JP4485778B2 - Tetraazaporphyrin dye and optical filter using the same - Google Patents

Description

  The present invention relates to a tetraazaporphyrin dye mixture and an optical filter using the dye mixture. More specifically, the color purity of luminescent colors such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), fluorescent display tube, field emission display is improved. The present invention relates to a tetraazaporphyrin dye mixture useful as an optical filter material to be attached to the optical filter, and an optical filter using the dye mixture.

  Image display devices such as liquid crystal display (LCD), plasma display panel (PDP), electroluminescence display (ELD), cathode ray tube display (CRT), fluorescent display tube, field emission display are red, blue, green A color image is displayed with a combination of three primary colors. However, these displays have a problem in that the red light portion of visible light cannot be accurately reproduced because extra light (wavelength in the range of 570 to 605 nm) is included in the light emission from the three primary color phosphors. Yes.

  In order to suppress light of this unnecessary emission wavelength, it is effective to use a dye that selectively absorbs light of that wavelength, and an optical filter that does not transmit light in a specific wavelength band has been proposed. For example, JP-A-58-153904, JP-A-59-221943, JP-A-60-22102, JP-A-2000-193820, JP-A-2001-131345, JP-A-2001-183522. It is disclosed in the gazette.

  However, since the dyes disclosed in these prior arts have a broad absorption wavelength band, they also block wavelength bands other than the specific wavelength band that should be blocked originally, so that the color purity of the emitted color is insufficient. Moreover, in the optical filter using the pigment | dye currently disclosed by prior art, the room for improvement is left in the weather resistance.

On the other hand, examples of using a tetraazaporphyrin compound isomer mixture for optical recording media have been proposed (JP-A-11-116574 and JP-A-11-1000052), but a mixture of specific isomers of a tetraazaporphyrin compound. There is no disclosure about.
JP 58-153904 A JP 59-221943 A JP 60-22102 A JP 2000-193820 A JP 2001-131345 A JP 2001-183522 A JP-A-11-116574 Japanese Patent Laid-Open No. 11-100500

  In view of the above prior art, the present invention selectively cuts light of a specific wavelength generated in various displays, particularly in a plasma display panel, and has a high visible light transmittance that does not hinder the color purity of the display. An object of the present invention is to provide a useful tetraazaporphyrin dye mixture and an optical filter using the dye mixture as a practical filter material having excellent weather resistance.

  As a result of intensive studies to solve the above problems, the present inventors have cut off excess light in the wavelength band of 570 to 605 nm, which is a problem, by using a specific tetraazaporphyrin dye mixture, The present inventors have found that an optical filter having excellent weather resistance can be produced, and have completed the present invention.

That is, the present invention
1. A tetraazaporphyrin compound isomer represented by the general formula (1), and a tetraazaporphyrin dye mixture comprising the tetraazaporphyrin compound isomer represented by the general formula (2),

[In the formula, R represents a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group, and M represents two hydrogen atoms. An atom, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal is represented. ]
2. 2. The dye mixture according to 1, wherein the gram extinction coefficient in the solution is 200,000 (ml / g.cm) or more,
3. An optical filter comprising a dye mixture according to 1 or 2 in a substrate;
About.

According to the present invention, a practical filter material having a high visible light transmittance that selectively cuts light of a specific wavelength generated in various displays, particularly plasma display panels, and does not impair the color purity of the display. As a useful tetraazaporphyrin dye mixture and an optical filter using the dye mixture can be provided.

The present invention is described in detail below.

  The tetraazaporphyrin dye mixture of the present invention comprises tetraazaporphyrin compound isomers represented by the following general formulas (1) and (2).

[In the formula, R represents a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group, and M represents two hydrogen atoms. An atom, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal is represented. ]

