JP2008145480A - Composition for optical filter, optical filter and front filter for display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for optical filter containing at least one kind of a squalirium metal chelate compound, to provide a pigment which has a preferable hue on color reproducibility in a visible region and has satisfactory solidness such as weatherability and preservable property, and to provide an optical filter and a front filter for display which contain the pigment. <P>SOLUTION: The composition for optical filter contains at least one kind of squalirium metal chelate pigment expressed by a general formula (1) of Mä(SQ)<SB>1</SB>(W<SB>1</SB>)<SB>m</SB>(W<SB>2</SB>)<SB>n</SB>}X. In the general formula (1), M represents a metal ion. SQ represents a squalirium compound expressed by a general formula (2), wherein W<SB>1</SB>and W<SB>2</SB>independently represent monodentate or bidentate ligand respectively and may be the same with each other or may be different from each other. (l) is 1 or 2, (m), (n) represent integers of 0 to 2 and satisfy l+m+n≥2 and X represents a counter ion necessary for neutralizing charges. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an optical filter containing a squarylium metal chelate 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 organic EL displays and FED displays have been put to practical use, and it is speculated that the demand for displays will greatly increase in the future.

  Among these, light-emitting displays such as plasma displays and CRTs obtain and display three primary colors of red, blue, and green by various methods such as irradiating a light emitter with an electron beam or ultraviolet light. There is a need for a color adjustment filter that corrects the color balance of the three colors without adversely affecting the color emission.

  The color adjusting filter dye is required to have good absorption characteristics in the visible range, for example, having a large molar extinction coefficient, a small half-value width, and no side absorption. At the same time, from the viewpoint of optical filter production, high solubility in various organic solvents and high compatibility with binders are required. Furthermore, since the display is assumed to be used for a long time, the display is required to have high weather resistance, particularly high light resistance.

  In a plasma display, it is necessary to add a dye having absorption in the vicinity of 560 to 620 nm in order to improve the color purity or raise the color temperature. In addition, since this wavelength region includes light emission from neon gas in the panel, an optical filter that absorbs such unnecessary light emission is required. In response to such demands, various dyes have been proposed. Among them, squarylium dyes have excellent absorption characteristics such as a large molar extinction coefficient and a small half-value width, and optical filters using the same, Front filters for plasma displays have been proposed (see, for example, Patent Documents 1 to 4).

  However, the squarylium dye described in the above document has a problem that durability, particularly light resistance is not sufficient, and it is unsuitable for practical use. Moreover, there existed a problem that solubility was inadequate and compatibility with a binder was insufficient resulting from this.

Also known are squarylium metal chelate dyes and compositions comprising a squarylium compound and a metal ion-containing compound, and inks, color toners, organic electroluminescent elements, and color filters using the same (for example, see Patent Document 5). However, the use of squarylium metal chelate dyes as optical filter compositions is not envisaged.
JP 2001-183522 A JP 2001-188121 A JP 2004-86133 A JP 2004-99711 A JP 2001-342364 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for an optical filter containing at least one squarylium metal chelate compound, and further to a hue that is preferable in terms of color reproducibility in the visible range. Another object of the present invention is to provide a dye having good fastness such as weather resistance and storage stability, an optical filter containing the dye, and a front filter for display.

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

  1. An optical filter composition comprising at least one squarylium metal chelate dye represented by the following general formula (1).

General formula (1) M {(SQ) _l (W ₁ ) _m (W ₂ ) _n } X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and May be different from each other, l is 1 or 2, m and n each represent an integer of 0 to 2, l + m + n ≧ 2, and X represents a counter ion necessary for neutralizing the charge. To express.)

(In the formula, A represents any organic group, and B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms, and form a 6-membered aromatic ring. R ₁ , R ₂ , R 4 ₃ and R ₄ each represent an electron pair, a hydrogen atom or a substituent, and each may be further bonded to each other to form a ring.
2. 2. The optical filter composition as described in 1 above, wherein M is an ion of cobalt, nickel, copper or zinc.

3. The substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, heterocyclic group, alkoxy group, cyclo Alkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, An alkylsulfonyl group, an arylsulfonyl group, an amino group, an azo group, an alkylsulfonyloxy group, a cyano group, a nitro group, a halogen atom, and a hydroxyl group, and the organic group represented by A is an aryl group, heteroaryl Group, heterocyclic group or 3. The optical filter composition as described in 1 or 2 above, which is represented by the formula (1-A).

Formula (1-A) A ₁ = C (R) —
(In the formula, A ₁ represents a 5-membered ring or a 6-membered ring, and may have a group having the same meaning as the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ described above at an arbitrary position. R represents a hydrogen atom or a substituent, and the substituent is the same as the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ described above.
4). 4. An optical filter comprising at least one optical filter composition according to any one of items 1 to 3.

  5. 5. The display front filter according to claim 4, wherein the optical filter is a display front filter.

  6). When the display front filter is used for a plasma display, the dye represented by the general formula (1) contained in the display front filter has an absorption maximum in a range of 560 to 620 nm. Front filter for display as described in 4.

