JP5250837B2 - Novel squarylium metal complex compound, dye and composition containing the same, color toner, ink, optical recording medium, color filter, and front filter for display - Google Patents

Description

  The present invention relates to a novel squarylium metal complex compound, a dye and a composition containing the same, a color toner, an ink, an optical recording medium, a color filter, and a front filter for a display.

  Dyes known as dyes and pigments are widely used in various applications such as fiber dyeing materials, resin and paint coloring materials, photography, printing, photocopiers, image forming materials in printers, and light absorbing materials for color filters. It's being used. In recent years, various image forming dyes for color hardcopy using ink jet, electrophotography, silver salt photography, thermal transfer, etc. have been proposed, and with the progress of electronics imaging, dyes for solid imaging tubes and filters for color liquid crystal televisions and semiconductors. The demand for dyes for optical recording media using lasers is increasing, and the field of use of dyes is expanding. With the expansion of the use field of such dyes, the demands for dye materials are becoming stricter year by year, particularly regarding fastness such as light resistance and chemical resistance.

  The present inventors have developed a dye material having a squarylium skeleton. The squarylium dye has the advantages that the hue can be easily adjusted by the variety of molecular designs and that the molecular absorption characteristics are excellent. Further, it is a useful pigment 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 at two carbon atoms located on the diagonal line. If the two aromatic substituents are the same, this is called a symmetric squarylium compound (or symmetric squarylium dye) for convenience, and if not, an asymmetric squarylium compound (or asymmetric squarylium dye). It is called.

  Thermal transfer recording materials, electrophotographic toners, near-infrared absorbers (see, for example, Patent Documents 1 to 3) and the like are known as squarylium compounds coordinated to metals and having a chelate structure. Is specified only in the following two cases (see Patent Documents 4 and 5).

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

  However, the squarylium compound used here is only a combination of 5-hydroxypyrazole and methylindoline, and the metal is only Al.

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

  These structures A, B and C are characterized in that a chelate structure is formed between a metal having a coordination atom having an active hydrogen of a hetero five-membered ring directly bonded to the oxygen atom of the squaric acid skeleton and the squaric acid skeleton. It is.

  For the chelate of a metal with a 6-membered ring substituent directly bonded to the oxygen atom of the squaric acid skeleton or a coordination atom that is a part of the constituent element, a compound of the following structure D and the metal A near-infrared absorber using a complex is disclosed (see Patent Document 3).

  Furthermore, in this 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, it is unclear whether it has a chelate structure. It is.

  Also disclosed are inks, electrophotographic toners and the like using a mixture of the following structure F and a metal ion-containing compound (see Patent Document 2).

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 the mixture of the squarylium compound and the metal ion-containing compound shows a good color tone, the light resistance, moisture resistance and heat resistance are still insufficient, and further development of a material excellent in fastness has been demanded.
JP 2000-265077 A JP 2001-342364 A JP 2000-159776 A International Publication No. 02/50190 Pamphlet International Publication No. 04/7447 Pamphlet

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

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

1. A squarylium metal complex compound represented by the following general formula (2);

  (In the formula, M represents a metal atom. R ¹ ~ R ³ Is a hydrogen atom or a substituent, and A is any organic group. n is 1 or 2. X is a monodentate or bidentate secondary ligand, and p is an integer of 0-2. W represents a counter ion, and q is an integer of 0 to 3. )
2. 2. The squarylium metal complex compound according to 1, wherein the squarylium metal complex compound represented by the general formula (2) is a squarylium metal complex compound represented by the following general formula (3);

  (In the formula, M represents a metal atom. R ¹ ~ R ³ Is a hydrogen atom or a substituent, and A is any organic group. n is 2 or 3. )
3. In the general formula (2) or (3), the organic group A is an aryl group, a heterocyclic group, or the following general formula (1-A);

(Where A ₁ Represents a 5-membered or 6-membered ring and R ′ ¹ Represents a hydrogen atom or a substituent. )
4). 4. The squarylium metal complex according to any one of 1 to 3 above, wherein in the general formula (2) or (3), the metal atom M is any one of copper, nickel, cobalt, aluminum, or zinc. Compound;
5. 5. The squarylium metal complex compound according to any one of 1 to 4, wherein the absorption maximum wavelength is in a visible light region;
6). A composition containing at least one dye described in 5 and a dispersion medium;
7). A toner comprising at least one dye described in 5 above;
8). An ink comprising at least one dye described in 5 above;
9. An optical recording medium comprising at least one dye described in 5 above;
10. A color filter comprising at least one dye described in 5 above;
11. A front filter for a display, comprising at least one dye described in 5 above;
12. The display front filter as described in 11 above, which has an absorption maximum at 12.560 to 620 nm.

  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 medium It was possible to provide a color filter and a front filter for a display.

  The pigment | dye of this invention is related with the squarylium metal complex compound which has the partial structure represented by the said General formula (1) characterized by having an absorption maximum wavelength in a visible light region.

  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).

  According to the inventors' investigation, by mixing and reacting a squarylium compound having a specific structure and a metal ion, via one oxygen atom of the squaric acid skeleton and one oxygen atom which is one of the substituents of the benzene ring. A chelate ring was formed, and a new squarylium metal complex compound could be obtained.

  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 to be caused by an improvement in stability due to metal chelate formation. A chelate complex is characterized in that one ligand is coordinated to a metal ion by a plurality of coordination sites, and thermodynamic and kinetic stabilization effects can be obtained by this chelate ring formation. This is generally referred to as a chelate effect, and is known to be stable to about 10 to the 10th power when the binding energy of a metal-ligand is compared with a normal complex that is not a chelate complex.

  In addition, in the squarylium metal complex compound of the present invention, by using a squarylium compound having a specific structure as a ligand, it is possible to control the metal and ligand ratio of the resulting metal chelate complex. It is considered that there is almost no metal and squarylium compounds that are not used, and that the degradation of the compounds and performance degradation due to these impurities can be suppressed is one factor in improving the performance. The specific structure here is 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 oxygen atom of the hydroxyl group and the oxygen atom of the squaric acid skeleton function as a chelate coordination atom, whereby the squarylium metal complex compound of the present invention is formed.

  Further, by introducing a hydroxyl group in place of a dialkylamino group as previously known at the p-position of the bond between the squaric acid skeleton and the benzene ring, a more robust squarylium metal complex compound can be obtained. Could be provided.

  Hereinafter, although the squarylium metal complex compound of this invention, a pigment | dye, a composition using the same, a color toner, an ink, a color filter, and the front filter for a display are demonstrated, this invention is not limited to these.

<< Metal Complex Compound Represented by General Formulas (1) to (3) >>
In the squarylium metal complex compound in the present invention, the partial structure which is the essence of the invention is shown by the following general formula (1), and the whole structure is represented by the following general formulas (2) and (3).

  In the general formulas (1) to (3), M represents a metal atom and is bonded to one oxygen atom of the squaric acid skeleton and an oxygen atom derived from a hydroxyl group which is one of the substituents of the benzene ring to form a chelate ring. It is characteristic to form.

  The metal atom M is not particularly limited as long as it forms a chelate structure with respect to the squarylium compound. The chelate structure here refers to binding to the metal atom M at a plurality of coordination positions with respect to a ligand having a specific structure (here, squarylium compound), and forming a ring structure with the metal and the ligand. Represent. Regarding the metal atom M, for example, copper, nickel, cobalt, zinc, aluminum, beryllium, iron, silver, chromium, manganese, iridium, vanadium, titanium, ruthenium, molybdenum, tin, bismuth, osmium, magnesium, calcium, strontium, barium Gallium, germanium, platinum, gold, mercury and the like. It is preferable that it is a periodic table 3-12 group, More preferably, it is a metal ion contained in the periodic table 7-12 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, aluminum are particularly preferable in terms of handling. Or it is more preferable to be chosen from zinc.

  In General formula (1), R represents a substituent, m represents the integer of 0-3. Although there is no restriction | limiting in particular as a substituent represented by R, For example, 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, a dodecyl group, Trifluoromethyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), acylamino group (eg acetylamino group, benzoylamino group etc.), alkylthio Group (for example, methylthio group, ethylthio group, etc.), arylthio group (for example, phenylthio group, naphthylthio group, etc.), alkenyl group (for example, vinyl group, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl) Group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group Cyclohexenyl group etc.), halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (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 methylsulfinyl group etc.), aryl Sulfinyl group (for example, phenylsulfinyl group), phosphono group, acyl group (for example, acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylamine) Nocarbonyl 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 (for example, methanesulfonamide group, benzenesulfonamide group, etc.) ), Cyano group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, etc.), Heterocyclic oxy group, siloxy group, acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethyl group) Amino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group) Etc.), imide 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.) , Al Xoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.) , Heterocyclic thio groups, thioureido groups, carboxyl groups, carboxylic acid salts, hydroxyl groups, mercapto groups, nitro groups, and the like. These substituents may be further substituted with the same substituent. These substituents may be further substituted with the same substituent, and the substituents may be further bonded to each other to form a ring. Preferred substituents for R include alkyl groups, cycloalkyl groups, alkenyl groups, halogen atoms, heterocyclic groups, alkylsulfonyl groups, arylsulfonyl groups, phosphono groups, acyl groups, sulfonamido groups, cyano groups, alkoxy groups, aryloxy Group, heterocyclic oxy group, sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group, anilino group, imide group, carboxyl group, carboxylic acid salt, hydroxyl group, mercapto group, nitro group, etc. More preferably, at least one is an alkyl group, a hydroxyl group or an amino group.

