WO2007148621A1 - Light-shielding agent - Google Patents
Light-shielding agent Download PDFInfo
- Publication number
- WO2007148621A1 WO2007148621A1 PCT/JP2007/062091 JP2007062091W WO2007148621A1 WO 2007148621 A1 WO2007148621 A1 WO 2007148621A1 JP 2007062091 W JP2007062091 W JP 2007062091W WO 2007148621 A1 WO2007148621 A1 WO 2007148621A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- ring
- light
- general formula
- cyanine dye
- Prior art date
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- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 claims abstract description 70
- 125000001424 substituent group Chemical group 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 10
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 82
- -1 fluoroalkyl sulfonic acid cation Chemical class 0.000 claims description 58
- 230000003287 optical effect Effects 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 30
- 239000003960 organic solvent Substances 0.000 abstract description 10
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 93
- 150000001875 compounds Chemical class 0.000 description 27
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 150000003839 salts Chemical group 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 6
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- 125000003277 amino group Chemical group 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 101100226146 Drosophila mojavensis Est-5 gene Proteins 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
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- 229910052759 nickel Inorganic materials 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
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- 125000003884 phenylalkyl group Chemical group 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 238000000411 transmission spectrum Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 125000005916 2-methylpentyl group Chemical group 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 3
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 3
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
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- 125000005023 xylyl group Chemical group 0.000 description 3
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- UREZNYTWGJKWBI-UHFFFAOYSA-M benzethonium chloride Chemical compound [Cl-].C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OCCOCC[N+](C)(C)CC1=CC=CC=C1 UREZNYTWGJKWBI-UHFFFAOYSA-M 0.000 description 2
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical group C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 2
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical group C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical group C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
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- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
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- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001806 thionaphthenyl group Chemical group 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical group S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
- C09B23/086—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines more than five >CH- groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/0018—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 with means for preventing ghost images
Definitions
- the present invention relates to a light-shielding agent that absorbs in the near-infrared light region, has excellent near-infrared absorption performance, heat ray absorption performance, visible light transmission performance, light resistance, heat resistance, stable performance,
- the present invention relates to an optical filter that can stably display a color tone when used in a display such as a suitsa display, an infrared absorption filter for digital cameras, and a heat ray absorption filter.
- a plasma display is a video display device that uses gaseous plasma discharge light. It has a color purity comparable to that of a cathode ray tube, is easy to achieve full color, and has a wide viewing angle, making it compatible with high-definition television broadcasting. Development and mass production of large-sized video display devices are underway.
- Satoshi Uchiike “The Journal of the Institute of Image Information and Television Engineers”, No. 51, No. 4, pp. 459 to 463 (1997) and Masahei Nozaki, “Monthly Display”, No. 6, Vol. 4, No.
- the plasma display in principle, has a so-called “neon orange color” around a wavelength of 600 nm that is emitted when excited neon atoms return to the ground state. '' And unnecessary near-infrared radiation are unavoidable, and when mixed with red light emission, there is a problem that a vivid red display with good color purity cannot be obtained or the infrared remote control malfunctions. .
- Japanese Patent Application Laid-Open No. 9-241520 discloses a near-infrared ray.
- a front member using an organic dye compound of nickel complex type, azo type, or anthraquinone type as an absorbent is disclosed in Japanese Patent Application Laid-Open No. 10-128898.
- a front member using a compound has been proposed.
- Japanese Patent Application Laid-Open No. 2002-90521 proposes an optical filter using a cyanine dye.
- cyanine dyes used as near-infrared absorbers have a maximum absorption wavelength in the vicinity of 85 Onm, and have a problem that they are slightly shorter than desired absorption wavelengths.
- the present invention effectively blocks unnecessary artificial light, particularly near infrared rays, radiated from the image display device in the front member for image display devices, and also provides near-infrared rays of natural light. It is an object of the present invention to provide a light-shielding agent excellent in solubility in organic solvents, light resistance, and environmental resistance and its use. Another object of the present invention is to obtain a desired absorption wavelength by further increasing the absorption wavelength in a light-shielding agent comprising a cyanine dye.
- cyanine dyes having a sulfonyl group at the meso position of the methine chain have an absorption maximum in the vicinity of a wavelength of 900 nm, such as plasma displays. It has been found that when used as a front member attached to a video display device, unnecessary light emitted from the video display device is effectively blocked. In addition, such cyanine dyes are excellent in light resistance and environmental resistance in organic solvents and in the state of thin films. It was found that it can be produced well.
- the present invention solves the above problems by providing a light-shielding agent comprising a cyan dye having a sulfo group at the meso position represented by the general formula 1.
- Z and Z represent a monocyclic or condensed aromatic ring or heterocyclic ring
- R 6 represents the same or different aliphatic hydrocarbon group or aromatic hydrocarbon group, and these aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent.
- R represents a hydrogen atom or a substituent
- L represents an atomic group necessary for forming a cyclic structure
- X m1 represents an m-valent counter ion, m is 1 to 3, and c is 0 or 1.
- the present invention solves the above problems by providing an optical filter using a light-shielding agent comprising a cyanine dye represented by the general formula 1.
- FIG. 1 shows transmission spectrum data in the thin film state of the cyanine dye chemical formula 26 of the present invention and the comparative compound chemical formula 274, respectively.
- the present invention provides a light-shielding agent comprising a cyanine dye represented by the general formula 1 and
- the present invention relates to an optical filter using such cyanine dye.
- Z represents a monocyclic or condensed aromatic ring or heterocyclic ring.
- Aromatic rings in Z and Z may have a substituent.
- Aromatic rings in Z and Z may have a substituent.
- a benzene ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, biphenyl ring, etc. and as a heterocyclic ring, for example, an imidazoline ring, an imidazole ring, a benzimidazole ring, an ⁇ naphtho ring, etc.
- Examples of the substituent in Z and Z include a methyl group, an ethyl group, a vinyl group, and propylene.
- R to R represent the same or different aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
- Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, an isopropyl group, a 1-propyl group, a 2-propyl group, and a 2-propyl group.
- aromatic hydrocarbon groups there are phenol group, o tolyl group, m-tolyl group, p tolyl group, xylyl group. Group, mesityl group, o-tame group, m-tameyl group, p-tameryl group, biphenylyl group, benzyl group, and phenethyl group. Further, these aliphatic hydrocarbon groups or aromatic hydrocarbon groups may have a substituent. Examples of the substituent include, for example, the same substituents as those in Z and Z.
- R and R, and R and R can be bonded to form a 3- to 8-membered ring. 3 to 8 member ring
- a cyclohexane ring As a cyclohexane ring, a cyclopentane ring, a cyclopropane ring, a dimethylcyclohexane ring, a tetrahydran pyran ring, a piperidine ring, a tetrahydro ring, which contains carbon, oxygen, sulfur and nitrogen atoms.
- An example is a thiopyran ring.
- R and R further include ethyl sulfonic acid and its ion, propyl sulfone.
- Alkyl sulfonic acid groups such as acid and its ion, butyl sulfonic acid and its ion, 1-methylpropylsulfonic acid and its ion, acetic acid and its ion, propionic acid and its ion, etc. And an alkyl carboxyl group.
- the cationic species when it has a salt structure includes inorganic ions such as lithium, sodium and potassium and organic ions such as triethylamine, tributylamine, morpholine, piperidine, pyrrolidine and ammonia.
- R represents a hydrogen atom or a substituent, and examples of the substituent include a methyl group, an ethyl group, a bur group, a propyl group, an isopropyl group, an isopropyl group, a 1 probe group, and a 2-probe group.
- Base group 2-propyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2 butyr group, 1, 3 butadiene group, pentyl group, isopentyl group, neopentyl group, tert pentyl group Group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group, 2 pentene-4-yl group, hexyl group, isohexyl group, 5-methylhexyl group
- Aromatic carbonization such as alkyl group such as syl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group, phenol group, o-tolyl group, m -tolyl group, p-tolyl group and xylyl group
- the aryl group include a hydrogen group, a benzyl group, a phenyl group, and
- alkyl group, aryl group, and alkylaryl group include, in addition, an arylino group, an amino group, A substituent such as an alkylamino group, a halogen group, a nitro group, an alkoxy group, a cyan group, or an alkyl group may be bonded.
- R represents, in addition to the above-described substituents of the above-mentioned substituents, an optionally substituted alino group, amino group, halogen group, nitro group, alkoxy group, cyano group, optionally substituted alkylamino group. Examples include groups.
- L represents an atomic group necessary for binding to the methine chain moiety and forming a cyclic structure.
- Cyclic structures include double bonds and one or more Z or heteroatoms, such as cyclobutene ring, cyclopentene ring, cyclohexene ring, benzene ring, indonaphthene ring, dehydrodecalin ring, pyridine ring, dihydropyridine.
- Examples thereof include monocyclic or condensed polycyclic rings such as a ring, a tetrahydropyridine ring, a furan ring, a dihydrofuran ring, a thiophene ring, a dihydrothiophene ring, and a hexahydroquinoline ring.
- X m_ represents an m-valent counter ion that keeps the general formula 1 neutral, and m is 1 to 3, and may not be present in some cases to keep neutral (in this case, The value of c in Equation 1 represents 0).
- the counter ion include hexafluorophosphate ion, halogen ion, phosphate ion, perchlorate ion, periodate ion, hexafluoroantimonate ion, hexafluorostannate ion, and boron hydrofluoric acid.
- Ions inorganic acid ions such as tetrafluoroborate ion, thiocyanate, benzene sulphonate, benzene disulphonate, naphthalene sulphonate, ⁇ -toluene sulphonate , Alkyl sulfonate ions, benzene carbonate ions, benzene dicarboxylate ions, benzene tricarboxylate ions, alkyl carboxylate ions, trihaloalkyl carboxylate ions, alkyl sulfate ions, trialkyl alkyl sulfate ions, nicotinate ions, etc.
- Ions as well as azo, bisphenyldithionole, thiocatecono Chelate, thiobis Hue methylate chelate, Bisujioru - Fei - a metal complex ion of diketone are employed.
- counter ions containing fluorine atoms such as hexafluorophosphate ion, borohydrofluoride ion, tetrafluoroborate ion, trifluorosulfonate ion, nonafluorobutanesulfur Phosphonate, di (trifluoromethylsulfol) imido-one, di (2,2,2-trifluoroethylsulfol) imido-one, di (3, 3, 3, Trifluoropropyl sulfone) imido-one, di (4, 4, 4 trifluorobutylsulfol) imido-one, di (perfluoroethylsulfol) imido-one, di (perfluro)
- Counter ions such as isopropylsulfonyl) imido-one and di (perfluorobutylsulfol) imido-one are soluble in the solvent
- cyanine dyes used in the present invention include those represented by chemical formula 1 to chemical formula 257, for example. These cyanine dyes have an absorption maximum in the near-infrared region having a wavelength longer than 850 nm, preferably from 850 to lOOOnm. Furthermore, the molecular extinction coefficient at the maximum absorption wavelength (hereinafter, the molecular extinction coefficient at the maximum absorption wavelength is abbreviated as “ ⁇ ”) is usually larger than 1 X 10 5, but the visible light absorption is small.
- cyanine dyes are highly soluble in various organic solvents, especially ketone-based, halogenated hydrocarbon-based, ether-based, and ester-based organic solvents, they can be dissolved in organic solvents. Since it is easy to apply to the transparent base material, which is the main component of the front member, it is highly resistant to ambient light such as natural light and artificial light. There is a feature that the ability is difficult to attenuate. Similarly, similar effects can be expected when used for applications that block near-infrared light in natural light. Examples of the compound include compounds represented by general formulas 11 to 121. Specific examples of compounds are shown in the corresponding table.
- the cyanine dyes of the present invention are produced by FM Harmer, "Heterocyclic ccompine saponins" and related 'compounds, Cynine Dyes, and ⁇ Related ⁇ ompounds), Nyung Wuili ⁇ ⁇ 7 and 'Sons Clohn' Wiley '&' Sons), published in 1964, and by DM Sturmer, 'Hetero Cyclic 'Compounds 1 Special' Tsubix'in ⁇ Hair mouth cyclic ⁇ Heterocyclic ⁇ Compounds- Special ⁇ topics ⁇ i ⁇ ⁇ cyclic 'chemistry ", Chapter 18, Section 14, 482-515 Page, John Wiley & Sons, published in 1977, “Rodds 'Chemistry' of 'Carbon' Compounds ⁇ 2nd.
- the light-shielding agent containing the cyanine dye of the present invention may contain a stabilizer.
- the stabilizer include, for example, JP-A-60-234892 and JP-A-5- No. 43814, JP-A-6-239028, JP-A-9-309886, JP-A-10-45757, and the like.
- dithiol metal complex salt examples include a dithiol metal complex represented by the general formula 2.
- R 1 to R 4 in the general formula 2 are a hydrogen atom, an alkyl group, an aryl group, and a shear group, respectively.
- R and R, and R and R are connected to each other.
- An aromatic ring such as a benzene ring or a naphthalene ring can be formed, and these aromatic rings may have a substituent.
- substituents include the same substituents as those bonded to the aromatic ring in the general formula 1.
- M is a group II to group IV metal in the periodic table.
- transition metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Mo, and Cd are preferable, and Fe, Co, Cu, Ni, and Zn are more preferable.
- n is a cation that keeps Formula 2 neutral.
- cations are quaternary ammonium salts or quaternary phosphonium salts.
- the quaternary ammonia salts include tetramethyl ammonium, tetraethyl ammonium, tetraptyl ammonium, octyltrileum ammonia, trimethyl ammonium ammonia, and tributylbutyl ammonium.
- the quaternary phosphonium salts include tetramethylphosphonium, tetraethylphosphonium, tetrobinchinosephosphonium, octyltrichinenophosphonin, phenyltrimethinorephosphonium, triphenyl. -Rubutyl phosphor, triphenyl pendyl phosphor and tetraphenyl phosphor. However, it does not exist when the metal complex itself is neutral.
- metal complex stabilizers can be used as they are by mixing with the light-shielding agent of the present invention, and those having a salt structure can be used by substituting the char-on species of the present invention.
- dimum salt examples include a dimum salt represented by the general formula 3.
- Rc is a substituent selected from an alkyl group, a halogenated alkyl group, a cyanoalkyl group, a aryl group, a hydroxyl group, a phenol group and a phenylalkyl group, and these are the same. Or different. Rc is not particularly limited as long as it is the above-mentioned substituent, but an alkyl group having a straight chain or a side chain having 1 to 8 carbon atoms, a halogenated alkyl group, a cyanoalkyl group, etc. are preferred. The linear alkyl group is particularly preferred.
- particularly preferable ones include ethyl group, propyl group, butyl group, amyl group, isopropyl group, isobutyl group, isoamyl group and the like.
- a phenylalkyl group can also be mentioned as another preferable example.
- the alkyl group preferably has 1 to 8 carbon atoms.
- the fur group in the phenyl alkyl group may not have a substituent, but an alkyl group, a hydroxyl group, a sulfonic acid group, an alkyl sulfonic acid group, a nitro group, an amino group, an alkoxy group,
- the halogenated alkyl group and the group power of halogen power may have at least one substituent selected.
- Cal phenyl group preferred tool force does not have a substituent Hue - The Ruarukiru group, a benzyl group, phenethyl group, Hue - Rupuropiru group, phenylene Lou a methylpropyl group, Hue - Lou ⁇ methylpropyl Group, a phenylbutyl group, a phenylpentyl group, a phenyloctyl group, and the like. Particularly preferred are benzyl and phenethyl groups.
- ⁇ is a key-on for forming a salt and is a key-on species that keeps the general formula 5 neutral.
- the anion species are an organic acid and an inorganic acid, and are not particularly limited.
- dim-um salt examples include Chemical Formula 264 to Chemical Formula 268.
- the above-mentioned dithiol metal complex and dimonium salt can be used in combination as a stabilizer. At that time, two or more different types can be used in combination.
- the used member of the present invention includes at least a transparent base material as a main component of the used member and a light-shielding agent. And a cyanine dye represented by the general formula 1.