  According to the present invention, an optical filter composition having excellent light resistance and improved environmental preservation could be provided. This composition has excellent spectral absorption characteristics and weather resistance, and also has high compatibility with a dispersant, exhibits high light resistance and environmental preservation, and provides an optical filter and a front filter for display containing the same. I was able to.

  The present invention will be described in more detail. The composition for optical filters of this invention is a composition for optical filters containing the squarylium metal chelate compound which consists of a squarylium compound and a metal ion as represented by the said General formula (1).

  Hereinafter, a composition for an optical filter containing at least one squarylium metal chelate compound, a dye having a favorable hue in terms of color reproducibility in the visible region, and good fastness such as weather resistance and storage stability, and the dye The optical filter and the front filter for display will be described, but the present invention is not limited to these.

<< Composition for optical filter containing squarylium metal chelate compound represented by general formula (1) >>
The squarylium metal chelate compound in the present invention is represented by the general formula (1).

  In the formula, M represents a metal ion. The metal M is not particularly limited as long as it is generally available. For example, copper, nickel, cobalt, zinc, aluminum, beryllium, iron, silver, chromium, manganese, iridium, vanadium, titanium, ruthenium, molybdenum, tin, bismuth. , Osmium, magnesium, calcium, strontium, barium, gallium, germanium, platinum, gold, mercury and the like. It is preferable that it is an element contained in periodic table group 3-12 group, More preferably, it is a metal ion contained in periodic table group 7-12 group. The valence is preferably a divalent or trivalent metal, and more preferably a divalent metal. Among these, specifically, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osmium, iridium or platinum is preferable, and copper, cobalt or zinc is particularly preferable from the viewpoint of handling. It is more preferable.

  SQ in the general formula (1) represents a squarylium compound represented by the general formula (2).

_{Wherein, B 1, B 2, B} 3 and B ₄ is a carbon atom or a nitrogen atom, form an aromatic ring. At this time, at least one of B ₁ , B ₂ , B ₃ and B ₄ is preferably a carbon atom, more preferably at least two are carbon atoms, and more preferably all are carbon atoms. .

R ₁ , R ₂ , R ₃ and R ₄ represent an electron pair, a hydrogen atom or a substituent. Specifically, when any of B ₁ , B ₂ , B ₃ and B ₄ is a nitrogen atom, the corresponding R ₁ , R ₂ , R ₃ and R ₄ represent an electron pair. When B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms, the corresponding R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. At this time, the number of substituents represented by R ₁ , R ₂ , R ₃ and R ₄ is not particularly limited but is preferably 2 or more, more preferably 3 or more. Specific examples of the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group). Group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.) , Alkynyl groups (for example, ethynyl group, propargyl group, etc.), aryl groups (for example, phenyl group, naphthyl group, etc.), heteroaryl groups (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyramidyl group) , Triazyl group, imidazolyl group, pyrazolyl group, thiazolyl group, benzimidazolyl group, ben Zooxazolyl 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 (eg, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.) , Alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio groups (for example, cyclopentylthio group, cyclohexylthio group, etc.), arylthio groups For example, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, Phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), phosphoryl group (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylamino) Sulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminos Phonyl 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, phenyl) Carbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide Groups (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexyl group) Rubonylamino 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, cyclohexylureido 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, dodecylsulfonyl group, etc.) , Arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino) Dimethylamino group, butylamino group, dibutylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), azo group (for example, phenylazo), alkyl Examples include a sulfonyloxy group (for example, methanesulfonyloxy), a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, and the like. These substituents may be further substituted with the same substituent, or the substituents may be further bonded to each other to form a ring.

Among these, preferred substituents for R ₂ include a hydroxyl group, an alkenyl group, an alkoxy group, and an alkyl group, more preferably a hydroxyl group and an alkoxy group, and still more preferably a hydroxyl group and an alkoxy group.

Preferred substituents for R ₁ , R ₃ and R ₄ are alkyl groups, cycloalkyl groups, alkenyl groups, halogen atoms, heterocyclic groups, alkylsulfonyl groups, arylsulfonyl groups, phosphono groups, acyl groups, sulfonamido groups, cyano groups. Group, alkoxy group, aryloxy group, heterocyclic oxy group, sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group, anilino group, imide group, carboxyl group, carboxylic acid salt, hydroxyl group, mercapto group , A nitro group and the like are preferable, and at least one is more preferably an alkyl group, a hydroxyl group, an alkoxy group or an amino group. From the viewpoint of improving solubility, at least one substituent is a straight chain having 4 or more carbon atoms. Or it is preferable to have a branched alkyl group.

A represents an arbitrary organic group, and examples of the organic group include the same groups as the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ described above, preferably an aryl group, heteroaryl Group, a heterocyclic group is mentioned, More preferably, an aryl group, a heterocyclic group, or the substituent represented by the following general formula (1-A) is mentioned, Furthermore, it is preferable that it is a heterocyclic group. Ring A and ring A ₁ are preferably 5- to 7-membered rings, more preferably 5- or 6-membered rings, and ring A ₁ is more preferably a 5-membered ring.