In the general formula (2) or (3), R ^{1 to} R ³ represent a hydrogen atom or a substituent, and specific examples thereof include the same as R. Preferred substituents for R ^{1 to} R ³ are preferably an alkyl group, alkenyl group, aryl group, heteroaryl group, alkoxy group, amino group, amide group, acetyl group, cyano group, nitro group, hydroxyl group and the like. In order to improve the solubility of the compound, at least one is preferably a substituent having a long-chain alkyl.

  A represents an arbitrary organic group, and examples of the organic group include a group having the same meaning as the substituent represented by R described above, preferably an aryl group and a heterocyclic group. Further, from the viewpoint of fastness, an aryl group, a heterocyclic group or a substituent represented by the general formula (1-A) is more preferable. The aryl group preferably has at least one of an alkyl group, an acylamino group, an amino group, a sulfonamide group, and a hydroxyl group as a substituent, and the heterocyclic group is a 5-membered nitrogen-containing heterocyclic ring. More preferably.

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

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

R ′ 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. R ′ ¹ is preferably a hydrogen atom, an alkyl group or a halogen atom,
A hydrogen atom, an alkyl group, a halogen atom, or an aryl group is more preferable, a hydrogen atom or an alkyl group is more preferable, a methyl group or an ethyl group is further preferable, and a hydrogen atom is most preferable.

  Moreover, the said General formula (1) is a partial structure in the metal complex in this invention. The 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 will be described 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, or The partial structure represented by the tautomer is referred to as a main ligand, and the ligand represented by X in parentheses having p is referred to as a subligand.

  In addition, 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, but is preferably a symmetric type from the viewpoint of simplicity of synthesis.

  In the general formula (2), X is a sub-ligand, and the sub-ligand X is not particularly limited. For example, JP-A Nos. 2000-251957, 2000-31723, 2000-323191, Examples described in JP-A Nos. 2001-6760, 2001-59062, and 2001-60467 are listed. In addition, as a so-called ligand used for forming a conventionally known metal complex, the trader may have a known ligand as necessary.

  Specifically, halogen ion, hydroxide ion, ammonia, pyridine, amine (for example, methylamine, diethylamine, tributylamine, etc.), cyanide ion, cyanate ion, thiolate ion, thiocyanate ion, and bipyridines, amino Various chelate ligands such as polycarboxylic acids and 8-hydroxyquinoline are exemplified.

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

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

  Moreover, the compound represented by the following general formula (4) is more preferable as a ligand.

In the general formula (4), E ₁ represents a substituent, E ₂ represents an electron-withdrawing group having a Hammett substituent constant (σp) of 0.1 to 0.9, R ′ represents an alkyl group, an aryl group, It represents a heterocyclic group, an alkoxy group, an aryloxy group, or an amino group, and may have a substituent.

A substituent having a σp value of 0.1 to 0.9 represented by E ₁ and E ₂ will be described. As the value of Hammett's substituent constant σp here, Hansch, C .; It is preferable to use the values described in the report of Leo et al. (For example, J. Med. Chem. 16, 1207 (1973); ibid. 20, 304 (1977)).

  For example, as a substituent or atom having a value of σp 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, trifluoromethanesulfonylmethyl, perfluorobutyl), aliphatic, aromatic or heterocyclic acyl groups (eg formyl, acetyl, benzoyl), aliphatic, aromatic or heterocyclic sulfonyl groups (eg , Trifluoromethanesulfonyl, methanesulfonyl, benzenesulfonyl), carbamoyl group (eg, carbamoyl, methylcarbamoyl, phenylcarbamoyl, 2-chloro-phenylcarbamoyl), alkoxycarbonyl group (eg, methoxycarbonyl, Toxylcarbonyl, diphenylmethylcarbonyl), substituted aromatic groups (for example, pentachlorophenyl, pentafluorophenyl, 2,4-dimethanesulfonylphenyl, 2-trifluoromethylphenyl), heterocyclic residues (for example, 2-benzooxa Zolyl, 2-benzthiazolyl, 1-phenyl-2-benzimidazolyl, 1-tetrazolyl), azo group (eg, phenylazo), ditrifluoromethylamino group, trifluoromethoxy group, alkylsulfonyloxy group (eg, methanesulfonyloxy) ), Acyloxy groups (eg acetyloxy, benzoyloxy), arylsulfonyloxy groups (eg benzenesulfonyloxy), phosphoryl groups (eg dimethoxyphosphonyl, diphenylphosphoryl), sulfamoyl groups (eg N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl) Is mentioned.

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

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

The substituent represented by E ₁ has the same meaning as R in the general formula (1), but preferably an alkyl group, an aryl group, a heterocyclic group, a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, Examples thereof include an alkylsulfonyloxy group, and an electron-withdrawing group is preferable.

E ₁ and E ₂ are preferably a halogenated alkyl group (particularly a fluorine-substituted alkyl group), a carbonyl group, a cyano group, an alkoxycarbonyl group, an alkylsulfonyl group, an alkylsulfonyloxy group, and the like.

  Preferred substituents for R ′ 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 a carbon number. 4 to 18 alkoxy groups and aryloxy groups. Most preferably, it is a C6-C16 alkoxy group.

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

  From the viewpoint of preferably obtaining the effects described in the present invention, the type of ligand in the complex is preferably composed of 1 to 2 types, and more preferably 1 type.

  In the general formula (2), W is an arbitrary counter ion, and typical cations represented by W are inorganic or organic ammonium ions (for example, tetraalkylammonium ions and pyridinium ions), alkali metal ions. While the anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluoride ion, chloride ion, bromide ion, iodide). Ions), substituted aryl sulfonate ions (eg, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ions (eg, 1,3-benzene disulfonate ion, 1,5-naphthalenedisulfonate ion) , 2,6-naphthalenedisulfonic acid ion), a Kill sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion, enolate (acetyl) Acetonate, hexafluoroacetylacetonate), hydroxide ion, sulfite ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkylcarboxylate ion, arylcarboxylate ion, tetraalkylborate, salicinate, benzoate, Examples include hexafluoroantimony.

  Moreover, in the said General formula (2) or (3), n is an integer of 1-3, p is an integer of 0-2, q is an integer of 0-3. 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 to consist 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).

  Although the typical example of the squarylium metal complex compound represented by General formula (1)-(3) in this invention below is shown, this invention is not limited to this.

  Examples of the squarylium compounds in the squarylium metal complex compounds represented by the general formulas (1) to (3) according to the present invention include, for example, JP-A-5-155144, JP-A-5-239366, JP-A-5-339233, and JP-A-5-339233. 2000-345059, 2002-363434, 2004-86133, 2004-238606, etc., Law, K. et al. Y. et al. , J .; Org. Chem. It can be synthesized by referring to a conventionally known method described in 1992, 57, 3278, etc.

  Moreover, the squarylium metal complex of this invention is obtained by making the raw material which gives the metal ion which has a squarylium compound and coordination ability react at the temperature between room temperature and 120 degreeC in a solvent for 3 to 24 hours. It is preferable that the raw material providing the metal ions has a ratio of the number of moles of the squarylium compound to the number of moles of the raw materials providing the metal ions of 1.0 to 3.0: 1.0. At this time, an acid or a base may be added to the reaction system.

  Examples of raw materials that give metal ions include bis (acetylacetonate) copper, copper acetate, copper bromide, copper nitrate, copper oxalate, copper sulfate, copper chloride, copper perchlorate, copper tetrafluoroborate, cyanide Copper iodide, copper iodide, copper trifluoromethanesulfonate, copper thiocyanate, nickel acetate, nickel sulfate, nickel (carbonate), nickel nitrate, nickel chloride, nickel bromide, nickel tetrafluoroborate, bis (acetylacetonate) Nickel, nickel perchlorate, zinc acetate, zinc bromide, zinc chloride, zinc nitrate, zinc tetrafluoroborate, zinc bis (acetylacetonate), cobalt nitrate, cobalt nitrite, cobalt acetate, bis (acetylacetonate) Cobalt, cobalt bromide, cobalt chloride, cobalt oxalate, cobalt thiocyanate and general Metal ion compounds having a ligand represented by (4) is used. At this time, from the viewpoint of improving solubility and compatibility with the dispersion medium, it is preferable that the raw material for giving metal ions has an organic substance as a counter salt. Examples of such materials include diketonate metal compounds and general formula (4). The compound which is made is mentioned.