- the “light-shielding agent” as used in the present invention is used for such a member to substantially block unnecessary light or natural light, particularly light in the near-infrared region, emitted by video display equipment.
- a light-absorbing organic compound or a composition containing a light-absorbing organic compound is meant.
- the amount of the above Shianin dyes respectively are generally in the range of per unit area L ⁇ 1000mgZm 2 of the optical filter, is favored properly 5: a LOOmgZm 2.
- the transparent base material has a light transmittance of 50% or more, preferably 70% or more in the entire visible region, for example, ABS resin, polyacrylate resin, polyacrylate ester resin, Realylate resin, polyester resin, polyethersulfone resin, polyvinyl chloride resin Polyolefin resin, polycarbonate resin, polyacetic acid resin resin, polystyrene resin, polymethacrylic acid resin, polymethacrylic acid ester resin, and glass, ceramic, etc. Are used in appropriate combination. Among these, in terms of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, polyester resin, polyethersulfone resin, polyolefin resin, polycarbonate resin. Particularly preferred are fats, polymethacrylic acid coffins and polymethacrylic ester coffins.
- the optical filter according to the present invention includes, for example, a film shape, a sheet shape, a panel, and the like, which are represented by the general formula 1, and after mixing the cyanine dye into such a transparent base material, It is expressed by general formulas 1 to 3 in close contact with one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc.
- a light-shielding layer of cyanine dye is formed.
- the thickness of the transparent base material depends on the material of the transparent base material and the area of the used part, from the viewpoint of strength, it is usually 0.5 mm or more, preferably 1 mm or more, while the point of mass. Is usually adjusted within a range of 10 mm or less, preferably 5 mm or less.
- the transparent base material may not be directly attached to the use part, but the transparent base material may be bonded once to a glass plate or the like according to the shape of the use part, and the glass plate may be attached to the use part. is there.
- the transparent substrate is formed to be relatively thin, for example, in the form of a film or a sheet, and an adhesive layer or the like for bonding the transparent substrate to a glass plate is formed on one side thereof.
- the transparent base material and cyanine dye are melt-kneaded and, if necessary, made into pellets, etc., and then extrusion molding, injection Molding, press molding, etc. depending on the shape of the display part in the video display device, or mixing the raw material monomer and cyanine dye of the transparent substrate and casting polymerization according to the shape of the display part
- a cyanine dye in the latter method of providing a cyanine dye layer in close contact with a transparent substrate, for example, if necessary, a cyanine dye can be used in the presence of a binder, for example, chloroform, cyclohexanone, Ethyl methyl ketone, isopropyl methyl ketone and other ketones, halogenated hydrocarbons, ethylene glycol monopropyl ether
- a transparent base material that is dissolved or dispersed in an appropriate organic solvent such as an ether type or an ester type and formed into, for example, a film shape, a sheet shape, or a panel shape, depending on the shape of the use part Apply the solution or dispersion prepared in the same way to the film or sheet of the same material as on the transparent substrate, and then apply the film or sheet to the shape of the part to be used. Adhere to one or both sides of the transparent substrate that has been molded accordingly.
- Examples of the noinder include ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, cellulose acetate-based resin, vinyl acetate resin, cellulose-based resin, nylon, phenol-based resin, and phenoxy.
- examples of these include resin, polyester resin, polyethylene methacrylate resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinylpropylene resin, and polymethylmetatalate resin. Used in combination as appropriate.
- Such a binder is usually used in a mass ratio of 10 to 1,000 times, preferably 50 to 500 times with respect to the cyanine dye of the present invention.
- the solid cyanine dye is dispersed as fine particles having a particle diameter of 0.1 to 10 m, preferably 0.5 to 5 m.
- a solution or dispersion containing a cyanine dye to a transparent substrate or the like, for example, a dubbing method, a flow coating method, a spray method, a bar coating method, a gravure coating method, which is widely used in the field.
- a roll coating method, a blade coating method, an air knife coating method, and the like are applied, and these are applied in appropriate combinations as necessary.
- the light-shielding agent of the present invention is widely used in this field together with the cyanine dye represented by the general formula 1 within a range not departing from the object of the present invention, including the stabilizers listed above.
- the cyanine dye represented by the general formula 1 for example, amino salt compounds, amino compounds, aminothiol nickel complex compounds, anthraquinone compounds, imumum compounds, cyanine compounds, dimonium compounds, dithiol nickel complexes Systemic compounds, triallylmethane compounds, naphthoquinone compounds, nitroso compounds and their metal salts, phthalocyanine compounds, carbon black, indium tin oxide, near infrared absorbers containing antimony tin oxide, benzotriazole compounds, benzophenone compounds, Hydroxybenzoate compound, titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate UV absorber containing such, further May contain one or more of an antioxidant, a flame retardant, a stabilizer, a lub
- the cyanine dyes of the present invention when used in combination with near-infrared absorbers and ultraviolet absorbers as described above, markedly improve the light resistance of the organic dye compounds contained in these dyes. Effectively suppresses discoloration, denaturation, and decomposition.
- the cyanine dye of the present invention that blocks near-infrared rays can be advantageously used as a near-infrared absorbing agent or a near-infrared blocking agent alone or in combination with other compounds that absorb near-infrared rays.
- the optical filter of the present invention together with the cyanine dye represented by the general formula 1, is generally used in the field as necessary, for example, silver, silver-palladium alloy, indium oxide, Contains indium oxide tin oxide (ITO), electromagnetic wave shielding agent containing zinc oxide, metal oxide, metal fluoride, metal silicide, metal boride, metal carbide, metal nitride, metal sulfide, etc. Do not interfere with the use of one or more anti-reflective agents. These materials are usually capable of forming as a layer independent of the light-shielding layer by cyanine dye on the transparent substrate by a method such as vacuum deposition, sputtering, ion plating, or ion beam assist. On the film or sheet of the same material as in the transparent substrate, the UV blocking layer, electromagnetic wave blocking layer, antireflection layer, etc.
- ITO indium oxide tin oxide
- electromagnetic wave shielding agent containing zinc oxide, metal oxide, metal fluoride, metal silicide, metal
- One or more are formed, and the film or sheet is bonded to a transparent substrate.
- this optical filter is provided with a non-glare layer for suppressing glare and widening the viewing angle, a hard coat layer for protecting the surface, and an optical filter, as required. It does not interfere with the provision of one or more adhesive layers, etc. for attaching to a plate.
- the optical filter according to the present invention is selected from the cyanine dyes represented by the general formula 1 having an appropriate absorption range according to the wavelength of light to be blocked. It selectively blocks unwanted light in the near infrared region radiated from video display equipment that does not impair the color purity of the three primary colors of the image, especially near infrared light in plasma displays, providing excellent contrast and color reproducibility. High-quality images can be obtained, and the infrared remote control does not malfunction due to near infrared rays.
- the optical filter of the present invention can be applied, for example, a direct-view television using a cathode ray tube
- Examples include light-emitting panel televisions that use plasma displays and electroluminescent displays, non-light-emitting panel televisions that use liquid crystal displays, and rear projection televisions that incorporate liquid crystal projectors.
- the optical filter according to the present invention can be applied very advantageously to a light-emitting panel television using a plasma display, an electroluminescence display, or the like that easily emits unnecessary light in principle.
- a quencher refers to one having a function of de-exciting (taenting) an active molecule in an excited state.
- Each of the cyanine dyes of the present invention represented by the chemical formula 114 and the chemical formula 179, the comparative compound represented by the chemical formula 269 and the chemical formula 270, respectively, and a metal complex (“EST— 5 ”(manufactured by Sumitomo Seika) was mixed at a mass ratio of 1: 1.
- Each of the mixture of cyanine dye and EST-5 was dissolved in methylene chloride to prepare a solution containing 0.1% by mass of cyanine dye, and then added to methyl ethyl ketone (hereinafter referred to as “ME Kj”).
- ME Kj methyl ethyl ketone
- the absorbance at the maximum absorption wavelength ( ⁇ max) at that time was measured and stored in a brown bottle at room temperature (25 ° C) and stored in the dark.
- the absorbance of the solution was measured, and the absorbance after 24 hours Z was calculated as a percentage of the absorbance value of the initial solution (the residual ratio of dye), which was used as a measure for the solution storage stability of cyanine dye.
- the comparative compound shows only a stability of a dye residual ratio of 10% or less, while the present invention is 70% in a mixed solution with a metal complex quencher (“EST-5”).
- a pigment residual ratio of% or more was shown.
- the comparative example is the EST-5 used as Quenchia While the function could not be extracted and the solution stability was very low, the present invention was able to effectively utilize the quenching function.
- the cyanine dye of the present invention represented by the chemical formula 4 and the chemical formula 146, the comparative compound represented by the chemical formula 271 and the chemical formula 272, respectively, and 0.1% by mass of the cyanine dye and the quencher (“IRG-023”) manufactured by Nippon Kayaku Co.) 0.6 wt 0/0, polymethyl methacrylate Tari rate (manufactured by "PMMA” Aldori Tutsi) 2.
- IRG-023 0.6 wt 0/0
- polymethyl methacrylate Tari rate manufactured by "PMMA” Aldori Tutsi
- cyanine dye of the present invention represented by the chemical formula 83 and the chemical formula 126 and the comparative compound represented by the chemical formula 273, respectively, 0.1 mass% of the cyanine dye and Quentyaichi (“IRG-02 3” manufactured by Nippon Gyaku Co., Ltd.) ) 0.6 weight 0/0, polymethyl methacrylate Tari rate ( "PMMA” manufactured by Aldrich) 2. 5 wt 0/0 were dissolved in MEK solvent. A thin film of each solution was formed on a polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance at 675 nm was measured (absorbance of the initial thin film).
- the compound of the comparative example showed a change in hue of 6% or more when heated at 90 ° C for 24 hours, whereas the cyanine dye of the present invention. Showed a small change rate of about 3%.
- the conventional near-infrared absorbing dye used in the comparative example decomposes with the passage of time when the heat resistance is low, the absorption coefficient in the near-infrared region decreases, and further, absorption occurs in the visible light region due to the decomposition, Visible light transmittance decreased, and the color tone was lost due to yellow coloration.
- the cyanine dye of the present invention has high heat resistance, and it is difficult for coloration in the visible light region due to decomposition of the dye with little decrease in absorption in the near infrared region. Compared with the existing cyanine dyes, the present invention has been shown to be superior in optical design, in which the hue hardly changes!
- the cyanine dye of the present invention represented by the chemical formula 4, the chemical formula 144, the chemical formula 161, the comparative compound represented by the chemical formula 271, the chemical formula 274, and the chemical formula 275 are used.
- the light stability was examined. Cyanine dye 0.1% by mass and polymethyl Metatalitate (“PMMA” manufactured by Aldrich) was dissolved in MEK solvent. Each solution was formed into a thin film by spin coating on a polycarbonate substrate. The absorption of the thin film at that time was measured, and the absorption rate of the dye at ⁇ max was determined and taken as 100%.
- PMMA polymethyl Metatalitate
- the compound of the comparative example had a dye residual ratio of 40% or less, and the cyanine dye of the present invention had a high value of 60% or more.
- the dye residual ratio was shown.
- the present invention showed high light resistance even with the dye alone.
- a thin film of the cyanine dye of the present invention and chemical formula 26 alone was prepared in the same manner as in Example 4, and the transmission spectrum was measured. The obtained transmission spectrum data is shown in Fig. 1.
- the cyanine dye of the present invention has a maximum absorption wavelength on the longer wavelength side than the conventional cyanine dye, so that while cutting the desired near-infrared wavelength region, At the same time, it has high characteristics as an optical filter with little visible absorption, 850 ⁇ ! ⁇ 1 Optical filters can be created without impairing the purity of the three primary colors by efficiently cutting light in the near-infrared region of OOOnm.
- a wavelength longer than lOOnm was achieved compared to the conventional near-infrared absorbing dye used in the comparative example. From this, it is possible to propose that the dye of the present invention efficiently cuts light having a desired wavelength in the vicinity of 850 to lOOOnm, and it has been shown that it has high characteristics.
- All of the optical filters in this example that effectively block the unnecessary light emitted from the video display device that does not impair the color purity of the three primary colors of the video can be used for video display devices such as plasma displays. It can be advantageously applied.
- An indium tin oxide alloy was laminated on the side of the optical filter produced by the method of Example 6 on the side where the light-shielding layer of cyanine dye was formed in an argon-Z oxygen mixed gas stream.
- a non-glare layer of a commercially available poly (methyl methacrylate) resin panel (trade name “MR-NG”, manufactured by Mitsubishi Rayon Co., Ltd.) having a non-glare layer is formed on the surface opposite to the front member. The surfaces were bonded together to obtain two types of front members for video display equipment.
- the front members of this example that effectively block unwanted light radiated from video display equipment that does not cause glare and impair the color purity of the three primary colors of the video are all plasma display. It can be advantageously applied to video display devices such as the first.
- the cyanine dye used in the present invention has an absorption maximum in the near-infrared region, and does not impair the color purity of the three primary colors of an image for a video display device such as a plasma display. Since the unnecessary light emitted from the image display device is effectively blocked, a high-quality image with excellent contrast and color reproducibility can be obtained. It is extremely useful as an optical filter that can be attached to video display equipment such as a plasma display as a light-shielding agent without fear of malfunction.
- the cyanine dye used in the present invention is excellent in light resistance and environmental resistance in an organic solvent, it is possible to produce an optical filter having a low light-blocking ability with good work efficiency even when used for a long period of time. It will be.
- the cyanine dye used in the present invention has the property that the maximum absorption wavelength reaches around lOOOnm depending on the structural design, so when it is used in combination with other organic dye compounds to form a light shielding layer in an optical filter, This has the advantage that the amount of the organic dye compound is small.
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Abstract
An object is to provide a light-shielding agent which can effectively intercept an undesirable artificial light (particularly, a near infrared ray) emitted from an image display device in a front member of the image display device, which can also effectively intercept a near infrared ray in natural light, and which is excellent in solubility in an organic solvent, light resistance and environment resistance, and also provide use of the light-shielding agent. Another object is to elongate the absorption wavelength of a cyanine dye and achieve a desirable absorption wavelength in the cyanine dye. Thus, disclosed is a light-shielding agent comprising a cyanine dye having a sulfonyl group at the meso-position represented by the general formula 1. [General formula 1] wherein Z1 and Z2 independently represent a monocyclic or fused-cyclic aromatic or heterocyclic ring which may have a substituent; R1 to R6 independently represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may have a substituent, provided that R3 and R4 or R5 and R6 may together form a 3- to 8-membered ring; R7 represents a hydrogen atom or a substituent; L represents a group of atoms required for the formation of a cyclic structure; Xm- represents a counter ion having a valency of m; m represents an integer ranging from 1 to 3; and c is 0 or 1.