Formula (1-A) A ₁ = C (R) —
A ₁ represents a 5-membered ring or a 6-membered ring. Examples of the 5-membered ring represented by A ₁ include pyrazolidinedione ring, isoxazolone ring, pyrazolone ring, pyrrolidone ring (for example, 1H-pyrrole-2 (5H) -One ring), thioxathiazolidinone ring (for example, rhodanine ring, 4-thoxaimidazolidin-2-one ring, 5-thioximidazolidin-2-one ring), pyrrolotriazole ring (for example, 7, 7a-dihydro-1H-pyrrolo [1,2-b] [1,2,4] triazole ring, 7,7a-dihydro-1H-pyrrolo [2,1-c] [1,2,4] triazole ring) A pyrazolotriazole ring (for example, 7,7a-dihydro-1H-pyrazolo [5,1-c] [1,2,4] triazole ring, 7,7a-dihydro-1H-pyrazolo [1,5-b] [1,2,4] birds Azole ring), pyrazolopyrimidine ring, imidazole ring (for example, 4H-imidazole ring), imidazolopyrazole ring, pyrrole ring, isoxazolidinedione ring, thioximidazolidinone ring (for example, 4-thiaximidazolimidazoline-2- On-ring), imidazolidinedione ring (eg hydantoin ring), imidazolidinedithione ring (eg imidazolidine-2,4-dithione ring), thiazolidinedione ring, pyrazoledione ring, indole ring, etc. You may have a group synonymous with the substituent represented by R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > mentioned above in the position.

Examples of the 6-membered ring represented by A ₁ include a cyclohexadiene ring (1,3-cyclohexadiene ring, 1,4-cyclohexadiene ring), a dihydropyridine ring (1,4-dihydropyridine ring, 3,4-dihydro). Pyrosine ring), 4H-pyran ring, 4H-thiopyran ring, pyridone ring (eg, pyridine-2 (3H) -one ring), pyridinethione ring (eg, pyridine-2 (3H) -thione ring), pyridinedione Ring (for example, pyridine-2,4 (3H, 5H) -dione ring), barbituric acid ring, thiobarbituric acid ring, oxazine ring, thiazine ring, dihydropyrimidinedione ring (for example, dihydropyrimidine-4,6 (1H , 5H) -dione ring), dihydropyrimidine dithione ring (for example, dihydropyrimidine-4,6 (1H, 5H) -dithione ring), A xazinedione ring (for example, 4H-1,3-oxazine-4,6 (5H) -dione ring), an oxadiazine ring (for example, 4H-1,2,3-oxadiazine ring), May have the same group as the substituents represented by R ₁ , R ₂ , R ₃ and R ₄ described above.

R represents a hydrogen atom or a substituent, and the substituent is the same as the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ described above. R is preferably a hydrogen atom, an alkyl group or a halogen atom, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.

  The squarylium compound has a squaric acid skeleton at the center of the molecule, and has a structure having a substituent composed of an aromatic compound at two carbon atoms located on the diagonal line. If the two aromatic substituents are the same, this is referred to as a symmetric squarylium compound (or symmetric squarylium dye) for convenience, otherwise an asymmetric squarylium compound (or asymmetric squarylium dye). ). The squarylium compound used in the squarylium metal chelate compound of the present invention may be a symmetric squarylium compound or an asymmetric squarylium compound, but is preferably asymmetric from the viewpoint of color tone adjustment. As the asymmetric type, it is preferable that the substituents are different and the ring structures are different. More preferably, in general formula (2), ring A is a heterocyclic ring, and such a heterocyclic ring is a 5-membered ring. More preferably, specific examples include a pyrazolone ring, a pyrrolidone ring, a pyrrolotriazole ring, a pyrazolotriazole ring, an imidazole ring, an imidazolopyrazole ring, a pyrrole ring, a pyrazoledione ring, and an indole ring.

W ₁ and W ₂ each independently represent a monodentate or bidentate ligand and may be the same or different.

Examples of W ₁ and W ₂ include JP 2000-251957, JP 2000-31723, JP 2000-323191, JP 2001-6760, JP 2001-59062, and JP 2001-60467. Etc. are mentioned. 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.

  Specific examples are shown below, but the present invention is not limited thereto. 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.

  Moreover, the compound represented by the following general formula (3) is more preferable as a ligand.

In the general formula (3), E ₁ and E ₂ each represent an electron withdrawing group having a Hammett substituent constant (σp) of 0.1 or more and 0.9 or less, R ′ represents an alkyl group, an aryl group, a heterocyclic group, Represents an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.