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

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

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

  The pigment | dye in this invention points out that the absorption maximum wavelength exists in a visible region (380-780 nm) in the squarylium metal complex represented by the said General Formula (1)-(3). Since the squarylium metal complex of the present invention has good spectral characteristics, the extinction coefficient in the wavelength region shifted by about 100 nm from the absorption maximum wavelength is 1/100 to 1/1000 of the absorption coefficient of the absorption maximum, It is characterized by substantially no absorption in the wavelength range from the absorption maximum to the 60 nm long wave or short wave. As described above, the dye in the present invention is characterized by having preferable spectral characteristics in the visible range.

  The dye of the present invention is preferably used as a composition with a dispersing agent or a composition in which a solvent is further added thereto for film-forming stability and the like.

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

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

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

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

  The resin used in the present invention by homopolymerizing or copolymerizing these is, for example, a copolymer resin such as benzyl methacrylate / ethyl acrylate or butyl acrylate, or a copolymer resin such as methyl methacrylate / 2-ethylhexyl methacrylate. In addition, a copolymer resin of methyl methacrylate / methacrylic acid / stearyl methacrylate / acetoacetoxyethyl methacrylate, a copolymer resin of styrene / acetoacetoxyethyl methacrylate / stearyl methacrylate, and styrene / 2-hydroxyethyl methacrylate / stearyl methacrylate Examples of the copolymer include a copolymer resin such as 2-ethylhexyl methacrylate / 2-hydroxyethyl methacrylate.

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

"ink"
The ink containing at least one kind of the coloring matter of the present invention is used for image recording as an inkjet recording liquid, and even if only one kind of the coloring matter of the present invention is used, two or more kinds of coloring matters are used in combination. It may 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 exhibits the effects of the present invention particularly when an aqueous solvent is used. . As the aqueous solvent, water (for example, ion-exchanged water is preferable) and a water-soluble organic solvent are generally used.

  Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, 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, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ethers (eg, ethylene glycol monomethyl) Ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether Etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetraethylenepentamine, polyethylene , Pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl- 2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg, dimethyl sulfoxide, etc.), sulfones (eg, sulfolane, etc.), urea, acetonitrile, acetone, etc. Is mentioned.

  The aqueous solvent as described above can be used as it is if the dye of the present invention is soluble in the solvent system.

  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, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill). , Jet mill, ang mill, etc.), or the dye is dissolved in a soluble organic solvent, and then dispersed in the solvent system together with a polymer dispersant and a surfactant. Further, when it is an insoluble liquid or a semi-molten product as it is, it can be dissolved as it is or in a soluble organic solvent and dispersed in the solvent system together with a polymer dispersant or a surfactant.

  When the coloring matter of the present invention is insoluble in the solvent system, it is preferably finely divided and dispersed in the solvent system, and more preferably dispersed in fine particles having an average particle size of 150 nm or less.

  The average particle diameter is a volume average particle diameter, and a circle-converted average particle diameter obtained from an average value of a projected area of a transmission electron microscope (TEM) photograph (obtained for at least 100 particles or more) Is required. The coefficient of variation can be determined by determining the volume average particle size and its standard deviation and dividing the standard deviation by the volume average particle size. Alternatively, the volume average particle diameter and the standard deviation thereof can be obtained using a dynamic light scattering method.

  In addition, it is preferable to dissolve the pigment in an organic solvent in which the pigment of the present invention is soluble and then disperse it in an aqueous solvent together with the oil-soluble polymer as a fine particle dispersion.

  Specific examples of the method for preparing the aqueous solvent used for such an ink jet recording liquid include, for example, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515 and 7. Reference can be made to the methods described in the publications of -1185854.

  Next, the oil-soluble polymer will be described. There is no restriction | limiting in particular as said oil-soluble polymer, Although it can select suitably from said dispersing agent group according to the objective, A vinyl polymer is mentioned suitably. Examples of the vinyl polymer include conventionally known ones, which may be any of a water-insoluble type, a water-dispersed (self-emulsifying) type, and a water-soluble type. In view of the above, a water dispersion type is preferable.

The water-dispersible vinyl polymer may be any of an ion dissociation type, a non-ionic dispersible group-containing type, or a mixture thereof.
Examples of the ion dissociation type vinyl polymer include a vinyl polymer containing a cationic dissociable group such as a tertiary amino group, and a vinyl polymer containing an anionic dissociative group such as a carboxylic acid and a sulfonic acid. . Examples of the nonionic dispersible group-containing vinyl polymer include vinyl polymers 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 vinyl polymer containing an anionic dissociable group, a nonionic dispersible group containing type vinyl polymer, and a mixed type vinyl polymer are preferable.

  As a monomer which forms the said vinyl polymer, the following are mentioned, for example. That is, acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, vinyl ethers and the like can be mentioned. Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl Vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyl Examples include oxyethyl phosphate and dioctyl-2-methacryloyloxyethyl phosphate.

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

  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, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable. Acrylic acid, methacrylic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfone Acid, 2-acrylamido-2-methylbutanesulfonic acid is more preferable.

  Examples of the monomer having a cationic dissociable group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl atacrylate.

  Examples of the monomer containing a nonionic dispersible group include an ester of polyethylene glycol monoalkyl ether and a carboxylic acid monomer, an ester of polyethylene glycol monoalkyl ether and a sulfonic acid monomer, polyethylene glycol monoalkyl ether and phosphorus. Examples thereof include an ester with an acid monomer, a vinyl group-containing urethane formed from a polyethylene glycol monoalkyl ether and an isocyanate group-containing monomer, and a macromonomer containing a polyvinyl alcohol structure. As a repeating number of the ethyleneoxy part of the said polyethylene glycol monoalkyl ether, 8-50 are preferable and 10-30 are more preferable. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably 1-20, and more preferably 1-12.

  These monomers may be used alone to form a vinyl polymer, or two or more may be used in combination to form a vinyl polymer. The purpose of the vinyl polymer (Tg adjustment, solubility) It can be appropriately selected according to improvement, dispersion stability, etc.

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

  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 dispersing or dissolving in combination with a resinous dispersant or binder. More preferably, it is used in combination with a dispersant.

  For a 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 inkjet recording liquid is heated and jetted.

  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, microwax. Crystallin wax, petrolactam, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid) Acid), organic acid esters (for example, esters of the above-mentioned organic acids with alcohols such as glycerin, diethylene glycol, and ethylene glycol), alcohols (for example, dodecanol, tetradecanol, hexadecanol, eicosano) , Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetracenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, teleaphthalyl alcohol , Hexanediol, decanediol, dodecanediol, tetradecandiol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosanediol, octanediol, phenylpropylene glycol, bisphenol A, paraalphacumylphenol Etc.), ketones (eg benzoylacetone, diacetobenzene, benzophenone, tricho Non, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic amide, lauric amide, stearic amide, ricinoleic amide, palmitic amide , Tetrahydrofuranic acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, N, N'-ethylenebislauric acid amide, N, N'- Ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis behenic acid amide, N, N'-xylylene bis stearic acid amide , N, N'-Buchi Lenbis stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-cysteallyl sebacic acid amide, Like N, N'-distearyl terephthalamide, N, N'-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid (1: 2: 2 molar ratio) A reaction product of dimer acid, diamine and fatty acid such as tetraamide), sulfonamide (eg, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), Silicone KR215, 216, 220 (Shin-Etsu Corn), etc.), coumarones (for example, Escron G-90 (Nippon Chemical Co., Ltd.)), cholesterol fatty acid esters (for example, stearic acid cholesterol, palmitic acid cholesterol, myristic acid cholesterol, behenic acid cholesterol, lauric acid cholesterol, melisin) Acid cholesterol, etc.), saccharide fatty acid esters (sucrose stearate, sucrose palmitate, sucrose behenate, saccharose laurate, sucrose melinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, melicine Acid lactose, etc.).

  The phase change temperature in the solid-liquid phase change of the solid (phase change) solvent is preferably 60 to 200 ° C, and more preferably 80 to 150 ° C.

  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 can also be dispersed or dissolved in combination with a resinous dispersant or binder. It can also be used.

  For specific methods for preparing such phase change solvents, the methods described in JP-A Nos. 5-186723 and 7-70490 can be referred to.

The ink jet recording liquid of the present invention using the water-based, oil-based, or solid (phase change) solvent as described above and dissolving or dispersing the dye of the present invention has a viscosity at the time of flight of 4 × 10 ⁻² Pa · s. The following is preferable, and 3 × 10 ⁻² Pa · s or less is more preferable.

Further, the surface tension of the ink jet recording liquid of the present invention is preferably 2 × 10 ⁻⁴ to 10 ⁻³ N / cm, and more preferably 3 × 10 ⁻⁴ to 8 × 10 ⁻⁴ N / cm. preferable.

