WO2008035554A1 - Novel squarylium metal complex compound, dye, and composition, color toner, ink, optical recording medium, color filter and front filter for display containing the same - Google Patents

Abstract

It is intended to provide a novel squarylium metal complex compound, and further to provide a dye which has a hue preferable for color reproducibility in the visible range and is excellent in fastness such as weather resistance and storage stability, and a composition, an ink, a toner, an optical recording medium, a color filter and a front filter for display containing the dye. This squarylium metal complex compound is characterized by having a partial structure represented by the following general formula (1). (In the formula, M represents a metal atom, R represents a substituent, and m represents an integer of 0 to 3. A represents an organic group.)

Description

 Specification

 Novel squarylium metal complex compounds, dyes and compositions containing them, color toners, inks, optical recording media, color filters, and front filter for displays

 Technical field

 [0001] The present invention relates to a novel squarylium metal complex compound, a dye, and a composition containing the same

, Color toner, ink, optical recording medium, color filter, and front filter for display.

 Background art

 [0002] Colorants known as dyes and pigments include various dyes such as fiber dyes, resin and paint colorants, photographs, printing, photocopiers, printers, image forming materials, and color filter light absorbers. Widely used in applications. In recent years, various image forming dyes for color hardcopy using inkjet, electrophotography, silver halide photography, thermal transfer, etc. have been proposed, and with the progress of electronics imaging, dyes for filters for solid-state image pickup tubes and color LCD TVs. Demand for dyes for optical recording media using semiconductor lasers and the like is increasing, and the field of dye use is expanding. As the use of these dyes expands, the demands on color material materials, especially fastness such as light resistance and chemical resistance, are becoming stricter year by year.

[0003] The present inventors have developed a dye material having a squarylium skeleton. Squarium dyes have the advantage that they can be easily adjusted in hue due to the variety of molecular designs and have excellent molecular absorption characteristics. In addition, it is a useful dye material that exhibits good performance in terms of light resistance, heat resistance, moisture resistance, and the like. 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 on the carbon atom located on the diagonal line. If these two aromatic substituents are the same, this is called a symmetric squarylium compound or a symmetric squarylium dye for convenience, and an asymmetric squarylium compound is asymmetric if they are different. Type squarylium pigment). [0004] Thermally transfer recording materials, electrophotographic toners, near-infrared absorbers (see, for example, patent documents;! To 3), and the like are known as squarylium compounds coordinated to a metal and forming a chelate structure! / However, there are only two cases where the complex structure is clearly specified! / (See Patent Documents 4 and 5).

 Patent Document 4 discloses a squarylium metal complex structure represented by the following structure A.

[0006] [Chemical 1-1] Structure A

[0007] However, the squarylium compound used here is only a combination of 5-hydroxypyrazole and methylindoline, and the metal is only A1.

 Patent Document 5 discloses a squarylium metal complex represented by the following structure B and structure C.

[0009] [Chemical 1-2]

Structure B

[0010] In these structures A, B and C, a chelate structure is formed between a coordination atom having a 5-membered ring active hydrogen bonded directly to an oxygen atom of a squaric acid skeleton and a squaric acid skeleton, and a metal. It is characteristic to take.

 [0011] For a chelate of a metal with a substituent of a six-membered ring directly bonded to the oxygen atom of the squaric acid skeleton or a coordination atom that is a part of the constituent element and a metal, A near-infrared absorber using a complex with a metal is disclosed (see Patent Document 3).

 [0012] [Chemical 1-3]

[0013] Further, in the publication, only the following structure E is exemplified as a specific compound, and although the elemental analysis value is described for the mixture of structure E and metal, the chelate structure is described. It is unknown whether it has.

[0014] [Chemical 1-4]

[0015] Also disclosed is an ink, a toner for electrophotography, and the like using a mixture of the following structure F and a metal ion-containing compound (see Patent Document 2).

[0016] [Chemical 1-5]

[0017] The squarylium compound is characterized by having the same 6-membered ring and having a dialkylamino group at the P-position of the bond with the squaric acid skeleton. Although this mixture of squarylium compound and metal ion-containing compound shows good color tone, it still has insufficient light resistance, moisture resistance, and heat resistance, and development of a material with excellent fastness has been demanded. .

 Patent Document 1: Japanese Patent Laid-Open No. 2000-265077

 Patent Document 2: JP 2001-342364 A

 Patent Document 3: Japanese Unexamined Patent Publication No. 2000-159776

 Patent Document 4: Pamphlet of International Publication No. 02/50190

 Patent Document 5: International Publication No. 04/7447 Pamphlet

 Disclosure of the invention

 Problems to be solved by the invention

[0018] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel lithium metal complex compound, which has a favorable hue in terms of color reproducibility in the visible range, and weather resistance. It is intended to provide a dye having good fastness such as storage stability, a composition containing the dye, an ink, a toner, an optical recording medium, a color filter, and a front filter for display. Means for solving the problem

[0019] The above object of the present invention is achieved by the following configurations.

 [0020] 1. A squarylium metal complex compound having a partial structure represented by the following general formula (1).

[0021] [Chemical 1]

(In the formula, M represents a metal atom. R represents a substituent, m represents an integer of 0 to 3. A represents an arbitrary organic group.)

 2. The squarylium metal complex compound having a partial structure represented by the general formula (1) is a squarylium metal complex compound represented by the following general formula (2):

2. The squarylium metal complex compound according to 1.

[0023] [Chemical formula 2] General formula (2)

(In the formula, M represents a metal atom.! ~~ is a hydrogen atom or a substituent, A is any organic group, n is 1 or 2. X is a monodentate or bidentate subcoordination. P is an integer from 0 to 2. W represents a counter ion and q is an integer from 0 to 3.)

3. The squarylium metal complex compound having the partial structure represented by the general formula (1) or the squarylium metal complex compound represented by the general formula (2) is represented by the following general formula (3). 3. Said 1 or 2 which is a squarylium metal complex compound The squarylium metal complex compound.

[0025] [Chemical 3]

[In the formula, M represents a metal atom.! ~ Is a hydrogen atom or a substituent, A is an arbitrary organic group, and n is 2 or 3.)

 4. In the general formulas (1) to (3), the organic group A is an aryl group, a heterocyclic group, or the following general formula (1-A), The squarylium metal complex compound described in 1.

 [0027] [Chemical 4]

[In the formula, A represents a 5-membered ring or a 6-membered ring, and ¹ represents a hydrogen atom or a substituent.]

 1

 5. In the above general formulas (1) to (3), the metal atom M is one of copper, nickel, cobalt, aluminum or zinc! The squarylium metal complex compound as described in 1 above.

 [0029] 6. The squarylium metal complex compound according to any one of the above !! to 5, wherein the absorption maximum wavelength is in a visible light region.

[0030] 7. A composition comprising at least one dye described in 6 above and a dispersion medium.

 [0031] 8. A toner comprising at least one dye described in 6 above.

[0032] 9. An ink comprising at least one dye described in 6 above.

[0033] 10. An optical recording medium comprising at least one dye described in 6 above. [0034] 11. A color filter comprising at least one dye described in 6 above

Yes

 [0035] 12. A front filter for a display, comprising at least one dye described in 6 above.

 [0036] 13. The display front filter as described in 12 above, which has an absorption maximum at 560 to 620 nm.

 The invention's effect

 [0037] According to the present invention, a novel squarylium metal complex compound could be provided. This compound is a dye having excellent spectral absorption characteristics, weather resistance, and storage stability, and also exhibits high weather resistance and storage stability even when used as a composition with a dispersant. Color toner, ink, optical recording Media, color filters and front filters for displays could be provided. BEST MODE FOR CARRYING OUT THE INVENTION

 [0038] The dye of the present invention relates to a squarylium metal complex compound having a partial structure represented by the general formula (1), which has an absorption maximum wavelength in a visible light region.

 [0039] The squarylium metal complex represented by the general formula (1) has a partial structure, and the general structure of the squarylium metal complex of the present invention is represented by the general formula (2) or the general formula (3). The

 [0040] According to the study by the inventors, by mixing and reacting a squarylium compound having a specific structure and a metal ion, one oxygen atom of the squaric acid skeleton and oxygen which is one of the substituents of the benzene ring. A chelate ring was formed through the atom, and a new squarylium metal complex compound was obtained.

[0041] In the present invention, the effect that the squarylium metal complex compound of the present invention is more excellent in light resistance and storage stability than the squarylium compound is presumed that stability improvement due to metal chelate formation is one factor. The Chelate complexes are characterized by the fact that one ligand is coordinated to a metal ion by multiple coordination sites, and this chelate ring formation provides a thermodynamic and kinetic stabilization effect. . This is generally referred to as the chelate effect, and it is known that the bond energy of metal ligands is 10 to 10 times more stable than ordinary complexes that are not chelate complexes! [0042] Further, in the squarylium metal complex compound of the present invention, the ratio of the metal and the ligand of the metal chelate complex to be generated can be controlled by using a squarylium compound having a specific structure as a ligand. In addition, we believe that there is almost no unchelated metal and squalium compounds, and that the degradation of the compounds and performance degradation caused by these impurities can be one of the factors that improve performance. The The specific structure here means that the adjacent carbon atom of the carbon to which the squaric acid skeleton and the benzene ring are bonded has a hydroxyl group as a substituent as represented by the general formulas (1) to (3). The squarylium metal complex compound of the present invention is formed by the oxygen atom of the hydroxyl group and the oxygen atom of the squaric acid skeleton acting as a chelate coordination atom.

 [0043] Further, by introducing a hydroxyl group instead of a dialkylamino group as previously known at the p-position of the bonding position between the squaric acid skeleton and the benzene ring, a more robust squarylium metal. A complex compound could be provided.

 [0044] Hereinafter, the squarylium metal complex compound of the present invention, a coloring matter, a composition using the same, a color toner, an ink, a color filter, and a display front filter will be described, but the present invention is not limited thereto.

 <Metal Complex Compound Represented by General Formulas (1) to (3)>

 The squarylium metal complex compound in the present invention has a partial structure which is the essence of the invention by the following general formula (1), and the whole structure is represented by the following general formulas (2) and (3).

 [0046] In the general formulas (1) to (3), M represents a metal atom and bonded to one oxygen atom of the squaric acid skeleton and an oxygen atom derived from a hydroxyl group that is one of the substituents of the benzene ring. It is characterized by forming a chelate ring.

[0047] The metal atom M is not particularly limited as long as it forms a chelate structure with respect to the squarylium compound. Here, a chelate structure means that a specific structure of a ligand (here, a squarylium compound) binds to a metal atom M at a plurality of coordination positions and forms a ring structure with the metal and the ligand. Represents that. As for the metal atom M, for example, copper, nickel, cobalt, zinc, aluminum, beryllium, iron, silver, chromium, manganese, iridium, vanadium, titanium, norenium, molybdenum, tin, bismuth, osmium, magnesium, canoleum, strontium, For example, it can be used for example, norlium, gallium, germanium, platinum, gold, mercury. wear. Periodic table 3 to 12 is preferably a group 12 and more preferably a metal ion contained in the periodic table 7 to 12 group. The valence is preferably a divalent or trivalent metal. Among these, specifically, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, rhodium, palladium, silver, osmium, iridium or platinum are preferable, and copper, nickel, cobalt are particularly preferable in terms of handling. More preferably, it is selected from aluminum or zinc.

In the general formula (1), R represents a substituent, and m represents an integer of 0 to 3. The substituent represented by R is not particularly limited, and examples thereof include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert butyl group, a pentyl group, a hexyl group, an octyl group, Dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), isylamino group (eg, acetylamino group, benzoylamino group, etc.) Group), alkylthio group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthinorethio group, etc.), alkenyl group (for example, bur group, 2-propenyl group, 3 —Butul group, 1-methyl-3-propenyl group, 3-pentur group, 1-methyl-3-butur group, 4 hexenyl group, cyclo Hexenyl group etc.), halogen atoms (eg fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl groups (eg propargyl group etc.), heterocyclic groups (eg pyridyl group, thiazolyl group, oxazolyl group) , Imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (eg, methylsulfifer group) ), Arylsulfier groups (eg, phenylsulfier groups, etc.), phosphono groups, acyl groups (eg, acetyl groups, bivaloyl groups, benzoyl groups, etc.), strong rubamoyl groups (eg, aminocarbonyl groups, methyl groups, etc.) Aminocarbonyl group, dimethylaminocarbonyl group, butyramide Carbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group) Hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, Phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), cyano group, alkoxy group (eg, methoxy group, Ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg, acetylyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt , Aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexyloleamino group, dodecinoleamino group, etc.), anilino group (for example, phenylamino group, Black mouth Luamino group, Toluidino group, Anisidino group, Naphtylamino group, 2-Pyridylamino group, etc., Imido group, Ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group) , Phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, Ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxy carbonyl group), heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxyl group, merca DOO group, and each group and a nitro group. These substituents may be further substituted with the same substituent. These substituents may be further substituted with the same substituent, or the substituents may be further bonded to each other to form a ring. Preferred substituents for R include alkyl group, cycloalkyl group, alkenyl group, halogen atom, heterocyclic group, alkylsulfonyl group, arylsulfonyl group, phosphono group, acyl group, sulfonamido group, cyano group, alkoxy group, aryloxy group. 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, nitrite It is more preferable that at least one group or the like is an alkyl group, a hydroxyl group or an amino group.