In the tetraazaporphyrin compound isomers represented by the general formulas (1) and (2), as specific examples of R,
Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2 -Methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylpropyl group, 1,1,2-trimethylpropyl group, 1-ethyl-2- Methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,4,4-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, n- Undecyl group, n-dodecyl group, 1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo Substituted or unsubstituted carbon atoms of 1-20 carbon atoms such as -pentyl-2,2-dimethylpropyl group, 1-cyclo-hexyl-2,2-dimethylpropyl group Alkyl group;
Benzyl, nitrobenzyl, cyanobenzyl, hydroxybenzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, dichlorobenzyl, methoxybenzyl, ethoxybenzyl, trifluoromethylbenzyl, naphthylmethyl, nitro A substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms such as a naphthylmethyl group, a cyanonaphthylmethyl group, a hydroxynaphthylmethyl group, a methylnaphthylmethyl group, a trifluoromethylnaphthylmethyl group;
Methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group N-hexyloxy group, n-dodecyloxy group, methoxyethyl group, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropyl group, 2-methoxybutyl group, etc. An alkoxy group of
Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutyl A substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms such as a thio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, 1,1-dimethylpropylthio group;
Phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, dichlorophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N, N-dimethylamino A substituted or unsubstituted aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a nitronaphthyl group, a cyanonaphthyl group, a hydroxynaphthyl group, a methylnaphthyl group, a trifluoromethylnaphthyl group;
4 to 4 carbon atoms such as pyrrolyl group, thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoyl group, imidazoloyl group, benzoxazoyl group, benzothiazoyl group, benzoimidazolyl group, benzofuranyl group, indoyl group, isoindoyl group 20 substituted or unsubstituted heteroaryl groups;
C6-C20 substituted or unsubstituted aryl such as phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group An oxy group;
C6-C20 substitution such as phenylthio group, 2-methylphenylthio group, 4-methylphenylthio group, 4-t-butylphenylthio group, 2-methoxyphenylthio group, 4-iso-propylphenylthio group Or an unsubstituted arylthio group;
Etc.

Examples of the divalent metal represented by M in the above general formula include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh ( II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg ( II), Pb (II), Sn (II) and the like.
Examples of monosubstituted trivalent metals include Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-Br, Ga-F, Ga-I, In-Cl, In-Br. , In-F, In-I , Tl-Cl, Tl-Br, Tl-F, Tl-I, Al-Cl, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In-C _{6 H 5, In-C 6} H 4 (CH 3), Mn (OH), Mn (OC 6 H 5) , Mn _{(OSi (CH 3) 3)} , Fe-Cl, include Ru-Cl, etc..
Examples of disubstituted tetravalent metals include CrCl ₂ , SiCl ₂ , SiBr ₂ , SiF ₂ , SiI ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeF ₂ , GeI ₂ , SnCl ₂ , SnF ₂ , SnBr ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ GeR ₂ [R represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof. ],
Si (OR ′) ₂ , Sn (OR ′) ₂ , Ge (OR ′) ₂ , Ti (OR ′) ₂ , Cr (OR ′) ₂ [R ′ is an alkyl group, phenyl group, naphthyl group, trialkyl Represents a silyl group, a dialkylalkoxysilyl group and derivatives thereof. ], Sn (SR ″) ₂ , Ge (SR ″) ₂ and [R ″ each represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof. ] Etc. are mentioned.
Examples of oxymetals include VO, MnO, TiO and the like.

  Preferable examples of M include the divalent metal and the oxymetal. More preferable examples in terms of absorption strength and weather resistance include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Pd (II), Mn (II), VO is mentioned.

  The tetraazaporphyrin compound isomer mixture represented by the general formulas (1) and (2) is obtained from the tetraazaporphyrin compound isomer mixture represented by the following general formulas (1) to (4). It is obtained by removing the tetraazaporphyrin compound isomer represented by (4).

[In the formula, R represents a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group, and M represents two hydrogen atoms. An atom, a divalent metal atom, a trivalent or tetravalent substituted metal atom, or an oxy metal is represented. ]

  The tetraazaporphyrin compound isomer mixture represented by general formulas (1) to (4) is a maleonitrile compound represented by general formula (5) or 2,5-diimino represented by general formula (6). It is obtained by reacting a pyrrole compound with a metal derivative.

[Wherein, R represents a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group. ]

In the maleonitrile compound represented by the general formula (5) or the 2,5-diiminopyrrole compound represented by the general formula (6), as specific examples of R,
The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms;
The substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms;
The substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms;
The substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms;
The substituted or unsubstituted aryl group having 6 to 20 carbon atoms;
The substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms;
The substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms;
Examples thereof include substituted or unsubstituted arylthio groups having 6 to 20 carbon atoms.

  The maleonitrile compound represented by the general formula (5) or the 2,5-diiminopyrrole compound represented by the general formula (6) and the metal derivative are preferably reacted in an organic solvent.

  As an example of the organic solvent, the boiling point may be 100 ° C. or higher. Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidone, 1-chloronaphthalene, tetrahydronaphthalene, benzyl alcohol, quinoline, N, N-dimethylaminoethanol. , N-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol Etc.

