 10 minutes. To this was added dibromopropanol (5.2 g, 24 mmol), and the mixture was stirred at room temperature for 3 hours, poured into 300 mL of water, and extracted with chloroform. The extract was desolvated and recrystallized from methanol to obtain Compound 8. Yield 80%.
[0210] [製造例 9]化合物 9の合成 [0210] [Production Example 9] Synthesis of Compound 9
[化 30]
Figure imgf000067_0001
[Chemical 30]
Figure imgf000067_0001
[0211] 製造例 8で合成した化合物 8 (5g、 21mmol)、ナトリウムメトキシド（3. 4g、 63mmo 1)およびメタノール（250mL)を窒素雰囲気下 60°Cにて撹拌を行った。メタノール 10 OmLに溶かした塩化ニッケル 6水和物（5g、 21mmol)を反応液中に加えた後、 60 °Cで 4時間撹拌して室温に戻した。反応液に 1%HC1水溶液 50mLをカ卩え、撹拌、ろ 過し、化合物 9を得た。収率 68%。 [0211] Compound 8 (5 g, 21 mmol) synthesized in Production Example 8, sodium methoxide (3.4 g, 63 mmol 1) and methanol (250 mL) were stirred at 60 ° C under a nitrogen atmosphere. Nickel chloride hexahydrate (5 g, 21 mmol) dissolved in 10 mL of methanol was added to the reaction solution, and the mixture was stirred at 60 ° C. for 4 hours and returned to room temperature. To the reaction solution, 50 mL of a 1% HC1 aqueous solution was added, stirred and filtered to obtain Compound 9. Yield 68%.
[0212] [製造例 10]P— 43の合成  [0212] [Production Example 10] Synthesis of P-43
[化 31]  [Chemical 31]
Figure imgf000067_0002
Figure imgf000067_0002
P- 4 3  P- 4 3
[0213] 製造例 9で合成した化合物 9 (1. 5g、 3. lmmol)、ジブロモデカン（0. 9g、 3. lm mol)、K CO (1. 16g、8. 44mmol)およびジメチルホルムアミド（DMF ;40ml)を [0213] Compound 9 (1.5 g, 3. 1 mmol), dibromodecane (0.9 g, 3. lm mol), K 2 CO 3 (1.16 g, 8.44 mmol) and dimethylformamide (DMF) synthesized in Preparation Example 9 ; 40ml)
2 3  twenty three
四つ口フラスコに加え、窒素雰囲気下 80°Cで 8時間撹拌した。反応終了後ろ過し、 ろ液のエバポレーシヨンを行い、水 Zメタノール = 1Z2の溶液に滴下し、さらに少量 の HC1水溶液を加えて、反応物の洗浄を行い、ろ過して目的物である上記 P— 43を 回収した。収率 50%。  The mixture was added to a four-necked flask and stirred at 80 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, the solution is filtered, and the filtrate is evaporated. The solution is added dropwise to a solution of water Z methanol = 1Z2, and a small amount of HC1 aqueous solution is added to wash the reaction product, followed by filtration. 43 were recovered. Yield 50%.
[0214] [実施例 6] [0214] [Example 6]
下記化合物 10、化合物 11 (特開 2005— 232185号公報参照）、化合物 12 (特許 第 3699464号公報参照）および P— 43を、各々固形分 25%のポリメチルメタクリレ ート（Mw= 200, 000)溶液 (溶剤：酢酸ェチル Zトルエン = 1 : 1)に、固形分に対し て約 2%混合し、 PETフィルムに塗工した。これらのフィルムについて、 100°Cで 400 時間および 800時間の耐熱試験を行い、試験前後における各フィルムについて化合 物の極大吸収波長の透過率を測定し、その差（ΔΤ)を算出（％)した。結果を表 12 に示す。 The following compound 10, compound 11 (see JP 2005-232232A), compound 12 (see patent 3699464) and P-43 are each made of polymethyl methacrylate (Mw = 200, 000) solution (solvent: ethyl acetate Ztoluene = 1: 1), about 2% of solid content was mixed and coated on PET film. These films were subjected to heat resistance tests at 100 ° C for 400 hours and 800 hours, and the transmittance of the maximum absorption wavelength of each compound before and after the test was measured, and the difference (ΔΤ) was calculated (%). . Table 12 shows the results. Shown in
[0215] [化 32]  [0215] [Chemical 32]
Figure imgf000068_0001
Figure imgf000068_0001
化合物 1 0 化合物 1 1 化合物 1 2  Compound 1 0 Compound 1 1 Compound 1 2
[0216] [表 12]
Figure imgf000068_0002
[0216] [Table 12]
Figure imgf000068_0002
[0217] 表 12から、化合物 10、化合物 11、化合物 12に比べて本発明の Ρ— 43の方が耐熱 性に優れて 、ることが分かる。 [0217] From Table 12, it can be seen that Ρ-43 of the present invention is superior in heat resistance compared to Compound 10, Compound 11, and Compound 12.