Description
明 細 書 Specification
遮光剤 Sunscreen
技術分野 Technical field
[0001] 本発明は、近赤外光領域で吸収を示す遮光剤に関し、近赤外線吸収性能、熱線 吸収性能、可視光線透過性能、耐光性、耐熱性に優れ、安定した性能を有し、ブラ ズマディスプレイ等のディスプレイ、デジカメ用赤外線吸収フィルター、熱線吸収フィ ルター等に使用した場合、安定して色調を表示できる光学フィルターに関する。 背景技術 The present invention relates to a light-shielding agent that absorbs in the near-infrared light region, has excellent near-infrared absorption performance, heat ray absorption performance, visible light transmission performance, light resistance, heat resistance, stable performance, The present invention relates to an optical filter that can stably display a color tone when used in a display such as a zuma display, an infrared absorption filter for digital cameras, and a heat ray absorption filter. Background
[0002] 高品位テレビ放送の開始に伴って、プラズマディスプレー方式のテレビ受像機の需 要が急増して ヽる。プラズマディスプレーは気体のプラズマ放電光を利用する映像表 示機器であり、ブラウン管に匹敵する色純度を有し、フルカラー化が容易であるうえ に、視野角が大きいことから、高品位テレビ放送に対応する大型映像表示機器として 開発と量産化が進められている。ところが、内池平榭、『映像情報メディア学会誌』、 第 51卷、第 4号、 459乃至 463頁(1997年)や野崎正平ら、『月刊ディスプレー』、第 6卷、第 4号、 72乃至 77頁(2000年)などに報告されているように、プラズマディスプ レーは、原理上、励起されたネオン原子が基底状態へ戻る際に放出される波長 600 nm付近の、いわゆる、「ネオンオレンジ色」の発光や不用な近赤外線の輻射が避け られず、これらは、赤色発光に混ざると、色純度の良い、鮮やかな赤色表示が得られ なくなったり、赤外線リモコンの誤動作を招来するという問題がある。 [0002] With the start of high-definition television broadcasting, the demand for plasma display television receivers has increased rapidly. A plasma display is a video display device that uses gaseous plasma discharge light. It has a color purity comparable to that of a cathode ray tube, is easy to achieve full color, and has a wide viewing angle, making it compatible with high-definition television broadcasting. Development and mass production of large-sized video display devices are underway. However, Satoshi Uchiike, “The Journal of the Institute of Image Information and Television Engineers”, No. 51, No. 4, pp. 459 to 463 (1997) and Masahei Nozaki, “Monthly Display”, No. 6, Vol. 4, No. 4, 72– As reported on page 77 (2000), the plasma display, in principle, has a so-called “neon orange color” around a wavelength of 600 nm that is emitted when excited neon atoms return to the ground state. '' And unnecessary near-infrared radiation are unavoidable, and when mixed with red light emission, there is a problem that a vivid red display with good color purity cannot be obtained or the infrared remote control malfunctions. .
[0003] この問題を解決するために、従来より、プラズマディスプレーの表示部へ近赤外線 吸収剤を用いる前面部材を取り付ける方法が提案され、例えば、特開平 9— 24152 0号公報には、近赤外線吸収剤としてニッケル錯体系、ァゾ系、アントラキノン系の有 機色素化合物を用いる前面部材が、また、特開平 10— 128898号公報には、複素 環系、アントラキノン系、ジチオールニッケル錯体系の有機色素化合物を用いる前面 部材が提案されている。また特開 2002— 90521号公報にはシァニン色素を用いた 光学フィルターが提案されて 、る。 [0003] In order to solve this problem, a method of attaching a front member using a near-infrared absorber to a display unit of a plasma display has been proposed. For example, Japanese Patent Application Laid-Open No. 9-241520 discloses a near-infrared ray. A front member using an organic dye compound of nickel complex type, azo type, or anthraquinone type as an absorbent is disclosed in Japanese Patent Application Laid-Open No. 10-128898. A front member using a compound has been proposed. Japanese Patent Application Laid-Open No. 2002-90521 proposes an optical filter using a cyanine dye.
[0004] ところが、これらの有機色素化合物の多くは、有機溶剤における溶解性が低いこと
から、有機溶剤に溶解して合成樹脂などによる前面部材の透明基材へ塗布する作 業に支障をきたし、また、自然光や人工光などの環境光に対する耐光性が充分でな いので、長期間用いると、前面部材の遮光能が低下し易いという問題があった。またHowever, many of these organic dye compounds have low solubility in organic solvents. Therefore, it has hindered the work of dissolving in an organic solvent and applying to the transparent base material of the front member with synthetic resin, etc., and it is not sufficiently light resistant to ambient light such as natural light or artificial light, When it is used, there is a problem that the light shielding ability of the front member tends to decrease. Also
、従来、近赤外線吸収剤として用いられているシァニン色素は、最大吸収波長が 85 Onm付近にあり、所望する吸収波長よりやや短!、と!/、う問題があった。 Conventionally, cyanine dyes used as near-infrared absorbers have a maximum absorption wavelength in the vicinity of 85 Onm, and have a problem that they are slightly shorter than desired absorption wavelengths.
発明の開示 Disclosure of the invention
[0005] 斯かる状況に鑑み、この発明は、映像表示機器用前面部材において、映像表示機 器から輻射される不用な人工光、特に近赤外線を効果的に遮断するとともに、自然 光の近赤外線をも有効に遮断し、有機溶剤における溶解性と耐光性、耐環境性に優 れた遮光剤とその用途を提供することを課題とする。またシァニン色素を含んでなる 遮光剤において吸収波長をさらに長波長化させ、所望の吸収波長を得ることを課題 とする。 In view of such circumstances, the present invention effectively blocks unnecessary artificial light, particularly near infrared rays, radiated from the image display device in the front member for image display devices, and also provides near-infrared rays of natural light. It is an object of the present invention to provide a light-shielding agent excellent in solubility in organic solvents, light resistance, and environmental resistance and its use. Another object of the present invention is to obtain a desired absorption wavelength by further increasing the absorption wavelength in a light-shielding agent comprising a cyanine dye.
[0006] 本発明者が鋭意研究し、検索したところ、ヘプタメチン系シァニン色素において、メ チン鎖のメソ位にスルフォニル基を有するシァニン色素は、波長 900nm付近に吸収 極大を有し、プラズマディスプレーなどの映像表示機器へ取り付ける前面部材に用 いると、映像表示機器カゝら輻射される不用な光を効果的に遮断することが判明した。 また、斯カゝるシァニン色素は有機溶剤中、及び薄膜状態における耐光性、耐環境性 に優れ、長期間用いても、色合いが変化しにくぐ遮光能が減弱し難い光学フィルタ 一を作業効率良く作製し得ることが判明した。 [0006] As a result of diligent research and search by the present inventors, among heptamethine cyanine dyes, cyanine dyes having a sulfonyl group at the meso position of the methine chain have an absorption maximum in the vicinity of a wavelength of 900 nm, such as plasma displays. It has been found that when used as a front member attached to a video display device, unnecessary light emitted from the video display device is effectively blocked. In addition, such cyanine dyes are excellent in light resistance and environmental resistance in organic solvents and in the state of thin films. It was found that it can be produced well.
[0007] すなわち、この発明は、一般式 1で表されるメソ位にスルフォ-ル基を有するシァ- ン色素を含んでなる遮光剤を提供することによって前記課題を解決するものである。 That is, the present invention solves the above problems by providing a light-shielding agent comprising a cyan dye having a sulfo group at the meso position represented by the general formula 1.
[0008] 一般式 1 : [0008] General Formula 1:
[化 1]
[Chemical 1]
[0009] 一般式 1にお!/、て、 Z、 Zは単環式又は縮合環式の芳香環又は複素環を表し、そ [0009] In general formula 1! /, Z and Z represent a monocyclic or condensed aromatic ring or heterocyclic ring, and
1 2 1 2
れら芳香環又は複素環は置換基を有していてもよい。 R These aromatic rings or heterocyclic rings may have a substituent. R
1乃至 R 1 to R
6は互いに同じか異な る脂肪族炭化水素基又は芳香族炭化水素基を表し、それら脂肪族炭化水素基又は 芳香族炭化水素基は置換基を有していてもよい。また、 R 6 represents the same or different aliphatic hydrocarbon group or aromatic hydrocarbon group, and these aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent. R
3と R、 R 3 and R, R
4 5と R 4 5 and R
6は結合し、 3 乃至 8員環を形成することが出来る。 Rは水素原子、又は置換基を表し、 Lは、環状 構造を形成するのに必要な原子群を表す。 Xm一は、 m価の対イオンを表し、 mは、 1 乃至 3であり、 cは、 0又は 1である。 6 can combine to form a 3- to 8-membered ring. R represents a hydrogen atom or a substituent, and L represents an atomic group necessary for forming a cyclic structure. X m1 represents an m-valent counter ion, m is 1 to 3, and c is 0 or 1.
[0010] さらに、この発明は、一般式 1で表されるシァニン色素を含んでなる遮光剤を用いる 光学フィルターを提供することによって前記課題を解決するものである。 [0010] Furthermore, the present invention solves the above problems by providing an optical filter using a light-shielding agent comprising a cyanine dye represented by the general formula 1.
図面の簡単な説明 Brief Description of Drawings
[0011] [図 1]図 1は、本発明のシァニン色素 化学式 26と、比較化合物 化学式 274、それ ぞれの薄膜状態での透過スペクトルデータである。 FIG. 1 shows transmission spectrum data in the thin film state of the cyanine dye chemical formula 26 of the present invention and the comparative compound chemical formula 274, respectively.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 既述のとおり、この発明は、一般式 1で表されるシァニン色素を含んでなる遮光剤とAs described above, the present invention provides a light-shielding agent comprising a cyanine dye represented by the general formula 1 and
、斯カるシァニン色素を用いる光学フィルターに関するものである。 The present invention relates to an optical filter using such cyanine dye.
一般式 1 : General formula 1:
[0013] [化 2]
[0013] [Chemical 2]
一般式 1にお!/、て、 Z、 Zは単環式又は縮合環式の芳香環又は複素環を表し、そ In formula 1,! /, Z, Z represents a monocyclic or condensed aromatic ring or heterocyclic ring.
1 2 1 2
れら芳香環又は複素環は置換基を有していてもよい。 Z及び Zにおける芳香環とし These aromatic rings or heterocyclic rings may have a substituent. Aromatic rings in Z and Z
1 2 1 2
ては、例えば、ベンゼン環、ナフタレン環、ァズレン環、アントラセン環、フエナントレン 環、ビフエ二ル環、などが、また、複素環としては、例えば、イミダゾリン環、イミダゾー ル環、ベンゾイミダゾール環、 α ナフトイミダゾール環、 β ナフトイミダゾール環、 インドール環、イソインドール環、インドレニン環、イソインドレニン環、ベンゾインドレ ニン環、ピリジノインドレニン環、ォキサゾリン環、ォキサゾール環、イソォキサゾール 環、ベンゾォキサゾール環、ピリジノォキサゾール環、 a ナフトォキサゾール環、 j8 ナフトォキサゾール環、セレナゾリン環、セレナゾール環、ベンゾセレナゾール環、 β ナフトセレナゾール環、 13 ナフトセレナゾール環、チアゾリン環、チアゾール環 、イソチアゾール環、ベンゾチアゾール環、 β—ナフトチアゾール環、 β—ナフトチア ゾール環、テルラゾリン環、テルラゾール環、ベンゾテルラゾール環、 (X ナフトテル ラゾール環、 β ナフトテルラゾール環、さらには、アタリジン環、アントラセン環、イソ キノリン環、イソピロール環、イミダノキサリン環、インダンジオン環、インダゾール環、 インダリン環、ォキサジァゾール環、力ルバゾール環、キサンテン環、キナゾリン環、キ ノキサリン環、キノリン環、クロマン環、シクロへキサンジオン環、シクロペンタンジオン 環、シンノリン環、チォジァゾール環、チォォキサゾリドン環、チォフェン環、チォナフ テン環、チォバルビツール酸環、チォヒダントイン環、テトラゾール環、トリアジン環、 ナフチリジン環、ピぺラジン環、ピラジン環、ピラゾール環、ピラゾリン環、ビラゾリジン 環、ピラゾロン環、ピラン環、ピリジン環、ピリダジン環、ピリミジン環、ピリリウム環、ピロ リジン環、ピロリン環、ピロール環、フエナジン環、フエナントリジン環、フエナント口リン 環、フタラジン環、プテリジン環、フラザン環、フラン環、プリン環、ベンゾォキサジン環
、ベンゾピラン環、モルホリン環、口ダニン環などが挙げられる。 For example, a benzene ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, biphenyl ring, etc., and as a heterocyclic ring, for example, an imidazoline ring, an imidazole ring, a benzimidazole ring, an α naphtho ring, etc. Imidazole ring, β-naphthimidazole ring, indole ring, isoindole ring, indolenine ring, isoindolenin ring, benzoindolenin ring, pyridinoindolenin ring, oxazoline ring, oxazole ring, isoxazole ring, benzoxazole ring, Pyridinooxazole ring, a naphthoxazole ring, j8 naphthoxazole ring, selenazoline ring, selenazole ring, benzoselenazole ring, β naphthoselenazole ring, 13 naphthoselenazole ring, thiazoline ring, thiazole ring, Isothiazole ring, benzothia Ring, β-naphthothiazole ring, β-naphthothiazole ring, tellurazoline ring, tellurazole ring, benzotelrazole ring, (X naphthotelrazole ring, β naphthotelrazole ring, and atalidine ring, anthracene ring, isoquinoline Ring, isopyrrole ring, imidanoxaline ring, indandione ring, indazole ring, indalin ring, oxadiazole ring, force rubazole ring, xanthene ring, quinazoline ring, quinoxaline ring, quinoline ring, chroman ring, cyclohexanedione ring, cyclopentanedione ring , Cinnoline ring, thiadiazole ring, thixazolidone ring, thiophene ring, thionaphthene ring, thiobarbituric acid ring, thiohydantoin ring, tetrazole ring, triazine ring, naphthyridine ring, piperazine ring, pyrazine ring, pyrazole , Pyrazoline ring, virazolidine ring, pyrazolone ring, pyran ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrylium ring, pyrrolidine ring, pyrroline ring, pyrrole ring, phenazine ring, phenanthridine ring, phenanthorin ring, phthalazine ring , Pteridine ring, furazane ring, furan ring, purine ring, benzoxazine ring Benzopyran ring, morpholine ring, dandanine ring, and the like.
[0015] Z及び Zにおける置換基としては、例えば、メチル基、ェチル基、ビニル基、プロピ [0015] Examples of the substituent in Z and Z include a methyl group, an ethyl group, a vinyl group, and propylene.
1 2 1 2
ル基、イソプロピル基、イソプロぺ-ル基、 1 プロぺ-ル基、 2—プロぺ-ル基、 2— プロピ-ル基、ブチル基、イソブチル基、 sec—ブチル基、 tert ブチル基、 2—ブテ -ル基、 1, 3 ブタジェ-ル基、ペンチル基、イソペンチル基、ネオペンチル基、 ter t ペンチル基、 1ーメチルペンチル基、 2—メチルペンチル基、 2—ペンテ-ル基、 2 ペンテンー4 ィ-ル基、へキシル基、イソへキシル基、 5—メチルへキシル基、へ プチル基、ォクチル基、ノエル基、デシル基、ドデシル基などの脂肪族炭化水素基、 シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロへキ セニル基などの脂環式炭化水素基、フエ二ル基、 o トリル基、 m—トリル基、 p—トリ ル基、キシリル基、メシチル基、 o タメ-ル基、 m タメ-ル基、 p タメ-ル基、ビフ ェ-リル基などの芳香族炭化水素基、メトキシ基、エトキシ基、プロポキシ基、イソプロ ポキシ基、ブトキシ基、イソブトキシ基、 sec ブトキシ基、 tert ブトキシ基、ペンチ ルォキシ基、フエノキシ基などのエーテル基、メトキシカルボ-ル基、エトキシカルボ ニル基、プロポキシカルボ-ル基、ブトキシカルボ-ル基、ァセチル基、ベンゾィルォ キシ基などのエステル基、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、プロピルアミノ基、ジプロピルアミノ基、イソプロピルアミノ基、ジイソプロピ ルァミノ基、ブチルァミノ基、ジブチルァミノ基、イソブチルァミノ基、ジイソブチルアミ ノ基、 sec ブチルァミノ基、 tert ブチルァミノ基、ペンチルァミノ基、ジペンチルァ ミノ基、ァ-リノ基、 o トリイジノ基、 m—トルイジノ基、 p トルイジノ基、キシリジノ基 基、ジフヱ-ルァミノ基などのアミノ基、キノリル基、ピペリジノ基、ピリジル基、モルホリ ノ基などの複素環基、フルォロ基、クロ口基、ブロモ基、ョード基などのハロゲン基、ヒ ドロキシ基、カルボキシ基、スルフォン酸基、シァノ基、ニトロ基、さら〖こは、これらの組 合わせによる置換基が挙げられる。 Group, isopropyl group, isopropylene group, 1 propylene group, 2-propellyl group, 2-propyl group, butyl group, isobutyl group, sec —butyl group, tert butyl group, 2 —Butyl group, 1, 3 Butagel group, pentyl group, isopentyl group, neopentyl group, ter t pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group, 2 pentene group -Hexyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, Noel group, decyl group, dodecyl group and other aliphatic hydrocarbon groups, cyclopropyl group, cyclobutyl group, Cyclopentyl group, cyclohexyl group, cyclohexenyl group and other alicyclic hydrocarbon groups, phenyl group, o tolyl group, m -tolyl group, p-tolyl group, xylyl group, mesityl group, o-tame -Group, m-group, p-group , Aromatic hydrocarbon group such as biphenyl group, ether such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec butoxy group, tert butoxy group, pentyloxy group, phenoxy group Group, methoxycarbon group, ethoxycarbonyl group, propoxycarbon group, butoxycarbon group, acetyl group, benzoyl group, ester group, methylamino group, dimethylamino group, ethylamino group, jetamino group, propyl group Amino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec butylamino group, tert butylamino group, pentylamino group, dipentylamino group, amino-lino Group, o trii Dino group, m-toluidino group, p toluidino group, xylidino group, amino group such as diphenyl-lumino group, quinolyl group, heterocyclic group such as piperidino group, pyridyl group, morpholino group, fluoro group, black mouth group, A halogen group such as bromo group and iodine group, a hydroxyl group, a carboxy group, a sulfonic acid group, a cyano group, a nitro group, and arabic group may be substituted by a combination of these.