The amount of the solvent used is 1 to 100 times by weight, preferably 1 to 100 times that of the maleonitrile compound represented by the general formula (5) or the 2,5-diiminopyrrole compound represented by the general formula (6). 20 times by weight.
The reaction temperature is 90 to 350 ° C, preferably 90 to 200 ° C.
The reaction time is preferably 1 to 20 hours.

  As metal derivatives used in the reaction, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn, Al, Ga, Examples include In, Tl, Cr, Si, Zr, Ge, Sn, V and halides thereof, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides, complexes, and the like.

  Further, an organic base may be added to the reaction as a catalyst. Specific examples of the organic base include 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonene.

  The maleonitrile compound represented by the general formula (5) is described in J.P. Gen. Chem. The 2,5-diiminopyrrole compound represented by the general formula (6) can be produced according to the method described in USSR, 47, 1954- (1977) and the like, and the maleonitrile compound represented by the general formula (5) is used as the 2,5-diiminopyrrole compound. It can be produced by reacting ammonia in alcohol in the presence of sodium. The 2,5-diiminopyrrole compound represented by the general formula (6) may be isolated during the production process, but preferably a metal derivative is charged in the same system to obtain the general formulas (1) to (4). A tetraazaporphyrin compound isomer mixture represented by the formula:

  Furthermore, by removing the tetraazaporphyrin compound isomers represented by the general formulas (3) and (4) from the tetraazaporphyrin compound isomer mixture represented by the general formulas (1) to (4), Although the tetraazaporphyrin compound isomer mixture represented by (1) and (2) is obtained, the method is not particularly limited, and a conventionally known method can be used. Examples thereof include recrystallization from a solvent, column purification using silica gel or alumina, removal of tetraazaporphyrin compound isomers represented by general formulas (3) and (4) by adsorption, and the like.

  The mixing ratio of the tetraazaporphyrin compound represented by the general formula (1) and the tetraazaporphyrin compound represented by the general formula (2) is not particularly limited, but the tetraaza represented by the general formula (1) The content of the porphyrin compound with respect to the total amount of the dye mixture is 1 to 99% by weight. Preferably it is 1-50 weight%, More preferably, it is 5-20 weight%.

The tetraazaporphyrin compounds represented by the general formulas (1) to (4) of the present invention have mutually different absorption wavelength ranges and gram extinction coefficients depending on isomers. Since the isomer represented by the general formula (1) and the isomer represented by the general formula (2) have a smaller difference in maximum absorption wavelength compared to other isomers and a large Gram extinction coefficient, the absorption band is Especially sharp. Furthermore, the weather resistance is also excellent. Therefore, the isomer mixture represented by the general formula (1) and the isomer mixture composed only of the isomer represented by the general formula (2) are different from the isomers represented by the general formula (2) in comparison with the mixture containing other isomers. It is a dye mixture particularly useful as an optical filter material to be attached in order to improve the color purity.
Table 1 shows specific examples of the dye mixture of the present invention.

  The optical filter of the present invention comprises at least one tetraazaporphyrin dye mixture composed of tetraazaporphyrin isomers represented by general formulas (1) and (2) having a maximum absorption wavelength at 570 to 605 nm in a substrate. It is a seed-containing material, and it is contained in the base material referred to in the present invention. Of course, it is contained in the base material, and is applied to the surface of the base material, sandwiched between the base material and the base material. It means the state.

  Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass, and there is no particular limitation as long as the light transmittance at a wavelength of 400 to 700 nm is 40% or more. Specific examples include polyimide, polysulfone (PSF), polyethersulfone (PES), polyethylene terephthalate (PET), polymethylene methacrylate (PMMA), polycarbonate (PC), polyetheretherketone (PEEK), polypropylene (PP ) And triacetylcellulose (TAC). In particular, acrylic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA), and polycarbonate resins are preferable.

  Although there will be no restriction | limiting in particular if the thickness of a base material has a certain amount of mechanical strength, Usually, they are 20 micrometers-10 mm, 20 micrometers-1 mm are preferable, and 20 micrometers-200 micrometers are especially preferable.

  The method for producing the optical filter of the present application using the above tetraazaporphyrin dye mixture is not particularly limited, but (1) a method for inclusion in a transparent adhesive, and (2) inclusion in a polymer molded body. A method, (3) a method of coating a polymer molded body or glass surface, and the like.