  The dye of the present invention is preferably used in the range of 0.1 to 25% by mass of the ink jet recording liquid, and more preferably in the range of 0.5 to 10% by mass.

  The resin-type dispersant used in the present invention is preferably a polymer compound having a molecular weight of 1,000 to 1,000,000. When these are used, 0.1 to 50% by mass in the ink jet recording liquid is used. It is preferable to contain.

  The inkjet recording liquid of the present invention has a viscosity adjusting agent, a surface tension adjusting agent, a specific resistance depending on the purpose of improving ejection stability, compatibility with a print head and ink cartridge, storage stability, image storage stability, and other various performances. A regulator, a film forming agent, a dispersant, a surfactant, an ultraviolet absorber, an antioxidant, an anti-fading agent, an antifungal agent, an antirust agent, and the like can also be added.

  The ink jet recording liquid of the present invention is not particularly limited with respect to the recording method used, but can be preferably used as an ink jet recording liquid for an on-demand ink jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type). it can.

"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 colorant 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.

  As the binder resin for forming the base, all binders generally used for toners can be used. For example, a styrene resin, an acrylic resin, a styrene / acrylic resin, a polyester resin, and the like can be given. In addition, for the purpose of imparting toner fluidity improvement or charging 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 surfaces are treated with an alkyl group-containing coupling agent or the like are preferably used. The number average primary particle diameter of these is preferably 10 to 500 nm, and the addition amount thereof is preferably 0.1 to 20% by mass with respect to the toner.

  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, ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent for improving the charging characteristics may be added as necessary, but is preferably colorless from the viewpoint of color development, for example, having a quaternary ammonium salt structure or a calixarene structure. And the like.

  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, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the color toner of the present invention is applied is not particularly limited. For example, a method of forming an image by repeatedly forming a color image on a photoconductor to form an image, or a photoconductor Examples include a method in which the formed image is sequentially transferred to an intermediate transfer member or the like, a color image is formed on the intermediate transfer member or the like, and then transferred to an image forming member such as paper to form a color image.

<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.

  The dye of the present invention used for the optical information recording medium of the present invention may be one using only one kind of the dye of the present invention or may be a combination of two or more kinds of the dye of the present invention. Moreover, it may be used in combination with a dye outside the present invention. Further, the content of the dye of the present invention in the recording layer is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, and most preferably 90 to 100% by mass with respect to the dry mass of the entire recording layer. Furthermore, in the recording layer in the present invention, a dye that can be used in a conventional optical information recording medium may be used in combination with the dye in the present invention as long as the effect of the present invention is not affected.

  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 pregrooves having a constant track pitch are formed, or a light reflecting layer and a recording layer on the substrate. A structure having a layer and a protective layer in this order is preferable. In addition, two laminated bodies in which a recording layer and a light reflection layer are provided on a transparent disk-shaped substrate on which pregrooves having a constant track pitch are formed are bonded so that each recording layer is inside. The configuration is also preferable.

  The optical information recording medium of the present invention can use a substrate on which a pre-groove having 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 μm, more preferably in the range of 0.2 to 0.5 μm, particularly 0.2 to 0.5 μm. It is preferably in the range of 0.4 μm. The depth of the pregroove is preferably in the range of 0.01 to 0.18 μm, more preferably in the range of 0.01 to 0.15 μm, and particularly in the range of 0.02 to 0.15 μm. Is preferred. The width of the adjacent pregroove is preferably in the range of 0.05 to 0.4 μm, more preferably in the range of 0.08 to 0.3 μm, and particularly in the range of 0.1 to 0.25 μm. 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.

  The substrate of the optical information recording medium of the present invention is required to be substantially transparent (transmittance of 80% or more) in the wavelength region (350 to 900 nm) of laser light used for recording / reproduction. It can be arbitrarily selected from various materials used as substrates for information recording media. Examples of substrate materials include acrylic resins such as glass, polycarbonate, and polymethyl methacrylate, vinyl chloride resins such as polyvinyl chloride and vinyl chloride 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 viewpoints of moisture resistance, dimensional stability, price, and the like.

  A subbing 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 force, and preventing alteration of the recording layer. Examples of the material for the undercoat layer include polymethyl methacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleic anhydride copolymer, polyvinyl alcohol, N-methylol acrylamide, styrene / vinyl toluene copolymer, chlorosulfone. Polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate copolymer, polymer materials such as polyethylene, polypropylene, polycarbonate, and silane coupling And a surface modifier such as an agent. 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 extrusion coating. can do. The thickness of the undercoat layer is generally in the range of 0.005 to 20 μm, preferably in the range of 0.01 to 10 μm.

  The recording layer can be formed by a method such as vapor deposition, sputtering, CVD or solvent coating, and among these, solvent coating is preferred. In this case, the dye, further quencher, binder, etc., if desired, are dissolved in a solvent to prepare a coating solution, and then the coating solution is applied to the substrate surface to form a coating film, followed by drying. be able to.

  Examples of the solvent 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; chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane and chloroform; dimethylformamide and the like Amide; Hydrocarbon such as methylcyclohexane; Ether such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane; Alcohol such as ethanol, n-propanol, isopropanol, n-butanol, diacetone alcohol; 2,2,3,3-tetra Fluorinated solvents such as fluoropropanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether And the like can be given.

  The above solvents can be used alone or in combination of two or more in consideration of the solubility of the dye used. Various additives such as an antioxidant, a UV absorber, a plasticizer, and a lubricant may be further added to the coating solution depending on the purpose.

  In the case of using a binder, examples of the binder include natural organic polymer materials such as gelatin, cellulose derivatives, dextran, rosin and rubber; and hydrocarbon resins such as polyethylene, polypropylene, polystyrene and polyisobutylene, poly Vinyl resins such as vinyl chloride, polyvinylidene chloride, polyvinyl chloride / polyvinyl acetate copolymer, acrylic resins such as polymethyl acrylate and polymethyl methacrylate, polyvinyl alcohol, chlorinated polyethylene, epoxy resin, butyral resin, Examples include synthetic organic polymers such as rubber derivatives and initial condensates of thermosetting resins such as phenol / formaldehyde resins.

  When a binder is used in combination as the recording layer material, the amount of binder used is generally in the range of 0.01 to 50 times (mass ratio), preferably 0.1 to 5 times the metal complex. It is in the range of mass (mass ratio). Thus, the density | concentration of the pigment | dye in the coating liquid prepared is in the range of 0.01-10 mass% generally, Preferably it exists in the range of 0.1-5 mass%.

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 to 0.5 μm, preferably in the range of 0.015 to 0.3 μm, and more preferably in the range of 0.02 to 0.1 μm.

  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 may be formed on both surfaces of the substrate.

  The recording layer can contain various anti-fading agents in order to improve the light resistance of the recording layer. As the anti-fading agent, a singlet oxygen quencher is generally used. As the singlet oxygen quencher, those described in publications such as known patent specifications can be used. Specific examples thereof include JP-A Nos. 58-175893, 59-81194, 60-18387, 60-19586, 60-19586, 60-35054, 60-36190, 60-36191, 60-44554, 60-44555, 60-44389, 60-44390, 60-54892, 60-47069, 63-20995, JP 4-25492, JP-B-1-38680, JP-A-6-26028, etc., German Patent 350,399, and the Journal of the Chemical Society of Japan, October 1992, page 1141, etc. Can be mentioned. As an example of a preferable singlet oxygen quencher, a compound represented by the following general formula (B) can be exemplified.

In the formula, R _a represents an alkyl group which may have _a substituent, and Q ⁻ represents an anion. R _a is generally an optionally substituted alkyl group having 1 to 8 carbon atoms, and is preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Examples of the substituent of the alkyl group include a halogen atom (eg, F, Cl), an alkoxy group (eg, methoxy, ethoxy), an alkylthio group (eg, methylthio, ethylthio), an acyl group (eg, acetyl, propionyl), an acyloxy group (Eg, acetoxy, propionyloxy), hydroxy group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), alkenyl group (eg, vinyl), and aryl group (eg, phenyl, naphthyl). Among these, a halogen atom, an alkoxy group, an alkylthio group, and an alkoxycarbonyl group are preferable. Preferred examples of the Q ⁻ anion include ClO ₄ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ , and SbF ₆ ⁻ .

  Examples of the compound represented by the general formula (B) are shown in Table 1.

  The amount of the anti-fading agent such as the singlet oxygen quencher used is usually in the range of 0.1 to 50% by mass, preferably 0.5 to 45% by mass, based on the amount of the metal complex of the present invention. The range is more preferably 0.5 to 40% by mass, particularly preferably 1 to 25% by mass.

  It is preferable to provide a light reflection layer adjacent to the recording layer for the purpose of improving reflectivity during information reproduction. The light-reflecting substance that is the material of the light-reflecting layer is a substance having a high reflectance with respect to laser light. Examples thereof include Mg, Se, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, 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, Mention may be made of metals such as Bi and semi-metals or stainless steel.