[0218] [実施例 7] [0218] [Example 7]
化合物 10、化合物 11、化合物 12および Ρ— 43を、各々固形分 25%のアクリル系 粘着材（モノマー組成：アクリル酸ブチル 60%、アクリル酸イソブチル 30%、アクリル 酸 3%、アクリル酸 2 ェチルへキシル 7%、溶剤組成：酢酸ェチル 80%、トルエン 20%)に、固形分に対して約 2. 0%混合し、 PETフィルムに塗工した。これらフィルム について、温度 80°C、湿度 80%条件下での 24時間および 48時間の耐湿熱試験を 行い、試験前後における各フィルムについて化合物の極大吸収波長の透過率を測 定し、その差（ΔΤ)を算出（％)した。結果を表 13に示す。  Compound 10, Compound 11, Compound 12, and Ρ-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. ΔΤ) was calculated (%). The results are shown in Table 13.
[0219] [表 13] 表 1 3_ [0219] [Table 13] Table 1 3_
化合物 1 0 化合物 1 1 化合物 1 2 P - 4 3  Compound 1 0 Compound 1 1 Compound 1 2 P-4 3
24時間 ΔΤ (%) 2 0 1 5 3 0 9  24 hours ΔΤ (%) 2 0 1 5 3 0 9
48時間 Δ Τ (%) 3 2 2 1 4 2 1 2 [0220] 上記表 13から、化合物 10、化合物 11、化合物 12に比べて本発明の P— 43のほう が粘着剤中における耐熱性が優れて 、ることが分かる。 48 hours Δ Τ (%) 3 2 2 1 4 2 1 2 [0220] From Table 13 above, it can be seen that P-43 of the present invention is superior in heat resistance in the pressure-sensitive adhesive as compared with Compound 10, Compound 11, and Compound 12.
[0221] [実施例 8] [0221] [Example 8]
化合物 10、化合物 11、化合物 12および P— 43を、各々固形分 25%のポリメチルメ タクリレート（Mw= 200000)溶液 (溶剤：酢酸ェチル Zトルエン = 1： 1)に固形分に 対して約 2. 0%、またそれぞれにチオールニッケル色素 (ィ匕合物 5) 1. 0%を混合し 、 PETフィルムに塗工した。これらフィルムについて、温度 80°C、湿度 80%条件下で の 24時間および 48時間の耐湿熱試験を行い、試験前後における 850nmおよび 10 OOnmにおける各フィルムの透過率を測定し、各波長における透過率の差（ ΔΤ)を 算出（％)した。結果を表 14に示した。  Compound 10, Compound 11, Compound 12, and P-43 were each added to a polymethylmethacrylate (Mw = 200000) solution (solvent: ethyl acetate Ztoluene = 1: 1) with a solid content of 25%. In addition, 1.0% of thiol nickel dye (Compound 5) was mixed with each and coated on a PET film. These films were subjected to 24-hour and 48-hour humidity and heat resistance tests at 80 ° C and 80% humidity, and the transmittance of each film at 850 nm and 10 OOnm before and after the test was measured. Difference (ΔΤ) was calculated (%). The results are shown in Table 14.
[0222] [表 14] 表 1 4
Figure imgf000069_0001
[0222] [Table 14] Table 1 4
Figure imgf000069_0001
[0223] 上記表 14から、色素二種類混合時でも、化合物 10、化合物 11、化合物 12に比べ て本発明の P— 43のほうが耐熱性に優れていることが分かる。 [0223] From Table 14 above, it can be seen that 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.
[0224] [実施例 9] [Example 9]
P— 23、 P— 43を、各々固形分 25%のポリメチルメタクリレー卜（Mw= 100, 000) 溶液 (溶剤トルエン）に固形分に対して約 2%混合し、 PETフィルムに塗工し、 80°C、 3分乾燥した。これらのフィルムについて湿度 90%、温度 100°Cの条件で 48時間の 耐湿熱試験を行い、試験前後の各フィルムの Haze値、色味変化 Ay値を実施例 5と 同様にして測定あるいは算出した。結果を表 15に示す。  P-23 and P-43 were mixed in a polymethyl methacrylate (Mw = 100, 000) solution (solvent toluene) with a solid content of 25%, approximately 2% of the solid content, and applied to a PET film. , Dried at 80 ° C for 3 minutes. These films were subjected to a moisture and heat resistance test for 48 hours at a humidity of 90% and a temperature of 100 ° C, and the Haze value and color change Ay value of each film before and after the test were measured or calculated in the same manner as in Example 5. . The results are shown in Table 15.
[0225] (比較例 2) [0225] (Comparative Example 2)
米国特許第 5089585号明細書に基づく下記化合物 13を、固形分 25%のポリメチ ルメタタリレート（Mw= 100000)溶液 (溶剤トルエン）に固形分に対して約 2%混合 し、 PETフィルムに塗工し、 80°C、 3分乾燥した。このフィルターに対して湿度 90%、 温度 100°Cの条件で 48時間の耐湿熱試験を行!、、試験前後のフィルターの Haze 値、色味変化 Ay値を実施例 5と同様にして測定あるいは算出した。結果を表 15に 示す。 The following compound 13 based on US Pat. No. 5,089,585 is mixed in a polymethyl methacrylate (Mw = 100000) solution (solvent toluene) with a solid content of 25%, about 2% of the solid content, and coated on a PET film. And dried at 80 ° C. for 3 minutes. 90% humidity for this filter, A moisture and heat resistance test was conducted for 48 hours at a temperature of 100 ° C., and the Haze value and color change Ay value of the filter before and after the test were measured or calculated in the same manner as in Example 5. The results are shown in Table 15.