A substituent having a σp value represented by E ₁ and E ₂ of 0.1 or more and 0.9 or less 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, ethoxycarbonyl) Bonyl, diphenylmethylcarbonyl), substituted aromatic groups (eg pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (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 ( For example, acetyloxy, benzoyloxy), arylsulfonyloxy group (for example, benzenesulfonyloxy), phosphoryl group (for example, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl group (for example, N-ethylsulfuryl) Amoyl, 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 (eg methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (eg pentafluorophenyl, 2,4-dimethanesulfonylphenol) ), Heterocyclic residues (eg, 1-tetrazolyl), azo groups (eg, phenylazo), alkylsulfonyloxy groups (eg, methanesulfonyloxy), phosphoryl groups (eg, dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl groups, etc. Is 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.

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 halogenated alkyl group or a cyano group, and even more preferably a halogenated alkyl group. E ₂ is preferably a cyano group, a nitro group, an alkylsulfonyl group or a carbonyl group, more preferably a cyano group or an alkylsulfonyl group.

  Preferred substituents for R ′ include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and an amino group, and more preferably an alkyl group having 2 to 18 carbon atoms or a carbon number. 1 to 18 alkoxy groups and aryloxy groups.

  Specific examples of the ligand represented by the general formula (3) are shown below, but the present invention is not limited thereto.

  X represents a counter ion when a counter ion is required to neutralize the charge. For example, whether a compound is a cation, an anion, or has a net ionic charge depends on its metal, Depends on ligand and 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, whereas anions are specifically either inorganic or organic anions. For example, a halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion) ), Aryl disulfonate ions (for example, 1,3-benzenedisulfonate ions, 1,5-naphthalenedisulfonate ions, 2,6-naphthalenedisulfonate ions), alkyl sulfate ions (for example, methyl sulfate ions), sulfate ions , Thiocyanate ion , Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, enolate (acetylacetonate, hexafluoroacetylacetonate), hydroxide ion, sulfite ion, Examples thereof include nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkylcarboxylate ion, arylcarboxylate ion, tetraalkylborate, salicinate, benzoate, hexafluoroantimony and the like.

  m and n represent an integer of 0-2. At this time, l + m + n ≧ 2, preferably 6 ≧ l + m + n ≧ 2, more preferably 6 ≧ l + m + n ≧ 3, and most preferably l + m + n = 4.

  Although the typical example of the squarylium metal chelate compound represented by General formula (1) in this invention below is shown, this invention is not limited to this.

  Examples of the squarylium compound represented by the general formula (2) in the squarylium metal chelate compound represented by the general formula (1) according to the present invention include, for example, JP-A-5-155144, JP-A-5-239366, Reference is made to conventionally known methods described in JP-A-5-339233, JP-A-2000-345059, JP-A-2002-363434, JP-A-2004-86133, JP-A-2004-238606, etc. Can be synthesized.

  In addition, the squarylium metal chelate compound of the present invention comprises a squarylium compound represented by the general formula (2) and a raw material (metal ion-containing compound) that gives a metal ion having coordination ability in a solvent at room temperature to 120 ° C. It is obtained by reacting at a temperature of 3 to 24 hours. In another preferred embodiment, the squarylium compound and the raw material providing the metal ion having coordination ability are pulverized into fine particles, or various dispersing machines (for example, a ball mill, a sand mill, an atomizer together with a polymer dispersant and a surfactant). A lighter, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a jet mill, an ang mill, etc.) are preferably mixed while being dispersed in the form of fine particles because energy required for the reaction can be reduced.

  There is no limitation on the mixing ratio (molar ratio) of the chelatable compound and the compound represented by the general formula (1). When squarylium compound: metal ion-containing compound = 1: Y, Y is preferably 0.8. 1 to 100, more preferably 0.3 to 10, and still more preferably 0.5 to 2.

  Examples of raw materials that give metal ions include bis (acetylacetonate) copper, copper acetate, copper bromide, copper nitrate, copper oxalate, copper sulfate, copper chloride, copper perchlorate, copper tetrafluoroborate, cyanide Copper iodide, copper iodide, copper trifluoromethanesulfonate, copper thiocyanate, nickel acetate, nickel sulfate, nickel (carbonate), nickel nitrate, nickel chloride, nickel bromide, nickel tetrafluoroborate, bis (acetylacetonate) Nickel, nickel perchlorate, zinc acetate, zinc bromide, zinc chloride, zinc nitrate, zinc tetrafluoroborate, zinc bis (acetylacetonate), cobalt nitrate, cobalt nitrite, cobalt acetate, bis (acetylacetonate) Cobalt, cobalt bromide, cobalt chloride, cobalt oxalate, cobalt thiocyanate and mono Such metal ion compounds having a ligand represented by the formula (3) is used. At this time, from the viewpoint of improving solubility and compatibility with the binder, the raw material that gives metal ions preferably has an organic substance as a counter salt, and examples thereof include a diketonate compound and a general formula (3). Compounds.

  Examples of the acid include organic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, and p-toluenesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid. The amount is preferably 0.1 to 2.0 equivalent (molar ratio) with respect to the squarylium compound.