In general formula (2) or (3),! ^ ~ Represents a hydrogen atom or a substituent, and specific examples thereof include the same as R. ! Preferred substituents for ^ ˜ are alkyl groups, A alkenyl group, an aryleno group, a heteroaryl group, an alkoxy group, an amino group, an amide group, an acetyl group, a cyano group, a nitro group, a hydroxyl group and the like are preferable. In order to improve the solubility of the compound, at least one is preferably a substituent having a long-chain alkyl.

[0050] A represents an arbitrary organic group, and examples of the organic group include the same groups as the substituents represented by R described above, preferably an aryl group and a heterocyclic group. Further, from the viewpoint of fastness, more preferred are aryl groups, heterocyclic groups, and substituents represented by the above general formula (1 A). Further, as the aryl group, it is more preferable to have at least one of an alkyl group, an acylamino group, an amino group, a sulfonamide group, and a hydroxyl group as a substituent. Is more preferable.

 [0051] A1 represents a 5-membered ring or a 6-membered ring, and the 5-membered ring represented by A1 includes a virazolidinedione ring

, Isoxazolone ring, pyrazolone ring, pyrrolidone ring (eg 1H pyrrole 1 2 (5H) on ring), thoxa thiazolidinone ring (eg rhodanine ring, 4 thixamidazolidin 1 2 on ring, 5 thiximidazo Lysine mono-2-one ring), pyrrolotriazole ring (、, 7, 7a dihydro mono 1H pyro [1, 2-b] [l, 2, 4] triazo, mono nore ring, 7, 7a— Dihydro-1H—pyro-mouth [2, l -c] [l, 2, 4] triazole ring), pyrazolotriazole ring (, 7, 7a dihydro- 1H pyrazo, mouth [5, 1— c ] [l, 2, 4] triazo, 1 nore ring, 7, 7a -dihydro 1 1H-pyrazo mouth [1, 5, 4] [l, 2, 4] triazole ring), pyrazo mouth pyrimidine ring, imidazole ring ( For example, 4H-imidazole ring), imidazolopyrazole ring, pyrrole ring, isoxazolidinedione ring, thixomi Zolizinone ring (for example, 4-thiomidazolidin-2-one ring), imidazolidinedione ring (for example, hydantoin ring), imidazolidindithione ring (for example, imidazolidine 2,4 dithione ring), thiazolidinedione ring, pyrazoledione ring, indole ring, etc. These may have a group having the same meaning as the above-mentioned substituent represented at any position.

[0052] Examples of the 6-membered ring represented by A1 include a cyclohexagen ring (1,3 cyclohexagen ring, 1,4-cyclohexagen ring), a dihydropyridine ring (1,4-dihydropyridine ring, 3,4-dihydropyrazine ring), 4H-pyran ring, 4H-thiopyran ring, pyridone ring (eg pyridine-2 (3H) -one ring), pyridinethione ring (eg pyridine-2 (3H) — H ON ring), pyridinedione ring (eg, pyridine-2, 4 (3H, 5H) -dione ring), barbyl acid ring, thiobarbituric acid ring, oxazine ring, thiazine ring, dihydropyrimidinedione ring (for example, Dihydropyrimidine 1,4,6 (1H, 5H) -dione ring), dihydropyrimidine dithione ring (eg, dihydropyrimidine-4,6 (1H, 5H) -dithione ring), oxazinedione ring (eg, 4H-1, 3-oxazine 4, 6 (5H) -dione ring), oxaziazine ring (for example, 4H-1,2,3 oxaziazine ring) and the like, and these are the substituents represented by Ra described above at an arbitrary position. Have a synonymous group! /!

[0053] ¹ represents a hydrogen atom or a substituent, and the substituent is a group having the same meaning as the substituent represented by R described above. ¹ is preferably a hydrogen atom, an alkyl group or a halogen atom,

 More preferably a hydrogen atom, an alkyl group, a halogen atom or an aryl group, more preferably a hydrogen atom or an alkyl group, still more preferably a methyl group or an ethyl group, and most preferably a hydrogen atom. .

 [0054] The general formula (1) is a partial structure in the metal complex of the present invention. The above general formula (2) or (3) represents the overall structure of the compound in the present invention, and in order to obtain the effects described in the present invention, the squarylium compound is preferably the main ligand. The main ligand and the sub-ligand are explained using the metal complex according to the present invention. For example, when n≥p in the general formula (2), a partial structure shown in parentheses having n, Alternatively, a partial structure represented by a tautomer thereof is called a main ligand, and a ligand represented by X in parentheses having p is called a sub-ligand.

 [0055] Further, the squarylium compound used in the squarylium metal complex compound of the present invention may be a symmetric squarylium compound or an asymmetric squarylium compound. It is preferable.

[0056] In the general formula (2), X is a subligand, and the subligand X is not particularly limited. For example, JP 2000-251957, 2000-311723, 2000- No. 323191, 2001-6760, 2001-59062, 2001-60467, etc. In addition, as a so-called ligand used for forming a conventionally known metal complex, the trader has a known ligand as a ligand as necessary. It may be.

 [0057] Specifically, halogen ions, hydroxide ions, ammonia, pyridine, amines (eg, methylamine, jetylamine, tributylamine, etc.) cyanide ions, cyanate ions, thiolate ions, thiocyanate ions, and biviridine And various chelating ligands such as aminopolycarboxylic acids and 8-hydroxyquinoline.

 [0058] The monodentate ligand is coordinated by an acyl group, a carbonyl group, a thiocyanate group, an isocyanate group, a cyanate group, an isocyanate group, a halogen atom, a cyano group, an alkylthio group, an arylthio group, an alkoxy group or an aryloxy group. Preference is given to ligands or ligands consisting of dialkyl ketones or carbonamides.

 [0059] The bidentate ligand is an acyloxy group, an oxalylene group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group. And a ligand coordinated by a trithiocarbonate group, an alkylthio group or an arylthio group, some! /, Or a ligand comprising a dialkyl ketone or a carbonamide.

 [0060] In addition, a compound represented by the following general formula (4) is more preferable as a ligand.

[0061] [Chemical 5]

[0062] In the general formula (4), E represents a substituent, E is no, and the Met substituent constant (H) is 0.;

 1 2

 0.9 represents an electron-withdrawing group, and represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.

[0063] A substituent represented by E and E having a σ ρ value of 0; Here

 1 2

 As the value of Met's substituent constant σ ρ, the straight line described in the report of Hansch, C. Leo et al. (For example, J. Med. Chem. 16 1207 (1973); ibid. 20 304 (1977)) is used. I like to learn.

[0064] For example, as a substituent or atom having a value of σ ρ of 0.10 or more, 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, chloromethyl, trifluoromethylthiomethyl, trifluorochloromethanesulfonylmethyl, perfluorobutyl), aliphatic, aromatic or polycyclic acyl groups (for example, formyl, acetyl, Benzoyl), aliphatic, aromatic or bicyclic sulfonyl groups (for example, trifluoromethanesulfonyl, methanesulfonyl, benzensulfonyl), rubamoyl groups (for example, rubamoyl, methylcarbamoyl, phenol rubamoyl, 2- Chloro-phenylcarbamoyl), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), substituted aromatic groups (eg, pentachlorophenyl, pentafluorophenyl, 2,4 dimethanesulfurphenyl) 2-trifluoromethylphenyl), heterocyclic residues (eg, 2-benzoxazolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo groups (eg, , Phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (for example, methanesulfonoxyl), acyloxy group (for example, acetyloxy, benzoyloxy), arylsulfonyloxy group (for example, benzene) Sulfonyloxy), phosphoryl groups (eg, dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N— (2-dodecyloxychetyl) sulfamoyl , N ech lou N dodecyl sulfamoyl, N, N jetil Sulfamoyl) and the like

Yes

Substituents having a value of σ ρ of 0.35 or more include cyano groups, nitro groups, carboxyl groups, fluorine-substituted alkyl groups (for example, trifluoromethyl, perfluoronorolobutyl), aliphatic, aromatic or complex Cyclic isacyl groups (eg, acetyl, benzoyl, formyl), aliphatic, aromatic or heterocyclic sulfonyl groups (eg, trifluoromethanesulfonyl, methanesulfonylonole, benzenesulfonyl), strong rubamoyl groups (eg, strong rubamoyl, methyl canolamoinole, Phenylenorecanomole, 2-chlorophenenorecanolevainole), ananoloxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, diphenylmethylcarbonyl), fluorine or sulfonyl group substituted aromatic group (eg pentafluoro) Phenyl, 2, 4 Methanesulfonyl Yul-phenyl), heterocyclic group (e.g., 1 Tetorazoriru), § zone group (e.g., Fueniruazo), alkylsulfonyl O carboxymethyl group (e.g., methanesulfonic two Noroxy), phosphoryl group (for example, dimethoxyphosphoryl, diphenylphosphoryl), sulfamoyl group and the like.

[0066] Examples of the substituent having a value of σ ρ of 0.60 or more include a cyano group, a nitro group, an aliphatic group, an aromatic group or a heterocyclic sulfonyl group (for example, triphenylolomethanesulfonyl, difluoromethanesulfonyl). , Methanesulfonyl, benzenesulfonyl) and the like.

[0067] The substituent represented by Ε has the same meaning as R in the general formula (1),

 1

 Examples of such an electron-withdrawing group include an alkyl group, aryl group, heterocyclic group, carbonyl group, cyano group, alkoxycarbonyl group, alkylsulfonyl group, and alkylsulfonyloxy group.

[0068] As Ε and Ε, a halogenated alkyl group (especially a fluorine-substituted alkyl group),

 1 2

 Examples include a norebonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, and an alkylsulfonyloxy group.

 [0069] Preferred substituents of [0069] include an alkyl group having 2 to 20 carbon atoms, an alkoxy group having 2 to 20 carbon atoms, an aryloxy group, and an amino group, and more preferably an alkyl group having 4 to 18 carbon atoms. Or an alkoxy group having 4 to 18 carbon atoms and an aryloxy group. Most preferred is an alkoxy group having 6 to 16 carbon atoms.

 [0070] Specific examples of the ligand represented by the general formula (4) are shown below, but the present invention is not limited thereto.

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[0075] From the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 12 types, and more preferably 1 type.

[0076] In the general formula (2), W is an arbitrary counter ion, and a typical cation represented by W is an inorganic or organic ammonium ion (for example, a tetraalkylamine). Monions, pyridinium ions), alkali metal ions and protons, while the anions may be either inorganic or organic anions, for example, halogen anions (eg, fluoride ions). Chloride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (eg p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion ( For example, 1,3-benzenedisulfonate ion, 1,5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, Phosphate ion, acetate ion, trifluoromethanesulfonic acid ion, enolate (acetylacetate, hexafluoroacetylacetonate), hydroxide ion, sulfite ion, nitrate ion, nitrite ion, carbonate ion Perchlorate ion, aralkyl carboxylate ion, arylecarboxylate ion, tetraalkylborate, salicinate, benzoate, hexafluoroantimony and the like.

 [0077] In the general formula (2) or (3), n is an integer from !! to 3, p is an integer from 0 to 2, and q is an integer from 0 to 3. The squarylium metal complex compound of the present invention is preferably neutral as a whole, more preferably neutral in the absence of a counter ion, that is, q is 0. Furthermore, it is more preferable that it consists only of a main ligand and a metal ion. In this case, p and q are both 0, and the squarylium metal complex compound of the present invention is represented by the general formula (3).

 [0078] The following is a force showing typical specific examples of squarylium metal complex compounds represented by the general formulas (1) to (3) in the present invention. The present invention is not limited to this.

[0079] [Chemical 10]

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[0094] [Chemical 25]

F3COCHN OH q o NHCOCF3

F3COCHN OH qo NHCOCF3

, Fe

6]

6]

本発明に係る前記一般式（1)〜（3)で表されるスクァリリウム金属錯体化合物にお けるスクァリリウムィ匕合物は、 列えば、特開平 5— 155144号、同 5— 239366号、同 5 — 339233号、特開 2000— 345059号、同 2002— 363434号、同 2004— 86133 号、同 2004— 238606号等の公報、 Law, K. Y. et al. , J. Org. Chem. 1992, 57, 3278等に記載された従来公知の方法を参考にして合成することができる。

The squarylium compounds in the squarylium metal complex compounds represented by the general formulas (1) to (3) according to the present invention are, for example, JP-A Nos. 5-155144, 5-239366, 5 — 339233, JP 2000-345059, 2002-363434, 2004-86133, 2004-238606, Law, KY et al., J. Org. Chem. 1992, 57, 3278 Etc. can be synthesized with reference to conventionally known methods described in the above.

 [0097] Further, the squarylium metal complex of the present invention reacts a raw material that gives a metal ion having coordination ability with a squarylium compound at a temperature between room temperature and 120 ° C for 3 to 24 hours. Can be obtained. It is preferable that the raw material providing the metal ion has a ratio of the number of moles of the squarylium compound and the number of moles of the raw material supplying the metal ion of 1.0 to 3.0: 1.0. At this time, an acid or a base may be added to the reaction system.

