JP2009025601A - Optical filter and front filter for display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical filter and a front filter for a display, the filter containing a metal ion-containing compound having a specific structure and a near IR ray absorbing dyestuff and excellent in weather resistance, particularly, light resistance and heat resistance. <P>SOLUTION: The optical filter and a front filter for a display contain at least one kind of near IR ray absorbing dye and at least one kind of metal ion-containing compound expressed by general formula (X-1):M(X<SB>1</SB>)<SB>m</SB>(X<SB>2</SB>)<SB>1</SB>_(W<SB>1</SB>)<SB>s</SB>. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical filter containing at least one near-infrared absorbing dye and at least one metal ion-containing compound, and a front filter for display.

  In recent years, various displays such as a plasma display, a CRT, a fluorescent display tube, and a liquid crystal display have been developed as display panels for various electronic devices including large-sized wall-mounted televisions, and the demand for such displays has increased. In addition, new display technologies such as EL display and FED display have been put into practical use, and it is speculated that the demand for displays will greatly increase in the future.

  In recent years, plasma displays that are attracting attention as thin large-screen displays have a problem in that home appliances and electronic devices that use a near-infrared remote controller malfunction due to near-infrared rays (approximately 800 to 1200 nm) emitted from the plasma display. . One solution to the above problem is that a near-infrared absorbing optical filter comprising an optical film using a near-infrared absorbing dye as a constituent element is disposed on the front surface of the plasma display and is emitted from the display. However, since the plasma display emits electromagnetic waves, heat rays and ultraviolet rays in addition to the above-mentioned near infrared rays, the front filter is likely to deteriorate. In recent years, thinning of the front filter has been demanded for the purpose of reducing costs and improving light transmittance. However, the thinning of the front filter is affected not only by electromagnetic waves, heat rays and ultraviolet rays emitted from the display, but also by outside air. The conventional front filter has not been sufficiently durable.

  Various near-infrared absorbing dyes for use in near-infrared absorbing optical filters have been proposed. Among them, organic dyes have a high degree of freedom in molecular design, so the absorption wavelength can be easily controlled. However, it is possible to select a simple method such as laminating a layer in which a dye is dispersed or dissolved in a resin on a base material, the processability and productivity are good, and the degree of freedom in optical design is relatively large. Widely used. However, since organic dyes are generally susceptible to discoloration and discoloration due to heat, light, and outside air, various methods for improving durability when added to an optical film (for example, Patent Document 1). -6) have been proposed.

  Patent Document 1 discloses an optical filter containing a salt compound of a near-infrared absorbing dye having a specific structure and a deterioration inhibitor. However, although the light resistance is improved, there is no description about the effect of heat resistance and thinning of the front filter.

  For the purpose of improving visible light transmittance, infrared absorption performance, and light resistance, Patent Document 2 discloses an optical filter containing a metal complex compound of a near-infrared absorbing dye having a specific structure. There are no examples, and no mention is made of the effects of heat resistance and thinning of the front filter. Patent Document 3 and Patent Document 4 disclose optical filters containing a metal complex compound, and Patent Document 5 and Patent Document 6 disclose a metal complex compound, a metal complex compound, and a near infrared absorbing dye having another specific structure. Although optical filters are disclosed, all of the optical filters derived from the metal complex compounds described herein have been disclosed for light resistance, heat resistance, and heat and humidity resistance, but near infrared rays of other specific structures There is no description about the durability and the effect of thinning the front filter when combining absorbing dyes.

On the other hand, attempts have been made to improve the light resistance and heat resistance of organic dye-containing compositions by using metal-containing compounds in combination with organic dye-containing compositions (see, for example, Patent Documents 7 to 9). ing. However, although all of these attempts are effective for visible light absorbing dyes, an optical filter containing a near infrared dye and the front surface for display are used for the purpose of further improving the durability of the near infrared absorbing optical filter. Examples of using specific metal ion-containing compounds as a means to improve the light resistance, heat resistance, and electromagnetic waves and heat rays emitted from the display, as well as the influence of outside air, as well as the above-mentioned problems in filters There are no known optical filters and display front filters containing specific metal ion-containing compounds and near-infrared absorbing dyes.
JP 2002-350632 A JP 2000-159776 A JP-A-63-112592 Japanese Patent No. 3812751 JP 2005-165265 A JP 2006-126226 A Japanese Patent Laid-Open No. 3-197088 JP 2001-342364 A JP 2007-31425 A

  The present invention has been made in view of the above circumstances, and as a result of studies by the present inventors, the above-mentioned problems are caused by an optical filter and a front filter for display containing a metal ion-containing compound having a specific structure and a near-infrared absorbing dye. Found that it can be solved. An object of the present invention is to provide an optical filter and a display front filter containing a metal ion-containing compound having a specific structure and a near-infrared absorbing dye.