[0226] [化 33]  [0226] [Chemical 33]
Figure imgf000070_0001
Figure imgf000070_0001
化合物 1 3 (分子量 7000)  Compound 1 3 (Molecular weight 7000)
[0227] [表 15] 表 1 5 [0227] [Table 15] Table 1 5
Figure imgf000070_0002
Figure imgf000070_0002
[0228] 表 15力ら、 P— 23および P— 43のフィルターの Haze値は比較例 2のフィルターの Haze値に比べ非常に小さぐさらに P— 23および P— 43のフィルターの Haze値は 試験前後において殆ど変わらないのに対し、比較例 2の Haze値は試験後 P— 23お よび P— 43に比べ増大しており、 P 23および P— 43の方が比較例と比べて Haze 値変化が小さい事も分かる。また表 15から、色味変化 Ay値も P— 23および P— 43 の方が比較例 2と比べて小さ 、ことが分かる。これは化合物 13の榭脂相溶性が低 ヽ ことと、分子骨格の耐久性が低いことに起因しており、本発明のフィルターの方が耐 久性に優れて 、ることを意味して 、る。 [0228] 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
[0229] 実施例 1〜9より本発明の近赤外線吸収剤は溶剤に対する溶解性、榭脂に対する 相溶性および耐久性に優れた材料であるということが明ら力となった。  [0229] From Examples 1 to 9, it became clear that the near-infrared absorber of the present invention is a material excellent in solubility in solvents, compatibility with rosin and durability.
[0230] [P— 51の合成]  [0230] [Synthesis of P-51]
以下の合成スキームにしたがって、製造例 11〜 13にて P - 51を合成した。  P-51 was synthesized in Production Examples 11 to 13 according to the following synthesis scheme.
[化 34] [Chemical 34]
Figure imgf000071_0001
Figure imgf000071_0001
P— 5 1  P— 5 1
[0231] [製造例 11]化合物 14の合成 [Production Example 11] Synthesis of Compound 14
フエ-ルグリオキサールに代えてチェ-ルグリオキサールを用い、またブロモェチ ルベンゼンに代えてクロ口ェチルベンゼンを用いたことを除き製造例 1と同様に合成 を行い、上記化合物 14を得た。収率 53%。  Synthesis was carried out in the same manner as in Production Example 1 except that chelate glyoxal was used in place of phenylglyoxal and chloroethylbenzene was used in place of bromoethylbenzene to obtain the above compound 14. Yield 53%.
[0232] [製造例 12]化合物 15の合成 [Production Example 12] Synthesis of Compound 15
化合物 1に代えて製造例 11で得られたィ匕合物 14を用いることを除き製造例 2と同 様に合成を行い、上記化合物 15を得た。収率 22%。  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%.
[0233] [製造例 13] P— 51の合成 [0233] [Production Example 13] Synthesis of P-51
化合物 2に代えて製造例 12で得られたィ匕合物 15を用い、またビスフエノール Aに 代えてテトラクロ口ビスフエノール Aを用いたことを除き製造例 3と同様に合成を行い、 P— 51を得た。収率 80%。  Synthesis was carried out in the same manner as in Production Example 3 except that Compound 15 obtained in Production Example 12 was used in place of Compound 2, and Tetrachloro Bisphenol A was used in place of Bisphenol A. 51 was obtained. Yield 80%.
[0234] [P— 52の製造] [0234] [Manufacturing P-52]
以下の合成スキームにしたがって、製造例 14〜 16にて P - 52を製造した。  P-52 was produced in Production Examples 14 to 16 according to the following synthesis scheme.
[化 35]
Figure imgf000072_0001
[Chemical 35]
Figure imgf000072_0001
P— 5 2  P— 5 2
[0235] [製造例 14]化合物 16の合成 [Production Example 14] Synthesis of Compound 16
フエ-ルグリオキサールに代えて 2'—クロ口フエ-ルグリオキサールを用い、またブ ロモェチルベンゼンに代えてエトキシナフチルチオールを用いたことを除き製造例 1 と同様に合成を行い、上記化合物 16を得た。収率 73%。  Synthesis was carried out in the same manner as in Production Example 1 except that 2′-chlorophenol glyoxal was used instead of phenylglyoxal and ethoxynaphthylthiol was used instead of bromoethylbenzene. Got. Yield 73%.
[0236] [製造例 15]化合物 17の合成 [0236] [Production Example 15] Synthesis of compound 17
化合物 1に代えて製造例 14で得られたィ匕合物 16を用いることを除き製造例 2と同 様に合成を行い、上記化合物 15を得た。収率 25%。  Synthesis was carried out in the same manner as in Production Example 2 except that Compound 16 obtained in Production Example 14 was used in place of Compound 1, and Compound 15 was obtained. Yield 25%.
[0237] [製造例 16]P— 52の合成 [0237] [Production Example 16] Synthesis of P-52
化合物 2に代えて製造例 15で得られたィ匕合物 17を用い、またビスフエノール Aに 代えてジブ口モドデカンを用いたことを除き製造例 3と同様に合成を行い、 P— 52を 得た。収率 80%。  Synthesis was carried out in the same manner as in Production Example 3 except that Compound 17 obtained in Production Example 15 was used in place of Compound 2, and dib mouth mododecane was used in place of bisphenol A. Obtained. Yield 80%.