 [0098] Examples of raw materials for providing metal ions include bis (acetylacetate) copper, copper acetate, copper bromide, copper nitrate, copper oxalate, copper sulfate, copper chloride, copper perchlorate, and tetrafur. Copper boroborate, copper cyanide, copper iodide, copper trifluoromethanesulfonate, copper thiocyanate, nickel acetate, nickel sulfate, nickel (carbonate), nickel nitrate, nickel chloride, nickel bromide, tetrafluoro Nickel boroborate, bis (acetylacetate) nickel, nickel perchlorate, zinc acetate, zinc bromide, zinc chloride, zinc nitrate, zinc tetrafluoroborate, bis (acetylacetate) Zinc, cobalt nitrate, cobalt nitrite, cobalt acetate, bis (acetylacetate) cobalt, cobalt bromide, cobalt chloride, cobalt oxalate, cobalt thiocyanate And metal ion compounds having a ligand represented by the general formula (4) are used. In this case, from the viewpoint of improving the solubility and the compatibility with the dispersion medium, it is preferable that the raw material that gives metal ions has an organic substance as a counter salt. Examples of such a compound include diketonate metal compounds and general formula (4). And the compounds represented.

 [0099] 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 used is preferably 0 · ;! to 20 · 20 equivalents (molar ratio) to the squarylium compound.

[0100] Examples of the solvent include halogenated hydrocarbon solvents such as chloroform and dichloromethane, aromatic solvents such as toluene and xylene, ether solvents such as tetrahydrofuran and methyl-tert-butyl ether, and esters such as ethyl acetate. Solvents, alcohol solvents such as methanol and ethanol, water, etc., and the amount used is relative to the squarylium compound. The amount is preferably 1 to 500 times (mass ratio).

[0101] The squarylium metal complex dye of the present invention will be described below.

[0102] The dye in the present invention refers to a squarylium metal complex represented by the above general formulas (1) to (3) having an absorption maximum wavelength in the visible region (380 to 780 nm). Since the squarylium metal complex of the present invention has good spectral characteristics, the extinction coefficient in a wavelength region shifted by about lOO nm from the absorption maximum wavelength is 1/100 to 1/100 or less of the absorption coefficient of the absorption maximum. In fact, it is characterized by having no absorption in the wavelength range of 60nm longwave or shortwave from the absorption maximum. As described above, the dye in the present invention is preferable in the visible region and has a V ヽ spectral characteristic.

[0103] The dye of the present invention is preferably used as a composition with a dispersant or a composition in which a solvent is further added to the composition for film-forming stability or the like.

[0104] As the dispersion medium, (meth) acrylate resin, polyester resin, polyamide resin, polyimide resin, polystyrene resin, polyepoxy resin, polyester resin, amino resin, fluorine resin, Phenolic resins, polyurethane resins, polyethylene resins, polychlorinated bur resins, polybutyl alcohol resins, polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins, amide resins, etc. Preferably, (meth) acrylate resins, polystyrene resins, polyethylene resins, polychlorinated bur resins, poly butyl alcohol resins, etc. are preferably used, most preferably (meth) acrylate. Resin and polystyrene resin. These copolymers are also preferred.

[0105] (Meth) acrylate resin is synthesized by homopolymerizing or copolymerizing various meta acrylate monomers or acrylate monomers, and by varying the monomer species and monomer composition ratio, The desired (meth) acrylate 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 the (meth) acrylate monomer, In the present invention, it can be used by mixing a plurality of other resins together with the poly (meth) acrylate resin.

[0106] As a monomer component for forming the (meth) acrylate resin used in the present invention Are, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, open pill (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl ( (Meth) Atylate, t-Butyl (Meth) Atylate, Stearyl (Meth) Atylate, 2-Hydroxyethyl (Meth) Atylate, Acetotaxetyl (Meth) Atylate, Dimethylaminoethyl (Meth) Atylate , 2-Hydroxypropyl (meth) atalylate, Di (ethyleneglycolole) ethinoleethenole (meth) acrylate, Ethyleneglycololemethinolelite Tel (meth) acrylate, Isobonyl (meth) acrylate Ethyltrimethylammonium (meth) atarylate, trifluoro Ethyl (meth) acrylate, Octafluoropentyl (meth) acrylate, 2-acetamidomethyl (meth) acrylate, 2-Methoxy ethyl (meth) acrylate, 2 Dimethylaminoethyl (meth) acrylate , 3 Trimethoxysilane propinole (meth) acrylate, benzyl (meth) acrylate, tridecyl (meth) acrylate, 4-h-meth) acrylate, octadecyl (meth) acrylate, 2-jetylaminoethyl (meth) ) Phthalate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, glycidyl (meth) acrylate, etc. S, preferably (meth) acryl Acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (methyl ) Atarylate, butyl (meth) acrylate, stearinole (meth) acrylate, 2-hydroxyethyl (meth) acrylate, acetatetoxetyl (meth) acrylate, benzyl (meth) acrylate, tridecinole (meta) ) Atarylate, dodecinole (meth) acrylate, 2-ethylenohexylate (meth) acrylate.

A polystyrene resin is a homopolymer of a styrene monomer, a random copolymer or a block copolymer obtained by copolymerizing another monomer having an unsaturated double bond copolymerizable with a styrene monomer, A graft copolymer is mentioned. Furthermore, blends and polymer alloys in which such polymers are blended with other polymers are also included. Examples of the styrene monomer include styrene, α-methyl styrene, α-ethyl styrene, α-methyl styrene ρ methyl styrene, ο methyl styrene, m-methyl styrene, p-methyl styrene, etc. , M chlorostyrene, p chloro styrene, p bromo styrene, dichron styrene, dib mouth styrene, trichronol Forces including nuclear halogenated styrene such as tylene and tribromostyrene Among them, styrene and α-methylolstyrene are preferable.

[0108] By homopolymerizing or copolymerizing these, the resin used in the present invention is, for example, a copolymer resin such as benzyl methacrylate / ethyl acrylate or butyl acrylate, or methyl methacrylate. / 2—Copolymer resin such as ethylhexyl methacrylate, methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyxetyl methacrylate copolymer resin, and styrene / acetoxate Copolymer resin of til methacrylate / stearyl methacrylate, styrene / 2-hydroxyethyl methacrylate / stearyl methacrylate copolymer, and 2-ethyl hexyl methacrylate / 2 —Examples include copolymer resins such as hydroxyethyl methacrylate.

 Next, the ink, toner, optical recording medium, color filter and front filter for display of the present invention will be described in detail.

[0110] 《Ink》

 The ink containing at least one of the dyes of the present invention is used for image recording as an ink jet recording liquid, and even if only one kind of the dye of the present invention is used, it is a combination of two or more kinds of dyes. It may also be used in combination with a dye outside the present invention.

 The ink jet recording liquid containing the dye of the present invention can use various solvent systems such as an aqueous solvent, an oil-based solvent, and a solid (phase change) solvent, and particularly exhibits the effects of the present invention when an aqueous solvent is used. To do. As the aqueous solvent, water (for example, ion exchange water is preferable) and a water-soluble organic solvent are generally used.

[0111] Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanolol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, benzyl alcohol, etc.), polyhydric alcohols (eg, , Ethylene glycol, Diethylene glycol, Triethylene glycol, Polyethylene glycol, Propylene glycol, Dipropylene glycol, Polypropylene glycol, Butylene glycol, Hexane dinore, Pentandionol, Glycerin, Hexantrio Nore, Chioji Glico No., etc.), polyhydric alcohol ethers (for example, ethylene glycol monomethyl etherenole, ethylene glycol monoethyl etherenole, ethylene glycol mono nomono mono butenoate ethere, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl mono) Butinoleethenore, Propylene Glycolanol Monomethinorete Nore, Propylene Glycolenole Monobutenoleetenore, Ethylene Glyco Monoremonomethinoreate Acetate, Triethylene Glycol Monomethyl Ether, Triethylene Glycol Monoethyletenore, Ethylene glycol monophenol enenoate, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diamine) Ethanolamine, triethanolanolamine, N-methinoresinethanolamine, N-ethenoresinethanolamine, monomorpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepenta Mines, polyethyleneimines, pentamethyljetylenetriamines, tetramethylpropylenediamines, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclic rings (For example, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone), sulfoxides (for example, dimethyl sulfoxide), sulfones (For example, sulfolane), urea, acetonite Ril, acetone and the like.

 [0112] The aqueous solvent as described above can be used with a force S that can be used as soon as possible if the dye of the present invention is soluble in the solvent system.

 [0113] On the other hand, when the dye of the present invention is insoluble in the solvent system as it is, the dye is mixed with various dispersing machines (for example, ball mill, sand mill, attritor, Ronore mill, agitator mill, Henschel mixer, colloid minore, ultrasonic Using a homogenizer, pearl mill, jet mill, ang mill, etc.), or after dissolving the dye in a soluble organic solvent, disperse it in the solvent system together with the polymer dispersant or surfactant. You can. Furthermore, if it is an insoluble liquid or semi-molten material as it is, it can be dissolved in an organic solvent that is as it is or in a soluble state, and dispersed in the solvent system together with a polymer dispersant or a surfactant. Monkey.

[0114] When the dye of the present invention is insoluble in the solvent system, it is preferable to make it fine particles and disperse them in the solvent system. S is preferably dispersed in fine particles having an average particle size of 150 nm or less. More preferably.

 [0115] The average particle diameter is a volume average particle diameter, and the average particle diameter in terms of a circle obtained from the average value of the projected area (obtained for at least 100 particles) of a transmission electron microscope (TEM) photograph. Is obtained by converting into a spherical shape. The coefficient of variation can be obtained by calculating the volume average particle diameter and its standard deviation and dividing the standard deviation by the volume average particle diameter. Alternatively, the volume average particle diameter and its standard deviation can be obtained by using a dynamic light scattering method.

 [0116] In addition, it is preferable that the dye is dissolved in an organic solvent in which the dye of the present invention is soluble, and then dispersed in an aqueous solvent as a fine particle dispersion together with the oil-soluble polymer.

 [0117] Specific methods for preparing an aqueous solvent used for such an ink jet recording liquid include, for example, JP-A-5-148436, 5-295312, 7-97541, and 7-82515. Nos. 7-118584, etc. can be referred to.

 [0118] Next, the oil-soluble polymer will be described. There is no restriction | limiting in particular as said oil-soluble polymer, The force bull polymer which can be suitably selected from said dispersing agent group according to the objective is mentioned suitably. Examples of the bull polymer include conventionally known polymers, and any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type may be used. In view of the above, a water dispersion type is preferable.

 [0119] Examples of the water-dispersible bull polymer include those of an ion dissociation type, a non-ionic dispersible group-containing type, or a mixture type thereof.

 Examples of the ion dissociation type bull polymer include a bull polymer containing a cationic dissociable group such as a tertiary amino group and a bull polymer containing an anionic dissociable group such as carboxylic acid and sulfonic acid. . Examples of the nonionic dispersible group-containing type bull polymer include a bull polymer containing a nonionic dispersible group such as a polyethyleneoxy chain. Among these, from the viewpoint of dispersion stability of the colored fine particles, an ion dissociation type bull polymer containing an anionic dissociable group, a non-ionic dispersible group containing type bull polymer, and a mixed type bull polymer are preferable.

[0120] Examples of the monomer that forms the bull polymer include the following. That is, acrylic acid esters, methacrylic acid esters, bur esters, acrylic amides, methacrylamides, olefins, bur ethers, and the like can be mentioned. That Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, jetyl maleate, dimethyl maleate, dibutyl maleate, jetyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl Ruketone, phenol vinyl ketone, methoxyethyl vinyl ketone, N-buluoxazolidone, N-burpi mouthlidone, vinylidene mouthride, methylenemalone nitrile, vinylidene, diphenol two-a

Examples thereof include feto, dibutyl-2-acryloyloxychetyl phosphate, dioctyl-2-methacryloyloxychetyl phosphate, and the like.

[0121] Examples of the monomer having a dissociable group include a monomer having an anionic dissociable group and a monomer having a cationic dissociable group.

[0122] Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer. Among these, acrylic acid

Acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2- methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferred. Acrylamide

—2-Methylbutanesulfonic acid is more preferred.

[0123] Examples of the monomer having a cationic dissociable group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl acrylate.

[0124] Further, examples of the monomer containing a nonionic dispersible group include, for example, an ester of a polyethylene glycol monoremonoalkyl ether and a carboxylic acid monomer, a polyethylene glycol monorenoquinoleatenore, and a sulphonic acid monomer. Estenoles of polyethylene glycolenole monoenolequinoleateolene and phosphoric acid monomer, macromolecules containing polybutyl alcohol structure, urethane containing urethane group formed from polyethylene glycolenomonoalkylene ether and isocyanate group-containing monomer And monomers. The repeating number of the ethyleneoxy part of the polyethylene glycol monoalkyl ether is preferably 8 to 50 force S, more preferably 10 to 30 force S. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably 1-20, more preferably 1-12! /. [0125] These monomers may be used alone to form a bull polymer, or two or more of these monomers may be used in combination to form a bull polymer. , Solubility improvement, dispersion stability, etc.)

[0126] The oil-based solvent used in the present invention uses an organic solvent. Examples of oil solvents include alcohols, esters, ethers, ketones, hydrocarbons, amides, and the like.

[0127] The oil-based solvent as described above can be used by dissolving the dye of the present invention as it is, and can also be used by being dispersed or dissolved in combination with a resinous dispersant or binder. It is more preferable to use in combination with a dispersant from the viewpoint of soil adjustment and the like.

 [0128] For the specific method for preparing the oil-based solvent used in such an ink jet recording liquid, the methods described in JP-A-3-231975 and JP-A-5-508883 can be referred to.

 The solid (phase change) solvent used in the present invention is a phase change solvent that is a solid at room temperature as a solvent and is in a molten liquid state when the ink jet recording liquid is heated and jetted.