  The above object of the present invention can be achieved by the following configuration.

1. An optical filter comprising at least one near-infrared absorbing dye and at least one metal ion-containing compound represented by the following general formula (X-1).
Formula (X-1)
M (X ₁ ) _m (X ₂ ) _l · (W ₁ ) _s
Wherein, M represents a divalent ion of Zn or Cu, X ₁ and X ₂ represents a monodentate or bidentate ligand each independently may be different even in the same, X ₁ And X ₂ may be linked. m, l, and s each represent an integer of 0 to 2, and m + l> 1. (W ₁ ) _s represents a counter ion necessary for neutralizing the charge. However, at least one of the ligands represented by X ₁ or X ₂ is the following general formula (X-1a). ]

[Wherein, E ₁ represents a substituent, E ₂ represents a hydrogen atom or a substituent, and R represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group. ]
2. 2. The optical filter as described in 1 above, wherein the metal ion of the metal ion-containing compound represented by the general formula (X-1) is Cu.

  3. A front filter for a display, wherein the optical filter according to 1 or 2 is used.

  According to the present invention, an optical filter having excellent weather resistance, particularly light resistance and heat resistance, can be provided. Furthermore, by using this optical filter, it was possible to provide a front filter for display having excellent spectral absorption characteristics and weather resistance, in particular, sufficient weather resistance even when the front filter is thinned.

  The present invention will be described in more detail.

  Hereinafter, although the optical filter containing the metal ion containing compound and near-infrared absorption pigment | dye of this invention, and the front filter for a display are demonstrated, this invention is not limited to these.

(Metal ion-containing compounds)
The present invention contains at least one metal ion-containing compound represented by the general formula (X-1).

  In the general formula (X-1), M represents a divalent ion of Zn or Cu, and is preferably Cu.

X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, which may be the same or different, and X ₁ and X ₂ may be linked. Examples of X ₁ and X ₂ include JP 2000-251957, JP 2000-311723, JP 2000-323191, JP 2001-6760, JP 2001-59062, JP 2001-60467, and the like. As described in the above. Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (such as methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, aminopolycarboxylic acid Various chelate ligands such as acids, 8-hydroxyquinoline and the like can be mentioned, and the chelate ligands are exemplified in “Chelical Chemistry” by Keihei Ueno.

  As a monodentate ligand, a ligand coordinated by an acyl group, carbonyl group, thiocyanate group, isocyanate group, cyanate group, isocyanate group, halogen atom, cyano group, alkylthio group, arylthio group, alkoxy group or aryloxy group Or a ligand composed of dialkyl ketone or carbonamide is preferred.

  As bidentate ligands, acyloxy group, oxalylene group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate A ligand coordinated by a group, an alkylthio group or an arylthio group, or a ligand comprising a dialkyl ketone or a carbonamide is preferred.

  Although the example of a ligand is shown below, this invention is not limited to these. It should be noted that the structural formula shown here is only one of the limit structures among the possible resonance structures, and the distinction between a covalent bond (indicated by-) and a coordination bond (indicated by ...) is also formal. It does not represent an absolute distinction.

In the present invention, at least one of the ligands represented by X ₁ or X ₂ of the metal ion-containing compound represented by the general formula (X-1) is the general formula (X-1a).

In the general formula (X-1a), when E ₁ and E ₂ are substituents, specifically, examples of the substituent include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, trifluoromethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group etc.), alkenyl group ( For example, vinyl group, allyl group, etc.), alkynyl group (eg, ethynyl group, propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heteroaryl group (eg, furyl group, thienyl group, pyridyl group) , Pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, pyrazolyl group, thiazolyl Group, benzimidazolyl group, benzooxazolyl group, quinazolyl group, phthalazyl group, etc.), heterocyclic group (also called heterocyclic group, for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, Methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, , Phenoxy group, naphthyloxy group, etc.), alkylthio group (eg, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexene) Silthio group), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.) , Aryloxycarbonyl groups (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl groups (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group) Butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylamino Sulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, Dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy) Group), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcal Bonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group) Dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2- Pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexyl) Ureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2- Ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) Group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group For example, amino group, ethylamino group, dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group), azo Group (for example, phenylazo), alkylsulfonyloxy group (for example, methanesulfonyloxy), cyano group, nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group and the like are more preferable. Is an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido Group, sulfinyl group, alkylsulfonyl group, arylsulfonyl group, amino group, cyano group, halogen atom, hydroxyl group, alkenyl group, aryl group, heteroaryl group, heterocyclic group, more preferably alkyl group, cycloalkyl group , Alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, acyl group, acyloxy group, amide group, carbamoyl group, cyano group, halogen atom, hydroxyl group, alkenyl group, and more preferably Is an alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, aryloxy group, acyl group, amide group, carbamoyl group, cyano group, halogen atom, hydroxyl group, alkenyl group.