[0238] [P— 53の合成] [0238] [Synthesis of P-53]
以下の製造例 17〜 19にて下記繰り返し単位を有する P - 53を合成した。 [化 36] In the following Production Examples 17 to 19, P-53 having the following repeating units was synthesized. [Chemical 36]
Figure imgf000073_0001
Figure imgf000073_0001
Figure imgf000073_0002
Figure imgf000073_0002
[0240] 窒素雰囲気下 5°Cにおいて、ジクロロェタン 100mlおよび TiCl (30mmol)撹拌下 [0240] Under a nitrogen atmosphere at 5 ° C, with stirring of 100 ml of dichloroethane and TiCl (30 mmol)
4  Four
、ブチォ-ルクロライド（20mmol)をゆっくり滴下し、その後フエ-ルプロピルクロライ ド（20mmol)を滴下した。室温に戻し 8時間撹拌した。反応液を氷水にゆっくり滴下 し、分液後硫酸マグネシウムで有機層を乾燥し、脱溶剤を行った。へキサンで再結晶 を行い、白色固体 (上記化合物 18)を得た。この固体を、窒素雰囲気下、ジクロロメタ ンに溶かし、撹拌下、臭素 20mmolを室温にて加えた。 3時間撹拌後脱溶剤を行い 、黄色のオイル状物質をへキサンで再結晶を行い、淡黄色固体 (上記化合物 19)を 得た。収率 53%。  Butyl chloride (20 mmol) was slowly added dropwise, and then phenylpropyl chloride (20 mmol) was added dropwise. It returned to room temperature and stirred for 8 hours. The reaction solution was slowly added dropwise to ice water, and after separation, the organic layer was dried over magnesium sulfate to remove the solvent. Recrystallization from hexane gave a white solid (Compound 18 above). This solid was dissolved in dichloromethane under a nitrogen atmosphere, and 20 mmol of bromine was added at room temperature with stirring. After stirring for 3 hours, the solvent was removed, and the yellow oily substance was recrystallized from hexane to obtain a pale yellow solid (Compound 19 above). Yield 53%.
[0241] [製造例 18]化合物 20の合成 [0241] [Production Example 18] Synthesis of compound 20
[化 38]
Figure imgf000074_0001
[Chemical 38]
Figure imgf000074_0001
化合物 2 0  Compound 2 0
[0242] 化合物 1に代えて製造例 17で得られたィ匕合物 19を用い、また、 NiCl · 6Η Οに代 [0242] Compound 19 obtained in Production Example 17 was used in place of Compound 1, and NiCl 6
2 2 えて塩化パラジウムを用いたことを除き製造例 2と同様に合成を行い、化合物 20を得 た。収率 15%。  2 2 Compound 20 was obtained in the same manner as in Production Example 2 except that palladium chloride was used. Yield 15%.
[0243] [製造例 19] Ρ— 53の合成 [0243] [Production Example 19] Synthesis of Ρ-53
[化 39]  [Chemical 39]
Figure imgf000074_0002
Figure imgf000074_0002
Ρ— 5 3  Ρ— 5 3
[0244] 化合物 2に代えて製造例 18で得られたィ匕合物 20を用い、またビスフエノール Αに 代えてビスクロロヒドロキシジフエ-ルスルフイドを用いたことを除き製造例 3同様に合 成を行い、 P— 53を得た。収率 76%。 [0244] Synthesis was performed in the same manner as in Production Example 3 except that Compound 20 obtained in Production Example 18 was used in place of Compound 2, and bischlorohydroxydiphenylsulfide was used in place of bisphenol フ. To obtain P-53. Yield 76%.
[0245] [P— 54の合成]  [0245] [Synthesis of P-54]
以下の製造例 20〜22にて下記繰り返し単位を有する P— 54を製造した。 [化 40] In the following Production Examples 20 to 22, P-54 having the following repeating units was produced. [Chemical 40]
Figure imgf000075_0001
Figure imgf000075_0001
Figure imgf000075_0002
Figure imgf000075_0002
化合物 2 2  Compound 2 2
[0247] 窒素雰囲気下 5°Cにおいて、ジクロロェタン 100mlおよび TiCl (30mmol)撹拌下 [0247] Under nitrogen atmosphere at 5 ° C, with stirring of 100 ml of dichloroethane and TiCl (30 mmol)
4  Four
、メチルチオェチォ-ルクロライド（20mmol)をゆっくり滴下し、その後フエ-ルェチ ルクブロマイド（20mmol)を滴下した。室温に戻し 8時間撹拌した。反応液を氷水に ゆっくり滴下し、分液後硫酸マグネシウムで有機層を乾燥し、脱溶剤を行った。へキ サンで再結晶を行い、白色固体 (上記化合物 21)を得た。この固体を窒素雰囲気下 ジクロロメタンに溶かし、撹拌下、臭素 20mmolを室温にてカ卩えた。 3時間撹拌後脱 溶剤を行い、黄色のオイル状物質をへキサンで再結晶を行い、淡黄色固体 (上記化 合物 22)を得た。収率 70%。  Then, methylthioethyl chloride (20 mmol) was slowly added dropwise, followed by dropwise addition of phenol bromide (20 mmol). It returned to room temperature and stirred for 8 hours. The reaction solution was slowly dropped into ice water, and after separation, the organic layer was dried over magnesium sulfate to remove the solvent. Recrystallization from hexane yielded a white solid (Compound 21 above). This solid was dissolved in dichloromethane under a nitrogen atmosphere, and 20 mmol of bromine was collected at room temperature with stirring. After stirring for 3 hours, the solvent was removed, and the yellow oily substance was recrystallized from hexane to obtain a pale yellow solid (Compound 22 above). Yield 70%.