[0130] Such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, Paraffin wax, microcrystalline wax, petrolatum, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxy stearic acid , Dihydroxystearic acid, etc.), organic acid esters (for example, esters of organic acids such as glycerin, diethylene glycolol, and esters with ananolone such as ethylene glycolanol), alcohols (eg, dodecanol, tetradecanol, hexade strength) No , Econosanol, Docosanol, Tetracosanol, Hexacosanol, Octacosanol, Dodecenore, Myricinorenoreconole, Tetrasenore, Hexadesenore, Eicosenore, Docosenore, Pinenglycolenore, Reno, Chilenore Teleaphthalyl alcohol, hexanediol, decanediol, dodecanediol, tetradecanediol, hexadecanediol, Docosa: diol, tetracosanediol, tvneol, phenylglycerin, eico sanji-nore, octane-nore, phenenorepropylene glycolenole, bis-phenolenol A, milphenol, etc.), ketone (e.g., benzoylacetone, Diacetobenzen, benzophenone, tricosanone, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide) , Palmitic acid amide, Tetrahydrofuranic acid amide, Erlic acid amide, Myristic acid amide, 12-Hydroxystearic acid amide, N-stearylergic acid amide, N-olyl stearin §

Reaction products of dimer acid, diamine and fatty acid, such as tetramer of acid dimer / ethylene diamine / stearic acid (1: 2: 2 molar ratio), sulfonamide (eg, paratoluene sulphonamide, ethyl) Benzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), silicones KR215, 216, 2 20 (Shin-Etsu Silicone), etc.), coumarones (eg, Escron G-90 (Shinichi) ), Cholesterol fatty acid esters (eg, cholesterol stearate, cholesterol palmitate, cholesterol myristate, cholesterol, behenate, cholesterol, laurate cholesterol, etc.), sugar fatty acids Esters (saccharose stearate, palmitate Sucrose behenate, saccharose behenate, saccharose laurate, latatostearate, latatonormitate, latatomyristate, latatobehenate, latatolaurate, latato mellate, etc. The solid-liquid phase change temperature of the solvent is 60-200 ° C That power S preferred, more preferably 80-150 ° C.

[0132] The solid (phase change) solvent as described above can be used by dissolving the dye of the present invention as it is in a heated molten solvent, and also in combination with a resinous dispersant and a binder. It can be used after dispersing or melting.

[0133] Specific methods for preparing such phase change solvents are described in JP-A-5-186723 and 7-.

Reference can be made to the method described in each of the publications of 70490.

[0134] The ink jet recording liquid of the present invention in which the above-described aqueous, oily, solid (phase change) solvent is used or the dye of the present invention is dissolved or dispersed has a viscosity at the time of flight of 4 X 10 — ² Pa's or less is preferable, and 3 X 10— ² Pa · s or less is more preferable! /.

[0135] The ink jet recording liquid of the present invention is 2 X 10- ⁴ ~ surface tension at the time of flight; 10_ ³

It is more preferable N / cm is preferred instrument ^{3 X 10- 4 ~8 X 10- 4} N / cm.

[0136] The dye of the present invention is preferably used in the range of 0.5% to 25% by mass of the ink jet recording liquid, and more preferably in the range of 0.5% to 10% by mass.

[0137] The resin type dispersant used in the present invention is preferably a high molecular weight compound having a molecular weight of 1,000 to 1,000,000. . ;!~ Five

It is preferable to contain 0% by mass!

[0138] The inkjet recording liquid of the present invention includes a viscosity modifier, surface tension, and the like according to the purpose of improving ejection stability, compatibility with print head and ink cartridge, storage stability, image storage stability, and other various performances. A regulator, a specific resistance modifier, a film forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an antifading agent, an antifungal agent, an antifungal agent, and the like can also be added.

[0139] The inkjet recording liquid of the present invention is not particularly limited with respect to the recording method used.

1S Can be preferably used as an inkjet recording liquid for an on-demand inkjet printer. On-demand methods include electromechanical conversion methods (for example, single-cavity type, double-cavity type, bender type, piston type, shear mode type, shared wall type, etc.), electrothermal conversion type (for example, thermal Specific examples include a cjet type, bubble jet (registered trademark) type, electrostatic attraction type (eg, electric field control type, slit jet type, etc.), discharge type (eg, spark jet type). That's the power S. [0140] Toner

 The toner (color toner) of the present invention is characterized by containing the coloring matter of the present invention. The content of the coloring matter of the present invention is not particularly limited as long as the toner exhibits sufficient spectral absorption characteristics, but is preferably 2 to 30% by mass in the toner particles. In addition to the dye of the present invention, the color toner is mainly composed of a binder resin, a release agent, a charge control agent, and an external additive.

 [0141] As the binder resin for forming the matrix, all binders generally used for toners can be used. Examples include styrene resins, acrylic resins, styrene / acrylic resins, polyester resins, and the like. In addition, for the purpose of imparting toner fluidity improvement or charge control, external additives such as inorganic fine powder and organic fine particles may be added to the toner. As the external additive, silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. The number average primary particle diameter is preferably 10 to 500 nm, and the addition amount thereof is preferably 0.;! To 20% by mass with respect to the toner.

 [0142] Further, as a release agent added to the toner particles for the purpose of improving the heat fixing property, a release agent conventionally used for toner can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and noraffin status. These addition amounts are preferably 1 to 5% by mass in the toner.

 [0143] The charge control agent for improving the charging characteristics may be added as necessary, but colorless is preferred from the viewpoint of color development. For example, a quaternary ammonium salt structure, potassium Examples thereof include those having a xuarene structure.

 [0144] When the color toner of the present invention is used for a two-component developer, it is used by mixing with a carrier. As the carrier, an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier in which the surface of the magnetic material particle is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 m in volume average particle size.

[0145] The image forming method to which the color toner of the present invention is applied is not particularly limited. However, for example, a method in which a color image is repeatedly formed on a photoconductor and then transferred to form an image, or an image formed on the photoconductor is sequentially transferred to an intermediate transfer body, etc. And a method of forming a color image by transferring the image to an image forming member such as paper.

[0146] <Optical recording medium>

 Next, the optical recording medium (optical information recording medium) and the optical information recording method of the present invention will be described in detail.

 [0147] The dye of the present invention used for the optical information recording medium of the present invention is a combination of two or more of the dyes of the present invention, even if only one kind of the dye of the present invention is used. Alternatively, it may be used in combination with a dye other than the present invention. Further, the content of the dye of the present invention in the recording layer is 30 to 100% by mass, preferably 60 to 100% by mass, more preferably 90 to 100% by mass, based on the dry mass of the entire recording layer. Most preferred. Further, in the recording layer of the present invention, a dye that can be used for a conventional optical information recording medium as long as it does not affect the effect of the present invention may be used in combination with the dye of the present invention! / ,.

 [0148] The optical information recording medium of the present invention includes various configurations. The optical information recording medium of the present invention has a configuration in which a recording layer, a light reflecting layer, and a protective layer are arranged in this order on a disc-like substrate on which a pre-loop of a constant track pitch is formed, or a light reflecting layer, a recording layer on the substrate. A configuration having a recording layer and a protective layer in this order is preferable. In addition, two laminates in which a recording layer and a light reflection layer are provided on a transparent disk-like substrate on which a pre-loop of a certain track pitch is formed are joined so that each recording layer is on the inside. The configuration is also preferable.

[0149] The optical information recording medium of the present invention can use a substrate on which a pre-loop with a narrower track pitch is formed as compared with CD-R and DVD-R in order to achieve higher recording density. . In the case of the optical information recording medium of the present invention, the track pitch is preferably in the range of 0.2 to 0.8 μΐη, and more preferably in the range of 0.2 to 0.5 m. In particular, it is preferably in the range of 0.2-0.4πι. The depth of the predano leve is preferably in the range of 0.01—0.18 in, more preferably in the range of 0.01-0.1.5 m, in particular 0.02-0.1. It is preferably in the range of 5 mm. Adjacent predaloop width Is preferably in the range of 0 · 05—0.4 πι, more preferably in the range of 0.08 to 0.3 〃m, particularly in the range of 0.1 to 0.25 〃m. It is preferable.

 As an example of the optical information recording medium of the present invention, a manufacturing method having a recording layer, a light reflecting layer, and a protective layer in this order on a disc-like substrate will be described below.

 [0151] The substrate of the optical information recording medium of the present invention has a wavelength region of laser light used for recording and reproduction (

 350 to 900 nm) is required to be substantially transparent (transmittance of 80% or more), and various material forces used as substrates for conventional optical information recording media. it can. Examples of the substrate material include acrylic resins such as glass, polycarbonate, and polymethylmethacrylate, chlorinated resins such as polychlorinated bulls and chlorinated copolymers, epoxy resins, amorphous polyolefins, and polyesters. You may use them together. These materials can be used as a film or as a rigid substrate. Among the above materials, polycarbonate is preferable from the viewpoint of moisture resistance, dimensional stability, price, and the like.

 [0152] An undercoat layer may be provided on the surface of the substrate on which the recording layer is provided for the purpose of improving flatness, improving adhesive strength, and preventing alteration of the recording layer. Materials for the undercoat layer include, for example, polymethyl methacrylate, acrylic acid 'methacrylic acid copolymer, styrene' maleic anhydride copolymer, polybutyl alcohol, N-methylol acrylamide, and styrene 'butanol copolymer. , Chlorosulfonated polyethylene, nitrocellulose, polychlorinated butyl, chlorinated polyolefin, polyester, polyimide, butyl acetate / butyl chloride copolymer, ethylene 'butyl acetate copolymer, polyethylene, polypropylene, polycarbonate and other high-molecular substances, and A surface modifier such as a silane coupling agent can be used. The undercoat layer is formed by dissolving or dispersing the above substances in an appropriate solvent to prepare a coating solution, and then applying this coating solution to the substrate surface by a coating method such as spin coating, dip coating, or eta-stretch coating. The power to do S. The thickness of the undercoat layer is generally in the range of 0.005 to 20 in, preferably in the range of 0.0;! To 10 m.

[0153] The recording layer can be formed by a method such as vapor deposition, sputtering, CVD, or solvent coating. Among these, solvent coating is preferred. In this case, a coating solution is prepared by dissolving the dye, and further, a quencher, a binder, etc., if desired, in a solvent. This can be done by applying it to the substrate surface to form a coating film and then drying it.

 [0154] Solvents for the coating solution include esters such as butyl acetate, ethyl lactate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; dichloromethane, 1,2-dichloroethane, black mouth Chlorinated hydrocarbons such as form; Amides such as dimethylformamide; Hydrocarbons such as methylcyclohexane; Etherenoles such as dibutyl ether, jetinoreethenole, tetrahydrofuran and dioxane; Ethanol, n-propanol, isopropanol, n-butanol, diacetone Alcohols such as alcohols; Fluorinated solvents such as 2, 2, 3, 3-tetrafluoropropanol; ethylene glycol monomethyl etherenole, ethylene glycol monoethanolino ethere, propylene glycol monoethanolo ether And the like da recall ethers.

 [0155] The above solvents may be used alone or in combination of two or more in consideration of the solubility of the dye used. Various additives such as antioxidants, UV absorbers, plasticizers, and lubricants may be added to the coating solution depending on the purpose.

 [0156] When binders are used, examples of binders include gelatin, cellulose derivatives, dextran, rosin, natural organic polymer materials such as rubber; and hydrocarbons such as polyethylene, polypropylene, polystyrene, polyisobutylene, etc. Resins, poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl chloride), poly (butyl acetate copolymer), etc., acrylic resins such as poly (methyl acrylate) and poly (methyl methacrylate), poly (bull alcohol), chlorinated poly (ethylene) And synthetic organic polymers such as initial condensates of thermosetting resins such as epoxy resins, butyral resins, rubber derivatives, phenol formaldehyde resins, and the like.

[0157] When a binder is used in combination as the recording layer material, the amount of binder used is generally in the range of 0.0;! To 50 times (mass ratio) with respect to the metal complex, preferably 0.;! ~ 5 times the amount (mass ratio). The concentration of the dye in the coating solution this way are prepared is generally 0.01 to; the range of 10 mass _^0/0, preferably 0.; in the range of 1-5 mass ^_0/0!.

 [0158] Examples of the coating method include a spray method, a spin coating method, a dip method, a roll coating method, a blade coating method, a doctor roll method, and a screen printing method.

The recording layer may be a single layer or a multilayer. The thickness of the recording layer is generally in the range of 0.01-0.5.111, and preferably in the range of 0.015—0.3 mm, more preferably in the range of 0.02—0.1 m. of There are n cars.

 [0159] The recording layer constituting the optical recording medium may contain other types of dyes, various resins, surfactants, antistatic agents, dispersants, antioxidants, crosslinking agents, and the like. . The recording layer may be formed on one surface of the substrate or on both surfaces of the substrate.

 [0160] In order to improve the light resistance of the recording layer, the recording layer can contain various anti-fading agents. A singlet oxygen quencher is generally used as the anti-fading agent. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A-58-175693 and 59.

— 81 194, 60—18387, 60—19586, 60—19587, 60—350 54, 60—36190, 60—36191, 60—44554, 60 -44555, 60-44389, 60-44390, 60-54892, 60-47069, 63

— No. 209995, Japanese Patent Laid-Open No. 4-25492, Japanese Patent Publication No. 1-38680, and No. 6-26028, German Patent No. 350, 399, and Journal of the Chemical Society of Japan, October 1992, No. 1 141 The thing of description on a page etc. can be mentioned. An example of a preferred singlet oxygen quencher is a compound represented by the following general formula (B).