  Specific examples of the transparent adhesive listed in (1) include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), ethylene-vinyl acetate adhesives (EVA), and the like. , Polyvinyl ether, saturated amorphous polyester, melamine resin and other sheet-like or liquid pressure-sensitive adhesives. The addition amount of the tetraazaporphyrin dye mixture is usually 10 ppm to 30% by weight, preferably 10 ppm to 20% by weight, and particularly preferably 10 ppm to 10% by weight.

  (2) As a method for inclusion in the polymer molded body, (A) a method of kneading a dye mixture into a resin and heat molding, and (B) a resin or a resin monomer and a dye mixture are dispersed in an organic solvent. And a method for preparing a polymer molded body by casting and casting.

  The resin used in (A) is preferably as highly transparent as possible when a plate or film is prepared. Specifically, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate, Polyarylate, polyetherketone, polycarbonate, polyethylene, polypropylene, nylon 6 and other polyamides, polyimide, cellulose resin such as triacetyl cellulose, polyurethane, polytetrafluoroethylene and other fluorine resins, polyvinyl chloride and other vinyl compounds, poly Addition polymer of acrylic acid, polyacrylic acid ester, polyacrylonitrile, vinyl compound, polymethacrylic acid, polymethacrylic acid ester, polyvinylidene chloride and other vinylidene compounds, vinylidene fluoride / trifluoroethylene copolymer Body can copolymers of ethylene / vinyl compound-vinyl acetate copolymer, or a fluorine-based compound, polyether such as polyethylene oxide, epoxy resins, polyvinyl alcohol, and polyvinyl butyral.

  The processing conditions vary slightly depending on the dye mixture and base polymer used, but the dye mixture is added to the base polymer powder or pellets and heated to 150-350 ° C and dissolved. After that, a method of forming a plate by molding, a method of forming a film with an extruder, a raw fabric with an extruder, stretching 2 to 5 times uniaxially or biaxially at 30 to 120 ° C., 10 And a method of forming a film having a thickness of ˜200 μm.

  In addition, when kneading, an additive used for ordinary resin molding such as plasticity may be added. The addition amount of the dye mixture varies depending on the absorption coefficient, the thickness of the polymer molded body to be produced, the target absorption strength, the target transmission characteristics / transmittance, etc., but is usually from 1 ppm to the weight of the base polymer molded body. 20 wt%, preferably 1 ppm to 10 wt%, particularly preferably 1 ppm to 5 wt%.

  In the casting method (B), a dye mixture is added and dissolved in an organic solvent solution of a resin or resin monomer, and if necessary, a plasticizer, a polymerization initiator and an antioxidant are added, and the required surface state is obtained. A plate or a film can be produced by pouring onto a mold or drum and volatilizing / drying the solvent or volatilizing / drying the solvent.

Examples of resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, Examples thereof include polyvinyl-modified resins (PVA, EVA, etc.) or resin monomers of those copolymer resins.
Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.

  The concentration of the dye mixture varies depending on the absorption coefficient of the dye mixture, the thickness of the plate or film, the target absorption strength, the target transmission characteristics / transmittance, etc., but is usually 1 ppm to 20 with respect to the weight of the resin or resin monomer. % By weight. Moreover, resin (or resin monomer) density | concentration is 1 to 90 weight% normally with respect to the whole coating material (namely, organic solvent solution of resin or resin monomer).

  Examples of the method for coating the polymer molded body or glass surface mentioned in (3) include a method in which a tetraazaporphyrin dye mixture is dissolved in a binder resin and an organic solvent to form a paint, and an uncolored acrylic emulsion paint is coated with tetraaza. Examples thereof include a method of dispersing a finely pulverized (50 to 500 nm) porphyrin pigment mixture into an acrylic emulsion water-based paint.

  As binder resins, aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, polyvinyl resins. Examples thereof include system-modified resins (PVB, EVA, etc.) or copolymer resins thereof.

  Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, and mixtures thereof.

  The concentration of the dye mixture varies depending on the absorption coefficient, coating thickness, target absorption strength, target visible light transmittance, and the like, but is usually 0.1 ppm to 30% by weight with respect to the weight of the binder resin. The resin concentration is usually 1 to 50% by weight with respect to the whole paint.