  Examples of the solvent include halogen-based hydrocarbon solvents such as chloroform and dichloromethane, aromatic solvents such as toluene and xylene, ether solvents such as tetrahydrofuran and methyl-tert-butyl ether, ester solvents such as ethyl acetate, methanol, Examples thereof include alcohol solvents such as ethanol, water and the like, and the amount used is preferably 1 to 500 times (mass ratio) with respect to the squarylium compound.

  The squarylium metal chelate compound of the present invention will be described below.

  The squarylium metal chelate compound in the present invention refers to a squarylium metal chelate compound represented by the general formula (1) having at least one absorption maximum wavelength in the visible region (380 to 780 nm). Since the squarylium metal chelate compound of the present invention has good spectral characteristics, the extinction coefficient in a wavelength region shifted by about 200 nm from the absorption maximum wavelength is 1/100 to 1/1000 or less of the absorption coefficient of the absorption maximum. It is characterized by substantially no absorption in the wavelength range from the absorption maximum to the 100 nm long wave or short wave. As described above, the squarylium metal chelate compound in the present invention is characterized by having preferable spectral characteristics in the visible region.

  Specific examples of the method for synthesizing the compound represented by the general formula (1) are shown below, but other compounds can be synthesized in the same manner, and the synthesis method is not limited thereto.

  [Synthesis Example 1]

<Synthesis of D-2>
To the reaction vessel, 8 ml of 1-butanol and 10 ml of toluene were added to 0.40 g of squaric acid, and further 1.00 g of 4-isopropylbenzene-1,3-diol was added. This reaction solution was irradiated with microwaves, reacted at 160 ° C. for 5 minutes, and the precipitated solid was collected by filtration and washed to obtain the desired squarylium compound (D-2): 0.91 g. The product was identified by MASS and H-NMR spectra and confirmed to be the target product.

  [Synthesis Example 2]

<Synthesis of MD-22>
D-2: 0.62 g was heated and dissolved in 10 ml of methanol, and nickel acetate tetrahydrate: 0.25 g of a methanol solution: 10 ml was added dropwise thereto and reacted at 50 ° C. for 2 hours as it was. The reaction solution was concentrated, and the precipitated crystals were filtered to obtain MD-22: 0.46 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

  [Synthesis Example 3]

<Synthesis of MD-89>
D-103: 0.90 g, Intermediate 1 (using X-116 as the ligand): 0.76 g of methanol: 30 ml was added and heated under reflux for 2 hours. Acetonitrile (15 ml) was added to the reaction solution and cooled to 5 ° C., and the precipitated crystals were filtered to obtain MD-89: 1.04 g. It identified by the MASS spectrum and elemental analysis, and confirmed that it was the target object.

  The composition for an optical filter of the present invention is a composition with a dispersant (binder) or a composition to which a solvent is further added for the purpose of film-forming stability in addition to the above-described squarylium metal chelate compound of the present invention. It is preferable that

  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 of the present invention are composed of a composition comprising at least one dye of the present invention in a base material. Of course, it means that it is applied to the surface of the base material, or is sandwiched between the base material and the like.

  The optical filter according to the present invention is characterized by having at least one absorption maximum in the visible region, and is known as a so-called color filter, and is arranged in a square as a whole by arranging a large number of RGB three colors in a grid. Is done. Then, light of a specific color is transmitted and the others are not blocked like a component used in a solid-state imaging device such as a CCD image sensor or a color display using liquid crystal. Therefore, it is used to reduce or block light in a specific wavelength range and to transmit other light.

  In addition, the front filter for display in 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. For this reason, the display front filter of the present invention is characterized by having at least one absorption maximum in the visible region. In order to realize this, the dye of the present invention is characterized by having an absorption maximum in the visible region in a solution state, and more preferably has an absorption maximum at 450 to 620 nm for color tone adjustment. In particular, in order to cut neon emission, it is preferable to have an absorption maximum at 560 to 620 nm, and more preferable to have an absorption maximum at 580 to 605 nm.

  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, etc.

  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 dye of the present invention 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 / trifluoro Styrene 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 the polymer molded body or glass surface mentioned in (3), a method of forming a composition after dissolving the dye of the present invention in a binder resin and an organic solvent, and an uncolored acrylic emulsion Examples thereof include a method of dispersing a finely pulverized (50 to 500 nm) pigment of the present invention into a paint to obtain an acrylic emulsion-based 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, it is preferable that the display front filter of the present invention has an electromagnetic wave shielding function and a near infrared ray 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 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 depositing metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, and 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.

  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. In addition, when a mesh, ink patterning, or development method is used, a film that absorbs or 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, 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.

  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 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.