  These substituents may be further substituted with the same substituent, or the substituents may be further bonded to each other to form a ring.

Either one or both of E ₁ and E ₂ are preferably an electron-withdrawing group, and an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less as an index indicating the degree of electron-withdrawing E ₁ is preferably a Hammett substituent constant (σp) of 0.35 or more and 0.9 or less, and more preferably both E ₁ and E ₂ are Hammett substituent constants. (Σp) is 0.35 or more and 0.9 or less.

  A substituent having a Hammett's substituent constant (σp) of 0.1 or more and 0.9 or less indicating the degree of electron withdrawing will be described. As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

  For example, a substituent or atom having a value of σp of 0.10 or more includes a chlorine atom, a bromine atom, an iodine atom, a carboxyl group, a cyano group, a nitro group, a halogen-substituted alkyl group (for example, trichloromethyl, trifluoromethyl, chloro Methyl, trifluoromethylthiomethyl, trifluoromethanesulfonylmethyl, perfluorobutyl), aliphatic, aromatic or heterocyclic acyl groups (eg formyl, acetyl, benzoyl), aliphatic / aromatic or heterocyclic sulfonyl groups (eg trifluoromethane) Sulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro-phenylcarbamoyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxy) Carbonyl, diphenylmethylcarbonyl), substituted aryl groups (eg pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic groups (eg 2-benzoxazolyl, 2- Benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg methanesulfonyloxy), acyloxy group (eg acetyl) Oxy, benzoyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy), phosphoryl group (for example, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, N-ethyl) Sulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) and the like.

  In addition, as a substituent having a σp value of 0.35 or more, a cyano group, a nitro group, a carboxyl group, a fluorine-substituted alkyl group (for example, trifluoromethyl, perfluorobutyl), an aliphatic, aromatic or heterocyclic acyl group (Eg, acetyl, benzoyl, formyl), aliphatic, aromatic or heterocyclic sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro) -Phenylcarbamoyl), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (for example, pentafluorophenyl, 2,4-dimethanesulfonate) Phenyl), a heterocyclic group (for example, 1-tetrazolyl), an azo group (for example, phenylazo), an alkylsulfonyloxy group (for example, methanesulfonyloxy), a phosphoryl group (for example, dimethoxyphosphoryl, diphenylphosphoryl), a sulfamoyl group, and the like. Can be mentioned.

  Examples of the substituent having a value of σp of 0.60 or more include a cyano group, a nitro group, an aliphatic / aromatic or heterocyclic sulfonyl group (for example, trifluoromethanesulfonyl, difluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl) and the like. It is done.

Further, the van der Waals (VDW) volume of the substituent represented by E ₁ and E ₂ is preferably 75 ³ or less, and more preferably 45 ³ or less. In particular, E ₂ preferably has a van der Waals (VDW) volume of 35 ³ or less.

  The van der Waals (VDW) volume of the substituent is a parameter obtained using the molecular simulation software Cerius 2 manufactured by Accelrys, Inc., but by introducing a substituent into the benzene ring and using the Driving Force Field, The molecular structure is optimized and defined as a Volume value obtained using the Connoy Surface. Some examples of van der Waals (VDW) volumes of specific substituents are shown below.

Substituent Å ³
Methyl group 25.4
Ethyl group 42.6
Isopropyl group 59.5
tert-Butyl group 76.2
Phenyl group 74.9
Methoxy group 34.0
Amino group 22.2
Hydroxyl group 16.7
Chlorine atom 22.4
Bromine atom 26.5
Fluorine atom 13.3
Trifluoromethyl group 42.5
Preferable examples of the substituent represented by E ₁ and E ₂ include a halogenated alkyl group, a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylsulfonyloxy group. E ₁ is more preferably a halogen-substituted alkyl group or a cyano group, more preferably a halogen-substituted alkyl group, and most preferably a fluorine-substituted alkyl group. E ₂ is more preferably a cyano group, a nitro group, an alkylsulfonyl group or a carbonyl group, more preferably a cyano group or a nitro group, and most preferably a cyano group.

  R is preferably an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group, and more preferable substituents are an alkyl group having 2 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. , An aryloxy group, and an amino group, more preferably an alkyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryloxy group, and most preferably an alkoxy group having 1 to 16 carbon atoms. is there.