 [0161] [Chemical 27]

—Translation B)

[0162] In the formula, R represents an alkyl group which may have a substituent, and Q- represents an anion. R 1 is generally an optionally substituted alkyl group having 1 to 8 carbon atoms, preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the substituent for the alkyl group include a halogen atom (for example, F, C1), an alkoxy group (for example, methoxy, ethoxy), an alkylthio group (for example, methylthio, ethylthio), an isyl group (for example, acetyl, propionyl), Acyloxy group (eg, acetoxy, propionyloxy), hydroxy group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), alkenyl group (eg, , Bur), and aryl groups (eg, phenyl, naphthyl). Of these, halogen atoms, alkoxy groups, alkylthio groups, and alkoxycarbonyl groups are preferred. Preferred examples of Q—anions include CIO—, AsF—, BF—, and SbF—.

 4 6 4 6 Touch with S.

 [0163] Table 1 shows examples of the compound represented by formula (B).

[0164] [Table 1]

[0165] The amount of the anti-fading agent such as the singlet oxygen quencher used is usually in the range of 0.;! To 50% by mass, preferably 0.5 to 0.5%, based on the amount of the metal complex of the present invention. The range is 45% by mass, more preferably 0.5 to 40% by mass, particularly preferably 1 to 25% by mass.

[0166] It is preferable to provide a light reflecting layer adjacent to the recording layer for the purpose of improving the reflectance during information reproduction. The light-reflecting material that is the material of the light-reflecting layer is a material that has a high reflectivity with respect to laser light. Examples of this are Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, and Mo. , W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Te, Pb, Po, Sn C) Metals such as Bi, semi-metals or stainless steels.

 [0167] These substances may be used alone or in combination of two or more kinds or as an alloy. Among these, Cr, Ni, Pt, Cu, Ag, Au, Al, and stainless steel are preferable. Particularly preferred are Au metal, Ag metal, A1 metal or alloys thereof, and most preferred are Ag metal, A1 metal or alloys thereof.

[0168] The light reflecting layer can be formed on the substrate or the recording layer, for example, by vapor deposition, sputtering or ion plating of the light reflecting material. The thickness of the light reflecting layer is generally in the range of 0 · 01—0.3.11, and in the range of 0.05 to 0.2.111. It is preferable.

 [0169] A protective layer is preferably provided on the light reflecting layer or the recording layer for the purpose of physically and chemically protecting the recording layer and the like. If a DVD-R type optical information recording medium is manufactured in the same manner, that is, if the recording layer is laminated on the inside using two substrates, it is not always necessary to provide a protective layer. Nare ,.

 [0170] Examples of materials used for the protective layer include: Zn—SiO, ZnS, SiO, SiO, MgF, Sn 2 O, Si N, and other inorganic substances, thermoplastic resins, thermosetting resins, UV curable resins, etc. The organic

2 3 4

 You can power up substances. The protective layer can be formed, for example, by laminating a film obtained by extrusion of plastic on the reflective layer through an adhesive. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating.

[0171] In the case of a thermoplastic resin or a thermosetting resin, these are dissolved in a suitable solvent to obtain a coating solution.

 After preparing the coating solution, it can also be formed by applying this coating solution and drying it. In the case of a UV curable resin, it can also be formed by preparing a coating solution as it is or by dissolving it in an appropriate solvent, and then applying this coating solution and curing it by irradiating with UV light. Can do. In these coating solutions, various additives such as antistatic agents, antioxidants and UV absorbers may be added according to the purpose. The thickness of the protective layer is generally 0.1111 to 1 mm (7) fiiH.

 [0172] Through the above steps, a laminate in which a recording layer, a light reflecting layer and a protective layer are provided on a substrate or a light reflecting layer, a recording layer and a protective layer are provided on a substrate can be produced.

 The optical information recording method of the present invention is carried out, for example, as follows using the optical information recording medium. First, while rotating the optical information recording medium at a constant linear velocity (3.84 m / s in the case of DVD-R format) or constant angular velocity, the optical information recording medium can be used for recording semiconductor laser light from the substrate side or the protective layer side. Irradiate light. By this light irradiation, the recording layer absorbs the light and the temperature rises locally, and physical or chemical changes (for example, generation of pits) occur to change the optical characteristics, so that information can be obtained. It is considered to be recorded.

[0174] In the present invention, semiconductor laser light having an oscillation wavelength in the range of 300 to 900 nm is used as recording light. As a light source for recording and reproduction of the optical information recording medium of the present invention Examples thereof include a solid-state laser, a gas laser, a dye laser, and a semiconductor laser. Since the metal complex of the present invention has particularly high recording sensitivity, it is suitable for recording and reproduction using a 635 nm or 650 nm semiconductor laser, a 532 nm YAG harmonic laser, or the like. On the other hand, a blue-violet semiconductor laser light having an oscillation wavelength in the range of 400 to 410 nm, an infrared semiconductor laser light having a central oscillation wavelength of 850 nm or 820 nm and a half wavelength using an optical waveguide device, the central oscillation wavelength is 425 nm or 410 nm, respectively. The blue-violet SHG laser light is also preferred! In particular, blue-violet semiconductor laser light is preferably used in terms of recording density. The information recorded as described above is reproduced by irradiating a semiconductor laser beam from the substrate side or the protective layer side while rotating the optical information recording medium at the same constant linear velocity as above and detecting the reflected light. It can be done with force S.

 [0175] Color filter

 When the coloring matter of the present invention is used for a color filter, when dispersing the coloring matter of the present invention in a resin base, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used.

 [0176] In the present invention, as the resin varnish, a varnish used for a conventionally known color filter coloring composition is used. As the dispersion medium, a solvent suitable for the resin varnish or an aqueous medium is used. In addition, conventionally known additives such as a dispersion aid, a smoothing agent, and an adhesive agent are added and used as necessary.

 [0177] As the resin varnish, a photosensitive resin varnish and a non-photosensitive resin varnish are used. Examples of the photosensitive resin varnish are photosensitive resin varnishes used for ultraviolet curable inks and electron beam curable inks. Non-photosensitive resin varnishes include, for example, relief printing inks, lithographic inks, intaglio inks. Varnishes used for printing inks such as stencil screen ink, varnishes used for electrodeposition coating, varnishes used for developers of electrostatic printing and electrostatic printing, varnishes used for thermal transfer ribbons, etc. can be used .

[0178] Examples of the photosensitive resin varnish include photosensitive cyclized rubber resin, photosensitive phenol resin, photosensitive polymetatalate resin, photosensitive polyamide resin, photosensitive polyimide resin, and the like. Polyester resin, polyester acrylate resin, polyepoxy Atallate resin, polyurethane acrylate resin, polyether acrylate resin

And varnishes such as polyol acrylate resins, and further varnishes with added monomers as reactive diluents. A photosensitive coloring composition can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the metal chelate dye of the present invention and the above varnish and drying by a conventionally known method. Moreover, it can replace with said photoinitiator and can use it as a thermopolymerizable coloring composition using a thermal polymerization initiator.

 [0179] In the case of forming a color filter pattern using the above photosensitive coloring composition, the photosensitive coloring composition is spin-coated on a transparent substrate, using a low-speed rotary coater, a roll coater, a knife coater, or the like. Apply the entire surface by coating, or print the entire surface by various printing methods or a partial printing that is slightly larger than the pattern! / \ After pre-drying, attach the photomask and expose it using an ultra-high pressure mercury lamp. Burn it. Subsequently, development and washing are performed, and a color filter pattern can be formed by performing post-beta as necessary.

[0180] Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose-based resins, styrene-based (co) polymers, polybutylpropylar resins, aminoalkyd resins, and polyester resins. , Amino resin-modified polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxetyl cellulose, styrene Water-soluble salts of maleic acid ester-based copolymers, water-soluble salts of (meth) acrylic acid ester-based (co) polymers, water-soluble amino alkyd resins, water-soluble amino polyester resins, water-soluble polyamide resins Can be used alone or in combination.

[0181] When a color filter pattern is formed using the above non-photosensitive coloring composition, the above-described various types of non-photosensitive coloring composition, for example, a color filter printing ink, are used on a transparent substrate. A method of printing a colored pattern directly on a substrate by the printing method, a method of forming a colored pattern on a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for color filters, an electronic printing method and an electrostatic printing method Or a color filter substrate after a colored pattern is once formed on the transferable substrate by the above method or the like. And the like. Next, baking is performed as necessary according to conventional methods, polishing for smoothing the surface, and top coating for protecting the surface. In addition, a black matrix is formed according to a conventional method to obtain an RGB color filter.

 [0182] <Front filter for display>

 The front filter for a display of the present invention has the dye of the present invention in the base material or contains at least one kind of the composition. In addition to being contained within the material, it means a state where it is applied to the surface of the base material, a state where it is sandwiched between the base material and the base material, and the like.

 [0183] In addition, the front filter for a display according to the present invention is disposed in front of a self-luminous display device such as a plasma display or an organic EL display, and is used to correct color tone or block light emission in an unnecessary wavelength region. It is done. Therefore, the display front filter of the present invention is characterized by having an 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 a fluorescent maximum having an absorption maximum at 400 to 620 nm for color tone adjustment. It is preferable to have an absorption maximum in a wavelength region corresponding to the valleys of the blue, green, and red spectra that are emitted from the light body. Examples of such a wavelength range include 350 to 400 nm, 480 to 520 nm and the like S. In particular, in order to cut off neon emission, it is preferable to have an absorption maximum at 560 to 620 nm. It is more preferable to have an absorption maximum at 580 to 605 nm.

 [0184] Examples of the substrate include a transparent resin plate, a transparent film, transparent glass, and the like, and are not particularly limited as long as the light transmittance at a wavelength of 400 to 7 OOnm is 40% or more. For example, polyimide, polysulfone (PSF), polyethersulfone (PES), polyethylene terephthalate (PET), polymethylene methacrylate (PMMA), polycarbonate (PC), polyetherol ether ketone (PEEK), polypropylene (PP), triacetyl cellulose (TAC), etc. S In particular, acrylic resins such as polyethylene terephthalate (PET), triacetyl cellulose (TAC), and polymethyl methacrylate (PMMA), and polycarbonate resins are preferably used.

[0185] The thickness of the base material is not particularly limited as long as it has a certain degree of mechanical strength. m ~; 10 mm, 20 mm ~, preferably 1 mm, 20 mm ~ 200 mm, particularly preferred! / 好.

[0186] The method for producing the front filter for a display of the present invention using the dye or the composition thereof is not particularly limited.

 (1) Method to include in transparent adhesive

 (2) Method for inclusion in polymer molding

 (3) Coating on polymer molded body or glass surface

 Methods and the like.

[0187] Specific examples of the transparent adhesives listed in (1) include acrylic adhesives, silicone adhesives, urethane adhesives, polybutyl petital adhesives (PVB), and ethylene vinyl acetate. Examples include adhesives (EVA), polybulle ethers, saturated amorphous polyesters, sheet-like or liquid adhesives such as melamine resin, among which acrylic adhesives, urethane adhesives, polybules A petital adhesive is preferred. The addition amount of the dye of the present invention is usually 10ppm~30 mass _^0/0, S preferably 10ppm~20 mass _^0/0 force, 10p pm~; 10 wt% is particularly preferred.

 [0188] The method of incorporating the polymer resin molding mentioned in (2) includes (A) a method of kneading a dye mixture into a resin and thermoforming, and (B) a resin or resin monomer in an organic solvent. And a method of producing a polymer molded body by a casting method by dispersing and dissolving a mixture of pigment and dye.

[0189] The resin used in (A) is preferably as transparent as possible when the plate or film is produced. Specifically, polyethylene terephthalate (PET), polyether sulfone (PES), polyethylene Naphthalate, polyarylate, polyetherketone, polycarbonate, polyamide such as polyethylene, polypropylene and nylon 6, cellulose resin such as polyimide and triacetyl cellulose, fluorine resin such as polyurethane and polytetrafluoroethylene, polychlorinated Bull compounds such as Bull, polyacrylic acid, polyacrylate esters, polyacrylonitrile, addition polymers of bur compounds, polymethacrylic acid, polymethacrylic acid esters, vinylidene compounds such as polyvinylidene chloride, vinylidene fluoride / trifluoroethylene Polymers, copolymers of ethylene / Bulle compound of acetate Bulle copolymer or a fluorine-based compound, polyether such as polyethylene O dimethylsulfoxide, epoxy resin , Polybulol alcohol, polybulbutyral and the like.

[0190] The processing conditions include a method in which a dye mixture is added to and mixed with a base polymer powder or pellet, heated to 150 to 350 ° C, dissolved, and then molded to form a plate, or an extruder. A method of forming a film with an extruder, a raw material with an extruder, 30 to; a method of stretching 2 to 5 times at 120 ° C and uniaxial to biaxial to make a film 10 to 200 111 thick, etc. Is mentioned. When mixing, additives such as plasticity used for normal resin molding may be added.

[0191] In the casting method of (B), a dye mixture is added and dissolved in an organic solvent solution or an organic solvent of a resin or resin monomer, and if necessary, a plasticizer, a polymerization initiator, and an antioxidant are added, A plate or film can be produced by pouring onto a mold or drum having the required surface state, solvent volatilization, drying or polymerization, solvent volatilization and drying.

 [0192] Resins used include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polybule resins, polyresins. Examples thereof include resin monomers of bulle alcohol resins, polymodified resins (PVA, 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.