  The front filter for display of the present invention can be suitably used as a neon cut filter that selectively blocks light emission of neon gas in the cell. As described above, the plasma display performs color display by phosphor emission, but when neon atoms are excited and return to the ground state, it is known to emit so-called neon orange light centered around 600 nm. (Journal of the Institute of Image Information and Television Engineers, Vol. 51, No. 4, p. 459 to 463 (1997)). For this reason, the plasma display has a disadvantage that a bright red color cannot be obtained due to a mixture of red and orange. In order to eliminate this defect, it is preferable to cut off neon light emission. When an optical filter that absorbs neon light emission is produced using the composition of the present invention, the dye of the present invention has a solution state of 560 to 620 nm. It preferably has an absorption maximum, and more preferably has an absorption maximum at 580 to 605 nm. At this time, the transmittance of the optical filter at the absorption maximum in the wavelength region of 560 to 620 nm is preferably in the range of 0.01 to 80%, and more preferably in the range of 1 to 70%. In order to improve the color reproducibility of the display, the absorption waveform in the wavelength region of 560 to 620 nm is preferably sharp. Specifically, in the absorption waveform at 560 to 620 nm, the half width value (the width of the wavelength region showing the absorbance at half of the absorbance at the absorption maximum) is preferably 15 to 100 nm, and more preferably 20 to 70 nm. More preferably, it is 25-50 nm.

Example 1
(Production of optical filter)
(Preparation of optical filter 1A)
A 20% dimethoxyethane solution of the squarylium metal chelate dye MD-2 of the present invention and a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) is mixed so that the dye has a ratio of 0.05%, and the mixture is placed on a glass substrate. Optical filter 1A was produced by coating with a bar coater and drying. This optical filter was light blue and was found to absorb visible light effectively.

(Preparation of optical filter 1B)
A 0.2% tetrahydrofuran solution of the squarylium metal chelate dye MD-2 of the present invention and a 20% methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone: toluene = 1: 1) of an acrylic resin (Dianal BR-80; manufactured by Mitsubishi Rayon Co., Ltd.) The mixture was mixed at a ratio of 1:10, and coated on a polyethylene terephthalate (PET) film (thickness 100 μm) with a bar coater and dried to prepare an optical filter 1B. This optical filter was light blue and was found to absorb visible light effectively.

(Production of optical filters 2A-23A, 2B-23B and comparative optical filters 24A-25A, 24B-25B)
Optical filters 2A to 23A and 2B to 23B of the present invention and comparative optical filters 24A to 25A and 24B to 25B were similarly prepared except that the dyes shown in Table 4 below were used instead of the squarylium metal chelate dye MD-2. did.

  The light resistance and environmental preservation of the obtained optical filter were evaluated by the following methods. The results are also shown in Table 4.

《Light resistance》
After the obtained optical filter was exposed with a xenon fade meter (70,000 Lux) for 72 hours, the reduction rate of the absorption spectral density at the maximum absorption wavelength in the visible region from the unexposed sample of the sample was evaluated, and the dye residual rate Was calculated.

Light resistance (%) = (Maximum absorption wavelength concentration of optical filter after exposure / Maximum absorption wavelength concentration of unexposed optical filter) × 100
Was evaluated according to the following evaluation criteria. It is preferable that it is above.

◎: Light resistance is 90% or more ◎: Light resistance is 80% or more and less than 90% ○: Light resistance is 70% or more and less than 80% △: Light resistance is 60% or more and less than 70% ×: Light resistance <60% << Environmental preservation >>
The optical filter immediately after production was put in a sealed container, stored in a thermostatic bath at 60 ° C. for 1 day, then stored in a freezer at −10 ° C. for 1 day, and after returning the sealed container to room temperature, the optical filter was taken out.

  The state of the surface was visually observed and evaluated in four stages based on the following evaluation criteria. A and B are levels at which there is no problem in practical use, and indicate that environmental preservation is excellent.

A: Optical filter devitrification, cracks, cracks, etc. are not observed before and after storage B: Slight devitrification is observed after storage, but there is no practical problem C: Obvious devitrification is observed D: Crack , Cracks, etc. were observed.

  Table 4 shows that the optical filter of the present invention is excellent in light resistance and environmental preservation.

Example 2
(Preparation of optical filter C)
The squarylium metal chelate dye MD-44 of the present invention is 20% methyl ethyl ketone of polystyrene resin (St / HEMA / SMA = 30/40/30 copolymer, St: styrene, HEMA: 2-hydroxyethyl methacrylate, SMA: stearyl methacrylate). / Toluene mixed solution (methyl ethyl ketone: toluene = 9: 1) was mixed to a ratio of 0.01%, coated on a glass substrate with a bar coater, and dried to prepare an optical filter C. This optical filter had a purple color, and it was found that even a composition containing a binder effectively absorbs visible light.

(Preparation of optical filter D)
An optical filter D was prepared in the same manner except that the polyester resin of the optical filter 1A was changed to a polyvinyl chloride resin. This optical filter has a light blue color, and it has been found that even a composition with a changed binder effectively absorbs visible light.