  Specific examples of the ligand represented by the general formula (X-1a) are shown below, but the present invention is not limited thereto.

  W represents a counter ion necessary to neutralize the charge. For example, whether a compound containing a metal ion is a cation, an anion, or has a net ionic charge depends on the metal, ligand. , And depending on the substituent. When the substituent has a dissociable group, it may be dissociated and have a negative charge. In this case, the charge of the whole molecule is neutralized by X. Typical cations are inorganic or organic ammonium ions (eg tetraalkylammonium ions, pyridinium ions), alkali metal ions and protons, while the anions can be either inorganic or organic anions. , For example, halogen anion (eg, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl Disulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanic acid Ion, persalt Acid ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, enolate (acetylacetonate, hexafluoroacetylacetonate), hydroxide ion, sulfite ion, nitrate ion, Examples thereof include nitrite ion, carbonate ion, perchlorate ion, alkyl carboxylate ion, aryl carboxylate ion, tetraalkylborate, salicinate, benzoate, hexafluoroantimony and the like. s is an integer of 0 to 2, and is preferably 0.

  Although the typical example of the metal ion containing compound represented by the said general formula (X-1) is given to the following, this invention is not limited to this.

(Near-infrared absorbing dye)
The present invention contains at least one near infrared absorbing dye.

  Near-infrared absorbing dyes include nitroso compounds and their metal complexes, polymethine dyes (cyanine, oxonol, croconium, squarylium, pyrylium, azurenium), dithiol complex compounds, phthalocyanine compounds, naphthalocyanine compounds, tri Examples include allylmethane dyes, immonium dyes, diimmonium dyes, naphthoquinone compounds, anthraquinone compounds, amino compounds, and aminium salt compounds.

  Among these, particularly, an immonium dye, a diimmonium dye, a naphthoquinone compound, an anthraquinone compound, an amino compound, an aminium salt compound, a polymethine dye, or a triallylmethane dye is preferable, and an immonium dye or diimmonium dye is more preferable. It is a dye, an aminium salt compound, a polymethine dye, or a triallylmethane dye, more preferably an immonium dye, a diimmonium dye, or a polymethine dye, and a diimonium dye or polymethine dye is even more preferable. Of the polymethine dyes, croconium, squarylium, and pyrylium polymethine dyes are preferred. The diimmonium dye is preferably one represented by the following general formula (I).

In the general formula (I), R _{1 to} R ₈ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an aralkyl group, or an alkynyl group. R _{9 to} R ₁₂ may be the same or different and each represents a hydrogen atom, a halogen atom, an amino group, a cyano group, a nitro group, a carboxyl group, an alkyl group, or an alkoxyl group. R _{1 to} R ₁₂ which can be bonded to a substituent may have a substituent. X ⁻ represents an anion.

When R _{1 to} R _{8 in} the general formula (I) are (a) an alkyl group, (b) an aryl group, (c) an alkenyl group, and (d) an aralkyl group, the following groups can be exemplified.

(A) Alkyl group: methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, n-amyl group, n-hexyl group, n-octyl Group, 2-hydroxyethyl group, 2-cyanoethyl group, 3-hydroxypropyl group, 3-cyanopropyl group, methoxyethyl group, ethoxyethyl group, butoxyethyl group, etc. (b) aryl group: phenyl group, fluorophenyl group, Chlorophenyl group, tolyl group, diethylaminophenyl group, naphthyl group, etc. (c) Alkenyl group: vinyl group, propenyl group, butenyl group, pentenyl group, etc.

  (D) Aralkyl group: benzyl group, p-fluorobenzyl group, p-chlorophenyl group, phenylpropyl group, naphthylethyl group and the like.

In addition, examples of the (e) halogen atom, (f) amino group, (g) alkyl group, and (h) alkoxyl group of R _{9 to} R _{12 in} the general formula (I) include the following groups.

(E) Halogen atom: fluorine, chlorine, bromine, etc. (f) Amino group: diethylamino group, dimethylamino group, etc. (g) Alkyl group: Methyl group, ethyl group, propyl group, trifluoromethyl group, etc. (h) Alkoxyl group : Methoxy group, ethoxy group, propoxy group and the like.

Examples of X ⁻ in the above general formula (I) include fluorine ion, chlorine ion, bromine ion, iodine ion, perchlorate ion, hexafluoroantimonate ion, hexafluorophosphate ion, and tetrafluoroboric acid. Anions such as ions and bis (trifluoromethanesulfonyl) imido ions.