[0016] R乃至 Rは互いに同じか異なる脂肪族炭化水素基又は芳香族炭化水素基を表し [0016] R to R represent the same or different aliphatic hydrocarbon groups or aromatic hydrocarbon groups.
1 6 1 6
、脂肪族炭化水素基としては、例えば、メチル基、ェチル基、ビニル基、プロピル基、 イソプロピル基、イソプロぺ-ル基、 1 プロぺ-ル基、 2—プロぺ-ル基、 2—プロピ ニル基、ブチル基、イソブチル基、 sec ブチル基、 tert ブチル基、 2—ブテュル
基、 1, 3 ブタジェ-ル基、ペンチル基、イソペンチル基、ネオペンチル基、 tert— ペンチル基、 1ーメチルペンチル基、 2—メチルペンチル基、 2—ペンテ-ル基、 2— ペンテン 4 ィ-ル基、へキシル基、イソへキシル基、 5—メチルへキシル基、ヘプ チル基、ォクチル基、ノニル基、デシル基、ドデシル基などの脂肪族炭化水素基、シ クロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロへキセ ニル基などの脂環式炭化水素基などが挙げられ、芳香族炭化水素基としては、フエ -ル基、 o トリル基、 m—トリル基、 p トリル基、キシリル基、メシチル基、 o タメ- ル基、 m タメ二ル基、 p タメ二ル基、ビフヱ二リル基、ベンジル基、フヱネチル基な どが挙げられる。また、それら脂肪族炭化水素基又は芳香族炭化水素基は置換基を 有していてもよい。置換基としては、例えば、 Z及び Zにおける置換基と同じものが Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, a propyl group, an isopropyl group, an isopropyl group, a 1-propyl group, a 2-propyl group, and a 2-propyl group. Nyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2-butyl 1, 3, butagel group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentene group, 2-pentene-4-yl group, Hexyl, isohexyl, 5-methylhexyl, heptyl, octyl, nonyl, decyl, dodecyl and other aliphatic hydrocarbon groups, cyclopropyl, cyclobutyl, cyclopentyl, Examples thereof include alicyclic hydrocarbon groups such as cyclohexyl group and cyclohexenyl group. As aromatic hydrocarbon groups, there are phenol group, o tolyl group, m-tolyl group, p tolyl group, xylyl group. Group, mesityl group, o-tame group, m-tameyl group, p-tameryl group, biphenylyl group, benzyl group, and phenethyl group. Further, these aliphatic hydrocarbon groups or aromatic hydrocarbon groups may have a substituent. Examples of the substituent include, for example, the same substituents as those in Z and Z.
1 2 1 2
挙げられる。 Can be mentioned.
[0017] また、 Rと R、 Rと Rは結合し、 3乃至 8員環を形成することが出来る。 3乃至 8員環 [0017] R and R, and R and R can be bonded to form a 3- to 8-membered ring. 3 to 8 member ring
3 4 5 6 3 4 5 6
としては、炭素、酸素、硫黄、窒素原子を含んで形成される、シクロへキサン環、シク 口ペンタン環、シクロプロパン環、ジメチルシクロへサン環、テトラハイド口ピラン環、ピ ペリジン環、テトラハイドロチォピラン環などが挙げられる。 As a cyclohexane ring, a cyclopentane ring, a cyclopropane ring, a dimethylcyclohexane ring, a tetrahydran pyran ring, a piperidine ring, a tetrahydro ring, which contains carbon, oxygen, sulfur and nitrogen atoms. An example is a thiopyran ring.
[0018] R、 Rとしては、さらに、ェチルスルフォン酸及びそのァ-オン、プロピルスルフォン [0018] R and R further include ethyl sulfonic acid and its ion, propyl sulfone.
1 2 1 2
酸及びそのァ-オン、ブチルスルフォン酸及びそのァ-オン、 1-メチルプロピルスル フォン酸及びそのァ-オンなどのアルキルスルフォン酸基、酢酸及びそのァ-オン、 プロピオン酸及びそのァ-オンなどのアルキルカルボキシル基なども挙げられる。ま たそれが塩構造を有するときのカチオン種としては、リチウム、ナトリウム、カリウム等 の無機イオン及びトリェチルァミン、トリブチルァミン、モルホリン、ピぺリジン、ピロリジ ン、アンモニア等の有機イオンが挙げられる。 Alkyl sulfonic acid groups such as acid and its ion, butyl sulfonic acid and its ion, 1-methylpropylsulfonic acid and its ion, acetic acid and its ion, propionic acid and its ion, etc. And an alkyl carboxyl group. The cationic species when it has a salt structure includes inorganic ions such as lithium, sodium and potassium and organic ions such as triethylamine, tributylamine, morpholine, piperidine, pyrrolidine and ammonia.
[0019] Rは水素原子、又は置換基を表し、置換基としては、メチル基、ェチル基、ビュル 基、プロピル基、イソプロピル基、イソプロべ-ル基、 1 プロべ-ル基、 2—プロべ- ル基、 2—プロピ-ル基、ブチル基、イソブチル基、 sec ブチル基、 tert ブチル基 、 2 ブテュル基、 1, 3 ブタジェ-ル基、ペンチル基、イソペンチル基、ネオペンチ ル基、 tert ペンチル基、 1ーメチルペンチル基、 2—メチルペンチル基、 2—ペンテ -ル基、 2 ペンテンー4 ィ-ル基、へキシル基、イソへキシル基、 5—メチルへキ
シル基、ヘプチル基、ォクチル基、ノニル基、デシル基、ドデシル基などのアルキル 基、フエ-ル基、 o—トリル基、 m—トリル基、 p—トリル基、キシリル基などの芳香族炭 化水素基、ベンジル基、フエ-ルェチル基、フエ-ルプロピル基などのァリールアル キル基が挙げられ、これらのアルキル基、ァリール基、アルキルァリール基には、さら に、ァ-リノ基、アミノ基、アルキルアミノ基、ハロゲン基、ニトロ基、アルコキシ基、シァ ノ基、アルキル基などの置換基が結合してもよい。 Rは、上記の置換基の上記の置 換基の他に、任意に置換されたァ-リノ基、アミノ基、ハロゲン基、ニトロ基、アルコキ シ基、シァノ基、任意に置換されたアルキルアミノ基などを挙げることが出来る。 [0019] R represents a hydrogen atom or a substituent, and examples of the substituent include a methyl group, an ethyl group, a bur group, a propyl group, an isopropyl group, an isopropyl group, a 1 probe group, and a 2-probe group. Base group, 2-propyl group, butyl group, isobutyl group, sec butyl group, tert butyl group, 2 butyr group, 1, 3 butadiene group, pentyl group, isopentyl group, neopentyl group, tert pentyl group Group, 1-methylpentyl group, 2-methylpentyl group, 2-pentyl group, 2 pentene-4-yl group, hexyl group, isohexyl group, 5-methylhexyl group Aromatic carbonization such as alkyl group such as syl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group, phenol group, o-tolyl group, m -tolyl group, p-tolyl group and xylyl group Examples of the aryl group include a hydrogen group, a benzyl group, a phenyl group, and a phenylpropyl group. These alkyl group, aryl group, and alkylaryl group include, in addition, an arylino group, an amino group, A substituent such as an alkylamino group, a halogen group, a nitro group, an alkoxy group, a cyan group, or an alkyl group may be bonded. R represents, in addition to the above-described substituents of the above-mentioned substituents, an optionally substituted alino group, amino group, halogen group, nitro group, alkoxy group, cyano group, optionally substituted alkylamino group. Examples include groups.
[0020] Lは、メチン鎖部分と結合し、環状構造を形成するのに必要な原子群を表す。環状 構造としては、二重結合及び Z又はへテロ原子を 1又は複数有する、例えば、シクロ ブテン環、シクロペンテン環、シクロへキセン環、ベンゼン環、インドナフテン環、デヒ ドロデカリン環、ピリジン環、ジヒドロピリジン環、テトラヒドロピリジン環、フラン環、ジヒ ドロフラン環、チォフェン環、ジヒドロチォフェン環、へキサヒドロキノリン環などの単環 式又は縮合多環式のものが挙げられる。 [0020] L represents an atomic group necessary for binding to the methine chain moiety and forming a cyclic structure. Cyclic structures include double bonds and one or more Z or heteroatoms, such as cyclobutene ring, cyclopentene ring, cyclohexene ring, benzene ring, indonaphthene ring, dehydrodecalin ring, pyridine ring, dihydropyridine. Examples thereof include monocyclic or condensed polycyclic rings such as a ring, a tetrahydropyridine ring, a furan ring, a dihydrofuran ring, a thiophene ring, a dihydrothiophene ring, and a hexahydroquinoline ring.
[0021] Xm_は一般式 1を中性に保つ m価の対イオンを表し、 mは、 1乃至 3であり、中性に 保っために場合によっては存在しないことがある(この場合、一般式 1における cの値 は 0を表す)。対イオンとしては、例えば、六弗化燐酸イオン、ハロゲンイオン、燐酸ィ オン、過塩素酸イオン、過沃素酸イオン、六弗化アンチモン酸イオン、六弗化錫酸ィ オン、硼弗化水素酸イオン、四弗硼素酸イオンなどの無機酸イオンや、チォシアン酸 ィ才ン、ベンゼンスノレホン酸ィ才ン、ベンゼンジスノレフォン酸ィ才ン、ナフタレンスノレホ ン酸イオン、 ρ—トルエンスルホン酸イオン、アルキルスルホン酸イオン、ベンゼンカル ボン酸イオン、ベンゼンジカルボン酸イオン、ベンゼントリカルボン酸イオン、アルキ ルカルボン酸イオン、トリハロアルキルカルボン酸イオン、アルキル硫酸イオン、トリハ 口アルキル硫酸イオン、ニコチン酸イオンなどの有機酸イオン、さらには、ァゾ系、ビ スフェニルジチォ一ノレ系、チォカテコーノレキレート系、チオビスフエノレートキレート系 、ビスジオール—ひ—ジケトン系の金属錯体イオンなどが採用される。 [0021] X m_ represents an m-valent counter ion that keeps the general formula 1 neutral, and m is 1 to 3, and may not be present in some cases to keep neutral (in this case, The value of c in Equation 1 represents 0). Examples of the counter ion include hexafluorophosphate ion, halogen ion, phosphate ion, perchlorate ion, periodate ion, hexafluoroantimonate ion, hexafluorostannate ion, and boron hydrofluoric acid. Ions, inorganic acid ions such as tetrafluoroborate ion, thiocyanate, benzene sulphonate, benzene disulphonate, naphthalene sulphonate, ρ-toluene sulphonate , Alkyl sulfonate ions, benzene carbonate ions, benzene dicarboxylate ions, benzene tricarboxylate ions, alkyl carboxylate ions, trihaloalkyl carboxylate ions, alkyl sulfate ions, trialkyl alkyl sulfate ions, nicotinate ions, etc. Ions, as well as azo, bisphenyldithionole, thiocatecono Chelate, thiobis Hue methylate chelate, Bisujioru - Fei - a metal complex ion of diketone are employed.
[0022] そのうち、弗素原子を含む対イオン、例えば、六弗化燐酸イオン、硼弗化水素酸ィ オン、四弗硼素酸イオン、トリフルォロスルフォン酸ァ-オン、ノナフルォロブタンスル
フォン酸ァ-オン、ジ(トリフルォロメチルスルフォ -ル)イミドア-オン、ジ(2, 2, 2—ト リフルォロェチルスルフォ -ル)イミドア-オン、ジ (3, 3, 3, トリフルォロプロピルス ルフォ -ル)イミドア-オン、ジ(4, 4, 4 トリフルォロブチルスルフォ -ル)イミドア- オン、ジ(ペルフルォロェチルスルフォ -ル)イミドア-オン、ジ(ペルフルォロプロピ ルスルフォ -ル)イミドア-オン、ジ(ペルフルォロブチルスルフォ -ル)イミドア-オン 等の対イオンは、光学フィルターに用いる場合に、その製造時に使用する溶剤に対 する溶解性、或いは、光学フィルター内での安定性に優れていることから特に好まし い。 [0022] Among them, counter ions containing fluorine atoms, such as hexafluorophosphate ion, borohydrofluoride ion, tetrafluoroborate ion, trifluorosulfonate ion, nonafluorobutanesulfur Phosphonate, di (trifluoromethylsulfol) imido-one, di (2,2,2-trifluoroethylsulfol) imido-one, di (3, 3, 3, Trifluoropropyl sulfone) imido-one, di (4, 4, 4 trifluorobutylsulfol) imido-one, di (perfluoroethylsulfol) imido-one, di (perfluro) Counter ions such as isopropylsulfonyl) imido-one and di (perfluorobutylsulfol) imido-one are soluble in the solvent used in the production of optical filters. Or, it is particularly preferable because of its excellent stability in the optical filter.
[0023] この発明で用いるシァニン色素の具体例としては、例えば、化学式 1乃至化学式 2 57で表されるものが挙げられる。これらのシァニン色素は、波長 850nmより長波長、 好ましくは、波長 850乃至 lOOOnmの近赤外領域に吸収極大を有する。更に吸収極 大波長における分子吸光係数 (以下、吸収極大波長における分子吸光係数を「 ε」 と略記する。)も通常、 1 X 105以上と大きぐ逆に可視光部の吸収が小さいことから、 例えば、プラズマディスプレーなどの映像表示機器へ取り付ける前面部材へ用いると 、映像の三原色の色純度を損なうことなぐ映像表示機器から輻射される不用な近赤 外光を効果的に遮断するので、コントラストと色再現性に優れた高画質の映像が得ら れ、し力も、赤外線リモコンが近赤外線によって誤動作することもない。 [0023] Specific examples of cyanine dyes used in the present invention include those represented by chemical formula 1 to chemical formula 257, for example. These cyanine dyes have an absorption maximum in the near-infrared region having a wavelength longer than 850 nm, preferably from 850 to lOOOnm. Furthermore, the molecular extinction coefficient at the maximum absorption wavelength (hereinafter, the molecular extinction coefficient at the maximum absorption wavelength is abbreviated as “ε”) is usually larger than 1 X 10 5, but the visible light absorption is small. For example, when used on a front member attached to an image display device such as a plasma display, it effectively blocks unwanted near infrared light radiated from the image display device without impairing the color purity of the three primary colors of the image. High-quality images with excellent color reproducibility can be obtained, and the infrared remote control does not malfunction due to near infrared rays.