[0248] [製造例 21]化合物 23の合成 [Production Example 21] Synthesis of Compound 23
[化 42]
Figure imgf000076_0001
[Chemical 42]
Figure imgf000076_0001
化合物 2 3  Compound 2 3
[0249] 化合物 1に代えて製造例 20で得られたィ匕合物 22を用い、また、 NiCl · 6H Oに代 [0249] Compound 22 obtained in Production Example 20 was used instead of Compound 1, and NiCl 6H O was used instead.
2 2 えて塩化コバルトを用いたことを除き製造例 2と同様に合成を行い、上記化合物 23を 得た。収率 11%。  2 2 Compound 23 was obtained in the same manner as in Production Example 2 except that cobalt chloride was used. Yield 11%.
[0250] [製造例 22] [0250] [Production Example 22]
[化 43] [Chemical 43]
Figure imgf000076_0002
Figure imgf000076_0002
[0251] 化合物 2に代えて製造例 21で得られたィ匕合物 23を用いることを除き製造例 3と同 様に合成を行い、 P— 54を得た。収率 78%。 [0251] 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%.
[0252] [P— 55の合成] [0252] [Synthesis of P-55]
以下の製造例 23〜25にて下記繰り返し単位を有する P— 55を製造した。 In the following production examples 23 to 25, P-55 having the following repeating units was produced.
[化 44]
Figure imgf000077_0001
[Chemical 44]
Figure imgf000077_0001
P— 5 5  P— 5 5
[製造例 23]化合物 24の合成 [Production Example 23] Synthesis of Compound 24
[化 45]  [Chemical 45]
Figure imgf000077_0002
Figure imgf000077_0002
化合物 2 4  Compound 2 4
[0254] 製造例 8においてジブロモプロパノールに代えてブロモェタンおよびブロモエタノ ルを用いることを除き同様の方法で合成を行い、シリカゲルカラムクロマトグラフィー により分離 (へキサン:酢酸ェチル = 2 : 1)を行い、化合物 24を得た。収率 20%。 [0254] Synthesis was performed in the same manner as in Production Example 8 except that bromoethane and bromoethanol were used instead of dibromopropanol, and separation was performed by silica gel column chromatography (hexane: ethyl acetate = 2: 1). Got 24. Yield 20%.
[0255] [製造例 24]化合物 25の合成  [Production Example 24] Synthesis of Compound 25
[化 46]  [Chem 46]
Figure imgf000077_0003
Figure imgf000077_0003
化合物 2 5  Compound 2 5
[0256] 化合物 8に代えて製造例 23で合成した化合物 24を用いることを除き製造例 9と同 様の方法で合成を行い、化合物 25を得た。収率 30%。 Synthesis was performed in the same manner as in Production Example 9 except that Compound 24 synthesized in Production Example 23 was used instead of Compound 8, and Compound 25 was obtained. Yield 30%.
[0257] [製造例 25] P— 55の合成 [0257] [Production Example 25] Synthesis of P-55
[化 47]
Figure imgf000078_0001
[Chemical 47]
Figure imgf000078_0001
P— 5 5  P— 5 5
[0258] 化合物 9に代えて製造例 24で合成した化合物 25を用い、また、ジブロムデカンに 代えてジブロモプロピオニックアシッドを用いることを除き製造例 10と同様の方法で 合成を行い、 P— 55を得た。収率 60% [0258] The compound 25 was synthesized in the same manner as in Production Example 10 except that Compound 25 synthesized in Production Example 24 was used instead of Compound 9, and dibromopropionic acid was used instead of dibromodecane. Got. Yield 60%
[0259] [製造例 26] P— 56の合成  [0259] [Production Example 26] Synthesis of P-56
[化 48]  [Chemical 48]
Figure imgf000078_0002
Figure imgf000078_0002
[0260] 製造例 5で合成した化合物 4の 15mmol、製造例 9で合成した化合物 9の 15mmol 、ブロモデカノール 15mmol K CO (150mmol)およびジメチルホルムアミド 100 [0260] 15 mmol of Compound 4 synthesized in Production Example 5, 15 mmol of Compound 9 synthesized in Production Example 9, bromodecanol 15 mmol K CO (150 mmol) and dimethylformamide 100
2 3  twenty three
mlを 90°Cで 6時間撹拌した後、反応液をろ過し、ろ液を 1%塩酸水溶液 1L中に滴下 した。固体をろ過し、メタノールでリスラリーを行い、 P— 56を得た。収率 85%  After stirring ml at 90 ° C for 6 hours, the reaction solution was filtered, and the filtrate was added dropwise to 1 L of 1% aqueous hydrochloric acid. The solid was filtered and reslurried with methanol to obtain P-56. Yield 85%
[0261] [実施例 10] [0261] [Example 10]
下記に本発明の重合体のいくつかについて、分子量 Mw Mnおよび近赤外線極 大吸収波長を示す。 分子量測定は東ソー株式会社製 高速 GPC ;HLC8120GPCを用い、溶媒 THF 、 UV検出 254nmにて行った。（ポリスチレン換算） 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)
[0262] [表 16] 表 1 6 [0262] [Table 16] Table 1 6
Figure imgf000079_0001
Figure imgf000079_0001
産業上の利用可能性  Industrial applicability
[0263] 上記したとおり、本発明の近赤外線吸収材料は、近赤外線吸収剤として有用であり 、本発明の近赤外線吸収剤はこれまでの同種の近赤外線吸収剤に比べて、格段の 溶解性と耐久性を付与できたため、例えば、光学フィルター用組成物、レーザー溶 着用組成物、レーザーマーキング用組成物、熱線遮断材用組成物または LED用組 成物などの近赤外線吸収剤など様々な用途に使用することが可能になった。  [0263] As described above, 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. For example, 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.