  These substances may be used alone or in combination of two or more 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, Al metal or alloys thereof, and most preferred are Ag metal, Al metal or alloys thereof.

  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 to 0.3 μm, and preferably in the range of 0.05 to 0.2 μm.

  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. In the case of adopting the same configuration as that for manufacturing a DVD-R type optical information recording medium, that is, a configuration in which the recording layer is bonded to the inside using two substrates, it is not always necessary to provide a protective layer. .

Examples of materials used for the protective layer include inorganic substances such as Zn—SiO ₂ , ZnS, SiO, SiO ₂ , MgF ₂ , SnO ₂ , Si ₃ N ₄ , thermoplastic resins, thermosetting resins, and UV curable resins. Organic substances such as resins can be mentioned. The protective layer can be formed, for example, by laminating a film obtained by extrusion of plastic on the reflective layer via an adhesive. Or you may provide by methods, such as vacuum evaporation, sputtering, and application | coating.

In the case of a thermoplastic resin or a thermosetting resin, it can also be formed by dissolving these in a suitable solvent to prepare a coating solution, and then applying and drying the coating solution. 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 a suitable solvent, and then applying the coating solution and curing it by irradiation with UV light. In these coating liquids, various additives such as an antistatic agent, an antioxidant, and a UV absorber may be added according to the purpose. The thickness of the protective layer is generally in the range of 0.1 μm to 1 mm.

  Through the above steps, it is possible to produce 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.

  The optical information recording method of the present invention is performed, for example, as follows using the optical information recording medium. First, recording light such as semiconductor laser light is irradiated from the substrate side or the protective layer side while rotating the optical information recording medium at a constant linear velocity (3.84 m / sec in the case of DVD-R format) or a constant angular velocity. To do. By this light irradiation, the recording layer absorbs the light and the temperature rises locally, causing a physical or chemical change (for example, generation of pits) and changing its optical characteristics, thereby recording information. It is thought that it is done.

  In the present invention, semiconductor laser light having an oscillation wavelength in the range of 300 to 900 nm is used as recording light. Examples of the light source for recording and reproducing the optical information recording medium of the present invention include a solid 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 beam having an oscillation wavelength in the range of 400 to 410 nm and an infrared semiconductor laser beam having a central oscillation wavelength of 850 nm or 820 nm are halved to 425 nm or 410 nm, respectively, using an optical waveguide device. Blue violet SHG laser light can also be mentioned as a preferred light source. In particular, it is preferable to use blue-violet semiconductor laser light 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. Can be done by.

"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 varnish, various dispersing means such as a two-roll mill, a three-roll mill, a sand mill, and a kneader can be used.

  In the present invention, as the resin varnish, a varnish used in a conventionally known colored composition for a color filter is used. As the dispersion medium, a solvent or an aqueous medium suitable for the resin varnish 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.

  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, electron beam curable inks, etc., and non-photosensitive resin varnishes include, for example, relief printing inks, planographic inks, intaglio gravure inks, Any of varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, and varnishes used for thermal transfer ribbons can be used.

  Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Examples of the varnish include polyester acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, polyol acrylate resins, and varnishes to which a monomer is added as a reactive diluent. 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 varnish, and then bricking it 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.

  When forming a color filter pattern using the above photosensitive coloring composition, spin coating the photosensitive coloring composition on a transparent substrate, coating the entire surface using a low-speed rotary coater, roll coater, knife coater, etc. Or performing full printing by various printing methods or partial printing slightly larger than the pattern, and after pre-drying, the photomask is brought into close contact, and exposure is performed using an ultrahigh pressure mercury lamp to print the pattern. Next, development and washing are performed, and post-baking is performed as necessary, whereby a color filter pattern can be formed.

  Examples of non-photosensitive resin varnishes include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, amino resin modified polyester resins , Polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethyl cellulose, water-soluble styrene-maleic acid ester copolymer Examples include salts, water-soluble salts of (meth) acrylic acid ester-based (co) polymers, water-soluble aminoalkyd resins, water-soluble aminopolyester resins, water-soluble polyamide resins, and the like. .

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

《Front filter for display》
The front filter for 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, and is contained in the base material referred to in the present invention means the inside of the base material. Of course, it means a state where it is applied to the surface of the substrate, a state where it is sandwiched between the substrates, and the like.

  In addition, the front filter for display in the present invention is disposed on the front surface of a self-luminous display device such as a plasma display or an organic EL display, and is used for color adjustment or blocking light emission in an unnecessary wavelength region. For this reason, the display front filter of the present invention is characterized by having 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 has 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. Examples of such a wavelength range include 350 to 400 nm, 480 to 520 nm, and the like. In particular, in order to cut off neon emission, it is preferable to have an absorption maximum at 560 to 620 nm, and more preferable to have an absorption maximum at 580 to 605 nm.

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

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

The method for producing the front filter for a display of the present invention using the dye or the composition thereof is not particularly limited,
(1) Method of containing in transparent adhesive (2) Method of containing in polymer molded body (3) Method of coating on polymer molded body or glass surface, etc.

  Specific examples of the transparent adhesive listed in (1) include acrylic adhesives, silicone adhesives, urethane adhesives, polyvinyl butyral adhesives (PVB), and ethylene-vinyl acetate adhesives (EVA). Etc., sheet-like or liquid pressure-sensitive adhesives such as polyvinyl ether, saturated amorphous polyester, melamine resin, etc., among which acrylic pressure-sensitive adhesives, urethane pressure-sensitive adhesives, and polyvinyl butyral pressure-sensitive adhesives are preferable. The addition amount of the dye of the present invention is usually 10 ppm to 30% by mass, preferably 10 ppm to 20% by mass, and particularly preferably 10 ppm to 10% by mass.

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

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

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

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

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

  As a method for coating the polymer molded body or glass surface mentioned in (3), a method in which the dye of the present invention is dissolved in a binder resin and an organic solvent to form a composition, and then a paint is formed, an uncolored acrylic emulsion Examples thereof include a method of dispersing a finely pulverized (50 to 500 nm) pigment of the present invention into a paint to obtain an acrylic emulsion-based aqueous paint. In the coating material, additives such as antioxidants used in ordinary coating materials may be added.

  Examples of binders include aliphatic ester resins, acrylic resins, melamine resins, urethane resins, aromatic ester resins, polycarbonate resins, aliphatic polyolefin resins, aromatic polyolefin resins, polyvinyl resins, polyvinyl alcohol resins, and polyvinyl resins. Examples thereof include a modified resin (PVB, EVA, etc.) or a copolymer resin thereof.

Examples of the solvent include halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvents, or mixtures thereof.
The concentration of the composition varies depending on the gram extinction coefficient, coating thickness, target absorption intensity, target visible light transmittance, and the like, but is usually 0.1 ppm to 30% by mass with respect to the mass of the binder resin. Moreover, resin concentration is 1-50 mass% normally with respect to the whole coating material.
The coating material produced by the above method is applied by forming a thin film on a substrate by a known method such as a bar coder, blade coater, spin coater, reverse coater, die coater, or spray coating method. be able to.

The front filter for display of the present invention preferably has an electromagnetic wave shielding function or a near infrared ray blocking function. As the electromagnetic wave shield, a laminate using a silver thin film or a metal mesh mainly using copper can be used. As a laminate using a silver thin film, a laminate in which a dielectric such as indium oxide, zinc oxide, titanium oxide and silver are alternately laminated is preferable. As the metal mesh, a fiber mesh obtained by vapor-depositing a metal on a fiber, an etching mesh that forms a pattern using a photolithography technique and obtains a mesh by etching, or the like can be used. In addition, a method of patterning with ink containing metal, a method of applying and developing and fixing silver halide, etc. are also preferably used.For the near red ray blocking function, when using an electromagnetic wave shield using a silver thin film, Because of scattering by free electrons, it is possible to simultaneously block near infrared rays. In addition, when a mesh, ink patterning, or development method is used, a film that absorbs or reflects near infrared rays is used separately.

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

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

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

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

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

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

  The front filter for display of the present invention can be suitably used as a neon cut filter that selectively blocks light emission of neon gas in the cell. As described above, a color display is performed by light emission of a phosphor in a plasma display. When neon atoms are excited and return to a ground state, so-called neon orange light centered around 600 nm (580 to 590 nm) is emitted. (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 that a bright red color cannot be obtained because orange is mixed with red. In order to eliminate this drawback, it is desired to cut off neon light emission. Therefore, when the compound of the present invention is used as a composition for a neon emission absorption filter, the compound of the present invention preferably has an absorption maximum at 560 to 620 nm in a solution state, and has an absorption maximum at 580 to 605 nm. It is further preferable to have 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 0.01 to 80%, and more preferably in the range of 1 to 70%. In order to improve the color reproducibility of the display, the absorption waveform in the wavelength region of 560 to 620 nm is preferably sharp. Specifically, in the absorption waveform at 560 to 620 nm, the half width value (the width of the wavelength region showing the absorbance at half of the absorbance at the absorption maximum) is preferably 15 to 100 nm, and more preferably 20 to 70 nm. More preferably, it is 25-50 nm.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

Example 1
(Synthesis of Exemplified Compound 1-4)
It was synthesized according to the following scheme.