  A commercially available product can be used as the diimmonium salt compound represented by the general formula (I). For example, Kayasorb IRG-022, IRG-023, IRG-024 (manufactured by Nippon Kayaku Co., Ltd.), CIR-1080, CIR-1081, CIR-1083, CIR-1085 (manufactured by Nippon Carlit) are suitable. It is.

  Specific examples of the near-infrared absorbing dye that can be suitably used include, for example, JP-A No. 2004-93767, JP-A No. 2004-69759, JP-A No. 2002-286931, JP-A No. 2002-122729, JP-A No. 2001-115050, JP-A-2001-115050, JP-A-2000-162431, JP-A-11-109126, JP-A-2006-139111 can be mentioned, but the present invention is limited to these. There is no.

  Furthermore, in addition to the above-mentioned near-infrared absorbing dye, carbon black which is an inorganic substance, indium tin oxide, antimony tin oxide, oxides of metals belonging to Group 4A, 5A or 6A of the periodic table, carbides, borides, etc. May be included.

  The optical filter containing the metal ion-containing compound and near-infrared absorbing dye of the present invention is preferably used as a composition with a binder (dispersing agent) or a composition further added with a solvent.

  Binders include (meth) acrylate resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyepoxy resins, polyester resins, amino resins, fluorine resins, phenol resins, polyurethane resins. Resins, polyethylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, aramid resins, etc. are preferable, but (meth) acrylates are preferred. Resin, polystyrene resin, polyethylene resin, polyvinyl chloride resin, polyvinyl alcohol resin and the like are preferably used, and (meth) acrylate resin and polystyrene resin are most preferable. These copolymers are also preferred.

  The (meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various methacrylate monomers or acrylate monomers, and by changing the monomer species and the monomer composition ratio, the desired (meth) acrylate is obtained. System resin can be obtained. In the present invention, it can be used together with a (meth) acrylate monomer and a copolymerizable monomer having an unsaturated double bond other than a (meth) acrylate monomer. Can also be used by mixing a plurality of other resins together with the poly (meth) acrylate resin.

  Examples of the monomer component forming the (meth) acrylate resin used in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. , Isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, dimethylaminoethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, ethylene glycol methyl ether (meth) acrylate, isobonyl (meth) acrylate Ethyltrimethylammonium chloride (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2-acetamidomethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-dimethylaminoethyl (Meth) acrylate, 3-trimethoxysilanepropyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dodecyl (meth) acrylate , Octadecyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (Meth) acrylate, glycidyl (meth) acrylate and the like can be mentioned, but (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, stearyl ( They are meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, dodecyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

  Polystyrene resins include homopolymers of styrene monomers, or random copolymers, block copolymers, and graft copolymers obtained by copolymerizing monomers with other unsaturated double bonds that can be copolymerized with styrene monomers. It is done. Furthermore, blends and polymer alloys obtained by blending such polymers with other polymers are also included. Examples of the styrene monomer include nuclear alkyl substitution such as styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc. Examples of the halogenated styrene include styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and tribromostyrene. Styrene and α-methylstyrene are preferred.

  Resins used in the present invention are synthesized by homopolymerization or copolymerization of these, for example, copolymer resins such as benzyl methacrylate / ethyl acrylate or butyl acrylate, and copolymers such as methyl methacrylate / 2-ethylhexyl methacrylate. Polymer resin, copolymer resin of methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyethyl methacrylate, copolymer resin of styrene / acetoacetoxyethyl methacrylate / stearyl methacrylate, styrene / 2-hydroxyethyl methacrylate / Examples include stearyl methacrylate copolymers, and copolymer resins such as 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate.

《Optical filter and front filter for display》
The optical filter and the front filter for display according to the present invention include a composition containing at least one metal ion-containing compound and a near-infrared absorbing dye in a substrate. The term “containing in the base material” as used in the present invention means, of course, a state of being applied to the surface of the base material, a state of being sandwiched between the base material and the like, etc.

  The optical filter according to the present invention is characterized by having at least one absorption maximum in the visible range, and is known as a so-called color filter. It transmits light of a specific color like a component used in a solid-state imaging device such as a CCD image sensor or a color display using liquid crystal, and reduces light in a specific wavelength range without blocking the others. Or, it is used to block light and transmit other light.

  The front filter for display according to the present invention is disposed on the front surface of a self-luminous display device such as a plasma display or an organic EL display, and is used for color adjustment or blocking light emission in an unnecessary wavelength region.