  In the case of the acrylic emulsion water-based paint, it can be obtained by dispersing a finely pulverized pigment (tetraazaporphyrin dye mixture) (50 to 500 nm) in an uncolored acrylic emulsion paint as described above. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

  The paint produced by the above method forms a coating film on a transparent polymer film, transparent resin, transparent glass, etc. by a coating method such as a bar coder, blade coater, spin coater, reverse coater, die coater, or spray. By doing, a pigment | dye (tetraazaporphyrin pigment mixture) can be contained in this coating film.

  For the evaluation of color purity and color coordinates, a normal color meter can be used, or a spectral radiance meter can be used to calculate from the wavelength dispersion information. In actual measurement, each of the three primary colors is displayed, (x, y) at that time is measured, then a filter is attached, (x, y) is measured, and the change at this time ( (Δx, Δy) may be evaluated.

  The optical filter of the present invention preferably has an electromagnetic wave shielding function and a near infrared blocking function. As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used. As a laminate using a silver thin film, a dielectric (DE) such as indium oxide, zinc oxide, and titanium oxide and silver (M) are alternately formed into DE / M / DE / M / DE (5 layers). Those prepared are preferred. The number of stacked layers is preferably 3 to 11 layers, but this is not limited to the total number, and in order to increase adhesion and durability, an ultra-thin film is inserted between M and DE so as not to disturb the optical properties. Also good. As the metal mesh, a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, or the like can be used.

As for the near-red ray blocking function, when an electromagnetic wave shield using a silver thin film is used, near-infrared rays can be simultaneously blocked due to scattering by silver free electrons. When a mesh is used, a film that absorbs near infrared rays or a film that reflects near infrared rays is used separately.
Furthermore, a functional transparent layer such as a known antireflection layer, antiglare layer, hard coat layer, antistatic layer or antifouling layer can be added to the optical filter of the present invention.

  Next, the configuration of the optical filter will be described with reference to the drawings. 1 to 4 are cross-sectional views illustrating an example of an optical filter in the present invention.

  FIG. 1 shows a schematic cross-sectional view of an optical filter when a transparent adhesive layer 20 containing a pigment mixture is laminated on a transparent substrate 10. FIG. 2 shows a schematic cross-sectional view of an optical filter composed only of the transparent adhesive layer 20 containing the pigment mixture. FIG. 3 shows a schematic cross-sectional view of an optical filter composed only of the transparent substrate 10 containing the dye mixture. FIG. 4 shows a schematic cross-sectional view of an optical filter in which a coating layer 30 containing a pigment mixture is laminated on a transparent substrate 10.

  Examples of the present invention will be shown below, but the present invention is not limited thereto.

Synthesis of tetraazaporphyrin compound isomer mixture A 69.0 g of a compound represented by the following structural formula (5-a) and 17.3 g of sodium ethoxide were dispersed in 970 g of n-amyl alcohol, and ammonia gas was added at 50 ° C. with stirring. Infused for 3 hours. After stopping the blowing of ammonia gas, the temperature was raised to 90 ° C., and 21.0 g of vanadium trichloride was charged at the same temperature. The temperature was raised to 120 ° C., stirred at the same temperature for 2 hours, and then cooled to room temperature. 200 g of toluene was charged, insoluble matters were filtered off, the filtrate was concentrated under reduced pressure, and then 400 g of methanol was charged. The precipitate was filtered, washed with methanol, and dried, and then the filter cake was purified by column (silica gel / toluene: hexane = 4: 6 vol.) To obtain 3 components of the following isomer of purple component. From the following analysis, it was confirmed to be the target product. The yield of each isomer component is also described.

  The absorption maximum in toluene and the gram extinction coefficient of each component thus obtained were as follows.

  Furthermore, (1-a) and (2-a) were mixed at the same ratio as the above yield, and the absorption maximum in toluene and Gram extinction coefficient of mixture A were as follows.

Synthesis of tetraazaporphyrin compound isomer mixture B 10.0 g of 1,8-diazabicyclo [5,4,0] -7-undecene represented by the following structural formula (5-a) was added to 74.0 g of n-amyl alcohol. 8.9 g was dispersed, the temperature was raised to 95 ° C. with stirring, and 3.8 g of cuprous chloride was charged at the same temperature. The temperature was raised to 135 ° C., stirred at the same temperature for 5 hours, and then cooled to room temperature. After the reaction solution was concentrated under reduced pressure, 140 g of methanol was charged. The precipitate was filtered, washed with methanol and dried, and then the filter cake was purified by column (silica gel / toluene: hexane = 5: 5 vol.) To obtain 3 components of the following isomer of purple component. From the following analysis, it was confirmed to be the target product. The yield of each isomer component is also described.