 [0193] As a method for coating the polymer molded body or glass surface mentioned in (3), a method of dissolving the dye of the present invention in a binder resin and an organic solvent to form a composition, and then forming a paint, uncolored And an acrylic emulsion-based water-based paint by dispersing a finely pulverized (50 to 50 Onm) pigment of the present invention in the acrylic emulsion paint. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

 [0194] Examples of the noinder include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polybule resins, polyresins. Examples thereof include a bull alcohol resin, a polyvinyl modified resin (PVB, EVA, etc.) or a copolymer resin thereof.

[0195] Solvents include halogens, alcohols, ketones, esters, and aliphatic hydrocarbons. The concentration of the composition varies depending on the gram extinction coefficient, coating thickness, desired absorption intensity, desired visible light transmittance, etc. The amount is usually 0.1 lpp 111 to 30% by mass with respect to the mass of the binder resin. The resin concentration is usually from!

 The paint 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, reno coater, die coater, or spraying. Can be crafted.

[0196] The front filter for display of the present invention preferably has an electromagnetic wave shielding function or a near-infrared shielding function. As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used. A laminate using a silver thin film is preferably a laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated. As the metal mesh, there can be used a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern by etching using a technique of photolithography, and the like. In addition, a method of performing battering with an ink containing a metal, a method of applying and developing and fixing silver halide, etc. are also suitably used.

 Regarding the near-red ray blocking function, when an electromagnetic wave shield using a silver thin film is used, it is possible to simultaneously block near-infrared rays 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 or antifouling layer can be added to the display front filter of the present invention.

[0198] In addition, UV-blocking acrylic plates may be used as substrates, and UV-blocking acrylic plates may be used as substrates, or UV-absorbing layers may be formed on one or both sides of the substrate. The composition for a front film for a display of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include salicylic acid derivatives (UV-1), benzophenone derivatives (UV-2), Nzotriazole derivatives (UV-3), acrylonitrile derivatives (UV-4), benzoic acid derivatives (UV-5), or organometallic complex salts (UV-6). Phenyl, 4-tert-phenylsalicylic acid, etc. are used as (UV-2), such as 2-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and (UV-3) as 2- (2 (-Hydroxy 1 5 '-methyl phenyl) 1 benzotriazole, 2-(2' -hydroxy 3 '-5-Gipuccino refeninore) 5-black mouth Benzotriazonore etc. (UV-4) , 2-ethylhexyl 2 siano 3, 3 '— diphenylatarylate, methyl-α-cyano β-(ρ methoxyphenyl) acrylate, etc. (UV —5) include resorcinol monomonobenzoate, 2', 4 '—Di-t-butyl Nitrogen 3,5—t-butyl 4-hydroxybenzoate, etc. (UV—6) include Nikke Norebisoctylphenylsulfamide, Ethyl 3,5-dibutyltinoleyl 4-hydroxybenzyl phosphate nickel A salt etc. can be mentioned.

 [0199] The above-described ultraviolet absorber preferably used in the present invention is a benzotriazole-based ultraviolet absorber or a UV absorber excellent in the effect of preventing deterioration of optical devices such as polarizing plates, liquid crystal elements, and plasma displays having high transparency. Nzophenone UV absorbers are preferred and less unwanted coloring! / Benzotriazole UV absorbers are particularly preferred! /.

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

 [0201] 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 any particular limitation. Can do.

[0202] A plasma display panel display device is a device that displays a color image according to the following principle. A display electrode pair is provided between the front glass plate and the rear glass plate, and cells corresponding to each pixel (R (red), G (green), B (blue)) provided between the two glass plates are provided. Xenon gas or neon gas is sealed in the cell, 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, xenon gas and neon gas in the cell are excited and emitted, and ultraviolet rays are generated. By irradiating the ultraviolet rays with the ultraviolet rays, visible light corresponding to each pixel is generated. And on the back glass plate An address electrode is provided, and a signal is applied to the address electrode to control which discharge cell is displayed and display a color image.

[0203] The display front filter according to the present invention can be suitably used as a neon cut filter for selectively blocking emission of neon gas in a cell. As described above, in the plasma display, the force of performing color display by the light emission of the phosphor S, so-called neon centering around 600 nm (580 to 590 nm) when neon atoms return to the ground state after being excited. It is known to emit orange light (Journal of the Institute of Image Information and Television Engineers, Vol. 51, No. 4, P. 459—463 (1997)). For this reason, the plasma display has a drawback in that a bright red color cannot be obtained by mixing orange with red! In order to eliminate this drawback, it is desired to cut off neon emission. Therefore, when the compound of the present invention is used as a composition for a neon emission absorption filter, it is preferable that the compound of the present invention has an absorption maximum at 560 to 620 nm in a solution state at 580 to 605 nm. More preferably, it has an absorption maximum. At this time, the transmittance of the filter at the absorption maximum in the wavelength region of 560 to 620 nm is preferably in the range of 0.0;! To 80%; and more preferably in the range of! To 70%. In order to improve the color reproducibility of the display, it is preferable that the absorption waveform in the wavelength region of 560 to 62 Onm is sharp. Specifically, the absorption waveform at 560 to 20 nm is preferably 20 to 70 nm with a half-width value (the width of the wavelength region showing the absorbance at half the absorption maximum) of 15 to 100 nm. Is more preferably 25 to 50 nm.

 Example

 [0204] Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited to these examples. In the examples, “%” is used to indicate “mass%” unless otherwise specified.

[0205] Example 1

 (Synthesis of Exemplified Compound 14)

 It was synthesized according to the following scheme.

[0206] [Chemical 28]

[0207] 2,4 bis (2,6 dihydroxy-4-oxocyclohexa 2,5-dienylidene) cyclobutane-1,3-dione (20g) as a ligand was heated to 50 ml of ethanol and heated quickly. To this solution, copper (II) perchlorate hexahydrate, 0.68 g of ethanol solution was added dropwise over 30 minutes, and the mixture was heated and stirred for 5 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the precipitate was collected by filtration. This was recrystallized to obtain 0.50 g of the target exemplified compound (14).

 [0208] The results of elemental analysis were consistent by adding two molecules of ethanol to the target complex.

 [0209] Elemental analysis (C H CuO)

 36 28 18

 Theoretical value (%) C 53.24; H 3.48; Cu 7.82

 Found (%) C 53.41; H 3.55; Cu 7.63

 max 564nm; λ 26nm; ε 27000 (ethyl acetate solvent)

 1/2

 (Synthesis of Exemplified Compound 1 10)

 Exemplified compounds, except that 0.90g of 2,4bis (2hydroxy-4-oxocyclohexa-2,5 genylidene) cyclobutane-1,3 dione was used for the self-ligand and 0.37g of nickel acetate (11) tetrahydrate was used for the metal 14 In the same manner as in Synthesis Example 4, the exemplified compound (1 10

 ) 0.39 g was obtained.

[0210] Elemental analysis (C H NiO)

 32 16 12

 Theoretical value (%) C 59.02; H 2.48; Ni 9.01

 Measured straight (%) C 58.98; H 2.35; Ni 8.88

 max 600nm; λ 64.5nm; ε 53000 (ethyl acetate solvent)

 1/2

 (Synthesis of Exemplified Compound 2-25)

 2— ((2 Hydroxy-4-oxocyclohexa-2,5-geridene) dio

3, 3 Trimethinolane Dream 0.80g, metal with bis (a Cetylacetonate) Except that 0.29 g of copper (11) was used, 0.44 g of the exemplified compound (2-25) was obtained in the same manner as the synthesis example of the exemplified compound 1-4. The results of elemental analysis showed that the addition of one moisture molecule to the target complex! / Was consistent.

[0211] Elemental analysis (C H CuNO)

 44 36 2 9

 Theoretical value (%) C, 66.03; H, 4.53; Cu, 7.94; N, 3.50

 Found (%) C, 66.12; H, 4.62; Cu, 8.10; N, 3.41

 (Synthesis of Exemplified Compound 1 12)

 As a ligand, 1.40 g of 2,4 bis (2,3 hydroxy-4-oxocyclohexa-2,5-geridene) cyclobutane-1,3-dione was dissolved in a mixed solvent of 70 ml of ethyl acetate and 15 ml of acetic acid. To this solution, 0.60 g of aluminum tris (ethyl acetate acetate) was added, and the mixture was stirred at 50 ° C to 60 ° C for 4 hours. After allowing to cool, the precipitate was collected by filtration and dried to obtain 1.21 g of the desired example compound (1-12).

[0212] Elemental analysis (C H AIO)

 48 24 24

 Theoretical value (%) C, 56.99; H, 2.39; A1, 2.67

 Found (%) C, 57.14; H, 2.49; A1, 2.55

 (Synthesis of Exemplified Compound 1 18)

 It was synthesized according to the following scheme.

[0213] [Chemical 29]

[0214] 1,4-Bis (2,6-dihydroxy-4-oxocyclohexa-2,5-dienylidene) monocyclobutane-1,3-dione as a ligand, 1.65 g, was dissolved in 50 ml of methanol. Bis (decyl-2 cyano 4, 4, 4 trifluoro-3-oxobutanoate) Cu (I 1) 1.76 g of methanol solution was added dropwise over 30 minutes, and the mixture was heated and stirred for 2 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the precipitate was collected by filtration. This was recrystallized from methanol to obtain 1.54 g of the intended exemplary compound (1-18). The elemental analysis shows that the target structure is free of 1 molecule of water!

[0215] Elemental analysis (C H CuFNO)

 31 36 3 12

 Theoretical value (%) C, 50.65; H, 4.94; Cu, 8.64; N, 1.91

 Found (%) C, 50.48; H, 5. ll; Cu, 8.55; N, 2.00

 max, 564nm; λ, 26nm; ε, 27000 (Ethinole acetate solvent)

 1/2

 (Synthesis of Exemplified Compound 2-50)

 2- (1-Butyl-3 Methyl-5-oxobilazolidene) -4 (2-6-dihydroxy-4-oxocyclohexer 2,5 geuridane) cyclobutane 1,3 dione 0 · 70g as a ligand, bis on metal (1- (4 (Ethoxycarbonyl) phenoxy) -3 (Methoxycarbonyl) -4 oxopentebutyoxy) The target metal in the same manner as in the synthesis example of Exemplified Compound (1-18) except that 1.39 g of copper was used. 0.42 g of the complex (2-50) was obtained.

[0216] Elemental analysis (C H CuNO)

 34 33 2 13

 Theoretical value (%) C, 55.10; H, 4.49; Cu, 8.57; N, 3.78

 Found (%) C, 55.23; H, 4.62; Cu, 8.41; N, 3.86

 Example 2 (Visible light absorption filter)

 (Visible light absorption filter 1 A)

 A 0.5% dimethoxyethane solution of Exemplified Compound (11) of the present invention was prepared, and coated on a glass substrate with a bar coater and dried to prepare a coated glass. This film had a reddish purple color, and it was found that the compound of the present invention effectively absorbs visible light.

[0217] (Visible light absorption filter 1B)

A 1.0% tetrahydrofuran solution of the exemplary compound (11) of the present invention and a 20% dimethoxyethane solution of a polyester resin (dispersion medium) are mixed in a ratio of 2: 8, and coated on a glass substrate with a bar coater and dried. Thus, a coating film was prepared. This film had a reddish purple color, and the compound of the present invention was able to effectively absorb visible light even in a composition containing a dispersion medium. [0218] (Visible light absorption filter 2A 11A 2A1 IB of the present invention and comparative visible light absorption filter 12A 14A 12B to 14B)

 The visible light absorbing filter 2A 11 A 2B 1 IB of the present invention and the comparative visible light absorbing filter 12A 14A 12B 14B were similarly used except that the dye used was changed from the exemplified compound (11) to the dye shown in Table 2. Produced. Here, the dye of filter 13A and 13B, comparison compound 1 + MS-1, is a mixture of comparison compound 1 and bis (acetylacetate) nickel in dimethoxyethane solution or tetrahydrofuran solution. It was.

 [0219] [Chemical 30] H

,:.

^ Comparison 2

[0220] One of the produced visible light absorption filters was evaluated!

[0221] (Light resistance)

 % Decrease in reflection spectral density at the maximum absorption wavelength in the visible region from an unexploded sample after 24 hours of xenon light (70000 rutus) using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd. (Dye remaining rate%) was calculated and evaluated according to the following criteria.

 [0222] (Dye remaining rate%) = (Maximum absorption wavelength concentration of exposed sample / Maximum absorption wavelength concentration of unexposed sample) X 100

 ◎◎: Dye remaining rate is 95% or more

 A: Dye remaining rate is 90% less than 95%

 ○: Dye remaining rate is less than 80% and 90%

Δ: Dye remaining rate is less than 80% Practically, a dye residual ratio of 90% or more is preferable.

[0223] (Heat and heat resistance)

 For wet heat resistance, the visible light absorption filter was stored at 60 ° C and 90% RH for 14 days, and then the chromaticity before and after storage using a color difference meter CR-400 (manufactured by Konica Minolta Sensing). Changes, that is, AEab values were measured and evaluated as follows.

[0224] AA: AEab is less than 1.5, chromaticity change is indistinguishable

 A: AEab is less than 1.5-3.2 and almost no change in chromaticity is felt

 B: AEab is less than 3.2 to 6.5 and looks the same color sensuously

 C: Change in chromaticity is recognized with AEab force less than .5-10.0

 D: When the AEab force is 0.0 or more, the color appears to be a different color with a large chromaticity change.

 The evaluation results are shown in Table 2.