[0024] カロえて、これらのシァニン色素は、諸種の有機溶剤、とりわけ、ケトン系、ハロゲンィ匕 炭化水素系、エーテル系、エステル系の有機溶剤における溶解性が高いことから、 有機溶剤に溶解して前面部材の主体となる透明基材へ塗布する作業が容易となるう えに、自然光や人工光などの環境光に対する耐光性、耐環境性が大きいことから、 長期間用いても前面部材の遮光能が減弱し難い特徴がある。同様に自然光の内、 近赤外光を遮断する用途に用いても、同様の効果が期待できる。例示化合物として 、例えば、一般式 1 1乃至一般式 1 21で表される化合物が挙げられる。具体的な 化合物例を対応する表に示す。 [0024] Since these cyanine dyes are highly soluble in various organic solvents, especially ketone-based, halogenated hydrocarbon-based, ether-based, and ester-based organic solvents, they can be dissolved in organic solvents. Since it is easy to apply to the transparent base material, which is the main component of the front member, it is highly resistant to ambient light such as natural light and artificial light. There is a feature that the ability is difficult to attenuate. Similarly, similar effects can be expected when used for applications that block near-infrared light in natural light. Examples of the compound include compounds represented by general formulas 11 to 121. Specific examples of compounds are shown in the corresponding table.
[0025] 一般式 1 1 : [0025] General formula 1 1:
[0026] [表 1] [0026] [Table 1]
[0027] 一般式 1 [0027] General formula 1
[0028] [表 2] [0028] [Table 2]
一般式一 で表される化合物 Compound represented by general formula 1
は、フエニル基 Is a phenyl group
[0029] 一般式 1 3: [0029] General Formula 1 3:
[化 5] [Chemical 5]
[0030] [表 3]
化学式 No R 1 R2 R3 R4 R5 R6 R7 X一[0030] [Table 3] Chemical formula No R 1 R2 R3 R4 R5 R6 R7 X
37 C2H5 CH3 CH3 CH3 CH3 Ph (CF3S02)2N"37 C 2 H 5 CH 3 CH 3 CH 3 CH 3 Ph (CF 3 S0 2 ) 2 N "
38 CH3 CH3 CH3 CH3 CH3 CH3 Ph (CF3S02)2N~38 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 Ph (CF 3 S0 2 ) 2 N ~
39 CH3 CH3 CH3 CH3 CHa CH3 Ph PFR—39 CH 3 CH 3 CH 3 CH 3 CH a CH 3 Ph PF R —
40 2π5 CH2Ph CH3 CH2Ph CH3 Ph (CF3S02)2N—40 2 π 5 CH 2 Ph CH 3 CH 2 Ph CH 3 Ph (CF 3 S0 2 ) 2 N—
41 CH3 CH3 0 0 Ph (CF3S02)2N"41 CH 3 CH 3 0 0 Ph (CF 3 S0 2 ) 2 N "
42 C2H4Ph C2H4Ph CH3 C2H5 CH3 C2H5 P h C4F9S03"42 C 2 H 4 Ph C 2 H 4 Ph CH 3 C 2 H 5 CH 3 C 2 H 5 P h C 4 F 9 S0 3 "
43 C3H 6S03 CH3 CH3 CH3 CH3 P h - 43 C 3 H 6 S0 3 CH 3 CH 3 CH 3 CH 3 P h-
44 C2H5 C2H5 CH3 CH3 CH3 CH3 P h (CF3CF2S02)2N— 44 C 2 H 5 C 2 H 5 CH 3 CH 3 CH 3 CH 3 P h (CF 3 CF 2 S0 2 ) 2 N—
[0031] 一般式 1 4 : [0031] General Formula 1 4:
[化 6] [Chemical 6]
[0032] [表 4] [0032] [Table 4]
1—4 1-4
[化 7] [Chemical 7]
[0034] [表 5] [0034] [Table 5]
[0035] 一般式 1 6: [0035] General Formula 1 6:
[化 8]
[Chemical 8]
[0036] [表 6] [0036] [Table 6]
1 6 1 6
[0037] —般式 1 7: [0037] — General Formula 1 7:
[化 9]
[Chemical 9]
[0038] [表 7] [0038] [Table 7]
一般式 1 7で表される化合物 Compound represented by general formula 17
* Phは、フ: ニル基 * Ph is fu: Nyl group
[0039] 一般式 1 [0039] General formula 1
[0040] [表 8]
1_8 [0040] [Table 8] 1_8
* Ph * Ph
[0041] 一般式 1 9: [0041] General Formula 1 9:
[0042] [表 9] [0042] [Table 9]
1一 9 1 1 9
[0044] [表 10] [0044] [Table 10]
1一 10 1 1 10
* Ph * Ph
[0045] 一般式 1 11 : [0045] General Formula 1 11:
[化 13]
[Chemical 13]
[0046] [表 11] 1 11 [0046] [Table 11] 1 11
< Ph <Ph
[0047] 一般式 1 12: [0047] General Formula 1 12:
[化 14] [Chemical 14]
[0048] [表 12]
1一 12 [0048] [Table 12] 1 1 12
[0049] 一般式 1 13: [0049] General Formula 1 13:
[化 15] [Chemical 15]
[0050] [表 13]
1_13 [0050] [Table 13] 1_13
*Ph * Ph
[0051] 一般式 1 14: [0051] General Formula 1 14:
[0052] [表 14] [0052] [Table 14]
1_14 1_14
*Ph * Ph
[0053] 一般式 1 15: [0053] General Formula 1 15:
[0054] [表 15] 1_15 [0054] [Table 15] 1_15
' Ph 'Ph
[0055] 一般式 1 16: [0055] General Formula 1 16:
[化 18] [Chemical 18]
[0056] [表 16]
1_ 16 [0056] [Table 16] 1_ 16
: Ph : Ph
[0057] 一般式 1 17: [0057] General Formula 1 17:
[0058] [表 17] [0058] [Table 17]
一 One
* Ph * Ph
[0059] 一般式 1 18: [0059] General Formula 1 18:
[化 20]
[Chemical 20]
[0060] [表 18] 1 18 [0060] [Table 18] 1 18
[0061] 一般式 1 [0061] General formula 1
[化 21] [Chemical 21]
[0062] [表 19] 1 _ 19 [0062] [Table 19] 1 _ 19
化学式 No R1 R2 3 4 R5 R6 R7 X" Chemical Formula No R1 R2 3 4 R5 R6 R7 X "
234 2H5 C2H5 CH3 CH3 CH3 CH3 Ph (CF,S0?)?N"234 2 H 5 C 2 H 5 CH 3 CH 3 CH 3 CH 3 Ph (CF, S0 ? ) ? N "
235 CH3 CH3 C2H5 CH3 C2H5 CH3 Ph (CFaS0?)?N"235 CH 3 CH 3 C 2 H 5 CH 3 C 2 H 5 CH 3 Ph (CF a S0 ? ) ? N "
236 CH3 CH3 CH3 CH3 CH3 CH3 Ph PFfi―236 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 Ph PF fi ―
237 C2H5 C2H5 CH2Ph CH3 CHzPh CH3 Ph (CF3S02)?N"237 C 2 H 5 C 2 H 5 CH 2 Ph CH 3 CH z Ph CH 3 Ph (CF 3 S0 2 ) ? N "
238 CH3 C2H5 0 0 Ph (CF3S02)2N"238 CH 3 C 2 H 5 0 0 Ph (CF 3 S0 2 ) 2 N "
239 C2H4Ph C2H4Ph CH3 C2H5 CH3 C2H5 Ph C S(239 C 2 H 4 Ph C 2 H 4 Ph CH 3 C 2 H 5 CH 3 C 2 H 5 Ph CS (
240 eS 0 CH2Ph CH3 CH2Ph CH3 Ph -240 e S 0 CH 2 Ph CH 3 CH 2 Ph CH 3 Ph-
241 C2H5 C2H5 CH3 CH3 CH3 CH3 Ph (CF¾CF?S0?)?N"
[0063] 一般式 1一 20 : 241 C 2 H 5 C2H5 CH 3 CH 3 CH 3 CH 3 Ph (CF ¾ CF ? S0 ? ) ? N " [0063] General formula 1-20:
[化 22] [Chemical 22]
[0064] [表 20] [0064] [Table 20]
1一 20 1 1 20
[0065] 一般式 1一 21: [0065] Formula 1 1 21:
[化 23] [Chemical 23]
[0066] [表 21]
1_21 [0066] [Table 21] 1_21
* Ph * Ph
[0067] 本発明のシァニン色素は、エフ'ェム 'ハーマー (F. M. Harmer)著、「ヘテロサイク リック 'コンパゥンズーシァニンダイズ 'アンド ·リレイテッド'コンパゥンズ (Heterocycli c ·し ompounds · Cynine · Dyes · and · Related ·じ ompounds)」、ンョン ·ゥイリ ~~ · 7 ンド 'サンズ社 Clohn 'Wiley ' & ' Sons)、 1964年発行、およびデ一'ェム'スターマ 一 (D. M. Sturmer)著、「ヘテロサイクリック 'コンパゥンズ一スペシャル 'トツビクス'ィ ン ·ヘア口サイクリック ·ケ^ストリ一 (Heterocyclic · Compounds― Special · topics · i η· heterocyclic ' chemistry)」、第 18章、第 14節、 482〜515頁、ジョン ·ウィリ^ ~ · アンド'サンズ社 (John 'Wiley & ' Sons)、 1977年発行、「口ッズ 'ケミストリ一'ォブ •カーボン ·コンノ ゥンズ (Rodds ' Chemistry' of ' Carbon' Compoundsゝ 2nd. Ed . Vol. IV、 1977年発行、第 15章、 369〜422頁、エルセピア,サイエンス'ノ ブリツ ク.カンパ-一.インク(Elsevier · Science · Publishing · Company · Inc)社、特開平 6— 313939号公報および特開平 5— 88293号公報等を参考にして容易に合成で きる。 [0067] The cyanine dyes of the present invention are produced by FM Harmer, "Heterocyclic ccompine saponins" and related 'compounds, Cynine Dyes, and · Related · ompounds), Nyung Wuili ~~ · 7 and 'Sons Clohn' Wiley '&' Sons), published in 1964, and by DM Sturmer, 'Hetero Cyclic 'Compounds 1 Special' Tsubix'in · Hair mouth cyclic · Heterocyclic · Compounds- Special · topics · i η · cyclic 'chemistry ", Chapter 18, Section 14, 482-515 Page, John Wiley & Sons, published in 1977, “Rodds 'Chemistry' of 'Carbon' Compoundsゝ 2nd. Ed. Vol. IV, published in 1977, Chapter 15, Pp. 369-422, referring to Elsevier, Science, Publishing, Company, Inc., JP-A-6-313939, JP-A-5-88293, etc. And can be easily synthesized.
[0068] また、本発明のシァニン色素を含んでなる遮光剤には、安定化剤を含有してもよく 、安定化剤としては、例えば、特開昭 60— 234892号公報、特開平 5— 43814号公 報、特開平 6— 239028号公報、特開平 9— 309886号公報、特開平 10— 45757 号公報等に記載のジチオール金属錯体塩、ジモ-ゥム塩等が挙げられる。 [0068] The light-shielding agent containing the cyanine dye of the present invention may contain a stabilizer. Examples of the stabilizer include, for example, JP-A-60-234892 and JP-A-5- No. 43814, JP-A-6-239028, JP-A-9-309886, JP-A-10-45757, and the like.
[0069] ジチオール金属錯体塩としては、一般式 2で表わされるジチオール金属錯体が挙 げられる。 [0069] Examples of the dithiol metal complex salt include a dithiol metal complex represented by the general formula 2.
[0071] 一般式 2における R 乃至 R はそれぞれ水素原子、アルキル基、ァリール基、シァ [0071] R 1 to R 4 in the general formula 2 are a hydrogen atom, an alkyl group, an aryl group, and a shear group, respectively.
10 13 10 13
ノ基等の置換基を挙げることが出来る。また、 R と R 、R と R が互いに連結してベ And a substituent such as a group. R and R, and R and R are connected to each other.
10 11 12 13 10 11 12 13
ンゼン環またはナフタレン環などの芳香環を形成することが出来、これら芳香環は置 換基を有してもよい。また、置換基としては、例えば、一般式 1における芳香環に結合 する置換基と同じものが挙げられる。 An aromatic ring such as a benzene ring or a naphthalene ring can be formed, and these aromatic rings may have a substituent. Examples of the substituent include the same substituents as those bonded to the aromatic ring in the general formula 1.
[0072] Mは、周期表の II族から IV族の金属をあげることが出来る。そのうち、 Cr、 Mn、 Fe 、 Co、 Ni、 Cu、 Zn、 Pd、 Moまたは Cd等の遷移金属が好ましぐさらに好ましくは、 F e、 Co、 Cu、 Niまたは Znである。 [0072] M is a group II to group IV metal in the periodic table. Of these, transition metals such as Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Mo, and Cd are preferable, and Fe, Co, Cu, Ni, and Zn are more preferable.
[0073] nは一般式 2を中性に保つカチオンである。カチオンの例としては 4級アンモ-ゥム 塩または 4級ホスホ-ゥム塩が挙げられる。 4級アンモ-ゥム塩としては、テトラメチル アンモ-ゥム、テトラエチルアンモ-ゥム、テトラプチルアンモ-ゥム、ォクチルトリェチ ルアンモ-ゥム、フエ-ルトリメチルアンモ-ゥム、トリフエ-ルブチルアンモ-ゥム、トリ フエ-ルペンジルアンモ-ゥム、テトラフエ-ルアンモ-ゥムを挙げることが出来る。 4 級ホスホ-ゥム塩としては、テトラメチルホスホ-ゥム、テトラエチルホスホ-ゥム、テト ラブチノレホスホニゥム、ォクチルトリェチノレホスホニゥム、フエニルトリメチノレホスホニゥ ム、トリフエ-ルブチルホスホ-ゥム、トリフエ-ルペンジルホスホ-ゥム、テトラフエ二 ルホスホ-ゥムを挙げることが出来る。ただし、金属錯体自身が中性の際には存在し ない。 [0073] n is a cation that keeps Formula 2 neutral. Examples of cations are quaternary ammonium salts or quaternary phosphonium salts. The quaternary ammonia salts include tetramethyl ammonium, tetraethyl ammonium, tetraptyl ammonium, octyltrileum ammonia, trimethyl ammonium ammonia, and tributylbutyl ammonium. Mental, triphenyl penumum and tetraferumum. The quaternary phosphonium salts include tetramethylphosphonium, tetraethylphosphonium, tetrobinchinosephosphonium, octyltrichinenophosphonin, phenyltrimethinorephosphonium, triphenyl. -Rubutyl phosphor, triphenyl pendyl phosphor and tetraphenyl phosphor. However, it does not exist when the metal complex itself is neutral.
[0074] 具体的な例としては以下の化学式 258乃至化学式 263のものが挙げられる。 [0074] Specific examples include those represented by the following chemical formulas 258 to 263.
[0075] 化学式 258 :
[0075] Chemical Formula 258:
[0076] 化 [0076]
[0077] 化学式 260: [0077] Chemical Formula 260:
[化 27] [Chemical 27]
(C4H9)4N + (C 4 H 9 ) 4 N +
[0079] 化学式 262 : [0079] Formula 262:
[化 29] [Chemical 29]
[0080] 化学式 263 : [0080] Chemical Formula 263:
[化 30] [Chemical 30]
[0081] これらの金属錯体安定化剤はそのまま、本発明の遮光剤に混合し併用でき、塩構 造のものは、本発明のァ-オン種と置換して用いることができる。 [0081] These metal complex stabilizers can be used as they are by mixing with the light-shielding agent of the present invention, and those having a salt structure can be used by substituting the char-on species of the present invention.
[0082] また、ジィモ -ゥム塩としては、一般式 3で表わされるジィモ -ゥム塩が挙げられる。 [0082] Examples of the dimum salt include a dimum salt represented by the general formula 3.