Claims

請求の範囲 下記一般式 [ 1 ]または [2]で表される繰り返し単位を有する近赤外線吸収材料。 一般式 [1] : [化 1] R 1— Y. 丫3一 R3 _ A \ / M - R2- Y2 s 、5へ Y4— R4 一般式 [2] [化 2] A near-infrared absorbing material having a repeating unit represented by the following general formula [1] or [2]. General formula [1]: [Chemical 1] R 1— Y. 丫 3 ichi R3 _ A \ / M-R2- Y2 s, to 5 Y4— R4 General formula [2] [Chemical 2]
(一般式 [1]および [2]中、 Mは金属原子を表し、 R1および R4は、それぞれ独立して 、置換もしくは未置換のァリール基、置換もしくは未置換のへテロアリール基、または 、置換もしくは未置換のアルキル基を表し、 R2および R3は、それぞれ独立して、置換 もしくは未置換のァリーレン基、置換もしくは未置換のへテロアリーレン基、または、置 換もしくは未置換のアルキレン基を表し、また R1と R2、 R3と R4は互いに結合して環を 形成してもよぐ 〜丫4は直接結合もしくはヘテロ原子を表し、 Aは直接結合もしくは 二価の有機残基を表す。 ) (In the general formulas [1] and [2], M represents a metal atom, R 1 and R 4 each independently represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or Represents a substituted or unsubstituted alkyl group, and 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 alkylene group. R 1 and R 2 , R 3 and R 4 may be bonded to each other to form a ring to 丫4 represents a direct bond or a hetero atom, and A represents a direct bond or a divalent organic residue. Represents a group.)
[2] 請求の範囲 1に記載の近赤外線吸収材料において、一般式 [ 1 ]で表される繰り返し 単位が下記一般式 [3]で表される繰り返し単位であり、また一般式 [2]で表される繰 り返し単位が下記一般式 [4]で表される繰り返し単位であることを特徴とする近赤外 線吸収材料。  [2] In the near-infrared absorbing material according to claim 1, the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [3], and is represented by the general formula [2] A near-infrared ray absorbing material, wherein the repeating unit represented is a repeating unit represented by the following general formula [4].
一般式 [3] :  General formula [3]:
[化 3]
Figure imgf000081_0001
一般式 [4] [Chemical 3]
Figure imgf000081_0001
General formula [4]
[化 4] [Chemical 4]
Figure imgf000081_0002
Figure imgf000081_0002
(一般式 [3]および [4]中、 M、
Figure imgf000081_0003
R4および Aは請求の範囲 1で定義したも のと同一のものである。 ) (In general formulas [3] and [4], M,
Figure imgf000081_0003
R 4 and A are the same as defined in claim 1. )
請求の範囲 1に記載の近赤外線吸収材料において、一般式 [ 1 ]で表される繰り返し 単位が下記一般式 [5]で表される繰り返し単位であり、また一般式 [2]で表される繰 り返し単位が下記一般式 [6]で表される繰り返し単位であることを特徴とする近赤外 線吸収材料。 In the near-infrared absorbing material according to claim 1, the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [5], and is represented by the general formula [2]. A near-infrared ray absorbing material, wherein the repeating unit is a repeating unit represented by the following general formula [6].
一般式 [5] : General formula [5]:
[化 5] [Chemical 5]
Figure imgf000081_0004
一般式 [6]
Figure imgf000081_0004
General formula [6]
[化 6]
Figure imgf000082_0001
[Chemical 6]
Figure imgf000082_0001
(一般式 [5]および [6]中、 M
Figure imgf000082_0002
R4および Aは請求の範囲 1で定義したも のと同一のものである。 ) (In general formulas [5] and [6], M
Figure imgf000082_0002
R 4 and A are the same as defined in claim 1. )
請求の範囲 1に記載の近赤外線吸収材料において、一般式 [ 1 ]で表される繰り返し 単位が下記一般式 [7]で表される繰り返し単位であり、また上記一般式 [2]で表され る繰り返し単位が下記一般式 [8]で表される繰り返し単位であることを特徴とする近 赤外線吸収材料。  In the near-infrared absorbing material according to claim 1, the repeating unit represented by the general formula [1] is a repeating unit represented by the following general formula [7], and is represented by the above general formula [2]. A near-infrared absorbing material, wherein the repeating unit is a repeating unit represented by the following general formula [8].