[0225] [Table 2]

Finale No. Dye Light resistance Moisture and heat resistance Remarks

 1 A (1-1) ◎◎ A A The present invention

 2 A (1 -9) © A The present invention

3 A (1 -12) A The present invention

4 A (1-15) ◎ A A The present invention

5 A (1 -18) ◎ A The present invention

 6 A (1-23) A A The present invention

 7 A (-10) A A The present invention

 8 A (2-22) A The present invention

 9 A (2-37) ◎ A A The present invention

 10A (2-66) ◎ A The present invention

11A (3-1) ◎ B The present invention

12A Comparative Compound 1 Δ D Comparative Example

13A Comparative compound 1 + MS— 1 0 D Comparative example

14A Comparative compound 2 0 C Comparative example

1 B (1-1) ◎◎ A A The present invention

 2 B (1-9) ◎◎ A A The present invention

 3 B (1-12) ◎◎ A A The present invention

 4 B (1-15) ◎◎ A A The present invention

 5 B (1-18)

 6 B (1-23) ◎◎ A A The present invention

 7 B (2- 10) ◎◎ A The present invention

 8 B (2-22) ◎◎ A A The present invention

 9 B (2-37) ◎ A A The present invention

 10 B (2-66) A The present invention

11B (3-1) ◎ A The present invention

 12B Comparative compound 1 〇 D Comparative example

13 B Comparative compound 1 + MS— 1 ◎ B Comparative example

14 B Comparative compound 2 〇 B Comparative example

From the table, it can be seen that the dye of the present invention effectively absorbs visible light and is a visible light absorption filter excellent in light resistance and heat and moisture resistance. Furthermore, by using the dye of the present invention as a mixture with a dispersion medium, it is possible to provide a visible light absorption filter that exhibits superior light resistance and wet heat resistance and is excellent in fastness.

[0227] On the other hand, when the comparative unchelated squarylium compound (12A) is used, the light resistance and heat-and-moisture resistance are significantly inferior, and even when used as a mixture with a dispersion medium, the robustness is the present invention. It turns out that it does not reach to the dye of this. Also squarylium compounds and gold In the case of filters 13A and 13B using a genus mixture as a pigment, there is a problem with moisture and heat resistance, which is insufficient in practical use. In addition, even in the case of filters 14A and 14B using the comparative compound 2 which is a chelate dye having a dialkylamino group at the p-position of the 6-membered squaric acid skeleton as the dye, the light resistance and heat and humidity resistance are the dyes of the present invention. However, the dye of the present invention is excellent in fastness such as light resistance and wet heat resistance, and can provide a visible light absorption filter with little change in dye concentration and color change over a long period of time.

[0228] Example 3 (ink)

 (Synthesis of colored fine particle dispersion)

 15 g of polybutyral as an oil-soluble polymer (BL-S manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 350) and 8 g of the exemplary compound (13) of the present invention and 150 g of ethyl acetate as pigments are placed in a separate flask. After the inside was substituted with N, the polymer and the dye were completely dissolved by stirring. Subsequently, 150 g of an aqueous solution further containing 3 g of sodium lauryl sulfate was dropped and stirred, and then emulsified for 300 seconds using an ultrasonic disperser (UH-150, manufactured by SMT Co., Ltd.). Thereafter, ethyl acetate was removed under reduced pressure to prepare a colored fine particle dispersion. Hereinafter, the dispersion thus prepared is abbreviated as a colored fine particle dispersion.

 [0229] (Preparation of water-based ink)

The coloring composition prepared as described above, respectively, as the finishing Ca ^ fin click content of the dye, was weighed in an amount of 2 mass _^0/0, 15% ethylene glycol, glycerol 15%, Sir Finolhu 465 ( (Manufactured by Nissin Chemical Industry Co., Ltd.) 0.3%, and the remainder was pure water, and further filtered through a 2 m membrane filter to remove dust and coarse particles to obtain an ink composition IJ1. Except that the exemplified compound (13) was replaced with the dyes shown in Table 3, IJ 2 to 10 were obtained in the same manner. For IJ-11, however, Comparative Compound 3, 7.24g and Bis (acetylacetonate) nickel 2.82g were dissolved and mixed in ethyl acetate, then polyvinyl butyral was added, and the same procedure was followed. IJ 11 was obtained.

[0230] [Chemical 31]

[0231] (Sample preparation and evaluation)

 Furthermore, each ink was printed on Konica Photojet paper Photolike QP glossy paper (manufactured by Konica Minolta Co., Ltd.) using a commercially available Epson inkjet printer (PM-800), and the evaluation of the obtained image was as follows. It went about the item.

 [0232] (Color tone)

 For each coated sample, a four-step evaluation was performed by visual evaluation using 10 monitors. 〇 or more

 It is desirable that

[0233] A: Vivid and clear color

 Y: Vivid color

 △: Dull color

 X: dirty color

 (Light resistance)

 Using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd., the rate of decrease in the reflection spectral density% at the maximum absorption wavelength in the visible region from the unexploded sample after 72 hours of xenon light (70000 rutus) was calculated. Calculated and evaluated according to the following criteria.

[0234] Decrease rate% (Dye remaining rate%) = (Maximum absorption wavelength concentration of exposed sample / Maximum absorption wavelength concentration of unexposed sample) X I 00

 A: Dye remaining rate is 90% or more

 B: Dye remaining ratio is 85% to 90%

 C: Dye remaining rate is 80-85%

D: Dye remaining rate is less than 80% (water resistant)

 With a micropipette, water was dripped onto each of the obtained prints, and after 1 minute, rubbing with a finger to visually determine whether the print was disturbed or not.

 ◎: Virtually no change is seen! /,

 ○: Disturbed! / Even if the image can be identified (allowable level)

 X: Image is distorted so that it cannot be identified

 (Heat resistant)

 Each sample was stored for 30 days under conditions of 50 ° C. and 80% RH, and the dye residual ratio was calculated and evaluated in the same manner as light resistance.

[0235] A: Dye remaining ratio is 90 to 95%

 ○: Dye remaining rate is less than 85-90%

 Δ: Dye remaining rate is less than 80-85%

 X: The pigment remaining rate is less than 80%, and the color appears cloudy visually.

 It is practically preferable that the pigment residual rate is 85% or more (◎, ○)!

 [0236] Table 3 shows the results of the evaluation.

 [0237] [Table 3]

As is apparent from the table, it can be seen that the ink of the present invention has a vivid color tone and is superior in light resistance, water resistance and heat and humidity resistance to the comparative example.

[0239] On the other hand, it can be seen that comparative ink IJ 9 using chelate! /, Na! /, And squarylium compounds as dyes is significantly inferior in light resistance and water resistance. In addition, comparative ink IJ 10 using comparative compound 4, which is a metal chelate dye, is superior in terms of color tone and water resistance, but has problems in light resistance and wet heat resistance. Comparative ink IJ 11 using a mixture as a pigment does not have excellent color tone, and has light resistance, water resistance and heat and humidity resistance. As a result, it was found that by using the coloring matter of the present invention, an ink having excellent fastness and good image storage stability could be provided.

[0240] Example 4 (toner)

 <Production of toner>

 (Manufacture of color toners: grinding method)

100 parts by mass of a polyester resin, 8 parts by mass of a mixture of the compound of the present invention described in Table 4 and comparative compounds 3, 4 and comparative compound 3 and MS-2 in a molar ratio of 2: 1, 3 parts by mass of propylene was mixed, milled, pulverized and classified to obtain powders each having a volume average particle size of 8.5 _β m. Further, 100 parts by mass of this powder and silica fine particles (number average primary particle size 12ηm) 1.0 part by mass were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain color toners 1 to 9 by a pulverization method. .

[0241] [Chemical 32]

[0242] (Production of color toner: polymerization method)

 In an aqueous solution in which 5 g of sodium dodecyl sulfate was dissolved in 200 ml of pure water, 15 g of a mixture of the compound of the present invention and the comparative compound described in Table 4 and MS-2 was added, and the mixture was stirred and ultrasonically applied to give an aqueous dispersion. While heating the aqueous dispersion containing the dye of the present invention and the low molecular weight polypropylene (number average molecular weight = 3200), the solid content concentration was adjusted to 30% by mass with the surfactant. An emulsified dispersion emulsified in water was prepared in advance.

[0243] The above dispersion was mixed with 60 g of a low molecular weight polypropylene emulsion dispersion, After adding 220 g of nomer, 40 g of n-butyl acrylate monomer, 12 g of methacrylic acid monomer, and 5.4 g of t-dodecyl mercaptan as a chain transfer agent and 2000 ml of degassed pure water, stirring was performed under a nitrogen stream. While maintaining at 70 ° C for 3 hours, emulsion polymerization was carried out.

 [0244] To 1000 ml of the resulting dispersion of dye-containing resin fine particles, sodium hydroxide was added to adjust the pH to 7.0, and then 270 ml of a 2.7 mol% aqueous potassium chloride solution was added, followed by isopropyl alcohol. 160 ml of polyoxyethylene octyl phenyl ether having an average degree of polymerization of ethylene oxide of 10 and Og dissolved in 67 ml of pure water were added and the reaction was carried out by stirring at 75 ° C. for 6 hours.

 [0245] The obtained reaction solution was filtered, washed with water, dried and crushed to obtain colored particles. The colored particles and silica fine particles (number average primary particle size 12 nm) 1.0 part by mass were mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain color toners 10 to 18 by a polymerization method.

 [0246] (Production of developer)

 To 10 parts by mass of these color toners, 900 parts by mass of carrier iron powder “EFV250 / 400” (manufactured by Nippon Iron Powder) was uniformly mixed to obtain a “developer”.

 [0247] <Evaluation of Toner>

 (Evaluation equipment)

The above color toner and developer are set in the developing machine of a commercially available color image forming device “Koni-Force 9331” (manufactured by Konica Mica Business Technologies Co., Ltd.) that employs an electrophotographic method, and the following evaluation items are evaluated. It was. In order to clarify the difference in color toner performance, the color toner was evaluated so that it could be used in all four color development units. As evaluation samples, reflection images (images on paper) and transmission images (OHP images) were prepared on paper and OHP, respectively. The color toner adhesion amount was adjusted to be in the range of 0.65 to 0.75 mg / cm ² . Each image sample obtained was evaluated for light resistance, heat and humidity resistance, and transparency of OHP images.

[0248] (Light resistance)

For lightfastness, measure the image density immediately after recording, and then measure the image density again after irradiating the image with xenon light (70000 lux) for 14 days using a weather meter (Atlas C. 165). The residual ratio of dye (%) from the difference in image density before and after irradiation with xenon light Calculated and evaluated according to the following criteria. The image density was measured using a reflection densitometer (X-Rite310TR). The evaluation results are shown in Table 4 below.

[0249] ◎◎: Dye remaining rate is 95% or more

 A: Dye remaining rate is less than 90-95%

 ○: Dye remaining rate is less than 85-90%

 Δ: Dye remaining rate is less than 75-85%

 X: Dye remaining rate is less than 75%

 (Heat resistant)

 For heat and humidity resistance, measure the image density immediately after recording, store it for 14 days under conditions of 50 ° C and 80% RH, measure the image density again, and determine the residual ratio of dye from the difference in image density before and after. (%) Was calculated and evaluated. The image density was measured using a reflection densitometer (X-Rite310TR) and evaluated according to the following criteria. In addition, the color change was observed visually.

[0250] ◎◎: Dye remaining rate is 95% or more

 A: Dye remaining rate is less than 90-95%

 ○: Dye remaining rate is less than 80-90%

 Δ: Dye remaining rate is less than 80%, and the color appears slightly cloudy by visual inspection.

 X: The pigment remaining rate is less than 80%, and the color appears to be cloudy visually.

 (Transparency of OHP image)

 The transparency of the OHP image was evaluated based on the spectral transmittance at each of the following wavelengths. For the spectral transmittance, a 330-type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) is used. The spectral transmittance was measured at Yellow 570 nm, magenta 650 nm, and cyan 500 nm, and evaluated according to the following criteria.

[0251] ○: Spectral transmittance is 80% or more and transparency is very good.

 Δ: Spectral transmittance is 70 to 80%, transparency is good and there is no practical problem

 X: Spectral transmittance is 70% or less, resulting in poor transparency and practical problems.

[0252] Table 4 shows the results of the evaluation.

[0253] [Table 4]

 [0254] As is apparent from the table, the image produced using the color toner of the present invention showed good moisture heat resistance, high res and HP quality, and the color toner of the present invention was used as a full color toner. Is suitable. Furthermore, an image produced using the color toner of the present invention has good light resistance and can be stored for a long time.

 [0255] Example 5 (optical recording medium)

 (Preparation of optical recording medium 1)

 On a polycarbonate substrate with a diameter of 12.7 cm, a recording layer (thickness 90 nm) is applied using the dye (16) of the present invention, a reflective layer (Ag, thickness lOOnm), a protective film (ultraviolet hard). Acrylic resin having a thickness of 5πι) was sequentially formed according to a conventional method to produce an optical recording medium 1 of the present invention.

 [0256] (Production of optical recording media 2 to 4)

 Comparative optical recording media 2 to 5 were produced in the same manner except that the dyes shown in Table 5 below were used instead of the dye (16) used in the production of the optical recording medium 1. However, in optical recording media 2 and 5, a mixture of a dye and 1.0% by mass of an anti-fading agent (Β-6) was applied as a recording layer. When the reflectances of the optical information recording media 1 to 5 thus produced were measured, they each showed a good value of 70% or more.