  The absorption maximum in toluene and the gram extinction coefficient of each component thus obtained were as follows.

  Furthermore, (1-b) and (2-b) were mixed at the same ratio as the above yield, and the absorption maximum in toluene and the gram extinction coefficient of mixture B were as follows.

[Comparative Example 1]
In Example 1, the absorption maximum in toluene and the gram extinction coefficient of Mixture A2 in which Component A (3-a) was further mixed with Mixture A in the yield ratio of Example 1 were as follows.

Mixture A was dispersed and dissolved in an ethyl acetate / toluene (50:50 wt%) solvent to prepare a dye-containing diluent for an acrylic pressure-sensitive adhesive so as to have a concentration of 1150 ppm. Acrylic adhesive / pigmented diluent (80: 20% by weight) is mixed and coated on a polyethylene terephthalate film (Teijin Limited, thickness 75 μm) with a batch die coater and dried to produce an optical filter. did. The transmittance of the filter was measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The transmittance at the absorption maximum at 594 nm was 16.0%.
When the filter is mounted on a transmissive liquid crystal display (with a color filter) with red emission chromaticity (x, y) = (0.614, 0.332), (Δx, Δy) = (+ 0.004). , -0.009).

An optical filter was produced in the same manner as in Example 3 except that the mixture B was used instead of the mixture A. The transmittance of the filter was measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The transmittance at the absorption maximum at 584 nm was 15.0%.
When the filter is mounted on a transmissive liquid crystal display (with a color filter) with red emission chromaticity (x, y) = (0.614, 0.332), (Δx, Δy) = (+ 0.003). , -0.008).

When the optical filter produced in Example 3 was mounted on a plasma display panel with red emission chromaticity (x, y) = (0.631, 0.370), (Δx, Δy) = (+ 0.035). , -0.031).

The optical filter produced in Example 3 was mounted on an ultraviolet cut acrylic plate [thickness 2 mm].
The transmittance of the acrylic plate with a filter was measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The transmittance at the absorption maximum at 594 nm was 16.4%.
Furthermore, when the light resistance test was performed by irradiating the filter-coated acrylic plate with a xenon lamp [58.5 mW / cm ² ], the transmittance at 594 nm was 16.0% in 1000 hours, and the filter was hardly deteriorated. I couldn't see it.

[Comparative Example 2]
An optical filter was produced in the same manner as in Example 3 except that the mixture A2 was used instead of the mixture A. Further, the optical filter was mounted on an ultraviolet cut acrylic plate [thickness 2 mm].
The transmittance of the acrylic plate with a filter was measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. The transmittance at the absorption maximum at 596 nm was 16.1%.
Furthermore, when the light resistance test was performed by irradiating the acrylic plate with a filter with a xenon lamp [58.5 mW / cm ² ] for 1000 hours, the transmittance at 596 nm was 60% in 500 hours, and the deterioration of the filter was observed. It was.

According to the present invention, a practical filter material having a high visible light transmittance that selectively cuts light of a specific wavelength generated in various displays, particularly plasma display panels, and does not impair the color purity of the display. As a useful tetraazaporphyrin dye mixture and an optical filter using the dye mixture can be provided.

Sectional drawing which shows an example of an optical filter Sectional drawing which shows an example of an optical filter Sectional drawing which shows an example of an optical filter Sectional drawing which shows an example of an optical filter

Explanation of symbols

10 Transparent foundation 20 Transparent adhesive layer 30 Coat layer

Claims (4)

A tetraazaporphyrin dye comprising a mixture of a tetraazaporphyrin compound isomer represented by the general formula (1) and a tetraazaporphyrin compound isomer represented by the general formula (2).

[In the formula, R represents a t-butyl group , M represents Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Pd (II), Mn (II) or Represents VO . ] Tetraazaporphyrins obtained by removing tetraazaporphyrin compound isomers represented by general formulas (3) and (4) from tetraazaporphyrin compound isomer mixtures represented by general formulas (1) to (4) Pigment .

[In the formula, R represents a t-butyl group, M represents Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Pd (II), Mn (II) or Represents VO. ] The dye according to claim 1 or 2, having a gram extinction coefficient in a solution of 200,000 (ml / g.cm) or more in a wavelength band of 570 to 605 nm . In the substrate, an optical filter comprising the color element according to any one of 1 to 3.

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