一般式 [7] :  General formula [7]:
[化 7]  [Chemical 7]
Figure imgf000082_0003
一般式 [8]
Figure imgf000082_0003
General formula [8]
[化 8]  [Chemical 8]
Figure imgf000082_0004
Figure imgf000082_0004
(一般式 [7]および [8]中、 M
Figure imgf000082_0005
R4および Aは請求の範囲 1で定義したも のと同一のものである。 ) (In general formulas [7] and [8], M
Figure imgf000082_0005
R 4 and A are the same as defined in claim 1. )
[5] 請求の範囲 1 4のいずれかに記載の近赤外線吸収材料において、 Mがニッケル、 白金、コバルト、パラジウムもしくは銅であることを特徴とする近赤外線吸収材料。 [5] The near-infrared absorbing material according to any one of claims 14 to 14, wherein M is nickel, platinum, cobalt, palladium, or copper.
[6] 請求の範囲 1 5のいずれかに記載の近赤外線吸収材料において、 Ri R4の少なく とも一つが置換基を有する基であることを特徴とする近赤外線吸収材料。 [6] The near-infrared absorbing material according to any one of claims 1 to 5, wherein Ri R 4 is at least A near-infrared absorbing material, wherein one of them is a group having a substituent.
[7] 請求の範囲 1〜6のいずれかに記載の近赤外線吸収材料において、 R1と R2、および /または、 R3と R4が結合して共役または非共役の環を形成して 、ることを特徴とする 近赤外線吸収材料。 [7] The near-infrared absorbing material according to any one of claims 1 to 6, wherein R 1 and R 2 and / or R 3 and R 4 are bonded to form a conjugated or non-conjugated ring. A near-infrared absorbing material.
[8] 請求の範囲 1〜7のいずれかに記載の近赤外線吸収材料において、 Aが、 NHC O 、 一 CONH 、 一 NHCOO 、 一 OCONH 、 一 O 、 一 S 、 一 NH—、 一 COO 、 一 OCO 、 一 SO —、 一 CO 、 一 C = C一、 一 N=N 、 一 S— S—、置  [8] The near-infrared absorbing material according to any one of claims 1 to 7, wherein A is NHC 2 O, 1 CONH, 1 NHCOO, 1 OCONH, 1 O, 1 S, 1 NH—, 1 COO, 1 OCO, 1 SO —, 1 CO, 1 C = C, 1 N = N, 1 S— S—,
2  2
換もしくは未置換のァリーレン基、置換もしくは未置換のへテロアリーレン基、置換も しくは未置換のアルキレン基、および置換もしくは未置換のアミノ基力 なる群より選 ばれた基を任意に組み合わせて成る二価の有機残基であることを特徴とする近赤外 線吸収材料。  A group selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted alkylene group, and a substituted or unsubstituted amino group. A near-infrared absorbing material characterized by being a divalent organic residue.
[9] 請求の範囲 8に記載の近赤外線吸収材料において、 A力 下記一般式 [9]で表され る基であることを特徴とする近赤外線吸収材料。  [9] The near infrared ray absorbing material according to claim 8, wherein the A force is a group represented by the following general formula [9].
一般式 [9] :  General formula [9]:
[化 9]
Figure imgf000083_0001
[Chemical 9]
Figure imgf000083_0001
(式中、 1〜：^3は、それぞれ独立して、直接結合あるいは— NHCOO—、 -OCON H 、 一 O 、 一 S 、 一 NH 、 一 COO 、 一 OCO 、 一 SO —、 一 CO 、 一 C (Wherein 1 to 3 are independently a direct bond or —NHCOO—, —OCON H, 1 O, 1 S, 1 NH, 1 COO, 1 OCO, 1 SO —, 1 CO, 1 C
2  2
=C一、 N=N—または— S— S を表し、 n1および n2は 0または自然数を表す。） = C, N = N—or —S—S, n 1 and n 2 represent 0 or a natural number. )
[10] 請求の範囲 1〜9のいずれかに記載の近赤外線吸収材料において、該近赤外吸収 材料が、 2種以上の異なる繰り返し単位を有することを特徴とする近赤外線吸収材料 [10] The near infrared ray absorbing material according to any one of claims 1 to 9, wherein the near infrared ray absorbing material has two or more different repeating units.
[11] 請求の範囲 1〜10のいずれかの近赤外線吸収材料力もなる近赤外線吸収剤。 [11] A near-infrared absorber which also has the near-infrared absorbing material power of any one of claims 1 to 10.
[12] 請求の範囲 11に記載の近赤外線吸収剤の少なくとも一種を含有する近赤外線吸収 組成物。 [12] A near-infrared absorbing composition comprising at least one of the near-infrared absorbers according to claim 11.
[13] 請求の範囲 12に記載の近赤外線吸収組成物において、前記近赤外線吸収剤が 2 種以上の近赤外線吸収剤カゝらなることを特徴とする近赤外線吸収組成物。 [13] The near-infrared absorbing composition according to claim 12, wherein the near-infrared absorbing agent comprises two or more kinds of near-infrared absorbing agents.
[14] 請求の範囲 12または 13に記載の近赤外線吸収組成物において、請求の範囲 11に 記載の近赤外線吸収剤以外の近赤外線吸収剤が更に含有されることを特徴とする 近赤外線吸収組成物。 [14] The near-infrared absorbing composition according to claim 12 or 13, further comprising a near-infrared absorbing agent other than the near-infrared absorbing agent according to claim 11. object.