  In the present invention, the near-infrared absorbing filter is a filter having a low transmittance in the near-infrared region with a wavelength of 800 to 1200 nm and a high transmittance in the visible light region with a wavelength of 400 to 800 nm. The transmittance in the near infrared region is preferably as low as possible, specifically 40% or less, more preferably 30% or less. When the transmittance of the near-infrared region is high, when the near-infrared absorbing film of the present invention is used as a constituent member of the front filter of the plasma display, the absorption of the near-infrared emitted from the plasma display is insufficient, It is impossible to prevent malfunction of an electronic device using a near infrared remote controller. When used as a display filter, the visible light region has a higher transmittance, preferably 50% or more, more preferably 60% or more. When the transmittance in the visible light region is low, the color of the display is hindered and an image with low luminance is obtained.

  The adjustment of the transmittance can be controlled by the kind of the above-mentioned near-infrared absorbing dye and the abundance of the near-infrared absorbing dye per unit area.

  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. For example, polyimide, polysulfone (PSF), polyethersulfone (PES), polyethylene terephthalate (PET), polymethylene methacrylate (PMMA), polycarbonate (PC), polyetheretherketone (PEEK), polypropylene (PP), triacetyl A cellulose (TAC) etc. are mentioned. In particular, acrylic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA), polycarbonate resins, and the like are preferably used.

  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 invention and the front filter for display using the optical filter composition is not particularly limited,
(1) Method of containing in transparent adhesive (2) Method of containing in polymer molded body (3) Method of coating on 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), and ethylene-vinyl acetate adhesives (EVA). Etc., sheet-like or liquid pressure-sensitive adhesives such as polyvinyl ether, saturated amorphous polyester, melamine resin, etc., among which acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and polyvinyl butyral pressure-sensitive adhesives are preferable. The addition amount of the pigment is usually 10 ppm to 30% by mass, preferably 10 ppm to 20% by mass, and particularly preferably 10 ppm to 10% by mass.

  (2) The polymer resin molded body listed in (2) includes (A) a method of kneading a dye mixture into a resin and heat molding, and (B) an organic solvent containing a resin or resin monomer and a dye mixture. Examples thereof include a method in which a polymer molded body is prepared by dispersing and dissolving and casting.

  The resin used in (A) is preferably as transparent as possible when a plate or film is produced. Specifically, polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate, poly Polyamides such as arylate, polyetherketone, polycarbonate, polyethylene, polypropylene and nylon 6, cellulose resins such as polyimide and triacetyl cellulose, fluorine resins such as polyurethane and polytetrafluoroethylene, vinyl compounds such as polyvinyl chloride, polyacrylic Acid, polyacrylic acid ester, polyacrylonitrile, addition polymer of vinyl compound, polymethacrylic acid, polymethacrylic acid ester, vinylidene chloride such as polyvinylidene chloride, vinylidene fluoride / trifluoroe Ren copolymers, 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.

  Processing conditions include adding and mixing the dye mixture to the base polymer powder or pellets, heating and dissolving at 150 to 350 ° C., molding, and forming a plate, and filming with an extruder And a method of preparing a raw material with an extruder and stretching the film in a uniaxial or biaxial manner at 2 to 5 times at 30 to 120 ° C. to form a film having a thickness of 10 to 200 μm. In addition, when kneading, an additive used for ordinary resin molding such as plasticity may be added.

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

  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.

  As a method of coating on the polymer molded body or glass surface mentioned in (3), a method of forming a composition after dissolving the metal ion-containing compound and pigment of the present invention in a binder resin and an organic solvent, Examples thereof include a method of dispersing an uncolored acrylic emulsion paint obtained by finely pulverizing (50 to 500 nm) the metal ion compound of the present invention and squarylium pigment into an acrylic emulsion aqueous paint. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

  Examples of binders 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, and polyvinyl resins. Examples thereof include 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 composition varies depending on the gram extinction coefficient, coating thickness, target absorption intensity, target visible light transmittance, and the like, but is usually 0.1 ppm to 30% by mass with respect to the mass of the binder resin. Moreover, resin concentration is 1-50 mass% normally with respect to the whole coating material.

  The coating material produced by the above method is applied by forming a thin film on a substrate by a known method such as a bar coder, blade coater, spin coater, reverse coater, die coater, or spray coating method. be able to.

  Furthermore, the front filter for display of the present invention preferably has an electromagnetic wave shielding 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 laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated is preferable. 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. In addition, a method of patterning with a metal-containing ink, a method of applying silver halide, developing and fixing, and the like are also preferably used.

  Furthermore, a functional transparent layer such as a known antireflection layer, antiglare layer, hard coat layer, antistatic layer, and antifouling layer can be added to the display front filter of the present invention.