(Production of optical filter E)
A 0.5% tetrahydrofuran solution of the squarylium metal chelate dye MD-91 of the present invention and a 20% dimethoxyethane solution of hot-melt polyester resin (Diabond Kogyo Co., Ltd., trade name: SP3300X1) are mixed at a ratio of 2: 8. The polyester film for peeling (Toyobo Co., Ltd., trade name: MRF75, thickness 75 μm) was coated with a bar coater and dried. Next, a polyester film (manufactured by Toyobo Co., Ltd., trade name: A4300, thickness 100 μm) was attached to the coated surface using a hot roll laminator. Finally, the polyester film for peeling was peeled off, the SP3300X1 coated surface was made the glass side, the surface was heated with an iron of about 100 ° C. for 1 minute, and bonded to a glass substrate to produce an optical filter E. This optical filter exhibited a blue color, and it was found that even a composition with a changed binder effectively absorbs visible light.

Example 3
《Front filter for display》
(Preparation of front filter 1 for display)
Polyethylene terephthalate (PET) film (thickness: 100 μm), 0.2 g of 0.2% methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 1: 1) of squarylium metal chelate dye (MD-44) of the present invention, polyester resin After mixing 6.5 g of a 20% methyl ethyl ketone / toluene mixed solution, it was coated and dried with a bar coater to obtain a display front filter 1 having a coating film having a thickness of 5 μm. The transmittance curve of the display front filter 1 has a minimum value at 598 nm, and there is no clear minimum value other than this. That is, since the minimum wavelength of visible light transmittance is in the wavelength region of 560 to 620 nm of neon light emission, it can be seen that the front filter for display has high transmittance and can effectively absorb neon light emission. .

  Using a xenon fade meter (70,000 Lux), xenon light was exposed for 48 hours from the side opposite to the dye-coated surface of the front filter for display 1 and the dye residual% at the visible region maximum absorption wavelength was calculated. 2%. Moreover, the dye residual rate after exposure for 10 days was 50.6%, and it was a front filter for display having neon light emission cut filter performance with good light resistance.

(Preparation of front filter 2 for display)
A PET film (thickness: 100 μm) was mixed with 0.6 g of a 0.5% tetrahydrofuran solution of the squarylium metal chelate dye (MD-111) of the present invention and 5.0 g of a 35% dimethoxyethane solution of an acrylic resin, and then a bar coater. Was applied and dried to obtain a display front filter 2 having a coating film thickness of 5 μm. The transmittance curve of the display front filter 2 has a minimum value at 588 nm, and there is no clear minimum value other than this. That is, since the minimum wavelength of visible light transmittance is in the wavelength range of 560 to 620 nm of neon light emission, the front filter for display has high transmittance and can effectively absorb neon light emission.

(Preparation of front filter 3 for display)
An ultraviolet absorbing coating solution (Sumitomo Osaka Cement Co., Ltd.) containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on a PET resin on the opposite side of the dye-containing layer surface of the display front filter 1 is a bar coater. Was coated and dried to form a UV absorbing layer having a thickness of 3 μm to obtain a front filter 3 for display. The minimum wavelength of the visible light transmittance of the display front filter 3 was the same as that of the display front filter 1 without change.

  Using a xenon fade meter (70,000 Lux), xenon light was exposed for 10 days from the ultraviolet absorption layer surface of the front filter 3 for display, and the dye residual percentage at the maximum absorption wavelength in the visible region was calculated to be 74.3%. It was a front filter for a display having a neon light emission cut filter performance having an ultraviolet absorption layer and excellent in light resistance.

(Preparation of front filter 4 for display)
A near-infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium is formed on the PET resin surface opposite to the dye-containing layer surface of the display front filter 1. Of 0.5% cyclohexanone solution and 6% polyester resin 20% cyclohexanone solution are mixed, coated with a bar coater, dried, and a coating film having a film thickness of 6 μm. A front filter 4 was obtained. The display front filter 4 was measured with a Hitachi spectrophotometer (U-3500). The wavelengths at the minimum transmittance were 588 nm and 1100 nm.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed for 10 days from the near-infrared absorption layer surface of the display front filter 4 for 10 days, the dye residual percentage at the maximum absorption wavelength in the visible region was calculated to be 66.0%. Met. That is, it can be seen that this is a front filter for display having excellent light resistance and neon emission cut filter performance having a near infrared absorption layer.

(Preparation of front filter 5 for display)
0.5 g cyclohexanone solution of the above near infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium hexafluoroantimonate) In addition, 0.5 g of a 0.4% cyclohexanone solution of the squarylium metal chelate dye (MD-90) of the present invention is mixed with 6.5 g of a 20% cyclohexane solution of a polyester resin, and applied to a PET film (thickness 100 μm) with a bar coater. After processing and drying, a display front filter 5 ′ having a coating film with a thickness of 6 μm was obtained. The display front filter 5 'was measured with a Hitachi spectrophotometer (U-3500). The wavelengths at the minimum transmittance were 591 nm and 1100 nm.

  Further, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole is ultraviolet-rayed on the near-infrared absorbing dye of the front filter 5 'for display and the PET resin surface opposite to the surface containing the squarylium metal chelate dye of the present invention. An ultraviolet absorbing coating solution contained as an absorbent was coated with a bar coater and dried to form an ultraviolet absorbing layer having a thickness of 3 μm to obtain a front filter 5 for display.