[0083] 一般式 3 : [0083] General Formula 3:
[化 31]
[Chemical 31]
N(Rc)2 N (Rc) 2
[0084] 一般式 3における、 Rcは、アルキル基、ハロゲン化アルキル基、シァノアルキル基、 ァリール基、ヒドロキシル基、フエ-ル基およびフエ-ルアルキル基力 選ばれる置換 基であり、これらは同一であっても異なっていてもよい。 Rcとしては、上記置換基であ れば特に限定はされないが、炭素数 1〜8の直鎖若しくは側鎖を有するアルキル基、 ハロゲンィ匕アルキル基、シァノアルキル基等が好ましぐ炭素数 2〜6の直鎖アルキ ル基が特に好ましい。特に好ましいものの具体例としては、例えば、ェチル基、プロピ ル基、ブチル基、アミル基、イソプロピル基、イソブチル基、イソアミル基等が挙げられ る。また、好ましい別の例として、フエニルアルキル基を挙げることも出来る。フエニル アルキル基において、アルキル基の炭素数は、 1〜8であることが特に好ましい。更に 、フエ-ルアルキル基におけるフ -ル基は、置換基を有していなくてもよいが、アル キル基、水酸基、スルホン酸基、アルキルスルホン酸基、ニトロ基、アミノ基、アルコキ シ基、ハロゲン化アルキル基及びハロゲン力 なる群力 選ばれる少なくとも 1種の置 換基を有していてもよい。このうち、置換基を有していないフエニル基が好ましぐ力 かるフエ-ルアルキル基としては、ベンジル基、フエネチル基、フエ-ルプロピル基、 フエ二ルー a メチルプロピル基、フエ-ルー β メチルプロピル基、フエ-ルブチ ル基、フエ-ルペンチル基、フエ-ルォクチル基等が挙げられる。特に、ベンジル基 及びフ ネチル基が特に好まし 、。 [0084] In the general formula 3, Rc is a substituent selected from an alkyl group, a halogenated alkyl group, a cyanoalkyl group, a aryl group, a hydroxyl group, a phenol group and a phenylalkyl group, and these are the same. Or different. Rc is not particularly limited as long as it is the above-mentioned substituent, but an alkyl group having a straight chain or a side chain having 1 to 8 carbon atoms, a halogenated alkyl group, a cyanoalkyl group, etc. are preferred. The linear alkyl group is particularly preferred. Specific examples of particularly preferable ones include ethyl group, propyl group, butyl group, amyl group, isopropyl group, isobutyl group, isoamyl group and the like. Moreover, a phenylalkyl group can also be mentioned as another preferable example. In the phenylalkyl group, the alkyl group preferably has 1 to 8 carbon atoms. Further, the fur group in the phenyl alkyl group may not have a substituent, but an alkyl group, a hydroxyl group, a sulfonic acid group, an alkyl sulfonic acid group, a nitro group, an amino group, an alkoxy group, The halogenated alkyl group and the group power of halogen power may have at least one substituent selected. Among Cal phenyl group preferred tool force does not have a substituent Hue - The Ruarukiru group, a benzyl group, phenethyl group, Hue - Rupuropiru group, phenylene Lou a methylpropyl group, Hue - Lou β methylpropyl Group, a phenylbutyl group, a phenylpentyl group, a phenyloctyl group, and the like. Particularly preferred are benzyl and phenethyl groups.
[0085] Ζは塩を形成するためのァ-オンであり、一般式 5を中性に保つァ-オン種である。 [0085] Ζ is a key-on for forming a salt and is a key-on species that keeps the general formula 5 neutral.
このァニオン種は有機酸、及び無機酸であり、特に限定されない。 The anion species are an organic acid and an inorganic acid, and are not particularly limited.
[0086] ジィモ -ゥム塩の具体的な例としては化学式 264乃至化学式 268が挙げられる。 [0086] Specific examples of the dim-um salt include Chemical Formula 264 to Chemical Formula 268.
[0088] 化学式 265: [0088] Formula 265:
[化 33] [Chemical 33]
[0089] 化学式 266: [0089] Chemical Formula 266:
(C4H9)2N (C 4 H 9 ) 2 N
[0090] 化学式 267: [0090] Formula 267:
[化 35] [Chemical 35]
[0091] 化学式 268: [0091] Chemical Formula 268:
[化 36]
[Chemical 36]
[0092] さらに、上述したジチオール金属錯体及びジィモ -ゥム塩は、安定化剤として組み 合わせて用いることも出来る。またその際に、それぞれ、異なる 2種以上を併用して用 いることも出来る。 [0092] Further, the above-mentioned dithiol metal complex and dimonium salt can be used in combination as a stabilizer. At that time, two or more different types can be used in combination.
[0093] さて、斯カるシァニン色素を含有する遮光剤を用いる本件発明の光学フィルターに ついて説明すると、この発明の使用部材は、少なくとも、使用部材の主体となる透明 基材と、遮光剤として一般式 1で表されるシァニン色素とによって構成される。なお、 この発明でいう「遮光剤」とは、斯カる使用部材へ用いることによって、映像表示機器 力 放出される不用な光、或いは自然光、とりわけ、近赤外領域の光を実質的に遮 断する、吸光性有機化合物又は吸光性有機化合物を含有する組成物を意味するも のとする。本発明の光学フィルターにおいて、上記のシァニン色素の使用量はそれ ぞれ、通常、光学フィルターの単位面積当たり l〜1000mgZm2の範囲であり、好ま しくは 5〜: LOOmgZm2である。 [0093] Now, the optical filter of the present invention using the light-shielding agent containing such cyanine dye will be described. The used member of the present invention includes at least a transparent base material as a main component of the used member and a light-shielding agent. And a cyanine dye represented by the general formula 1. The “light-shielding agent” as used in the present invention is used for such a member to substantially block unnecessary light or natural light, particularly light in the near-infrared region, emitted by video display equipment. A light-absorbing organic compound or a composition containing a light-absorbing organic compound is meant. In the optical filter of the present invention, the amount of the above Shianin dyes respectively are generally in the range of per unit area L~1000mgZm 2 of the optical filter, is favored properly 5: a LOOmgZm 2.
[0094] 透明基材としては、全可視領域において、光透過率が 50%以上、好ましくは、 70 %以上の、例えば、 ABS榭脂、ポリアクリル酸榭脂、ポリアクリル酸エステル榭脂、ポ リアリレート榭脂、ポリエステル榭脂、ポリエーテルスルホン榭脂、ポリ塩化ビニル榭脂
、ポリオレフイン榭脂、ポリカーボネート榭脂、ポリ酢酸ビュル榭脂、ポリスチレン榭脂 、ポリメタクリル酸榭脂、ポリメタクリル酸エステル榭脂、さらには、ガラス、セラミックな どが挙げられ、必要に応じて、これらは適宜組み合わせて用いられる。これらのうちで 、光透過率及び機械的強度の点で、ポリアクリル酸榭脂、ポリアクリル酸エステル榭 脂、ポリアリレート榭脂、ポリエステル榭脂、ポリエーテルスルホン榭脂、ポリオレフイン 榭脂、ポリカーボネート榭脂、ポリメタクリル酸榭脂、ポリメタクリル酸エステル榭脂が 特に好ましい。 [0094] The transparent base material has a light transmittance of 50% or more, preferably 70% or more in the entire visible region, for example, ABS resin, polyacrylate resin, polyacrylate ester resin, Realylate resin, polyester resin, polyethersulfone resin, polyvinyl chloride resin Polyolefin resin, polycarbonate resin, polyacetic acid resin resin, polystyrene resin, polymethacrylic acid resin, polymethacrylic acid ester resin, and glass, ceramic, etc. Are used in appropriate combination. Among these, in terms of light transmittance and mechanical strength, polyacrylic acid resin, polyacrylic acid ester resin, polyarylate resin, polyester resin, polyethersulfone resin, polyolefin resin, polycarbonate resin. Particularly preferred are fats, polymethacrylic acid coffins and polymethacrylic ester coffins.
[0095] この発明の光学フィルタ一は、一般式 1で表される、シァニン色素を斯力る透明基 材へ混合した後、使用部の形状に応じた、例えば、フィルム状、シート状、パネル状 などに成形するか、あるいは、使用部の形状に応じてフィルム状、シート状、パネル 状などに成形しておいた透明基材の片面又は両面に密着させて一般式 1乃至 3で表 される、シァニン色素による遮光層を形成する。透明基材の厚みとしては、透明基材 の材質や使用部の面積にもよるけれども、強度の点からは、通常、 0. 5mm以上、好 ましくは、 1mm以上に、一方、質量の点からは、通常、 10mm以下、好ましくは、 5m m以下の範囲で加減する。使用の状況によっては、使用部へ透明基材を直接取り付 けるのではなぐ透明基材を使用部の形状に応じたガラス板などへ一旦貼合し、その ガラス板を使用部へ取り付けることがある。斯カる場合には、透明基材を厚さが比較 的薄い、例えば、フィルム又はシート状に形成し、その片面へ透明基材をガラス板へ 貼合するための粘着層などを形成する。 The optical filter according to the present invention includes, for example, a film shape, a sheet shape, a panel, and the like, which are represented by the general formula 1, and after mixing the cyanine dye into such a transparent base material, It is expressed by general formulas 1 to 3 in close contact with one or both sides of a transparent substrate that has been formed into a film, sheet, panel, etc. A light-shielding layer of cyanine dye is formed. Although the thickness of the transparent base material depends on the material of the transparent base material and the area of the used part, from the viewpoint of strength, it is usually 0.5 mm or more, preferably 1 mm or more, while the point of mass. Is usually adjusted within a range of 10 mm or less, preferably 5 mm or less. Depending on the situation of use, the transparent base material may not be directly attached to the use part, but the transparent base material may be bonded once to a glass plate or the like according to the shape of the use part, and the glass plate may be attached to the use part. is there. In such a case, the transparent substrate is formed to be relatively thin, for example, in the form of a film or a sheet, and an adhesive layer or the like for bonding the transparent substrate to a glass plate is formed on one side thereof.
[0096] 透明基材ヘシァニン色素を混合する前者の方法においては、例えば、透明基材と シァニン色素とを溶融混練し、必要に応じて、ー且ペレット状などにした後、押出成 形、射出成形、プレス成形などの方法により、映像表示機器における表示部の形状 に応じて成形するか、あるいは、透明基材の原料モノマーとシァニン色素とを混合し 、表示部の形状に応じて注型重合させる。 [0096] In the former method of mixing the transparent base material hesyanin dye, for example, the transparent base material and cyanine dye are melt-kneaded and, if necessary, made into pellets, etc., and then extrusion molding, injection Molding, press molding, etc. depending on the shape of the display part in the video display device, or mixing the raw material monomer and cyanine dye of the transparent substrate and casting polymerization according to the shape of the display part Let
[0097] 一方、透明基材へ密着させてシァニン色素の層を設ける後者の方法においては、 例えば、必要に応じて、バインダーを共存させて、シァニン色素を、例えば、クロロホ ルム、シクロへキサノン、ェチルメチルケトン、イソプロピルメチルケトンをはじめとする ケトン系、ハロゲン化炭化水素系、エチレングリコールモノプロピルエーテルをはじめ
とするエーテル系、エステル系などの適宜有機溶剤に溶解又は分散させ、使用部の 形状に応じて、例えば、フィルム状、シート状、パネル状などに成形しておいた透明 基材の片面又は両面へ直接塗布するか、あるいは、同様にして調製した溶液又は分 散液を透明基材におけると同様の材質のフィルム又はシート^ ^一且塗布した後、そ のフィルム又はシートを使用部の形状に応じて成形しておいた透明基材の片面又は 両面へ貼合する。 [0097] On the other hand, in the latter method of providing a cyanine dye layer in close contact with a transparent substrate, for example, if necessary, a cyanine dye can be used in the presence of a binder, for example, chloroform, cyclohexanone, Ethyl methyl ketone, isopropyl methyl ketone and other ketones, halogenated hydrocarbons, ethylene glycol monopropyl ether One or both sides of a transparent base material that is dissolved or dispersed in an appropriate organic solvent such as an ether type or an ester type and formed into, for example, a film shape, a sheet shape, or a panel shape, depending on the shape of the use part Apply the solution or dispersion prepared in the same way to the film or sheet of the same material as on the transparent substrate, and then apply the film or sheet to the shape of the part to be used. Adhere to one or both sides of the transparent substrate that has been molded accordingly.
[0098] ノインダーとしては、例えば、エチレン 酢酸ビニル共重合榭脂、エチレンービ- ルアルコール共重合榭脂、酢酸セルロース系榭脂、酢酸ビニル榭脂、セルロース系 榭脂、ナイロン、フエノール系榭脂、フエノキシ榭脂、ポリエステル榭脂、ポリェチルメ タクリレート榭脂、ポリカーボネート榭脂、ポリスチレン榭脂、ポリスルホン樹脂、ポリビ -ルプチラール榭脂、ポリメチルメタタリレート榭脂などが挙げられ、必要に応じて、こ れらは適宜組み合わせて用いられる。斯カるバインダーは、この発明のシァニン色素 に対して、質量比で、通常、 10乃至 1, 000倍、好ましくは、 50乃至 500倍用いられ る。シァニン色素を分散液にして塗布する場合には、固状のシァニン色素を粒子径 0 . 1乃至 10 m、好ましくは、 0. 5乃至 5 mの微粒子にして分散させる。 [0098] Examples of the noinder include ethylene-vinyl acetate copolymer resin, ethylene-vinyl alcohol copolymer resin, cellulose acetate-based resin, vinyl acetate resin, cellulose-based resin, nylon, phenol-based resin, and phenoxy. Examples of these include resin, polyester resin, polyethylene methacrylate resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyvinylpropylene resin, and polymethylmetatalate resin. Used in combination as appropriate. Such a binder is usually used in a mass ratio of 10 to 1,000 times, preferably 50 to 500 times with respect to the cyanine dye of the present invention. When the cyanine dye is applied as a dispersion, the solid cyanine dye is dispersed as fine particles having a particle diameter of 0.1 to 10 m, preferably 0.5 to 5 m.
[0099] シァニン色素を含有する溶液や分散液を透明基材などへ塗布するには、斯界にお いて汎用される、例えば、デイツビング法、フローコート法、スプレー法、バーコート法 、グラビアコート法、ロールコート法、ブレードコート法、エアーナイフコート法などが適 用され、必要に応じて、これらは適宜組み合わせて適用される。 [0099] In order to apply a solution or dispersion containing a cyanine dye to a transparent substrate or the like, for example, a dubbing method, a flow coating method, a spray method, a bar coating method, a gravure coating method, which is widely used in the field. A roll coating method, a blade coating method, an air knife coating method, and the like are applied, and these are applied in appropriate combinations as necessary.
[0100] この発明の遮光剤は、先に挙げた安定化剤を含めて、この発明の目的を逸脱しな い範囲で、一般式 1で表される、シァニン色素とともに、斯界において汎用される、例 えば、アミ-ゥム塩系化合物、ァミノ化合物、アミノチオールニッケル錯体系化合物、 アントラキノン系化合物、ィモ-ゥム系化合物、シァニン系化合物、ジィモ -ゥム系化 合物、ジチオールニッケル錯体系化合物、トリアリルメタン系化合物、ナフトキノン系 化合物、ニトロソ化合物及びその金属塩、フタロシアニン系化合物、カーボンブラック 、酸化インジウム錫、酸化アンチモン錫などを含有する近赤外線吸収剤、ベンゾトリア ゾール化合物、ベンゾフエノン化合物、ヒドロキシベンゾエート化合物、酸化チタン、 酸化亜鉛、酸化セリウム、酸化鉄、硫酸バリウムなどを含有する紫外線吸収剤、さら
には、酸化防止剤、難燃化剤、安定剤、滑剤、帯電防止剤、耐熱老化防止剤、離型 剤の 1又は複数を含んでいてもよい。この発明のシァニン色素は、上記のごとき近赤 外線吸収剤や紫外線吸収剤と併用すると、これらに含まれる有機色素化合物の耐光 性を著明に改善し、それらが自然光、人工光などの環境光によって退色、変性、分 解されるのを効果的に抑制する。なお、近赤外線を遮断するこの発明のシァニン色 素は、単独又は近赤外線を吸収する他の化合物と組み合わせて、近赤外線吸収剤 若しくは近赤外線遮断剤として有利に用いることができる。 [0100] The light-shielding agent of the present invention is widely used in this field together with the cyanine dye represented by the general formula 1 within a range not departing from the object of the present invention, including the stabilizers listed above. For example, amino salt compounds, amino compounds, aminothiol nickel complex compounds, anthraquinone compounds, imumum compounds, cyanine compounds, dimonium compounds, dithiol nickel complexes Systemic compounds, triallylmethane compounds, naphthoquinone compounds, nitroso compounds and their metal salts, phthalocyanine compounds, carbon black, indium tin oxide, near infrared absorbers containing antimony tin oxide, benzotriazole compounds, benzophenone compounds, Hydroxybenzoate compound, titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate UV absorber containing such, further May contain one or more of an antioxidant, a flame retardant, a stabilizer, a lubricant, an antistatic agent, a heat resistant antiaging agent, and a release agent. The cyanine dyes of the present invention, when used in combination with near-infrared absorbers and ultraviolet absorbers as described above, markedly improve the light resistance of the organic dye compounds contained in these dyes. Effectively suppresses discoloration, denaturation, and decomposition. The cyanine dye of the present invention that blocks near-infrared rays can be advantageously used as a near-infrared absorbing agent or a near-infrared blocking agent alone or in combination with other compounds that absorb near-infrared rays.