  In addition, for UV protection, an ultraviolet cut acrylic plate may be used for the substrate, or an ultraviolet absorbing layer may be formed on one or both sides of the substrate, but the front film for display of the present invention absorbs UV. An agent may be included. Examples of ultraviolet absorbers include salicylic acid derivatives (UV-1), benzophenone derivatives (UV-2), benzotriazole derivatives (UV-3), acrylonitrile derivatives (UV-4), benzoic acid derivatives (UV-5), or organic There are metal complex salts (UV-6) and the like (UV-1) are phenyl salicylate, 4-t-tylphenylsalicylic acid, etc., and (UV-2) is 2-dihydroxybenzophenone, 2-hydroxy- 4-methoxybenzophenone and the like (UV-3) include 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole, 2- (2'-hydroxy-3'-5'-di-butyl) Phenyl) -5-chlorobenzotriazole and the like (UV-4) is 2-ethylhexyl-2-cyano-3,3'-di Phenyl acrylate, methyl-α-cyano-β- (p-methoxyphenyl) acrylate and the like (UV-5) include resorcinol-monobenzoate, 2 ′, 4′-di-t-butylphenyl-3.5 -T-butyl-4-hydroxybenzoate and the like (UV-6) include nickel bis-octylphenylsulfamide, nickel salt of ethyl-3,5-di-t-butyl-4-hydroxybenzyl phosphate, etc. Can be mentioned.

  The ultraviolet absorber described above preferably used in the present invention has high transparency and is excellent in the effect of preventing deterioration of an optical device such as a polarizing plate, a liquid crystal element, or a plasma display, and a benzotriazole ultraviolet absorber or a benzophenone ultraviolet absorber. A benzotriazole-based ultraviolet absorber with less unnecessary coloring is particularly preferable.

  In addition to these, an antioxidant, a polymerization initiator, and the like can be appropriately added as necessary.

  In order to obtain an electronic display or a plasma display panel display device using the display front filter of the present invention, any known display device or commercially available display device can be used without particular limitation.

  A plasma display panel display device is a device that displays a color image according to the following principle. A cell corresponding to each pixel (R (red), G (green), B (blue)) provided between two glass plates is provided between the front glass plate and the rear glass plate, and the cell Xenon gas or neon gas is sealed in the inside, and a phosphor corresponding to each pixel is applied to the back glass plate side in the cell. Due to the discharge between the display electrodes, the xenon gas and neon gas in the cell are excited to emit light, and ultraviolet rays are generated. By irradiating the phosphor with this ultraviolet ray, visible light corresponding to each pixel is generated. Then, an address electrode is provided on the rear glass plate, and by applying a signal to the address electrode, which discharge cell is displayed is controlled, and a color image is displayed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

Example 1
Production of Evaluation Sample 1-A (Production of Optical Filter 1-A1)
For 100% by mass of polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.)
Near-infrared absorbing dye A: 5% by mass,
Metal ion-containing compound MS-14 of the present invention: 3% by mass was weighed.

  Transfer the weighed polyester resin, pigment, and metal ion-containing compound to the same container, add methyl ethyl ketone so that the polyester resin solids mass is 25% by mass, and thoroughly mix the composition of the present invention with an ultrasonic disperser. Dispersed (Composition: 1-a). The composition was coated on a PET film substrate having a thickness of 100 μm formed by biaxial stretching with a bar coater so that the near infrared transmittance at the near infrared absorption maximum wavelength of the filter was 3%. The sample thus obtained was designated as optical filter 1-A1.

(Manufacture of optical filter 1-A2)
The optical filter 1-A1 was manufactured in the same manner except that the PET film substrate having a film thickness of 100 μm formed by biaxial stretching was changed to a PET film having a film thickness of 25 μm formed by biaxial stretching. Thus, an optical filter (sample: 1-A2) was produced.

  The manufactured optical filters 1-A1 and 1-A2 of the present invention were evaluated for heat resistance according to the following criteria.

(Heat resistance test)
An optical filter was attached to the adapter and heated for 100 hours only from the back side of the dye-coated surface of the substrate using warm air kept at a temperature of 40 ° C. and a humidity of 90%. During the test, the dye-coated surface side was kept under a nitrogen atmosphere.

  After 100 hours, in the optical filters 1-A1 and 1-A2, almost no change in the near-infrared transmittance at the near-infrared absorption maximum wavelength of the filter was observed (less than 1%).

Production of Evaluation Sample 2-A (Production of Optical Filter 2-A1)
An optical filter (sample: 2-A1) was produced in the same manner as in the production of the optical filter 1-A1 except that the PET film substrate having a film thickness of 100 μm was changed to a TAC film substrate having a film thickness of 80 μm.