  Using a xenon fade meter (70,000 Lux), when the xenon light was exposed for 48 hours from the ultraviolet absorption layer surface of the front filter 5 for display, the dye residual ratio% at the maximum absorption wavelength in the visible region was calculated. In addition, the dye residual ratio after exposure for 10 days was 82.1%. When the squarylium metal chelate dye of the present invention is used in the same layer as the near-infrared absorbing dye, a front filter for display having excellent light resistance can be provided.

(Preparation of front filter 6 for display)
Using a coating liquid prepared with the above-mentioned display front filter 5 on a PET film (thickness: 100 μm) using ITO indium oxide monoxide and using an argon gas and an oxygen gas to produce an ITO thin film. An infrared absorption layer and a neon emission absorption layer were laminated with a thickness of 6 μm. Furthermore, when the surface of the PMMA plate with an antiglare layer on the opposite surface, which is not coated with a non-glare layer, is bonded to the ITO surface of the filter, a plasma display panel filter is produced. A good front filter 6 for a display with a high value could be produced.

(Preparation of front filter 11 for display)
A display front filter 11 was prepared in the same manner as the display front filter 1 except that the squarylium compound D-2 was used instead of the squarylium metal chelate dye MD-44 of the present invention.

  The dye residual ratio after exposure for 48 hours from the ultraviolet absorbing layer surface using a xenon fade meter (70,000 Lux) was 60.7%, and the dye residual ratio after 10 days exposure was 10.8%. Met. From the above, the display front filter 11 is greatly inferior in light resistance compared to the display front filter 1 of the present invention, and the display front filter using the squarylium metal chelate-containing composition of the present invention is extremely light resistant. It turns out that it is excellent in.

(Preparation of front filter 12 for display)
A display front filter 12 was prepared in the same manner as the display front filter 5 except that the squarylium compound D-128 was used instead of the squarylium metal chelate dye MD-111 of the present invention.

  The dye residual rate% after exposure to xenon light from the UV absorbing layer surface for 48 hours using a xenon fade meter (70,000 Lux) was 62.2%, and the dye residual rate after 10 days exposure was 11.6%. Met. The display front filter 12 is significantly inferior in light resistance to the display front filter 5 of the present invention, and the display front filter using the squarylium metal chelate-containing composition of the present invention is very excellent in light resistance. I understand that.

  From the above, by using the squarylium metal chelate-containing composition of the present invention, an optical filter excellent in light resistance and environmental preservation, and also neon light emission that is also excellent in light resistance, high transmittance, and can effectively absorb neon light emission. A front filter for a display having an absorption filter, an ultraviolet absorption layer, an infrared absorption layer, and the like could be provided.

It is a transmission spectrum of the optical filter represented by the optical filter 10B of the present invention.

Claims (6)

An optical filter composition comprising at least one squarylium metal chelate dye represented by the following general formula (1).
General formula (1) M {(SQ) _l (W ₁ ) _m (W ₂ ) _n } X
(In the formula, M represents a metal ion. SQ represents a squarylium compound represented by the following general formula (2), W ₁ and W ₂ each independently represent a monodentate or bidentate ligand, and May be different from each other, l is 1 or 2, m and n each represent an integer of 0 to 2, l + m + n ≧ 2, and X represents a counter ion necessary for neutralizing the charge. To express.)

(In the formula, A represents any organic group, and B ₁ , B ₂ , B ₃ and B ₄ are carbon atoms or nitrogen atoms, and form a 6-membered aromatic ring. R ₁ , R ₂ , R 4 ₃ and R ₄ each represent an electron pair, a hydrogen atom or a substituent, and each may be further bonded to each other to form a ring. 2. The optical filter composition according to claim 1, wherein M is an ion of cobalt, nickel, copper, or zinc. The substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, heterocyclic group, alkoxy group, cyclo Alkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, phosphoryl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, sulfinyl group, An alkylsulfonyl group, an arylsulfonyl group, an amino group, an azo group, an alkylsulfonyloxy group, a cyano group, a nitro group, a halogen atom, and a hydroxyl group, and the organic group represented by A is an aryl group, heteroaryl Group, heterocyclic group or It is represented by Formula (1-A), The composition for optical filters of Claim 1 or 2 characterized by the above-mentioned.
Formula (1-A) A ₁ = C (R) —
(In the formula, A ₁ represents a 5-membered ring or a 6-membered ring, and may have a group having the same meaning as the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ described above at an arbitrary position. R represents a hydrogen atom or a substituent, and the substituent is the same as the substituent represented by R ₁ , R ₂ , R ₃ and R ₄ described above. An optical filter comprising at least one optical filter composition according to any one of claims 1 to 3. The front filter for a display, wherein the optical filter according to claim 4 is a front filter for a display. When the front filter for display is used in a plasma display, the dye represented by the general formula (1) contained in the front filter for display has an absorption maximum in a range of 560 to 620 nm. 5. The front filter for display according to 5.

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