[0101] また、この発明の光学フィルタ一は、一般式 1で表される、シァニン色素とともに、必 要に応じて、斯界において汎用される、例えば、銀、銀—パラジウム合金、酸化イン ジゥム、酸化インジウム一酸化錫混合物 (ITO)、酸化亜鉛などを含有する電磁波遮 断剤、金属酸化物、金属弗化物、金属珪化物、金属硼化物、金属炭化物、金属窒 化物、金属硫化物などを含有する反射防止剤などの 1又は複数と併用することを妨 げない。これらの材料は、通常、例えば、真空蒸着法、スパッタリング法、イオンプレ 一ティング法、イオンビームアシスト法などの方法により、透明基材上へシァニン色素 による遮光層とは独立した層として形成する力 あるいは、透明基材におけると同様 の材質のフィルム又はシート上へ紫外線遮断層、電磁波遮断層、反射防止層などの [0101] Further, the optical filter of the present invention, together with the cyanine dye represented by the general formula 1, is generally used in the field as necessary, for example, silver, silver-palladium alloy, indium oxide, Contains indium oxide tin oxide (ITO), electromagnetic wave shielding agent containing zinc oxide, metal oxide, metal fluoride, metal silicide, metal boride, metal carbide, metal nitride, metal sulfide, etc. Do not interfere with the use of one or more anti-reflective agents. These materials are usually capable of forming as a layer independent of the light-shielding layer by cyanine dye on the transparent substrate by a method such as vacuum deposition, sputtering, ion plating, or ion beam assist. On the film or sheet of the same material as in the transparent substrate, the UV blocking layer, electromagnetic wave blocking layer, antireflection layer, etc.
1又は複数を形成し、そのフィルム又はシートを透明基材へ貼合する。 One or more are formed, and the film or sheet is bonded to a transparent substrate.
[0102] さらに、この光学フィルタ一は、必要に応じて、ぎらつきを抑え、視野角を広げるた めのノングレア層、表面を保護するためのハードコート層、光学フィルターを映像表 示機器やガラス板などへ取り付けるための粘着層などの 1又は複数を設けることを妨 げない。 [0102] Furthermore, this optical filter is provided with a non-glare layer for suppressing glare and widening the viewing angle, a hard coat layer for protecting the surface, and an optical filter, as required. It does not interfere with the provision of one or more adhesive layers, etc. for attaching to a plate.
[0103] 斯くして得られるこの発明の光学フィルタ一は、一般式 1で表される、シァニン色素 において、遮断すべき光の波長に応じた適宜の吸収域を有するものを選択すること によって、映像の三原色の色純度を損なうことなぐ映像表示機器から輻射される近 赤外領域の不用な光、とりわけ、プラズマディスプレーにおける近赤外線などを選択 的に遮断するので、コントラストと色再現性に優れた高画質の映像が得られ、しかも、 赤外線リモコンが近赤外線によって誤動作することもない。この発明の光学フィルタ 一を適用し得る映像表示機器としては、例えば、ブラウン管を用いる直視型テレビ、
プラズマディスプレー、電界発光ディスプレーなどを用いる発光型パネル方式のテレ ビ、液晶ディスプレーを用いる非発光型パネル方式のテレビ、液晶プロジェクターが 内蔵されたリアプロジェクシヨン方式のテレビなどが挙げられる。これらのうちでも、こ の発明の光学フィルタ一は、原理上、不用な光を輻射し易いプラズマディスプレーや 電界発光ディスプレーなどを用いる発光型パネル方式のテレビへ極めて有利に適用 することができる。 [0103] The optical filter according to the present invention thus obtained is selected from the cyanine dyes represented by the general formula 1 having an appropriate absorption range according to the wavelength of light to be blocked. It selectively blocks unwanted light in the near infrared region radiated from video display equipment that does not impair the color purity of the three primary colors of the image, especially near infrared light in plasma displays, providing excellent contrast and color reproducibility. High-quality images can be obtained, and the infrared remote control does not malfunction due to near infrared rays. As an image display device to which the optical filter of the present invention can be applied, for example, a direct-view television using a cathode ray tube, Examples include light-emitting panel televisions that use plasma displays and electroluminescent displays, non-light-emitting panel televisions that use liquid crystal displays, and rear projection televisions that incorporate liquid crystal projectors. Among these, the optical filter according to the present invention can be applied very advantageously to a light-emitting panel television using a plasma display, an electroluminescence display, or the like that easily emits unnecessary light in principle.
[0104] 以下、この発明の実施の形態につき、実施例に基づいて説明する。 Hereinafter, embodiments of the present invention will be described based on examples.
実施例 1 Example 1
[0105] <シァニン色素の溶液保存安定性 クェンチヤ一含有条件 > [0105] <Containment stability of cyanine dye in solution>
溶液状態おける本発明のシァニン色素の安定性を調べた。本発明にお ヽてクェン チヤ一とは励起状態にある活性分子を脱励起させる(タエンチングさせる)機能を有 するものを指す。化学式 114、化学式 179で表される本発明のシァニン色素、化学 式 269、化学式 270で表される比較ィ匕合物をそれぞれ用い、各シァニン色素とタエ ンチヤ一として用いられる金属錯体 (『EST— 5』:住友精化製)を質量比 1: 1に混合 した。それぞれの、シァニン色素と EST— 5の混合物を塩化メチレンに溶解し、シァ ニン色素を 0. 1質量%含有する溶液を作成した後、メチルェチルケトン (以下、「ME Kjと言う。 )にて 140倍希釈を行った。その際の吸収極大波長( λ max)における吸光 度とを測定し、室温下(25°C)、褐色瓶に入れ、遮光状態にて保存した。 24時間後の 溶液の吸光度を測定し、 24時間後の吸光度 Z初期溶液の吸光度の値の百分率 (色 素残存率)を計算し、シァニン色素の溶液保存安定性の目安とした。 The stability of the cyanine dye of the present invention in a solution state was examined. In the present invention, a quencher refers to one having a function of de-exciting (taenting) an active molecule in an excited state. Each of the cyanine dyes of the present invention represented by the chemical formula 114 and the chemical formula 179, the comparative compound represented by the chemical formula 269 and the chemical formula 270, respectively, and a metal complex (“EST— 5 ”(manufactured by Sumitomo Seika) was mixed at a mass ratio of 1: 1. Each of the mixture of cyanine dye and EST-5 was dissolved in methylene chloride to prepare a solution containing 0.1% by mass of cyanine dye, and then added to methyl ethyl ketone (hereinafter referred to as “ME Kj”). The absorbance at the maximum absorption wavelength (λ max) at that time was measured and stored in a brown bottle at room temperature (25 ° C) and stored in the dark. The absorbance of the solution was measured, and the absorbance after 24 hours Z was calculated as a percentage of the absorbance value of the initial solution (the residual ratio of dye), which was used as a measure for the solution storage stability of cyanine dye.
[0106] 化学式 269 (比較例):
[0106] Chemical Formula 269 (Comparative Example):
[表 22] [Table 22]
表 22 Table 22
表 22の結果から、比較化合物については、色素残存率が 10%以下の安定性しか 示さないのに対して、本発明は金属錯体クェンチヤ一 (『EST— 5』)との混合溶液中 で 70%以上の色素残存率を示した。比較例はクェンチヤ一として用いた EST— 5の
機能を引き出すことができず、溶液安定性が非常に低いのに対し、本発明はクェン チング機能を有効に活用できることが分力つた。また、これは本発明の色素が溶液中 での安定性に優れていることが示されると共に、光学フィルター作成時の安定性、作 業性に寄与されることがわ力つた。 From the results shown in Table 22, the comparative compound shows only a stability of a dye residual ratio of 10% or less, while the present invention is 70% in a mixed solution with a metal complex quencher (“EST-5”). A pigment residual ratio of% or more was shown. The comparative example is the EST-5 used as Quenchia While the function could not be extracted and the solution stability was very low, the present invention was able to effectively utilize the quenching function. In addition, this indicates that the dye of the present invention is excellent in stability in a solution, and that it contributes to stability and workability when producing an optical filter.
実施例 2 Example 2
[0110] <シァニン色素の光安定性 クェンチヤ一含有条件 > [0110] <Photostability of cyanine dye Quenchia-containing condition>
化学式 4、化学式 146で表される本発明のシァニン色素、化学式 271、化学式 272 で表される比較ィ匕合物を用い、それぞれ、シァニン色素 0. 1質量%とクェンチヤ一(『 IRG— 023』日本化薬製) 0. 6質量0 /0、ポリメチルメタタリレート(『PMMA』 アルドリ ツチ製) 2.
各溶液を、ポリカーボネート基盤上にス ピンコート法にて薄膜を作成した。その際の薄膜吸収を測定し、 λ maxにおける色素 の吸収率を求め 100%とした。その後、『キセノンウエザーメータ XL— 75』 (スガ試 験機製)を用いて、測定条件: 180WZm2、槽内温度: 15°C、湿度: 60%にて 1時間 露光を行った。吸収極大波長における、「1時間露光後の吸光度 Z初期薄膜の吸光 度」の値を 100分率で表したものを色素残存率とし、シァニン色素の耐光性の目安と した。 The cyanine dye of the present invention represented by the chemical formula 4 and the chemical formula 146, the comparative compound represented by the chemical formula 271 and the chemical formula 272, respectively, and 0.1% by mass of the cyanine dye and the quencher (“IRG-023”) manufactured by Nippon Kayaku Co.) 0.6 wt 0/0, polymethyl methacrylate Tari rate (manufactured by "PMMA" Aldori Tutsi) 2. Each solution was formed into a thin film by spin coating on a polycarbonate substrate. The absorption of the thin film at that time was measured, and the absorption rate of the dye at λ max was determined and set to 100%. Thereafter, using “Xenon Weather Meter XL-75” (manufactured by Suga Test Instruments Co., Ltd.), exposure was carried out for 1 hour under measurement conditions: 180 WZm 2 , bath temperature: 15 ° C., humidity: 60%. The value of “absorbance after 1 hour exposure Z absorbance of the initial thin film” at the absorption maximum wavelength, expressed as a percentage, was used as a measure of the light resistance of the cyanine dye.
[0111] 化学式 271 (比較例): [0111] Chemical Formula 271 (Comparative Example):
[化 39] [Chemical 39]
[0112] 化学式 272 (比較例): [0112] Chemical Formula 272 (Comparative Example):
[化 40]
[Chemical 40]
[0113] [表 23] [0113] [Table 23]
[0114] 表 23の結果に見られるとおり、キセノンランプを 1時間照射すると、比較例の化合物 が 75%以下の色素残存率に対し、本発明のシァニン色素は、 80%近い高い色素残 存率を示した。これは光安定性において、本発明が優れていることを示しており、既 存のシァニン色素と比較して、本発明はその遮光能がより長期間持続することを物語 つている。 [0114] As can be seen from the results in Table 23, when the xenon lamp was irradiated for 1 hour, the cyanine dye of the present invention had a high dye residual ratio of nearly 80%, whereas the compound of the comparative example had a dye residual ratio of 75% or less. showed that. This indicates that the present invention is superior in light stability, and the present invention demonstrates that the light-shielding ability lasts for a longer period of time compared to the existing cyanine dyes.
実施例 3 Example 3
[0115] <シァニン色素の熱安定性 クェンチヤ一含有条件 > [0115] <Thermal stability of cyanine dyes
化学式 83、化学式 126で表される本発明のシァニン色素、化学式 273で表される 比較化合物を用い、それぞれ、シァニン色素 0. 1質量%とクェンチヤ一(『IRG— 02 3』 日本ィ匕薬製) 0. 6質量0 /0、ポリメチルメタタリレート(『PMMA』 アルドリッチ製) 2 . 5質量0 /0を MEK溶剤に溶解させた。各溶液を、ポリカーボネート基盤上にスピンコ ート法にて薄膜を作成した。その際の薄膜吸収を測定し、 675nmにおける吸光度を 測定した (初期薄膜の吸光度)。その後、真空乾燥機『DP— 43』 (ャマト科学製)を用 いて、測定条件を槽内温度: 90°Cにて 24時間加温を行った。 24時間加熱後、再度 675nmにおける薄膜の吸光度を測定し、「(初期薄膜の吸光度 24時間後の吸光 度) Z初期薄膜の吸光度」の値の 100分率で表したものを変化率として求めた。 Using the cyanine dye of the present invention represented by the chemical formula 83 and the chemical formula 126 and the comparative compound represented by the chemical formula 273, respectively, 0.1 mass% of the cyanine dye and Quentyaichi (“IRG-02 3” manufactured by Nippon Gyaku Co., Ltd.) ) 0.6 weight 0/0, polymethyl methacrylate Tari rate ( "PMMA" manufactured by Aldrich) 2. 5 wt 0/0 were dissolved in MEK solvent. A thin film of each solution was formed on a polycarbonate substrate by spin coating. The thin film absorption at that time was measured, and the absorbance at 675 nm was measured (absorbance of the initial thin film). After that, using a vacuum dryer “DP-43” (manufactured by Yamato Kagaku), the measurement was performed at a temperature of 90 ° C. for 24 hours. After heating for 24 hours, the absorbance of the thin film at 675 nm was measured again, and the value expressed as 100% of the value of `` (Absorbance of initial thin film after 24 hours) Z Absorbance of initial thin film '' was obtained as the rate of change. .
[0116] 化学式 273 (比較例):
[0116] Chemical Formula 273 (Comparative Example):
(CF3S02)2N (CF 3 S0 2 ) 2 N
[0117] [表 24] [0117] [Table 24]
表 24 Table 24
[0118] 表 24の結果に見られるとおり、 90°Cにて 24時間加温を行うと、比較例の化合物が 6%以上の色合いの変化率を示したのに対し、本発明のシァニン色素は、 3%程度 の小さい変化率を示した。比較例で用いた従来の近赤外線吸収色素は、耐熱性が 低ぐ時間の経過と共に分解し、近赤外線領域の吸光係数が低下し、更には分解に より可視光線領域に吸収が生じてしまい、可視光透過率が低下し、黄色に呈色して 色調を損なってしまった。これに比して、本発明のシァニン色素は、耐熱性が高ぐ 近赤外線領域の吸収低下が少なぐ色素の分解による可視光領域の呈色も発生し 難かった。既存のシァニン色素と比較して、本発明は色合いが変化しにくぐ光学設 計上優れて!/、ることが示された。 [0118] As can be seen from the results in Table 24, the compound of the comparative example showed a change in hue of 6% or more when heated at 90 ° C for 24 hours, whereas the cyanine dye of the present invention. Showed a small change rate of about 3%. The conventional near-infrared absorbing dye used in the comparative example decomposes with the passage of time when the heat resistance is low, the absorption coefficient in the near-infrared region decreases, and further, absorption occurs in the visible light region due to the decomposition, Visible light transmittance decreased, and the color tone was lost due to yellow coloration. On the other hand, the cyanine dye of the present invention has high heat resistance, and it is difficult for coloration in the visible light region due to decomposition of the dye with little decrease in absorption in the near infrared region. Compared with the existing cyanine dyes, the present invention has been shown to be superior in optical design, in which the hue hardly changes!