  As a ligand, 1.20 g of 2,4-bis (2,6-dihydroxy-4-oxocyclohexa-2,5-dienylidene) cyclobutane-1,3-dione was dissolved in 50 ml of ethanol by heating. To this solution, a copper (II) perchlorate hexahydrate, 0.68 g 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 (1-4).

  The elemental analysis results showed good agreement by adding two molecules of ethanol to the target complex.

Elemental analysis (C ₃₆ H ₂₈ CuO ₁₈ )
Theoretical value (%) C, 53.24; H, 3.48; Cu, 7.82
Found (%) C, 53.41; H, 3.55; Cu, 7.63
λmax, 564 nm; λ _1/2 , 26 nm; ε, 27000 (ethyl acetate solvent)
(Synthesis of Exemplified Compound 1-10)
0.90 g of 2,4-bis (2-hydroxy-4-oxocyclohexa-2,5-dienylidene) cyclobutane-1,3-dione as a ligand and nickel (II) acetate tetrahydrate as a metal Except for using 0.37 g, Exemplified Compound (1-10) was synthesized in the same manner as in Synthesis Example of Exemplified Compound 1-4.
) 0.39 g was obtained.

Elemental analysis (C ₃₂ H ₁₆ NiO ₁₂₎
Theoretical value (%) C, 59.02; H, 2.48; Ni, 9.01
Found (%) C, 58.98; H, 2.35; Ni, 8.88
λ max, 600 nm; λ _1/2 , 64.5 nm; ε, 53000 (ethyl acetate solvent)
(Synthesis of Exemplified Compound 2-25)
The ligand is 2-((2-hydroxy-4-oxocyclohexa-2,5-dienylidene) dioxocyclobutylidene) methyl-1,3,3-trimethylindolium 0.80 g and the metal is bis (acetyl Acetonate) Except for using 0.29 g of copper (II), 0.44 g of Exemplified Compound (2-25) was obtained in the same manner as in Synthesis Example of Exemplified Compound 1-4. The results of elemental analysis showed good agreement by adding one water molecule to the target complex.

Elemental analysis _{(C 44 H 36 CuN 2 O} 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)
1.40 g of 2,4-bis (2,3-hydroxy-4-oxocyclohexa-2,5-dienylidene) cyclobutane-1,3-dione as a ligand was dissolved in a mixed solvent of 70 ml of ethyl acetate and 15 ml of acetic acid. did. To this solution, 0.60 g of aluminum tris (ethyl acetoacetate) was added and 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 target exemplified compound (1-12).

Elemental analysis (C ₄₈ H ₂₄ AlO ₂₄₎
Theoretical value (%) C, 56.99; H, 2.39; Al, 2.67
Found (%) C, 57.14; H, 2.49; Al, 2.55
(Synthesis of Exemplified Compound 1-18)
It was synthesized according to the following scheme.

  2,4-bis (2,6-dihydroxy-4-oxocyclohexa-2,5-dienylidene) -cyclobutane-1,3-dione (1.65 g) as a ligand was dissolved in 50 ml of methanol. Bis (decyl-2-cyano-4,4,4-trifluoro-3-oxobutanoate) Cu (II), 1.76 g of methanol solution was added dropwise thereto 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 using methanol to obtain 1.54 g of the intended exemplary compound (1-18). The elemental analysis values showed good agreement by adding one molecule of water to the target structure.

Elemental analysis _{(C 31 H 36 CuF 3 NO} 12)
Theoretical value (%) C, 50.65; H, 4.94; Cu, 8.64; N, 1.91
Found (%) C, 50.48; H, 5.11; Cu, 8.55; N, 2.00
λmax, 564 nm; λ _1/2 , 26 nm; ε, 27000 (ethyl acetate solvent)
(Synthesis of Exemplified Compound 2-50)
2- (1-Butyl-3-methyl-5-oxopyrazolidene) -4- (2,6-dihydroxy-4-oxocyclohexa-2,5-dienylidene) cyclobutane-1,3- as the ligand Except that 0.70 g of dione and 1.39 g of bis (1- (4- (ethoxycarbonyl) phenoxy) -3- (methoxycarbonyl) -4-oxopentenyloxy) copper were used for the metal, the above exemplified compound (1- 182) 0.42 g of the target metal complex (2-50) was obtained in the same manner as in the synthesis example.

Elemental analysis (C ₃₄ H ₃₃ CuN ₂ O 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 1A)
A 0.5% dimethoxyethane solution of the exemplary compound (1-1) 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 was reddish purple, and it was found that the compound of the present invention effectively absorbs visible light.

(Visible light absorption filter 1B)
A 1.0% tetrahydrofuran solution of the exemplary compound (1-1) of the present invention and a 20% dimethoxyethane solution of a polyester resin (dispersion medium) are mixed at a ratio of 2: 8, and coated on a glass substrate with a bar coater. A coating film was prepared by drying. This film was reddish purple, and it was found that the compound of the present invention effectively absorbs visible light even in a composition containing a dispersion medium.

(Visible light absorption filters 2A-11A, 2B-11B of the present invention and comparative visible light absorption filters 12A-14A, 12B-14B)
The visible light absorption filters 2A to 11A and 2B to 11B of the present invention and the comparative visible light absorption filters 12A to 14A were similarly changed except that the dye used was changed from the exemplified compound (1-1) to the dyes shown in Table 2. 12B-14B were produced. Here, as the dye of the filters 13A and 13B, the comparative compound 1 + MS-1, a solution obtained by sufficiently mixing the comparative compound 1 and bis (acetylacetonato) nickel in a dimethoxyethane solution or a tetrahydrofuran solution was used as the dye.

  The following evaluation was performed about the produced visible light absorption filter.

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

(Dye remaining rate%) = (exposed sample maximum absorption wavelength concentration / unexposed sample maximum absorption wavelength concentration) × 100
A: Dye residual ratio is 95% or more A: Dye residual ratio is 90% to less than 95% B: Dye residual ratio is 80% to less than 90% Δ: Dye residual ratio is less than 80% Practical dye residual ratio 90 % Or more is preferable.

(Moisture and heat resistance)
For heat and humidity resistance, the visible light absorption filter was stored for 14 days under conditions of 60 ° C. and 90% RH, and then the chromaticity change before and after storage using a color difference meter CR-400 (manufactured by Konica Minolta Sensing). That is, ΔEab value was measured and evaluated as follows.

AA: Change in chromaticity cannot be discerned when ΔEab is less than 1.5 A: ΔEab is less than 1.5 to 3.2 and almost no change in chromaticity is observed B: ΔEab is less than 3.2 to 6.5 C: ΔEab is less than 6.5 to 10.0, and chromaticity change is recognized D: ΔEab is 10.0 or more, and chromaticity change is large and looks like another color The evaluation results are shown in Table 2.

  From the table, it can be seen that the coloring matter of the present invention effectively absorbs visible light and is a visible light absorption filter excellent in light resistance and moisture and heat resistance. Furthermore, when the dye of the present invention is used as a mixture with a dispersion medium, it can provide a visible light absorption filter having excellent light resistance and moist heat resistance and excellent fastness.

  On the other hand, when the comparative unchelated squarylium compound (12A) is used, the light resistance and moist heat resistance are greatly inferior, and when used as a mixture with a dispersion medium, the fastness is significantly higher than that of the dye of the present invention. It turns out that it is less than. Further, in the case of the filters 13A and 13B using a mixture of a squarylium compound and a metal as a pigment, there is a problem in heat and moisture resistance, which is insufficient in practical use. Even in the case of the 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 same as those of the dye 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 dye density change and color change over a long period of time.

Example 3 (Ink)
(Synthesis of colored fine particle dispersion)
As an oil-soluble polymer, 15 g of polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 350), 8 g of the exemplary compound (1-3) of the present invention and 150 g of ethyl acetate as a pigment are placed in a separable flask. Was substituted with N ₂ and stirred to completely dissolve the polymer and the dye. Subsequently, 150 g of an aqueous solution further containing 3 g of sodium lauryl sulfate was added dropwise and stirred, and then emulsified for 300 seconds using an ultrasonic disperser (UH-150 type, 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.

(Preparation of water-based ink)
The colored fine particle dispersions prepared as described above were each weighed in an amount of 2% by mass as the finished dye content ink, and 15% ethylene glycol, 15% glycerin, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) The ink composition IJ-1 was obtained by preparing 0.3% with the remainder being pure water and further filtering through a 2 μm membrane filter to remove dust and coarse particles. IJ-2 to 10 were obtained in exactly the same manner except that the exemplified compound (1-3) was replaced with the dyes shown in Table 3. However, for IJ-11, 7.24 g of Comparative Compound 3 and 2.82 g of bis (acetylacetonato) nickel were dissolved and mixed in ethyl acetate, polyvinyl butyral was added, and the same treatment was performed thereafter. 11 was obtained.