[0257] [Chemical 33] Feminized food ·

[0258] (Evaluation of optical recording media)

 Information was recorded on these samples by changing the power with a 658 nm semiconductor laser, and reproduction was performed at 0.8 mW.

 [0259] Using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd., the same recording / reproduction experiment was performed after 24 hours of light exposure, and the calculation was performed based on the dye concentration before and after light exposure. Dye remaining ratio (%) The minimum recording power and the number of reproductions were determined.

 [0260] Table 5 shows the results of the evaluation.

 [0261] [Table 5]

 [0262] As is apparent from the table, the optical recording medium of the present invention;! To 3 was able to perform good recording and reproduction satisfying the DVD standard. In addition, it was revealed that the recording and reproducing characteristics were particularly excellent in light resistance.

[0263] On the other hand, the optical recording medium 3 for comparison shows a phenomenon in which the reflectance decreases with the reproduction light of the laser, causing a reproduction failure, and the optical recording media 3 and 4 cannot be recorded even by light exposure with a xenon fade meter. It was. When the residual ratio of the dye was measured, it was found that the comparative optical recording media 3 and 4 significantly decreased the residual ratio after light exposure. [0264] Example 6 (color filter)

 <Production of color filter>

 (Production of color filter CF-1)

 In order to obtain an RGB color filter, a red (R) mosaic pattern, a green (G) mosaic pattern, and a blue (B) mosaic pattern were formed on a glass plate by the following method. Using the components shown below, photosensitive coating agents for color filters of red (R), green (G) and blue (B) were prepared. The photosensitive polyimide resin varnish used is a photosensitive polyimide resin varnish containing a photosensitizer.

[0265] (Components of photosensitive coating agent for color filters)

 R:

 Dye of the present invention: (1 21) 10 parts

 50 parts of photosensitive polyimide resin varnish

 40 parts of N-methyl-2-pyrrolidone

 G:

 Dye of the present invention: (2-63) 10 parts

 50 parts of photosensitive polyimide resin varnish

 40 parts of N-methyl-2-pyrrolidone

 B:

 Color material B—1 10 parts

 50 parts of photosensitive polyimide resin varnish

 40 parts of N-methyl-2-pyrrolidone

The glass plate treated with the silane coupling agent was set on a spin coater, and the above-mentioned red color filter photosensitive coating agent was first spin-coated at 300 rpm for 5 seconds and then at 20 OOrpm for 5 seconds. Next, pre-beta was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed with an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² .

[0266] Next! /, Developed and washed with a dedicated developer and rinse! /, A red mosaic pattern was formed on the glass plate. Followed by green mosaic pattern and blue mosaic The icy pattern was applied and baked in accordance with the above method using the above-mentioned G photosensitive coating agent for green color filter and B photosensitive coating agent for blue color filter. The color filter CF-1 was obtained.

 [0267] (Invention color filter CF—2 to 4 and comparative RGB color filter CF—5 to

 7)

 In the production of the color filter CF-1, the present invention was exactly the same except that the R dye (121), G dye (2-63), and B dye B-1 were changed to the dyes shown in Table 6. RGB power filter CF-2 to 4 and comparative RGB color filter CF-5 to 7 were prepared.

 [0268] [Chemical 34]

[0269] <Evaluation of color filter>

 The color tone, heat resistance, and light resistance of the obtained filter were evaluated by the following methods.

[0270] (Color tone)

 Each filter was evaluated on a three-point scale by visual evaluation using 10 monitors. 〇 It is desirable to be above.

 [0271] ◎: Bright and clear color

Y: Vivid color △: Dull color

 (Heat-resistant)

 The glass substrate with the undercoat layer on which the pattern was formed was heated with a hot plate at 200 ° C. for 3 hours so as to be in contact with the substrate surface, and the chromaticity change before and after heating, ie, A Eab was measured. A color difference meter CR-400 (manufactured by Konica Minolta Sensing) was used for the measurement of chromaticity. A smaller ΔEab value indicates that the heat resistance is better.

[0272] (Light resistance)

 The glass substrate with the undercoat layer on which the pattern was formed was irradiated with a xenon lamp for 10 days at 70,000 lutas, and then the chromaticity change, that is, the ΔEab value was measured. The color difference meter CR-400 (manufactured by Konica Minolta Sensing) was used for the measurement of chromaticity. A small value of ΔEab value indicates excellent light resistance.

 [0273] Table 6 shows the results of the evaluation.

 [0274] [Table 6]

 [0275] From the table, the color filter CF- ;! to CF-4 of the present invention is a comparative color filter CF

 Compared with 5 to CF-7, it has been found that the fastness such as heat resistance and light resistance has been remarkably improved, and it has excellent color tone, and it can be applied to liquid crystal color displays. It has excellent properties as a filter.

Example 7 (Front Filter for Display) A polyethylene terephthalate (PET) film (thickness: 100 μm) was mixed with a 0.4% methyl ethyl ketone / toluene mixed solution (methyl) of the dye (123) of the present invention. Ethyl ketone / toluene = 1: 1) 0.5 g, 6.5 g of a 20% methyl ethyl ketone / toluene mixed solution of polyester resin, and then coated with a bar coater and dried to give a film thickness of 5 m coating film was obtained. The transmittance curve of this coating film has a minimum value at 590 nm. In addition, there is a clear minimum value, and the minimum wavelength of visible light transmittance is in the neon emission wavelength region of 580 to 600 nm, so neon light that can effectively absorb neon light emission with high transmittance. We were able to provide emission cut filters and front filters for displays.

 [0277] (Preparation of coating film 2)

 To PET vinylolum (thickness: 100 m), 0.6 g of 0.5% methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 1: 1) of the dye (2-27) of the present invention, acrylic resin 35% methyl ethyl ketone / toluene mixed solution 4. After mixing Og, it was coated with a bar coater and dried to obtain a coating film having a thickness of 5 mm. The transmittance curve of this coating film has a minimum value of 593 nm, and there is no other clear minimum value. The minimum wavelength of visible light transmittance is 580 to 600 nm, which is the wavelength region of neon emission. Therefore, it was possible to provide a neon light-emitting cut filter and a display front filter that can effectively absorb neon light having a high transmittance.

 [0278] (Preparation of coating film 3)

 A UV absorbing coating solution (Sumitomo Osaka Cement Co., Ltd.) containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on the PET resin opposite to the metal complex-containing layer surface of the coating film 1 The film was coated with a coater and dried to form an ultraviolet absorbing layer having a film thickness of 3 Hm. In the filter, the minimum wavelength of the visible light transmittance did not change.

 [0279] Visible from unexploded sample of sample after xenon light was blown from UV absorption layer surface for 50 hours using Xenon Fade Meter (FAL-25X-HC. B. EC) manufactured by Suga Test Instruments Co., Ltd. The dye residual ratio% at the region maximum absorption wavelength was calculated to be 92.7%. In addition, the dye remaining rate% at the maximum absorption wavelength in the visible region after storage for 500 hours at 60 ° C and 90% RH was calculated to be 96.8%, indicating that the light resistance and heat and humidity resistance were good. Yes, we were able to provide a neon emission cut filter having a UV absorbing layer and a front filter for display.

 [0280] (Preparation of coating film 4)

Close to the PET resin side of the coating film 1 opposite to the metal complex-containing layer side. 0.5% cyclohexanone of infrared absorbing dye (N, N, N ', N ^f —tetrakis (p-dibutylaminophenyl) —p-phenylene dimonium hexafluoroantimonate) 0.3 g of the solution and 3 g of a polyester resin 20% cyclohexanone solution were mixed, coated with a bar coater and dried to obtain a coating film having a film thickness of 6111. The coating film was measured with a Hitachi spectrophotometer (U-3500). The wavelengths at the minimum value of transmittance were 590 nm and l lOOnm.

 [0281] Dye residue% at the maximum absorption wavelength in the visible region from the unexploded sample after xenon light was blown from the near-infrared absorbing layer surface for 50 hours using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd. Was calculated to be 88.0%. In addition, the dye remaining rate% at the maximum visible wavelength in the visible region of the sample after storage for 500 hours at 60 ° C and 90% RH was calculated to be 94.3%, which is a neon light emitting cut having a near infrared absorption layer. We were able to provide filters and front filters for displays.

 [0282] (Preparation of coating film 5)

 0.5% cyclohexane of the above near-infrared absorbing dye (N, N, N ', N'-tetrakis (p-dibutylaminophenol) p-phenol dimonium hexafluoride antimonate) Mix 0.5 g of hexanone solution and 0.4 g of 0.4% cyclohexanone solution of the dye (1-23) of the present invention into 6.5 g of 20% cyclohexane solution of polyester resin, and add PET film (thickness 100 m) was coated with a bar coater and dried to obtain a coating film having a thickness of 6 am. In addition, the coating film contains 2- (2'-hydroxy-5'methylphenyl) monobenzotriazole as an ultraviolet absorber on the surface of the PET resin opposite to the near-infrared absorbing dye and the metal complex-containing surface of the present invention. The UV absorbing coating solution was coated with a bar coater and dried to form a 311 m UV absorbing layer.

 [0283] Using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd., xenon light was blown from the UV absorbing layer surface for 50 hours, and the residual dye% at the visible region maximum absorption wavelength from the unexploded sample was calculated. However, it was 96.2%. In addition, the percentage of dye remaining at the maximum absorption wavelength in the visible region of the sample after storage for 500 hours at 60 ° C and 90% RH was calculated to be 95.8%.

[0284] (Production of coating film 6) Using a coating solution made of the above coating film 4 on a PET film (thickness: 100 μm) using an indium tin oxide oxide composite and an ITO thin film using argon gas and oxygen gas. A near-infrared absorption layer and a neon emission absorption layer were laminated at a thickness of 6 am. Furthermore, when the surface of the anti-glare layer with a thickness of 3 mm and the non-glare layer of the PMA plate with AR coating formed on the opposite surface was bonded to the ITO surface of the above filter, a plasma display panel filter was created. A good filter with high properties could be produced.

[0285] (Comparative example)

 A front filter for display having an ultraviolet absorbing layer was obtained in the same manner as the coating film 2 except that the comparative compound 8 was used instead of the compound (123) of the present invention.

[0286] [Chemical 35]

[0287] Using a xenon feather meter, the dye residual ratio% at the maximum absorption wavelength in the visible region from the unexploded sample after 50 hours of xenon light explosion from the ultraviolet absorbing layer surface was calculated. %Met. Further, the dye residual ratio% at the maximum absorption wavelength in the visible region of the sample after being stored at 60 ° C. and 90% RH for 500 hours was calculated to be 85.4%, compared with the case where the dye of the present invention was used. It was found to be inferior in light resistance and heat and humidity resistance.

 [0288] Further, a front filter for display having a near-infrared absorbing layer was obtained in the same manner as the coating film 3 except that the comparative compound 8 was used instead of the compound (123) of the present invention. The same light resistance test was conducted and the residual pigment ratio (%) was measured. As a result, it was 68.6%. The result of the same heat and humidity resistance test was 70.3%.

[0289] As described above, by using the metal complex of the present invention, a neon emission absorption filter and an ultraviolet ray absorption which can effectively absorb neon emission having excellent light resistance and moist heat resistance and high transmittance. Layer, infrared absorption layer, etc.-'could provide a front filter for

Claims

A squarylium metal complex compound having a partial structure represented by the following general formula (1):  [Chemical 1]

 (In the formula, M represents a metal atom. R represents a substituent, m represents an integer of 0 to 3. A represents an arbitrary organic group.)  The squarylium metal complex compound having a partial structure represented by the general formula (1) is a squarylium metal complex compound represented by the following general formula (2): The squarylium metal complex compound. General formula (2)

(In the formula, M represents a metal atom. I ^ to R ³ are hydrogen atoms or substituents, A is an arbitrary organic group, n is 1 or 2, and X is a monodentate or bidentate secondary group. And p is an integer of 0 to 2. W represents a counter ion, and q is an integer of 0 to 3.) [3] A squarylium metal complex compound having a partial structure represented by the general formula (1) or a squarylium metal complex compound represented by the general formula (2) is a squarylium represented by the following general formula (3): 3. The squarylium metal complex compound according to claim 1, which is a metal complex compound. [Chemical Formula 3 (3)

(In the formula, M represents a metal atom.! ~~ is a hydrogen atom or a substituent, A is an arbitrary organic group, and n is 2 or 3.) [4] In the general formulas (1) to (3), the organic group A is an aryl group, a heterocyclic group, or the following general formula (1A). The squarylium metal complex compound according to 1 above.  [Chemical 4 , 0 A) A _: -. (In the formula, A represents a 5- or 6-membered ring, and ¹ represents a hydrogen atom or a substituent.)  1  [5] In the general formulas (1) to (3), the metal atom M is any one of copper, nickel, cobalt, aluminum, or zinc! The term! /, Shear force, the squarylium metal complex compound according to item 1. [6] The squarylium metal complex compound according to any one of claims 1 to 5, wherein the absorption maximum wavelength is in a visible light region. [7] A composition comprising at least one dye according to claim 6 and a dispersion medium.  [8] A toner comprising at least one dye according to claim 6. [9] An ink comprising at least one dye according to claim 6. [10] An optical recording medium comprising at least one dye according to claim 6. [11] A color filter comprising at least one dye according to claim 6.  [12] A front filter for a display, comprising at least one dye according to claim 6.  [13] The display front filter according to claim 12, which has an absorption maximum at 560 to 620 nm.