実施例 4 Example 4
[0119] <シァニン色素の光安定性 色素単独条件 > [0119] <Photostability of cyanine dyes Conditions for dye alone>
化学式 4、化学式 144、化学式 161で表される本発明のシァニン色素、化学式 271 、化学式 274、化学式 275で表される比較ィ匕合物を用い、それぞれのシァニン色素 単独での薄膜条件下での光安定性を調べた。シァニン色素 0. 1質量%とポリメチル
メタタリレート (『PMMA』 アルドリッチ製)を MEK溶剤に溶解した。各溶液を、ポリ力 ーボネート基盤上にスピンコート法にて薄膜を作成した。その際の薄膜吸収を測定し 、 λ maxにおける色素の吸収率を求め 100%とした。その後、『キセノンウエザーメー タ XL— 75』 (スガ試験機製)を用いて、測定条件:180WZm2、槽内温度:15°C、 湿度: 60%にて 0. 5時間露光を行った。吸収極大波長における色素残存率を実施 例 2と同様の方法で求めた。結果を表 4に示す。 The cyanine dye of the present invention represented by the chemical formula 4, the chemical formula 144, the chemical formula 161, the comparative compound represented by the chemical formula 271, the chemical formula 274, and the chemical formula 275 are used. The light stability was examined. Cyanine dye 0.1% by mass and polymethyl Metatalitate (“PMMA” manufactured by Aldrich) was dissolved in MEK solvent. Each solution was formed into a thin film by spin coating on a polycarbonate substrate. The absorption of the thin film at that time was measured, and the absorption rate of the dye at λ max was determined and taken as 100%. Thereafter, using “Xenon Weather Meter XL-75” (manufactured by Suga Test Instruments Co., Ltd.), exposure was carried out for 0.5 hours under measurement conditions: 180 WZm 2 , bath temperature: 15 ° C., humidity: 60%. The dye residual ratio at the absorption maximum wavelength was determined in the same manner as in Example 2. The results are shown in Table 4.
[0120] 化学式 274 (比較例): [0120] Chemical Formula 274 (Comparative Example):
[化 42] [Chemical 42]
[0122] [表 25]
シァニン色素 色素残存率 備考 [0122] [Table 25] Cyanine dye Dye remaining rate Remarks
化学式 4 62% 本発明 Formula 4 62% The present invention
化学式 144 62% 本発明 Chemical formula 144 62% The present invention
化学式 161 61 % 本発明 Chemical formula 161 61% The present invention
化学式 271 25% 比較例 3 Chemical formula 271 25% Comparative Example 3
化学式 274 36% 比較例 6 Chemical formula 274 36% Comparative Example 6
化学式 275 20% 比較例 7 Chemical formula 275 20% Comparative Example 7
[0123] 表 25の結果に見られるとおり、キセノンランプを 0. 5時間照射すると、比較例の化 合物は 40%以下の色素残存率に対し、本発明のシァニン色素は 60%以上の高い 色素残存率を示した。既存のシァニン色素と比較して、本発明は色素単独において も高い耐光性を示した。 [0123] As shown in the results of Table 25, when the xenon lamp was irradiated for 0.5 hour, the compound of the comparative example had a dye residual ratio of 40% or less, and the cyanine dye of the present invention had a high value of 60% or more. The dye residual ratio was shown. Compared with existing cyanine dyes, the present invention showed high light resistance even with the dye alone.
実施例 5 Example 5
[0124] <シァニン色素の透過スペクトル > [0124] <Transmission spectrum of cyanine dye>
実施例 4と同様の方法で本発明のシァニン色素、化学式 26単独の薄膜を作成し、 その透過スペクトルを測定した。得られた透過スペクトルデータを図 1として示す。 A thin film of the cyanine dye of the present invention and chemical formula 26 alone was prepared in the same manner as in Example 4, and the transmission spectrum was measured. The obtained transmission spectrum data is shown in Fig. 1.
[0125] 図 1の結果に見られるとおり、本発明のシァニン色素は従来のシァニン色素よりも最 大吸収波長が長波長側に存在することから、所望の近赤外波長域をカットしながら、 同時に可視部の吸収が少なぐ光学フィルターとしての高い特性を有し、 850ηπ!〜 1 OOOnmの近赤外域の光を効率よくカットし、三原色の色純度を損なうことなく光学フ ィルターを作成することができる。また、比較例で用いた従来の近赤外線吸収色素と 比較して lOOnm以上の長波長化を実現した。このことより、本発明の色素は、 850乃 至 lOOOnm付近での所望の波長の光を効率的にカットすることが提案可能であり、 高!、特性を示すことが分力つた。 [0125] As seen in the results of Fig. 1, the cyanine dye of the present invention has a maximum absorption wavelength on the longer wavelength side than the conventional cyanine dye, so that while cutting the desired near-infrared wavelength region, At the same time, it has high characteristics as an optical filter with little visible absorption, 850ηπ! ~ 1 Optical filters can be created without impairing the purity of the three primary colors by efficiently cutting light in the near-infrared region of OOOnm. In addition, a wavelength longer than lOOnm was achieved compared to the conventional near-infrared absorbing dye used in the comparative example. From this, it is possible to propose that the dye of the present invention efficiently cuts light having a desired wavelength in the vicinity of 850 to lOOOnm, and it has been shown that it has high characteristics.
実施例 6 Example 6
[0126] <光学フィルター > [0126] <Optical filter>
飽和共重合ポリエステル系榭脂(商品名『バイロン 200』、東洋紡績株式会社製造) の 20質量%トルエン溶液 100質量部と、化学式 3、化学式 5で表されるシァニン色素 の 0. 5質量%シクロへキサノン溶液とを混合した後、トルエンをカ卩えて、ポリエステル 系榭脂の濃度を 9質量%に調整した。次いで、バーコ一ターを用いて、この溶液をポ
リエチレンテレフタレート製フィルム(商品名『T100E』、ダイヤホイルへキスト株式会 社製造、厚さ 100 /z m)の片面へ均一に塗布し、乾燥させることによって膜厚 4 /z mの コーティング膜を有する 2種類の光学フィルターを作製した。 100% by mass of a 20% by weight toluene solution of saturated copolymerized polyester resin (trade name “Byron 200” manufactured by Toyobo Co., Ltd.) and 0.5% by weight of cyanine dye represented by Chemical Formula 3 and Chemical Formula 5 After mixing with the hexanone solution, toluene was added to adjust the concentration of the polyester resin to 9% by mass. The solution is then poured using a bar coater. 2 types of coating film with a film thickness of 4 / zm by coating uniformly on one side of a film made of polyethylene terephthalate (trade name “T100E”, manufactured by Diamond Hoechst Co., Ltd., thickness 100 / zm) and drying. An optical filter was prepared.
[0127] 映像の三原色の色純度を損なうことなぐ映像表示機器カゝら輻射される不用な光を 効果的に遮断する本例の光学フィルタ一は、いずれも、プラズマディスプレーなどの 映像表示機器へ有利に適用できる。 [0127] All of the optical filters in this example that effectively block the unnecessary light emitted from the video display device that does not impair the color purity of the three primary colors of the video can be used for video display devices such as plasma displays. It can be advantageously applied.
実施例 7 Example 7
[0128] <映像表示機器用前面部材> [0128] <Front member for video display equipment>
実施例 6の方法により作製した光学フィルターのシァニン色素による遮光層を形成 した側へ、アルゴン Z酸素混合気流下、酸化インジウム一錫合金を積層した。さらに 、前面部材の反対側の面へ、ノングレア層を有する市販のポリメタクリル酸メチル榭脂 製パネル (商品名『MR—NG』、三菱レイヨン株式会社製造)のノングレア層の形成さ れて 、な 、面を貼合し、 2種類の映像表示機器用前面部材を得た。 An indium tin oxide alloy was laminated on the side of the optical filter produced by the method of Example 6 on the side where the light-shielding layer of cyanine dye was formed in an argon-Z oxygen mixed gas stream. In addition, a non-glare layer of a commercially available poly (methyl methacrylate) resin panel (trade name “MR-NG”, manufactured by Mitsubishi Rayon Co., Ltd.) having a non-glare layer is formed on the surface opposite to the front member. The surfaces were bonded together to obtain two types of front members for video display equipment.
[0129] ぎらつきを起こさず、映像の三原色の色純度を損なうことなぐ映像表示機器から輻 射される不用な光を効果的に遮断する本例の前面部材は、いずれも、プラズマディ スプレーをはじめとする映像表示機器へ有利に適用できる。 [0129] The front members of this example that effectively block unwanted light radiated from video display equipment that does not cause glare and impair the color purity of the three primary colors of the video are all plasma display. It can be advantageously applied to video display devices such as the first.
産業上の利用可能性 Industrial applicability
[0130] 叙述のごとぐこの発明で用いるシァニン色素は、近赤外領域に吸収極大を有し、 プラズマディスプレーなどの映像表示機器にぉ 、て、映像の三原色の色純度を損な うことなぐ映像表示機器カゝら輻射される不用な光を効果的に遮断するので、コントラ ストと色再現性に優れた高画質の映像が得られ、しかも、赤外線リモコンを使用する 際に、近赤外線によって誤動作する心配もなぐ遮光剤としてプラズマディスプレーな どの映像表示機器へ取り付ける光学フィルター用途として極めて有用である。 [0130] As described, the cyanine dye used in the present invention has an absorption maximum in the near-infrared region, and does not impair the color purity of the three primary colors of an image for a video display device such as a plasma display. Since the unnecessary light emitted from the image display device is effectively blocked, a high-quality image with excellent contrast and color reproducibility can be obtained. It is extremely useful as an optical filter that can be attached to video display equipment such as a plasma display as a light-shielding agent without fear of malfunction.
[0131] また、この発明で用いるシァニン色素は有機溶剤における耐光性、耐環境性に優 れていることから、長期間用いても、遮光能が減弱し難い光学フィルターを作業効率 良く作製し得ることとなる。カロえて、この発明で用いるシァニン色素は、構造デザイン により、最大吸収波長が lOOOnm付近に達する性質を具備するので、他の有機色素 化合物と組み合わせて光学フィルターにおける遮光層を構成する場合、併用する他
の有機色素化合物の量が少なくて済むという実益を有することとなる。 [0131] Further, since the cyanine dye used in the present invention is excellent in light resistance and environmental resistance in an organic solvent, it is possible to produce an optical filter having a low light-blocking ability with good work efficiency even when used for a long period of time. It will be. The cyanine dye used in the present invention has the property that the maximum absorption wavelength reaches around lOOOnm depending on the structural design, so when it is used in combination with other organic dye compounds to form a light shielding layer in an optical filter, This has the advantage that the amount of the organic dye compound is small.
斯くも顕著な効果を奏するこの発明は、斯界に貢献すること誠に多大な、意義のあ る発明であると言える。
It can be said that this invention having such remarkable effects is a very significant invention that contributes to the world.
Claims
[化 1] [Chemical 1]
1 2は単環式又は縮合環式の芳香環又は複素環を表し、それ ら芳香環又は複素環は置換基を有していてもよい。 R 12 represents a monocyclic or condensed aromatic ring or heterocyclic ring, and the aromatic ring or heterocyclic ring may have a substituent. R
1乃至 R 1 to R
6は互いに同じか異なる 脂肪族炭化水素基、芳香族炭化水素基を表し、それら脂肪族炭化水素基又は芳香 族炭化水素基は置換基を有していてもよい。また、 R R 6 represents the same or different aliphatic hydrocarbon group and aromatic hydrocarbon group, and these aliphatic hydrocarbon group or aromatic hydrocarbon group may have a substituent. R R
3と R 、 R 3 and R, R
4 5と 6は結合し、 3乃至 4 5 and 6 are combined, 3 to
8員環を形成することが出来る。 Rは水素原子、又は置換基を表し、 Lは、環状構造 を形成するのに必要な原子群を表す。 Xm一は、 m価の対イオンを表し、 mは、 1乃至 3 の整数であり、 cは、 0又は 1である。 An 8-membered ring can be formed. R represents a hydrogen atom or a substituent, and L represents an atomic group necessary for forming a cyclic structure. X m1 represents an m-valent counter ion, m is an integer of 1 to 3, and c is 0 or 1.
[2] 一般式 1における Rが芳香族炭化水素基である請求の範囲第 1項に記載の遮光剤 [2] The light-shielding agent according to claim 1, wherein R in the general formula 1 is an aromatic hydrocarbon group
[3] 一般式 1における Xm_が、フッ素原子で飽和置換されたフルォロアルキルスルフォン 酸ァ-オン、ジ(フルォロアルキルスルフォ -ル)イミドア-オン、 PF 一、 BF一から選 [3] X m_ in the general formula 1 is selected from fluoroalkyl sulfonic acid cation saturated with a fluorine atom, di (fluoroalkyl sulfonyl) imido-one, PF 1 and BF 1
6 4 ばれるァ-オンである請求の範囲第 1項又は第 2項に記載の遮光剤。 6 4. The light-shielding agent according to claim 1, which is a light-on.
[4] 請求の範囲第 1項乃至第 3項の 、ずれかに記載の遮光剤を含んでなる光学フィルタ
[4] An optical filter comprising the light-shielding agent according to any one of claims 1 to 3
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JP2011225761A (en) * | 2010-04-22 | 2011-11-10 | Shin-Etsu Chemical Co Ltd | Near-infrared absorptive film-forming material and laminate film |
US20110287364A1 (en) * | 2008-12-18 | 2011-11-24 | Agfa Graphics Nv | Lithographic printing plate precursor |
US8685622B2 (en) | 2009-04-24 | 2014-04-01 | Agfa Graphics Nv | Method for preparing a lithographic printing plate |
US20150261080A1 (en) * | 2012-10-11 | 2015-09-17 | Agfa-Gevaert | Infrared dyes for laser marking |
WO2017094858A1 (en) * | 2015-12-01 | 2017-06-08 | 旭硝子株式会社 | Optical filter and imaging device |
CN107108987A (en) * | 2014-12-01 | 2017-08-29 | 陶氏环球技术有限责任公司 | Polymer composition, shrink film and its obtained method |
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JPH09120115A (en) * | 1995-06-29 | 1997-05-06 | Eastman Kodak Co | Photographic element containing cyanine dye |
JP2000025350A (en) * | 1998-06-24 | 2000-01-25 | Eastman Kodak Co | Infrared absorption cyanine coloring agent for laser coloring agent transfer |
JP2002090521A (en) * | 2000-07-06 | 2002-03-27 | Fuji Photo Film Co Ltd | Optical filter |
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US20110287364A1 (en) * | 2008-12-18 | 2011-11-24 | Agfa Graphics Nv | Lithographic printing plate precursor |
US8778590B2 (en) * | 2008-12-18 | 2014-07-15 | Agfa Graphics Nv | Lithographic printing plate precursor |
US8685622B2 (en) | 2009-04-24 | 2014-04-01 | Agfa Graphics Nv | Method for preparing a lithographic printing plate |
US9069245B2 (en) | 2010-04-22 | 2015-06-30 | Shin-Etsu Chemical Co., Ltd. | Near-infrared absorptive layer-forming composition and multilayer film |
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KR101755595B1 (en) * | 2010-04-22 | 2017-07-07 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Near-infrared absorptive layer-forming composition and multilayer film |
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CN107108987A (en) * | 2014-12-01 | 2017-08-29 | 陶氏环球技术有限责任公司 | Polymer composition, shrink film and its obtained method |
WO2017094858A1 (en) * | 2015-12-01 | 2017-06-08 | 旭硝子株式会社 | Optical filter and imaging device |
JP6202230B1 (en) * | 2015-12-01 | 2017-09-27 | 旭硝子株式会社 | Optical filter and imaging device |
CN107430225A (en) * | 2015-12-01 | 2017-12-01 | 旭硝子株式会社 | Optical filter and camera device |
CN107430225B (en) * | 2015-12-01 | 2019-11-08 | Agc株式会社 | Optical filter and photographic device |
US10598834B2 (en) | 2015-12-01 | 2020-03-24 | AGC Inc. | Near-infrared light blocking optical filter having high visible light transmission and an imaging device using the optical filter |
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