(Sample preparation and evaluation)
Furthermore, each ink was printed on Konica photo jet paper Photolique QP glossy paper (manufactured by Konica Minolta Co., Ltd.) using a commercially available Epson inkjet printer (PM-800), and the obtained images were evaluated as follows. I went about the item.

(Color tone)
For each coated sample, a four-stage evaluation was performed by visual evaluation with 10 monitors. ○ It is desirable to be above.

◎: Vivid and clear color ○: Vivid color △: Dull color ×: Dirty color (light resistance)
Using a xenon weather meter manufactured by Suga Test Instruments Co., Ltd., calculate the% 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 (70,000 lux) explosion. The evaluation was based on the following criteria.

Reduction rate% (dye residual rate%) = (exposed sample maximum absorption wavelength concentration / unexposed sample maximum absorption wavelength concentration) × 100
A: Dye remaining ratio is 90% or more B: Dye remaining ratio is 85% to 90%
C: Dye remaining ratio is 80 to 85%
D: Dye remaining rate is less than 80% (water resistance)
With a micropipette, water was dropped on each of the obtained prints, and after 1 minute, rubbing with a finger to visually determine whether or not the print was disturbed. ◎: Substantially no change was observed. : Images can be identified even if they are disturbed (acceptable level)
×: Image is distorted to the extent that it cannot be identified (heat and humidity resistance)
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.

A: Dye remaining ratio is 90 to 95%
○: Dye remaining rate is less than 85 to 90% Δ: Dye remaining rate is less than 80 to 85% ×: Dye remaining rate is less than 80% and the color appears to be cloudy visually Dye remaining rate is 85% or more (◎, ○) Is practically preferable.

  Table 3 shows the evaluation results.

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

  On the other hand, it can be seen that the comparative ink IJ-9 using a comparative non-chelated squarylium compound as a coloring matter 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 excellent in terms of color tone and water resistance, but has problems in light resistance and wet heat resistance. It was found that the comparative ink IJ-11 using the mixture as a coloring matter was not excellent in color tone, and inferior in light resistance, water resistance and heat and humidity resistance, and was excellent in fastness and good image storage stability by using the coloring matter of the present invention. Ink could be provided.

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, polypropylene 3 The mass part was mixed, ground meat, pulverized, and classified to obtain powders each having a volume average particle size of 8.5 μm. Further, 100 parts by mass of this powder and 1.0 part by mass of silica fine particles (number average primary particle size 12 nm) were mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain color toners 1 to 9 by a pulverization method.

(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 subjected to ultrasound to give an aqueous dispersion. The emulsion is emulsified in water so that the solid content concentration becomes 30% by mass with a surfactant while heating the aqueous dispersion containing the pigment of the present invention and low molecular weight polypropylene (number average molecular weight = 3200). An emulsified dispersion was prepared in advance.

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

  To 1000 ml of the resulting dispersion of dye-containing resin fine particles, sodium hydroxide was added to adjust the pH to 7.0, 270 ml of a 2.7 mol% aqueous potassium chloride solution was added, 160 ml of isopropyl alcohol, and ethylene 9.0 g of polyoxyethylene octyl phenyl ether having an average degree of polymerization of oxide of 10 was dissolved in 67 ml of pure water and added, and the reaction was carried out by stirring at 75 ° C. for 6 hours.

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

(Development 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”.

<Evaluation of toner>
(Evaluation equipment)
The above color toner and developer were set in a developing machine of a commercially available color image forming apparatus “Konica 9331” (manufactured by Konica Minolta Business Technologies Co., Ltd.) adopting an electrophotographic method, and the following evaluation items were evaluated. . In order to clarify the difference in color toner performance, the evaluation was made by modifying the color toner so that it can be used in all four color developing units. The evaluation sample produced the reflection image (image on paper) and the transmission image (OHP image) on paper and OHP, respectively. The color toner was prepared in an amount of 0.65 to 0.75 mg / cm ² . About each obtained image sample, light resistance, heat-and-moisture resistance, and the transparency of an OHP image were evaluated.

(Light resistance)
For light resistance, after measuring the image density immediately after recording, using a weather meter (Atlas C.165), the image was irradiated with xenon light (70000 lux) for 14 days, and then the image density was measured again. The dye residual ratio (%) was calculated from the difference in image density before and after the xenon light irradiation, and evaluated according to the following criteria. The image density was measured using a reflection densitometer (X-Rite 310TR). The evaluation results are shown in Table 4 below.

A: Dye remaining ratio is 95% or more A: Dye remaining ratio is 90 to less than 95% B: Dye remaining ratio is less than 85 to 90% B: Dye remaining ratio is 75 to less than 85% ×: Dye remaining ratio is 75 <% (Heat and humidity resistance)
For heat and humidity resistance, the image density immediately after recording was measured and stored for 14 days under the conditions of 50 ° C. and 80% RH. Then, the image density was measured again, and the dye residual ratio (% ) Was calculated and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR) and evaluated according to the following criteria. In addition, the color change was observed visually.

A: Dye residual ratio is 95% or more A: Dye residual ratio is less than 90-95% B: Dye residual ratio is less than 80-90% B: Dye residual ratio is less than 80% X: Dye 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 of each of the following wavelengths. Spectral transmittance was measured by using a 330-type self-recording spectrophotometer (manufactured by Hitachi, Ltd.), measuring the visible spectral transmittance of a color toner image with reference to an OHP sheet on which no color toner is carried, yellow 570 nm, magenta Spectral transmittances at 650 nm and cyan 500 nm were determined and evaluated according to the following criteria.

○: Spectral transmittance is 80% or more and transparency is very good and good Δ: Spectral transmittance is 70 to 80% and transparency is good and no practical problem ×: Spectral transmittance is 70% or less and transparency is poor Practical problem.

  Table 4 shows the evaluation results.

  As is apparent from the table, an image produced using the color toner of the present invention exhibits good wet heat resistance and high OHP quality, and the color toner of the present invention is suitable for use as a full-color toner. Furthermore, since an image produced using the color toner of the present invention has good light resistance, it can be stored for a long time.

Example 5 (Optical Recording Medium)
(Preparation of optical recording medium 1)
A recording layer (thickness: 90 nm) was coated on a polycarbonate substrate with a groove having a diameter of 12.7 cm using the dye (1-6) of the present invention, a reflective layer (Ag, thickness of 100 nm), and a protective film (ultraviolet curing). Acrylic resin (thickness: 5 μm) was sequentially formed according to a conventional method to produce the optical recording medium 1 of the present invention.

(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 (1-6) used in the production of the optical recording medium 1. However, in the optical recording media 2 and 5, a mixture of a dye and 1.0% by mass of an anti-fading agent (B-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.

(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.

  In addition, using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd., the same recording and reproduction experiment was conducted after 24 hours of light exposure, and the dye remaining calculated from the dye concentration before and after the light exposure. The rate (%), minimum recording power, and number of reproductions were determined.

  The evaluation results are shown in Table 5.

  As is apparent from the table, the optical recording media 1 to 3 of the present invention were able to perform good recording and reproduction satisfying the DVD standard. In addition, it has become clear that the recording and reproducing characteristics have particularly excellent light resistance.

  On the other hand, the optical recording medium 3 for comparison had a phenomenon that the reflectance was lowered by the reproduction light of the laser, causing a reproduction failure, and the optical recording media 3 and 4 could not be recorded even by light irradiation with a xenon fade meter. When the dye residual ratio was measured, it was found that in the comparative optical recording media 3 and 4, the residual ratio after light exposure was greatly reduced.

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 red (R), green (G) and blue (B) color filters were prepared. The used photosensitive polyimide resin varnish is a photosensitive polyimide resin varnish containing a photosensitizer.

(Components of photosensitive coating agent for color filters)
R:
Dye of the present invention: (1-21) 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts G:
Dye of the present invention: (2-63) 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts B:
Color material B-1 10 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts A glass plate treated with a silane coupling agent is set on a spin coater, and the above red R color filter photosensitivity The functional coating agent was first spin-coated at 300 rpm for 5 seconds and then at 2000 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² .

  Next, development and washing were performed with a dedicated developer and a dedicated rinse, and a red mosaic pattern was formed on the glass plate. Subsequently, the green mosaic pattern and the blue mosaic pattern were applied and baked in accordance with the above-described method using the above G green color filter photosensitive coating agent and B blue color filter photosensitive coating agent. Then, according to a conventional method, a black matrix was formed to obtain a color filter CF-1.