[15] 請求の範囲 14に記載の近赤外線吸収組成物において、請求の範囲 11に記載の近 赤外線吸収剤以外の近赤外線吸収剤が、ニッケル錯体系色素、フタロシア-ン系色 素およびジィモ -ゥム系色素から選ばれた少なくとも一種の近赤外線吸収剤であるこ とを特徴とする近赤外線吸収組成物。  [15] The near-infrared absorbing composition according to claim 14, wherein the near-infrared absorbing agent other than the near-infrared absorbing agent according to claim 11 is a nickel complex dye, a phthalocyanine dye, and dimo- A near-infrared absorbing composition, characterized in that it is at least one near-infrared absorber selected from um dyes.
[16] 請求の範囲 13または請求の範囲 14に記載の近赤外線吸収組成物において、該近 赤外線吸収組成物に含まれる近赤外線吸収剤は、最大近赤外線吸収波長の異なる 少なくとも 2種の近赤外線吸収剤からなることを特徴とする近赤外線吸収組成物。  [16] The near-infrared absorbing composition according to claim 13 or claim 14, wherein the near-infrared absorbing agent contained in the near-infrared absorbing composition has at least two kinds of near-infrared rays having different maximum near-infrared absorption wavelengths. A near-infrared absorbing composition comprising an absorber.
[17] 請求の範囲 12〜 16のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物に更にバインダー榭脂が含まれることを特徴とする近赤外線吸収組成 物。  [17] The near infrared ray absorbing composition according to any one of claims 12 to 16, wherein the near infrared ray absorbing composition further contains a binder resin.
[18] 請求の範囲 12〜17のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物に更に溶剤が含まれることを特徴とする近赤外線吸収組成物。  [18] The near infrared ray absorbing composition according to any one of claims 12 to 17, wherein the near infrared ray absorbing composition further contains a solvent.
[19] 請求の範囲 12〜18のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が塗布用組成物であることを特徴とする近赤外線吸収組成物。 [19] The near infrared ray absorbing composition according to any one of claims 12 to 18, wherein the near infrared ray absorbing composition is a coating composition.
[20] 請求の範囲 12〜 19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が粘着または接着剤組成物であることを特徴とする近赤外線吸収組 成物。 [20] The near infrared ray absorbing composition according to any one of claims 12 to 19, wherein the near infrared ray absorbing composition is an adhesive or adhesive composition. .
[21] 請求の範囲 12〜 19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物がレーザー溶着用組成物であることを特徴とする近赤外線吸収組成 物。  [21] The near infrared ray absorbing composition according to any one of claims 12 to 19, wherein the near infrared ray absorbing composition is a laser welding composition.
[22] 請求の範囲 12〜 19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物がレーザーマーキング用組成物であることを特徴とする近赤外線吸収 組成物。  [22] The near infrared ray absorbing composition according to any one of claims 12 to 19, wherein the near infrared ray absorbing composition is a laser marking composition.
[23] 請求の範囲 12〜 19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が熱線遮断材用組成物であることを特徴とする近赤外線吸収組成物 [23] The near infrared ray absorbing composition according to any one of claims 12 to 19, wherein the near infrared ray absorbing composition is a composition for a heat ray shielding material.
[24] 請求の範囲 12〜 19のいずれかに記載の近赤外線吸収組成物において、該近赤外 線吸収組成物が LED用組成物であることを特徴とする近赤外線吸収組成物。 [24] The near infrared ray absorbing composition according to any one of claims 12 to 19, wherein the near infrared ray absorbing composition is a composition for LED.
[25] 基材上に、請求の範囲 1〜10のいずれかに記載の近赤外線吸収材料を含む層が形 成されてなる積層体。  [25] A laminate in which a layer containing the near-infrared absorbing material according to any one of claims 1 to 10 is formed on a substrate.
[26] 請求の範囲 25に記載の積層体において、前記近赤外線吸収材料を含む層が、請 求の範囲 12〜20のいずれかに記載の近赤外線吸収組成物により形成されているこ とを特徴とする積層体。  [26] The laminate according to claim 25, wherein the layer containing the near-infrared absorbing material is formed of the near-infrared absorbing composition according to any one of claims 12 to 20. A featured laminate.
[27] 請求の範囲 1〜： LOのいずれかに記載の近赤外線吸収材料を含む近赤外線吸収フィ ノレム。  [27] Claims 1 to: A near-infrared absorbing finalom comprising the near-infrared absorbing material according to any one of LOs.
[28] 請求の範囲 25または 26に記載の積層体を含んでなる光学フィルター。  [28] An optical filter comprising the laminate according to claim 25 or 26.
[29] 請求の範囲 28記載の光学フィルターにおいて、該光学フィルターがプラズマデイス プレイ用であることを特徴とする光学フィルター。  [29] The optical filter according to claim 28, wherein the optical filter is used for a plasma display.
[30] 請求の範囲 28記載の光学フィルターにおいて、該光学フィルターが液晶ディスプレ ィ用であることを特徴とする光学フィルター。 [30] The optical filter according to claim 28, wherein the optical filter is for a liquid crystal display.
[31] 請求の範囲 28記載の光学フィルターにおいて、該光学フィルターが CCDカメラ用で あることを特徴とする光学フィルター。 [31] The optical filter according to claim 28, wherein the optical filter is for a CCD camera.
[32] 請求の範囲 28記載の光学フィルターにおいて、該光学フィルターが CMOSイメージ センサ用であることを特徴とする光学フィルター。 32. The optical filter according to claim 28, wherein the optical filter is for a CMOS image sensor.
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