(Manufacture of optical filter 2-A2)
An optical filter (sample: 2-A2) was produced in the same manner except that the PET film substrate having a film thickness of 100 μm was changed to a TAC film substrate having a film thickness of 20 μm in the production of the optical filter 1-A1.

  About the produced optical filter 2-A1 and 2-A2 of this invention, the heat test was evaluated by the following reference | standard.

(Heat resistance test)
An optical filter was attached to the adapter, and heated for 2000 hours only from the back side of the dye-coated surface of the substrate using warm air kept at a temperature of 40 ° C. and a humidity of 90%. During the test, the dye-coated surface side was kept under a nitrogen atmosphere.

  After 100 hours, almost no change in near-infrared transmittance at the absorption maximum wavelength of near-infrared light of the optical filters 2-A1 and 2-A2 was observed (less than 1%).

(Evaluation sample: production of 3-A to 21-A)
Optical filters 3-A to 21-A were produced in the same manner as in the production of the evaluation sample 1-A, except that the dye, the metal ion-containing compound, and the substrate were changed as shown in Table 3 below. In addition, the addition ratio (X) of the pigment | dye and the addition ratio (Y) of a metal ion containing compound in a table | surface are respectively the addition ratios when the solid content mass of a binder is 100 mass%.

  The compounds used are as follows.

Dye near-infrared absorbing dye A squarylium type (structure is described in chemical formula 13)
Near-infrared absorbing dye B Croconium-based (structure is shown below)
Near-infrared absorbing dye C IR-301 (Yamada Chemical) Polymethine near-infrared absorbing dye D Adeka Arcles TY-100 (Asahi Denka Kogyo) Cyanine near-infrared absorbing dye E IRG-022 (Nippon Kayaku) near diimmonium Infrared absorbing dye F squarylium metal complex compound (structure is shown below)
Near-infrared absorbing dye G Tetrabutylammonium bis (2-methylaminobenzenethiol) nickelate complex Metal ion-containing compound comparison Metal ion-containing compound H Di-butyltin malate stabilizer [P-5T (manufactured by Tokyo Fine Chemical Co., Ltd.)] ]
Comparative metal ion-containing compound I Nickel metal compound (structure is shown below)
Base material base I Filter A1: PET film with a film thickness of 100 μm formed by biaxial stretching, Filter A2: PET film base material with a film thickness of 25 μm formed by biaxial stretching II Filter A1: Film thickness 80 μm TAC film, filter A2: 40 μm TAC film

  As described above, the evaluation samples 1-A to 15-A including the optical filter of the present invention are sufficiently stable filters that are less affected by the outside air due to the thinning of the base material than the samples including the comparative optical filter. As a result, the present invention can provide an excellent optical filter.

Example 2
(Manufacture of front filter for display)
《Front filter for display》
(Preparation of front filter 1 for display of the present invention)
Ethyl acetate, near-infrared absorbing dye: 0.9% by mass / (resin solid content), and a metal ion-containing compound MS-14 of the present invention in an acrylic adhesive main agent solution [Olivein BPS5896 (manufactured by Toyo Ink Manufacturing Co., Ltd.)] : 0.450% by mass / (resin solid content) and a polyisocyanate curing agent [BXX4773 (manufactured by Toyo Ink Manufacturing Co., Ltd.)] were added, and this visible light absorbing adhesive was made of polyethylene terephthalate (PET) film (thickness 50 μm). The film was coated with a bar coater and dried, and a PET film (thickness 50 μm) was bonded to this surface with a roller to obtain a display front filter 1. The transmittance curve of the front filter for display has a minimum value at 821 nm, and a near-infrared absorption filter and a front filter for display that can effectively absorb near-infrared light can be provided.

Claims (3)

An optical filter comprising at least one near-infrared absorbing dye and at least one metal ion-containing compound represented by the following general formula (X-1).
Formula (X-1)
M (X ₁ ) _m (X ₂ ) _l · (W ₁ ) _s
Wherein, M represents a divalent ion of Zn or Cu, X ₁ and X ₂ represents a monodentate or bidentate ligand each independently may be different even in the same, X ₁ And X ₂ may be linked. m, l, and s each represent an integer of 0 to 2, and m + l> 1. (W ₁ ) _s represents a counter ion necessary for neutralizing the charge. However, at least one of the ligands represented by X ₁ or X ₂ is the following general formula (X-1a). ]

[Wherein, E ₁ represents a substituent, E ₂ represents a hydrogen atom or a substituent, and R represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group. ] The optical filter according to claim 1, wherein the metal ion of the metal ion-containing compound represented by the general formula (X-1) is Cu. A front filter for a display, wherein the optical filter according to claim 1 is used.