(Preparation of color filter CF-2-4 of the present invention and comparative RGB color filter CF-5-7)
In the production of the color filter CF-1, the present invention was exactly the same except that the R dye (1-21), the G dye (2-63), and the B dye B-1 were changed to the dyes shown in Table 6. RGB color filters CF-2 to 4 and comparative RGB color filters CF-5 to 7 were prepared.

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

(Color tone)
Each filter was evaluated in three stages by visual evaluation using 10 monitors. ○ It is desirable to be above.

◎: Vivid and clear color ○: Vivid color △: Dull color (heat resistance)
The glass substrate with the undercoat layer on which the pattern image 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 then the chromaticity change before and after heating, that is, ΔEab 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 better heat resistance.

(Light resistance)
The glass substrate with the undercoat layer on which the pattern image was formed was irradiated with a xenon lamp at 70000 lux for 10 days, and then the chromaticity change, that is, the ΔEab value 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 better light resistance.

  The evaluation results are shown in Table 6.

  From the table, the color filters CF-1 to CF-4 of the present invention have significantly improved fastness such as heat resistance and light resistance compared to the comparative color filters CF-5 to CF-7, and the color tone is also improved. It was found that it had excellent properties, and had excellent properties as a color filter applicable to liquid crystal color displays and the like.

Example 7 (Front filter for display)
(Preparation of coating film 1)
A polyethylene terephthalate (PET) film (thickness: 100 μm), 0.5 g of a 0.4% methyl ethyl ketone / toluene mixed solution (methyl ethyl ketone / toluene = 1: 1) of the dye (1-23) of the present invention, 20% of a polyester resin After mixing 6.5 g of a methyl ethyl ketone / toluene mixed solution, it was coated with a bar coater and dried to obtain a coating film having a thickness of 5 μm. The transmittance curve of this coating film has a minimum value at 590 nm, there is no other clear minimum value, and the wavelength of the minimum value 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 emission cut filter and a display front filter that have high transmittance and can effectively absorb neon emission.

(Preparation of coating film 2)
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 on a PET film (thickness 100 μm), 35% methyl ethyl ketone / toluene mixed of acrylic resin After mixing 4.0 g of the solution, it was coated with a bar coater and dried to obtain a coating film having a thickness of 5 μm. The transmittance curve of this coating film has a minimum value at 593 nm, there is no other clear minimum value, and the wavelength of the minimum value 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 emission cut filter and a display front filter that have high transmittance and can effectively absorb neon emission.

(Preparation of coating film 3)
An ultraviolet absorbing coating solution (Sumitomo Osaka Cement Co., Ltd.) containing an isocyanate resin as a binder and zinc oxide as an ultraviolet absorber on a PET resin on the side opposite to the metal complex-containing layer surface of the coating film 1 with a bar coater Coating and drying were performed to form an ultraviolet absorbing layer having a thickness of 3 μm. In the filter, the minimum wavelength of visible light transmittance was not changed.

  Visible region maximum absorption wavelength from unexploded sample of xenon light after 50 hours of explosion from UV absorbing layer surface using xenon fade meter (FAL-25X-HC.B.EC) manufactured by Suga Test Instruments Co., Ltd. The dye residual ratio% was calculated to be 92.7%. Further, the dye residual rate% at the visible region maximum absorption wavelength of the sample after being stored in 60 ° C. and 90% RH for 500 hours was calculated to be 96.8%, and the light resistance and moist heat resistance were good. A neon light emission cut filter having an absorption layer and a front filter for display could be provided.

(Preparation of coating film 4)
The near infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium is formed on the PET resin surface opposite to the metal complex-containing layer surface of the coating film 1. 0.5 g cyclohexanone solution of hexafluoroantimonate) and 3 g polyester resin 20% cyclohexanone solution were mixed, coated with a bar coater and dried to obtain a coating film having a thickness of 6 μm. This coating film was measured with a Hitachi spectrophotometer (U-3500). The wavelengths at the minimum value of the transmittance were 590 nm and 1100 nm.

  When a xenon fade meter manufactured by Suga Test Instruments Co., Ltd. was used to calculate the dye residual percentage at the visible region maximum absorption wavelength from the unexploded sample of the sample after the xenon light was blown from the near infrared absorption layer surface for 50 hours, It was 88.0%. Moreover, when the dye residual rate% in the visible region maximum absorption wavelength of the sample after being stored in 60 ° C. and 90% RH for 500 hours was calculated, it was 94.3%, a neon emission cut filter having a near infrared absorption layer, We were able to provide a front filter for display.

(Preparation of coating film 5)
0.5 g cyclohexanone solution of the near infrared absorbing dye (N, N, N ′, N′-tetrakis (p-dibutylaminophenyl) -p-phenylenediimonium hexafluoroantimonate) 0.5 g of a 0.4% cyclohexanone solution of the dye (1-23) of the present invention is mixed with 6.5 g of a 20% cyclohexane solution of a polyester resin, applied to a PET film (thickness 100 μm) with a bar coater, and dried. Thus, a coating film having a thickness of 6 μm was obtained. Further, 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole is contained as an ultraviolet absorber on the near infrared absorbing dye of the coating film and the PET resin surface opposite to the metal complex-containing surface of the present invention. The ultraviolet absorbing coating solution was coated with a bar coater and dried to form an ultraviolet absorbing layer having a thickness of 3 μm.

  Using a xenon fade meter manufactured by Suga Test Instruments Co., Ltd., when the xenon light was blown from the ultraviolet absorbing layer surface for 50 hours, the percent residual dye at the visible region maximum absorption wavelength from the unexploded sample was calculated. 2%. Further, the dye residual ratio% at the visible region maximum absorption wavelength of the sample after being stored in 60 ° C. and 90% RH for 500 hours was 95.8%.

(Preparation of coating film 6)
Near-infrared absorption using a coating solution prepared with the coating film 4 on a PET film (thickness: 100 μm) using an indium tin monoxide complex and using an argon gas and an oxygen gas to produce an ITO thin film. The neon light-emitting absorption layer was laminated with a thickness of 6 μm. Furthermore, when the surface of the PMMA plate with anti-glare layer on the opposite surface and the non-glare layer on the AR coated PMMA plate is bonded to the ITO surface of the above filter, a plasma display panel filter was created. It was possible to produce a good filter with a high value.

(Comparative example)
A display front filter 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 (1-23) of the present invention.

  When xenon light was blown from the ultraviolet absorbing layer surface for 50 hours using a xenon feather meter, the residual ratio of the dye at the visible region maximum absorption wavelength from the unexploded sample was calculated to be 73.1%. . Moreover, when the dye residual ratio% at the visible region maximum absorption wavelength of the sample after storage in 60 ° C. and 90% RH for 500 hours was calculated, it was 85.4%, compared with the case where the dye of the present invention was used. It turned out that it is inferior to light resistance and heat-and-moisture resistance.

  Further, a display front filter having a near infrared absorption layer was obtained in the same manner as the coating film 3 except that the comparative compound 8 was used instead of the compound (1-23) of the present invention. When the same light resistance test was conducted and the residual ratio (%) of the dye was measured, it was 68.6%. The result of the same heat and humidity resistance test was 70.3%.

  As described above, a front surface for a display having a neon emission absorption filter, an ultraviolet absorption layer, an infrared absorption layer, etc., which has excellent light resistance and moist heat resistance by using the metal complex of the present invention, has high transmittance, and can effectively absorb neon emission. Could provide a filter.

Claims (12)

A squarylium metal complex compound represented by the following general formula (2) .
(In the formula, M represents a metal atom. R ^{1 to} R ³ are a hydrogen atom or a substituent, 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.) Squarylium metal complex compound represented by previous following general formula (2) is, squarylium metal complex compound according to claim 1, characterized in that the squarylium metal complex compound represented by the following general formula (3).
(In the formula, M represents a metal atom. R ^{1 to} R ³ are a hydrogen atom or a substituent, A is an arbitrary organic group, and n is 2 or 3.) The squarylium metal complex compound according to claim 1 or 2, wherein in the general formula (2) or (3) , the organic group A is an aryl group, a heterocyclic group, or the following general formula (1-A). .
(In the formula, A ₁ represents a 5-membered ring or a 6-membered ring, and R ′ ¹ represents a hydrogen atom or a substituent.) The squarylium metal according to any one of claims 1 to 3, wherein in the general formula (2) or (3) , the metal atom M is any one of copper, nickel, cobalt, aluminum, or zinc. Complex compound. It is a squarylium metal complex compound of any one of Claims 1-4, Comprising: The pigment | dye characterized by the absorption maximum wavelength being in a visible light region. A composition comprising at least one dye according to claim 5 and a dispersion medium. A toner comprising at least one dye according to claim 5 . An ink comprising at least one dye according to claim 5 . An optical recording medium comprising at least one dye according to claim 5 . A color filter comprising at least one dye according to claim 5 . A front filter for a display comprising at least one dye according to claim 5 . The front filter for a display according to claim 11, which has an absorption maximum at 560 to 620 nm.